chemistry, physics and technology of surface - IBN

National Academy of Sciences of Ukraine

Chemistry Division

Chuiko Institute of Surface Chemistry

Scientific Council of

"Chemistry and Technology of Surface Modification"

Ukrainian conference with international participation

"CHEMISTRY, PHYSICS AND

TECHNOLOGY OF SURFACE"

devoted to the 30th anniversary of the founding of

Chuiko Institute of Surface Chemistry of NAS of Ukraine

and

Workshop NANOSTRUCTURED BIOCOMPATIBLE / BIOACTIVE

MATERIALS

(FP7-PEOPLE-2013-IRSES-GA-2013-612484)

Book of abstracts

1718 May 2016

Kyiv

Ukraine

2

Матеріали Всеукраїнської конференції з міжнародною участю «Хімія,

фізика і технологія поверхні» і семінару «Наноструктуровані біосумісні /

біоактивні матеріали» – Київ, 2016. – 196 с.

Proceedings of Ukrainian conference with international participation

"Chemistry, physics and technology of surface" devoted to the 30th anniversary

of the founding of Chuiko Institute of Surface Chemistry of NAS of Ukraine and

Workshop "Nanostructured biocompatible / bioactive materials" – Kyiv, 2016.

– 196 p.

Материалы Всеукраинской конференции с международным участием

«Химия, физика и технология поверхности» и семинара

«Наноструктурированные биосовместимые / биоактивные материалы» –

Киев, 2016. – 196 с.

Збірник містить тези доповідей, які було представлено на конференції.

Тематика конференції: теорія хімічної будови та реакційна здатність

поверхні твердих тіл; фізико-хімія поверхневих явищ; хімія, фізика та

технологія наноматеріалів; медико-біологічні та біохімічні аспекти

дослідження високодисперсних матеріалів. Збірник призначено для

наукових та інженерно-технічних працівників і студентів. Тези доповідей

подано в авторській редакції.

ISBN 978-966-02-7921-6

Надруковано за ухвалою Вченої ради Інституту хімії поверхні

ім. О.О. Чуйка Національної академії наук України (протокол №6 від

26. 04. 2016).

Інститут хімії поверхні ім. О.О. Чуйка

Національної академії наук України, 2016

Chuiko Institute of Surface Chemistry of

National Academy of Sciences of Ukraine, 2016

Институт химии поверхности им. А.А. Чуйко

Национальной академии наук Украины, 2016

3

Conference organizators

National Academy of Sciences of Ukraine

Chemistry Division

Chuiko Institute of Surface Chemistry

Scientific Council "Chemistry and Technology of Surface Modification"

Scientific committee

Kartel M.Т., Dr. (Chem.), Prof., Academician of NAS of Ukraine – chairman

Belyakova L.A., Dr. (Chem.), Prof. (Ukraine) – vice-chairman

Brei V.V., Dr. (Chem.), Prof., Corr. Member of NAS of Ukraine

Gorbyk P.P., Dr. (Phys. & Math.), Prof. (Ukraine)

Gun'ko V.М., Dr. (Chem.), Prof. (Ukraine)

Deryło-Marczewska A., Dr. Habil. of Chem., Prof. (Poland)

Eremenko A.M., Dr. (Chem.), Prof. (Ukraine)

Zub Yu.L., Dr. (Chem.), Prof. (Ukraine)

Lupascu T., Dr. Habil. of Chem., Prof., Corr. Member of AS of Moldova

Mikhalovsky S.V., Prof. (Great Britain, Republic of Kazakhstan)

Ogenko V.M., Dr. (Chem.), Prof., Corr. Member of NAS of Ukraine

Poddenezhny Е.N., Dr. (Chem.) (Republic of Belarus)

Rozenbaum V.М., Dr. (Phys. & Math.), Prof. (Ukraine)

Savel‟ev Yu.V., Dr. (Chem.) (Ukraine)

Strizhak P.E., Dr. (Chem.), Prof., Corr. Member of NAS of Ukraine

Tarasevych Yu.I., Dr. (Chem.), Prof., Corr. Member of NAS of Ukraine

Tertykh V.А., Dr. (Chem.), Prof. (Ukraine)

Turov V.V., Dr. (Chem.), Prof., Corr. Member of NAS of Ukraine – vice-

chairman

Fomkin А.А., Dr. (Phys. & Math.) (Russia)

Kholin Yu.V., Dr. (Chem.), Prof. (Ukraine)

Organizing committee

Laguta I.V., PhD (Chem.) – scientific secretary of conference

Bolbukh Yu.M., PhD (Chem.) – secretary of workshop

Davydenko L.O., PhD (Chem.)

Gavrylyuk О.О., PhD (Phys. & Math.)

Galaburda М.V., PhD (Chem.)

Linnik О.P., PhD (Chem.)

Pylypchuk Ye.V., PhD (Chem.)

Prokopenko S.L., PhD (Chem.)

Snegir S.V., PhD (Phys. & Math.)

4

Conference Program

May 17, Tuesday

9:00 – 9:45 Registration of participants

10:00 – 10:10 Opening of the Conference in the Chuiko Institute of Surface Chemistry of

NAS of Ukraine

Academician of NAS of Ukraine, Professor M.T. Kartel

Oral Session 1

Chair: Professor M.T. Kartel

10:10 – 10:35 V.M. Gun’ko1, E.M. Pakhlov

1, V.I. Zarko

1, J. Skubiszewska-Zięba

2. Infrared

spectroscopy as a tool for textural and structural characterization of individual and

complex fumed oxides (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland).

10:35 – 11:00 Yu.L. Zub. Sol-gel chemistry and nanotechnology (Chuiko Institute of

Surface Chemistry, NAS of Ukraine, Kyiv).

11:00 – 11:20 coffee break

Oral Session 2

Chair: Professor Yu.L. Zub

11:20 – 11:40 A.M. Fainleib1, V.A. Bershtein

2, K.G. Gusakova

1, D. Kirilenko

2,

P.N. Yakushev2, V.A. Ryzhov

2, N.S. Lavrenyuk

1. Subnanosizing - a novel approach to

densely crosslinked сyanate esters/silica composites obtained by sol-gel synthesis (1Institute of Macromolecular Chemistry, NAS of Ukraine, Kyiv,

2Ioffe Institute, RAS, Russia,

St.-Petersburg)

11:40 – 12:00 N. Smirnova. Nanosized TiO2-based mixed oxide films for environmental

photocatalysis (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

12:00 – 12:20 Yu. Bolbukh1, P. Klonos

2, P. Pissis

2, V. Tertykh

1. Study of

thermomechanical properties of composites based on sol-gel silica and

2-hydroxyethylmethacrylate (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2National Technical University of Athens, Physics Department, Greece).

12:20 – 12:40 Y.Y. Shlapa, S.O. Solopan, A.G. Belous. Synthesis of weakly agglomerated

(La,Sr)MnO3 nanoparticles and creation of the organic-inorganic composite structures

based on them (Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine,

Kyiv).

12:40 – 13:00 O. Linnik1, N. Chorna

1, N. Smirnova

1, N. Stefan

2, I.N. Mihailescu

2. Pulsed

laser deposited TiO2 based films: synthesis, electronic structures and photocatalytic

activity (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2National Institute for

Lasers, Plasma and Radiation Physics, Ilfov, Romania).

13:00 – 14:00 break

5

Oral Session 3

Chair: Professor V.M. Rozenbaum

14:00 – 14:20 M. Studziński1, Yu.M. Bolbukh

2, R.B. Kozakevych

2, V.A. Tertykh

2.

Synthesis and structure investigation of porous and nonporous materials with enhanced

magnetic permeability (1Planar Chromatography Department, Chair of Physical Chemistry,

Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland, 2Chuiko Institute

of Surface Chemistry, NAS of Ukraine, Kyiv).

14:20 – 14:40 O.A. Khaynakova1, N.G. Kobylinska

2, M. Diaz-Garcia

1, V.N. Zaitsev

2.

Magnetic chelating nanocomposites: synthesis, functionalization and analytical

implications for solid phase extraction (1Department of Analytical and Physical Chemistry,

University of Oviedo, Spain, 2Department of Analytical Chemistry, Taras Shevchenko

National University of Kyiv, Ukraine).

14:40 – 15:00 O.M. Odnovolova1, D.S. Sofronov

1, S.M. Desenko

1, A.A. Beda

2.

Characteristics of formation of iron and manganese oxide particles and their sorption

properties (1STC «Institute for Single Crystals», NAS of Ukraine, Kharkiv,

2Taras

Shevchenko National University of Kyiv, Ukraine).

15:00 – 15:20 N.O. Perlova1, O.V. Perlova

1, Yu.S. Dzyazko

2, V.F. Sazonova

1,

I.Yu. Halutskaya1. Removal of the uranium(VI) compounds from model solutions with

sorbents of different nature (1Faculty of Chemistry, Odessa I.I. Mechnikov National

University, Ukraine, 2Vernadsky Institute of General and Inorganic Chemistry, NAS of

Ukraine, Kyiv).

15:20 – 15:40 V.S. Kuts. Nanoclusters (SiC)n as a base of nanostructured materials for

electrodes of lithium-ion batteries (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).


16:00 – 17:00 Poster session I (1-73)

May 18, Wednesday

Oral Session 4

Chair: Professor V.M. Gun’ko

10:00 – 10:20 N.O. Mchedlov-Petrossyan1, N.N. Kamneva

1, V.V. Tkachenko

1,

A.I. Marynin2, E. Osawa

3. The interfacial properties and colloidal behaviors of detonation

nanodiamond species in water (1Department of Physical Chemistry, Kharkov V. Karazin

National University, Ukraine, 2National University of Food Technologies, Kyiv, Ukraine,

3NanoCarbon Research Institute, Ltd, AREC (Asama Research Extension Center), Faculty of

Textile Science and Technology, Shinshu University, Nagano, Japan).

10:20 – 10:40 А. Derylo-Marczewska, M. Blachnio, A.W. Marczewski. Effect of structural

and surface properties of adsorbent on adsorption equilibria and kinetics (Faculty of

Chemistry, Maria Curie-Sklodowska University, Lublin, Poland).

6

10:40 – 11:00 A.W. Marczewski, M. Sęczkowska,

A. Deryło-Marczewska. Temperature

effects in adsorption equilibrium and kinetics of selected aromatic compounds on active

carbons (Maria Curie-Skłodowska University, Lublin, Poland).

11:00 – 11:20 L.V. Henao-Holguin1, V. Meza-Laguna

1, E.V. Basiuk

2, V.A. Basiuk

1,

T.Yu. Gromovoy3. One step covalent functionalization of C60 and pristine multi-walled

carbon nanotubes with crown ethers (1Instituto de Ciencias Nucleares, Universidad

Nacional Autonoma de Mexico, 2Centro de Ciencias Aplicadas y Desarrollo Tecnologico,

Universidad Nacional Autonoma de Mexico, Mexico, 3Chuiko Institute of Surface Chemistry,

NAS of Ukraine, Kyiv).


Oral Session 5

Chair: Professor A.M. Eremenko

11:40 – 12:00 M. Sęczkowska, A.W. Marczewski, A. Deryło-Marczewska, A. Chrzanowska.

Study of adsorption of selected organics from aqueous solutions on active carbon in the

multicomponent system (Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin,

Poland).

12:00 – 12:20 Ya.V. Panasiuk, G.V. Korzhak, A.E. Raevskaya, O.L. Stroyuk.

Photocatalytic hydrogen production in systems based on hydrazine (dimethylhydrazine)

and graphitic carbon nitride (L.V. Pysarzhevsky Institute of Physical Chemistry, NAS of

Ukraine, Kyiv).

12:20 – 12:40 D.M. Haliarnyk, O.M. Bakalinska, M.T. Kartel. Carbon nanomaterials as

catalysts in reactions of organic peroxides decomposition (Chuiko Institute of Surface

Chemistry, NAS of Ukraine, Kyiv).

12:40 – 13:00 O.A. Viltsaniuk1, P.V. Belyaev, N.M. Rezanova

2, R.A. Lutkovskyi

1.

Nanocomposite suture materials and drugs for prevention and treatment of

postoperative purulent complications and inflammatory diseases (1Vinnytsya National

Pirogov Memorial Medical University, 2Kyiv National University of Technology And Design,

Ukraine).

13:00 – 14:00 break

Oral Session 6

Chair: Professor V.A. Tertykh

14:00 – 14:20 А. Chrzanowska1, A. Deryło-Marczewska

1, A.W. Marczewski

2,

M. Sęczkowska1. Analysis of structure and morphology of the MCF surface with

adsorbed protein molecules (1Department of Physicochemistry of Solid Surface,

2Department of Radio- and Colloid Chemistry, Faculty of Chemistry, Maria Curie-

Skłodowska University, Lublin, Poland).

14:20 – 14:40 L.M. Soldatkina, M.A. Zavrichko. Adsorption of anionic dyes on corn

stalks modified with polyaniline: kinetics and thermodynamic studies (Odessa

I.I. Mechnikov National University, Ukraine).

7

14:40 – 15:00 G.M. Starukh. ZnAl layered double hydroxide sorbent/photocatalyst for

removal of negatively and positively charged organic compounds (Chuiko Institute of


15:00 – 15:20 N.O. L.M. Soldatkina, V.O. Novotna. Adsorption of anthocyanins from the

chokeberry extracts on bentonite (Odessa I.I. Mechnikov National University, Ukraine).

15:20 – 15:40 A.A. Yanovska1,2

, S.B. Bolshanina2, A.S. Stanislavov

1, A.K. Soni

3.

Hydroxyapatite-alginate microspheres loaded with nimesulide for biomedical

application (1Institute of Applied Physics, NAS of Ukraine, Sumy,

2Sumy State University,

Ministry of Education and Science of Ukraine, 3Kusum Pharm, Sumy, Ukraine).


16:00 – 17:00 Poster session II (74-144)

17:00 Conference Closing

Poster presentations:

1. Theory of chemical structure and reactivity of solid surface

1. E.M. Demianenko, A.G. Grebenyuk, V.V. Lobanov, V.A. Tertykh. Progressive surface

alkoxylation at interaction of silica with dialkyl carbonates (Chuiko Institute of


2. V. Galysh1,2

, R. Kozakevych2, M. Kartel

2. Sorption properties of cellulose and

lignocellulose materials towards sodium diclofenac (1Department of Ecology and Plant

Polymers Technology, National Technical University of Ukraine “KPI”, 2Chuiko Institute


3. A.G. Grebenyuk. Quantum chemical study on pressure-induced phase transitions in

arsenic nanoparticles in confined space (Chuiko Institute of Surface Chemistry, NAS of

Ukraine, Kyiv).

4. N.V. Nikolenko1, S.I. Okovytyy

2, I.S. Samchileev

1, A.V. Dubenko

1, V.A. Solovov

1.

Charge-controlled adsorption for wide-gap polar adsorbents (1Ukrainian State

Chemical Technology University, Dnipropetrovsk, 2Oles Honchar Dnipropetrovsk

National University, Ukraine).

5. N.D. Paliychuk, T.R. Tatarchuk. Surface properties of spinel cobalt ferrite (Vasyl

Stefanyk Precarpathian National University, Ivano-Frankivsk, Ukraine).

6. R.V. Garmash1, A.Yu. Chernyak

1, Yu.A. Beznosyk

1, O.V. Smirnova

2, A.G. Grebenyuk

2,

V.V. Lobanov2. Quantum chemical studies on O2 and H2O molecules adsorption on

the anatase face (001) (1National Technical University of Ukraine “KPI”,

2Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

7. A.V. Vakaliuk1, L.M. Grishchenko

1, T.M. Bezugla

1, V.Z. Radkevich

2. Modification of

carbon fibres with S-containing functional groups (1Taras Shevchenko National

University of Kyiv, Ukraine, 2Institute of Physical Organic Chemistry National Academy

of Sciences of Belarus, Minsk).

8

2. Physical chemistry of surface phenomena

8. L.S. Andriyko1, V.I. Zarko

1, V.M. Gun‟ko

1, A.I. Marynin

2, A.I. Ukrainets

2.

Kosmotropes effect of Cl- and NO3

- anions on colloidal properties of nanosilica

(1Chuiko Institute of Surface Chemistry,

2National University of Food Technology, Kyiv,

Ukraine).

9. L.S. Andriyko1, V.I. Zarko

1, V.M. Gun‟ko

1, A.I. Marynin

2, A.I. Ukrainets

2. The

graphene oxide dispersity in aqueous medium (1Chuiko Institute of Surface Chemistry,

NAS of Ukraine, 2National University of Food Technology, Kyiv, Ukraine).

10. T. Lupaşcu, N. Timbaliuc, A. Beshliu. Study of the surface chemistry of activated

carbon obtained by chemical activation (Institute of Chemistry, Academy of Sciences of

Moldova).

11. T. Budnyak1, D. Sternik

2, Yu. Bolbukh

1, A. Deryło-Marczewska

2, V. Tertykh

1. Hybrid

materials based on chitosan and sol-gel silicas (1Chuiko Institute of Surface Chemistry,

NAS of Ukraine, Kyiv, 2Maria Curie-Sklodowska University, Lublin, Poland).

12. V. Chernii1, I. Tretyakova

1, Y. Dovbii

1, S. Korobko

1, O. Severynovska

2, R. Czerwieniec

3.

Synthesis and mass spectrometric fragmentation of the phthalocyanine complexes of

zirconium and hafnium with out-of-plane coordinated protocatechuic aldehyde (1Vernadsky Institute of General and Iinorganic Chemistry, NAS of Ukraine,

2Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv, 3Universitat Regensburg, Institut fur

Physikalische und Theoretische Chemie, Regensburg, Germany).

13. А. Chrzanowska1, A. Deryło-Marczewska

1, A.W. Marczewski

2, M. Sęczkowska

1.

Synthesis and characterization of MCFs with tunable porous structure for

immobilization of biopolymers (1Department of Physicochemistry of Solid Surface

Faculty of Chemistry, Maria Curie-Skłodowska University, 2Department of Radio- and

Colloid Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin,

Poland).

14. T.Ia. Datsko, V.I. Zelentsov. Effect of microstructure of modified diatomite on its

adsorption properties (The Institute of Applied Physics of the Academy of Sciences of

Moldova).

15. V.M. Rozenbaum1, M.L. Dekhtyar

2, L.I. Trakhtenberg

3, S.H. Lin

4. Photoinduced

diffusion molecular transport (1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

2Institute of Organic Chemistry NAS of Ukraine, Kyiv,

3Semenov Institute of Chemical

Physics of RAS, Moscow, 4Department of Applied Chemistry, National Chiao Tung

University, Hsinchu, Taiwan).

16. E.N. Fadieiev, S.S. Smola, N.V. Rusakova. Luminescent properties of hybrid

materials based on silicon dioxide and β-diketonato-1,10-phenanthroline complexes

of Eu(III) (A.V. Bogatsky Physico-Chemical Institute, NAS of Ukraine, Odessa).

17. I.A. Shpak, S.S. Fomanyuk, G.Y. Kolbasov. Gasochromic properties of V2O5/Pt-films

(Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine, Kyiv).

18. O.A. Dudarko1, A.R. Gaidai

2, V.V. Sliesarenko

1, N.A. Prybora

2, Yu.L. Zub

1. Synthesis

of mesoporous materials for extraction of heavy and rare-earth metal ions (1Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv, 2National Pedagogical

Dragomanov University, Kyiv, Ukraine).

19. O.I. Gichan. Influence of the mass transfer function on dynamic instabilities of a

model electrocatalytic process (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).

9

20. M. Ignatovych. Doped lithium tetraborate as advanced luminescent materials:

spectroscopy and dosimetric characteristics (Chuiko Institute of Surface Chemistry,


21. V.I. Kanevskii1, V.M. Rozenbaum

1, V.S. Sidorenko

2, D.I. Pobokin

1. Influence of

surface plazmon resonance on distribution of Poynting vector in the presence of gold

nanocylinder (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Faculty of

Radiophysics, Taras Shevchenko National University of Kyiv, Ukraine).

22. V.N. Kaurkovska, A.G. Grebenyuk. Theoretical study on transformations of formic

acid on vanadium dioxide surface (Chuiko Institute of Surface Chemistry, NAS of

Ukraine, Kyiv).

23. M.O. Khodykina1, K.D. Pershina

2, K.A. Kazdobin

1. Electrochemical properties of

composites based on the system of the immobilized enzyme preparation Raphanus

sativus l. Var. Niger – graphene (1Vernadsky Institute of General and Inorganic

Chemistry NAS of Ukraine, 2Joint Department of Electrochemical Energetics NAS of

Ukraine, Kyiv).

24. T.O. Kiose1,2

, K.O. Golubchik1,2

, T.L. Rakytska1, R.M. Dlubovskiy

2, A.L. Kara

1,

V.Y. Volkova1. Structural-adsorption characteristics of natural and chemically modified

clinoptilolite (1Faculty of Chemistry, Odessa I.I. Mechnikov National University,

2Рhysico-

Chemical Institute of Environment and Human’ Protection, Odessa, Ukraine).

25. О.Ye. Tsomyk, Т.Ye. Korochkova, V.M. Rozenbaum. Brownian rotor as a high-

temperature ratchet (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

26. M.V. Kosevich, O.A. Boryak, V.V. Chagovets, V.S. Shelkovsky, V.V. Orlov. Mass

spectrometric study of silver nanoclusters production in ethylene glycol medium (B. Verkin Institute for Low Temperature Physics and Engineering of NAS of Ukraine,

Kharkov).

27. T. Lupascu1, R. Nastas

1, A. Ivanets

2, L. Postolachi

1, T. Azarova

2, V. Rusu

1,

T. Kuznetsova2, O. Petuhov

1, I. Ginsari

1, T. Goreacioc

1,3. Porous structure of active

carbons modified with manganese compounds (1Institute of Chemistry of Academy of

Sciences of Moldova, Chisinau, 2Institute of General and Inorganic Chemistry, National

Academy of Sciences of Belarus, Minsk, 3Institute of Ecology and Geography of Academy

of Sciences of Moldova, Chisinau).

28. B.V. Lytovchenko, O.Yu. Semchuk, O.O. Havryliuk. Heat transfer in porous media

(Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

29. F.D. Manilevich, L.F. Kozin, A.I. Lisogor, A.V. Kutsyi. Electrochemical and surface

investigations of carbide cathodes for hydrogen evolution from water (Vernadsky

Institute of General and Inorganic Chemistry, NAS of Ukraine, Kyiv).

30. R. Nastas1, T. Lupascu

1, L. Postolachi

1, V. Rusu

1, O. Petuhov

1, I. Ginsari

1,

T. Goreacioc1,2

. Active carbons modified with manganese compounds (1Institute of

Chemistry of Academy of Sciences of Moldova, 2Institute of Ecology and Geography of

Academy of Sciences of Moldova, Chisinau).

31. O. Petuhov. Comparative study of hydrogen and nitrogen adsorption onto

microwave activated carbon (Institute of Chemistry of Academy of Sciences of Moldova,

Chisinau).

32. V.M. Gun‟ko1, V.I. Zarko

1, O.V. Goncharuk

1, A.K. Matkovsky

1, O.S. Remez

1,

J. Skubiszewska-Zieba2. Nature and morphology of fumed oxides and features of

interfacial phenomena (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Maria Curie-Sklodowska University, Lublin, Poland).

10

33. G.G. Repich1, O.V. Severynovska

2, S.I. Orysyk

1, V.I. Pekhnyo

1. Features

fragmentation of mono- and binuclear transition metal complexes under conditions

of MALDI mass spectrometry (1Vernadsky Institute of general and inorganic chemistry,

NAS of Ukraine, 2Chuiko Institute of surface chemistry, NAS of Ukraine, Kyiv).

34. V.F. Sazonova, M.A. Kozhemiak. Adsorption of the tributylphosphate on aluminium

oxide (Faculty of Chemistry, Odessa I.I. Mechnicov National University, Ukraine).

35. M. Sęczkowska, A.W. Marczewski, A. Deryło-Marczewska, A. Chrzanowska.

Comparison of adsorption of benzoic acid and its derivatives on active carbon (Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland).

36. L.A. Karachevtseva1, K.A. Parshyn

1, O.V. Mischanchuk

2, V.O. Pokrovskiy

2.

Temperature programmed desorption mass spectrometry in studies of local chemical

states in structures of macroporous silicon covered by the layer of microporous

silicon (1V.Ye. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,

2Chuiko


37. V.O Pokrovskiy1, O.V. Ischenko

2. Mass spectrometry in heterogeneous catalysis

(1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Taras Shevchenko

National University of Kyiv, Ukraine).

38. A.F. Tymchuk. The surfactants adsorption by natural sorbents (Odessa

I.I. Mechnikov National University, Ukraine).

39. O. Yershova, V. Konovalova, T.G. Meshkova. Magneticaly-active polysulfone

membranes (National University of „Kyiv-Mohyla Academy”, Ukraine).

40. M.G. Zhludenko, O.A. Bieda, E.V. Ischenko. Activity of bulk and Al2O3-supported

Co/Ni catalysts for carbon dioxide methanation (Taras Shevchenko National University

of Kyiv, Ukraine).

3. Chemistry, physics and technology of nanomaterials

41. P.P. Gorbyk, I.V. Dubrovin, N.V. Abramov, D.V. Shaban. Сarbon modified single-

domain nanoparticles of solid solutions (Fе1-X CоХ)Fе2O4. (Chuiko Institute of Surface


42. D. Aravopoulou1, M. Souli

1, K. Kyriakos

2, A. Miasnikova

3, J. Adelsberger

2, A. Meier-

Koll2, A.M. Bivigou-Koumba

3, A. Laschewsky

3, C.M. Papadakis

2, A. Kyritsis

1. Thermal,

dielectric and structural studies on thermoresponsive polymers of complex

architecture (1Department of Physics, National Technical University of Athens, Greece,

2Physik-Department,

Technische Universitet, Munchen,

3Department of Chemistry,

Universitet Potsdam, Germany).

43. E.V. Basiuk1, I.J. Ramirez-Calera

1, V. Meza-Laguna

2, E. Abarca-Morales

1,

T.Yu. Gromovoy3, V.A. Basiuk

2.

Solvent-free functionalization of carbon-based

nanomaterials with amines: from fullerene C60 to buckypaper (1Centro de Ciencias

Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, 2Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Mexico,

3Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

44. L.A. Belyakova. Chemical construction of catalytic active sites on the surface of

ceramic membrane materials (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).

45. V.M. Bogatyrov1, M.V. Galaburda

1, O.I. Oranska

1, M.V. Borysenko

1, J. Skubiszewska-

Zięba2. Synthesis and adsorption of methylene blue by Ni/C nanocomposites (

1Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv, 2Faculty of Chemistry, Maria Curie-

Skłodowska University, Lublin, Poland).

11

46. M.V. Bondarenko, T.A. Khalyavka, S.V. Camyshan. Photocatalytic properties of

titanium dioxide modified with carbon (Institute for Sorption and Problems of

Endoecology, NAS of Ukraine, Kyiv).

47. T.I. Borodinova1, V.I. Styopkin

2, Ya.Y. Lopatina

2, V.E. Kutsenko

2, A.A. Vasko

2.

Formation of gold nanoprisms on mica surface (1F.D. Ovcharenko Institute of

Biocolloid Chemistry, NAS of Ukraine, 2Institute of Physics, NAS of Ukraine, Kyiv).

48. N.V. Bortnyk, A.V. Brichka, O.M. Bakalinska, S.Ya. Brichka, M.T. Kartel. Catalase-

mimetic activity of nanoporous carbon KAU decorated with nanoceria (Chuiko


49. T.M. Budnyak1, M. Błachnio


2, A.W. Marczewski

2,

V.A. Tertykh1. Application of chitosan-silica hybrid composites for removal of dyes

from aqueous solutions (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

Ukraine, 2Maria Curie-Sklodowska University, Lublin, Poland)

50. T.M. Budnyak1, A. Gładysz-Płaska

2, A.V. Strizhak

3, Ie.V. Pylypchuk

1, D. Sternik

2,

M. Majdan2, I.V. Komarov

3, V.А. Tertykh

1. Uranium(VI) sorption by silica with

grafted phosphonic acid derivatives (1Chuiko Institute of Surface Chemistry, NAS of

Ukraine, Kyiv, 2Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin,

Poland, 3Taras Shevchenko National University of Kyiv, Ukraine).

51. N. Chorna, O. Linnik, N. Smirnova. Synthesis, optical and photocatalytic properties

of mesoporous iron-doped titania films (Chuiko Institute of Surface Chemistry, NAS of

Ukraine, Kyiv).

52. Kh.V. Demydova1, O.I. Demchyna

1, I.Yu. Yevchuk

1, T.F. Samoylenko

2.

Viscoelastic

properties of organic-inorganic composites based on acrylic monomers and TEOS (1Department of Physico-chemistry of Fossil Fuels L.M. Lytvynenko Institute of Physico-

organic Chemistry and Coal Chemistry, NAS of Ukraine, Lviv, 2Institute of

Macromolecular Chemistry, NAS of Ukraine, Kyiv).

53. N.M. Dolaberidze, V.G. Tsitsishvili, N.A. Mirdzveli, M.O. Nijaradze. Synthesis of

nanozeolite-like material (Petre Melikishvili Institute of Physical and Organic Chemistry

of Ivane Javakhishvili Tbilisi State University, Georgia).

54. P.P. Gorbyk1, O.P. Dmytrenko

2, I.V. Dubrovyn

1, T.O. Busko

2, I.S. Matviichuk

2.

Synthesis and structure of TiO2 thin nanocomposite films (1Chuiko Institute of Surface

Chemistry, NAS of Ukraine, Kyiv, 2Department of Physics, Department of Physics

Functional Materials, Taras Shevchenko National University of Kyiv, Ukraine).

55. L. Dzubenko1, O. Sapyanenko

1, P. Gorbyk

1, V. Plavan

2, N. Rezanova

2. The features of

fiber-forming processes in the melts of polypropylene-polyvinyl alcohol-glycerol-

hydrophobic silica (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Kyiv

National University of Technologies & Design, Ukraine).

56. L. Eprikashvili, I. Rubashvili, T. Kordzakhia, M. Zautashvili. Removal of volatile and

tobacco-specific N-nitrosamines from tobacco smoke using Georgian natural zeolites (Ivane Javakhishvili Tbilisi State University; Petre Melikishvili Institute of Physical and

Organic Chemistry, Tbilisi, Georgia).

57. G.V. Fedorenko, L.P. Oleksenko, N.P. Maksymovych, I.P. Matushko, G.I. Skolyar,

O.P. Ripko. Nanosized Pd/SnO2 materials for adsorption semiconductor sensors to

methane (Department of Chemistry, Taras Shevchenko National University of Kyiv,

Ukraine).

58. K. Gdula1, E. Skwarek

1, A. Dąbrowski

1, I.V. Melnyk

2, Y.L. Zub

2. Adsorption kinetic of

Ag(I) ions onto mono-functionalized polysiloxanes with magnetic properties (1Faculty

of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland, 2Chuiko Institute of


12

59. K. Gdula, A. Dąbrowski, E. Skwarek. Adsorption of Ag(I) ions onto amine-

functionalized magnetic nanoparticles (Faculty of Chemistry, Maria Curie-Skłodowska

University, Lublin).

60. K. Gdula1, E. Skwarek

1, A. Dąbrowski

1, I.V. Melnyk

2, Y.L. Zub

2. Electrochemical

properties of mono-functionalized polysiloxanes with magnetic properties (1Faculty

of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland, 2Chuiko Institute of


61. B.M. Gorelov1, A.M. Gorb

2, O.I. Polovina

2, S. Wacke

3, Z. Czapla

3. Nanosized oxide

filler’s impact on dielectric -relaxation in unsaturated polyester resin (1Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv, 2Taras Shevchenko National

University of Kyiv, Ukraine, 3Department of Physics, Opole University of Technology,

Poland).

62. K. Gusakova1, O. Grigoryeva

1, O. Starostenko

1, A. Fainleib

1, D. Grande

2. Effect of

porosity on thermal characteristics of thin film materials based on cyanate ester

resins (1Institute of Macromolecular Chemistry, NAS of Ukraine, Kyiv,

2Institut de Chimie

et des Materiaux Paris-Est, UMR 7182 CNRS – Universite Paris-Est Creteil Val-de-

Marne, France).

63. O. Grigoryeva, O. Starostenko, L. Bardash, A. Fainleib. Thermostable polymeric

nanomaterials obtained by in situ method (Institute of Macromolecular Chemistry, NAS

of Ukraine, Kyiv).

64. M. Grochowicz, M. Maciejewska. Synthesis of polymeric microspheres with grafted

poly(geranyl methacrylate) chains (Department of Chemistry, Faculty of Chemistry,

Maria Curie-Sklodowska University, Lublin, Poland).

65. K. Gusakova1, A. Fainleib

1, O. Grigoryeva

1, O. Starostenko

1, V. Sakhno

2,

A. Borzakovskiy2, E. Espuche

3, F. Gouanve

3, D. Grande

4. Designing track etched

nanoporous films from polycyanurate-based thermosets (1Institute of Macromolecular

Chemistry, NAS of Ukraine, Kyiv, 2Institute of Nuclear Research, NAS of Ukraine, Kyiv,

3Universite de Lyon, Universite Lyon 1, CNRS-UMR 5223 Ingenierie des Materiaux

Polymeres, 4

Institut de Chimie et des Materiaux Paris-Est, UMR 7182 CNRS – Universite

Paris-Est Creteil Val-de-Marne, France).

66. N.A. Havrylyuk. Graphene oxide as filler in polymer nanocomposites (Chuiko


67. O.O. Havryliuk, O.Yu. Semchuk. Theoretical calculations of the temperature field

distribution in the silicon periodic nanostructures during thermal annealing (1Chuiko


68. L.V. Karabanova, L.A. Honcharova. POSS-containing nanocomposites based on

sequential semi-interpenetrating polymer networks (Institute of Macromolecular


69. O.M. Kamіnskiy1, N.V. Kusyak

1, A.L. Petranovska

2, S.P. Turanska

2, P.P. Gorbyk

2.

Adsorption of Au3+

ions from water solutions by Fe3O4/HA nanocomposites (1Ivan

Franko Zhytomyr State University, Ukraine, 2Chuiko Institute of Surface Chemistry, NAS

of Ukraine, Kyiv).

70. A.V. Karakurkchi, N.D. Sakhnenko, M.V. Ved‟, A.S. Gorohivskiy. Nanostructured

catalytic cobalt containing PEO-coatings on alloy AL25 (National Technical

University “Kharkiv Polytechnic Institute”, Ukraine).

71. G.N. Kashin, I.V. Dubrovin, P.P. Gorbyk. Nanosized structures of zinc oxide: methods

of fabrication, properties and perspectives of applications (Chuiko Institute of Surface


13

72. А. Khodko1, N. Kachalova

1, Iu. Mukha

2, S. Snegir

2. Solvent effects on cyclization

dynamics of diarylethene derivatives (1Institute of Physics, NAS of Ukraine,

2Chuiko


73. I.S. Kolesnyk, O.Ya. Dzhodzhyk, V.V. Konovalova, A.F. Burban. Modification of

polysulfone membrane surface with SnO2 nanoparticles by “layer-by-layer” method (National University of “Kyiv-Mohyla Academy”, Ukraine).

74. D. Korytko, N. Volvach, S. Gryn, S. Alekseev. Nanosized non-porous silicon carbide

surface chemistry (Taras Shevchenko National University of Kyiv, Ukraine).

75. О.S. Кukolevska1, I.I. Gerashchenko

1, E.M. Pakhlov

1, T.I. Yushchenko

2. Synthesis and

research of nanocomposites with regulated drug release on basis of poly(2-

hydroxyethyl methacrylate) (1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv, 2Vinnytsia National Pyrogov Memorial Medical University, Ukraine)

76. A.P. Kusyak1, A.L. Petranovska

2, S.P. Turanska

2, P.P. Gorbyk

2. Adsorption of La

3+ ions

with nanocomposites based on single-domain Fe3O4 modified with SiO2, TiO2 (1Ivan

Franko Zhytomyr State University, Ukraine, 2Chuiko Institute of Surface Chemistry, NAS

of Ukraine, Kyiv).

77. O.M. Lavrynenko, O.Yu. Pavlenko, Yu.S. Shchukin, P.O. Kosorukov. Stabilization of

the spinel ferrite nanoparticles with oleic acid species involved as a surfactant (F.D. Ovcharenko Institute of Bio-Colloid Chemistry, NAS of Ukraine, Kyiv).

78. B.O. Linova1, S.D. Kobylianska

1, A.G. Bilous

1, I.O. Dulina

2. Influence of processing

conditions on the quality of Li1,3Al0,3Ti1,7(PO4)3 films with NASICON structure (1Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine,

2Institute for

Problems in Materials Science, NAS of Ukraine, Kyiv).

79. Yu. Bolbukh1, T. Lupascu

2, I. Povar

2, S. Rogalsky

3, V. Tertykh

1, M. Rusu

2. Hybride

polymer composites with incorporated biologically active substances: spectral studies (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Institute of Chemistry of

the Academy of Sciences of Moldova, Chisinau, 3Institute of Bioorganic Chemistry and

Petrochemistry, NAS of Ukraine, Kyiv).

80. L.A. Belyakova, D.Yu. Lyashenko. Silicas with thiosemicarbazide groups for cation

sorption from nitrate solutions (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).

81. M. Maciejewska, J. Osypiuk-Tomasik, B. Podskościelna, M. Grochowicz. Synthesis,

characterization and modification of porous DMN-GMA microspheres (Faculty of

Chemistry, Maria Curie-Skłodowska University, Lublin, Poland).

82. R.V. Mazurenko, N.V. Abramov, S.N. Makhno, P.P. Gorbyk. Nickel ferrite

nanoparticles modified with copper iodide: synthesis, structural, electrical and

magnetic properties (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

83. I.V. Melnyk1,2

, N.V. Stolyarchuk2, Yu.L. Zub

2, M. Vaclavikova

1. Regulation of the

porosity and the surface layer structure of silica nanoparticles with bifunctional

surface layer using one-step sol-gel technique (1Institute of Geotechnics, SAS, Kosice,

Slovak Republic, 2Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

84. O. Мykhailenko. Formation of double-walled nanotube-bis(cyclopentadienyl)nickel

complexes by “host-guest” type (Taras Shevchenko National University of Kyiv,

Ukraine).

85. D.B. Nasiedkin, A.G. Grebenyuk, Yu.V. Plyuto. Silicate coatings for high-temperature

corrosion protection of steel (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kiev).

14

86. O.I. Oranska, Yu.I. Gornikov. Solid-state reactions in composites Nd2O3−fumed silica

with different content of Nd2O3 (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).

87. Yu.K. Pirskyy, T.M. Panchyshyn, A.V. Gaidin, A.S. Tupchienko. Formation of

platinum nanoparticles on the carbon black (Vernadsky Institute of General and

Inorganic Chemistry, NAS of Ukraine, Kyiv, Ukraine)

88. I.S. Petrik1, A.M. Eremenko

1, N.P. Smirnova

1, A.V. Rudenko

2, Y.S. Marikvas

2.

Structural and optical properties of antibacterial materials based on Ag and Ag/Cu

nanoparticles (1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

2Institute of

Urology, National Academy of Medical Sciences of Ukraine, Kyiv).

89. Yu.K. Pirskyy, O.S. Krupennikova, L.F. Sharanda, V.M. Ogenko. Catalytically active

silica-containing films based on CNT with Pd and Co for oxygen reaction (Vernadsky

Institute of General and Inorganic Chemistry, NAS of the Ukraine, Kyiv).

90. E.N. Poddenezhny1, O.V. Davidova

1, N.E. Drobyshevskaya

1, A.A. Boiko

1,

А.А. Аlexeenko1, M.V. Borysenko

2. Starch-based biodegradable composite materials

with polypropylene and plasticisers (1Sukhoi Gomel State Technical University,

Belarus, 2Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

91. E.N. Poddenezhny1, O.V. Davidova


1, A.A. Boiko

1,

А.А. Аlexeenko1, A.V. Pavlenok

1, M.V. Borysenko

2. Preparation of powdered

luminescent materials based on yttrium oxide and yttrium-aluminum garnet by a

new combustion method (1Sukhoi Gomel State Technical University, Belarus,

2Chuiko


92. L. Postolachi, V. Rusu, T. Lupascu. Characterisation of natural and modified

Ghidirim diatomite (Republic of Moldova) (Institute of Chemistry of Academy of

Sciences of Moldova).

93. S.L. Prokopenko, G.M. Gunja, S.N. Makhno, P.P. Gorbyk. Electrophysical properties

of heterostructures PbS/CdS (Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).

94. I. Protsak1, M. Studziński

2,

Yu. Bolbukh1, V. Tertykh

1. Chromatographic study of

fragmentation products of polymethylphenylsiloxane (1Chuiko Institute of Surface

Chemistry, NAS of Ukraine, Kyiv, 2Faculty of Chemistry, Maria Curie-Sklodowska

University, Lublin, Poland)

95. I.V. Pylypchuk1, A.L. Petranovska

1,

S.P. Turanska1, О.М. Korduban

2, P.P. Gorbyk

1.

Synthesis of polyfunctional boron-gadolinium-containing magnetosensitive

nanocomposites (1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

2G.V. Kurdyumov Institute for Metal Physics, NAS of Ukraine, Kyiv).

96. V.M. Gun‟ko1, V.I. Zarko

1, O.V. Goncharuk

1, A.K. Matkovsky

1, O.S. Remez

1,

J. Skubiszewska-Zieba2. Influence of external conditions on the textural

characteristics of fumed metal and metalloid oxides and their composites (1Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv, 2Maria Curie-Sklodowska

University, Lublin, Poland).

97. N.M. Rezanova1, Y.O. Budash

1, V.Y. Bulakh

1, L.S. Dzubenko

2, O.O. Sapyanenko

2,

P.P. Gorbyk2. Compatibilization effect in nanofilled polymer blends (

1Kyiv National

University of Technologies & Design, Ukraine, 2Chuiko Institute of Surface Chemistry,


98. N.V. Roik, L.A. Belyakova, M.O. Dziazko. Kinetic and equilibrium studies of

doxorubicin adsorption on MCM-41-type silica surface (Chuiko Institute of Surface


15

99. N.D. Sakhnenko, M.V. Ved‟, A.V. Galak. Modified titanium oxide coatings for

environmental technologies (National Technical University “Kharkiv Polytechnical

Institute”, Ukraine)

100. D.P. Savitskyi. Extraction of graphene oxide from natural coal (Dumanskii Institute

of Colloid and Water Chemistry, NAS of Ukraine, Kyiv).

101. Yu. Grebel‟na1,2

, S. Makhno1, Yu. Sementsov

1. An effective method for graphene

nanoplatelets production by anode oxidation of expanded graphite (1Chuiko Institute

of Surface Chemistry, NAS of Ukraine, Kyiv, 2«TMSpetsmash», Kyiv).

102. A.V. Vasin1, D.V. Kisel

1, Yu.P. Piryatinsky

2, G.Ya. Rudko

1, E.G. Gule

1, V.Ya. Degoda

3,

V.A. Tertykh4, Y.M. Bolbukh

4, S.V. Sevostianov

4, S.P. Starik

5, V.S. Lysenko

1,

A.N. Nazarov1, D.V. Savchenko

6. The effect of pyrolysis of organic and organosilicon

surface groups in fumed silica on photoluminescent properties (1Lashkaryov Institute

of Semiconductor Physics, NAS of Ukraine, 2Institute of Physics, NAS of Ukraine,

3Physical faculty of Taras Shevchenko National University of Kyiv,

4Institute of Surface

Chemistry, NAS of Ukraine, 5Bakul Institute of Superhard Materials, NAS of Ukraine,

6Physico-Mathematical Faculty, National Technical University “KPI”, Kyiv, Ukraine).

103. A.V. Sviatogor1, P.Y. Vezdenetskyi

1, S.V. Shulga

1, D.L. Starokadomsky

2 V.M. Ogenko

1.

Physical and mechanical properties of graphene/epoxy composites (1Vernadsky

Institute of General and Inorganic Chemistry, NAS of Ukraine, 2Chuiko Institute of


104. S.V. Shulga, P.Y. Vezdenetskyi, V.M. Ogenko. The "electronic nose" sensor based on

chemically modified graphene structures (Vernadsky Institute of General and Inorganic

Chemistry NAS of Ukraine, Kyiv).

105. V.V. Sliesarenko1, Y.S. Fetisova

2, O.A. Dudarko

1, Yu.L. Zub

1. Template synthesis of

bifunctional mesoporous silica containing phosphonic and carboxylic groups (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Faculty of Chemistry,

National University of «Kyiv-Mohyla Academy», Ukraine).

106. S.S. Smola, E.N. Fadieiev, N.V. Rusakova. Lanthanide aminopolycarboxylates in

hybrid silica nanomaterials: synthesis and spectroscopic properties (A.V. Bogatsky

Physico-Chemical Institute, NAS of Ukraine, Odessa).

107. E.V. Sokovykh, L.P. Oleksenko, N.P. Maksymovych, I.P. Matushko, V.P. Ruchko,

O.P. Ripko. Selectivity of gas sensors based on Pd/SnO2 materials in impulse heating

mode (Department of Chemistry, National Taras Shevchenko University of Kyiv,

Ukraine).

108. E.D. Solovyova, О.P. Fedorchuk, А.G. Belous.

Synthesis and properties of thick

nanocrystalline films of M-type barium ferrite and nickel ferrite with spinel

structure (Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine,

Kyiv).

109. O.M. Starostenko1, O.P. Grigoryeva

1, A.M. Fainleib

1, S. Koutsoumpis

2. Nanoporous

and microporous thermostable polyamidoimide/polyurethane films: structure and

properties (1Institute of Macromolecular Chemistry, NAS of Ukraine, Kyiv,

2Physics

Department, National Technical University of Athens, Greece).

110. I. Sulym1, D. Sternik

2, L. Oleksenko

3, L. Lutsenko

3, M. Borysenko

1, A. Derylo-

Marczewska2. Characterization of CeO2–ZrO2/SiO2 nanocomposites by Raman, XPS

and HREM techniques (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland,

3Department

of Chemistry, Taras Shevchenko National University of Kyiv, Ukraine).

16

111. I.M. Trofymchuk, N.V. Roik, L.A. Belyakova. β-Cyclodextrin-MCM-41 silica as

promising adsorbent for the trace amounts removal of aromatics from water (Chuiko


112. G.P. Tsintskaladze, T.V. Sharashenidze, M.A. Dzagania, N.B. Pirtskhalava,

N.O. Burkiashvili. Zeolitic nanomaterials accumulated with nitrate ions in agriculture

(Ivane Javakhishvili Tbilisi State University, Petre Melikishvili Institute of Physical and

Organic Chemistry, Tbilisi, Georgia).

113. G. Tsintskaladze, O. Lomtadze, M. Burjanagze, T. Sharashenidze, V. Gabunia,

N. Shalvashvili. Anti-corrosion and anti-fungal sulfur-zeolite nanoadditives for

concrete for special purposes (Ivane Javakhishvili Tbilisi State University, Petre

Melikishvili Institute of Physical and Organic Chemistry, Tbilisi, Georgia).

114. А.M. Fainleib1, O.M. Starostenko

1, A.V. Vashchuk

1, O.P. Grygoryeva

1, S.P. Rogalsky

2,

D. Grande3. Novel nanoporous polycyanurates created using ionic liquids as porogen

(1Institute of Macromolecular Chemistry, NAS of Ukraine,

2Institute of Bioorganic

Chemistry and Petrochemistry, NAS of Ukraine, Kyiv, 3Institut de Chimie et des

Materiaux Paris-Est, UMR 7182 CNRS – Universite Paris-Est Creteil Val-de-Marne,

France).

115. O. Vassiliadi, A. Panagopoulou, A. Kyritsis, P. Pissis. Calorimetric study of collagen-

water systems over wide range of hydration levels (National Technical University of

Athens, Greece).

116. E.F. Voronin, L.V. Nosach, V.M. Gun‟ko, M.V. Borysenko. Effect of mechanical

treatment of nanoscale hydrophilic and hydrophobic silicas on their thickening

efficiency in a nonpolar medium (Chuiko Institute of Surface Chemistry, NAS of

Ukraine, Kyiv).

117. Y.I. Sachanova, I.Yu. Yermolenko, N.D. Sakhnenko, M.V. Ved. Composition and

morphology of Fe-Co-Mo electrolytic alloys (National technical university “Kharkiv

polytechnic institute”, Ukraine).

118. K.G. Yunuskhodjaeva1, M.G. Ismailova

2, B.A. Imamaliev

2. Biochemical tests of new

lignin enterosorbent (1Uzbek Chemical and Pharmaceutical Research Institute,

Tashkent, 2Tashkent Pharmaceutical Institute, Uzbekistan).

4. Medical, biological and biochemical aspects of research of highly disperse

materials

119. G.V. Beketov, V.P. Kyslyi, A.I. Liptuga, O.V. Shynkarenko. Chemical modification of

polystyrene surface for ELISA applications (Lashkaryov Institute of Semiconductor

Physics, NAS of Ukraine, Kyiv).

120. V.M. Bogatyrov, S.M. Makhno, M.V. Galaburda, O.I. Oranska, Yu.I. Gornikov,

P.P. Gorbyk. Synthesis and electrical properties of copper/silica-containing carbon

nanocomposites (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).


1, O.I. Oranska

1, O.M. Zaichenko

2, K.S. Tsyganenko

2,

Ya.I. Savchuk2. Influence of photochemical aging on biocidal activity of

Ag-containing silica (1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

2Zabolotny

Institute of Microbiology and Virology, NAS of Ukraine, Kyiv).

122. K.O. Filatova1,2

, V. Sedlarik2

, A. Di Martino

2, A. Golovan

1, T.V. Krupska

1, V.V. Turov

1.

Chitosan-functionalized spherical nanosilica matrix as drug delivery system (1Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Kyiv, 2Center of Polymer Systems,

University Institute, Tomas Bata University in Zlin, Czech Republic).

17

123. M.V. Galaburda1, V.M. Bogatyrov

1, T. Lupascu

2, N.V. Kokosha

3, I. Povar

2.

Stabilization of Enoxil in the polymer matrix (1Chuiko Institute of Surface Chemistry,

NAS of Ukraine, Kyiv, 2Institute of Chemistry, Academy of Sciences of Moldova, Chisinau,

Republic of Moldova,3“International Center for Medical Technologies Implementation”

ltd.).

124. А.P. Golovan, T.V. Krupska, I.V. Siora, N.Y. Klymenko, O.А. Novikova, V.V. Turov.

Influence of nanosilica powder on winter wheat germination capacity (Chuiko

Institute of Surface Chemistry, NAS of Ukraine, Кyiv).

125. O.O. Kazakova. A quantum-chemical study of the antioxidant properties of natural

phenolic compounds (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

126. N.O. Khemych1, S.V. Prokhorenko

1,2, M.G. Popryaga, O.V. Shynkarenko

3,

R. Wojnarowska-Nowak2. Improvement analysis system of the signal transmission

parameters estimation analysis by the signal reflection from the thermal albedo

deviations surfaces (1Lviv Polytechnic National University, Ukraine,

2Centre for

Microelectronics and Nanotechnology, University of Rzeszow, Poland, 3Institute of

Semiconductor Physics, NAS of Ukraine, Kyiv).

127. Ie.V. Pylypchuk1, G.V. Khmil

2, S.V. Gorobets

2, P.P. Gorbyk

1. Hydroxyapatite self-

assembly from simulated body fluid on carboxylated surface of Ti-containing alloys (1Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv,

2National Technical

University of Ukraine "Kyiv Polytechnic Institute").

128. N.Y. Klymenko, І.V. Siora, E.А. Novikova, А.P. Golovan, Т.V. Krupskaya, V.V. Turov.

Nanosilica-yeast cells based system for remediation of water (Chuiko Institute of


129. R.B. Kozakevych1, Yu.M. Bolbukh

1, V.A. Tertykh

1, T.I. Petriv

2, V.V. Medvedev

2,

O.A. Rybachuk3, R.G. Vasyliev

4,5. Development of chitosan/carbon nanotubes

composites for neural tissue engineering (1Chuiko Institute of Surface Chemistry, NAS

of Ukraine, 2Romodanov Institute of Neurosurgery NAMS of Ukraine,

3Bogomolets

Institute of Physiology NAS of Ukraine, 4State Institute of Genetic and Regenerative

Medicine NAMS of Ukraine, 5Biotechnological laboratory ilaya.regeneration, Medical

company ilaya, Kyiv, Ukraine).

130. S.P. Turanska1, A.P. Kusyak

1, A.L. Petranovska

1, S.V. Gorobez‟

2, V.V. Turov

1,

P.P. Gorbyk1. Investigation of cytotoxic activity of magnetic-controlled

nanocomposites based on doxorubicin (1Chuiko Institute of Surface Chemistry, NAS of

Ukraine, 2National Technical University of Ukraine «Kyiv Polytechnic Institute», Kyiv).

131. I.V. Laguta1, O.N. Stavinskaya

1, R.V. Ivannikov

2, О.I. Dzyuba

2. Screening the plants

of Orchidaceae Juss. family for the antioxidant properties of the leaves extracts (1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

2M.M. Gryshko National

Botanic Garden, NAS of Ukraine, Kyiv).

132. N.O. Lipkovska, V.M. Barvinchenko, M.T. Kartel. A new approach to complex

standardization of silica – multiherbal nanodispersed preparations (Chuiko Institute


133. O.M. Lisova, S.N. Makhno, P.P. Gorbik. Effect of microwave low intensity

electromagnetic wave on the vital activity of yeast cells in the presence of graphene (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

134. Iu. Mukha, N. Vityuk, G. Eremenko, N. Ostapchuk, Ie. Pylypchuk, P. Gorbyk.

Synthesis of tryptophan-stabilized Fe3O4/Ag core-shell nanoparticles (Chuiko Institute


https://www.researchgate.net/profile/Oksana_Rybachuk

https://www.researchgate.net/profile/Roman_Vasyliev2

https://www.researchgate.net/institution/Bogomolets_Institute_of_Physiology_NASU


18

135. O. Otychenko1,2

, A. Parkhomey1, T. Babutina

1, I. Uvarova

1,2. Influence of technological

conditions on the physical and chemical properties of biogenic hydroxyapatite

dopped with ferromagnetic additives (1Frantsevich Institute for Problems in Materials

Science, Kyiv, 2National Technical University of Ukraine «Kyiv Polytechnic Institute»).

136. N. Petrov. The study of physicochemical properties of oxidized enotannins (Institute

of Chemistry, Academy of Sciences of Moldova, Chisinau).

137. E. Skwarek1, Y. Bolbukh

2, V. Tertykh

2, W. Janusz

1. Synthesis and properties of

hydroxyapatite/MWCNTs composites (1Faculty of Chemistry, Maria Curie-Skłodowska

University, Lublin, Poland, 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,

Kyiv).

138. T. Lupascu, N. Timbaliuc, A. Gonţa, N. Petrov. Obtaining and characterization of

enotannins by physicochemical methods (Institute of Chemistry, Academy of Sciences of

Moldova, Chisinau).


1, O.I. Oranska

1, M.V. Borysenko

1,

K.S. Tsyganenko2, Ya.I. Savchuk

2, O.M. Zaichenko

2. Synthesis and biocidal properties

of Cu-containing nanocomposites (1Chuiko Institute of Surface Chemistry, NAS of

Ukraine, 2Zabolotny Institute of Microbiology and Virology, NAS of Ukraine, Kyiv).

140. O.O. Viltsaniuk. Justification enterosorption nanodispersed silica drugs use in

complex treatment of community-acquired pneumonia at patients with

immunosuppression (Vinnytsya National Pirogov Memorial Medical University,

Ukraine).

141. N. Vityuk1, Iu. Mukha

1, G. Grodzyuk

2,3, A. Eremenko

1. Bimetallic gold/silver alloy

nanoparticles prepared in the presence of tryptophan (1Chuiko Institute of Surface

Chemistry, NAS of Ukraine, 2L. V. Pisarzhevskii Institute of the Physical Chemistry, NAS

of Ukraine, 3NanoMedTeсh LLC, Kyiv, Ukraine).

142. N.N. Vlasova. Amino acid adsorption onto nanocrystalline ceria surface (Chuiko


143. N.A. Volkova, E.V. Pavlovich, M.S. Yukhta, A.N. Goltsev. Effect of gold

nanoparticles on morphological and functional characteristics of bone marrow

mesenchymal stromal cells (Laboratory of Biotechnology and Applied Nanotechnology,

Department of Cryopathophysiology and Immunology, Institute for Problems of

Cryobiology and Сryomedicine, NAS of Ukraine, Kharkov).

144. T. Kulik, B. Palianytsia. Application of temperature-programmed desorption mass

spectrometry to study the interaction of dextran polymeric chains with fumed silica

surface (Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv).

http://www.ncbi.nlm.nih.gov/pubmed/?term=Volkova%20N%5Bauth%5D

19

Infrared spectroscopy as a tool for textural and structural

characterization of individual and complex fumed oxides

V.M. Gun’ko1, E.M. Pakhlov

1, V.I. Zarko

1, J. Skubiszewska-Zięba

2

1Chuiko Institute of Surface Chemistry, NAS of Ukraine,

17 General Naumov Str., Kyiv 03164, Ukraine, 2Faculty of Chemistry, Maria Curie-Skłodowska University,

20-031 Lublin, Poland

The effects of sizes of nanoparticles and surface content of silica in

individual (silica) and complex fumed metal and metalloid oxides (FMO) on the

infrared (IR) spectra in the range of the SiO asymmetrical stretching vibrations

were analyzed. This allows us to obtain correlation functions between integral

intensity of a band at SiO 1200 cm1

(w2, attributed to a surface of silica) or

the ratio w2/w1 (w1 corresponds to contribution at SiO 1100 cm1

attributed to

bulk transverse optical (TO) modes) and the diameter (d) of silica nanoparticles

(Fig.). The results of the IR spectra analysis were compared with the results of

the Auger electron spectroscopy (AES), giving surface content of different

oxides in complex FMO, and the textural characteristics estimated from the

nitrogen adsorption isotherms. The nanoparticulate morphology of FMO

analyzed using TEM and SEM images shows a relatively broad size distribution

of nanoparticles including core-shell nanoparticles that can affect the SiO band

intensity and position related to the silica phase. The use of the correlation w2(d)

or w2/w1(d) functions gives appropriate results in respect to the textural

characteristics of fumed silicas and the surface content of silica in complex

FMO in comparison with the adsorption and AES data.

Fig. Relationship between the nanoparticle diameter (d) and contribution (w) and position of

the second band of the SiOSi asymmetric stretching vibrations for fumed silicas (with

increasing value of d in a line A-500, A-300, A-150, OX-50, and A-50), and a relationship

between positions of bands at 1100 and 1200 cm1

and the value of d.

20

Sol-gel chemistry and nanotechnology

Yu.L. Zub

Chuiko Institute of Surface Chemistry, NAS of Ukraine,

17 General Naumov Str., Kyiv 03164, Ukraine, [email protected]

The first works by the employees of the Institute of Physical Chemistry of

AS of UkrSSR on the application of the hydrolytic polycondensation reaction of

silicon derivatives for producing polyorganosiloxane xerogels appeared over

50 years ago [1]. Later, there were given two inventors' certificates to

O.O. Chuiko‟s research team from the same Institute [2] for the preparation of

polysiloxane xerogels with amine and carboxyl groups via sol-gel method.

However, the systematic development of the direction associated with the

application of the sol-gel method for the production of novel materials started in

1991 in Chuiko ISC of NAS of Ukraine [3]. Nowadays, multiple research teams

in ISC, as well as in other scientific organizations of Ukraine, use the sol-gel

method to produce novel materials. Therefore, current report focuses on the

development of this method in our research team for the past 25 years.

Our research started with the synthesis of xerogels with 3-aminopropyl

groups in the surface layer using the sol-gel method. We were interested in the

factors affecting the porous structure of such objects and the content of the

ligand groups. It was shown that such xerogels adsorb copper(II) ions forming

complexes 1 : 2. Further research in this direction resulted in the synthesis and

study of xerogels with oxygen-, nitrogen-, sulfur-, and phosphor-containing

complexing groups. Substitution of tetraethoxysilane with bridged alkoxysilanes

resulted in xerogels with high specific surface area about 1000 m2/g. The

experience was applied to the research of mesoporous materials derived by the

template method. Possessing high specific surfaces and complexing groups

content, they are promising for application in adsorption, catalysis,

biotechnology, and many other fields. Using the background of the previous

analyses, we broadened the area of our investigations to magnetic carriers,

functionalized membranes, etc.

1. I.B. Slinyakova; T.I. Denisova, Organosilicon-based adsorbents. Preparation, properties,

application, Kiev: Naukova Dumka, 1988.

2. Inventor's certificate 164680 of USSR, Method for producing organosilicagel/ Chuiko A.A.,

Pavlik G.E., Neumark I.E. 19.08.64. Inventor's certificate 182719 of USSR, method for

producing silicagel with aminoalkyl groups / Chuiko A.A., Pavlik G.E., Budkevich G.B.,

Neumark I.E. 09.06.66.

3. N. Yakubovich, Yu.L. Zub, A.A. Chuiko et al., // Heterog. Catal.: 7th Int. Symp., 29

September – 3 October 1991: Proc. – Bourgas, Bulgaria, 1991. - Part 1. – P. 551–556 and

567 – 571.

21

Nanosized TiO2-based mixed oxide films for environmental

photocatalysis

N. Smirnova



Titanium dioxide nanomaterials find a promising application in

environmental photocatalysis, for the generation of electricity in the solar and

fuel cells, gas sensors, optical and protective coatings, electrochemical devices

etc. TiO2 effectiveness could be improved by mixing with other oxides that

control structure-sorption, optical and electronic properties. Coupling of two

semiconductors was used to achieve a more efficient separation of

photogenerated electron-hole pair that led to improvement of the photoactivity.

Sol-gel technology is one of the most practically useful techniques to prepare

nanostructured complex oxide mixtures with atomic level mixing of the

components. Depending on the component ratios and conditions of thermal

treatment the sol-gel method allows obtaining: 1) the products of replacement of

the titanium ions in TiO2 crystal lattice by transition metal ions; 2) solid

solutions (Ti1-хZrхO2) or 3) spinel phases – ZnTiO3, Zn2Ti3O8, Ti2ZrO6 and

Fe2Ті2О7.

TiO2 films alone and TiO2/oxide composites were characterized using

hexane adsorption, XRD, XPS, Raman and UV/vis spectroscopy. Band gap

energy and the position of flatband potentials were estimated by

photoelectrochemical measurements. On the base of analysis of the detail XPS

spectra it was found the formation of Ti–O–Zn, Ti–O–Zr, Si–O–Ti, Si–O–Zr,

Si–O–Ti–O–Zr bonds. Detected by XPS oxygen and silicon peak positions

evolution correlated with Eg reduction of analyzed mixed oxides and with the

photocatalytic behavior of the films as well. The phase composition, electronic

structure, electrochemical characteristics and their effect on the photocatalytic

activity of sol-gel obtained mixed oxide films based on TiO2 have been

disscused. It was found that the photocatalytic activity depends on the phase

composition and crystalline size that modify the TiO2 band gap. The size effect

on the phase stability of nanostructures is manifested in the stabilization of new

phases, which is not characteristic to a bulk crystal. An enhancement of

photocatalytic activity of zirconia-doped films in comparison with that of pure

TiO2 originated from an anodic shift of the valence band edge potential.

Catalytic activity of mesoporous TiO2/ZnO and TiO2/ZrO2 films in the process

of Cr(VI) to Cr(III) photoreduction was improved with increasing of surface

acidity and specific surface area of the samples.

22

Study of thermomechanical properties of composites based on

sol-gel silica and 2-hydroxyethylmethacrylate

Yu. Bolbukh1, P. Klonos

2, P. Pissis

2, V. Tertykh

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National Technical University of Athens, Physics Department,

Iroon Polytechneiou 9, Zografou Campus, 15780 Athens, Greece

Organic/inorganic hybrid composites created by incorporating a silica

network into the structure of polymeric materials can greatly extend the fields of

their potential applications as drug delivery systems, implants, other advanced

nanocomposites. In this study, we have concentrated on an influence of the silica

precursor nature on the structure and thermomechanical properties of in situ-

formed polymeric films. The composites were obtained by the radical

polymerization of monomer 2-hydroxyethylmethacrylate (HEMA) with the

simultaneous hydrolysis and polycondensation of different alkoxysilanes. For

the formation of silica network tetraethoxysilane (TEOS), vinyltriethoxysilane

(VTES), 3-aminopropyltriethoxysilane (APTES), and a mixture of vinyl- and

3-aminopropyl- triethoxysilanes (VTES/APTES) were applied. Filling degree of

the inorganic component (SiO2) for all hybrid composite films was 10 wt. %. A

-100

-80

-60

-40

-20

0

0 60 120 180

T oC

Pe

ne

tra

tio

n L

, %

1

2

3

4

5

B

-15

-11

-7

-3

1

5

9

0 60 120 180

T oC

d( D

H)/

dT

, µ

m/o

C

pHEMA

pHEMA/TEOS

pHEMA/VTES

pHEMA/APTES

pHEMA/VTES-APTES

Fig. Changes in deformation

(A) and derivative dimension

(B) for polyHEMA (1) and

hybrid polymeric films with

TEOS (2), VTES (3),

APTES (4), VTES/APTES

(5).

It was found (Fig.) that a most significant effect on the structure of the

polymeric film has introducing APTES or VTES: amine-containing alkoxysilane

presence results in the formation of mobile fluid system (curve 4), whereas

vinyl-containing alkoxysilane delivers the polymer cross-linking. Application of

VTES/APTES mixture promote a formation of the flexible but stable uniform

structure of the hybrid material (curve 5).

Acknowledgements

The research leading to these results has received funding from the People Programme (Marie

Curie Actions) of the European Union‟s Seventh Framework Programme FP7/2007-2013/

under REA grant agreement n° PIRSES-GA-2013-612484.

mailto:[email protected]

23

Synthesis of weakly agglomerated (La,Sr)MnO3 nanoparticles and

creation of the organic-inorganic composite structures based on

them

Y.Y. Shlapa, S.O. Solopan, A.G. Belous

Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine,

32/34 Palladin Ave., Kyiv 03680, Ukraine, [email protected]

Nowadays ferromagnetic materials find wide practical application in

engineering and medicine [1]. However, these materials can have some

physicochemical properties, which are not typical of bulk materials, during the

transition to nanoscale sizes. At the same time, such nanoparticles must meet

certain requirements with the aim of practical using them in medicine

(especially in hyperthermia): they must be weakly agglomerated and effectively

heat under an alternating magnetic field to necessary temperatures (42 – 45°C).

At present, Fe3O4 magnetite nanoparticles often use as the inducers of

hyperthermia, because they are biocompatible and crystallize at the synthesis

temperature. However, this material has high Curie point (585°C), and the

heating control is impossible. Recently, heterosubstituted lanthanum-strontium

La1-xSrxMnO3 manganites are of particular interest. In contrast to magnetite

nanoparticles, manganite has an essential advantage: its Curie point depends on

the chemical composition and can be changed in the range of 20-70°C [2] that

allows maintaining of necessary temperature (42-45°C) automatically.

This study is dedicated to the investigations of synthesis of weakly

agglomerated La1-xSrxMnO3 nanoparticles with perovskite structure via sol-gel

method with further mechano-chemical treatment and creation of the composite

structures with biocompatible organic reagents (polysorbate 80, polyethylene

glycol, L-proline) based on these nanoparticles.

It is shown the possibility of the influence on the size of ferromagnetic

La1-xSrxMnO3 nanoparticles and their agglomeration after sol-gel synthesis by

using different technics of mechano-chemical treatment of synthesized

amorphous precursor. Nanoparticles with the particle size ≈35 nm, which

demonstrate weak agglomeration and SLP=23 W/g, were obtained after the

action of ultrasound for 2 hours. A number of organic-inorganic composite

structures with such organic shells as polysorbate 80, polyethylene glycol and

L-proline were created based on these particles. Manganite nanoparticles coated

with polysorbate 80 demonstrate the less agglomeration and high SLP values.

1. M. Colombo, S. Carregal-Romero, M. F. Casula et al, Chem. Soc. Rev. 41 (2012) 4306.

2. S. Vasseur, E. Duguet, et al. J. Magn. Magn. Mater. 302 (2006) 315.

24

Pulsed laser deposited TiO2 based films: synthesis, electronic

structures and photocatalytic activity

O. Linnik1, N. Chorna

1, N. Smirnova

1, N. Stefan

2, I.N. Mihailescu

2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National Institute for Lasers, Plasma and Radiation Physics,

409 Atomistilor Str., Magurele, PO Box MG-36, RO-77125, Ilfov, Romania

The intensive development of industry, farming and agriculture

technology leads to the widespread contamination of air, soil and water sources.

The design and development of photocatalysts based on titania allowing their

use under visible-light irradiation are under extent investigation. Some

approaches are known, as the doping with d-block metals and/or non-metals as

well as the dye sensitization mechanism.

Active under visible light photocatalysts based on doped titania were

obtained via Pulsed Laser Deposition method. Photocatalytic activity is

monitored by applying the photoreduction of dichromate ions under UV and

visible light. The influence of zirconium ions and its content as well as synthesis

conditions on the efficiency of nitrogen incorporation into titania structure that,

in turn, determines the electronic structure and photocatalytic ability of the

semiconductive materials, are discussed. A substitutional nitrogen rather than an

interstitial one is mainly responsible for the observed photoactivity. It is pointed

that substitutional nitrogen is responsible for band gap narrowing or formation

of intra-gap localized states within semiconductor band gap. The band gap

energy values are sharply decreased, while the relative intensity of substitutional

nitrogen XPS peaks is increased. Pulsed laser synthesis of TiO2 films in N2/CH4

atmosphere not only leads to nitrogen incorporation but also to the formation of

surface defects. An appropriate ratio of gas mixture, optimum zirconia content,

suitable pressure and temperature during synthesis were found for the synthesis

of high active of semiconductive films. The correlation between the zirconia

content and the efficiency of substitutional N incorporation is established as the

distortion of ТіО2 lattice occurred due to the larger radius of neighbour

zirconium ions. The highest photocatalytic conversion yields are obtained for

nitrogen-doped 10% ZrO2/TiO2 synthesized in N2:CH4=5:1 at 100 Pa and at

450º C under both UV and visible light.

25

Nanoclusters (SiC)n as a base of nanostructured materials for

electrodes of lithium-ion batteries

V.S. Kuts



It is known that coating of silicon micro- or nanoparticles with carbon leads

to an increase in the reversible capacity, number of charge-discharge cycles, and

the Coulomb part of the first cycle of the electrodes from silicon-carbon

composites (Si/C) obtained by crushing silicon mixed with graphite in a ball mill

or by deposition of carbon atoms from the gas phase (or plasma). Such methods

provide an addition of both individual atoms C and their nanoclusters Cm (m = 2,

3, etc.) to the silicon clusters Sin that can lead to the formation of amorphous

(CmSin) and fullerene-like silicon-carbon nanostructures (SiС)n. The electrode

materials with the concentration of carbon in the Si/C composite close to 30%,

suitable for structures (SiC)n, have the best performance electrochemical

characteristics. The existence of these structures has been proven in [1] based on

the results of quantum-chemical calculations on the interaction between Si-C

fragments. In this paper, the formation of nanoclusters (SiC)2<n <12 has been

studied due to sequential implementation of two carbon atoms into nanoclusters

Si12 (Figure) by methods of quantum chemistry (PM7; B3LYP with basis set

6-31G (d, p)). The structure (SiC)12 is completely (by the number of four- and

six-membered cycles, the corners and lengths of links) adequate to that of

composite (SiC)12 grounded by authors of [1], and positive charges are focused

on silicon subsystem whereas negative ones - on the carbon subsystem.

Nanoclusters (SiC)n can form stable associative agglomerates m(SiC)n (m = 2, 3,

...) with higher electron affinities than those of monomers.

In such systems, the charge/discharge processes practically (up 1%) do not

change the values of electroactive volume of the silicon-carbon matrix

V((SiC)12). Thus, the processes of lithiation/delithiation should not affect the

characteristics of the shunts and, therefore, qualitative electrochemical

properties of such electrode materials should be stable under a significant

increase in the number of charge/discharge cycles. The specific electric capacity

of (SiC)n-based composites can reach the value of 3000mA•h/g, so making them

a very winning material for use in lithium ion batteries.

1. R. Wang, D. Zhang, C. Liu, Chemical Physics Letters. 411 (2005) 333.

26

Synthesis and structure investigation of porous and nonporous

materials with enhanced magnetic permeability

M. Studziński1, Yu.M. Bolbukh

2, R.B. Kozakevych

2, V.A. Tertykh

2

1Planar Chromatography Department, Chair of Physical Chemistry,

Faculty of Chemistry, Maria Curie-Skłodowska University,

pl. Maria Curie-Skłodowskiej 3, 20-031 Lublin, Poland,

[email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,


Magnetic field is a one of the basic interactions creating known universe.

It is also one of the important factors, existing in the Earth‟s biosphere,

influencing many processes of animated and unanimated nature. The

consequence of that fact it is often used as a tool in various human activities.

Magnetic field is broadly used in communication, transport, medicinal therapy,

electronics optics and gains more and more attention in area of chemical

sciences [1-3].

Incorporating a ferro- and superparamagnetic iron oxide nanoparticles

(SPIONs) into the structure of silica and carbon materials may greatly broaden

their spectrum of applications in area of sorption, catalysis, inorganic synthesis,

and many others. The key role plays the possibility of placing them in demanded

area and alternating their properties using external magnetic field, as it can be

observed during magnetic drug targeting process [4, 5]. Another possibility is

application of those materials for precise heat transfer using microwaves [5].

In our study, we have concentrated on two main aspects. The first one was

to investigate the influence of synthesis conditions (temperature, order and

method of reagent addition etc.) on magnetic iron oxide crystallite sizes. The

second one regarded possible methods of implementation of obtained

magnetosensitive particles into structures of silica, colloidal graphite and carbon

nanotubes. All procedures were also verified under the criteria of simplicity and

low cost of preparation of desired materials.

Acknowledgements


Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/

under REA grant agreement n° PIRSES-GA-2013-612484

1. P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.M. Tarascon, Nature 407 (6803) (2000) 496.

2. A. Tari, R.W. Chantrell, S.W. Charles, J. Popplewell, Physica B & C 97 (1) (1979) 57.

3. M. Mahmoudi, A. Simchi, M. Imani, P. Stroeve, A. Sohrabi, Thin Solid Films 518 (15) (2010)

4281.

4. M.W. Freeman, A. Arrott, J.H.L. Watson, J. Appl. Phys. 31 (5) (1960) S404.

5. A. K. Hauser, R. J. Wydra, N. A. Stocke, K.W. Anderson, J. .Z. Hilt, J. Contr. Rel. 219 (2015) 76.

27

Magnetic chelating nanocomposites: synthesis, functionalization and

analytical implications for solid phase extraction

O.A. Khaynakova1, N.G. Kobylinska

2, M. Diaz-Garcia

1, V.N. Zaitsev

2

1Department Analytical and Physical Chemistry, University of Oviedo,

Av. Julian Claveria 8, 33006-Oviedo, Spain 2Department of Analytical Chemistry, Taras Shevchenko National University of

Kyiv, 64 Volodymirska St, Kyiv, 01601, Ukraine, [email protected]

In recent years, the number of research groups involved in magnetic

nanoparticles has increased exponentially. These particles have many important

applications especially in engineering nanodevices, in the biomedical industry,

and also useful for environmental processes, analyses, catalysis, etc. Among the

new explored magnetic particles magnetite (Fe3O4) has one of the most

potential. In this work, a novel magnetic nanocomposite with immobilized

N-ethylenediaminetriacetatic groups was developed for solid phase extraction

heavy metals from aqueous solution. The magnetite nanoparticles were prepared

by two techniques: co-precipitation iron(II) and iron(III) salts and hydrothermal

treatment. The superparamagnetic nanoparticles coated with a thin silica oxide

layer were synthesized by means sol–gel methods. A thorough chemical and

structural characterization has been carried out by means of TEM, XRD, XPS,

elemental analysis, FTIR and VRM measurements.

The morphology and structure of obtained solids were investigated by

TEM. The TEM image of Fe3O4 nanoparticles prepared in aqueous medium

reveals a size distribution in the range of 6.0±2.0 nm and silica shell about 2 nm.

The XPS spectrum of as-synthesized Fe3O4 nanoparticles shows strong bands

due to iron at 724,4 eV (Fe2p1/2), 709,9 eV (Fe2p3/2). The Fe/O atomic ratio for

particles prepared by co-precipitation methods is 0.73, for hydrothermal – 0.74

(for reference Fe3O4 is 0.75). The FTIR spectra of samples has sharp absorption

bands at 1080, 960 and 803 cm-1

assigned to the characteristic vibration of SiO2,

which indicates that the silica has successfully coated surface of

nanocrystallites. For these nanocomposites saturated magnetization value was

82 emu/g. The elemental analysis shows the presence of nitrogen after the

reaction with N-ethylenediaminetriacetate-silanes which corroborates the

attachment of the chelating moieties to the surface of the nanocomposites. The

concentration of chelating groups was found as 0,32 mmol/g.

The potential in adsorbent properties of these nanocomposites for Fe(IIІ),

Cu(II), Pb(II), Cd(II), Zn(II) in batch approach was used. The adsorption

capacity was evaluated using AAS. It was observed that magnetic chelating

nanocomposites removed all the studied metals with efficiency (90-99 %).

Acknowledgements

The authors would like to thanks the EU program FP7-PEOPLE-2009-IRSES (project

№247603) for financial support.

28

Characteristics of formation of iron and manganese oxide

particles and their sorption properties

O.M. Odnovolova1, D.S. Sofronov

1, S.M. Desenko

1, A.A. Beda

2

1STC «Institute for Single Crystals», NAS of Ukraine,

60 Lenin Ave., Kharkiv 61001, Ukraine, [email protected] 2Taras Shevchenko National University of Kyiv, [email protected]

Sorption is a simple and effective purification method, which is used for post-

treatment of waste water. Iron and manganese oxides based sorbents are of practical

interest due to their excellent sorption properties. The purpose of the present work is to

investigate the influence of the preparation conditions on the morphological and

sorption properties of iron and manganese oxide particles.

The influence of the preparation conditions (T, concentration, pH, anion in a

salt precursor) on the formation of micro- and nanoparticles of iron and manganese

oxides is described. The precipitation temperature was established to be the main

factor influencing on the formation Fe3O4 phase by precipitation from an aqueous

solution. The particles obtained at temperatures above 80°С have the largest values of

magnetization. The specific surface area does not depend on the precipitation

conditions and is in the range of 120 to 130 m2/g. The anion of the salt precursor

influences significantly on the Fe2O3 formation. The decomposition of iron(III) nitrate

at 450°С leads to small particles with Ssp of 140 to 150 m2/g, and the decomposition of

iron(III) chloride leads to large cubic and oval particles with sizes of 0.5 to 2 μm (Ssp

of about 30 m2/g). The decomposition of iron(II) oxalate at 175°С leads to maghemite

as a main phase. Large aggregated agglomerates of hematite with size of several dozen

of microns consisting of smaller particles are formed by precipitation of iron

hydroxide from aqueous solutions and subsequent annealing at 450°С regardless of pH

of the solution and the iron salt precursor. Investigation of the sorption properties of

the obtained particles demonstrated that iron oxides the most effectively removed ions

of such metals as Cu, Eu, Ce in the pH range of 5 to 9. With a 5-fold increase in the

specific surface area, a 1.5 to 2 fold increase in sorptive capacity was observed for all

investigated metals. It was found that an interaction between Mn2+

and MnO4- in

alkaline media yielded manganese oxohydroxide with excellent sorption properties as

a main phase. The value of the specific surface area for these particles increases with

decrease in synthesis temperature and concentrations of Mn2+

and MnO4- ions in

synthesis solutions. The degree of Cu, Co, Cd, Zn, Sr, Eu, Ce removal is more than

90% in the pH range of 3 to 9, and the sorptive capacity towards cobalt is 128 mg/g.

However, the sorptive capacity is reduced during ageing of the precipitate (5-fold for 6

months of storage). MnO2 particles obtained by decomposition of manganese(II)

nitrate have low sorptive capacity (6.4 mg/g towards cobalt) under the same

conditions.

Fe3O4/MnO(ОH) structures were obtained, and their sorptive capacities towards

cobalt were determined.

29

Removal of the uranium(VI) compounds from model solutions

with sorbents of different nature

N.O. Perlova1, O.V. Perlova

1, Yu.S. Dzyazko

2, V.F. Sazonova

1,

I.Yu. Halutskaya1

1Faculty of Chemistry, Odessa I.I. Mechnikov National University,

2 Dvoryanska Str., Odessa 65082, Ukraine, [email protected] 2Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine,

32/34 Palladin Ave., Kyiv 03142, Ukraine, [email protected]

The problem of uranium compounds removal from aqueous solutions

remains valid for many years. To solve this problem, the sorption methods are

used widely. A search of sorbents, which would combine availability,

cheapness, possibility of regeneration, absorption efficiency in a wide range of

pH, temperature, and concentration, is an important task.

The aim of this work was to establish an efficiency of sorbents of different

nature towards removal of uranium compounds from model solutions.

The research objects were aqueous solutions of uranium(VI) acetate with

concentration of (0.1-2.0)∙10-4

mol l-1

, which contained also 0.02 M H2SO4,

HNO3, HCl (pH 2.0-2.5) or NaHCO3 (pH 8.0). These reagents are used for

treatment of uranium-containing minerals. Inorganic zirconium-silica sorbents,

Dowex HCR-S cation exchange resin and organic-inorganic sorbents, which

were obtained by modification of this resin with nanopartilces of zirconium

hydrophosphate, FIBAN fibrous sorbents (cation exchanger FIBAN K-1, anion

exchanger FIBAN A-6 and ampholyte exchanger FIBAN AK-22B) were used as

sorbents. Sorption experiments were carried out under static conditions at 293K.

The studies have shown that all investigated sorbents remove uranium

compounds effectively from the model solutions. The removal degree reaches

95-100% under optimal conditions, which were found for each particular

system. Characteristics of the sorbents (specific surface, pore size, particle size, functional groups that are included) determine their optimal consumption.

Constants of film diffusion rate, particle diffusion coefficients of U(VI), rate

constants of pseudo-first and pseudo-second order have been determined.

Sorption isotherms are processed using the Langmuir, Freundlich, Dubinin-

Radushkevich and Frumkin-Fowler-Guggenheim equations. The calculated

values of constants of these equations indicated a significant affinity of U(VI)

compounds to the sorbents and ion exchange mechanism of sorption. It was

found that the sorbents could be regenerated for 88-100% by 1 M solutions of

NaCl, HCl, H2SO4 and NaHCO3.

30

The interfacial properties and colloidal behaviors of detonation

nanodiamond species in water

N.O. Mchedlov-Petrossyan1, N.N. Kamneva

1, V.V. Tkachenko

1,

A.I. Marynin2, E. Osawa

3

1Department of Physical Chemistry, Kharkov V. Karazin National University,

61022, Kharkov, Ukraine, [email protected] 2National University of Food Technologies,

68 Volodymyrska Str., Kyiv 01601, Ukraine 3NanoCarbon Research Institute, Ltd, AREC (Asama Research Extension

Center), Faculty of Textile Science and Technology, Shinshu University,

3-15-1 Tokida, Ueda, Nagano 386-8567, Japan, [email protected]

This report presents some new data concerning the properties of hydrosols

of detonation diamond. The size of the primary particles is 2.8± 0.6 nm as found

via DLS study. The positively charged species consist of the 2 nm diamond core

and the non-diamond interfacial layer. The previously considered dramatic

increase in size of the aggregates on dilution was already explained by us in

terms of the periodic colloidal structures (colloid crystals) in concentrated

solutions [1-2]. Now we further this study with taking into account the aging

processes which occur in the hydrosols. This aging manifests itself in decrease

in the critical concentration of coagulation (CCC), i.e., in the colloidal stability

decrease. This effect was observed using both sodium chloride and sodium

n-dodecylsulfate as electrolytes-coagulators. However, the restoration of the

CCCs appeared to be possible when proper amount of HCl is introduced into the

system. The positive charge of colloidal aggregates is confirmed both by zeta-

potential ( ) measurements and dye adsorption. Among the series of

rhodamines, hydroxyxanthenes, and sulfonephthaleins, the negatively charged

dye ions readily adsorb on the aggregates, contrary to the cationic dyes. The

estimating of the interfacial electrical charge, , was accomplished using a set

of acid-base indicators. This procedure is well-established for lyophilic colloids,

such as surfactant micellar systems, reverse microemulsions, etc., but not for

lyophobic ones. In this study, the result obtained is quite reliable: > .

1. N.O. Mchedlov-Petrossyan, N.N. Kamneva, A.I. Marynin, A.P. Kryshtal, E. Ōsawa,

Physical Chemistry Chemical Physics, 17 (2015) 16186.

2. N.O. Mchedlov-Petrossyan, N.N. Kamneva, A.P. Kryshtal, A.I. Marynin,

V.B. Zakharevich, V.V. Tkachenko. Ukrainian J. Phys, 60 (2015) 936.

31

Effect of structural and surface properties of adsorbent on

adsorption equilibria and kinetics

A. Derylo-Marczewska, M. Blachnio, A.W. Marczewski

Faculty of Chemistry, Maria Curie-Sklodowska University,

Maria Curie-Sklodowska sq. 3, 20-031 Lublin, Poland

The adsorption methods of water purification by using various adsorbents

are intensively investigated in order to increase the process effectiveness. The

effect of adsorbent structure and surface properties, adsorbate physicochemical

properties, process conditions are studied to correlate the values of parameters

characterizing the adsorption system with adsorption of a given solute.

In the presented paper the influence of activated carbon characteristics on

the removal effectiveness of selected herbicides from aqueous solutions is

discussed. As adsorbents the commercial carbon Filtrasorb F300 and the Norit

experimental carbon RIB were used in the unmodified and modified forms. Both

carbons were oxidized by ozone or HNO3 and then thermally treated. As

adsorbates the following herbicides were chosen: 2,4-dichlorophenoxyacetic

acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA),

4-chlorophenoxyacetic acid (4-CPA),. The carbon structure and surface

characteristics were obtained from nitrogen adsorption/desorption isotherms and

potentiometric titration, respectively. The adsorption isotherms were obtained by

using the static method, and the concentration vs. time profiles were measured

by applying the UV-Vis spectrophotometer with a flow cell. The experimental

isotherms were analyzed by using the Generalized Langmuir (GL) equation

taking into account the system energetic heterogeneity, whereas the kinetic data

were studied by applying the semi-empirical multi-exponential equation. The

dependences between carbon porosity and surface properties, and adsorption

uptake and rate were discussed.

A moderate influence of adsorbent porosity on adsorption uptake and rate

was found for the investigated systems. Taking into account the adsorption half-

times and the course of concentration profiles it was stated that adsorption

process was faster on F300 carbon with lower micropore volume in comparison

to RIB carbon. A strong effect of acid/base properties of carbons on adsorption

of herbicides was found. Increase of concentration of oxygen surface groups

decreased the adsorption uptake to a large extent; it also effected the adsorption

rate – in the case of such carbons the adsorption processes were much slower as

a result of slower diffusion and changes of adsorbate-adsorbent interactions.

Acknowledgements

The authors are grateful to European Community, Seventh Framework Programme

(FP7/2007–2013), Marie Curie International Research Staff Exchange Scheme (IRSES grant

No 612484) for financial support of this work.

32

Temperature effects in adsorption equilibrium and kinetics of

selected aromatic compounds on active carbons

A.W. Marczewski, M. Sęczkowska, A. Deryło-Marczewska

Maria Curie-Skłodowska University, Maria Curie-Skłodowska Sq. 3,

20-031 Lublin, Poland, [email protected]

Adsorption on active carbons is one of well-established methods of

removal of toxic aromatic compounds from waters. However, in the

environment and industrial processes one of difficult-to-control variables is

temperature – especially if we take into account other seasonal weather effects

involving also changing rainwater level or flooding. In a general way adsorption

of organics on active carbon may be described by using theory of adsorption on

energetically heterogeneous solids [1, 2] evolved from Langmuir isotherm [3].

Adsorption kinetics is another important factor when using microporous

granular adsorbent with diffusion [4, 5] or adsorption/desorption rate-controlling

steps [6-9].

Adsorption equilibrium and kinetics of 4-chlorophenoxyacetic acid

(4-CPA) and 3-bromophenoxypropionic acid (3-BrPP) herbicides on RIB carbon

(Norit) in a range of temperatures were investigated. It was found that

adsorption increased with the increase of temperature (as opposed to adsorption

of vapors) and the same was obtained for adsorption rate. However, definitions

of rate coefficients are model-dependent and we decided to use adsorption half-

times instead. Adsorption half-times are experimental values and are not model

dependent, but may be easily calculated from rate constants. Data analysis

showed that half-time temperature dependences are similar to the Arrhenius and

Eyring equations‟ plots.

Acknowledgements




1. M. Jaroniec, R. Madey, Physical Adsorption on Heterogeneous Solids, Elsevier,

Amsterdam 1988.

2. A.W. Marczewski, M. Jaroniec, Monatsh. Chem. 114 (1983) 711.

3. I. Langmuir, Phys. Rev. 8 (1916) 149; J. Am. Chem. Soc. 40 (1918) 1361.

4. J. Crank, Mathematics of diffusion, Clarendon Press, Oxford 1975.

5. G. McKay, M. El Geundi, M.M. Nassar, Process Safety Environ. Prot. 74 (1996) 277.

6. A.W. Marczewski, Appl. Surf. Sci. 253 (2007) 5818; 256 (2010) 5145.

7. A.W. Marczewski, Langmuir 26 (2010) 15229.

8. A.W. Marczewski, J. Colloid Interface Sci. 361 (2011) 603.

9. A.W. Marczewski, A. Deryło-Marczewska, A. Slota, Adsorption 19 (2013) 391.

33

One step covalent functionalization of C60 and pristine

multi-walled carbon nanotubes with crown ethers

L.V. Henao-Holguín

1, V. Meza-Laguna

1, E.V. Basiuk

2, V.A. Basiuk

1 ,

T.Yu. Gromovoy3

1Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México,

Circuito Exterior C. U., 04510, México, D.F., Mexico 2Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional

Autónoma de México, Circuito Exterior C. U., 04510, México, D.F., Mexico 3Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv, Ukraine.

[email protected]

The goal of the present work was to test the feasibility of simple, one-step

and solvent-free covalent functionalization of pristine multi-walled carbon

nanotubes (MWNTs) and fullerene C60 (as a model system) with amino-

substituted crown ethers, namely, 4-aminobenzo-15-crown-5 and 4-aminobenzo-

18-crown-6. The attachment technique proposed is based on thermal instead of

chemical activation, and can be considered as ecologically friendly. The

covalent attachment of substituted crown ethers 4-aminobenzo-15-crown-5 and

4-aminobenzo-18-crown-6 onto fullerene C60 and pristine MWNTs occurs under

solvent-free conditions at 160–170 oC. For C60, the nucleophilic addition of

aminobenzo-crowns apparently takes place at the 6,6 bonds of pyracylene units.

In the case of pristine MWNTs, the reaction mechanism is believed to rely upon

the reactivity of pentagonal and other defects (similar to pyracylene units of C60,

responsible for spherical curvature of the closed ends and sidewall kinks.The

hybrids of crown ethers with MWNTs were characterized by means of scanning

and transmission electron microscopy, Fourier-transform infrared and Raman

spectroscopy, as well as thermogravimetric analysis. The functionalized C60

samples were additionally studied by means of 13

C cross-polarization magic

angle spinning nuclear magnetic resonance spectroscopy and laser

desorption/ionization time-of-flight mass spectrometry.

The approach proposed allows for a facile preparation of crown ether-

functionalized pristine MWNTs and C60 without contamination with other

chemical reagents, detergents and solvents; this advantage is especially

important for a vast variety of nanotube applications ranging from

nanoelectronics to nanomedicine.

Acknowledgements

Financial support from the National Autonomous University of Mexico (UNAM; grant

DGAPA-IN101313).

34

Study of adsorption of selected organics from aqueous solutions

on active carbon in the multicomponent system

M. Sęczkowska, A.W. Marczewski, A. Deryło-Marczewska,

A. Chrzanowska



[email protected]

Adsorption methods using activated carbon are commonly used in the

technology of water treatment and waste water. Adsorption is a multistep

process and each phase can take place at different times. The rate of the whole

process will be determined by the slowest step. The efficiency of adsorption is

influenced by many factors related to the properties of the adsorbent (specific

and external surface area, type and volume of pore, surface charge) and

adsorbate (molecular size of the adsorbate, differences in solubility), process

conditions (pH), temperature and the presence of other substances [1-2].

The main aim of this study was to investigate adsorption kinetics in a

multicomponent aqueous system. For this purpose methylene blue (MB; Sigma-

Aldrich), 4-nitrobenzoic acid (4-NBA; Merck) and ibuprofen (IBP; Sigma-

Aldrich) and granular active carbon GAC 1240W (Norit) were selected. Kinetic

measurements were conducted by using Cary 100 spectrophotometer (Varian

Inc., Australia) with a flow cell. Multi-exponential equation (m-exp) was fitted

to the data. This equation may describe a series of parallel first order processes

or approximate a series of follow-up processes [3-7].

Fig. Comparison of adsorption kinetics of MB and 4-

NBA on GAC in single and multi-component

systems

Acknowledgements




1. S. Chiron, A. Fernandez-Alba, A. Rodriguez, E. Garcia-Clavo, Water Res., 34 (2000) 366.

2. L. Clausen, I. Fabricius, L. Madsen, J. Environ. Qual., 30 (2001) 846.

3. A.W. Marczewski, Appl. Surf. Sci., 253 (2007) 5818.

4. A.W. Marczewski, Appl. Surf. Sci., 256 (2010) 5145.

5. A.W. Marczewski, Langmuir, 26 (2010) 15229.

6. A.W. Marczewski, A. Deryło-Marczewska, A. Slota, Adsorption, 19 (2013) 391.

7. A.W. Marczewski, J. Colloid Interface Sci., 361 (2011) 603.

35

Photocatalytic hydrogen production in systems based on

hydrazine (dimethylhydrazine) and graphitic carbon nitride

Ya.V. Panasiuk, G.V. Korzhak, A.E. Raevskaya, O.L. Stroyuk

L.V. Pysarzhevsky Institute of Physical Chemistry, NAS of Ukraine,

31 Nauky av., Kyiv 03028; [email protected]

Graphitic carbon nitride (GCN) is a layered organic semiconductor

featuring reasonable sensitivity to the visible light, photocatalytic activity in a

variety of redox-processes, as well as a high chemical and photochemical

stability. Further improvement of the photocatalytic activity of GCN is an

important milestone of developing of new photocatalytic systems and processes.

We have found that treatment of GCN synthesized from melamine at

500 °С on air by the concentrated nitric acid makes it an active photocatalyst of

molecular hydrogen production from aqueous solutions of hydrazine,

N2H4H2SO4 and asymmetric dimethylhydrazine (a-DMG) in the presence of

Pd/SiO2 as a co-catalyst. In solutions of N2H4 and a-DMG with a concentration

lower than 2–3 M the photocatalytic activity of GCN is comparable to that of

nanocrystalline TiO2 Evonik P25. However, in more concentrated solutions of

the donors the photocatalytic activity of TiO2 P25 rapidly deteriorates while the

GCN retains the capability of water reduction even in pure N2H4 and a-DMG.

The quantum yield of photocatalytic hydrogen production with the

participation GCN grows with an increase in the treatment duration tacid, reaches

a maximal value of 0.6–0.7% at tacid = 2 h and then decreases. Simultaneously,

the treatment results in enhancement of photoluminescence (PL) of GCN and a

short-wave shift of both absorption and PL bands of GCN indicating partial

disruption of its aromatic structure.

Analysis of X-ray photoelectron spectra of the GCN samples produced at

different tacid showed that the treatment with concentrated HNO3 results in

partial destruction of heptazine building blocks of GCN with elimination of

pyridinic N as well as in formation of COOH-groups. These structural defects

most probably act as traps of the photogenerated charge carriers facilitating their

participation in radiative recombination (as shown by PL measurements) and

secondary photocatalytic processes. The extreme dependence of the H2

evolution rate upon tacid can be interpreted as a result of interplay of

simultaneous enhancing of the radiative recombination and the photoactivity as

a result of the acid treatment. The work was supported by the Complex program of fundamental research of

National Academy of Sciences of Ukraine "Fundamental problems of development of new

nanomaterials and nanotechnologies" (project #32/16-N) and by the State Fund For

Fundamental Research of Ukraine (project #F64/36-2016).

36

Carbon nanomaterials as catalysts in reactions of organic

peroxides decomposition

D.M. Haliarnyk, O.M. Bakalinska, M.T. Kartel



Organic compounds, especially organic peroxides (OP) are widely used in

many processes as a source of free radicals, their radical decomposition is

studied in detail, but the catalytic decomposition of OP is still not well

investigated. Carbon nanomaterials (CNM) such as activated carbon (AC),

carbon nanotubes (CNT) are extensively used as catalysts for organic and

inorganic synthesis. CNM can be effective catalysts for the decomposition of

organic peroxides. That‟s why the aim of this work is to study the catalytic

activity of CNM in the model reaction of benzoyl and lauroyl peroxides (BP and

LP) decomposition and compare with catalytic activity of natural enzyme.

AC (natural - KAU and synthetic - SKN) and CNT, their modified forms -

oxidized (SKNo, KAUo and CNTo); and nitrogen containing - obtained by urea

impregnation (KAU+N, KAUo+N) and followed by heat treatment (N-SKN,

N-KAU, N-CNT), KAUo-NH2 obtained by chemical immobilization of

1,5-diaminopentane on KAUo and catalase (from bovine liver, Fluka) have been

used as catalysts in reactions of OP decomposition. The investigated samples

were characterized: specific surface area and average pore radius – by

chromatographic method of low-temperature desorption of argon; sorption pore

volume – by desiccator method and elements composition by the Prehlya and

Dumas methods. Qualitative and quantitative characterization of functional

groups on the surface of CNM has been performed by the Böhm titration.

Michaelis constant (Km, mM) has been used to calculation of CNM and their

modified forms catalytic activity from kinetic data.

It was found that the catalytic activity (Km, mM) of the investigated

materials decreased in the following order: N-KAU > N-CNT > N-SKN > SKN

> SKNо > KAUo-NH2 > CNT > catalase > CNTо > KAU > KAUo+N > KAUо

> KAU+N in reaction of BP decomposition. The highest activity (more than

catalase one) - exhibit nitrogen-containing CNM (N-KAU, N-CNT, N-SKN).

The results of kinetic studies show that the activated carbon N-KAU is the most

active catalyst. It was shown that presence in carbon nanomaterials chemically

bonded with carbon structure nitrogen atoms increase their catalytic activity

while oxygen atoms reduce it. Thus, nitrogen containing materials N-KAU and

N-CNT can be used as efficient catalysts for the organic peroxides

decomposition.

37

Nanocomposite suture materials and drugs for prevention and

treatment of postoperative purulent complications and

inflammatory diseases

O.A. Viltsaniuk1, P.V. Belyaev, N.M. Rezanova

2, R.A. Lutkovskyi

1

1Vinnytsya National Pirogov Memorial Medical University,

56 Pirogov Str., Vinnytsya 21021, Ukraine, [email protected] 2Kyiv National University of Technology and Design,

2 Nemirovich-Danchenko St., Kyiv 01011, Ukraine

Problem of prevention and treatment of postoperative septic

complications and inflammatory diseases is one of the most urgent problems of

modern surgery. One of the causes of postoperative complications is the use of

suture materials without antimicrobial properties. We have developed new types

of modified polypropylene (PP) suture material with carbon nanotubes (CNT)

and group biguanidine antiseptics and have developed new drugs for the

treatment of purulent - inflammatory processes based on nanodispersed silica

(NDS) with cationic surface active antiseptic.

During performance study, we have used physical, chemical,

experimental, clinical and statistical research methods. Experimental studies

were conducted on laboratory animals according to international standards of

bioethics. The objects of clinical studies were 244 operated patients for acute

surgical pathology, which were divided into two groups. The core group was

treated according to developed method and at comparison group treatment was

conducted by conventional methods. Modification of PP by antiseptics and NDS

allowed to obtain a new kind of surgical suture material of high strength and

antimicrobial properties with absence of absorbability and capillarity. The study

of tissue response to the implantation of developed suture material in the

experiment revealed that the tissue reaction is moderate and no different than the

classic tissue reactions suture with PP. The use of designed suture material for

creation of bowel walls connection ensure high biological and physical strength

of connection and prevented peritoneal cavity infections. Stitching of

experimental infected rabbits wounds by created suture material in combination

with the previously washed by drug suspension, based on nanodispersed silica,

helped to prevent postoperative purulent complications and ensure a more

favorable course of reparative regeneration processes in the wound in comparing

to control group.

The results of experimental studies allowed to develop a program of

remedial measures have been used in the clinic. Using techniques developed in

the surgical treatment of patients with acute surgical pathology and purulent

inflammatory diseases had reduced the number of postoperative complications,

reduce the time patients stay in hospital and reduced postoperative mortality.

38

Analysis of structure and morphology of the MCF surface with

adsorbed protein molecules

A. Chrzanowska1, A. Deryło-Marczewska

1, A.W. Marczewski

2,

M. Sęczkowska1

1Department of Physicochemistry of Solid Surface Faculty of Chemistry, Maria

Curie-Skłodowska University, [email protected] 2Department of Radio- and Colloid Chemistry, Faculty of Chemistry, Maria

Curie-Skłodowska University, M. Curie-Skłodowska Sq.3,20-031 Lublin, Poland

The protein adsorption from solutions onto surface of mesoporous silica

materials attracts attention due to its scientific importance and application in

many areas such as catalysis, biology, medicine, biotechnology as well food

processing [1].

MCF adsorbents with various geometry structures were synthesized by

using the non-ionic triblock Pluronic copolymers (PE9400 and PE10500) as a

template and trimethylbenzene (TMB) as a pore expanding agent according to a

modified procedure outlined in the papers [2, 3]. The kinetics and equilibrium

adsorption processes of BSA and OVA proteins from aqueous solutions at

pH=7.4 on the series of MCF materials with different porosity were evaluated.

The results of study focused on a detailed analysis of structure geometry,

morphology and micro-nanostructure of the mesoporous MCF materials with

different porosity before and after immobilization of biomolecules. Proper

characterization of the porous structure of the protein/silica surface was

determined by means of the nitrogen adsorption/desorption isotherms. The

morphology and micro-nanostructure of MCF surface with adsorbed protein

layers were determined by using the atomic force microscope (AFM) and optical

profilometer (OP). Moreover, the scanning electron microscope with X-ray

microanalysis (SEM/EDS), transmission electron microscopy (TEM) and energy

dispersive X-ray spectroscopy (EDX) were used to characterize the surface

structure and the elemental composition (Si, C, O, N) of the investigated

protein/mesoporous silica composites.

Acknowledgements



no 612484) for financial support of this work.

1. C.E. Giacomelli, W. Norde, J. Colloid Interface Sci., 233 (2001) 234.

2. P. Schmidt-Winkel, W.W. Lukens Jr., D. Zhao, P. Yang, B.F. Chmelka, G.D. Stucky,

J. Am. Chem. Soc. 121 (1999) 254.

3. A. Derylo-Marczewska, A.W. Marczewski, I. Skrzypek, S. Pikus, Pol. J. Chem. 82 (2008)

205.

39

Adsorption of anionic dyes on corn stalks modified with

polyaniline: kinetics and thermodynamic studies

L.M. Soldatkina, M.A. Zavrichko

Odessa I.I. Mechnikov National University,

Dvoryanskaya St. 2, Odessa 65082, Ukraine, [email protected]

Nowadays particular attention is given to synthesis of new adsorbents –

composites, based on plant wastes which covered by polyaniline. For example,

these composites can improve the adsorption capacity of raw plant wastes

toward anionic dyes. Kinetic and thermodynamic studies of dye adsorption on

new adsorbents – composites are needed for their broad and effective

implementation in the practice of wastewater treatment. Besides, mathematical

modeling of adsorption bases on experimental kinetic curves and adsorption

isotherms and allows getting information about the mechanism of adsorption.

The aim of this paper was to analyze kinetics and thermodynamics of

adsorption of anionic dyes (Acid Red (AR) and Acid Orange (AR)) on adsorbent

– composite CS-PAN (corn stalks, modified with polyaniline and doped with

H3PO4), using different models and to suggest the mechanism of adsorption of

anionic dyes on CS-PAN.

The studies have shown that the optimal time of adsorption of anionic

dyes on CS-PAN at 303 and 313 K are 150 min and at 328 K – 120 min. The

experimental adsorption kinetic curves of anionic dyes on CS-PAN were

examined by pseudo-first-order and pseudo-second-order kinetic models and by

external and intra-particle diffusion models. The experimental adsorption

capacity values were in agreement with values of the theoretical adsorption

capacity that were calculated with the pseudo-second order model. High values

of correlation coefficients (> 0.99) were obtained for the pseudo-second-order

kinetic model, the external and intra-particle diffusion models. This means, that

anionic dyes are transported from the solution to the surface of CS-PAN occurs

in several steps such as external or film diffusion, pore diffusion, surface

diffusion and adsorption on the pore surface, or a combination of more than one

step through the adsorption process.

It was showed that adsorption of anionic dyes on CS-PAN better

described by the Langmuir adsorption isotherm equation than the Freundlich

adsorption isotherm equation. Thermodynamic adsorption parameters were

calculated and the mechanism of adsorption of anionic dyes on the adsorbent-

composite was proposed. Thus, adsorption of anionic dyes on CS-PAN is as a

result of electrostatic interactions, where forces of interaction are the physical

forces in adsorption reactions (e.g. dipole-dipole, dispersion, London-van der

Waals and H-bonding) between anionic dyes and imino-groups of CS-PAN.

40

ZnAl layered double hydroxide sorbent/photocatalyst for removal

of negatively and positively charged organic compounds

G.M. Starukh



Controlling pollution is the main concern of society today. Dye and

surfactant effluents pose certain hazards and environmental problems.

Adsorption is one of the most frequently used methods for dye removal. In this

way the application of layered double hydroxides (LDHs) and their calcined

products as adsorbents to selectively remove anionic pollutants from aqueous

solutions have attracted considerable attention in the recent decade. The LDHs

are reasonable to use for anionic surfactants removal.

Due to their anionic exchange capacity, LDHs are suitable for

intercalation and sorption of negatively charged species but are not applicable

for positively charged ones. The modification of LDH‟s surface with anionic

surfactants allows using it for sorption of many types of organic molecules. The

organic phase in the interlayer which is formed by the intercalated organic ions,

acted as an adsolubilization medium increasing the affinity of LDHs for organic

compounds.

Recently, LDHs have been intensively investigated as promising

heterogeneous photocatalysts because of their excellent intrinsic photo-response

characteristics, low cost, as well as facile preparation and modification [1].

LDHs as photocatalysts are expected to possess large energy-conversion

efficiency as a result of the high dispersion of active species in a layered matrix,

which facilitates the charge separation. Many LDH-based photocatalysts have

been developed via appropriate incorporation of photoactive components into

LDH host layers, sensitizing by interlayer functional molecules and construction

of nanocomposites.

The results on removal of anionic species (sodium dodecylsulfate, indigo

carmine dye) and cationic dye methylene blue using Zn-Al LDHs will be

presented. The adsorption and photocatalytical properties of as-synthesized,

calcined and modified with surfactant Zn-Al LDHs will be compared.

1. M. Shao, M. Wei, D. Evans, X. Duan, Layered Double Hydroxide Materials in D. Yan, M.

Wei (eds.), Photocatalysis in Photofunctional Layered Materials, Structure and Bonding,

Springer: Switzerland, 2015, p.105.

41

Adsorption of anthocyanins from the chokeberry extracts

on bentonite

L.M. Soldatkina, V.O. Novotna

Odessa I.I. Mechnikov National University

2 Dvoryanskaya Str., Odessa 65082, Ukraine, [email protected]

In recent years there is increasing interest in anthocyanins as natural food

colorants and as substances with certain therapeutic effects (anti-inflammatory,

anti-cardiovascular, anti-diabetic, anti-cancer) and for treatment of eyesight

disorders. Adsorption is one of the most effective methods of concentration,

removal and purification of anthocyanins from their extracts. However, data of

anthocyanin adsorption on cheap adsorbents are extremely scarce.

The objective of this study was to investigate the adsorption of

anthocyanins from chokeberry extracts on bentonite in static conditions and to

test the suitability of adsorption kinetic models for describing kinetic curves and

the suitability of the Langmuir and Freundlich adsorption models for describing

adsorption isotherms.

Fully ripe chokeberries were harvested in Vinnytsia region (Ukraine) in

2015, immediately frozen and kept at –20 oC until analysed. Chokeberries were

comminuted using a grater and extracted with 0.1 M HCl. Adsorbent was

bentonite from Dashukovsky deposit (Ukraine).

Kinetic adsorption curves of chokeberry anthocyanins on bentonite

demonstrated that the equilibrium time was approximately 60 min. The rates of

anthocyanin adsorption increased rapidly in the first 10 min, and then slowly

increased afterward, reaching equilibrium after 60 min. Experimental kinetic

adsorption data follow to pseudo-second-order kinetic model.

Experimental adsorption isotherms of chokeberry anthocyanins on

bentonite have been described by the Langmuir and Freundlich equations. The

Langmuir model provides a better fit to the equilibrium data than the Freundlich

model. The maximum adsorption capacity of chokeberry anthocyanins achieved

125 mg/g.

Thermodynamic parameters were evaluated to predict the nature of

adsorption process. Results revealed that the adsorption process in the range of

20 to 40 oC was spontaneous (–DG

o= 25.3-25.5 kJ/mol) and exothermic

(DHo= -23.3 kJ/mol). The positive values of change in standard entropy

(DSo=0,007 kJ/(mol·K)) suggest the increased randomness at the solid/solution

interface during the adsorption of chokeberry anthocyanins on bentonite.

This study showed that bentonite as adsorbent has good adsorption ability

toward chokeberry anthocyanins in their aqueous extracts.

42

Hydroxyapatite-alginate microspheres loaded with nimesulide for

biomedical application

A.A. Yanovska1,2

, S.B. Bolshanina2, A.S. Stanislavov

1, A.K. Soni

3

1Institute of Applied Physics, NAS of Ukraine,

58 Petropavlovskaya Str., 40000, Sumy, Ukraine, [email protected] 2Sumy State University, Ministry of Education and Science of Ukraine,

2 R. Korsakova Str., 40007, Sumy, Ukraine. 3Kusum Pharm, Sumy,

54 Skryabina Str., Sumy 40030, Ukraine,

Hydroxyapatite (HA), as a main component of bone tissue, is widely

applied in biomaterials production. It can be combined with various types of

biopolymers – collagen (naturally occured in bones), gelatin, chitosan and

alginate. In our work the microspheres, based on HA loaded with Nimesulide

(NIM) and sodium alginate (SA), were produced. Since HA has an excellent

adsorption ability it can be loaded with drugs. As a model drug we applied

Nimesulide having anti-inflammatory and antipyretic action, preventing

cartilage degradation and widely used in treatment of arthritis, osteoarthritis,

myalgia and edema.

Fig. Surface morphology of HA-SA-

NIM microsphere (SEM image)

HA was synthesed in the presence of

nimesulide under alkaline conditions.

Na-alginate solution with 3%

concentration was prepared fresh as

needed, using distilled water. Sorption

ability of HA was studied by measuring

optical density using photocolorimetry

(λ=440 nm). Nimesulide concentrations

after 3 hours and 16 hours of HA aging

were 172 and 187 mg/g respectively.

Microspheres (Fig.) were formed by mixing 3% alginate solution with

HA-NIM in relation 1:1 and dropping into 0.1 M CaCl2 solution. Sodium

alginate form complexes with Ca2+

ions due to the ion exchange. Ability of NIM

release from HA-NIM-SA samples was estimated by immersion microspheres

into physiological solution. 10 and 5 mg/g of NIM were released from

microspheres HA-NIM and HA-NIM-Alg respectively after 30 minutes of

immersion. Thus the presence of SA capsule decreased release of NIM from

microspheres. In the presence of HA the rate of NIM release decreased in

3 times.

43

Progressive surface alkoxylation at interaction of silica with

dialkyl carbonates

E.M. Demianenko, A.G. Grebenyuk, V.V. Lobanov, V.A. Tertykh



The final products of the interaction between silica and alkyl carbonates at

the elevated temperatures are appropriate tetraalkoxysilanes. It is important to

elucidate how the appearance of grafted methoxy-groups in the surface layer

effects on the processes of progressing alkoxylation silica. This can be done by

means of quantum chemistry that capable to analyze the spatial structure and

energy characteristics of the initial reagents (IR), transition states (TS) and the

reaction products (RP). Model studies on possible impact of methoxy-groups on

the following processes of alkoxylation of silica surface have been carried out,

disilicic acid interaction with dimethyl carbonate molecules being an example.

All the calculations have been carried out by means of the GAMESS (US)

program by density functional theory (DFT) method with functional B3LYP and

basis set 6-31G(d,p).

b

a

IR RP TS

Еact=332.4 kJ/mol

ΔЕreac=26.3 kJ/mol

Еact=331.0 kJ/mol

ΔЕreac=3.9 kJ/mol Fig. Areas of possible attack (a and b) due to the interaction of dimethyl carbonate with

methoxy-derivatives of disilicic acid

The results of quantum chemical calculations indicate that the interaction

of disilicic acid derivatives containing methoxy-groups at various positions with

a molecule of dimethyl carbonate (IR) occurs due to formation of a

six-membered cyclic transition state (see TS in Figure) and results in siloxane

rupture and the increasing number of the surface methoxy-groups. It has been

found that the next attack of dimethyl carbonate molecule takes place on the

silicon atom next to that bound with grafted methoxy-group (Figure b).

44

Sorption properties of cellulose and lignocellulose materials

towards sodium diclofenac

V. Galysh1,2

, R. Kozakevych2, M. Kartel

2

1Department of Ecology and Plant Polymers Technology,

National Technical University of Ukraine “KPI”,

37/4 Peremogy avenue, Kyiv 03056, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,

17 General Naumov Str., Kyiv 03164, Ukraine

Non-steroidal anti-inflammatory drugs are a group of drugs that are

characterized by analgesic, antipyretic and anti-inflammatory effects. Despite

the high efficiency in the treatment of various inflammatory processes, all

members of non-steroidal anti-inflammatory drugs cause mucosal damage of the

stomach. This problem can be overcome via immobilization of active substance

in different carriers. Diclofenac belongs to this group. Due to its clinical effect

and short biological half-life diclofenac-based pharmaceuticals are ideal

candidates for prolonged release formulations.

In our research work the possibility of application the plant polymer

carriers for this purpose was investigated. We studied the sorption properties of

long-fiber cellulose (bleached cotton fiber), microcrystalline cellulose (derived

from bleached cotton fibers) and lignocellulose materials (derived from apricot

seed shells) with different content of lignin and cellulose towards sodium

diclofenac. It was found out, that initial cotton fibers don't show sorption ability

on the drug, unlike microcrystalline cellulose – the effectiveness of diclofenac

sorption from the aqueous solution is 42%. To improve sorption capacity of

microcrystalline carrier its modification with amino-compound was done. Due

such treatment microcrystalline cellulose with 0.26 mmol/g amino groups was

obtained. The application of obtained material increases the effectiveness of

diclofenac sorption to only 60%, the content of free –NH2 groups is decreased

during sorption to 0.08 mmol/g. Mentioning lignocellulose matrix we must note

that the increase in cellulose content significantly increases the sorption

properties of materials towards diclofenac. Maximum sorption capacity of drug

is 80% and corresponds to a sample with a cellulose content of 60%.

Determination of kinetic characteristics of the process shows that the time

required to achieve equilibrium sorption is 60 min for microcrystalline cellulose

and lignocellulose matrix.

The obtained results show high absorption ability of plant polymers

towards sodium diclofenac and demonstrate the feasibility of application of such

carriers in the production of prolonged action drugs.

45

Quantum chemical study on pressure-induced phase transitions in

arsenic nanoparticles in confined space

A.G. Grebenyuk



Phase transitions in solids nowadays are widely studied by experimental

and theoretical methods. Those induced by external pressure in confined space

are of particular interest. This work is devoted to quantum chemical simulation

of pressure-induced structural rearragements in arsenic nanoparticles. According

to experimental data [1], bulk arsenic with A7 crystal structure under pressure of

25 GPa converts into A1 one. Cluster models with simple cubic structure have

been designed including 16, 32, and 64 arsenic atoms in boxes of 22, 34, and 50

helium atoms. Quantum chemical calculations of equilibrium spatial structure

and energy characteristics of the models have been carried out by restricted

Hartree-Fock method with use of SBKJC basis set and respective effective core

potential by means of Firefly8 program package [2]. The external pressure

applied was simulated by surrounding the stucture studied with a box of helium

atoms with fixed He-He distance (see Figure); its decreasing related to growth of

the pressure. When a definite pressure value was reached, due to optimizing

geometric parameters of the system, the structure of As cluster became A1-like.

The pressure value necessary to secure phase transition was calculated as the

first derivative of total energy of the system with respect to its volume.

As64 cluster in box of 50 helium atoms

For the As16@He22 model, the calculated external press of phase

transition was found to be 82.7 GPa. A passage to greater model (As32@He34)

gave more realistic result (49.8 GPa). The expanded model (As64@He50) gave

a result (28.4 GPa) rather close to the experimental value for bulk arsenic. Thus,

the parameters of phase transition in solids can be correctly estimated via

quantum chemical calculations of relatively simple models.

1. H. J. Beister, K. Strossner, K. Syassen, Phys. Rev. B 41 (1990) 5535.

2. M. W. Schmidt, K. K. Baldridge, J. A. Boatz et al., J. Comput. Chem. 14 (1993) 1347.


mailto:As16@He22

mailto:As32@He34

mailto:As64@He50

46

Charge-controlled adsorption for wide-gap polar adsorbents

N.V. Nikolenko1, S.I. Okovytyy

2, I.S. Samchileev

1,

A.V. Dubenko1, V.A. Solovov

1

1Ukrainian State Chemical Technology University, 8 Gagarin Av.,

Dnipropetrovsk 49005, Ukraine, [email protected] 2Oles Honchar Dnipropetrovsk National University,

72 Gagarin Av., Dnipropetrovsk 49010, Ukraine

The most promising way to predict the surface activity of a substance is

through a comparison of the electronic structures of the adsorbate and adsorbent.

From this viewpoint, orbital symmetry, effective charges on the atoms and

molecular orbital energies are the general parameters determining the result of

surface interaction.

As is well known, molecular interaction result can be estimated from

perturbation theory as the total of the contributions arising from pair interactions

between the orbitals of the adsorbate and adsorbent:

,

2

ji

ijiij SHE

D

where Hij is the matrix of the interaction function of the i and j orbitals, Sij is the

overlapping integral, and i and j are the energies of the molecular orbitals.

According to this equation, chemical reactivity arises from the difference

in energy between the highest occupied orbital of the donor and the lowest

unoccupied orbital of the acceptor. Two situations arise depending on the

relative magnitude of the energy difference: (i) for a large enough differences in

the energy, i j, the quantity DЕ is mainly determined by the magnitudes of Hij

and Sij; (ii) for rather small energy differences, the orbital interaction becomes

predominant.

By analogy, two approaches can also be considered in the case of

chemisorption: charge-controlled adsorption where the interaction is

determined by the charges of the adsorbate and adsorbent atoms; and orbital-

controlled adsorption where orbital energies of adsorbent and adsorbate are

close to each other.

Our investigations indicates that adsorption of the compounds with polar

functional groups onto wide-gap polar adsorbents (such as oxides, hydroxides,

spinel-type oxides, molybdates, titanates, carbonates, phosphates) is charge-

controlled. It was shown, that the adsorption of organic compounds onto wide-

gap polar adsorbents is controlled by the steric accessibility and by the values of

the greatest effective charges on the atoms taking part in the formation of

surface hydrogen or coordination bonds.

47

Surface properties of spinel cobalt ferrite

N.D. Paliychuk, T.R. Tatarchuk

Vasyl Stefanyk Precarpathian National University

57, Shevchenko Str., Ivano-Frankivsk 76018, Ukraine,

[email protected]

It is well known that pH has a great importance in cation sorption because

it influences chemical speciation of the metal in solution and also on the

ionization of chemically active sites on the sorbent. Thus, the net charge of

sorbent surface might play a crucial role in sorption processes, and the

characterization of protonation–deprotonation behavior of sorbent materials in

aqueous media could be useful to explain sorption mechanism. The pH at which

the sorbent surface charge takes a zero value is defined as point of zero charge

(pHpzc). The knowledge of pHpzc allows one to hypothesize on the ionization of

functional groups and their interaction with metal species in solution; at solution

pHs higher than pHpzc, sorbent surface is negatively charged and could interact

with metal positive species while at pHs lower than pHpzc, solid surface is

positively charged and could interact with negative species.

In this work, surface property of spinel ferrite CoFe2O4, obtained by

chemical co-precipitation method (NaOH as precipitant) and sol-gel method

(citric acid as fuel) was described. The structure and morphology of the

nanoparticles was characterized by differential thermal analysis, X-ray powder

diffraction, Fourier infrared spectroscopy, scanning electron microscopy. The

determination of pHPZC was performed as follows: 50 ml of 0.1 M NaCl solution

was added to Erlenmeyer flask. The pH of solution in each flask was adjusted

from 2 to 12 by adding appropriate amounts of 0.1 M HCl or 0.1 M NaOH

solutions. Then, 0.1 g of sample was added to each flask and the final pH was

measured after 48 h of shaking at room temperature. The pHPZC is the

intersection point of final pH versus initial pH curve with the line of blank

sample. In this study, the pHPZC of CoFe2O4, obtained by chemical co-

precipitation method, was about 7.72, while pHPZC of CoFe2O4, obtained by sol-

gel method, was about 6.95. The net surface charge on adsorbent is zero at this

pH. The adsorbent surface has a net positive charge at pH<pHPZC, while has net

negative charge at pH> pHPZC. Therefore, when the solution pH was above the

pHPZC, the ferrite surface was negatively charged. The negatively charged sites

on ferrite surface increased when pH increased. It could be seen that the

adsorption efficiency were strongly dependent on the initial solution pH. The

relationship between pH and absorbed amount of cationic dye methylene blue

has been discussed in this study in terms of electrostatic interactions between

MB and ferrite surface.

48

Quantum chemical studies on O2 and H2O molecules adsorption

on the anatase face (001)

R.V. Garmash1, A.Yu. Chernyak

1, Yu.A. Beznosyk

1, O.V. Smirnova

2,

A.G. Grebenyuk2, V.V. Lobanov

2

1National Technical University of Ukraine “Kyiv Polytechnic Institute”

37 Prosp. Peremohy, Kyiv 03056, Ukraine. 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,


Due to its optical properties, high chemical inertness, lack of toxicity, and

low cost, the properties of titanium dioxide, such as photocatalytic, sensory,

adsorption, electrical or catalytic, are increasingly used. It has a number of

disadvantages: low quantum efficiency of the process due to poor separation of

electron-hole pairs, limited absorption range in the UV region, which makes it

impossible to use the energy of sunlight. Molecular oxygen (O2) plays a key role

in many photocatalytic processes involving TiO2 surface. In particular, O2 acts

as an electron acceptor and is often used to suppress the recombination of

electrons and holes, which increases the lifetime of the excited state and hence

the quantum yield of the reactions.

Fig. The optimized geometry of Ti14H22O39 cluster simulated for anatase face (001)

In this work, the optimized parameters of the spatial structure and

adsorption energy for the oxygen complex were calculated by density functional

theory method (B3LYP/6-31G (d,p)), the latter being Ea (O2) = -7 kJ/mol on a

cluster Ti14H22O39 simulated for ideal anatase face (001) as well as related

findings for surfaces with oxygen vacancies (Fig.). Based on the results of

calculations, the probabilities have been estimated of triplet-singlet transitions in

the adsorption complex.

49

Modification of carbon fibres with S-containing functional groups

A.V. Vakaliuk1, L.M. Grishchenko

1, T. M. Bezugla

1, V.Z. Radkevich

2

1Taras Shevchenko National University of Kyiv,

64, Volodymyrska Str., Kyiv 01601, Ukraine, [email protected] 2Institute of Physical Organic Chemistry National Academy of Sciences of

Belarus,13, Surganov Str., Minsk 220072, Belarus, [email protected]

Acid-base catalysts are widely used in industrially important processes

such as esterification, hydrolysis, dehydration, alkylation, and isomerization.

The development of new low-temperature active catalysts of heterogeneous

catalytic processes with thermally and hydrolytically stable acidic centers is a

very important and attracts the attention of scientists.

Commercial carbon fibre Busofit obtained by carbonization and activation

of viscose was used as an initial material (SBET = 1380 m2/g, V = 0.63 cm

3/g).

Functionalization of carbon fibres (CFs) with S-containing groups was

performed by treatment of initial material with sulfur vapor at 500, 600, 700 and

800 °С. The reaction was carried out in an argon atmosphere for 1 h. Then the

samples were kept for 1 h at the temperature of synthesis to remove physically

adsorbed sulfur and cooled to the room temperature without disconnecting the

line feeding argon. Thereafter, the materials obtained were oxidized by 30%

H2O2 solution to prepare acidic catalysts. The temperature of sulfur vapor

treatment is indicated in the sample title.

Analysis of TPD-MS data shows that desorption of these groups occurs

with SO2 evolution (m/z 64) in the temperature range 85-550°C. This range is

rather wide and can be divided into two parts: low-temperature (85-250 °C) and

high-temperature (250-550 °C) ones with maxima at 190±10 and 300±10 °C,

respectively. Functional groups which decompose with the release of SO2 can be

identified as sulfo groups.

Analysis of TGA data shows that all modified samples demonstrate a

significant increase in weight loss in comparison with the initial ones. Also, in a

contrast to initial carbon fibre there are complex minima occurs at 245±10 °C on

the differential weight loss curves. In accordance with the TPD-MS data these

weight loss effect can be related to desorption of S-containing and O-containing

groups (e.g. carboxylic groups) from the modified CF surface.

Thus, the treatment of carbon fibres with sulfur vapour followed by

oxidation with hydrogen peroxide provides obtaining samples with acidic

S-containing groups in the surface layer. These materials have a sufficiently

high thermal stability.

50

Kosmotropes effect of Cl- and NO3

- anions

on colloidal properties of nanosilica

L.S. Andriyko1, V.I. Zarko

1, V.M. Gun’ko

1, A.I. Marynin

2, A.I. Ukrainets

2

1Chuiko Institute of Surface Chemistry, NAS of Ukraine

17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National University of Food Technology,

68 Volodymyrska Street, Kyiv 01033, Ukraine

The zeta potential of nanosilica/water/electrolyte system depends on the

both of silica and electrolyte concentration. The comparison of the effect of

kosmotropic Cl- and NO3

- anions on the zeta potential value in aqueous medium,

containing the same nanosilica concentration (5 wt. %) and salt range from

0.001 M to 0.1 M were carried out in this study.

According to reference data the mobility of ions Cl- and NO3

- at 25°C in

distilled water is similar. It allows evaluating the anions effect on the electrical

characteristics of nanosilica/water/electrolyte system.

It is known that anions with their

increasing ability to adsorb are ordered in

this sequence: Cl- < Br

- < NO3

- < I

- < NCS

-.

This fact allows suggesting a closer

location of the NO3- anion to SiO2 particles

surface in the electric double layer and

stronger affect on EDL thickness.

There is an extremum on the zeta

potential curve for univalent electrolytes

(NaCl, NaNO3) (Fig.). It evidences the

super equivalent adsorption of Na+ cations

in the Stern layer. Recharging of zeta

potential occurs in the presence of trivalent

cations (ξ potential has positive value over

the whole range of electrolyte

concentrations): in the case of anions NO3-

the extremum is observed at a lower

concentration of electrolyte in the system

nanosilica/water/electrolyte.

1E-3 0,01 0,1-8

-6

-4

-2

0

2

4

6

8

10 CA-300 = 5%wt

AlCl3

Al(NO3)3

pote

ncia

l (m

V)

Csalt, M

NaCl

NaNO3

Fig. Zeta potential as a function of salt

content for (□) NaCl, (■) NaNO3,

()AlCl3, () Al(NO3)3 at A-300 content

5 wt. % in the suspensions

51

The graphene oxide dispersity in aqueous medium

L.S. Andriyko1, V.I. Zarko

1, V.M. Gun’ko

1, A.I. Marynin

2, A.I. Ukrainets

2

1Chuiko Institute of Surface Chemistry, NAS of Ukraine

17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National University of Food Technology,

68 Volodymyrska Str., Kyiv 01033, Ukraine

Single- (SLGO) and multi-layer (MLGO) graphene oxides are the most

promising materials for applications for different purposes in industry and

medicine. MLGO was produced using natural flake graphite as a precursor

(flakes < 0.2 mm) using a modified method of ionic hydration and freeze-dried

has low bulk density and typical light brown color. During interaction of MLGO

with a mixture of water (2 g/g) and decane (1.5 g/g) the surface area in contact

with unfrozen liquids at T < Tf can be greater than 1000 m2/g that corresponds to

the formation of stacks with 3-5 carbon sheets (layers).

Graphene oxide, which was synthesized in Chuiko Institute of Surface

Chemistry, has about 11% oxygen atoms on its surface. The most part of active

sites having oxygen on MLGO surface are acidic sites (Brønsted type), because

MLGO aqueous suspensions at small concentrations (0.05 and 0.5 wt. %) have

рН values 2.90 and 2.26, correspondingly.

Fig., a shows monomodal particle size distribution with respect to the

light scattering intensity, volume and number of MLGO particles in aqueous

suspension (0.5 wt. %). The effective diameter of MLGO particles is 520 nm

(sonicated for 5 min with frequency 20 kHz). Decreasing of MLGO

concentration in aqueous suspension from 0.5 to 0.05 wt. % leads to bimodal

particle size distribution and Def is about 220-240 nm and 540-680 nm under the

same conditions of preparation of suspensions (Fig., b).

500 10000

10

20

30

40

50

60

0.5%wt

I (a

rb. un)

Diameter (nm)

I

V

N

520nma)

100 10000

5

10

15

20

25

30

I (a

rb.u

n.)

Diameter (nm)

I

V

N

680nm

540nm220nm

240nm

b) 0,05%wt

Fig. Particle size distributions with respect to the light scattering intensity, volume and number at

different content of MLGO in the aqueous suspensions

52

Study of the surface chemistry of activated carbon obtained by

chemical activation

T. Lupaşcu, N. Timbaliuc, A. Beshliu

Institute of Chemistry, Academy of Sciences of Moldova,

3 Academiei Str., MD 2028, [email protected]

The use of activated carbon sorbents in the water treatment technologies is

one of the most safe and effective methods of water treatment. Carbon materials,

obtained by chemical activation, have an important role in the immobilization of

heavy metal ions from aqueous solutions due to the fact, that different acidic

functional groups (carboxyl, phenolic, hydroxyl etc.) are producing on the

surface of adsorbents during the activation process [1, 2].

The purpose of this research was to study the surface chemistry of

activated carbon produced from plum stones (CAPr) and nut shells (CAN-7)

using the phosphoric acid as an activating agent. The quality indices (adsorption

of methylene blue and I2, humidity), the porous structure parameters (calculated

from nitrogen adsorption-desorption isotherms), the amount of total acidic

groups of the studied activated carbons were determined. Some of the obtained

results are given in the table.

Quality indices and porous structure parameters of activated carbons Sample Ssp,

m2/g

Vs,

см3/г

Vмi,

см3/г

Vмe,

см3/г

adsorption I2,

mg I2/mg AC Humidity,%

CAN-7 725 0.64 0.24 0.16 806.8 9.74

CAPr 801 0.54 0.25 0.28 895.1 3.75

In order to identify the functional groups on the surface of investigated

samples was used the Boehm method of titration with aqueous solutions of

NaHCO3, Na2CO3, NaOH and HCl. Analysis of the obtained results allows us to

notice the presence of a substantial amount of acidic functional groups for the

studied samples of activated carbons. Taking into account the fact that the

degree of sorption of heavy metal ions depends on the quantity and quality of

the acidic groups on the surface of adsorbent we can assume that the activated

carbons CAPr and CAN-7 will exhibit a high level of immobilization of heavy

metal ions and they can be used in the water treatment processes.

1. T. Lupaşcu. Activated carbon from vegetal raw materials. Monograph/ In Romanian

L.: ÎEP: Ştiinţa, Chişinău, 2004.

2. T. Lupaşcu,.Tehnologii moderne de obtinere a carbunilor activi si utilizarea lor pentru

protectia mediuluisi a sanatatii omului. Buletinul ASM, Seria ŞBCA, N 1 (2004) 170.

53

Hybrid materials based on chitosan and sol-gel silicas

T. Budnyak1, D. Sternik

2, Yu. Bolbukh


2,

V. Tertykh1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Maria Curie-Sklodowska University, 20-031 Lublin, Poland

Chitosan is a promising biopolymer in tissue engineering and as a

component of composite materials which could be applied in orthopedy and

dentistry. The combination of its properties, such as biocompatibility,

antimicrobial activity, the ability to create structures with predictable and

controlled pore volume, degradation rate allows one to consider chitosan as a

prospective material for bone implants creation. That is why the structures of

hybrid materials based on chitosan with incorporated inorganic component

attract great attention.

Hybrid films were synthesised by sol-gel formation of silica structures in

the chitosan solution. Tetraethoxysilane (TEOS) and 3-aminopropyl-

triethoxysilane (APTES) were used as precursors of the inorganic component for

polymer filling. In order to study an influence of alkoxysilane functionality on

the structure of obtained material the hybrid films with single alkoxysilane and

with mixtures of both alkoxysilanes in different ratios were obtained.

Furthermore, an effect of filling degree and an influence of a crosslinking agent

nature were investigated. The selected AFM micrographs are presented on

Figure. 1

2

3

Fig. AFM micrographs:

1 -Chitosan/TEOS 4 wt. %;

2 - Chitosan/TEOS 20 wt. %;

3 - Chitosan/TEOS 20 wt. %

+ Glutaraldehyde;

4 - Chitosan/TEOS 20 wt.% +

Epichlorohydrin;


+ APTES 1 wt. %;


+ APTES 4 wt. %.

4

5

6

Acknowledgements





54

Synthesis and mass spectrometric fragmentation of the

phthalocyanine complexes of zirconium and hafnium

with out-of-plane coordinated protocatechuic aldehyde

V. Chernii1, I. Tretyakova

1, Y. Dovbii

1, S. Korobko

1, O. Severynovska

2,

R. Czerwieniec3

1Vernadsky Institute of General and Iinorganic Chemistry, NAS of Ukraine,

32/34 prosp. Palladin, Kyiv 03142, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,

17 General Naumov Str., Kyiv 03164, Ukraine 3Universitat Regensburg, Institut fur Physikalische und Theoretische Chemie,

Universitätstr. 31, D-93053 Regensburg, Germany,

[email protected]

Phthalocyanine complexes of zirconium and hafnium (PcM) with

out-of-plane ligands have electro-, photoelectrocatalytic, electrochromic and

other useful properties. Their composition and structure is quite difficult to

determine due to the low solubility, therefore, actual problem is the selection of

the conditions of the mass spectrometry experiments provide information about

the structure of the obtained substances.

PcM with protocatechuic aldehyde were received by the reaction of the

ligand exchange (Scheme) and characterized by method of LDI mass

spectrometry. In mass spectra of both compounds were observed the intense

peaks, corresponding to molecular ion [PcML]+ and characteristic for

phthalocyanine complexes peaks, according to fragments peaks [PcM = O]+ with

relatively lower intensity.

Scheme. Synthesis of phthalocyanine complexes of zirconium and hafnium with protocatechuic

aldehyde

However, fragmentation for hafnium complex was started at higher laser

power, than for zirconium. This fact indicates its relative stability in “traumatic”

conditions, such as high temperature and vacuum.

Thus, based on the mass spectrometric data the composition of studied

compound as well as a set of physico-chemical properties can be characterized.

55

Synthesis and characterization of MCFs with tunable porous

structure for immobilization of biopolymers

A. Chrzanowska1, A. Deryło-Marczewska

1, A.W. Marczewski

2,

M. Sęczkowska1

1Department of Physicochemistry of Solid Surface Faculty of Chemistry, Maria Curie-

Skłodowska University, M. Curie-Skłodowska Sq.3, 20-031 Lublin, Poland 2Department of Radio- and Colloid Chemistry, Faculty of Chemistry, Maria Curie-

Skłodowska University, M. Curie-Skłodowska Sq.3, 20-031 Lublin, Poland

[email protected]

Studies of protein adsorption from solutions on the carbonaceous and

mesoporous silica materials are of great importance with regard to their

prominent role in bio-nanotechnology [1]. Therefore, it is important to

understand mechanisms of sorption processes of the compounds showing

biological activity at different interface boundaries.

Mesoporous silica materials are widely utilized as carriers of active

substances due to their highly developed internal structure and wider pores

which are suitable for the processes involving substances with large molecular

sizes. MCF adsorbents with different porosity were synthesized using the

nonionic triblock Pluronic copolymers as templates and trimethylbenzene as

organic cosolvent acting as pore expanding agent. This method was used to

prepare MCF materials with various structure properties according to a modified

procedure described in the papers [2, 3].

The basic parameters characterizing structural properties of the obtained

MCF adsorbents with tunable porous structure were determined from the

nitrogen adsorption/desorption isotherms: the BET specific surface area, the

micropore and total volumes, and the external surface area. Additionally, the

electrochemical character and surface charge of the MCF material without and

with adsorbed protein molecules were estimated by potentiometric titration. It

was found that the electrochemical character of pure silica surface is clearly

different than for the silica surface with adsorbed protein layer. Pure MCF

adsorbents have point of zero charge, pHpzc, near 4.9, however, as a result of

protein adsorption, their surfaces change electrochemical properties (become

amphiphilic), with pHpzc near 6.5 (close to pHpzc of proteins).

Acknowledgements



no 612484) for financial support of this work.

1. C.E. Giacomelli, W. Norde, J. Colloid Interface Sci., 233 (2001) 234.

2. P. Schmidt-Winkel, W.W. Lukens Jr., D. Zhao, P. Yang, B.F. Chmelka, G.D. Stucky, J. Am. Chem. Soc. 121

(1999) 254.

3. A. Derylo-Marczewska, A.W. Marczewski, I. Skrzypek, S. Pikus, Pol. J. Chem. 82 (2008) 205.

56

Effect of microstructure of modified diatomite on its adsorption

properties

T.Ia. Datsko, V.I. Zelentsov

The Institute of Applied Physics of the Academy of Sciences of Moldova

[email protected]

The effect of microstructural changes caused by structural-chemical

modification of diatomite with aluminosilicate nanoparticles on its adsorption

properties with respect to fluorine has been studied. The results show that

fluorine adsorption capacity of modified diatomite is considerably increased

from 10 to 58 mmol/g, the adsorption kinetics controlling mechanism has

changed: intraparticle diffusion for initial diatomite has replaced by external

diffusion; the some kind of synergism takes place after modification: the

adsorption capacity of aluminosilicate species grafted on the diatomite surface is

higher than of that of bulk aluminosilicate.

The surface modification of diatomite has been carried out by heating it in

NaOH solution with subsequent treatment with solution of aluminum salt and

ammonia. The amorphous surface silica partially is dissolved during the

treatment with NaOH with formation of aluminosilicate compound at the

addition of aluminum salt. The obtained aluminosilicate which is found to be

NaAlSiO4 with the individual particle range of about 10 nm deposited both on

the surface of the diatomite and on the inner surface of the macro- and larger

mesopores (10 nm), partially block them, which leads to the development of the

specific surface area of 81.8 m2/g, which is 2.5 times larger than the

corresponding value in the initial diatomite (37.5 m2/g), the pore blockage and

additional micropores introduced by microporous aluminosilicate increase the

volume of micropores, thereby increasing the surface area of modified

diatomite.

However despite the fact that the specific surface of the synthetic

aluminosilicate is much greater (183 m2/g), its adsorption capacity is 1.5 times

lower than that of the aluminosilicate grafted on the surface of diatomite. This

apparently is due to aluminum atom coordination change in the proximity of the

acidic silanol groups in the case of diatomite. Partial substitution of Si atoms in

silicates by Al atoms takes place as a result of their different valences an excess

negative charge, and the sorbent surface in solution adsorbs a greater number of

protons and its pHPZC is shifted to the higher values compared to initial diatomite

sample. In the process of fluorine adsorption at pH of natural water (7-9) the

surface charge of raw diatomite is negative, while that of modified diatomite is

positive. As a result, a positively charged surface of modified diatomite attracts

more fluoride ions.

57

Photoinduced diffusion molecular transport

V.M. Rozenbaum1, M.L. Dekhtyar

2, L.I. Trakhtenberg

3, S.H. Lin

4


17 Gen. Naumova Str., Kyiv 03164, Ukraine, [email protected] 2Institute of Organic Chemistry NAS of Ukraine,

5 Murmanskaya Str., Kyiv 02094, Ukraine, [email protected] 3Semenov Institute of Chemical Physics of RAS,

4 Kosygina Str., Moscow 11999, Russia, [email protected] 4Department of Applied Chemistry, National Chiao Tung University,

1001 Ta Hsuen Road, Hsinchu, Taiwan

We consider a Brownian photomotor, namely, the directed motion of a

Brownian nanoparticle in an asymmetric periodic potential [1] under the action

of periodic rectangular resonant laser pulses, which cause charge redistribution

in the particle [2]. Based on the kinetics for the photoinduced electron

redistribution between two or three energy levels of the particle, the time

dependence of its potential energy is derived and the average directed velocity is

calculated in the high-temperature approximation (when the spatial amplitude of

potential energy fluctuations are small relative to the thermal energy).

The thus developed theory of photoinduced molecular transport appears

applicable not only to conventional dichotomous Brownian motors (with only

two possible values of the potential energy) [1, 2] but to a much wider variety of

molecular nanomachines. The distinction between the realistic time dependence

of the potential energy and that for a dichotomous process (a step function) is

represented in terms of relaxation times (they can differ on the time intervals of

the dichotomous process). As shown, a Brownian photomotor has the maximum

average directed velocity at (i) large laser pulse intensities (resulting in short

relaxation times on laser-on intervals) and (ii) excited state lifetimes long

enough to permit efficient laser pumping but still much shorter than laser-off

intervals.

A Brownian photomotor with optimized parameters is exemplified by a

cylindrically shaped semiconductor nanocluster which moves directly along a

polar substrate due to periodically photoinduced dipole moment (caused by the

excited electron transition to a non-resonant level of the nanocylinder surface

impurity) [3].

1. P. Reimann, Phys. Rep. 361, 57 (2002).

2. M. L. Dekhtyar, A. A. Ishchenko, V. M. Rozenbaum, J. Phys. Chem. B 110, 20111 (2006).

3. M. L. Dekhtyar, V. M. Rozenbaum, L. I. Trakhtenberg, Russ. J. Phys. Chem. A 90, No. 7

(2016) (to be publ.).

http://www.maik.ru/ru/journal/physcha

58

Luminescent properties of hybrid materials

based on silicon dioxide and

β-diketonato-1,10-phenanthroline complexes of Eu(III)

E.N. Fadieiev, S.S. Smola, N.V. Rusakova

A.V. Bogatsky Physico-Chemical Institute, NAS of Ukraine,

Lyustdorfskaya doroga, 86, Odessa 65080, Ukraine, [email protected]

Spectral-luminescent properties of hybrid organic-inorganic materials

based on silicon dioxide and mixed-ligand complexes of Eu(III) and

1,10-phenanthroline and β-diketones were studied. Spectral criteria for

estimation of the uniformity of distribution of complexes in amorphous silica

matrix were proposed. Thus, a uniform distribution of emitting centers and the

absence of association was shown by significant broadening of 4f-luminescence

bands of Eu(III), single exponential decay of its emission and absence of

inflection in the plot of emission intensity vs the content of the complex in the

material. On the contrary the processes of association lead to double

exponential decay of Eu(III) emission, the appearance of the fracture on the

specified curve and linear spectra of 4f-luminescence peculiar to individual

parent compounds.

These criteria allowed to analyze the distribution of luminescent

complexes in submicrometer sized particles (200-400 nm) obtained by means of

the optimized Stöber method, as well as the structure of the adsorption layer on

the surface of aerosil of different brands. Despite the fundamental difference

between ways for obtaining the lanthanide-containing glassy hybrid materials,

submicroparticles and aerosil with adsorbed Eu(III) β-diketonates a trend of

association of non-covalently fixed compounds was revealed with increasing

their concentration in the matrix or on the surface, which similarly affects the

luminescent properties of the systems examined. The study of luminescence of

submicrospheres of silicon dioxide with different content of the complexes

showed that a large part of their molecules is in the associated form. We have

found the association of complexes of Eu(III) on the surface of aerosil, which

alters the luminescence spectra profile as well as excited state lifetimes of the

central atom.

59

Gasochromic properties of V2O5/Pt-films

I.A. Shpak, S.S. Fomanyuk, G.Y. Kolbasov


prospekt Palladina 32-34, Kyiv 03142, Ukraine, [email protected],

Improvement of technological processes, their environmental and

technical safety are determined by reliability and performance of automatic

analytical devices based on gas sensors, either autonomous or those, that are

parts of systems of control and regulation. The materials based on metal oxides

recently became an interest in the use as elements of the gas-sensitive systems.

They are characterized by changes of optical properties due to reversible

chemisorption of active gases on their surface. Films of vanadium oxide with a

platinum catalyst belong to such materials.

V2O5/Pt-films are able to reversibly change color in the presence of

hydrogen. For example, they change their color from green to yellow in a

hydrogen atmosphere. Then the reverse process occurs under the influence of

atmospheric oxygen. This effect can be explained by the occurrence of the

following reactions:

Pt

Н2→2Н++2е

- (1)

хН++V2O5→ HxV

V1-xV

IVxO5 (2)

HxVV

1-xVIV

xO5 + 0.5хО2 ↔ V2O5 + 0.5хН2О (3)

Measurement of the absorption spectra of this film showed, that light

absorption in the visible portion of the absorption spectrum is reduced, and

increased in the near infrared portion due to the influence of hydrogen. Change

in the optical response of such film at λ=750 nm was reversible. It is found that

rates of hydrogen reduction reaction and reverse oxidation in the air are close.

Reaction 3 equilibrium shifts towards the formation of green V2O5 in 1 minute in

the presence of oxygen. Such films can be used to control the presence of

oxygen in tanks containing hydrogen.

60

Synthesis of mesoporous materials for extraction of heavy and

rare-earth metal ions

O.A. Dudarko1, A.R. Gaidai

2, V.V. Sliesarenko

1, N.A. Prybora

2, Yu.L. Zub

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National Pedagogical Dragomanov University,

9 Pirogova Str., Kyiv, 01601 Ukraine, [email protected]

Nowadays the topical issue is the search of sorbents for metal ions from

aqueous solutions that would be regenerable, work at different pH values, possess

high selectivity and sorption capacity. The maintaining of high sorption properties

while using in many cycles and the maximum reduction of the sorbents price are

also important. We decided to combine our experience in the synthesis of

bifunctional xerogels by sol-gel method [1, 2] and monofunctional SBA-15 type

materials [3, 4] in order to apply it to the template method of synthesis to produce

bifunctional sorbents.

For this purpose, materials with spatially ordered structures (SBA-15-type)

based on sodium metasilicate (SM) with bifunctional PO/SH layer were

synthesized and approved as sorbents for heavy and rare earth elements. There

were also obtained bifunctional materials of the same type (based on TEOS), and

monofunctional silica with SH- and P(O)(OH)2 groups (both from TEOS and SM)

for comparison. We have also varied the acidity of media for mesophase processing

and the type of its heat treatment (hydrothermal or microwave).

Fig. Isotherm of N2 adsorption-desorption (at -196⁰C) with pore-size distribution (a) and

XRD of bifunctional sample with phosphonic and tiol groups (b)

Considering specific surface (~ 500 m2/g) and other physical and chemical

characteristics of these materials (Fig.), they can be regarded as potential sorbents

for some ions of heavy and rare earth elements.

1. O.A. Dudarko, Y.L. Zub et al., Zh. Prikl. Khim. 81 (2008) 118.

2. O.A. Dudarko, G.R.Yurchenko et al., Visnyk DonU. 2 (2009) 273.

3. O.A. Dudarko, C.Gunathilake et al., Colloids and Surfaces A, 482 (2015) 1.

4. O.A. Dudarko, C.Gunathilake et al., Colloids and Surfaces A 459 (2014) 4.

a b

61

Influence of the mass transfer function on dynamic instabilities of

a model electrocatalytic process

O.I. Gichan



The mass transfer function for different shape of an electrode/electrolyte

interface in a model electrocatalytic process with the potential-dependent

adsorption/desorption of electroactive species and a preceding chemical reaction

in the Nernst diffusive layer was calculated (Fig.). The role of this function in

appearance of dynamic instabilities leading to bistable steady states and periodic

oscillations of current in the non-equilibrium system was determined.

plane

cylinder

sphere

Fig. Contour plots of the mass transfer function of the model electrocatalytic process for

different shape of an electrode/electrolyte interface: plane, cylinder and sphere. The darker the

area the lower a value of the function is. Along a contour the function has the same value

62

Doped lithium tetraborate as advanced luminescent materials:

spectroscopy and dosimetric characteristics

M. Ignatovych



In the presentation review is proposed on systematic study on

spectroscopy and dosimetric characteristics of doped tetraborates.

Doped lithium tetraborate (LTB), as novel polyfunctional materials, are

under intensive investigations as they exhibit very promising characteristics as

laser host, scintilators and well-known dosimetric materials. Their chemical and

isotopic compositions permit the separate detection of neutron and gamma

doses. Doped LTB crystals possess the unique feature – tissue-equivalency –

thus are widely applied as thermoluminescent (TL) detectors for personal and

clinical dosimetry.

Despite the commercial production of some doped LTB and their very

successful applications, the basic physical characteristics such as the nature of

emitting centers, responsible for photoluminescenсе (PhL), radioluminescenсе

(RL), and thermoluminescence (TL) mechanisms are still ambiguous.

It will be considered in the presentation the spectral and dosimetric

properties of Cu-, Mn- and Ag-doped LTB.

The presentation includes the following items:

i) Spectrally resolved thermoluminescence of Cu-Ag and Mn doped LTB

single crystals and glasses;

ii) Thermoluminescence spectra and dosimetric properties of Cu- and

Mn-dopted LTB samples.

The main results obtained in the study are as follows:

1) TL emission bands for LTB:Cu, LTB:Mn, LTB:Ag proved be at different

wavelengths: 370, 608, 272 nm, respectively. It strongly points that the

dopants are directly involved as recombination centres in the TL process.

2) TL study of non-doped LTB and LTB:Cu single crystals confirmed that

TL sensitivity to gamma doses in the range of 10mGy-200 Gy of

LTB:Cu is 5 times larger in comparison to well-known commercially

produced dosimeters TLD-100 and TLD-700. High TL sensitivity of

non-doped LTB to thermal neutrons makes use of pair LTB:Cu and

non-doped LTB very promising for mixed-field dosimetry.

63

Influence of surface plazmon resonance on distribution of

Poynting vector in the presence of gold nanocylinder

V.I. Kanevskii1, V.M. Rozenbaum

1, V.S. Sidorenko

2, D.I. Pobokin

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Faculty of Radiophysics; Taras Shevchenko National University of Kyiv,

Glushkov ave. 2, Kyiv 03022, Ukraine, [email protected]

Light scattering by a gold nanocylinder is studied within the framework of

the conception of the Poynting vector in the resonance regime. It allows to trace

the distribution of energy streams at presence of the surface plasmon resonance.

Calculation procedure of scattering of plane electromagnetic waves by the gold

nanocylinder is presented in the optical range using the finite element method to

solve 3D vector Helmholtz equation.

It is shown that (i) the active energy of an inducted dipole in the

nanocylinder is mainly carried out though its sides; (ii) the spatial distribution of

the reactive energy of the dipole has a local character in the near-zone (the level

of the reactive energy is more than three times bigger in compare with the active

energy in this zone), (iii) it takes place the electromagnetic energy interchange

between incident plane waves and the inducted dipole in the nanocylinder (it

occurs two times during the period of these waves); (iv) the flux of the complete

Poynting vector in the resonance regime is more than an order of magnitude

larger than that without resonance [1].

Results of the calculations of scattering characteristics of plane

electromagnetic waves by a gold nanocylinder in the resonance regime (the

active, reactive components of the Poynting vector and the full Poynting vector

in the near-zone) are obtained for parallel polarized vectors of electric fields of

the incident waves relatively its axis, with the Poynting vector perpendicular to

this one.

1. V.I. Kanevskii, V.M. Rozenbaum, V.S. Sidorenko, D.I. Pobokin, Poverkhnost' 7 (2015) 42

(in Russian).

64

Theoretical study on transformations of formic acid on vanadium

dioxide surface

V.N. Kaurkovska, A.G. Grebenyuk



It is well known that separation of proton from the formic acid molecule

adsorbed on metal oxide surface occurs easily enough [1]. After separation of

proton, HCOO ion easily joins metal atom. We have studied the mechanism of

adsorption and decomposition of formic acid molecules over vanadium dioxide

surface.

V4O8·6H2O cluster was taken as a model mimicking vanadium dioxide

surface. The calculations were carried out by unrestricted Hartree-Fock-

Roothaan method with valence-only basis set SBKJC and respective effective

core potential by means of the PC GAMESS program package [2].

Calculations have been carried out on formic acid molecule

transformations caused by its contacts with the surface of semiconductor phase

in a state close to that of the phase transition point. When heated to the

temperature of phase transition, VO2 surface is known to loose water molecules

and to relax for a definite time without adsorption [3].

We consider two schemes of transformation of the adsorbed formic acid

molecule on vanadium dioxide surface preliminarily forming V-O-(C=O)-H

adsorption complex as well as water molecule. According to the first one, a

rotation takes place around the axis C=O followed by isolation of CO molecule

and formation of hydroxyl groups on vanadium dioxide surface.

According to the second scheme, due to its polarity, water molecule forms

a hydrogen bond with the bridging (esteric) oxygen atom so promoting cleavage

of both C-O and H-C bonds resulting in CO molecule isolation.

The data presented show that the process of decomposition of formic acid

molecule on VО2 surface is more likely corresponds to the scheme 2, i.e. the

most probable mechanism of the transformation of formic acid molecule on

vanadium dioxide surface is described by a multi-stages process: acid molecule

is adsorbed (accompanied by proton separation), adsorption complex interacts

with a water molecule, so that a carbon monoxide molecule and VOH group

are formed.

1. T. Miura, H. Kobayashi, K. Domen, J. Phys.Chem. B, 105 (2001) 10001.

2. M. W. Schmidt, K. K. Baldridge, J. A. Boatz et al., J. Comput. Chem. 14 (1993) 1347.

3. V. N. Kaurkovskaya, A. P. Shakhov, V. V. Lobanov, I. R. Entinzon, High Energy

Chemistry, 44(2) (2010) 101.

65

Electrochemical properties of composites based on

system of immobilized enzyme preparation

Raphanus sativus l. Var. Niger – graphene

M.O. Khodykina1, K.D. Pershina

2, K.A. Kazdobin

1

1Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine,

Paladin Avenue, 32/34, Kyiv 03142, Ukraine, [email protected],

[email protected] 2Joint Department of Electrochemical Energetics NAS of Ukraine,

Vernadsky Avenue, 38a, Kyiv, 03142, Ukraine, [email protected]

The development of biotechnology has extended the possibility of

using enzymes through the use of chemical control of structural, chemical and

catalytic properties of the native enzyme. The enzyme activity on a specific

substrate is primarily determined by its structural features and chemical nature

of the substrate [1]. The availability of such properties allowed formulating the

basic principles of selective interaction with an enzyme substrate, suggesting

differentiation of catalytic sites for substrates of different nature.

The changes in the mechanism and the selectivity of binding of the

components from enzyme mixture of the enzyme preparation Raphanus sativus

L. Var. Niger adsorbed on the kaolin and aerosil are proved by the couple of

physical and chemical methods. Electrochemical methods justified the

applicability of composite materials for energy conversion. It has been

established that the presence of strong proton-conducting properties of the

substrate accelerates the conversion of a proton-donor substrate and that

electron-conducting properties affect the conversion of an electron-donor

substrate.

The joint presence of metal ions of Fe, Cu, Ni, Zn is characteristic for

the class of superoxide dismutase enzymes [2]. This suggests the selective

isolation from a plant material or mixture of enzymes of this class, or a mixture

of peroxidase with superoxide dismutase. Immobilization of such compounds

must not only increase the oxidative activity of the composite, but also lead to a

dramatic change in its electrochemical properties.

Cyclic voltammetry have found that the system of the immobilized

enzyme preparation Raphanus sativus l. Var. Niger – graphene exhibits the

properties of a high-rate capacitor.

1. P. Bayer, Annual Review of Biochemistry 29 (1960) 15.

2. A. Miller, Current Opinion in Chemical Biology. 8 (2004) 162.

66

Structural-adsorption characteristics of natural and chemically

modified clinoptilolite

T.O. Kiose1,2

, K.O. Golubchik1,2

, T.L. Rakyts’ka1, R.M. Dlubovskiy

2,

A.L. Kara1, V.Y. Volkova

1

1Faculty of Chemistry, Odesa I.I. Mechnikov National University,

2, Dvoryanska St., Odesa 65082, Ukraine, [email protected] 2Рhysico-Chemical Institute of Environment and Human’ Protection,

3, Preobrazhenska St., Odessa 65082, Ukraine, [email protected]

Natural clinoptilolite (N-CLI) is a polyphase mineral containing

clinoptilolite, -quartz, mordenite, and hematite at certain ratios. We use

clinoptilolite in its acid-modified forms (H-CLIs) as a support for Pd(II)-Cu(II)

complexes (Pd-Cu/Н-CLIs) characterized by catalytic properties in the reaction

of CO oxidation. N-CLI used in the study was provided from Sokirnitskoye

deposit (Trans-Carpathian region). (0.25-3)Н-CLI-0.5H-CLI samples were

prepared by N-CLI boiling for 0.5 h in nitric acid solution at its concentrations

ranged from 0.25 to 3 M. Since water molecules directly participate in the

formation of Pd(II)-Cu(II) surface complexes, we investigated ad/desorption of

water vapor into/from N-CLI, (0.25-3)Н-CLI-0.5, and Pd-Cu/Н-CLIs using

well-known McBain gravimetric method. All water vapor ad/desorption

isotherms obtained were of the similar form with an expressed loop of capillary-

condensation hysteresis indicating the nonuniform porous structure with the

prevalence of meso- and macroporosity and their adsorption branch followed the

BET equation in its linear form up to P/Ps 0.3 (correlation factor R2 =

0.98-0.99). As can be seen from Table, as opposed to BET constant C (Q1)

decreased with CHNO3 (likely, due to weakening the energy of interaction

between water molecules and the adsorbent surface), аm and а parameters, as

well as the specific surface (Ssp) increase for H-CLIs and remain practically

unchanged after anchoring Pd(II)-Cu(II) complexes.

Table. Structural-adsorption characteristics of natural and chemically modified clinoptilolite

Sample

BET

equation constants а,

mmol/g

Q1,

kJ/mol Ssp, m

2/g

аm, mmol/g С

N-CLI 1.53 133.40 3.30 12.09 100

0.5Н-CLI-0.5 1.72 26.3 4.25 8.10 110

1Н-CLI-0.5 1.89 29.1 5.53 8.35 123

3Н-CLI-0.5 2.04 10.5 5.67 5.86 133

Pd-Cu/0.5Н-Кл-0.5 1.70 31.7 5.40 8.56 110

Pd-Cu/1Н-Кл-0.5 1.78 25.4 5.18 8.00 115

Pd-Cu/3Н-Кл-0.5 2.06 10.4 6.80 5.84 134

67

Brownian rotor as a high-temperature ratchet

О.Ye. Tsomyk, Т.Ye. Korochkova, V.M. Rozenbaum


17 General Naumov Str., Kyiv, 03164, Ukraine

The theory of high-temperature Brownian motors (or ratchets) – the

model devices that convert nonequilibrium fluctuations into the directed

mechanical motion of nanoscale objects – makes possible the analytical

calculation of the average velocity of nanoparticles as a function of the model

parameters [1]. These expressions are simplified especially if the function of

potential profile ( , )V x t is smooth. This function can be represented with the

sufficient accuracy as the sum of the first two harmonics of expansion in a

Fourier series in the spatial variable.

Brownian rotors that are existed on the surface (rotational motion of the

hydroxyl group on oxides surfaces as the simplest example) and function due to

the application of an external alternating electric field may be regarded as an

analogue of Brownian motors. In this case, motor-generated unidirectional

motion of nanoparticles is similar to the directed rotational motion of the rotor

[2]. The potential energy of a rotating particle as a function of time and rotation

angle can be presented in the additive-multiplicative form

( , ) ( ) ( ) ( )U t u t w . For a rotor that has the axis of second order of

symmetry, function ( )u can be described by the hindered rotation potential

( ) (1/ 2) (1 cos2 )u U D . The multiplicative part of the potential energy of

the dipole rotor can be written as ( )cosE t , where is the absolute value of

the dipole moment and ( )E t is the time-dependent electric field. In this

representation, the spatial part of the potential energy is the sum of the first two

harmonics that makes it possible to use the ratchet theory to study the frequency

dependence of the average angular velocity at different types of periodic

functions ( )E t . We have analyzed the two cases: a harmonic dependence

0( ) cosE t E t and a stepwise dependence describing dichotomous process

with the frequency . This analysis has demonstrated that the average angular

velocity in the first and second cases are proportional to 2 and ,

correspondingly. Thus, we have shown that the optimal operation mode for the

dipole rotor is realized at the stepwise change of the applied electric field.

1. V.M. Rozenbaum, JETP Lett. 88 (2008) 342.

2. V.M. Rozenbaum, O.Ye. Vovchenko, T.Ye. Korochkova. Phys. Rev. E 77 (2008) 061111.

68

Mass spectrometric study of silver nanoclusters production in

ethylene glycol medium

M.V. Kosevich, O.A. Boryak, V.V. Chagovets, V.S. Shelkovsky, V.V. Orlov

B. Verkin Institute for Low Temperature Physics and Engineering,

NAS of Ukraine,

Prospekt Nauky 47, Kharkov 61103, Ukraine, [email protected]

Surface phenomena involved in nucleation and growth of silver

nanoparticles are of applied interest since they govern the shape and size of

assembling nanoparticles in dependence of the type of medium and conditions

applied. In the present communication we report the data on initial stages of

silver nanoclusters formation in ethylene glycol (EG) medium obtained by low

temperature (LT) fast atom bombardment (FAB) mass spectrometry.

Formation of silver nanoparticles was stimulated by microwave treatment

of AgNO3 salt solution in EG. LT version of FAB was applied to keep volatile

EG liquid under vacuum conditions. Thus, the products and low molecular

weight (clusters) intermediates of nanosilver synthesis were detected by FAB

mass spectrometry directly in the liquid reaction medium in -80oC -5

oC

temperature range. The mass spectra contained characteristic set of protonated

EG clusters EGn•H+ (n = 1-6), Ag

+ cation (m/z 107/109) and its clusters with EG

EGn•Ag+. On increase of the solutes concentration due to EG noticeable

evaporation at temperatures approaching -5oC silver nanoclusters Agn

+ (n = 1-9)

were detected; they may be considered as nucleation entities for further larger

nanoparticles assembling. This row of clusters was characterised by “magic

numbers” or odd/even alteration that is higher abundances of clusters with odd n

numbers, which agred with earlier observations. The most interesting finding

was observation of hydrogen-containing silver clusters [AgnH]+ for clusters with

even n values 2, 4, 6 and corresponding isotopic distribution. Occurrence of a

core built of several silver ions and one hydrogen atom within supramolecular

metal-organic structures was recently reported in the relevant literature [1] and

the role of such small primary associates in silver nanoclusters formation in

complex organic media was discussed. We will use this information to estimate

the role of EGn•Ag+, Agn

+ and [AgnH]

+ small clusters recorded in mass

spectrometric experiments in the mechanisms and possible pathways of silver

nanoparticles assembling.

1. H. Schmidbaur, A. Schier, Angewandte Chemie, 127 (2015) 756.

69

Porous structure of active carbons modified with manganese

compounds

T. Lupascu1, R. Nastas

1, A. Ivanets

2, L. Postolachi

1, T. Azarova

2, V. Rusu

1,

T. Kuznetsova2, O. Petuhov

1, I. Ginsari

1, T. Goreacioc

1,3

1Institute of Chemistry of Academy of Sciences of Moldova,

3 Academiei Str,. Chisinau MD-2028, Republic of Moldova,

[email protected] 2Institute of General and Inorganic Chemistry, NAS of Belarus,

9/1 Surganova Str., Minsk, Republic of Belarus, 3Institute of Ecology and Geography of Academy of Sciences of Moldova,

1 Academiei Str., Chisinau MD-2028, Republic of Moldova

Active carbons have a distinguished ability for removing wide ranges of

compounds from gas, aqueous and organic phases. The high adsorptive capacity

of active carbons is due to the high density of surface functional groups, large

porosity and intense specific surface area. Surface modification of active

carbons by metals for better selectivity in catalytic activity is also an interesting

research area.

The aim of this work was to obtain modified active carbons with

manganese compounds and to study the relationship between the impregnation

used conditions (e.g., concentration of manganese solutions, thermal treatment,

time, atmosphere) on the manganese loading and porous texture of final

samples. Two active carbons with different surface chemistry have been used as

carbonaceous support, one with basic surface (pH 9.5) and other with acidic

surface (pH 4.0). The structural changes caused by modification were estimated

on the basis of nitrogen adsorption-desorption isotherms. Obtained results show

that depending on thermal treatment conditions samples synthesised from the

carbonaceous support with basic surface have an increase of BET surface area

by about 13-26%, and a significant increase of mesopore volume (by 2 times).

This effect can be explained by additional activation at 300 °C due to salts used

for impregnation. Modified samples, synthesised from the carbonaceous support

with acidic surface, are more stable to thermal treatment. The insignificant

reduction of BET surface area by about 5-10% is in good agreement with

obtaining yield of samples.

Acknowledgements

The present work was performed within Joint Moldova-Belarus Project “Metal supported

catalysts for water treatment: synthesis, properties and using” (Project Nos.

15.820.18.02.04/B and X15МЛД-021).

70

Heat transfer in porous media

B.V. Lytovchenko, O.Yu. Semchuk, O.O. Havryliuk



One of the promising areas of modern science associated with the study

and application of porous materials that have improved properties. At the same

time, it is necessary to explore the specificity of processing these materials,

including heat treatment.

The important characteristic of the porous material defining a majority of

its physical properties is the degree of porosity, which is defined by the

expression:

%100

pП ,

where and p – density of the porous and single-crystal sample, respectively.

Porosity is determined by gravimetric method and can range from 5 to 95%.

The heat transfer in porous media model uses the heat equation:

Qqt

TC effp

)( ,

Tkq eff ,

with the following material properties: – is the density; pC – is the heat

capacity at constant pressure; effpC )( – is the effective volumetric heat capacity

at constant pressure; q – is the conductive heat flux; effk – is the effective

thermal conductivity (a scalar or a tensor if the thermal conductivity is

anisotropic); Q – is the heat source (or sink) [1].

The effective volumetric heat capacity of the system is calculated from

pppeffp CC )( ,

where p – porosity of the material (volume fraction of the solid material) [2].

We have obtained distribution of temperature fields at different degrees of

porosity. Based on analysis of the temperature profiles influence of porosity on

heating of the material, changing its electrophysical and optical properties after

heat treatment, the change in the internal structure after the laser annealing can

be explained.

1. V. Starikovicius, Fraunhofer-Institut für Techno-und Wirtschaftsmathematik, Fraunhofer

(ITWM), (2003) 11.

2. Heat Transfer Module User‟s Guide. Heat Transfer in Porous Media, COMSOL

Multiphysics, version 4.3, (2012) 126.

71

Electrochemical and surface investigations of carbide cathodes for

hydrogen evolution from water

F.D. Manilevich, L.F. Kozin, A.I. Lisogor, A.V. Kutsyi


prospekt Palladina, 32/34, Kyiv 03680, Ukraine, [email protected]

Tungsten carbide has the highest electrocatalytic activity in hydrogen

discharge-ionization reactions among other carbides. This property together with

acceptable corrosion resistance, relatively low price and non-sensitivity to many

catalytic poisons are the reasons for using tungsten carbide instead of platinum

catalysts. In this work, tungsten carbide based electrodes have been made and

investigated in the reaction of hydrogen evolution from 1 M H2SO4 and 1 M

KOH solutions.

The electrodes were prepared by fritting tungsten carbide (WC) powder,

containing silver and vanadium dopes (10 wt. %), on a nickel mesh. By means

of polarization measurements it has been found that among the prepared

electrodes, those with silver dope are most active in hydrogen evolution from

H2SO4 solution, whereas vanadium doped electrodes are most active when

hydrogen is evolved from KOH solution. The overpotentials of hydrogen

evolution from acid solution at all investigated electrodes were approximately

two times lower than from alkaline solution.

Surface investigations carried out by means of Auger electron

spectroscopy (Jamp-10S, JEOL) showed that the made electrodes had a

developed surface and porous structure (see Fig.).

Fig. Surface micrographs ( 300) of some electrodes: (a) WC after polarization measurements, (b)

WC + Ag before polarization measurements, (c) WC + Ag after polarization measurements

The main elements on the electrode surfaces were O (53.62 - 64.18 at. %),

Ni (29.28 - 30.14 at. %), W (4.31 - 6.28 at. %) and C (1.20 - 12.08 at. %).

72

Active carbons modified with manganese compounds

R. Nastas1, T. Lupascu

1, L. Postolachi

1, V. Rusu

1, O. Petuhov

1, I. Ginsari

1,

T. Goreacioc1,2

1Institute of Chemistry of Academy of Sciences of Moldova,

3 Academiei Str., Chisinau MD-2028, Republic of Moldova 2Institute of Ecology and Geography of Academy of Sciences of Moldova,

1 Academiei Str., Chisinau MD-2028, Republic of Moldova,

[email protected]

It is well known that modification of carbonaceous adsorbents with metal

oxides improves their physicochemical characteristics, influencing the catalytic

activity in redox reactions. A number of catalysts consisted of various transition

metal oxides (Co, Ni, Mn, Fe, Cu etc.) on active carbons have been studied for

removal/oxidation of hydrogen sulphide, ammonium ions, dyes etc. Among

these catalysts, manganese oxides supported on active carbons have attracted

much interest due to their high catalytic activities.

The aim of this work was to highlight the influence of surface chemistry

of carbonaceous adsorbents on the manganese oxides loading. The initial

carbonaceous samples, as well as the modified by impregnation with manganese

salts were subjected to thermal analysis in order to choose the treatment

temperatures. The temperatures of 300, 450 and 600ºC have been chosen for

thermal treatment of impregnated samples.

Four series of samples containing manganese supported carbonaceous

adsorbents were prepared. Obtained results reveal the importance of surface

chemistry of carbonaceous adsorbents on the manganese loading.

Samples synthesised from the carbonaceous support with basic surface,

were obtained with a yield of 50-60%, while manganese was loaded in amount

of 1.44-1.65 % depending on applied method. The samples synthesised from the

carbonaceous support with acidic surface, were obtained with a higher yield (92-

98%), but with small quantities of loaded manganese.

Acknowledgements

The present work was performed within Joint Moldova-Belarus Project “Metal supported

catalysts for water treatment: synthesis, properties and using” (no 15.820.18.02.04/B, 2015-

2016).

73

Comparative study of hydrogen and nitrogen adsorption onto

microwave activated carbon

O. Petuhov

Institute of Chemistry of Academy of Sciences of Moldova,

3 Academiei Str., Chisinau MD-2028, Republic of Moldova,

[email protected]

Current research field of hydrogen storage is aimed at synthesis of

materials that would meet the criteria proposed by National Department of

Energy of USA [1].

The active carbons (AC) represent a broad class of adsorbents that are

widely studied for the processes of hydrogen storage [2]. The attractiveness of

AC is explained by large surface area and volume of micropores, possibility of

controlling their structure and low production price.

Microporous AC was prepared by impregnating the nut shells with KOH

in a 1:4 wt./wt. ratio and subsequent microwave activation. The microwave

activation was performed at 700 W for 5 minutes in nitrogen atmosphere.

Adsorption of gases (nitrogen and hydrogen) was measured at 77K. The

activated carbon (AC-2) possesses the best adsorption features with a maximum

capacity of retaining hydrogen of 3.82 wt. %.

To appreciate the specific surface area (S) of activated carbons, BET and

Langmuir models were used. As shown in Table 1, both BET and Langmuir

model, give similar results for nitrogen adsorption.

BET model showed lower values for the parameters obtained from the

adsorption isotherms of hydrogen, while Langmuir model is in a good

agreement with the results obtained from the nitrogen adsorption isotherms.

Table 1. Structure parameters of the activated carbons (AC) obtained by microwave

treatment.

AC

Nitrogen adsorption Hydrogen adsorption

S, m2/g Vs

cm3/g

S, m2/g Vs,

cm3/g BET Langmuir BET Langmuir

AC-1 1323 1360 0.752 672 1337 0.423

AC-2 1787 1797 1.198 1311 1802 0.955

The research leading to these results has received funding from the People Programme

(Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-

2013/ under REA grant agreement no. PIRSES-GA-2013-612484.

1. D.J. Durbin, C. Malardier-Jugroot. International Journal of Hydrogen Energy 38(34) (2013) 14595.

2. Y. Xia, Z. Yang, Y. Zhu. J. Mater. Chem. A 1 (2013) 9365.

74

Nature and morphology of fumed oxides and features of

interfacial phenomena

V.M. Gun’ko

1, V.I. Zarko

1, O.V. Goncharuk

1, A.K. Matkovsky

1,

O.S. Remez1, J. Skubiszewska-Zieba

2


17 General Naumov Str., Kyiv 03164, Ukraine 2Maria Curie-Sklodowska University, 20-031 Lublin, Poland

The particulate morphology of fumed (or pyrogenic) metal and metalloid

oxides (FMO) provides these materials with characteristics useful for fillers of

polymers, drug carriers, pigments, and thickeners. The properties of FMO

depend not only on their composition but also on treatment conditions and the

history of the materials. In contrast to individual FMO, complex (binary and

ternary) nanooxides can include not only simple uniform primary nanoparticles

but also core–shell nanoparticles (CSNP). Strong external actions (e.g.

cryogelation at 1000 atm) can lead to decomposition of CSNP that cause

significant changes in the textural and other characteristics of FMO. The

presence of CSNP in complex FMO can lead to non-monotonic changes in the

surface content of one of the components, e.g. alumina in silica/alumina and

alumina/silica/titania. Changes in the surface content of an active component

(e.g. alumina or titania in binary or ternary FMO based on silica) in complex

FMO can strongly affect the interfacial behaviour of adsorbates of low- and

high-molecular weights, as well as other important properties.

In current work the influence of cryogelation on the physical-chemical

properties of the FMO simple and complex such as silica/alumina, silica/titania,

and alumina/silica/titania was discussed. It was found that complex fumed

oxides can consist core–shell nanoparticles including crystalline or

polycrystalline cores and amorphous shells. In contrast to simple and small silica

or titania nanoparticles, complex core–shell nanoparticles (50–200 nm in size)

with titania or alumina cores and silica or alumina shells can be destroyed under

mechanochemical activation in a ball mill or a microbreaker that also affect the

structure of aggregates of nanoparticles and agglomerates of aggregates

becoming more compacted. This is accompanied by changes in color from white

to beige of different tints and changes in the UV–vis spectra in the 300–600 nm,

as well as changes in crystalline structure of alumina.

Acknowledgements



no 612484) for financial support.

75

Features fragmentation of mono- and binuclear transition metal

complexes under conditions of MALDI mass spectrometry

G.G. Repich1, O.V. Severynovska

2, S.I. Orysyk

1, V.I. Pekhnyo

1

1Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine,

32/34 prosp. Palladin, 03142 Kyiv, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,

17 Gen. Naumov Str., Kyiv 03164, Ukraine

527.101

350.153

342.168469.152

368.532

408.112422.407 458.146 509.115

20las(85_15)_RPPepMix_20Hz_15sh_60ns_Pos_3\0_E17\1\1SRef

0

500

1000

1500

Inte

ns. [

a.u.

]

359.010

381.341

449.451413.321

429.231

465.363520.830

1000las(85_15)_RPPepMix_20Hz_50sh_60ns_Pos_5\0_E19\1\1SRef

0

200

400

600

800

1000

Inte

ns. [

a.u.

]

340 360 380 400 420 440 460 480 500 520

m/z Fig. Fragment of MALDI mass spectra of mono- (a) and bidentate (b) copper complexes for positive

ion reflectron registration mode

This Figure shows the absence of molecular ion peak for both complexes.

In mass range less, than molecular ion mass, different fragments of ligand are

observed. There are many peaks, according to various associates of copper- and

hydrocarbon-containing fragments with one another in high molecular masses

region. In the case of bidentate copper complex the higher tendency to

association is demonstrated.

Such behavior of studied compounds correlates with the data obtained by

other methods, in particular by X-ray structural analysis. Thus, the results

obtained by MALDI in the conditions of mass spectrometric experiment, may be

characteristic for this class of substances.

76

Adsorption of the tributylphosphate on aluminium oxide

V.F. Sazonova, M.A. Kozhemiak

Faculty of Chemistry, Odessa I.I. Mechnicov National University,

2 Dvoryanskaya St., Odessa 65026, [email protected]

The aluminium oxide in apparent quantities contains in complex ores

which after processing ores with sulfuric acid passes in pulps. The subsequent

extraction from pulps of rare metals (zirconium, hafnium, lanthanide, gallium,

molybdenum, etc. [1]) using tributylphosphate (TBP) is complicated the big

losses of extractant. The possible reason of losses of extractant can be

adsorption TBP on the ingredients of ores present in pulp, in particular on

aluminum oxide.

In the given work results of the experiments, which have been carried out

with the purpose of finding-out of the basic regularities of TBP adsorption on

aluminium oxide, are presented.

The conducted studies have shown that the isotherms of the adsorption of

TBP on the surface of aluminium oxide have complicated character. By the

Giles classification they can be attributed to isotherms of L- and S-types. The

kind of isotherms indicates to polymolecular character of the adsorption. We can

assume that in the acidic medium the first adsorption layer is formed due to the

formation of hydrogen bonds between the oxygen atom of the phosphoryl group

of molecules of TBP and proton surface functionality (hydroxyl) group of the

adsorbent, and the next - at the expense of Van der Waals forces.

With increase of concentration of sulfuric acid from 1 up to 6 mol/l

adsorption grows. Increasing the solution temperature from 20 up to 50 oC

adsorption at first is decreasing (at 30 oC) and then increasing.

The opportunity of desorption TBP is shown by water and solutions of

sulfuric acid. The greatest completeness and rate of desorption is observed in

water. At addition in water of sulfuric acid rate and completeness of desorption

decreases. Particularly slowly TBP is desorbed into the 6 M solution of sulfuric

acid. Desorption is most effective then when it proceeds in the same medium in

which adsorption passed. With increase in temperature from 20 up to 50 oС rate

and completeness of desorption decreases.

TBP desorbed from the surface of aluminium in solution and then isolated

from solution by flotation can be joined with the basic extract and subjected to

the further processing.

1. R. Treybal, Liquid extraction, McGraw-Hill book Company INC, New York, 1966.

77

Comparison of adsorption of benzoic acid and its derivatives on

active carbon

M. Sęczkowska, A.W. Marczewski, A. Deryło-Marczewska,

A. Chrzanowska



[email protected]

In the era of intensive development of modern industries, the emission of

toxic substances including aromatic organic compounds remains a major

problem. An example of such a substance is benzoic acid and its derivatives.

Benzoic acid is used in food industry as a preservative or a flavor additive. This

compound and its nitro derivatives are also used in the synthesis of many

organic substances. These substances are relatively well soluble in water and can

easily migrate into the environment. In addition, the high reactivity of the above

(the presence of the aromatic ring in the molecule) can lead to the creation of

new, more or less toxic, compounds. Therefore, it is important that the water and

wastewater treatment takes into account this type of compounds [1-4].

Adsorption method using activated carbon has been used successfully in

the technology of removing contaminants (especially organic) from water and

wastewater [5, 6].

The main aim of this study was to compare adsorption of benzoic acid and

its derivatives from aqueous solutions on active carbon.

In this paper the adsorption equilibrium and kinetics for benzoic acid (BA;

Merck), 2-nitrobenzoic acid (2-NBA; Sigma-Aldrich), 3-nitrobenzoic acid

(3-NBA; Merck) and 4-nitrobenzoic acid (4-NBA; Merck) on active carbon

GAC 1240W (Norit) were examined. Kinetics experiments were performed by

using Cary 100 spectrophotometer (Varian Inc., Australia) with a flow cell in a

closed loop setup. Multi-exponential equation [7] was used to describe all

obtained kinetics data. Adsorption equilibrium measurements were carried out

by using Cary 4000 spectrophotometer (Varian Inc., Australia).

Acknowledgements

The research leading to these results has received funding from the People Programme (Marie Curie

Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/ under REA grant

agreement n° PIRSES-GA-2013-612484

1. Material safety data sheet, SIGMA-ALDRICH, 2-nitrobenzoic acid.

2. Material safety data sheet, MERCK, benzoic, 3-nitrobenzoic and 4-nitrobenzoic acids.

3. T. Dutkiewicz, Podstawy i Metody Oceny Środowiska Pracy, 56 (2008) 35.

4. U. Dmitruk, E. Zbieć, J. Dojlido, Ochrona Środowiska, 28 (2008) 25.

5. Q.-S. Liu, T. Zheng, P. Wang, J.-P. Jiang, N. Li, Chemical Engineering Journal, 157 (2010) 348.

6. K. Li, Y. Li, Z. Zheng, Journal of Hazardous Materials, 178 (2010) 553.

7. A.W. Marczewski, Applied Surface Science, 253 (2007) 5818.

78

Temperature programmed desorption mass spectrometry

in studies of local chemical states in structures of macroporous

silicon covered by the layer of microporous silicon

L.A. Karachevtseva1, K.A. Parshyn

1, O.V. Mischanchuk

2, V.O. Pokrovskiy

2

1V.Ye. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,


17 Gen. Naumov Str., Kyiv 03164, Ukraine, [email protected]

The mechanism of micropore formation in silicon by electrochemical

etching in the hydrofluoric acid is caused by generation and transportation of

non-equilibrium holes to electrochemically treated surface of n-type silicon as

the result of zone-zone electron-hole generation or of impact ionization in high

electric field.

The structures thus formed include the layers of microporous silicon on

macropore walls. The obtained layers of microporous silicon on the surface of

macropores exhibit special features: formation in direction normal to the

macropore surface and large surface area caused by macropore surface area [1].

The details of mass spectrometry device and experimental approach used in

present work may be found in [2]. The method allows to obtain information

about thermal stability of studied systems both for thermal desorption and the

thermal decomposition of the bulk sample. Experiments were carried out using

monopole mass spectrometer МХ7304А (Sumy, Ukraine) with electron

ionization, equipped by devices for the programmed heating of the sample and

the computer system of registration. Heating rate was 14°C/min, temperature

and mass ranges 40-800оС and 10–200 Da.

100 150 200 250 300

0

10

20

30 66

39

51

65

Интенсивность, отн. ед.

Температура, oC

67

The set of thermogramms allowing to

identify volatile decomposition

products of surface complexes and to

calculate parameters of desorption and

decomposition kinetics.

1. L.A. Karachevtseva, Composite silicon-based photonic crystals as light emission and

sensor elements, "Frontiers in Multifunctional Nanosystems”, Kluwer Academic

Publishers, Netherlands, 2002, p. 413–426.

2. V.O. Pokrovskiy, Surface, 2(17) (2010) 63 (in Russian).

79

Mass spectrometry in heterogeneous catalysis

V.O. Pokrovskiy1, O.V. Ischenko

2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Taras Shevchenko National University of Kyiv, [email protected]

The majority of chemical reactions are catalytic. That is why so important

is the information concerning processes occurring on the surface of heterogenic

catalysts, in particular about the values of binding energies of adsorbed particles

with the surface.

As far as heterogeneous catalytic reactions include the stage of desorption

of intermediate and final products from the heterogeneous catalyst surface, it is

also necessary to know kinetic parameters of desorption processes. Those

parameters may be obtained from thermal desorption curves i.e. from

temperature dependencies of desorption rate. Mass spectrometric techniques are

used to measure the number of particles desorbed from the surface which

experimental approach provides for the possibility to measure exactly all the

variety of molecules and atoms desorbed from the catalyst surface layer. To

observe completely the composition of catalyst surface layer in the process of

catalytic reaction, the samples, preliminarly studied in conditions of chemical

reaction and then, in reaction medium, are deposited into quartz cuvette of mass

spectrometer. In the Laboratory of catalysis of Taras Shevchenko University

both volume and deposited catalysts Fe, Fe-Со, Fe-Ni, Co-Mo, Fe-Mo of

ammonia synthesis reaction and also bulk and deposited oxide catalysts Fe-Со,

Fe-Сu, Co-Cu, Cu-Co-Fe of СО oxidation were investigated. It was shown that

high catalytic activity of metallic catalysts in ammonia synthesis is promoted by

presence on the sample surface under investigation of the dissociative β-form of

chemisorbed nitrogen with optimal binding energy. Completely different is the

case of CO oxidation reactions. In this case there is no necessity in complete

destruction of CO molecule – only slight weakening of the bond to allow joining

second oxygen atom. The high activity of oxide catalysts of CO oxidation is

caused by existence in the surface layer of relatively weakly bound -forms of

СО, which are bound to the surface through oxygen and desorb as СО2. Thus,

the large number of experimental data obtained in course of systematic

investigation of catalysts both for ammonia synthesis and CO oxidation has

shown that thermal desorption experimental technics including mass

spectrometric registration of volatile reaction products provides for detailed and

complete information about the state and processes occurring on active center of

catalyst.

This quick and efficient experimental technique may be used for testing

catalysts in conditions close to in situ experiments.

80

The surfactants adsorption by natural sorbents

A.F. Tymchuk

Odessa I.I. Mechnikov National University,

2 Dvoryanskaya Str., Odessa 65082, Ukraine, [email protected]

The technologies of adsorption require searching of the new adsorbents,

which are cheap and safe for ecology. These are may be natural adsorbents

chitin and chitosan. They are biodegradable. The analysis of the literature data

shows that chitin and chitosan adsorbents are used for the extraction of

surfactants, mineral oils, alcohols, heavy metals.

The researches are devoted to studying adsorption activity of natural

adsorbents chitin and chitosan in relation to representatives of cationic and

nonionic surfactants. They are used in many technological processes and

therefore they are the widespread pollutants of the water environment.

Chitosan and chitin that obtained from shells of crustacean were used as

adsorbents. The crushing of the adsorbent was made by using a mono-mill. The

subsequent dispersion into fractions was made by using a vibrating sifting

machine Analysette 3. The fraction with the size of particles (0.2-0.6)∙10-5

m

was selected for researches. The equations of Langmuir, Hill – De Boer, BET

were used for the description of surfactants adsorption. The calculation of the

constants of the equations was made by the graphic method with using the

equations in the linear form. A special computer program was used for the

calculation of adsorptions constants. The analysis of received isotherms showed,

that adsorption isotherms of anionic surfactants concerned to L-type [1],

isotherms of cationic and nonionic surfactants adsorption - to S-type according

to the Gilles classification. Processing of experimental data with using the

computer program gave the satisfactory conformity of the parameters of the

adsorption calculated by the various methods.

The results of IR-spectroscopic research of samples of adsorbents and

surfactants confirmed there was no chemical interaction in the researched

systems in the process of the adsorption. The formation of the hydrogen bonds

between the functional groups of chitosan and surfactants is observed.

Our researches have showed that cationic surfactants are extracted by

chitosan better than nonionic ones. The adsorption process in these systems

proceeds slowly. There are observed isotherms of S-type and the above

mentioned models can not be used. It is obvious that to increase the efficiency of

adsorption of nonionic surfactants it is necessary to start pre-activation of the

adsorbent. It was used the acetic acid, in which dissolved chitosan and created

nanoparticles of adsorbent directly in the surfactant solutions. In this case, the

adsorption is more efficient.

1. A.F. Tymchuk, Odessa National University Herald. Chemistry, 16 (2011) 97.

81

Magneticaly-active polysulfone membranes

O. Yershova, V. Konovalova, T.G. Meshkova

National University „Kyiv-Mohyla Academy”,

2 Skovoroda Str., Kyiv 04070, Ukraine, [email protected]

The magnetic field responsive membranes are unique for a number of reasons.

Chemical modification of the membrane surface imparts fouling resistance [1].

Movement of the magnetically responsive nano brushes leads to mixing at low

Reynolds number at the membrane surface. In this work industrial polysulfone (PS)

membranes Mycrodyn Nadir (Germany) with cut-off 30 kDa were chemically

modified to developed magnetically active membranes. Firstly, terminal hydroxyl

groups of PS react with ethylene glycol diglycidyl ether (EGDGE) to produce terminal

epoxy groups. Then PEI was bound to the epoxy groups for increasing loading

capacity. Second epoxidation produced final polymers containing reactive epoxy

groups on the membrane surface. Nanosized magnetite was covered by low molecular

weight PEI to functionalized surface of nanoparticles (NP) by reactive amino-groups.

The transport characteristics of modified membranes were investigated by the

ultrafiltration of polyvinylpirrolidone (PVP) aqueous solutions out in a standard stirred

cell Amicon 8050 (Millipore, USA) with magnetic field stirrer.

Fig., a demonstrates

that the membranes

with immobilized

magnetite at

concentrations of PVP

0.1% have almost

higher linear

dependence of the

volume flux on the

pressure than

membrane without

magnetite nanoparticles. This indicates about the lack of resistance boundary layer of

membrane and as the result - reducing of concentration polarization effect. The

increasing of the volume flux for magneto-active membranes occurs by reducing the

thickness of the diffusion layer. And the layer thickness depends on the Reynolds

turbulence parameter. Therefore, the movement of magnetic NP on the membrane

surface creates additional turbulence in the boundary layer that reduces concentration

polarization. As Fig., b shows rejection of PVP on magneto-active membranes also

higher then on membrane without magnetite. Reducing of rejection can be explained

by effect of orientation and deformation. So the addition turbulence eliminates

molecules deformation in boundary layer and rejection of polymer increased and

stabilized.

1. H. Himstedt, Q. Yang, Dasi L. Prasad and all., Langmuir, 27 (2011) 5574.

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5

50

100

150

200

250

300

350

400

450 2

1

Jv, l/m

2h

P, bar

a)

0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5

0

10

20

30

40

50

60

70

2

1

R, %

P, bar

b)

Fig. Volume flux (a) and Rejection (b) vs applied pressure for

membranes without magnetite (1) and with immobilized magnetite

(2) during ultrafiltraton of PVP 10 kDa

82

Activity of bulk and Al2O3-supported Co/Ni catalysts for carbon

dioxide methanation

M.G. Zhludenko, O.A. Bieda, E.V. Ischenko

Taras Shevchenko National University of Kyiv,

64/13 Volodymyrska Str., Kyiv 01601, Ukraine, [email protected]

The catalytic hydrogenation of carbon dioxide to methane, also called the

Sabatier reaction, is an important catalytic process of fundamental academic

interest with potential commercial application. Although the CO2 methanation is

thermodynamically favorable it remains difficult to realize because of the

significant kinetic barriers, because this reaction involves an eight-electron

reduction. The support has a significant influence on the morphology of the

catalytically active phases, adsorption, and catalytic properties therefore

comparison of bulk and supported metal based catalysts has been the focus of

significant research.

Catalysts were prepared by decomposition of metal nitrates in air and

reduced at 573 K for 1.5 h in a stream of hydrogen at 101.3 kPa. Experiments

were carried out in a flow system at a total pressure of 101.3 kPa with a total

flow rate of 100 cm3 min

-1 (50% Ar, 48% H2, 2% CO2). The surface layer

investigations were done by thermoprogrammed desorption with a quadrupole

mass spectrometer as a detector of desorbed particles (TPD MS).

Samples supported with Al2O3 have shown significantly higher activity

relative to bulk catalysts. This is probably related to a metal–support interaction

taking place between Co/Ni and the support, which modifies the electronic state

of the active metals, strongly affecting the activity. Investigations of the surface

layer showed the presence of fragments at m/z 14, 15, 16. These signals

correspond to CH2+, CH3

+, CH4

+ particles, respectively. The evolution curves of

all the particles have a similar form, indicating that these particles are products

of the same process.

These results provide some information about mechanism of the

methanation. Reasonable to assume that, the reaction proceeds according to

mechanism that proposes the dissociation of CO2 in CO and O adsorbed species.

The adsorbed CO would be the intermediate which could react with hydrogen to

form methane, without formation of formate [1-3].

Hence the additional kinetic experiments must be conducted in order to

discriminate possible mechanisms of the reaction.

1. K. Walter, O.V. Buyevskaya, D. Wolf, M. Baerns, Catal. Lett. 29 (1994) 261.

2. M. Marwood, PhD Thesis, Ecole Polytechnique de Lausanne, 1994.

3. G. Weatherbee, C. Bartholomew, J. Catal. 77 (1982) 460.

83

Сarbon modified single-domain nanoparticles of solid solutions

(Fе1-X CоХ)Fе2O4

P.P. Gorbyk, I.V. Dubrovin, N.V. Abramov, D.V. Shaban


17 Generala Naumova Str., Kyiv 03164, Ukraine, [email protected]

Single-domain nanoparticles of cobalt ferrite solid solutions (NPCF)

composition (Fe1-xCox)Fe2O4, where x = 0 † 1, Δx = 0.2 by the method of

chemical co-precipitation were synthesized. The NPCF by carbonization of

polyethylene glycol have been modified with carbon. Nanoparticles such as

core-shell structure C@(Fe1-xCox)Fe2O4 were obtained. The shape of the

hysteresis loops (the method of magnetic particle size) distribution of the

nanoparticles by volume were calculated, and they were compared with the

distributions obtained from TEM images. The dependence of the saturation

magnetization and the coercive force of the Co concentration values of the

NPCF ensembles were found. Based on the magnitude of the coercive force and

the residual magnetization the values of the crystallographic anisotropy constant,

Neel relaxation time of the magnetic moment NPCF and the size of their

absolute single-domain were obtained. The thickness of the carbon layers on

NPCF and specific surface composites within the shell model from the values of

the saturation magnetization of composites C@(Fe1-xCox)Fe2O4 were calculated.

-10 -5 0 5 10

-60

-30

0

30

60

-0,8 -0,4 0,0

0

20

M, em

u/g

H, kOe

1 2

3 4

5

M,

em

u/g

H, kOe

1

234

5

Fig. Hysteresis loops

NPCF series of samples

(x=0.8) with a carbon layer

thickness of 0.8 (1) to 4.4

nm (5).

Insets:

top - TEM image NPCF

with experimental (2) and

lognormal (1) distribution

by volume;

bottom - the initial area of

the hysteresis loops.

.

84

Thermal, dielectric and structural studies on thermoresponsive

polymers of complex architecture

D. Aravopoulou1, M. Souli

1, K. Kyriakos

2, A. Miasnikova

3, J. Adelsberger

2,

A. Meier-Koll2, A.M. Bivigou-Koumba

3, A. Laschewsky

3, C.M. Papadakis

2,

A. Kyritsis1

1National Technical University of Athens, Department of Physics,

Athens, Greece, [email protected] 2Technische Universitet Munchen, Physik-Department, Germany

3Universitet Potsdam, Department of Chemistry, Potsdam, Germany

Thermoresponsive copolymers have attracted considerable scientific

interest due to their unique properties and their potential applications [1, 2].

These materials respond strongly to a small change of temperature. When the

temperature of an aqueous solution of thermoresponsive polymer is raised above

a temperature (LCST) intra- and intermolecular aggregation takes place which

leads to collapse of the individual polymer chains and precipitation of the

polymer (macrophase separation). This behaviour is due to a balance between

attractive monomer–water interactions and monomer-monomer interactions. The

most important characteristic of a thermoresponsive polymer is thus the

intermolecular interaction in aqueous medium. The transition from a coil

structure (for temperatures below the cloud point) to a globular one (above the

cloud point) has been related to the competitive results of hydrogen bonding and

hydrophobic interactions [3, 4].

In the present work we employ quasi-elastic neutron spectroscopy

(QUENS), differential scanning calorimetry (DSC) and broadband dielectric

relaxation spectroscopy (DRS) techniques in order to study the

thermoresponsive transition and the organization of water in two series of

thermoresponsive polymers. The first series consists of homo - poly(N-iso-

propyl acrylamide) (PNIPAM) and copolymers of PNIPAM and polystyrene

(PS) (di-block P(S-b-NIPAM) and tri-block P(S-b-NIPAM-b-S) copolymers).

PNIPAM is one of the most widely studied thermosensitive materials. The

second series include block and star block copolymers containing

thermoresponsive blocks of poly(methoxy diethyleneglycol acrylate)

(PMDEGA) and PS blocks.

The combined study gives us results on the kinetics of the transition and

long-range morphology as a function of temperature and the water content.

1. V.O. Aseyev, H. Tenhu, F.M. Winnik, Adv. Polym. Sci., 29 (2011) 242.

2. E.S. Gil, S.M. Hudson, Prog. Polym. Sci., 29 (2004) 1173.

3. R. Liu, M. Fraylich, B.R. Saunders, Colloid Polym. Sci., 287 (2009) 627.

4. Y. Sekine, T. Ikeda-Fukazawa, J. Phys. Chem. B, 114 (2010) 3419.

85

Solvent-free functionalization of carbon-based nanomaterials with

amines: from fullerene C60 to buckypaper

E.V. Basiuk1, I.J. Ramírez-Calera

1, V. Meza-Laguna

2, E. Abarca-Morales

1,

T.Yu. Gromovoy3, V.A. Basiuk

2

1Centro de Ciencias Aplicadas y Desarrollo Tecnológico,

Universidad Nacional Autónoma de México,

Circuito Exterior C.U., 04510 México D.F., México, [email protected] 2Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México,

Circuito Exterior C.U., 04510 México D.F., México 3Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv, Ukraine

Carbon-based nanomaterials (CNMs) have gained much attention due to

their unique properties and broad applications. CNMs properties can be

modulated by applying different experimental procedures to modify their

structure. In this work, we demonstrated the possibility of simple, efficient and

environmentally friendly solvent-free functionalization of C60, multiwalled

carbon nanotubes (MWCNTs) and buckypaper (BPs) assembled from oxidized

MWCNTs (MWNTs-ox), by amines volatile under moderate vacuum. The three

representative amines employed had different structural features:

octadecylamine (ODA); 1-aminopyrene (AP); and 1,5-diaminonaphthalene

(DAN). The functionalization is performed at 150-180 °C under reduced

pressure. To confirm successful amine attachment were used a FT-IR, Raman,

X-ray photoelectron, 13

C NMR spectroscopy, thermogravimetric analysis, LDI-

ToF mass spectrometry, TPD with mass spectrometric detection, as well as SEM

and TEM electron microscopy. The nucleophilic addition of the aromatic amines

to C60 molecule was studied theoretically by using DFT (PBE GGA functional

with Grimme dispersion correction in conjunction with the DNP basis set). The

covalent attachment of amines AP, DAN and ODA, under solvent-free

conditions takes place on all studied here CNMs. The functionalization of BPs

relies on the formation of amide bonds with carboxylic groups of MWNTs-ox.

The highest amine content was found in the case of functionalization with ODA,

whereas the lowest one was observed in the case of DAN, with a possible

contribution of noncovalently bonded amine species in all three cases.

Interestingly, despite of some differences in spectral and morphological

characteristics for amine-functionalized BPs, the features they have in common

are a dramatically increased stability in water as compared to pristine BPs and a

relatively invariable (that is, functionalization-independent) electrical

conductivity. This work was supported by UNAM (grant DGAPA-IN100815) and CONACyT

(grant 251164). I.J.R.C. acknowledges CONACYT for a PhD fellowship.

86

Chemical construction of catalytic active sites on the surface of

ceramic membrane materials

L.A. Belyakova



The use of membrane materials as catalysts and realization for oxidation

reactions in membrane reactors seems promising due to increase in the product

yield and decrease of temperature and pressure of catalytic process.

It can be assumed that the chemical immobilization of biocatalysts of

oxidation processes on membrane surface will promote the implementation of

catalytic reactions at lower temperatures and pressures.

In this paper, new approaches of ceramic membrane materials

functionalization by chemical construction of active centers from fragments of

membrane surface and reagents in a solution were proposed. The advantages of

this design are rigid fixation of active sites on the surface, the absence of

diffusion and steric restrictions for adsorption interactions.

Macroporous ceramic tubular elements (15 cm in length, 2.5 cm in

diameter, composition 70 % Al2O3 + 30 % ZrO2) were used as starting

membranes. The chemical construction of supramolecular structures which are

biocatalyst models was carried out only on the outer surface of ceramic tubes in

order to perform the catalytic reactions in a membrane reactor mode.

Adsorption of molecular oxygen was studied as an individual gas or air

component at 25°C in a vacuum gravimetric device. Initial ceramic tubes were

almost not absorb oxygen. The outer surface functionalization of tubular

elements with macrocyclic metal complexes greatly enhances the adsorption of

molecular oxygen. The dependence of oxygen adsorption against chemical

composition and structure of synthesized surface macrocyclic compounds was

proved.

Functionalized membranes possess catalytic activity in oxidation of

organic compounds, for example, the complete oxidation of methane occurs

already at 250°C. Oxidation of methane to methanol and formaldehyde takes

place at 150−200°C and only to methanol − under mild conditions (1 atm., lower

than 100°C).

87

Synthesis and adsorption of methylene blue by Ni/C

nanocomposites

V.M. Bogatyrov1, M.V. Galaburda

1, O.I. Oranska

1, M.V. Borysenko

1,

J. Skubiszewska-Zięba2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Faculty of Chemistry, Maria Curie-Skłodowska University,

pl. Maria Curie-Skłodowskiej 3, 20-031 Lublin, Poland

Depending on the ratio of the components, porous nickel-carbon system

may be used as catalysts, magnetic adsorbents, magneto-rheological and

magnetic fluids. In this work Ni/C nanocomposites were obtained via pyrolysis

of mechanical mixtures of nickel acetate and different polymers (phenol-

formaldehyde resin, polyethylene glycol or polyvinyl alcohol). Pyrolysis of the

mixtures under argon atmosphere at 700 °C followed by reduction of nickel to

metallic state. Consequently nickel particles were coated by layers of ordered

carbon that stabilized the surface of the metal nanoparticles from the effects of

different environmental factors. It was of interest to investigate the adsorption-

structural properties of porous carbon composites with high content of nickel

(40-90 wt. %).

Obtained composite materials were

characterized by TG and DTG analyses.

Adsorption characteristics were studied by

low-temperature N2 sorption and methylene

blue (MB) adsorption. The Fig. shows that

MB adsorption decreases with decreasing

of the carbon content. The values of SBET of

the samples vary from 253 m2/g (46 wt. %

Ni) to 21 m2/g (77 wt. % Ni). MB

adsorption specific surface values vary from 147 m2/g (46 wt. % Ni) to 34 m

2/g

(89 wt. % Ni). The Figure shows the adsorption capacities of Ni/C

nanocomposites for methylene blue.

Stability of the nickel nanoparticles was determined by boiling of the

composites in the water for 1 h. In this case only on the XRD pattern of the

samples with the lowest carbon content appeared peaks corresponding to

reflexes of traces of nickel oxides. Thus, nickel-porous carbon nanocomposite

with high metal content were synthesized and characterized.

Acknowledgements



No 612484) for financial support of this project.

0,0 0,2 0,4 0,6 0,8 1,0 1,2

0

20

40

60

80

100

120

140

A,

MB

mg

/g c

om

po

site

C, MB mg/cm3 solution

CNi-(89%)

CNi-(77%)

CNi-(57%)

CNi-(46%)

CNi-(65%)

88

Photocatalytic properties of titania modified with carbon

M.V. Bondarenko, T.A. Khalyavka, S.V. Camyshan

Institute for Sorption and Problems of Endoecology, NAS of Ukraine

Photocatalysis has proven to be a promising technique for the degradation

of hazardous compounds in water solutions. An urgent problem in

photocatalysis is a search for photocatalytic systems active under visible light

irradiation which gives an opportunity of their widespread practical application.

Researchers are trying to shift the optical sensitivity of TiO2 from UV to the

visible-light region by many methods, such as metal loading, doping and

coupling of composite semiconductors. So, the aim of our work was to prepare

carbon/TiO2 composites and to test them under UV and visible light irradiation.

We chose cationic dyes safranin T and rhodamine B as the models of pollutants

to evaluate the degradation activity of composites.

The powders were obtained by two methods. In the first case samples

were obtained through citric route using titanium(IV) tetrabutoxide and carbon.

For pure titanium dioxide, the same mixture was used, but without addition of

activated carbon. In the second case samples were obtained using

mechanochemical processing in a ball mill Pulverisette-6 (Fritsch). The samples

were characterized by XRD, BET, SEM and TEM. Diffractograms of all

powders show intensive peaks which belong to anatase and rutile phases.

Analysis of SEM-images of the samples shows that they consist of roundish

agglomerates. Crystallite size in agglomerates of titanium dioxide as calculated

through Debye–Scherrer equation equals to 12 nm, in the case of composite

samples their values increased to 30 nm, which is confirmed by TEM. Analysis

of nitrogen sorption–desorption isotherms obtained at 20°C for the synthesized

samples shows the presence of a hysteresis loop which is the evidence for

mesoporous structure of the powders. The isotherms correspond to type IV of

IUPAC classification for mesoporous materials with H1 type of hysteresis loop.

The specific surface of the composites increases in comparison with pure

titanium dioxide. Composite samples were photocatalytically active in

destruction of cationic dyes under visible light irradiation, in contrast with pure

titanium dioxide which acts as photocatalyst only under UV irradiation.

Photocatalytic activity of modified samples obtained by the first method was

higher in all investigated systems. Photocatalytic reactions are satisfactorily

described by a kinetic equation of the first order. It has been found out that rate

of dye destruction increase when sorption of dyes increases.

Thus, composite materials proved to be perspective photocatalysts. They

might be used in environmental photocatalysis for industrial waste purification

of various organic impurities, in particular, dyes that are stable in the

environment.

89

Formation of gold nanoprisms on mica surface

T.I. Borodinova1, V.I. Styopkin

2, Ya.Y. Lopatina

2, V.E. Kutsenko

2,

A.A. Vasko2

1F.D. Ovcharenko Institute of Biocolloid Chemistry, NAS of Ukraine,

42 Acad. Vernadsky Blvd., Kyiv 03680, Ukraine, [email protected]

2Institute of Physics, NAS of Ukraine,

46 Nauky Prosp., Kyiv 03028, Ukraine, [email protected]

Reconstructed Au(111) surface obtained by vacuum evaporation on to

freshly cleaved mica crystals is widely used as substrate for scanning tunneling

microscopy (STM). We propose an alternative method for producing of laterally

extended Au(111) faces (up to ~10 µm) by growth of gold nanoprisms (NP) on

atomically flat mica surface. It has been shown in [1] that gold nanocrystals with

a thickness less than 100 nm can be formed in free volume of the mixture of

ethanol, ethylene glycol, chloroauric acid (precursor of gold) and

polyvinylpyrrolidone (PVP, stabilizer) at 80°C. The obtained crystals have

triangular or hexagonal shape with the lateral dimensions from 30 nm up to

20 microns depending on parameters of synthesis (concentrations of HAuCl4,

PVP and time). It has been found that the face (111) occupies a maximum of

total surface area and determines the crystal habit in NP.

We have found that the gold monocrystals and nanoparticles are being

formed simultaneously on mica surface. Both adding glycerin to the solution and

increasing of time of synthesis lead to preferential formation of gold NP.

The influence of the components of the growth medium on surface

wetting angle of freshly cleaved mica surfaces and annealed surfaces of Au(111)

has been analyzed. The shape and size of the gold NP was studied by scanning

electron microscopy (SEM). The thickness of NPs was estimated.

The electron microprobe analysis has revealed that the gold NP have not

impurities. Also, it has been found that the distribution of gold NP is accidental

on the mica surface.

Thus, the obtained results demonstrate alternative approach for creation of

Au(111) substrates suitable for STM researches.

1. T.I. Borodinova, V.I. Sapsay, V.R. Romanyuk, J. Nano-Electron. Phys, 7 (2015) 01032

(10).

90

Catalase-mimetic activity of nanoporous carbon KAU decorated

with nanoceria

N.V. Bortnyk, A.V. Brichka, O.M. Bakalinska, S.Ya. Brichka, M.T. Kartel



Natural enzymes have multiple applications in textile, food,

pharmaceutical, and other industries. However, their disadvantages (expensive,

not stable under environment changes) caused the search of the alternatives. As

a result, many materials have been reported to exhibit enzyme-mimetic activity,

among them noble metals nanoparticles, carbon nanomaterials, and some metal

nanooxides.

The purpose of this work is to study catalase-mimetic properties of

activated carbon KAU and its oxidized form decorated with cerium nanooxide.

The materials were obtained by the reaction of cerium nitrate deposition

in the presence of carbon in aqueous media at room temperature that can be

described by the reaction: 12NaOH + О2air

= 4СеО2 + 12NaNО3 + 6Н2О. The

synthesized samples were named by the estimated amount of nanoceria in it:

KAU–1CeO2, KAU–3CeO2, KAU–5CeO2, KAU–12CeO2, and KAU–20CeO2.

Real modifier content in the samples was determined by atomic emission

spectrometry.

The materials were characterized by SEM and TEM that proved the

presence of decorating nanoparticles on the surface of activated carbon.

Catalase–mimetic activity of nanocomposites and nanoceria was studied in the

reaction of H2O2 (~1 – 10 %) decomposition at room temperature and pH from 8

to 11. To obtain the kinetics data, the volume of released oxygen was measured.

Hydrogen peroxide concentration was determined using permanganatometry

method. The kinetics experiment lasted for 30 min while the reaction mixture

with total volume of 25 ml was continuously stirring. The enzyme–mimetic

activity of the materials was evaluated using the Michaelis constant (KM) that

was calculated from Lineweaver–Burke plot. For easier interpretation of

experimental data, the constant of affinity (Kaf =1/KM) was used.

The results showed an extremal correlation between enzyme–mimetic

activity and pH–value for nanoceria and nanoceria-containing nanocomposites

with the pH–optimum at 8.5 – 9.5. The decrease of catalytic activity with the

growth of nanoceria content can be explained by the agglomeration of the

nanoparticles.

91

Application of chitosan-silica hybrid composites for removal of

dyes from aqueous solutions

T.M. Budnyak1, M. Błachnio


2, A.W. Marczewski

2,

V.A. Tertykh1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Maria Curie-Sklodowska University,

2 Maria Curie Sklodowska Sq., 20-031 Lublin, Poland

Thousands of synthetic dyes are used for printing and dyeing industries

generating hazardous waste. Among the numerous techniques for dyes removal,

adsorption has shown the best results as it can be used to remove different types

of colouring materials. In order to decrease the cost of treatment, attempts have

been made to find inexpensive alternative adsorbents. Adsorption on

polysaccharide derivatives can be a low-cost procedure of choice in water

decontamination for extraction and separation of compounds, and a useful tool

for protecting the environment.

In our work we have synthesized chitosan-silica composites by sol-gel

method and physical adsorption of biopolymer. Obtained composites were

applied for extraction of the anionic azo dyes from the neutral aqueous

solutions. The commercial, anionic dyes, a type of sulfonated azodyes: orange II

(OII), acid orange 8 (AO8), orange G (OG), acid red 88 (AR88) and acid red 1

(AR1), which are characterized by one or two sulfonate groups and the presence

of bound to aromatic ring azo group (-N=N-) were used for that purpose. These

dyes are resistant to biological and chemical degradation. In order to verify

applicability of chitosan-silica composites for removing anionic dyes from

aqueous solutions the experimental equilibrium and kinetic data of adsorption

process were analysed. Additionally thermal behavior of dye-composites

systems was investigated.

Comparing the ability of dyes to adsorb on the composite it can be seen

that the maximum adsorption AR88 (0.48 mmol/g) exceeds five times that

obtained to AR1 (0.09 mmol/g). Adsorption for OII and AO8 are similar (0.25

and 0.20 mmol/g). Dye OG is only slightly better (0.12 mmol/g) removed from

the solution than AR1. AR88 as an adsorbate with the highest affinity to the

active sites of the composite is distinguished from the other dyes by the presence

of two naphthalene rings.

Acknowledgements





92

Uranium(VI) sorption by silica with grafted phosphonic acid

derivatives

T.M. Budnyak1, A. Gładysz-Płaska

2, A.V. Strizhak

3, Ie.V. Pylypchuk

1,

D. Sternik2, M. Majdan

2, I.V. Komarov

3, V.А. Tertykh

1



pl. Maria Curie-Skłodowskiej 3, 20-031 Lublin, Poland 3Taras Shevchenko National University of Kyiv,

64/13 Volodymyrska Str., Kyiv 01601, Ukraine

Three prospective adsorbents based on silica with grafted phosphonic acid

derivatives are proposed for the uranium(VI) extraction in current work. The

adsorption behaviour of the synthesized adsorbents with respect to uranium(VI)

from the aqueous media has been studied under varying operating conditions of

pH, concentration of uranium(VI), contact time, and desorption in the different

media. Different models were applied for investigation the adsorption process.

The obtained adsorbents were well characterized by various physicochemical

methods. The structures of the grafted surface P-containing compounds in the

synthesised adsorbents 1-3 are presented on the scheme:

Acknowledgements





93

Synthesis, optical and photocatalytic properties of mesoporous

iron-doped titania films

N. Chorna, O. Linnik, N. Smirnova



Global environmental contamination by various organic and inorganic

compounds requires the design of new functional materials based on the

semiconductors that are sensitive to visible light. Titanium dioxide is the wide-

used photocatalyst due to its unique properties such as chemical stability, non

toxicity and high photocatalytic activity. However, TiO2 only absorbs in the UV

part of the solar spectrum. The increase of the photocatalytic activity and the

ability to absorb visible light can be achieved by titania modification with

d-block metal ions (Cu2+

, Fe3+

, Ru4+

and others). Metal ions doping leads to

change the physical, optical, structural and photocatalytic properties of titania.

However, d-block metals may also act as recombination sites for the

photoinduced charge carriers lowering the activity of the semiconductors.

Despite the fact that a decrease in band gap energy that can be achieved by

metal doping, photocatalytic activity could not be remarkably enhanced.

The mesoporous films are prepared by sol-gel method using titanium

tetraisopropoxide as a source of titanium and unhydrous iron(III) chloride as a

doping agent. Thermal treatment of the films with different percentage of iron

ions (1, 5, 10, 25 and 50%) was performed at 450 °C. The analysis of the optical

spectra showed that the absorption band edge of iron doped TiO2 films is shifted

to the long-wavelength region comparing with undoped TiO2. The calculations

of band-gap values of the films showed that the introduction of iron ions in the

structure of TiO2 leads to its narrowing. The sharp narrowing of the band gap

energy to 2.7 eV was observed for the film with 50% content of Fe.

Photocatalytic activity is tested in the processes of tetracycline

hydrochloride (TC) degradation. It must be noted that TC adsorption on the

surface of the films is increased with increasing iron ions content in the structure

of titanium dioxide. The photocatalytic efficiency of iron doped titania films was

not significantly improved under UV light due to the increased electron-hole

recombination rate. However, under visible light, the films with 25 and 50 % of

iron ions exhibited the enhanced photocatalytic activity in more than two and

three times, respectively.

94

Viscoelastic properties of organic-inorganic composites on the

base of acrylic monomers and TEOS

Kh.V. Demydova1, O.I. Demchyna

1, I.Yu. Yevchuk

1, T.F. Samoylenko

2

1Department of Physico-chemistry of Fossil Fuels L.M. Lytvynenko

Institute of Physico-organic Chemistry and Coal Chemistry, NAS of Ukraine

3a Naukova Str., Lviv 79053, Ukraine; [email protected] 2Institute of Macromolecular Chemistry, NAS of Ukraine,

48 Kharkov shosse, Kyiv 02160, Ukraine

Nowadays proton conductive membranes in fuel cells are the subject of

intense research, since fuel cells are considered as an alternative source of

ecological energy. One of the important requirement for proton conductive

membrane along with high proton conductivity, thermal stability, mechanical

strength is good viscoelastic properties of membrane material, ensuring their

high performance. Organic-inorganic membranes on the base of acrylic

monomers (acrylamide, acrylonitrile, 3-sulfopropylacrylate potassium salt) have

been synthesized via photoinitiated polymerization with simultaneous sol-gel

process of added sol-gel system based on precursor – tetraethoxysilane. The

viscoelastic properties of organic-inorganic composites – the elasticity modulus

E and the loss tangent tg δ have been measured by DMA method (Fig.).

0 50 100 150 200 2500

1000

2000

3000

4000

t, oC

E1,

MP

a

0,0

0,2

0,4

0,6

0,8

1,0

1,2

tg

0 50 100 150 200 2500

1000

2000

3000

4000

E1,

MP

a

t, oC

0,0

0,2

0,4

0,6

0,8

1,0

1,2

tg

а) b)

Fig. Temperature dependences of E and tg δ for organic-inorganic composites of different

composition: а) - 10% silica, b) - 20% silica

In the studied organic-inorganic composites one can see a relaxation

transition in the temperature range of 20 - 100ºC, which corresponds to the

system transition into viscoelastic state. On the temperature dependence of tg δ

it appears in the form of peaks. There is a slight dependence of these

characteristics on the content of inorganic component.

95

Synthesis of nanozeolite-like material

N.M. Dolaberidze, V.G. Tsitsishvili, N.A. Mirdzveli, M.O. Nijaradze

Petre Melikishvili Institute of Physical and

Organic Chemistry of Ivane Javakhishvili Tbilisi State University,

31 A. Politkovskaia Sr., Tbilisi 0186, Georgia, [email protected]

Genetic links of natural zeolites and the results of studies of crystallization

processes of volcanogenic rocks enable us to use natural aluminum silicates in

the synthesis of nanozeolite materials, more so as they are the sources of

silicium and aluminum necessary for zeolite synthesis and can efficiently

replace artificially created aluminum silicate gels. Thus, their application is

justified both with the economic and ecologic point of view.

The goal of our research was to obtain fine dispersed zeolite-like material

free from admixes through crystallization of clinoptilolite-containing rock. The

object of research was clinoptilolite-containing rock (CtR) of Rkoni section,

Kaspi region (Georgia). At the first stage crystallization of natural clinoptilolite,

by the method developed by us yielded sodalite type fine dispersed material [1].

The present work pursued to prepare NaA type fine dispersed zeolite-like

material by further crystallization of sodalite obtained at the first stage, as the

intermediate product. At the second phase, the reaction mass was not a

suspension, but a gel, formed by acidic treatment of intermediate product.

Synthesis of alkali aluminum silicate gel was performed in Teflon flasks at 98-

100°C, using different corrected alkali concentration (20%) and duration length

(20 hr) than in the first stage.

Crystalline structure of the washed and dried final product and its quality

development was checked by X-ray diffraction method; the same method was

used to prove that it was NaA type zeolite-like material. Particle size of fine

dispersed material was determined by the electron microscopic method and it

equaled to 76 nm.

Simple scheme of formation of fine dispersed mineral varieties via

hydrothermal treatment of natural clinoptilolite can be imagined as follows:

CtR -- NaS--NaA

Porous structure of the obtained materials has been characterized by the

static adsorption method. Water vapor adsorption for sodalite a = 0,081 cm3/g,

while for NaA type zeolite-like material a = 0,243 cm3/g.

Thus, the study performed by us has rather reliably proved the fitness of

natural resources for preparation of synthesized nanozeolite products, which are

of rather significant practical value.

1. N.M. Dolaberidze, V.G. Tsitsishvili, N.A. Mirdzveli. M.O. Nijaradze, M.V. Alelishvili,

Materials Russian conference with participation of foreign scientists "Actual adsorption

theory problem, porosity and adsorptive selectivity "Moscow, Klyazma, 2015, p. 91.

96

Synthesis and structure of TiO2 thin nanocomposite films

P.P. Gorbyk1, O.P. Dmytrenko

2, I.V. Dubrovyn

1, T.O. Busko

2,

I.S. Matviichuk2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Taras Shevchenko National University of Kyiv, Department of Physics,

Department of Physics Functional Materials

The state of the environment demands new effective photocatalysts to be

manufactured. Titanium dioxide is an effective photocatalyst with high

efficiency and chemical stability. Its pure varieties have been studied for various

applications. Nevertheless, it is known that some studies have aimed at an

increase of its quantum yields in the photocatalysis by means of introduction of

transition metal ions or deposition of noble metals on its surface.

The ability of TiO2 to show some or other properties depends on its

chemical variety as well as structure and morphology. First of all, it depends on

methods of synthesis and application of various precursors. By synthesizing

nanocrystalline photocatalytic films based on titanium dioxide and doping such

films with ions of transition and noble metals we can find solutions aimed at

improving the efficiency of separation of charges in the processes of their

photogeneration. Nanoparticles of Ag and Au noble metals being deposited or

introduced in the matrix of titanium dioxide film can traps electrons thus

promoting the separation of photogenerated electron-hole pairs and interphase

transfer of electrons.

As the activity of photocatalysts depends on their crystalline, vibrational

or electronic structures this work has aimed at determination of physical

mechanisms of photocatalytic activity in thin films of TiO2 nanocomposites. In

contrast to solid specimens all features in Raman spectra from thin films of

titanium dioxide have low intensities and are widened due to the nanosized

crystalline structure. The peaks at 144, 305 and 402 cm-1

as well as the data of

X-ray diffraction indicate the anatase crystalline modification of these films.

The photoluminescence spectra from various nanocomposites on the basis of

TiO2 are characterized by a significant decrease in their features when the thin

films have been synthesized with a TiCl4 precursor, and it means that a decrease

in content of oxygen vacancies F+ and F-centers occurs. A strong suppression of

various features has been observed for the thin films of titanium dioxide doped

with nanoparticles of noble metals and it indicates the improvement of the

photocatalytic activity of such films.

97

The features of fiber-forming processes in the melts of

polypropylene-polyvinyl alcohol-glycerol-hydrophobic silica

L. Dzubenko1

, O. Sapyanenko1, P. Gorbyk1

, V. Plavan2, N. Rezanova2


17 Generala Naumova Str., Kyiv 03164, Ukraine, [email protected] 2Kyiv National University of Technologies & Design,

2 N.-Danchenko Str., Kyiv 01011, Ukraine, [email protected]

Goal of this work is to study effect of hydrophobic silica (HS) on the

phase transitions in polypropylene/poly(vinyl)alcohol/glycerol (PP/PVA/Glyc)

mixtures in conditions of polymer melt flowing and specific fiber forming

process realization. There were mass equation between of PP, PVA and Glyc in

ones of 30/70/7, and HS content in the mixture were 0.1; 0.5 and 1.0 wt. %.

When PP is in dispersion state the melting and crystallization processes are

changed significantly and simultaneously. When at PVA crystallization process

from extrudate melts of PP/PVA/Glyc/HS is realized at more high temperatures

of 130 144 °С, than analogical one, according to the virgin PVA at 125 °С.

There are weak exothermal effect in temperature range of 12098 °С at HS

content of 0.1 and 0.5 wt. % and exact exoeffect at 116 °С in temperature range

of 119104 °С when HS content of 1.0 wt. % and they are responsible on PP

crystallization in highly dispersed state as MF. This shows on low crystallinity

degree and broad crystallites distribution in dimensions. HS injection in

extrudates promotes to form MF, which are thinner and uniform by thickness.

Average MF‟s diameters are decreasing from 3.5 to 1.3-1.7 m, and, at the same

time, uniformity of their distribution by thickness (here is the dispersion of long

MF‟s distribution by diameters, being decreased from 1.5 to 1.3 - 0.9 m2

), and

undesirable structure content of: the parts - from 3.8 to 1.0-0.3 wt. % , the films

- from 9.7 to 1.1-5.5 wt. %. It is found that there is optimal value of HS content

in PP (0.5 wt. %).

98

Removal of volatile and tobacco-specific N-nitrosamines from

tobacco smoke using Georgian natural zeolites

L. Eprikashvili, I. Rubashvili, T. Kordzakhia, M. Zautashvili

Ivane Javakhishvili Tbilisi State University;

Petre Melikishvili Institute of Physical and Organic Chemistry,

31 A. Politkovskaya Str., Tbilisi 0186, Georgia, [email protected]

The present research has been shown the possibility of use of Georgian

natural zeolites – mordenite and clinoptilolite modified H-forms for removal of

nine volatile N-nitrosamines (VNA) and two tobacco-specific N-nitrosamines

(TSNA) from tobacco mainstream smoke. Previously, adsorption properties of

the above-mentioned zeolites modified H-forms were investigated towards

genotoxic compounds as sorbates - nine volatile N-nitrosamines namely

N-nitrosodimethylamine - NDMA, N-nitrosomethylethylamine - NMEA,

N-nitrosodiethylamine - NDEA, N-nitrosodipropylamine - DPNA, N-nitroso-

piperidine - NPIP, N-nitrosodibutylamine - NDBA, N-nitrosopyrrolidine -

NPYR, N-nitrosomorpholine - NMPA, N-nitrosodiphenylamine – NDPA and

two tobacco-specific N-nitrosamines 4-(methylnitrosamino)-1-(3-pyridyl)-1-

butanone (NNK) and N′-nitrosonornicotine (NNN).

It was specially constructed dynamic type laboratory equipment for

adsorption study of N-nitrosamines on zeolites modified H-forms which

comprises the following parts: 1. Quartz tube for burning tobacco; 2. Specially

made glassware with bubbler on glacial bath for N-nitrosamine absorption;

3. Vacuum pump. The smoke from tobacco burning in quartz tube was

conducted through organic solvent which absorbs all N-nitrosamine compounds

without any loses. A new, rapid and effective analytical GC-MS method of

quantitative determination of N-nitrosamines was developed and validated to

control the concentrations of the above-mentioned toxic compounds in test

solutions obtained from tobacco smoke.

Analytical data has been shown that studied mordenite modified H-form‟s

adsorptive capability is better than clinoptilolite H-form, more precisely;

mordenite H-form decreases the content of volatile N-nitrosamines in tobacco

smoke to 74 % and clinoptilolite H-form decreases to 63 %; mordenite H-form

decreases the content of tobacco-specific N-nitrosamines in tobacco smoke to

95% and clinoptilolite H-form decreases to 89 %. This phenomenon gives the

perspective of creation “ant-nitrosamine” cigarette.

99

Subnanosizing - a novel approach to densely crosslinked сyanate

esters/silica composites obtained by sol-gel synthesis

A.M. Fainleib1, V.A. Bershtein

2, K.G. Gusakova

1, D. Kirilenko

2,

P.N. Yakushev2, V.A. Ryzhov

2, N.S. Lavrenyuk

1

1Institute of Macromolecular Chemistry, NAS of Ukraine,

48 Kharkivske Shose, Kyiv 02160, Ukraine, [email protected] 2 Ioffe Institute, RA S, Russia,

26 Polytekhnicheskaya Str., St.-Petersburg 194021, Russia,

[email protected]

A series of polycyanurate (PCN)-based composites containing

0.01-10 wt. % silica, introduced by sol-gel method, was synthesized using

dicyanate ester of bisphenol E (DCBE), tetraethoxysilane and

3-aminopropyltrimethoxysilane as a coupling agent. Their nanostructure,

dynamics, and thermal/mechanical properties were characterized by means of

STEM/EDXS, Far-IR spectroscopy, DSC, DMA and laser-interferometric creep

rate spectroscopy (CRS) methods.

It was revealed that the most substantial positive impact on PCN

dynamics, thermal and mechanical properties is attained at ultra-low silica

contents, e.g., at 0.1 wt. % silica where Tg and modulus increase, respectively,

by 50o (Fig.) and 60%.

In this case, silica nanoclusters are absent in the composite, but EDXS analysis

indicates a presence and quasi-regular Si distribution in the matrix nanovolumes.

Therefore, only chemically incorporated silica nodes of subnanometric size in

the densely cross-linked PCN network could be implied. Such composites can

be designated as “polymer subnanocomposites”. Contrarily, formation of silica

nanoclusters and especially their aggregates at silica contents of 2-10 wt. % led

to the distinct negative impact on the matrix properties.

Fig. Glass transition temperatures of the PCN/Silica composites versus composition plots as

estimated by DSC (black circles) and DMA (crosslets). Black square designates Tg for the matrix.

100

Nanosized Pd/SnO2 materials for adsorption semiconductor

sensors to methane

G.V. Fedorenko, L.P. Oleksenko, N.P. Maksymovych, I.P. Matushko,

G.I. Skolyar, O.P. Ripko

Department of Chemistry, Taras Shevchenko National University of Kyiv,

64/13 Volodymyrska Str., Kyiv 01601, Ukraine, [email protected]

For detection of explosive gas leakages the adsorption semiconductor

sensors can be used due to their low cost, simple construction, low power

consumption and high sensitivity. Their sensing mechanism is based on catalytic

oxidation on the surface of the semiconductor gas sensitive layer. Chemisorbed

oxygen oxidizes a detected gas (e.g. hydrogen, methane, carbon monoxide,

ethanol vapor), which causes the change of the electrical resistance of the

sensor. The ratio between the electrical resistance in air (R0) and in the presence

of a gas (Rg) was chosen as a measure of the sensitivity of the sensors. The most

used materials for gas sensitive layer is tin dioxide because of its chemical

stability. However, the oxidation of some widely used gases such as methane on

the pure tin dioxide requires high temperatures (above 500 oC). That results in a

large power consumption and low response of the sensors. To solve this problem

catalytically active dopants can be added to gas sensitive layer.

In this work the influence of Pd additives on the sensitivity to methane

was studied. Palladium has been chosen as one of the most active catalysts for

the full oxidation of CH4. It is shown that the addition of palladium to the gas

sensitive layer of the sensors based on the nanosized SnO2 by wet impregnation

technique, using PdCl2 solutions (0.21×10-2

- 35×10-2

M), leads to the significant

increasing of the sensitivity to methane (in 8 - 9 times, Fig.), which makes

possible the reliable detection of the CH4 microconcentration in the air.

Fig. Dependences of the sensors response to 937 ppm CH4 on temperature for the

sensors based on nanosized Pd/SnO2 with different Pd loading

101

Adsorption kinetics of Ag(I) ions onto mono-functionalized

polysiloxanes with magnetic properties

K. Gdula1, E. Skwarek

1, A. Dąbrowski

1, I.V. Melnyk

2, Y.L. Zub

2

1Faculty of Chemistry, Maria Curie-Skłodowska University,

Maria Curie-Skłodowska Sq. 3, 20-031 Lublin, Poland,



Nowadays, an increasing interest in adsorption process, as one of the most

promising techniques useful in many fields of science and industry, can be

observed. What is more, the proper choice of the adsorbent plays a crucial role

in this method. Therefore, increasing interest in exploration of new methods

allowing synthesize materials for this purpose, is also observed. Nanotechnology

offers broad opportunities for designing and fabrication of new types of

adsorbents with enhanced properties.

In this work, adsorption kinetics of silver ions onto amine-functionalized

polysiloxanes with magnetic core, are presented. This group of materials is a

great example of novel adsorbents with enhanced properties obtained by

methods offered by nanotechnology. On the one hand, presence of amine groups

in the silica surface ensures adsorption sites for adsorbate molecules, on the

other hand magnetic cores built in the adsorbent structure, allow to easily

separation adsorbent from the solution. Each of these adsorbents was

synthesized by using sol-gel method, based on hydrolysis and condensation of

TEOS and a proper organosilane [1]. For this purpose, three organosilanes with

amine groups, were used.

One of the most important parameters describing adsorption process is

kinetic of adsorption. Here, we present results concerning kinetic of Ag(I) ions

onto functionalized polysiloxanes with magnetic core. Adsorption kinetic were

carried out in two different initial Ag(I) concentrations: 10-3

and 10-6

mol/dm3.

For each initial concentration, the better fits were obtained by using pseudo-

second order. In the case of 10-3

mol/dm3 concentration the equilibrium is

reached after about 3 hours, while in the case of 10-6

mol/dm3 concentration time

necessary to reach equilibrium is ca. 30 minutes.

Acknowledgements Authors are grateful to People Programme (Marie Curie Actions) of the FP7/2007-2013/

under REA, grant agreement no. PIRSES-GA-2013-612484 for the support of this work.

1. I.V. Melnyk, Y.L. Zub, B. Alonso, N.V. Abramov, P.P. Gorbik, Glass Phys. Chem. 38

(2012) 96.

102

Adsorption of Ag(I) ions onto amine-functionalized magnetic

nanoparticles

K. Gdula, A. Dąbrowski, E. Skwarek



[email protected]

In this work, functionalized with amine groups polysiloxanes with

magnetic core were synthesized and tested as adsorbents for silver ions. Such

materials have two main advantages: (1) amine groups presence on the silica

surface ensures adsorption sites for adsorbate molecules; (2) magnetic cores

built in the adsorbent structure, allow to separate adsorbent from the solution in

an easy way. Sol-gel procedure based on hydrolysis and condensation of TEOS

and a proper organosilane having amine groups, in the presence of F– as catalyst,

and particles of Fe3O4 as magnetic core, was used to obtain above-mentioned

materials. The whole procedure is detailed described by Melnyk et al. [1]. Two

different materials, differing in the type and amount of amine groups built in the

silica structure, were synthesized. As-obtained materials were characterized by

FT-IR spectroscopy, acid-base titration and elemental analysis and nitrogen

adsorption/desorption measurements.

The adsorption measurements were made by using radioisotope method.

The adsorption of Ag(I) ions was calculated from the loss of their concentration

from the solution using 2480 Automatic Gamma Counter. Adsorption process

was studied in the range of the initial concentration from 10-6

to 10-3

mol/dm3

NaNO3, as the function of pH, in the broad range of pH values from 5 to 9.

Effect of pH and different concentration of Ag(I) ions on adsorption at the

magnetic polysiloxane/electrolyte solution interface, and the changes of the

electrical double layer, were examined. The adsorption measurements have

shown that adsorption of Ag(I) ions increases with increasing pH value,

reaching the maximum at the pH8. It can be explained, that at such pH solution

amine groups present on the silica surface are in the form –NH2 while silver as

Ag+. Thus, electrostatic interactions between silver ions and silica surface, can

be present. The presence of Ag(I) ions in the solution influence on surface

properties of adsorbents, causing i.e. the increasing value of zeta potential.




(2012) 96.

103

Electrochemical properties of mono-functionalized polysiloxanes

with magnetic properties

K. Gdula1, E. Skwarek

1, A. Dąbrowski

1, I.V. Melnyk

2, Y.L. Zub

2





In order to check how type and amount of amine functional groups built in

the magnetic polysiloxane structure influence on electrochemical properties,

three different amine-functionalized materials were obtained. Each of examined

adsorbents were synthesized according to sol-gel method, detailed described in

[1]. In order to build amine functional groups in the polysiloxane structure, three

organosilanes having (1): (3-Aminopropyl)triethoxysilane (APTES), Bis-

(trimethoxysilylpropyl)amine (BTMPA) and (2) N-[3-(Trimethoxysilyl)propyl]-

ethylenediamine (TMPED), amine groups in the single organosilane molecule,

were used during each synthesis. The adsorbents were labelled as follows: A, B

and T.

In order to verify changes of the electrical double layer (EDL) both, zeta

potential and density of surface charge at the magnetic polysiloxane/electrolyte

solution interface, were measured. Above-mentioned measurements were

carried out in the broad range of pH from 2 to 9. Moreover, influence of ionic

strength on electrokinetic properties, were also studied. Those experiments were

carried out in the range of the initial electrolyte concentration (NaNO3) from

10-5

to 10-2

mol/dm3.

It was found that zeta potential is very stable in the broad range of pH for

each of examined materials. What is more, ionic strength has almost no

influence on zeta potential of the examined materials. For each material

pHIEP>8.




(2012) 96.

104

Nanosized oxide filler’s impact on dielectric -relaxation in an

unsaturated polyester resin

B.M. Gorelov1, A.M. Gorb

2, O.I. Polovina

2, S. Wacke

3, Z. Czapla

3


17 General Naumov Str., Kyiv 03164, Ukraine 2Taras Shevchenko National University of Kyiv,

4 Prospekt Hlushkov, Kyiv 03127, Ukraine, [email protected] 3Department of Physics, Opole University of Technology,

75 Ozimska, Opole 45271, Poland

Impact of nanosized oxide particles of titania (TiO2, rutile) and silica-

titania fumed compound (STO) on –dielectric relaxation in an orthophtalic

unsaturated styrene-cross-linked polyester resin have been experimentally

studied. The oxide particles were different from each other in particle‟s

diameter, the specific surface area, the number of active surface sites. The

filler‟s mass concentrations varied as 0.5, 1.5, 3.0, and 5.0%. The dielectric

spectroscopy and the thermal desorption mass-spectroscopy were used to trace

variations in nanocomposite‟s structure with increasing filler loading.

The temperature dependences of the dielectric permittivity (1) and the

dielectric losses (2) have been measured at fixed frequencies from 500 Hz to

5 MHz over the temperature range of 77–350 K. The –relaxation process is

clearly seen at frequencies 1 kHz < f < 100 kHz as broad 2(T)-peaks in both the

neat resin and its nanocomposites. There are certain differences in behaviour of

both peak's location T and its amplitude 2 (T) = 2 versus Cf,m between TiO2-

and STO-filled nanocomposites. For example, at 1 KHz the –process is the

most intensive at the loading of 5% in both the nanocomposites, whereas values

of 2 measured at small loadings (Cf,m 3%) are close to each other and vary

weakly with Cf,m. In contrast, at 50 KHz in TiO2-nanocomposites the

-relaxation is the most intensive at the loading of 3%, whereas in STO-

nanocomposites the –peaks vary weakly with Cf,m and are shifted towards

higher temperatures. The observed differences are likely due to different

numbers of oscillating bounded and unbounded fragments of the polymer chains

which contribute in the run of 2(f,T).

In order to ascertain atomic nature of the oscillating –relaxators the

numbers of unbounded (N) moieties of polymer chains have been evaluated by

using the correspondent thermal decomposition curves. It may be supposed, by

comparing N(Cf,m) and 2(Cf,m), that moieties containing the benzene ring or

ester can really play as the –relaxators in both the infilled resin and its

nanocomposites.

105

Effect of porosity on thermal characteristics of thin film materials

based on cyanate ester resins

K. Gusakova

1, O. Grigoryeva

1, O. Starostenko

1, A. Fainleib

1, D. Grande

2


48 Kharkivs’ke shose, Kyiv 02160, Ukraine, [email protected] 2Institut de Chimie et des Matériaux Paris-Est, UMR 7182 CNRS – Université

Paris-Est, Créteil Val-de-Marne, 2 rue Henri Dunant, Thiais 94320, France,

[email protected]

Modern high-tech market raises advanced demands to polymer films and

membranes used for reverse osmosis, nanofiltration, separation or extraction,

i.e., high thermal stability, inertness, excellent resistance towards solvents and

etching agents, etc. [1]. Cyanate Ester Resins (CER) can be considered as a

perfect candidate for the creation of thermostable (temperature of degradation,

Td > 400 oC) multipurpose membranes and films. However, generation of porous

or nanoporous structures can bring some additional changes to basic physical-

chemical characteristics of the final films.

Thus, the aim of the present work was to estimate the contribution of

porosity to thermal behavior of the nanoporous CER-based film materials.

In this context, 2 series‟ of nanoporous CER-based films have been

prepared using 1) partial extraction of poly-ε-caprolactone (PCL) from the

CER/PCL hybrid networks [2], or 2) incomplete conversion technique used at

CER films preparation and described in details in [3]. Nanoporous structure

formed was comprehensively characterized by SEM and DSC-based

thermoporometry methods. The effect of porous structure on thermal

characteristics of CER-based film materials was evaluated through comparative

analysis of DSC and TGA results obtained for the nanoporous samples and the

corresponding non-porous samples of the same compositions. DSC studies have

revealed an increase by 25-40 oC of the glass transition temperature (Tg) values

for the nanoporous CER-based films prepared by incomplete conversion

technique in comparison to the corresponding non-porous references. It was also

found that formation of nanoporous structure in the CER-based films did not

decrease their thermal stability, furthermore for some samples even some

increase of Td values up to Td 413437 oC have been fixed.

1. A. Fainleib A., Thermostable polycyanurates. Synthesis, modification, structure and properties,

Nova Science Publishers, New York, 2010.

2. O. Grigoryeva, K. Gusakova, A. Fainleib, D. Grande, Eur. Polym. J. 47 (2011) 1736.

3. A. Fainleib, K. Gusakova, O. Grigoryeva, O. Starostenko, D. Grande, Eur. Polym. J. 73(2015) 94.

106

Thermostable polymeric nanomaterials obtained by

in situ method

O. Grigoryeva, O. Starostenko, L. Bardash, A. Fainleib

Institute of Macromolecular Chemistry, NAS of Ukraine,

48 Kharkivs’ke shose, Kyiv 02160, Ukraine, [email protected]

Series of thermostable organic-inorganic nanocomposites based on

densely crosslinked polycyanurates (PCN) was synthesized by in situ method

using such nanofillers as epoxy-functionalized polyhedral oligomeric

silsesquioxanes (epoxy-POSS, containing from 1 to 8 epoxy groups) or

multiwalled carbon nanotubes (MWCNTs). The effect of nanofiller on structure-

property relationships of the organic-inorganic nanocomposites created was

investigated using FТIR spectroscopy, SEM, TEM, DSC, DMTA, TGA

methods. The PCN/epoxy-POSS and PCN/MWCNTs nanomaterials possessing

improved mechanical and thermal characteristics can be utilized as adhesives,

coatings, sealing compounds, etc. in airspace industry, microelectronics and

others.

The chemical interaction between the functional groups of in situ

synthesized polymer matrix and of the nanofillers used has been found in all

series of nanocomposites produced. For all the samples a catalytic effect of

epoxy-POSS or MWCNTs on polycyclotrimerization of dicyanate ester of

bisphenol E or A (DCBE or DCBA) was fixed depending on nanofiller content.

It was shown that formation of hybrid fragments in the PCN/epoxy-POSS

network resulted in some disorder of crosslinking structure of the PCN matrix

that increased the mobility of kinetic segments of PCN macromolecules and,

consequently, promoted reducing of apparent activation energy (Еа, from

Еа(PCN)137 kJ/mol to Еа(PCN/POSS)87 kJ/mol) accompanying by slight decrease

of the glass transition temperature (Тg) values (Тg(PCN)307˚C, Тg(PCN-

POSS)283˚C). Significant increase of the elasticity modulus Е‟ for PCN/epoxy-

POSS nanocomposites containing 2 and 5 wt.% of epoxy-POSS was registered

as well.

It has been established that the PCN/MWCNTs nanocomposites possess

high stability to thermal-oxidative destruction, high thermal conductivity and

storage modulus E‟. The increase in value of tensile strength at break (σb) by 62-

94 % compared to the unfilled PCN (σr≈115,9 MPa) for the samples with

MWCNTs content of 0.03-0.06 wt.% is fixed. It has been determined that the

percolation threshold for conductivity for the PCN/MWCNTs nanocomposites is

low and equal to 0.38 wt.% and their electrical properties can be changed in a

wide range.

107

Synthesis of polymeric microspheres with grafted

poly(geranyl methacrylate) chains

M. Grochowicz, M. Maciejewska

Department of Chemistry, Faculty of Chemistry,

Maria Curie-Sklodowska University,

ul. Gliniana 33, 20-614 Lublin, Poland, [email protected],

[email protected]

Surface modification of microspheres aimed at achieving their shell-

functionalization is an interesting tool for modifying their properties. In general,

two different approaches can be mentioned, the „grafting to‟ and the „grafting

from‟ approach. In the „grafting to‟ technique a reactive terminal group on a

functional polymer chain reacts with the activated surface of microspheres. The

benefit of the „grafting to‟ technique is that the employed linear polymer can be

thoroughly characterized before the conjugation. As a polymerization method

for obtaining polymeric chains, reversible addition-fragmentation

polymerization is often used (RAFT). The dithioester moiety of a RAFT agent

serves two purposes. Initially, the dithioester moiety functions as a RAFT agent

for obtaining polymer chains of predetermined molecular weight carrying RAFT

end groups; subsequently these dithioester functionalities can be employed as a

reactive heterodienophile in heteroatomic Diels Alder cycloaddition reaction

(HDA) with a functionalized diene.

Scheme 1. The modification reaction of microspheres.

The aim of this work was the functionalization of surface of copolymeric

microspheres obtained with glycidyl methacrylate (GMA) and 1,4-

dimethacryloyloxybenzene (1,4DMH) with the use of linear polymeric chains of

poly(geranyl methacrylate) which were obtained via RAFT polymerization.

Acknowledgements The research leading to these results has received funding from the People Programme (Marie


under REA grant agreement no. PIRSES-GA-2013-612484.

n

n

+N

O

O

CH3

CH3S

S

CH3CH3

CH3

S

CH3

CH3

S N

O

O

CH3CH3

CH3

RAFT-poly(GM)

functional

poly(GMA-co-14DMH)

poly(GM)-graft- poly(GMA-co-14DMH)

HDA

108

Designing track etched nanoporous films from polycyanurate-

based thermosets

K. Gusakova1, A. Fainleib

1, O. Grigoryeva

1, O. Starostenko

1, V. Sakhno

2,

A. Borzakovskiy2, E. Espuche

3, F. Gouanve

3, D. Grande

4


48 Kharkivs’ke shose, Kyiv 02160, Ukraine, [email protected] 2Institute of Nuclear Research, NAS of Ukraine,

47 Prospekt nauki, Kyiv 03680, Ukraine, [email protected] 3Université de Lyon, Université Lyon 1, CNRS-UMR 5223 Ingénierie des

Matériaux Polymères,69622 Villeurbanne, France 4Institut de Chimie et des Matériaux Paris-Est,

UMR 7182 CNRS – Université Paris-Est Créteil Val-de-Marne,

2 rue Henri Dunant, Thiais 94320, France, [email protected]

The present communication reveals peculiarities of creation of track

etched nanoporous thin film materials based on high-performance

polycyanurates (PCN) synthesized by polycyclotrimerization of Cyanate Ester

Resins in situ with linear polyurethane (LPU, molar mass of 40000 g/mol),

which is chemically grafted to the PCN network. Generation of nanoporous

structure was performed by α-particle irradiation of PCN/LPU films prepared

followed by specially developed track etching procedure. The main porosity

characteristics of the resulted films have been determined by using scanning

electron microscopy (SEM) and thermoporometry studies based on the

application of differential scanning calorimetry (DSC-thermoporometry). It was

found that depending on the composition and etching conditions the film

samples produced were characterized by rather narrow pore size distribution

extending from 15 up to 150 nm with an obvious predominance of pore

diameters sizing around 25-40 nm.

The effect of duration of track etching procedure and of additional

sensitization with γ-rays of the pre-irradiated samples (i.e. prior to track etching)

on the resulted morphology and membrane properties (namely, gas

permeability) of the nanoporous materials obtained has been evaluated.

Formation of more well-developed porous patterns with longer etching duration

has been established. Moreover, the samples exposed to the additional

γ-radiation were characterized by more homogeneous porous structure providing

much higher gas permeability coefficients as compared to their non-sensitized

analogues due to more selective track etching after sensitization. The

perspectives of the nanoporous materials produced as potential multipurpose

high-performance membranes have been also discussed.

109

Graphene oxide as filler in polymer nanocomposites

N.A. Havrylyuk



Interest in composite materials has grown rapidly since the middle of the

last century and has led to new types of composites with better properties. One

goal of modern materials science is to develop composites with superior

mechanical strength and better thermal and electrical properties while reducing

the weight and providing high resistance to external factors. Polymer composites

filled with graphene oxide (GO) and its derivatives have attracted tremendous

attention in both academic and commercial communities during the past years.

The extraordinary mechanical properties of GO prompt its incorporation

into a wide range of polymeric nanocomposite materials. However, similar to

other nanomaterials, the reinforcement efficiency of GO and its derivatives is

hindered by their agglomeration and poor compatibility with the polymers.

One important issue still to be addressed before GO can be produced on a

large scale from pregraphitic materials is the need to ensure a proper control of

their characteristics. It is well known that the characteristics of the parent

graphite (in terms of purity, crystallinity, homogeneity, etc.) play an important

role. It has been demonstrated that the size of the graphite crystals affects the

oxidation process and the functionalities and sheet size of the resulting GO [1].

This evidences that preferential attack occurs during oxidation at the boundaries

of the graphite crystallites and at the defects present in the basal planes [2].

Physical and chemical properties and effects of such factors as purity, dispersion

and surface state of nanofillers great potential for many applications, such as

functional fillers for polymer composites.

Due to their superior and unique properties, GO can produce a dramatic

improvement in various properties at a very low filler loading for polymer

composites, showing more efficiency in improving the mechanical, thermal and

electrical properties compared to other nano-fillers.

Composites exhibited improved electrical conductivity, mechanical

strength, enhanced electrocatalytic activity, and have been applied in the fields

of energy storage and conversion, electroanalysis and electronics. Systematic

work on extending the application scope of the composites would be of great

importance.

1. C. Botas, P. Álvarez, C. Blanco, R. Santamaria, M. Granda, P. Ares et al. Carbon, 2012,

50(1), 275.

2. E.L. Evans, J. de D. Lopez-Gonzalez, A. Martin-Rodrıguez, F. Rodrıguez-Reinoso Carbon,

1975;13(6), 461.

110

Theoretical calculations of the temperature field distribution in

the silicon periodic nanostructures during thermal annealing

O.O. Havryliuk, O.Yu. Semchuk



The idea that nanostructurization homogeneous and anisotropic media can

lead to new optical properties was proposed many years ago [1]. One of the

most effective methods nanostructurization is a thermal and laser annealing.

When thermal annealing of porous silicon with the surface is desorption

products of electrochemical treatment and changing its fluorescent properties

[2].

Disputes that are at the initial moment right rectangular shape, under

heating changing profile, their walls are scabrous and gradually they begin to

form protrusions. Over time, these performances increased in size, which after

long annealing can develop into a solid jumper that completely separates season

in two separate areas. Dimensions established jumpers, their thickness and

position depend strongly on the temperature distribution in a porous layer [3].

In this paper we have carried out numerical calculations of temperature

distribution in periodic structures on the surface of the silicon thermal annealing.

Dimensions periodic structures (microthread) are: diameter - 0.5 µm, height -

1 µm, the thickness of the silicon substrate - 0.5 µm. It is shown that this

structure reaches the annealing temperature is already 10 ns, and the heat flow is

directed to the middle microthread on the surface of the silicon (Fig.).

Temperature distribution can give an opportunity to explain structural changes,

electrical and optical properties of such structures after annealing.

Fig. The temperature profile in

the thermal annealing

periodically structured silicon

(T=1273 K, t=1 ns)

1. M. Born, E. Wolf, Principles of optics, Nauka: Moscow, 1973

2. V.A. Kisilev, S.V. Polisadin, A.V. Postnikov, Fizika i Tekhnika Poluprovodnikov, 31

(1997) 830.

3. B.M. Kostishko, A.V. Zolotov, Actual Problems of Solid-State Electronics and

Microelectronics (Divnomorskoye, Russia, September, 24 - 29, 2006) p.177.

111

POSS-containing nanocomposites based on sequential

semi-interpenetrating polymer networks

L.V. Karabanova, L.A. Honcharova

Institute of Macromolecular Chemistry, NAS of Ukraine,

48 Kharkiv Road, Kyiv 02160, Ukraine, [email protected]

The nanocomposites based on sequential semi-interpenetrating polymer

networks (semi-IPNs) consists of polyurethane (PU) and poly(hydroxypropyl-

methacrylate) (PHPMA) were synthesized and investigated.

1,2-propanediolisobutyl-POSS (POSS, 1 and 10 wt. %) was used as

functionalized nanofiller for PU polymer component. The presence of two

reactive hydroxy groups in POSS-diol allows to react with diisocyanates by

embedding in the main chain of PU. The stoihiometric ratio

[PU/POSS]/PHPMA=85/15 was in all cases. The nanocomposites were prepared

by photopolymerization. The effects induced by the POSS introduction on the

morphology and thermal properties of the nanocomposites were investigated by

SEM, DSC and TGA.

1,2-propanediolisobutyl-POSS Fig. 1. SEM cross-sectional

image of nanocomposite with

10 wt % POSS

Fig. 2. TGA curves of PU (1) and

semi-IPN nanocomposites with

0 (2), 1 (3) and 10 wt.% POSS (4)

From the DSC data the glass transition temperature (Tg) of the

nanocomposites was found to be increased with POSS content: from Tg=-61oC

(native semi-IPN) to Tg=-60oC and Tg=-59

oC (for nanocomposite with 1 and

10 wt. % POSS, respectively). From the TGA data the addition of POSS leads to

enhancement of nanocomposite‟s thermal stability. For native PU was found

Тd(max)=376oC. For the nanocomposites Тd(max) varied approximately 382-387

oC.

Fig. 1 shows SEM image of nanocomposite with 10 wt. % POSS. We

observed POSS particles aggregation in the form of rectangular microdomains.

Obviously, the POSS-diol, introduced in PU component acts as nanostructuring

agent. Fig 2. shows the TGA curves for investigated samples. The degradation

was observed in two steps, around 280-300oC and above 380

oC, which is

indicative of the soft and hard segments in polyurethane. The authors thank the staffs of the Center Collective Use of scientific Equipments

(CCUE) NASU in IMC on research by DSC, TGA and N.G. Kholodny Institute of Botany

NASU on research by SEM.

112

Adsorption of Au3+

ions from water solutions by Fe3O4/HA

nanocomposites

O.M. Kamіnskiy1, N.V. Kusyak

1, A.L. Petranovska

2, S.P. Turanska

2,

P.P. Gorbyk2

1Ivan Franko Zhytomyr State University,

40 V.Berdychevska Str., Zhytomyr 10008, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,


The use of sorbents with magnetic properties greatly facilitates the

separation and collection of substances and microbiological objects. The use of

nanotechnologies, modification and functionalization of sorbents surface helps

to adjust them for operation in different physical, chemical and biological

conditions and to impart adsorption selectivity.

The aim of this work is to research the influence of magneto-sensitive

nanostructures surface on Au3+

ions adsorption by single-domain Fe3O4, as the

example, and Fe3O4/hydroxyapatite (Fe3O4/HA) nanocomposite. The magnetite

synthesis was prepared with iron salts co-deposition. For the surface

modification of magnetite the number of initial components responsible molar

ratio of Ca : P of about 1.67 : 1.75 was required. Hydroxyapatite coating on the

surface of nanodispersed single-domain magnetite was obtained by the sol - gel

method.

The presence of hydroxyapatite and coating formation on magnetite

surface was proved with Fourier infrared spectroscopy investigations (Perkin

Elmer 1720) in 400-4000 cm-1

range and X-ray photoelectron spectroscopy

method (EC-2402 with PHOIBOS-100-SPECS energy analyzer). The adsorption

capacities (Amax) of original and modified magnetite surfaces were determined

by Au3+

ions concentration measuring using atomic absorption analysis in flame

acetylene-air mixture. Au3+

water solutions within 5-200 mg/l range

concentrations were used for the studies.

The adsorption activities of nano-sized non-modified Fe3O4 and Fe3O4/HA

composite were investigated. Thus, for Fe3O4 under 298 K, pH-3.0 Amax = 11.6

mg/g and R value (the level of extraction) is 81.8 %, whereas for Fe3O4/HA

nanocomposite in the same conditions Amax= 19.8 mg/g and R= 96 %. The

maximum Au3+

extraction from water solutions takes place in the first 50-60 min

and corresponds to obtained kinetic data. The increase in Au+3

ions equilibrium

concentration leads to adsorbents surface monolayer adsorption saturation. This

isotherm form can be described with the Langmuir equation.

113

Nanostructured catalytic cobalt containing PEO-coatings

on alloy AL25

A.V. Karakurkchi, N.D. Sakhnenko, M.V. Ved’, A.S. Gorohivskiy

National Technical University “Kharkiv Polytechnic Institute”

21 Frunze Str., Kharkiv 61002, Ukraine, [email protected]

One of the perspective ways to improve the performance of internal

combustion engines (ICE), such as the incomplete combustion of fuel and

formation of toxic components (CO, NOx), can be the use of catalysis in situ in

the combustion chamber. Catalytic processes are characterized by lower

temperatures of the fuel burning start as well as its higher completeness. It

seems appropriate to deposit a catalytic layer directly on the surface of ICE

pistons manufactured of AL25 complex alloyed silumins. At high temperatures,

significant advantages are shown by a family of catalysts based on cobalt oxides

which are formed on the surface of silumins by plasma electrolytic oxidation

(PEO) providing the incorporation of active components into an alumina matrix.

The aim of this study is to substantiate the electrolyte composition and the PEO

modes for the formation of a mixed oxide layer with high cobalt content on the

surface of the AL25 alloy.

The PEO of samples with surface of 2 cm2 was conducted using a B5-50

stabilized power supply in an electrolytic cell under conditions of forced cooling

of the electrolyte to a temperature of 20–30°C at a varied current density i in a

range of 2,0–10 A/dm2. PEO was implemented from working electrolytes

composition, g/l: K4P2O7 – 66–297; CoSO4 – 7.5–46.5.

It was shown that in the program PEO mode in indicated electrolyte dense

ceramic nanostructured coatings with high adhesion to the substrate can be

obtained on the surface of AL25 alloy. The composition of the electrolyte, the

starting current density and both sparking and final voltage strongly affect the

oxidation process and composition and relief of coatings surface. It was

established that the mechanism of AL25 alloy oxidation in cobalt-pyrophosphate

electrolytes significantly different from PEO in alkaline permanganate solution

[1]. Formed mixed oxide coatings have developed surface with Co content up to

30 wt. % (in terms of metal). The composition and morphology of the surface

causes high catalytic properties of synthesized materials, which confirmed the

results of testing in model CO oxidation reaction, neutralization of NOx, and fuel

combustion for various modes of engine operation.

1. N.D. Sakhnenko, M.V. Ved‟, D.S. Androshchuk, S.A. Korniy, Surface Engineering and

Applied Electrochemistry, 52 (2016) 145.

114

Nanosized structures of zinc oxide: methods of fabrication,

properties and perspectives of applications

G.N. Kashin, I.V. Dubrovin, P.P. Gorbyk



Being inexpensive, widely available and non-toxic zinc oxide (ZnO) is a

very promising semiconductor material. Its microstructural forms such as rods,

wires, whiskers and tubes are of particular interest. Unique mechanical, physical

and chemical properties of these modifications of structured zinc oxide ensure

wide prospects of their applications in microelectronics and optoelectronics

(light-emitting diodes and lasers operated in the visual and UV ranges), for

fabrication of gas sensors and field emission devices and also new composite

materials [1-3].

In this work we have analyzed various high- and low-temperature

methods (gas epitaxy, carbometric synthesis, hydrothermal, two-zone and some

others) that are used for fabrication of rods, wires, whiskers and tubes of zinc

oxide with at least one size in the nanometer range [4-6]. We have compared the

process conditions and abilities of the above methods as well as the properties of

various structures that have been synthesized by these methods. The properties

of the fabricated structures have been characterized by electron spectroscopy,

electron microscopy, anomic force microscopy, X-ray analysis,

photoluminescence spectroscopy.

The results of the comparative analysis of various methods used for

fabrication of rods, wires, whiskers and tubes of zinc oxide as well as the

physical and chemical properties of these structures show that the careful

selection of process methods and conditions will ensure the fabrication of micro

and nanostructured forms of zinc oxide with optimal characteristics for various

applications and allow researchers to control these characteristics in wide

ranges.

1. S.J. Pearton, D.P. Norton, K. Ip, W. Heo, T. Steiner, J. Vac. Sci. Technol. B, 22 (2004)

932.

2. C.P. Burke-Govey, N.O. V. Plank, J. Vac. Sci. Technol. B, 31 (2013) 06F101-1.

3. M.H. Sarvari, H. Sharghi, Tetrahedron, 61 (2005) 10903.

4. P.P. Gorbyk, I.V. Dubrovin, Yu.A. Demchenko, M.M. Filonenko, A.A. Dadykin,

Chemistry, physics and technology of surface, 14 (2008) 275.

5. P.P. Gorbyk, A.A. Dadykin, I.V. Dubrovin, Yu.A. Demchenko, G.N. Kashin, Surface,

issue. 1(16) (2009) 177.

6. P.P. Gorbyk, I.V. Dubrovin, Yu.A. Demchenko, G.N. Kashin, Yu.M. Litvin, Surface,

2(17) (2010) 214.

115

Solvent effects on cyclization dynamics of diarylethene derivatives

A. Khodko1, N. Kachalova

1, Iu. Mukha

2, S. Snegir

2

1Institute of Physics, NAS of Ukraine, Kyiv, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine, Kyiv, Ukraine

The photochromic molecules that can be reversely switched between two

well-defined forms by external optical and/or electrical stimulation are the

prospective elements for organic optoelectronics [1]. Among known molecules

(rotaxanes, stibenes, azobenzenes, etc.) the diarylethene molecules display the

key properties: thermal stability, good fatigue resistance, high optical response,

and minor structural change while switching [2]. Previously, we have studied

the subpicosecond cyclization process of diarylethene derivatives solved in

ethanol by ultrafast time-resolved transient absorption spectroscopy [3], but it

was shown [4] that the solvent polarity can also affect on the cyclization

dynamics. In this research, we reveal the unknown solvent effects on the

cyclization dynamics of two types of new furan-based diarylethene molecules

with optimal functional end-groups: TSC (i.e., thiosemicarbazone side chain)

and YnPhT (i.e., acetyl-protected thiol-end-group) using UV/Vis spectroscopy.

The diarylethene molecules were synthesized at the University of Konstanz

(Germany) [5]. The samples were studied at optimal concentration C=10-5

mol/l

in ethanol and in H2O-ethanol mixture (4:1).

We found that the formation of closed molecules occurs faster and in two

times more effective in pure ethanol then in more polar H2O-ethanol mixture for

both TSC and YnPhT derivatives. The absorption bands of closed form (CF) for

TSC and YnPhT molecules are slighlty (5 nm) shifted to short-wavelenght

region in H2O-ethanol mixture. Also, TSC molecules approximately ten times

higher level of absorbance then YnPhT molecules in equal concentration. In

conclusion, these types of diarylethene derivatives are solved better in ethanol,

but for further experiments with gold/silver nanoparticles H2O-ethanol mixture

can be also used as a solvent.

1. M. Irie, T. Fukaminato, K. Matsuda, S. Kobatake, Chemical Reviews, 114 (2014) 12174.

2. D. Kim, H. Jeong, H. Lee, W.-T. Hwang, J. Wolf, E. Scheer, T. Huhn, H. Jeong, T. Lee,

Advanced Materials, 26 (2014) 3968.

3. A. Khodko, V. Khomenko, O. Mamuta, S. Snegir, N. Kachalova, Proceedings of NAS of

Ukraine, 12 (2015) 57.

4. S. Aloïse, M. Sliwa, Z. Pawlowska, J. Réhault, J. Dubois, O. Poizat, G. Buntinx, A.

Perrier, F. Maurel, Sh. Yamaguchi, M. Takeshita, J Am Chem Soc, 132 (2010) 7379.

5. D. Sysoiev, T. Yushchenko, E. Scheer, U. Groth, U.E. Steiner, T.E. Exner, T. Huhn,

Chemical Communications, 48 (2012) 11355.

116

Modification of polysulfone membrane surface with SnO2

nanoparticles by “layer-by-layer” method

I.S. Kolesnyk, O.Ya. Dzhodzhyk, V.V. Konovalova, A.F. Burban

National University of “Kyiv-Mohyla Academy”,

2 Skovoroda str., Kyiv 04655, Ukraine, [email protected]

Ultrafiltration is an important process in food industry, especially in dairy

products preparation. But its usage is limited because of membranes pollution

and concentration polarization, which cause the decreasing of the permeate flux

over time. One of the methods of membranes enhancement of resistance to

contamination is immobilization of nanoparticles with photocatalytic activity on

their surface.

The industrial polysulfone membranes UF-PES-020H (Microdyn Nadir,

Germany) with cut-off 20 kDa were used for modification. The surface of

membranes was modified by “layer-by-layer” method. Polyethylenimine with

molecular weight of 750 kDa was used as positively charged polyelectrolyte, as

negatively charged ones sodium alginate, sodium carboxymethyl cellulose, κ-

carrageenan, and ι-carrageenan were used. As a final layer negatively charged

SnO2 nanoparticles, stabilized with polyelectrolyte solution, were deposited.

It was investigated that sodium alginate-polyethylenimine and sodium

carboxymethyl cellulose-polyethylenimine were effective polyelectrolyte pairs

for modification of membrane surface with SnO2 nanoparticles, whereas usage

of carrageenans did not provide uniform coating of membrane surface with

nanoparticles.

Process of milk ultrafiltration on modified membranes was studied.

Unmodified membrane showed a significant flux decrease after twenty minutes

of ultrafiltration, it was caused by deposition of milk components on its surface.

It was studied that the process of milk ultrafiltration on membranes, modified

SnO2 nanoparticles, remained stable for 8 hours. The quality of concentration

was evaluated by such characteristics as density, pH, lactose content, milk solids

in the filtrate and concentrate. Membrane modification with polyelectrolyte

layers and SnO2 nanoparticles allows entrap 20-40 % of lactose and 70 % of

calcium, which is favourable for the further cheese preparation.

117

Nanosized non-porous silicon carbide surface chemistry

D. Korytko, N. Volvach, S. Gryn, S. Alekseev


62 Volodymyrska Str., Kyiv 01601, Ukraine, [email protected]

Bulk silicon carbide is a widely known material in number of applications

related to its chemical resistivity along with mechanical stability and substantial

thermal conductivity.

Silicon carbide surface chemistry is challenging and the existing literature

data are contradictory and quite limited. First of all, it is because active

exploration of developed SiC surface species (nanoparticles, nanowires, porous

SiC) is dated to only last 10-15 years, and the vast majority of research was done

in the area of its physical (mechanical, optical, electrical) properties. At the

same time the chemical properties of nanostructured SiC, in particular, the

nature and reactivity of surface groups remained unnoticed by researchers.

Nanosized SiC is promising for exploring in different branches of materials

science and even biomedical investigations.The ability of colloid formation as

well as optical and biological properties of the nanoparticles is determined

significantly by the composition of the surface chemical groups.The materials

presented here can be useful in terms of working out an information about the

chemical behavior of 3C-SiC polytype as a model object when developing

optimal approaches to chemical treatment of mezoporous SiC of the same

crystalline modification.

TEM observations and powder XRD revealed that the investigated initial

SiC nanopowder consisted of 3C-SiC particles of 16 nm with 5-6 nm crystalline

domains. XPS studies proved the presence of SiO2 and free carbon impurities in

the samples. The presence of the carbon imparts them with some

hydrophobicity.The calcination of the SiC in the 600 oC to 900

oC range resulted

in carbon impurities oxidation and formation of surface SiO2 layer.The careful

examination of the samples surface made us to refute an assumption of so-called

silicon oxocarbide phase formation in oxidative heating conditions.

The SiC core decreased gradually with temperature increase: the SiO2

surface layer removed by dissolution in HF-HNO3, HF-ethanol mixtures or

KOH concentrated solution gave nanoparticles of reduced size.

The surface functionalities of the oxide-free SiC nanopowder depended on

the composition of the etching agent and were presented by -OH, -COOH and

Si-H groups.

This work was partially funded by IRSES project No 319013 «Silicon

carbide as a support for Co metal nanoparticles in Fischer-Tropsch synthesis».

118

Synthesis and research of nanocomposites with regulated drug

release on basis of poly(2-hydroxyethyl methacrylate)

О.S. Кukolevska1, I.I. Gerashchenko

1, E.M. Pakhlov

1, T.I. Yushchenko

2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Vinnytsia National Pyrogov Memorial Medical University,

56 Pyrogov Str., Vinnytsia 21018, Ukraine, [email protected]

One of the modern trends in manufacturing technology of surgical devices

(coatings, implants, catheters, drainages etc.) is the design of hydrogel therapy

systems that supply a prolonged release of bioactive substances outside. For this

purpose, the swelling poly(2-hydroxyethyl methacrylate) (PHEMA) is

considered as a promising material which can uniformly release incorporated

drugs into the water medium due to diffusion.

To regulate the release kinetics of the substances from PHEMA three

series (a–c) of samples with various porosity were synthesized and studied in

this work. The medicines, among that metronidazole, decamethoxine, silver

nitrate, zinc sulfate, glycine and tryptophan, were included into the PHEMA

matrix by different means: directly to the polymer (a); after immobilization on

the nanosilica surface (b); with nanosilica but separately one from other (c).

Thermal polymerization was iniciated by azobisisobutyronitrile and triethylene

glycol dimethacrylate was added as a crosslinking agent. The any amounts of

water were used for pore formation.

The obtained nanocomposite materials were entered into water medium

and release kinetics of the substances as well as a rate of swelling were

investigated. The porous structure of materials after swelling were studied

microscopically (×600). The interaction between nanosilica filler and polymer

matrix was examined by IR spectroscopy. The isotherms of adsoption of

substances on the nanosilica were studied to estimate the impact of the filler on

release kinetics. Additionally, the TGA/DTA analysis and the low temperature

adsorption of nitrogen (BET method) in the samples were carried out.

In this study the main feature was observed: including of drugs into a non-

porous matrix with nanosilica filler considerably slows down their release. This

caused both by adsorption of substances on the filler surface and by the

interaction of filler with polymer matrix that makes it more rigid and less

penetrating. In case of samples synthesized with pore forming agent the release

profiles for materials containing nanosilica and without it become almost alike.

Thus, enter of nanosilica as well as formation of pores with managed sizes

allow to regulate the release kinetics of any bioactive substances from

nanocomposite materials on the basis of poly(2-hydroxyethyl methacrylate).

119

Adsorption of La3+

ions with nanocomposites based on

single-domain Fe3O4 modified with SiO2, TiO2

A.P. Kusyak1, A.L. Petranovska

2, S.P. Turanska

2, P.P. Gorbyk

2

1Ivan Franko Zhytomyr State University,

40 V. Berdychevska Str., Zhytomyr10008, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,


Magnetosensitive nanocomposites with different surface types are the

most promising materials produced for various branches of industry. These

materials, taking into account their effectiveness and economic feasibility, are

still used for solving numerous urgent problems like removing, separating and

concentrating toxic compounds from natural and synthetic liquids, including the

technogenic liquids. The nano-sized single-domain magnetite possesses an

important place among other perspective materials used in creation of

nanocomposites.

In this work, nano-sized single-domain magnetite was synthesized, its

surface chemical modification was carried out, and adsorption properties of

Fe3O4, Fe3O4/TiO2 and Fe3O4/SiO2 nanostructures were researched regarding

La3+

ions. Magnetite was synthesized according to the reaction: Fe2+

+ 2Fe3+

+

8NH4OH → Fe3O4 + 4H2O + 8NH4+. Magnetite particles with fraction size of

10-30 nm corresponding to single-domain state with optimum magnetic

properties and specific surface area S=105 m2/g were used. To modify

nanoparticles we used tetraethoxysilane (TEOS), n-butylorthotitanates. The

composites were obtained from samples of magnetite by adsorption

modification (AM). So, we received the layered structure.

Research in adsorption properties of Fe3O4, Fe3O4/SiO2 (AM), and

Fe3O4/TiO2 (AM) nanocomposites with respect to La3+

cations was carried out

dynamically at pH = 6.5 and room temperature using standard solutions with 0.5

to 46 mg/l (m = 0.03g, V = 5 ml) concentrations. To research into pH influence,

acetate buffer (Co La3+

= 23 mg/l) was used. Adsorption capacity on the surface

of original and modified magnetite was determined by dynamic measuring of

La3+

concentration in solution with spectrophotometric method (λ = 655 nm).

Adsorption capacity of magnetite after its surface modification with SiO2 and

TiO2 increases. Adsorption saturation is reached after 15-30 minutes for all the

nanocomposites. The increase in Ag+ equilibrium concentration leads to

adsorption saturation. The best La3+

removal characteristics correspond to

Fe3O4/TiO2 (AM) surface.

120

Stabilization of the spinel ferrite nanoparticles with oleic acid

species involved as a surfactant

O.M. Lavrynenko, O.Yu. Pavlenko, Yu.S. Shchukin, P.O. Kosorukov

F.D. Ovcharenko Institute of Bio-Colloid Chemistry of NAS of Ukraine

42 Academic Vernadsky Ave, Kyiv 03142, Ukraine, [email protected]

Nowadays oleic acid has been widely used as a surfactant to obtain highly

disperse iron oxide particles and to take control over their surface

functionalization and properties [1]. As a rule, various organic species including

carboxylic acids are added into the system at the time of synthesis procedure,

especially when the process of co-precipitation [2] or thermal treatment [3] of

iron-containing salts takes place. High temperature decomposition of iron

compounds with oxygen-containing ligands such as oleic acid permits to form

iron oxide nanoparticles characterized by different particle‟s size and particle‟s

shape [4].

The present work is devoted to testing of oleic acid solutions with regard

to stabilization of spinel ferrite nanoparticles preliminary formed on the steel

surface under the rotation-corrosion dispergation conditions [5].

To prepare dispersion medium we used dilute solutions of oleic acid

(mass ratio 5, 10, 15, and 20 %) in hexane. Taking into account strong magnetic

interaction between the particles, the resuspendable spinel ferrite nanopowders

were demagnetized and added into the flasks filled with dispersion medium. The

suspension mixtures were stirred for 1 h at T=80°C until hexane evaporated and

the nanoparticles coated with the surfactant were rinsed several times by ethanol

to remove free surfactant molecules [6]. The obtained powders were dried at

room temperature afterwards the particles were placed into low-oxygen

atmosphere to prevent oxidation process. Hence, spinel ferrite nanoparticles

stabilized in a described way may be used as a raw material for further

application in nanotechnology as well as in biomedicine.

1. W. Wu, Q. He, Ch. Jiang, Nanoscale Res. Lett. 3 (2008) 397.

2. G. Kataby, M. Cojocaru, R. Prozorov, A. Gedanken, Langmuir 15 (1999) 1703.

3. M. Yin, A. Willis, F. Redl, [at all.], J. Mater. Res. 19 (4) (2004) 1208.

4. H. Si, Ch. Zhou, H. Wang, [at all.], J. of Coll. Interface Sci. 327 (2008) 466.

5. O.M. Lavrynenko, Yu.S. Shchukin, O.Yu. Pavlenko, P.A. Kosorukov, Material Sci. of

Nanostructures 1 (2014) 3.

6. L. Zhang, R. He, H.-Ch. Gu, Appl. Surf. Sci. 253 (5) (2006) 2611.

121

Influence of processing conditions on the quality of

Li1,3Al0,3Ti1,7(PO4)3 films with NASICON structure

B.O. Linova1, S.D. Kobylianska

1, A.G. Bilous

1, I.O. Dulina

2


32-34 Acad. Palladina Ave., Kyiv 03680, Ukraine, [email protected] 2Institute for Problems in Materials Science, NAS of Ukraine,

3 Krzhizhanovsky Str., Kyiv 03680, Ukraine, [email protected]

The development of electrolytes as thick films for solid-state batteries that

can contribute to miniaturization, provide more flexibility in designing

independent microelectronic devices and increase the possibility of their use in

medicine (batteries for implants) is relevant today. Among the known lithium

ion solid electrolytes, Li1,3Al0,3Ti1,7(PO4)3 (LATP) with NASICON structure

attracts great attention, which has high ionic conductivity in Li+ ions at room

temperature (σ ~ 10-4

Sm ∙ cm-1

) [1]. These materials are widely studied in the

form of bulk samples, while there is little information on the synthesis and study

of their electrical properties as thick films.

We have for the first time developed a technique and obtained thick

LATP films using the method of "tape casting" based on previously synthesized

nanoparticles and organic reagents such as: acetylacetone and isopropanol

(solvents), polymethylmethacrylate (a binder), dibutyl phthalate (a plasticizer)

dybutylfosfatom, hallotanninom (dispersants). We have also established their

optimal mass ratio.

On the basis of the data obtained it was established that the optimal

sintering temperature is 1000 °C. Three modes of heat treatment were studied to

determine the optimal conditions for heat treatment: 1) single-stage at the

heating speed of 60 °C/hour; 2) two-stage: slow heating at 20 °C/h to 500 °C,

then 10-hour holding and subsequent heating at the speed of 180 °C/hour;

3) two-stage with thermal shock at 500 °C, followed by heating at the speed of

180 °C/hour. It is shown that in the first case the LATP film is characterized by

cracks and is highly porous (~ 80%). The porosity of the films at the second and

third modes of heat treatment is 43 and 47%, respectively. To reduce the

porosity of the LATP films they were laminated. It is found that after lamination

the porosity of the films is 27 and 17%, when heating in the modes 2 and 3,

respectively.

Thus, it is found that the optimum modes to obtain dense LATP films are

two-stage heat treatment regimes and the use of lamination.

1. A. Varez et al., J. Mater. Chem., 11 (2001) 125.


122

Hybride polymer composites with incorporated biologically active

substances: spectral studies

Yu. Bolbukh1, T. Lupascu

2, I. Povar

2, S. Rogalsky

3, V. Tertykh

1, M. Rusu

2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Institute of Chemistry of the Academy of Sciences of Moldova,

3 Academiei Str., MD-2028 Chisinau, Republic of Moldova 3Institute of Bioorganic Chemistry and Petrochemistry, NAS of Ukraine,

50 Kharkivske shosse, Kyiv-160, Ukraine

As produced pHEMA is biocompatible, ensures biological and

morphological fixation to living tissues through swelling, though it is not

bioactive. Bioactive fixation has been obtained by modification of pHEMA.

Bioactive pHEMA-silica hybrids can be produced either by addition of silica

nanoparticles to HEMA monomer/pHEMA solution or using pHEMA solutions

and inorganic precursors such as tetraethoxysilane (TEOS) through in situ sol-

gel processes. Those materials combine swelling properties of pHEMA and

bioactivity of SiO2 gel, hence can construct a group of artificial materials

appropriate as scaffolds for tissue engineering or for soft tissue replacement [1].

For these materials a biocidal activity is one of the major parameters. From other

side, incorporation an organic compound can changes the structure and, as

result, properties of composite. That‟s why the goal of the study presented was

an investigation of structural characteristics of composites with incorporated

biocides.

Hybrid organic-inorganic composites on the basis of 2-hydroxyethyl

methacrylate (HEMA), aminopropyltriethoxysilane (APTES) and

vinyltriethoxysilane were obtained by the methods of sol-gel synthesis

simultaneously with a radical polymerisation.

Before polymerisation the bioactive substances were added into monomer

after dissolving. As active substances the polyhexamethylene guanidine salts

and ionic liquid 1-allyl-3-octylimidazolium bromide (ALDIM-Br) were used.

Parameters of composite structure were investigated using ATR-FTIR

spectroscopy. Was found that the polymeric structure had less affected by water-

soluble ALDIM-Br.

Acknowledgements




1. A. Costantini, G. Luciani, B. Silvestri, F. Tescione, F. Branda, J Biomed Mater Res Part

B: Appl Biomater 86B (2008) 98.

123

Silicas with thiosemicarbazide groups for cation sorption from

nitrate solutions

L.A. Belyakova, D.Yu. Lyashenko



Sorption technologies of extraction, concentration and disposal of toxic

substances from various environmental objects, as well as their use for the

synthesis of catalysts, the chemical analysis of drinking water, food and

medicinal compounds allow to solve many problems of endo- and exoecology.

Silica matrices are ideal for the synthesis of new materials with sorption

specificity because of high reactivity of surface silanol groups.

In the present study the comparative sorption of palladium, silver and

mercury cations from nitrate aqueous solutions was carried out on two

nanoporous silicas chemically modified with thiosemicarbazide.

Sorbent 1 was obtained by a three-step chemical modification of silica

surface at first 3-aminopropyltriethoxysilane, then cyanuric chloride and

thiosemicarbazide. Sorbent 2 was synthesized by grafting of thiosemicarbazide-

containing mono-tosyl-β-cyclodextrin to aminopropylsilica surface.

Sorption of cations of palladium, silver and mercury was studied as a

function of time and concentration of the equilibrium solutions. Sorption

equilibrium is reached within 0.5–1.0 h. Sorption isotherms demonstrate the

difference in sorption affinity in a series of studied cations:

Pd(II) < Ag(I) < Hg(II) (Table).

Silica sorbent

Content of

grafted

thiosemicarbazide

groups, mmol/g

Distribution coefficient, ml/g

Pd(II) Ag(I) Hg(II)

1 0.11 2700 3900 4900

2 0.09 29000 42000 330000

Higher sorption parameters of sorbent 2 are associated with

oligosaccharide presence in the structure of grafted functional groups.

The formation of “host – guest” inclusion complexes between the inner

cavity of grafted β-cyclodextrin molecules and nitrate-anions in a solution was

found. The negatively charged surface of silica, functionalized with

thiosemicarbazide-containing β-cyclodextrin, contributes to a more effective

sorption of Pd(II), Ag(I) and Hg(II).

124

Synthesis, characterization and modification of porous

DMN-GMA microspheres

M. Maciejewska, J. Osypiuk-Tomasik, B. Podskościelna, M. Grochowicz


pl. Maria Curie-Skłodowskiej 3, 20-031 Lublin, Poland, [email protected]

Distinguish properties of porous polymeric microspheres like highly

developed internal structure, hydrohobic/hydrophilic character, presence of

various functional groups make them very attractive from scientific and

industrial point of view. Porous polymers are effective materials for many

separation processes and are widely used as various kinds of sorbents [1-3].

They can be obtained from numerous types of monomers as well as by

modification of copolymers that contain reactive groups. One of the convenient

routs to incorporate new functional group into polymer matrix is ring-opening

reaction of oxirane ring with required agent [4]. Widespread practice is reaction

of epoxy group with amines [5]. This process leads not only to the introducing

the active pendant group to the network but also change the textural and thermal

properties of the newly obtained materials.

Herein we presents the synthesis and characterization of porous

copolymers glycydyl methacrylate (GMA) with di(methacryloiloxy)naphtalene

dimethacrylotrimethacrylate (DMN). They were synthesized through

suspension-emulsion copolymerization in the form of regular microspheres.

During the synthesis DMN served as a cross-linker and is responsible for the

mechanical and thermal properties of the resulting polymeric matrix. GMA

provided reactive epoxy groups that were modified by subsequent reaction with

diethylenetriamine. The molar ratio of the functional monomer to the cross-

linker was increased from 1:1 to 1:5. As a results set of ten various copolymers

was obtained. The obtained co-polymers were successfully modified with

diethylenetriamine. The increasing amount of functional monomer in the

polymerization mixture as well as the modification process considerably

changed the porous structure of the co-polymers. It was found out that the

modified co-polymers show affinity towards phenols.

1. M. Maciejewska, J.Osypiuk-Tomasik, J. Therm. Anal. Calorim., 111 (2013) 1595.

2. M. Maciejewska, J. Therm. Anal. Calorim . 119 (2015)1147.

3. M.T. Gokmen, F. Du Prez, Prog. Polym. Sci. 37 (2012) 365.

4. M. Maciejewska, D. Kołodyńska, Mat. Chem. Phys. 149 (2015) 43.

5. M. Maciejewska, Y. Bolukh, Adsorpt. Sci. Technol. 33 (2015) 617.

125

Nickel ferrite nanoparticles modified with copper iodide:

synthesis, structural, electrical and magnetic properties

R.V. Mazurenko, N.V. Abramov, S.N. Makhno, P.P. Gorbyk



Design of new nanocomposites is one of the promising areas of research.

Such materials can be created based on dispersed systems with enhanced surface

and strong interactions among its physical components based on

semiconductors, magnetites.

Nanoparticles Fe3O4 (NPM) received by chemical condensation of a

solution of salts and ferric double acting upon it excess alkali by reaction

Elmore. The samples necessary for the studies were prepared by a chemical

method for modifying nanosize magnetite (Fe3O4) during the course of release

of CuI from an aqueous solution of CuSO4 and КI, Na2S2O3 in the presence of

Fe3O4 to obtain modified magnetite (CuI/Fe3O4).

The real (σ') and imaginary (σ'') components of the complex electrical

conductivity (σ*=σ'+iσ'') at low frequencies (0.1, 1 and 10 kHz) were measured

using the immittance meter E7-14 by two-contacts method in the temperature

range from 298 to 425 K. The real (ε') and imaginary (ε'') components of the

complex permittivity in microwave range were measured using the

interferometer at a frequency of 9 GHz. The magnetic properties of the

composites were measured with a vibrating sample magnetometer at room

temperature (Fig.).

-10 -5 0 5 10

-60

-40

-20

0

20

40

60

0 1000 2000 30000,0

0,1

0,2

f(V

)

V, nm3

(1)

(2)

0 10 20 30 40 50 600,4

0,8

1,2

1,6

C CuI (% mass)

V/V0

D/D0

MS0/M

s0

Ssp/S

sp0

M,

em

u/g

H, kOe

1

2

3

4

As part of the centrally symmetric

spherical shell model based on the values

was calculated Ms at concentration CuI

in ensembles, average volume, external

diameter, density and specific surface

area of composites CuI/Fe3O4.

Distribution of the volume of the NPM

obtained from TEM images and

magnetic measurements (which are

subject to the Langevin dependence

0

( ) ( ) ss

B

M VHM H M n Vf V L dV

k T

) are identical.

Modification of NPM of CuI leads to a

significant increase in the values of

complex permittivity and conductivity of

both the low and high frequencies.

Fig. Hysteresis loops : 1 – NPM;

nanocomposites CuI/Fe3O4 (various

concentrations of CuI, %) 2 – 58, 3 – 40, 4 –

27. Inset: up – a lognormal distribution with

probability density; bottom – the

concentration dependence of the given

characteristics of the above parameters to

NPM ensemble

126

Regulation of the porosity and the surface layer structure of silica

nanoparticles with bifunctional surface layer using one-step

sol-gel technique

I.V. Melnyk1,2

, N.V. Stolyarchuk2, Yu.L. Zub

2, M. Vaclavikova

1

1Institute of Geotechnics, SAS,

45 Watsonova Str., Kosice 04001, Slovak Republic, [email protected]



One of the first silica nanoparticles with aminogroups were synthesized

by R.D. Badgley et al. [1] via modifying silica nanoparticles, or introducing

3-aminopropyltriethoxysilane (APTES) in the reactive solution with already-

formed silica particles i.e. almost one-step. The authors noted that modification

was very slow and the degree of surface functionalization of the silica particles

comprised 15-20% from the maximum possible, providing functional groups

content of 0.64-0.81 mmol/g. Later A. Van Blaaderen et al. [2] proposed one-

step method of obtaining aminosilica nanoparticles where alkoxysilanes (first

APTES, then tetraethoxysilane (TEOS)) were added to water-ethanol-ammonia

solution. Using this technique the authors produced nanoparticles with higher

content of functional groups. Our team also continued working in this direction

by varying the synthesis parameters [3, 4] and affecting the particles‟ size and

the number of functional groups. The major interest in the studies of silica

particles bearing amino functional groups lies in achieving control over their

stability to hydrolysis and especially over their availability and chemical

reactivity. Current abstract proposes to consider the one-step synthesis resulting

in the change of the particles‟ porosity and their surface composition. We

suggest using methyltriethoxysilane (MTES) to create a bifunctional surface

layer and bistriethoxysilylethane (BTESE) instead of TEOS as structuring agent.

The synthesized particles contain 2.0-3.8 mmol/g of amino groups, depending

on the ratio of alkoxysilanes, and the value of the specific surface area increased

from 43 to 132 m2/g, when MTES was used, and to 480 m

2/g for BTESE.

The research is financed from the SASPRO Programme No. 1298/03/01. The work

leading to these results has received funding from the People Programme (Marie Curie

Actions) of the European Union's Seventh Framework Programme under REA grant

agreement No. 609427. Research has been further co-funded by the Slovak Academy of

Sciences.

1. R.D. Badley, W.T. Ford, F.J. McEnroe, R.A. Assinks, Langmuir 6 (1990) 792.

2. A. Van Blaaderen, A.Vrij, J. Colloid Interface Sci. 156 (1993) 1. 3. I.V. Melnyk, etc., Proc. 3rd Int. Conf. «Nanomaterials: Application and Properties»,

16-21 Sept 2013, Alushta, Crimea, Ukraine 2(2) (2013) 02PCN40-1. 4. I.V. Melnyk, Chemistry Journal of Moldova 9(1) (2014) 123.

127

Formation of double-walled nanotube-bis(cyclopentadienyl)nickel

complexes by “host-guest” type

O. Мykhailenko


64 Volodymyrska Str., Kyiv 01601, Ukraine, [email protected]

Unique physical properties of cyclopentadienyl complexes of transition

metals [1] stimulate creation on their base of new intercalates with multi-walled

nanotubes (NT), since their ability to coordinate with d-metals that are able to

coordinate with NT [2, 3] allows to obtain new materials as effective elements

for photo- and magnetosensitive devices.

The initial structure was a С270 (5,5)@(10,10) NT. Intercalation of this NT

assumes placing an intercalate inside the (5,5) NT, into intertubular space, and

its differently oriented sorption on the outer surface of a (10,10) NT. The

intercalate is the nickelocene molecules – bis(cyclopentadienyl)nickel. The

computation was made by ММ+, РМ3 and Monte-Carlo methods. To obtain Kass

of the created intercalate-NT complex, there was used the UV-modified Benes-

Hildebrandt method [4].

There has been stated that up to ~455 К the fully intercalated system is

rather stable, while in case of gradual heating, two intercalate molecules from

the intertubular space and two molecules from the NT‟s outer side surface are

quickly extruded. Two of the four nickelocene molecules, from the outer side

surface of the (10, 10) NT, are desorbed when reaching ~620 К. The other two

molecules stay in the area of effective interaction range remaining sorbed up to

~730 К, while at higher temperatures there remains only one nickelocene

molecule. The two nickelocene molecules, from the inner (5,5) NT, are rather

stable regardless the temperature factor. And finally, the intercalate molecules

that were not desorbed from the NT‟s intertubular and intratubular space were

oriented to NT‟s walls by a cyclopentadienyl ring but not by the equatorial Н-

atoms. Finally, the theoretical computation of absorption UV-spectra of

(5,5)@(10,10) NT depending on the intercalate concentration in terms of the

Benes-Hildebrandt method proves that Kass = 36,2 l·mol-1

(R ≥ 0,998).

1. Ionescu M. I., Zhang Y., Li R. et al. Appl. Surf. Sci. 257(15) (2011) 6843.

2. Mykhailenko O. V., Prylutskyy Y. I., Komarov I. V. et al. Mat.-wiss. u. Werkstofftech. 47(2-3)

(2016) 203.

3. Mykhailenko O. V., Prylutskyy Y. I., Komarov I. V. et al. Nanoscale Research Letters. 11 (2016)

128.

4. Tersoff J. (1989) Modelling Solid–State Chemistry: Interatomic Potentials for Multicomponent

Systems. Phys. Rev. 39 (1989) 5566.

128

Silicate coatings for high-temperature corrosion protection of steel

D.B. Nasiedkin, A.G. Grebenyuk, Yu.V. Plyuto


17 General Naumov Str., Kiev 03164, Ukraine, [email protected]

Oxidation of steel in oxy-fuel combustion product atmosphere limits its

application in industrial practice. Once steel is exposed to oxidation conditions

above ~840 K, a multilayer scale constantly forms consisting of FeO (wustite)

layer next to steel surface, Fe3O4 (magnetite) and Fe2O3 (haematite) at the scale-

gas interface with FeO/Fe3O4/Fe2O3 relative thickness of 95/4/1.

The aim of the work is to develop the barrier coating preventing oxygen

transport to steel surface and thus to suppress its the progressive oxidation at

elevated temperatures in contact with oxy-fuel combustion products.

The formation on silicate coating on

steel surface was simulated by ab initio

Hartree-Fock method (within restricted

open-shell variant) with valence-only basis

set SBKJC and respective effective core

potential using the GAMESS (version 6.4)

program package. Within 300–1000 K

temperature interval, the calculated Gibbs energy for the reaction of silicate

species bonding to Fe2O3 cluster appears to be close to -270 kJ/mol ensuring the

formation of Fe2O3/silicate interlayer responsible for adhesion and protective

performance of continuous barrier silicate coating.

The water-borne silicate composition was

selected and optimized for protection of

cold rolled steel (a) at 920 K in air. The

increase of silicate composition

concentration (b – 0.5 М; c – 1.0 М; d –

2.0 М; e – 3.0 М) resulted in enhancement

of protective performance of 1-layer

coatings while the best result exhibited

3-layer coating applied from 2.0 М

composition (f). The as-synthesised and

working coatings were characterised by

FTIR and SEM. Acknowledgements

The ongoing collaborative project “Production of Coatings for New Efficient and Clean Coal

Power Plant Materials” (2013–2016) is supported by FP7 Specific Programme

“Nanosciences, Nanotechnologies, Materials and new Production Technologies” of the

European Union.

Bonding of silicate species

0 1 2 3 4 5 6 7 8 9 10 11

0

1

2

3

4

5

6

fe

d

c

b

Time, h

Weig

ht cha

nge

, m

g/c

m2

a

Performance of developed coatings

129

Solid-state reactions in composites Nd2O3 - fumed silica with

different content of Nd2O3

O.I. Oranska, Yu.I. Gornikov


17 General Naumov Str., Kyiv, 03164, Ukraine, [email protected]

At present, neodymium silicates and their composites are used in various

fields of technology as materials for lasers, solid state fuel cell, ceramics and

others because of their optical, electrical, chemical and mechanical properties.

In this work solid-state reactions in mixtures of fumed silica (specific

surface area of 300 m2/g) and neodymium oxide in the temperature range 1000-

1400 °C were studied. Initial mixtures contained from 6 to 50 mol. % of Nd2O3.

The samples were annealed in a muffle furnace in air at 1050 °C and heated in a

furnace of derivatograph Q-1500D to 1400 °C. XRD analysis of the products of

solid-state reactions was performed using diffractometer DRON-4-07(CuK).

According to the phase diagram of Nd2O3-SiO2 system neodymium

silicates Nd2SiO5, Nd2Si2O7, Nd9.33Si6O26 can be synthesized depending on the

ratio of neodymium and silicon oxides at temperature of 1400 °С. Based on our

data formation of neodymium silicate of Nd9.33Si6O26 was determined in all

samples with Nd2O3 content of 6-50 mol. % at 1050 °C.

The reaction time was dependent upon

the ratio of Nd2O3 and SiO2 in the

composites. It was at least two hours

in case of the sample with the smallest

content of neodymium oxide (Fig.,

curve 1). Formation of Nd2SiO5 and

Nd2Si2O7 observed at higher

temperatures up to 1400 °C in

samples with stoichiometric ratio of

the oxides of 1 : 1 and 1 : 2. Phase

Nd9.33Si6O26 remained stable in case of

oxides ratio 7 : 9 (Fig., curve 2).

Thus it was found that phase Nd9.33Si6O26 can be prepared at different

ratios of the oxides as a pure phase or component in the composite with SiO2 at

1050 °C. It is determined that the phase is an intermediate in the synthesis of

silicates Nd2SiO5 and Nd2Si2O7 in the system of Nd2O3- fumed silica.

10 20 30 40 50 60 70 80 900

1000

2000

3000

I, s

- 1

degr.

1

2

Fig. XRD patterns of the samples: (1)

annealed at 1050 °C with Nd2O3 of 6 mol.%

and (2) heating to 1400 °C with Nd2O3 of

44 mol.%

130

Formation of platinum nanoparticles on the carbon black

Yu.K. Pirskyy, T.M. Panchyshyn, A.V. Gaidin, A.S. Tupchienko


32-34 prospekt Palladina, Kyiv 03680, Ukraine, taras.if.ua @ gmail.com

For fuel cells, catalysts based on noble metals are active and stable. The

high cost and scarcity of metals call for their more effective use. The catalysts

having nanosized particles of metals or their oxides on their surface show as a

rule a higher activity than the catalysts containing larger particles. The formation

of metal nanoparticles on carbon carriers will make it possible to create a highly

developed nanostructured surface. Owing to the small size of nanoparticles,

active catalyst surface with a large number of active sites can be formed.

The aim of this work was to synthesize nanoscale electrocatalysts with

low platinum content for hydrogen-oxygen fuel cells based on XC-72 carbon

black and to investigate their electrochemical characteristics.

Platinum-containing nanoscale electrocatalysts were synthesized by the

polyol method using various media (ethylene glycol, dimethyl sulfoxide),

reductants (sodium borohydride, formaldehyde) and preparation methods (on a

water bath or by microwave processing). The obtained electrocatalysts were

investigated by scanning and transmission electron microscopy. It has been

shown that the particle size of the carbon carrier (XC-72 carbon black) is not

over 100 nm, and that the particle size of platinum deposited on it is 3-5 nm.

It has been found that the medium and synthesis methods affect the

characteristics of nanostructured Pt/C electrocatalysts. The use of different

synthesis methods facilitates the formation of nanoparticles of different size,

which influences the catalytic activity.The electrochemical characteristics are

also affected by the degree of purification of nanostructured electrocatalysts

owing to the blocking of active sites on the catalyst surface and agglomeration

of small nanoparticles into larger ones.

Thus, efficient electrocatalysts for hydrogen-oxygen fuel cells with low

platinum content have been obtained. It has been shown that by changing the

platinum reduction reaction conditions (medium, temperature, reductant feed

rate), one can control the formation of platinum nanoparticles of required size on

the carbon carrier surface.

131

Structural and optical properties of antibacterial materials based

on Ag and Ag/Cu nanoparticles

I.S. Petrik1, A.M. Eremenko

1, N.P. Smirnova

1, A.V. Rudenko

2,

Y.S. Marikvas2


17 General Naumov Str., Kyiv 03164, Ukraine. 2Institute of Urology, National Academy of Medical Sciences of Ukraine,

9-A Yu Kotsyubynskogo Str., Kyiv 04053, Ukraine, [email protected]

Silver nanoparticles (NP) in colloidal solutions and on the surface of silica

or textiles are increasingly used in medicine due to pronounced bactericidal

action and as an alternative to antibiotics. Bactericidal and antifungal activity of

copper ions and nanoparticles is also well known. Early we studied high

antiseptic action of bimetallic nanoscale composites (BMNP) Ag/Cu in colloidal

solutions and on the silica surface. However of particular interest for medical

purposes are textiles, modified by metal NP (towels, socks, underwear, etc.) via

physical or chemical methods of the ions reduction. Introduction of NP and

BMNP within textile promotes to their stabilizing that is an extremely

convenient way to use in medical practice. The main methods of introducing

NPs in tissue given in the literature, are energetically and economically costly.

In this paper we propose a simple and economic method of introduction of

nanoscale particles of silver and copper to textile materials in one step, without

the use of chemical stabilizers and reducing agents by ironing of fabrics

impregnated with corresponding salts, at 200-220oC. Ag NPs and BMNPs

Ag/Cu of size 20 ─ 60 nm are formed in the tissue during reduction of

corresponding ions involving structural units of cotton – residuals of β-glucose.

Formation of silver NP is confirmed in optical spectra by presence of SPR, as

well as oxide copper and small amount of Ag/Cu alloy. XRD measurements

indicate the formation of crystalline silver NP, and small amount of Ag2O. On

the surface tissue are formed also the trace amount of crystals of stromeyerite

CuAgS and dolerophanite Cu2OSO4, which do not exhibit bactericidal or toxic

effects. High antimicrobial properties of fabrics Ag and Ag/Cu composites are

demonstrated in experiments with gram-negative - E.coli, Pseudomonas

aeruginosa and gram-positive bacteria - S. aureus, along with this BMNP

Ag/Cu also revealed a strong fungicide action.

132

Catalytically active silica-containing films based on CNT with Pd

and Co for oxygen reaction

Yu.K. Pirskyy, O.S. Krupennikova, L.F. Sharanda, V.M. Ogenko

Vernadsky Institute of General and Inorganic Chemistry, NAS of the Ukraine,

prospekt Palladina 32-34, Kyiv 03680, Ukraine, [email protected]

Silica-based porous films fabricated by the sol-gel technique have a high

specific surface area, a high resistance to aggressive media and a high sensitivity

to various media. They are widely used for the creation of humidity, gas, chemical

and biological sensors. Such films can be deposited on ceramic membranes to

create active gas-selective membranes and membrane catalysts. The nanoparticle

distribution of catalytic additives over their surface plays an important part in

films on membranes and depends on particle size and oxidation level. At the

present time, the development of new technologies for the deposition of

catalytically active films on the electrode surface to create efficient current

sources and fuel cells is topical.

The aim of this work was to develop the synthesis of heteronanostructured

catalysts based on carbon nanotubes (CNTs) with Pd and Co, using the sol-gel

technique, and methods for the deposition of catalysts on the electrode as a

catalytically active film and to investigate their electrochemical characteristics.

The catalysts were synthesized by the sol-gel technique with addition of

oxidized CNTs and salts of appropriate metals (Co and Pd). Catalyst sols were

deposited as films on the surface of an electrode of hydrophobized carbon black

and treated at 300 oC under Ar or Ar-H2. The electrochemical measurements were

made on a PI-50-1.1 potentiostat in a three-electrode electrolytic cell at 20 oC.

It has been shown that the activity of catalysts in the oxygen

electroreduction reaction depends on the gas composition, atmosphere and

treatment temperature. The catalytically active Pd/SiO2/CNT - 300 oC film heat-

treated in Ar and H2 had the highest activity at the exchange current

j0=6.46∙10-3

A/g. The slope angles of stationary polarization curves for

electrocatalysts are b1=0.045 V and b2=0.116 V, indicating a mixed mechanism of

oxygen electroreduction, which proceeds both by a two-electron mechanism via

hydrogen peroxide formation and partially by a four-electron mechanism with

water formation. It has been found that the synthesis atmosphere Ar-H2 facilitates

the formation of a large amount of nanosized catalyst particles, uniformly

distributed over the surface, which leads to an increase in catalyst activity in the

oxygen electroreduction reaction. It has been shown that the sol-gel technique

allows the fabrication of catalytically active films based on CNTs with Pd and Co

with uniformly distributed active sites in the silica-carbon matrix and high

electrochemical characteristics.

133

Starch-based biodegradable composite materials with

polypropylene and plasticisers

E.N. Poddenezhny1, O.V. Davidova


1, A.A. Boiko

1,

А.А. Аlexeenko1, M.V. Borysenko

2

1Sukhoi Gomel State Technical University,

48 Oktiabria Av., Gomel 246746, Belarus, [email protected] 1Chuiko Institute of Surface Chemistry, NAS of Ukraine,


Among the great number of natural polymers starch generates more

interest. Owing to its complete biodegradability, low cost and renewability in

plants, starch is considered as a promising candidate for developing

biodegradable composite materials. In view of this, many efforts have been

exerted to develop starch-based polymers for conserving the petrochemical

resources and searching new applications. By combining the individual

advantages of starch and synthetic polymers, starch-based biodegradable

polymers are potential for applications in biomedical and environmental fields.

In this presentation the new

preparation method of biodegradable

starch-based polymers via physical and

chemical modification using sorbitol

and ethylene glycol plasticisers and a

mixture of polypropylene (PP)

homopolymer powder with 50% starch

with processing additives is discussed.

The product in the form of strip is made

by cold mixing of components and

reactive twin-screw compounding in

which a chemical coupling occurs

between the starch and PP matrix,

which accounts for the material‟s

excellent properties. At last, some

examples for various compositions of

starch-based composite materials have

been presented. The biodegradable

composite material starch-PP was characterized by X-ray diffraction (XRD),

scanning electron microscopy (SEM) and IR-spectroscopy. Bioplastic has higher

stiffness, strength, and heat resistance than un-filled PP but also has lower

elongation and impact toughness.

Fig. Biodegradable composite material

starch-PP

134

Preparation of powdered luminescent materials based on yttrium

oxide and yttrium-aluminum garnet by a new combustion method

E.N. Poddenezhny1, O.V. Davidova


1, A.A. Boiko

1,

А.А. Аlexeenko1, A.V. Pavlenok

1, M.V. Borysenko

2

1Sukhoi Gomel State Technical University,

48 Oktiabria Av.,Gomel 246746, Belarus, [email protected] 1Chuiko Institute of Surface Chemistry, NAS of Ukraine,


A new method of luminescent powders, based on the nitrate salts

combustion in the presence of complex organic fuel (urea and

hexamethylenetetramine, HMTA) was developed. The modes of synthesis are

optimized and structural and spectral-luminescent characteristics of the ultra-

dispersed powders of Y2O3:Bi, Eu and Y3Al5O12:Ce, with the sizes of 0.8-1.2 µ

were studied. The precursors were characterized by DTA and TG analysis and

so prepared products – by X-ray diffraction (XRD), scanning electron

microscopy (SEM), and IR spectroscopy. Doping of yttrium-aluminum garnet

with cerium at excitation 450 nm causes broadband luminescence in the range of

480-700 nm, additional processing of powders in the air at 900-1100°C leads to

a decrease in the luminescence

intensity by 1.5 as compared

with phosphor received by

burning at 650 C, owing to

formation of Ce4+

ions in a

structure of Y3Al5O12 under

heating.

Y2O3:Bi3+

, Eu3+

phosphors

were successfully synthesized

by combustion method at low

temperature (650°C) and in

short reaction time.

Photoluminescent spectra of

Y2O3:Bi3+

, Eu3+

particles

exhibited strong red

luminescent colour with

highest sharp band at 612 nm

under excitation in ultraviolet

at 254 and 394 nm.

Fig. Luminescent spectra of Y3Al5O12:Ce

135

Characterisation of natural and modified Ghidirim diatomite

(Republic of Moldova)

L. Postolachi, V. Rusu, T. Lupascu

Institute of Chemistry of Academy of Sciences of Moldova,

Republic of Moldova, [email protected]

Diatomite‟s highly porous structure, low density and high surface area

resulted in a number of industrial applications as filtration media for various

beverages and inorganic and organic chemicals. The diatomite from the

Ghidirim location of Republic of Moldova was used for investigations. The

detailed chemical composition of this diatomite is given in Table 1.

Table 1. Chemical composition of the raw material

Raw material SiO2 Al2O3 Fe2O3 CaO MgO LOI*

Diatomite (Ghidirim location) 85.4 3.0 1.9 1.8 0.6 6.3

*LOI – loss on ignition

The filtration quality is an important property of the adsorbents to be used

in water treatment, since most adsorption purification processes depend on

filtration. The filtration quality of diatomite could significantly improve after

treatment with different agents. The raw diatomite was modified by treatment

with Na2CO3 solution of different concentrations (1, 5, 10 and 20%, Table 2).

The filtration rate of raw and modified diatomites was determined using suction

filtration method.

The treatment of diatomite by sodium carbonate resulted in an increased

filtration rate. There was registered the higher filtration rate for sample treated

with Na2CO3 of 20% concentration, being of 38 mL∙m-2

s-1

.

Table 2. Physical-mechanical properties of the raw and modified diatomite

Property D* 1 5 10 20

Bulk density, g/cm3

0.44 0.44 0.46 0.64 0.67

Specific gravity, g/cm3 1.96 1.95 1.97 2.20 2.19

Filtration rate, mL m-2

s-1

0.78 4.91 13.97 15.02 37.90

*D – raw diatomite, 1 – diatomite treated with 1% Na2CO3, 5 – diatomite treated with 5% Na2CO3,

10-diatomite treated with 10% Na2CO3, 20 – diatomite treated with 20% Na2CO3.

136

Electrophysical properties of heterostructures PbS/CdS

S.L. Prokopenko, G.M. Gunja, S.N. Makhno, P.P. Gorbyk



Synthesis and study of semiconductor nanoparticles of various metal

sulphides are developing rapidly due to the unique photoelectric properties and a

wide use of these compounds in various fields. Its heterostructures may be used

to develop sensor that can detect harmful gases at room temperature. Simple

chemical method was used to surface coating of PbS nanoparticles onto CdS

nanowires to get high surface area nano-heterojunction.

Nanowires CdS were synthesized by crystallization of 0.004 M

Cd(NO3)2∙4H2O and 0.008 M thiourea from ethylenediamine C2H4(NH2)2

(30 ml) at 393K. After cooling to the ambient temperature the precipitate was

washed with distilled water, centrifuged and dried at 330K. Heterostructures

PbS/CdS were grown following conventional ion-exchange method. To form

PbS on CdS nanoparticles, Pb acetate solution was added to the dispersed

solution of CdS nanoparticles. Here, the Cd-ions are replaced by Pb-ions.

Crystalline structure and crystallite size of PbS/CdS was determined using

X-ray method. Diffractograms were recorded on a diffractometer DRON-4-07

(Fig.).

20 30 40 50 60 70

Inte

nsi

ty (

a.u

.)

degree

1

2

3

Fig. X-ray diffraction patterns of

nanowires and heterostructures:

1 – CdS,

2 – 2.5%PbS/CdS,

3 – 20%PbS/CdS

Recording diffuse reflectance spectra in coordinates F(R) = f (λ, nm),

where F(R) – the Kubelka-Munk function, carried out on a Lambda-35

spectrophotometer (Perkin-Elmer). Synthesized CdS having band gap energy of

2.4 eV. The real (ε') and imaginary (ε'') components of the complex permittivity

in microwave range were measured using the interferometer at a frequency of

9 GHz. Values of permittivity of heterostructure 10%PbS/CdS is ε'=1.59 and

ε''=0.12. Low value can be explained by a low bulk density of the measured

samples.

137

Chromatographic study of fragmentation products of

polymethylphenylsiloxane

I. Protsak1, M. Studziński

2, Yu. Bolbukh

1, V. Tertykh

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Faculty of Chemistry, Maria Curie-Sklodowska University,


Modified disperse silicas with grafted phenyl groups are applied as the

stationary phases and carriers in chromatography, as the fillers and thickeners.

Application of the phenyl-containing siloxane oligomers and their mixtures with

alkyl carbonates for modification of silica surface is undoubtedly interesting,

because dimethyl carbonate was proved to be active in the processes of splitting

siloxane bond in polyorganosiloxanes.

The study of products of polymethylphenylsiloxane deoligomerization can

be carried out from more favorable positions in comparison with

polydimethylsiloxanes because the phenyl-containing fragments absorb in

UV-spectrum and it allows one to determine reaction products using the size-

exclusion chromatography. Reaction mixtures of polymethylphenylsiloxane and

dimethyl carbonate for chromatographic analysis were prepared in the volume

ratio 2:1. Reagents were mixed in a shaking incubator (Benchtop Incubator

Shakers: Innova®40) at 50 and 150°C for 10 min. Due to microprocessor

thermocontroller inside the chamber of the incubator the temperature remained

constant during mixing. After that, a sample of 0.2 ml was taken from each

reaction mixture which was dissolved in 1 ml of THF.

The obtained results showed that after the interaction of dimethyl

carbonate and polymethylphenylsiloxane both at 50 and 150°C two phenyl-

containing products are formed: oligomers with the molecular mass

10161098 Da and dimers with the molecular mass 282289 Da.

Acknowledgements



under REA grant agreement no°PIRSES-GA-2013-612484.

138

Synthesis of polyfunctional boron-gadolinium-containing

magnetosensitive nanocomposites

I.V. Pylypchuk1, A.L. Petranovska

1, S.P. Turanska

1,

О.М. Korduban2, P.P. Gorbyk1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2G.V. Kurdyumov Institute for Metal Physics, NAS of Ukraine,

36 Academician Vernadsky Blvd., Kyiv 03680, Ukraine

The aim of the work is synthesis of new polyfunctional magnetosensitive

biocompatible B- and Gd-containing nanomaterials and investigation of their

properties.

As known, boron and gadolinium isotopes have the largest sections of

capture of slow neutrons, and their immobilization on a surface of

magnetosensitive carriers enables to realize the targeted delivery and

accumulation of nanocomposites, to control the processes of their movement

and course of nuclear reactions by the method of nuclear magnetic resonance. In

this connection, an interest of researchers is drawn by the nanostructures based

on single-domain nanosized biogenic magnetite, boron and gadolinium

compounds [1], for which promising fields of use may be medicine, including

neutron capture therapy, production of nuclear materials and isotopes and so on.

The nanocomposites of core/shell type, containing in their composition

nanosized magnetite (core), gadolinium oxide and ortho-thiocarborane (shell)

were synthesized. Ortho-thiocarborane is a boron-organic compound

В10Н10С2Н2, the colourless crystalline substance with a weak camphor smell,

the melting temperature is 287–293°С.

The properties of the synthesized nanocomposites are discussed.

Acknowledgements

The work was carried out with support of goal complex program of fundamental

investigations of the National Academy of Sciences of Ukraine “Fundamental problems in

creation of novel nanomaterials and nanotechnologies” (project 38/16-N).

1. P.P. Gorbyk, L.B. Lerman, A.L. Petranovska, S.P. Turanska, I.V. Pylypchuk, in:

A.Grumezescu (Ed), Fabrication and self-assembly of nanobiomaterials, applications of

nanobiomaterials, Elsevier, 2016, p. 289–334.

139

Influence of external conditions on the textural characteristics of

fumed metal and metalloid oxides and those composites

V.M. Gun’ko

1, V.I. Zarko

1, O.V. Goncharuk

1, A.K. Matkovsky

1,

O.S. Remez1, J. Skubiszewska-Zieba

2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Maria Curie-Sklodowska University, 20-031 Lublin, Poland

The non-monotonic changes in the surface composition can influence the

properties of the final materials (fumed metal and metalloid oxides (FMO) filled

polymers, nanocomposites, etc.). Therefore, deeper insight into such relationships as

properties vs. bulk/surface composition of complex FMO (silica/alumina, silica/titania,

and alumina/silica/titania), in comparison with related individual FMO affected by

certain additional material treatments, is of interest from both theoretical and practical

points of view, especially structural and adsorption characteristics of FMO after high-

pressure cryogelation studied.

Fig. Pore size

(SCV/SCR) distribu-

tions of initial and

differently treated FMO

(a) A-300 initial, ball-

milled for 6 h and

cryogel prepared in a

cryobomb at 208 K and

1000 atm for 12 h, (b)

AST1 initial, MCA in a

micro-breaker for 30

min and cryogel using

sonicated 20 wt.%

aqueous suspension

frozen in a cryobomb at

260 K for 24 h and 77.4

K for 4 h at 1000 atm,

(c) initial SA and

alumina, (d) initial ST.

Acknowledgements



no 612484) for financial support.


140

Compatibilization effect in nanofilled polymer blends

N.M. Rezanova1, Y.O. Budash

1, V.Y. Bulakh

1, L.S. Dzubenko

2,

O.O. Sapyanenko2, P.P. Gorbyk

2

1Kyiv National University of Technologies & Design,

N.-Danchenko Srt., Kyiv 01011, Ukraine, [email protected] 2Chuiko Institute of Surface Chemistry, NAS of Ukraine,


Modification of polymers and polymer blends by adding nano-additives is

a promising trend in polymer technology since it allows to augment them with

complex of new properties by regulating phasic structure and functional

characteristics of additives.

Goal of this study was to research a joint effect of nano-additive and

compatibilizing agent on structural processes in polypropylene/plasticized

polyvinyl alcohol (PP/PVA) blends. Objects of this study were as follows:

mixture of PP/PVA with component ratio 30/70 wt. % blend, compatibilizing

agent – sodium oleate, 3.0 wt. %, nano-additive – silver/silica complex agent

(Ag/SiO2), 1.0 wt. %. Morphology of extrudates was evaluated by polarized

light microscopy. Interfacial tension (γαβ) was calculated using the data of

kinetic disintegration of PP fluid jets in PVA matrix.

It was established that studied additives influence interfacial conditions in

modified blends and allow to regulate its phase structure. Besides, nano-

additives causes compatibilizing effect greater than sodium oleate, even when

added in a larger proportion; γαβ decreases from 0.73 mН/m in initial blend to

0.38 and 0.51 mН/m in blends with Ag/SiO2 and compatibilizing agent

respectively. Simultaneous use of both additives is even more effective.

It was shown that in the flow of blend melts PP is extracted into separate

phase, creating microfibers, films and particles in PVA matrix. Modifying effect

of nanoadditive and compatibilizing agent facilitates better fiber creation: PP

microfibers prevail in extrudate‟s structure, its mass concentration rises up to

97.9% while its diameter decreases from 3.5 µm in initial blend to 1.1 µm in

four-component blend. Numbers of particles and films decrease too.

Maximum effect from joint performance of nano-additive and

compatibilizing agent can be explained by decrease in interfacial tension at

polymer-polymer and nanoparticle-polymer interface along with increase in

components affinity through creating specific connections between PVA

functional groups, Ag/SiO2 nanoparticles and sodium oleate molecules.

Obtained results will allow to form the fine nanofilled microfibers with uniform

diameters and complex of new properties.

141

Kinetic and equilibrium studies of doxorubicin adsorption on

MCM-41-type silica surface

N.V. Roik, L.A. Belyakova, M.O. Dziazko


17 General Naumov Str., Kyiv, 03164, Ukraine, [email protected]

Doxorubicin (Dox) belongs to the most widely used anticancer

chemotherapy drugs applied for medication of breast, head, liver, lung, stomach,

pancreas and other cancers. However, the long-term treatment with Dox is

associated with toxic side effects, risk of myelosuppression and dose-related

cardiotoxicity. Minimization of undesired damages of healthy cells without

reducing therapeutic action of Dox can be attained using drug carrier systems,

particularly silica nanoparticles.

In the present work, to elucidate mechanism of interaction between Dox

and silica surface, adsorption of antitumor drug on mesoporous silica

nanoparticles of MCM-41 type was studied depending on contact time, pH of

phosphate buffer solution, and Dox concentration.

The dependences of Dox adsorption on silica surface on the time of

contact were analyzed by equations of Lagergren and Ho-McKay. High

correlation coefficients indicate that the kinetics of Dox adsorption on silica

surface at pH 5.0 and pH 7.0 can be fitted by pseudo-second order kinetic model

better than by pseudo-first one.

The experimental data on equilibrium Dox adsorption on MCM-41-type

silica were described by the Langmuir, Freundlich, Redlich-Peterson, and

Brunauer-Emmet-Teller isotherm models. Taking into account estimated

adsorption parameters and results of comparative study of experimental and

calculated isotherms, it was concluded that BET model is the most appropriate

for prediction of Dox equilibrium adsorption on MCM-41 silica from phosphate

buffer solution with pH 7.0, whereas experimental data obtained at pH 5.0 can

be described by Freundlich model. The main contribution in the adsorption at

pH 7.0 belongs electrostatic interactions of ionized silanol groups and positively

charged amino groups of Dox as well as cooperative forces between molecules

of Dox. Contrary situation is observed at pH 5.0 when non-ionized surface

silanol groups lose their ability to interact with protonated aminogroups of Dox.

As a result, substantial lowering of MCM-41 adsorption capacity is registered at

pH decreasing.

Obtained results can be useful in prediction of the most suitable way of

silica surface modification depending on desired dosage and release kinetics of

Dox.


142

Modified titanium oxide coatings for environmental technologies

N.D. Sakhnenko, M.V. Ved’, A.V. Galak

National Technical University “Kharkiv Polytechnical Institute”

21 Frunze Str., Kharkiv, Ukraine, [email protected]

Ti alloys with the specially modified surface are the promising

biomaterials to be used in the implants. For that application, the surface should

exhibit the high hardness, good wear resistance, low friction coefficient,

porosity and the good compatibility to the body tissues. Those properties have

been attained by the formation of Ti oxides layer and its alloying. The plasma

electrolytic oxidation (PEO) seems to be the very promising since it does not

need the sophisticated facilities, allows to form various types of Ti oxide and to

incorporate different species into the layer by modification of electrochemical

parameters and of electrolyte chemistry.

In present work some results concerning the chemical composition,

topography and corrosion resistance of the oxide layers formed on Ti by PEO

treatment in pyrophosphate electrolytes at application of interelectrode potential

100 to 130 V and alloying by transition metals has been presented. As seen in

Fig., the layer formed by PEO consists of the big rounded grains with the holes

(doughnut like) and of the mixture of the fine acicular grains and the surface

morphology depends on the composition of oxide. Such a structure may provide

the good substrate for the body cells deposition.

TiOx TiOx∙CoOy TiOx∙MnOy

Fig. Appearance of the surface of Ti after the PEO treatments in the different electrolytes

It is noted that with increasing voltage the amount of Mn (Co) and the

amount of P and the P/Ti ration increase, whereas the amount of K decreases,

causing the higher corrosion resistance of alloying oxide systems both in alkali

and Ringer solutions. The PEO oxidation and Co incorporation in the oxide

layer shifts the open circuit potential Eocp into the positive direction up to

+0.8 V; for TiOx∙MnOy system up to +0.6 V comparing to the TiOx +0.1 V.

Thus the phase composition as well as the topography and the grain size

of the formed PEO-layers exhibiting the structure and properties promising for

the bio-application can be varied by the modification of the electrolytes.

143

Extraction of graphene oxide from natural coal

D.P. Savitskyi

Dumanskii Institute of Colloid and Water Chemistry, NAS of Ukraine,

pr. Vernadskogo 42, Kyiv 03680, Ukraine, [email protected]

In spite of such a wide range of using of graphene and its oxides, the main

raw material for the synthesis of these substances is graphite. However, other

minerals exist in nature, which contain in the structure of the graphene layers.

These minerals could be a potential resource to produce graphene oxide.

Comparative X-ray analysis of carbonaceous materials shows some similarities

between graphite and coal of high stage of metamorphism. For example, the

distance between the aromatic layers of a hexagonal crystal lattice of graphite is

under normal conditions (d = 0.335 nm), the diameter of the aromatic layer (La =

20 nm) layer height (Lc = 58 nm). When the carbon content is more than 92% in

coal the diameter of the layer is sharply increased (La> 1 nm), which

corresponds to 30 atoms in the aromatic layer, the layer height (Lc = 1.2–2.4

nm), the distance between the aromatic layers (d = 0,346–0,355 nm). In general,

the coal structure, unlike graphite is not crystalline and mesomorphic it is a

planar hexagonal networks of carbon atoms bound to carbon peripherally open

chains bearing functional groups. Due to the similarity of the structure of

bituminous coal high stage of metamorphism of graphite, the main idea of this

work was to deliberate destruction of the coal structure and formed into a

nanodispersed carbon structures in the form of a colloidal graphene oxide

solution. For graphene oxide extraction was used acid treatment HNO3 and

H2SO4 (4:1) anthracite (Donetsk basin) with high content of carbon (95.5%)

under the temperature 120 °C. Transmission electron micrographs of samples

are shown in Figure.

a b

Fig. TEM micrographs of anthracite (a) and graphene oxide (b)

144

An effective method for graphene nanoplatelets production by

anode oxidation of expanded graphite

Yu. Grebel’na1,2

, S. Makhno1, Yu. Sementsov

1


17 Generala Naumova Str., Kyiv 03164, Ukraine, [email protected] 2«TMSpetsmash», Ltd., 5 Viskozna Str., Kyiv 02660, Ukraine, [email protected]

Nowadays study of the best way of synthesis of graphene nanostructures

(nanoparticles, nanoplatelets, nanoflakes, graphene monolayers) is actual. An

effective cheap method for graphene nanoplatelets (GNP) production with

control sizes and separation on sizes was developed on the bases of anodic

oxidation of condensed expanded graphite (EG). EG is a cluster nanoscale

system containing cylindrical, conical, slit-like defects with a middle cross-

section size about 0.7-20 nm [1]. Repeated «pseudo-intercalation» of condensed

EG “opened” up nanoscale defects in the EG structure getting nanoparticle

dispersion in an aqueous electrolyte solution. GNP separation has been provided

by membrane of polypropylene textile (Fig. 1). The GNP has been prepared by

the secondary "intercalation" of the electrodes from EG foil (Ukrainian

standards 26.8-30969031-002-2002 TU U) in the alkaline electrolyte (KOH) of

low concentration, current changed from 6.0 to 60.0 mA/cm2.

а b c

Fig. 1. The scheme of

EG anode oxidation: (+)

- anode, (-) – cathode,

1 and 2 – polypropylene

membranes

Fig. 2. SEM images of GNP on gold surface (the substrate is inclined at an

angle of 60º to the electronic probe), a –GNP; b, c – magnification of GNP;

a and b, respectively (marked with squares);

LCS particle size analysis showed that the solution contain two types of particles

- large particles (13 µ), which was soon sedimented and about 450 nm being

more stable.The GNP could be organized themselves into 3-dimensional

structure under certain condition that could be important for understanding of

the GNP interaction with different type of surfaces (Fig. 2). The spectra of our

GNP are typical for GNP, graphene multilayers and graphite [2].

1. G.І. Dovbeshko, V.S. Kopan et al, Metalophysics and the latest technology, 27 (2005) 1001.

2. Yu. Sementsov, G. Dovbeshko, S. Makhno et al, IV Intrnational conference Nanobiophysics 2015:

Fundamental and applied aspects, 1-4 october 2015, Kiyv, Ukrane, Book of abstracts, p. 98.

145

The effect of pyrolysis of organic and organosilicon surface

groups in fumed silica on photoluminescent properties

A.V. Vasin1, D.V. Kisel

1, Yu.P. Piryatinsky

2, G.Ya. Rudko

1, E.G. Gule

1,

V.Ya. Degoda3, V.A. Tertykh

4, Y.M. Bolbukh

4, S.V. Sevostianov

4,

S.P. Starik5, V.S. Lysenko

1, A.N. Nazarov

1, D.V. Savchenko

6

1Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine, Kyiv, Ukraine

2Institute of Physics, NAS of Ukraine, Kyiv, Ukraine

3Physical faculty of Taras Shevchenko National University of Kyiv, Ukraine

4Institute of Surface Chemistry, NAS of Ukraine, Kyiv, Ukraine

5Bakul Institute of Superhard Materials, NAS of Ukraine, Kyiv, Ukraine 6Physico-Mathematical Faculty, National Technical University “KPI”

Light emission properties of the carbon incorporated silica nanopowders

(SiO2:C) are analysed and discussed. Nanopowders have been synthesised by

chemical modification of surface of fumed silica (BET specific surface area of

295 m2/g) with ethanol, n-buthanol, tetramethoxysilane and

phenyltrimethoxysilane followed by thermal annealing in the inert atmosphere

(vacuum, pure nitrogen). It was demonstrated that pyrolysis of grafted surface

chemical compounds results in the development of broad band

photoluminescence that covers a spectral range from near-UV to near-IR. PL

of SiO2:C nanopowders exhibited some general properties: emission spectra

are composed of at least three bands, and relative contribution of these bands is

strongly dependent on annealing temperature i.e. increase of annealing

temperature results in quenching of UV band and enhancement of visible

emission. Emission, excitation (including X-ray excitation) and kinetic

properties of PL have been thoroughly studied along with structural

characterization by FTIR, Raman scattering and electron paramagnetic

resonance spectroscopy. Origin of light emitting centres was assigned to

silicon-carbon and carbon precipitates on the silica surface. Detailed structural

configuration of light-emitting centres is discussed. It is demonstrated that

proper tuning of the composition and annealing temperature of nanopowders

allows one to reach the color rendering index of white light emission as high as

97 under excitation by near-UV radiation. Origin of broad band tunable light

emission is discussed in term of surface defects of native nanosilica and

carbon-containing sites.

146

Physical and mechanical properties of graphene/epoxy

composites

A.V. Sviatogor1, P.Y. Vezdenetskyi

1, S.V. Shulga

1, D.L. Starokadomsky

2

V.M. Ogenko1


32/34 prospect Akademika Palladin, Kyiv 03142, Ukraine,



Creation of new polymer materials and modification of physical, chemical

and mechanical properties of industrial large-tonnage polymer materials by the

introduction of nano-scale fillers (including carbon) is an urgent task and leads

to polymers with desired properties, such as optical transparency, electrical

conductivity, or anisotropic properties [1 -3]. We used nano-scale graphite

suspension in ethanol with a concentration of 4 g/l.

In order to obtain a composite epoxy resin we injected filler dispersion

(0-5 % of nanoscale graphite), organic solvent was distilled under vacuum at

100 °C.

For tensile and compression testing in resin, previously liberated from the

solvent and air bubbles 12.5 wt.% hardener (polyethylenepolyamine) was added

and then resulting composite material was poured into the form.

The impact of electrochemically produced nanoscale graphite on strength

epoxy-composite is ambiguous. On the one hand positive reinforcing effect of

the filler show itself on steel splice pull test, on the other hand gain little effect

was shown on fiberglass splice pull test.

Perhaps this is due to better adhesion to steel than to fiberglass. We

should note that nanoscale graphite epoxy-composite improved impact strength

and pull strength increased 2-3 times compared with the unfilled samples.

1. H. Kim, A.A. Abdala, C.W. Macosko. Macromolecules, 43 (2010) 6515.

2. U.S. Patent Application No.: 61/713,131, USA. Рorous heterogeneous carbon material

consisting of carbon nanotubes, carbon nanofibers, amorphous carbon and silica by

catalytic pyrolysis of cellulose acetate polyisocyanate copolymer / Dubrovina L., Ogenko

V., Naboka O., Volkov S., Enoksson P., Gatenholm P. – 12.10.12.

3. Y.Zhu, et al., Adv. Mater. 22 (2010) 3906.

147

The "electronic nose" sensor based on chemically modified

graphene structures

S.V. Shulga, P.Y. Vezdenetskyi, V.M. Ogenko

Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine,

32/34 prospect Akademika Palladin, Kyiv 03142, Ukraine,

[email protected]

Online detection of gas mixtures components is a popular problem in the

various sectors of industry, ecology, medicine, and science. Compared with

widespread sensors based on semiconducting metal oxides, nanotubes [1-2],

which main drawbacks is the high noise level, the use of graphene as a gas

sensitive layer will allow to detect different gases.

Due to the high charge mobility in the graphene we can suppose decrease

in the electrical noise level in the measured signal. The method of preliminary

chemical modification of sensitive layer surface leads to response difference of

the conductive substrate to a detectable substrate.

Partially oxidized graphene multilayered structures have been modified by

covalently bonded to the surface substituents containing amino groups, fatty

acid residues. The samples obtained in the form of dispersion in ethanol with a

dry concentration of 4 g/l were deposited on cellulosic material. Analog signals

(sensitive layer resistance dependence on mixture gas component concentration)

were translated into digital form with microcontroller Arduino, connected to a

PC.

It is shown that a short sensitive layer relaxation time of the array of sensors

provides an online detection of the gas mixture components and the partial

pressure of the individual components.

1. J. Zhang et al., Carbon 98 (2016) 708.

2. N.S. Ramgire Electronic Nose Based on Nanomaterials: Issues, Challenges, and Prospects

ISRN Nanomaterials, 2013 (2013) Article ID 941581, 21 p

148

Template synthesis of bifunctional mesoporous silica containing

phosphonic and carboxylic groups

V.V. Sliesarenko1, Y.S. Fetisova

2, O.A. Dudarko

1, Yu.L. Zub

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Faculty of Chemistry, National University of «Kyiv-Mohyla Academy»,

2 Skovorody vul., Kyiv 04655, Ukraine.

Bifunctional mesoporous silica containing phosphonic ≡Si(CH2)2PO(OH)2

and carboxylic [≡Si(CH2)2COOH] groups in the surface layer has been obtained

using the template method (template – Pluronic P123). Sodium silicate has been

used as a silica precursor instead of TEOS, which significantly reduced the cost

of the final product. For comparison, monofunctional analogues of synthesized

silica were obtained by techniques developed in [1, 2] (P1 - with phosphonic, C1

- with carboxylic groups). XRD patterns have a shape typical for mesoporous

silica SBA-15 type (Fig.). The presence of the silane with carboxylic groups in

the reaction mixture has also resulted in the formation of ordered structures with

a high percentage of functionalization (P1C2 compare with P3).

0,1 0,2 0,3 0,4 0,5 0,6

q, A-1

P3

P2

P1

0,1 0,2 0,3 0,4 0,5 0,6

q, A-1

C1P1C1

P2C1

Fig. XRD patterns of mono- (P1, P2, P3, C1) and bifunctional (P1C1, P1C2) samples.

The presence of complexing groups in the obtained samples has been

confirmed by IR and solid-state 13

C and 31

P NMR spectroscopy. The obtained

samples are characterized by developed porous structure (SBET = 520-630 m2/g)

according to the adsorption data.

1. V.V. Sliesarenko, O.A. Dudarko, Yu.L. Zub, G.A. Seisenbaeva, V.G. Kessler, P. Topka,

O. Solcova, J Porous Mater 20 (2013) 1315.

2. V.V. Sliesarenko, O.A. Dudarko, Yu.L. Zub et al., Colloid Journal 76 (2014) 1.

149

Lanthanide aminopolycarboxylates in hybrid silica

nanomaterials: synthesis and spectroscopic properties

S.S. Smola, E.N. Fadieiev, N.V. Rusakova

A.V. Bogatsky Physico-Chemical Institute, NAS of Ukraine,

Lyustdorfskaya doroga, 86, Odessa 65080, Ukraine, [email protected]

In this work we present the results of studies of lanthanide (Nd(III),

Eu(III), Tb(III), Yb(III)) aminopolycarboxylates in hybrid nanomaterials. In

recent years an increasing attention is paid to study of new fluorescent

compounds as active components of nanomaterials. Lanthanide compounds are

of particular interest among emitting substances due to narrow and characteristic

luminescence bands in the visible or near IR region of the spectrum and large

values of the excited state lifetimes. The modification of inorganic silica

matrices with lanthanide complexes can significantly improve their spectral-

luminescent characteristics. Such materials, made in the form of silicate glasses,

films or fibers, are promising for the development of lasers, optical converters

and amplifiers emitting in a wide spectral range.

Ethylenediaminetetraacetic and diethylenetriaminepentaacetic acids were

used as ligands. The samples exhibit an intense 4f-luminescence in the visible

and near IR region. The comparison of luminescent characteristics of hybrids

with covalent and non-covalent anchoring of the complexes in the silica matrix

was made. Spectroscopic properties of chelated lanthanide ions changing from

molecular complexes to nanomaterials were analysed.

Fig. 4f-Luminescence spectrum of Eu(III)-containing hybrid material

and a fragment of its structure

150

Selectivity of gas sensors based on Pd/SnO2 materials in

impulse heating mode

E.V. Sokovykh, L.P. Oleksenko, N.P. Maksymovych, I.P. Matushko,

V.P. Ruchko, O.P. Ripko

Department of Chemistry, National Taras Shevchenko University of Kyiv,

62a Volodymyrska Str., Kyiv 01601, Ukraine, [email protected]

The highest sensitivity of adsorption semiconductor sensor to different

gases can be usually achieved at different temperatures. However, the

temperature range of the high sensitivity of these gases normally found in a

certain temperature range, thus in the measurement of a gas in the presence of

others gases their mutual influence is observed. Impulse heating mode allows to

heat the sensors and provide a temperature change over a wide range.

The aim of this work was to study the selectivity of the sensors based on

nanosized Pd/SnO2 to CO, CH4, H2 in the impulse heating mode.

Figure shows the profiles of change in the conductivity of sensor based on

Pd/SnO2 in the gas-air mixtures with 1000 ppm CO, CH4, H2 in impulse heating

mode.

0 10 20 30 40 50 60 70 80 90 100

50

100

150

200

250

300

350

,

S

time, sec

1000 ppm CH4

1000 ppm CO

40 ppm H2

heating

cooling0,45 W

Fig. Change of the sensor conductivity in the impulse heating mode (N=0.45 W) in gas-air mixtures

with 1000 ppm CO, 1000 ppm CH4 and 40 ppm H2

As can be seen from the Fig., for all analyzed gas the individual change of

conductivity can be used as characteristic to identify the gas. Value of maximum

conductivity of the sensor in designated period and slope or curve curse can be

used to determine the presence of different gases that are analyzed in impulse

heating mode.

151

Synthesis and properties of thick nanocrystalline films of M-type

barium ferrite and nickel ferrite with spinel structure

E.D. Solovyova, О.P. Fedorchuk, А.G. Belous


32-34 Acad. Palladina Ave., 03680, Kyiv, Ukraine, [email protected]

Current trends in communications and information transmission require

improvement of the existing UHF components and advancement into new

frequency bands [1]. A promising trend for technical applications is the

development of magnetically microwave (MW) materials for further their use in

active and passive components of electronic systems. The composite

heterostructures, comprising of polycrystalline α-Al2O3 bulk dielectric resonator

with a layer of high-density thick (thickness > 10 µm) films of ferromagnetic

materials can be used as such MW materials. In this work M-type barium ferrite

(BaFe12O19) and nickel ferrite (NiFe2O4) with spinel structure were used as

ferromagnetic component. For the manufacturing of such heterostructures the

film should have high density and homogeneity. One of the promising

techniques for thick crystalline films deposition is a tape-casting [2].

The aim of this work is to develop the high-density high-quality NiFe2O4

and BaFe12O19 thick films on the surface of the α-Al2O3 bulk dielectric

resonator.

Required organic suspensions for synthesis thick high-density high-

quality ferrite films were developed. Using these suspensions, thick (30-50 µm)

films were deposited on the surface of an α-Al2O3 dielectric resonator by tape-

casting method. The temperature range for the pre-heat treatment of the films

and its annealing conditions have been defined (Т = 450-5000С, thermal-shock

conditions). The microstructure properties of obtained thick ferrite films were

studied (Fig.).

Fig. The microstructure of the cross-section (a) and surface (b) of the BaFe12O19 film at T = 12000С

(SEM)

1. J.D Adam et. al., IEEE Trans. MTT. 50 (2002) 721.

2. V.G Harris et. al., J Magn Magn Mater 321 (2009) 2035.

152

Nanoporous and microporous thermostable

polyamidoimide/polyurethane films: structure and properties

O.M. Starostenko1, O.P. Grigoryeva

1, A.M. Fainleib

1, S. Koutsoumpis

2


48 Kharkivske shose, Kyiv 02160, Ukraine, [email protected] 2National Technical University of Athens, Physics Department,

Iroon Polytechneiou 9, Zografou Campus, Athens 15780, Greece,

[email protected]

Porous polyimide-based film materials are widely used as thermostable

membranes for separation of gases or liquids at high temperatures.

Polyurethanes having excellent physical-chemical and mechanical

characteristics can be used as effective modifier for polyimide membranes.

Thus, obtaining film materials from PI/PU blends allows increasing elasticity

and permeability, which are important in their application in separation

techniques.

In this work the series of polyamidoimide/polyurethane (PAI/PU) film

materials were prepared by in situ synthesis from polyamic acid (based on

trimellitic anhydride chloride and 4,4′-methylenedianiline) and PU (Mw≈40 000,

based on 4,4′-diphenylmethane diisocianate and oligobuthylene glycol adipate)

in N-methylpirrolidone (NMP) solution (20%) by heating from 25 to 250 ºC at

ramp of 0.5 oC/min followed by partial extraction of PU component in methyl

ethyl ketone and characterized. The polymer PAI/PU films with PU content c =

5, 15, 20, 25 and 30 wt.% were synthesized. The morphology and porous

structure of PAI/PU blends developed were confirmed by SEM and DSC-based

thermoporometry techniques. The formation of heterogeneous materials was

observed, and increasing amount of the PU component led to higher size of PU

domains in the system. It was found that the higher the PU amount removed

from the PAI/PU precursor the higher porosity of the resulted films. The average

pore diameters and pore volume values were found in the range of 36–46 nm

and 0.15–0.19 cm3·

g-1

, respectively, depending on the PU content. It was

established that porous PAI/PU films had higher thermal stability compared to

the precursor non-porous samples.

153

Characterization of CeO2–ZrO2/SiO2 nanocomposites

by Raman, XPS and HREM techniques

I. Sulym1, D. Sternik

2, L. Oleksenko

3, L. Lutsenko

3,

M. Borysenko1, A. Derylo-Marczewska

2



pl. Maria Curie-Skłodowska 3, 20-031 Lublin, Poland 3Department of Chemistry, Taras Shevchenko National University of Kyiv, 62a

Volodymyrska Str., Kyiv 01601, Ukraine

Ceria-based composite oxides, particularly ceria-zirconia, in different

stoichiometries, are effective supports or catalysts for important industrial

reactions and reactions directed towards environment protection, such as

oxidation of CO with O2 in the presence or absence of H2, cracking of heavy

oils, catalytic combustion of hydrocarbons et al.

The present work focuses on investigations of the influence of changes in

phase composition on the structural properties of CeO2–ZrO2/SiO2

nanomaterials and on their catalytic performance in CO oxidation in the

presence of H2. Morphology and structural peculiarities were characterized

using Raman spectroscopy (RS), X-ray photoelectron spectroscopy (XPS) and

high-resolution transmission electron microscopy (HRTEM).

CeO2–ZrO2/SiO2 nanocomposites were prepared by liquid-phase method

with the use of Zr(acac)4 and Ce(acac)3 solutions in CCl4, fumed SiO2

(S = 283 m2/g), and then subjected to thermal treatments at 550 °С. The content

of ZrO2 was constant and equal to 10 wt. % and the content of grafted CeO2 was

varied from 3 to 10 wt. % (CZS1 and CZS2, respectively).

Raman measurements indicated the presence of oxygen vacancies in the

case of CZS2 and an absence displacement of oxygen ions from their normal

lattice positions in both of the samples. XPS data revealed a significant quantity

of Ce3+

ions present in the composites, CZS2 composite was reacher in Ce3+

ions. In the case of CZS systems the TEM–HRTEM results showed the presence

of well-dispersed Zr–Ce–oxide nanocrystallites of the size ~ 8–36 nm over the

surface of amorphous SiO2. The prepared materials were tested in catalytic

reaction of CO oxidation in the presence of H2 and it was shown that CZS2

sample had better performance than CZS1 one.

Acknowledgements

The authors are grateful to European Community, Seventh Framework Programme (FP7/2007–2013), Marie

Curie International Research Staff Exchange Scheme (IRSES grant No 612484) for financial support of this

work. The research was partly carried out with the equipment purchased thanks to the financial support of the

European Regional Development Fund in the framework of the Polish Innovation Economy Operational

Program (contract no. POIG.02.01.00-06-024/09 Center of Functional Nanomaterials).

154

β-Cyclodextrin-MCM-41 silica as promising adsorbent for the

trace amounts removal of aromatics from water

I.M. Trofymchuk, N.V. Roik, L.A. Belyakova



MCM-41 silicas are ordered mesoporous materials with well-defined

uniform pores, high surface area and pore volume. The presence of highly

reactive silanol groups in sufficiently large and uniform pores opens up the

possibility for introduction of various organic functional moieties into the

surface layer of MCM-41. Among a large number of organic compounds for

silica functionalization, cyclodextrin (CD) macromolecules are very promising

because of their ability to form inclusion complexes with chemicals of suitable

geometry and functionality [1].

In this research, we realized sol-gel synthesis of β-CD-MCM-41 silica

using β-CD-containing silane in the presence of ionic template

(cetyltrimethylammonium bromide). β-CD-silane was prepared by modification

of 3-aminopropyltriethoxysilane with oligosaccharide activated by

N,N'-carbonyldiimidazole. The successful incorporation of CD moieties in silica

surface layer was verified by means of FT-IR spectroscopy and chemical

analysis. Obtained β-CD-MCM-41 silica was characterized by X-ray diffraction,

transmission electron microscopy, and low-temperature adsorption-desorption of

nitrogen.

Adsorption of benzene from aqueous solutions onto the surface of

β-CD-MCM-41 silica was studied as the function of time and equilibrium

concentration. Langmuir and Freundlich models were used to evaluate

adsorption processes and parameters. It was shown that in the region of small

equilibrium concentrations the higher adsorption of benzene is observed for

β-CD-MCM-41 silica in comparison with MCM-41 silica. This signifies that

β-CD-MCM-41 silica can act as effective adsorbent at low concentrations of

aromatics. The proposed synthesis approach may be applicable for obtaining of

ordered β-CD-containing functional materials with high affinity to aromatic

compounds of suitable geometry for water treatment.

1. E.M. Del Valle, Process Biochem. 41 (2004) 1033.

155

Anti-corrosion and anti-fungal sulfur-zeolite nano-additives for

concrete for special purposes

G. Tsintskaladze, O. Lomtadze, M. Burjanagze, T. Sharashenidze,

V. Gabunia, N. Shalvashvili

Ivane Javakhishvili Tbilisi State University,


31 A. Politkovskaya Str., Tbilisi 0186, Georgia,

[email protected]

In order to increase productivity of agricultural animals creation of more

favorable sanitary and hygienic conditions of their keeping is of great

importance. In connection with it, the design and quality of the floor is essential,

because the floor is the only element of the enclosing structures of livestock

buildings with which the animal comes in direct contact. For the construction of

floors of livestock buildings various materials of construction are used.

Significant place between these materials is occupied the concretes based on

cement, both in the pure form and with various additives and fillers.

During operation, floors in livestock rooms are exposed to the cumulative

influence of various physical, chemical and biological factors that leads to their

destruction. At the same time specific peculiarities of operation, in conditions of

livestock houses, can favor the allocation of chemicals from the structural

materials (with various additives) to the environment. They affect on the animal

organism during the direct contact or via the respiratory and digestive systems.

The new sulfur - zeolite nanomaterial by means of nano technologies have

been obtained. The structure and adsorption properties of the resulting material

were examined by X-ray diffractometry, infrared spectroscopy and absorption

methods. Concrete samples were prepared from the sulfur-zeolite nanomaterial,

their resistance against different cultures of mold fungi have been determined.

On the basis of obtained results, sulfur-zeolite nanomaterial can be used as a

cement additive for preparation of biocidal and anti corrosive concretes of

special purpose.

156

Zeolitic nanomaterials accumulated with nitrate ions in

agriculture

G.P. Tsintskaladze, T.V. Sharashenidze, M.A. Dzagania, N.B. Pirtskhalava,

N.O. Burkiashvili

Ivane Javakhishvili Tbilisi State University,


31 A. Politkovskaya Str., Tbilisi 0186, Georgia,

[email protected]

Part of the nitrogenous fertilizers are either washed out of the ground or

decomposed after introduction into the soil. Besides of the economic expenses,

the process causes contamination of agricultural products and environment

pollution that is ecologically dangerous.

In order to reduce negative effects of nitrogenous fertilizers, to minimize

their expenses and increase adsorption of nitrogen by plant, we devised a new

nano-technological method that enables to introduce nitrous fertilizers,

particularly ammonium nitrate, in the structure of natural zeolites. The obtained

nano-material „‟inorganic capsule-molecular sieve” might be used as

nitrogenous fertilizer enabling regulation of sequential transfer of nitrates into

the soil, minimization of the expenses of the fertilizer and reduction of ground

waters pollution by nitrates.

Investigation of the structures and properties of the new zeolite nano-

materials accumulated with nitrates was carried out by the chemical analysis, IR

spectroscopy and adsorption methods. On these bases it has been proved that the

zeolite structure has not been changed after the introduction of ammonium

nitrate into the pores of the zeolites at certain temperature by nanotechnology.

The mechanism of the sequential transfer of ammonium nitrate from the zeolite

structure has been established.

The obtained fertilizer is of the prolonging character and is ecologically

safe. Besides, it regulates adsorption of water, nitrogen, phosphor, potassium

and other microelements.

157

Novel nanoporous polycyanurates created using ionic liquids as

porogen

А.M. Fainleib1, O.M. Starostenko

1, A.V. Vashchuk

1, O.P. Grygoryeva

1,

S.P. Rogalsky2, D. Grande

3


48 Kharkivske shose, Kyiv 02160, Ukraine, [email protected] 2Institute of Bioorganic Chemistry and Petrochemistry, NAS of Ukraine,

50 Kharkivske shose, Kyiv 02160, Ukraine, [email protected] 3Institut de Chimie et des Matériaux Paris-Est,

UMR 7182 CNRS – Université Paris-Est Créteil Val-de-Marne,

2, rue Henri Dunant, 94320 Thiais, France, [email protected]

Cyanate ester resins (CERs) are high performance materials for airspace

and electronic applications, especially as polymer matrixes, working under

severe conditions (high temperatures, corrosive media) [1]. Recently several

papers have been published [2, 3] on generation of porous structure in

crosslinked CERs (polycyanurates) using different techniques. Ionic liquids

(ILs) have recently attracted widespread interest as green solvents due to their

unique properties, such as negligible vapour pressure, electrochemical and high-

temperature stability, incombustibility, recyclability. Another application of ILs

is as effective and reusable porogens in some polymeric materials [4]. This work

is focused on the new approach ‒ synthesis of porous CERs using 1-heptyl-

pyridinium tetrafluoroborate ionic liquid both as porogen and solvent.

The morphology and porosity parameters such as pores diameter and pore

size distribution of the samples studied were estimated by Scanning Electron

Microscopy equipped with an energy dispersive X-ray spectrometer and DSC-

thermoporometry, respectively.

It was found, that the average pore diameter values were found in the

range of 45-60 nm with pore size distribution of ~20-180 nm depending on the

porogen content (20-40 wt.%, correspondingly). It should be noted that synthesis

was carried out without using any conventional solvents and specific catalysts,

and that the ionic liquid used could be utilized repeatedly.

1. A. Fainleib (ed.). Thermostable polycyanurates. Synthesis, modification, structure and properties,

Nova Science Publisher: NY, 2011.

2. A. Fainleib, K. Gusakova, O. Grigoryeva, O. Starostenko, D. Grande, Eur. Polym. J., 73, (2015)

94.

3. D. Grande, O. Grigoryeva, A. Fainleib, K. Gusakova, Eur. Polym. J., 49, (2013) 2162.

4. D. Mecerreyes (ed.). Applications of ionic liquids in polymer science and technology. Springer-

Verlag: Berlin, Heidelberg, 2015.

158

Calorimetric study of collagen-water systems over wide range of

hydration levels

O. Vassiliadi, A. Panagopoulou, A. Kyritsis, P. Pissis

National Technical University of Athens,

Zografou Campus, 15780, Athens, Greece

The scope of this work is the study of the thermal transitions of protein

and hydration water in the case of hydrated collagen over wide range of

hydration levels. For this purpose, differential scanning calorimetry (DSC) (in

the temperature range from -120 to 230oC) was employed. The collagen samples

were in the form of compressed solid pellets, hydrated by equilibration above

saturated salt solutions in a hydration range from practically dry protein pellets

to 25 wt. % in water.

The crystallization and melting events for the hydrated samples were

studied by DSC. No glass transition was detected in the experimental

temperature range. Two main crystallization peaks were recorded: 1) The first

one was detected for all of the samples. It is very broad and exhibits a

crystallization temperature Tc ~ -5oC. The crystallization enthalpy, ΔHc, depends

on hydration level in a non linear way. 2) The second crystallization peak is

centered at about -450C, was detected for all of the samples but vanishes after

the evaporation of water during heating over 100oC. The corresponding ΔHc, is

almost stable and depends on hydration level in a non linear way. During

heating, a broad melting peak was observed for all of the samples with a melting

temperature Tm ~ 0oC, resembling the melting of bulk water. Its shape is

complex and seems to include more than one contributions.

The broad crystallization peak may be attributed to crystallization of

protein segments. This assumption is supported by the fact that this peak still

exists, even after the evaporation of water above 100oC or the denaturation of

collagen at about 2300C. The crystallization peak at lower temperatures possibly

corresponds to the crystallization of primary form of ice crystals confined within

the protein structure. Although this peak exists even in the case of the dry

sample, it disappears, as it was mentioned above, after evaporation of strongly

bound confined structural water over 100oC.

As a conclusion, DSC measurements showed that a small part of water

crystallizes during cooling while crystallization of protein segments occurs at

subzero temperatures.

159

Effect of mechanical treatment of nanoscale hydrophilic and

hydrophobic silicas on their thickening effidency in a nonpolar

medium

E.F. Voronin, L.V. Nosach, V.M. Gun’ko, M.V. Borysenko



Nanoscale fumed silica is used as an effective thickener of different both

polar and non-polar media. It is considered [1] that its high thickening properties

are caused by the formation of secondary structures between nanoparticles that

are coated with the silanol groups and forming mutual hydrogen bonds. Due to

substitution of silanol groups by organic ones, the thickening capability of

fumed silica decreases [1].

Mechanical treatment of fumed silica in a ball mill results in changes in its

morphological parameters, but a substantial portion the surface silanol groups

retained [2]. The aim of the study is to elucidate how mechanical treatment

effects on the thickening ability of the hydrophilic (A300) and hydrophobic

(AMD) fumed silica (SBET = 300 m2/g; Kalush, Ukraine). The pharmacopeia

vaseline oil was used as a non-polar medium. Viscosity measurements were

carried out with a ICI CONE & PLATE viscometer (Research Equipment). The

mechanical treatment of the fumed silica was carried out in a ball mill for 5 h

(A300-MT and AMD-MT samples). The thickening properties of the samples

were estimated by the concentration of gelation (CG).

Concentrations of gelation for the samples А300 and AMD were

respectively 9 and 5% by weight. The ratios of these values are close to those

given in the literature [1]. Mechanical treatment of the hydrophilic silica

considerably (5 times) lowered its thickening properties. To CG value of the

A300-MT sample was 26%. It has been found that the thickening capability of

mechanically treated hydrophobic silica AMD-MT is also decreased by

2.5 times. Its CG value was 23%.

Acknowledgements


(FP7/2007-2013), Marie Curie International Research Staff Exchange Scheme (grant no.

612484).

1. N.N. Kruglickij, V.Ja. Kruglickaja. Disperse structurs in orcanic and silicon mediums. Naukova Dumka:

Kiev, 1981, 316 p. (in Russian)

2. L.V. Nosach, E.F. Voronin, V.M. Gun‟ko, V.V. Sidorchuk, J. Skubiszewska-Zięba, R. Leboda. IR study of

nanosilica geometrically modified on mechanoactivation. – Int. Symp. devoted to the 80th anniversary of

Academician O.O.Chuiko "Modern problems of surface chemistry and physics", Kyiv, 2010, Progr. & Abstr.

Book, p.213-214.

160

Composition and morphology of Fe-Co-Mo electrolytic alloys

Y.I. Sachanova, I.Yu. Yermolenko, N.D. Sakhnenko, M.V. Ved

National technical university “Kharkiv polytechnic institute”,

Frunze 21, Kharkov 61002, Ukraine, [email protected]

Thin layers Fe-Co-Mo are promising high magnetic and catalytic

properties. Paper deals with the influence of electrolysis parameters on the

composition and morphology of above systems.

The coatings Fe-Co-Mo were deposited in direct current (dc) mode on the

substrate made of copper from the citrate bath at a concentration ratio of

electrolyte components (Fe3+

): (Co2+

):(MoO42–

) as 2: 2: 1 containing 0.08–0.09

mol/dm3 MoO4

2–. The surface treatment includes polishing, degreasing, etching

and thoroughly rinsing. Electrolysis was carried out at a temperature 20–25°C.

It was obtained uniform matt coating with iron content 53 at. %, cobalt

32 at.% and molybdenum 15 at.% at cathodic current density ic 2–3 A/dm2.

Molybdenum content in the alloy is increased up to 25 at.% with a simultaneous

decrease of Fe to 47 at.% with an unchanged cobalt content at the level of 30–32

at.% at higher current densities up to 5–6 A/dm2. This demonstrates the

competitive reduction of the iron and molybdenum in cathodic process. Such a

change in the quantitative composition of the coatings is reflected in the surface

morphology which varies from a crystal (Fig. a) to fine-globular (Fig. c). At the

same time, one can see decreasing current efficiency from 70 to 60% with the

rise of current density associated with an increase in the hydrogen evolution

reaction contribution in the total cathodic process.

The coatings composition, at%:

Fe – 53; Co – 32; Mo – 15 Fe – 48; Co – 30; Mo – 22 Fe – 47; Co – 28; Mo – 25

a b c

Fig. The morphology of the coating alloy Fe-Co-Mo at a cathodic current density ic, A/dm2:

3 (a), 4 (b), 5 (c). Magnification ×1000

It was shown that the variation of electrolysis parameters allows obtaining

coatings with an extended range of content alloying components, which allows

controlling the composition and properties of the coatings.

161

Biochemical tests of new lignin enterosorbent

K.G. Yunuskhodjaeva

1, M.G. Ismailova

2, B.A. Imamaliev

2

1Uzbek Chemical and Pharmaceutical Research Institute,

40 Do’rmon yo’li Str., Tashkent 100125, Uzbekistan, [email protected] 2Tashkent Pharmaceutical Institute,

45 Oybek Str., Tashkent 100015, Uzbekistan

One the main criterion for severity of pathological process of different

etiology is the level of intoxication related to decrease of detoxicative functions

of body systems [1].

The purpose of our research is to study the adsorption activity of Zerotox,

the new lignin enterosorbent, with respect to a number of toxic metabolites.

Adsorption activity of the drug has been studied based on its capability to clear

dated human blood plasma from toxic metabolites and decomposition products

in vitro. Reduction of decomposition products in comparison to base value has

served as the evaluation criterion. Biochemical researches have been conducted

on the HUMALYZER Primus biochemical analyzer.

Research results have established that the Zerotox drug reduces the toxic

metabolites content in dated plasma on the 30th, 60

th and 120

th minutes of the

testing in a statistically accurate way (refer to Table below).

Toxic metabolites sorption dynamics (Мtm; р=0.05; n=6)

Item Base level 30th

minute 60th

minute 120th

minute

Total protein

g/l

80.24

(76.40†83.94)

60.92

(60.30†61.56)

58.31

(56.05†60.56)

59.07

(56.51†61.62)

Urea

mmol/l

11.65

(9.98†13.32)

4.88

(3.25†6.52)

6.06

(4.65†7.47)

7.29

(5.85†8.74)

Creatinin

mcmol/l

120.78

(117.12†124.48)

80.33

(76.79†84.16)

82.36

(78.60†86.11)

87.65

(78.02†97.27)

Total bilirubin

mcmol/l

16.44

(14.27†18.60)

8.47

(5.73†11.20)

10.29

(7.48†13.09)

6.43

(3.45†9.40)

Direct bilirubin

mcmol/l

20.68

(20.98†24.38)

15.09

(7.81†22.37)

16.99

(13.29†20.69)

9.23

(5.88†12.58)

Hence, analysis of the obtained data has showed that mentioned

enterosorbent demonstrates sound sorption performance with respect to toxic

components the content of which increases during pathological changes in body.

1. V.G. Nikolaev, S.V.Mikhalovsky, N.M. Gurina, Modern Entherosorbents and Mechanisms of

Their Actions, Efferent therapy, 2005, р. 11, 3-18.

162

Chemical modification of polystyrene surface

for ELISA applications

G.V. Beketov, V.P. Kyslyi, A.I. Liptuga, O.V. Shynkarenko

Lashkaryov Institute of semiconductor physics, NAS of Ukraine,

41 Nauk Pr., Kyiv 03028, Ukraine, [email protected]

We are reporting on simple, inexpensive, and environment-friendly

method for hydrophilization of polystyrene surface which has strong potentiality

for use in manufacturing of enzyme-linked immunosorbent assay (ELISA)

plates as an adsorption-promoting technique.

ELISA is a biochemical assay widely used in immunological diagnostics

for detection of peptides, proteins, antibodies, hormones etc. It is an essentially

heterogeneous assay, in which separation of some component of the liquid

analytical probe is performed by adsorbing them specifically onto a physically

immobilized solid phase. The solid support is usually constructed as a multiple-

well polystyrene plate known as the "ELISA plate". The critical issue in

manufacturing the ELISA plates is achievement of an optimal adsorption

capacity and affinity for the specified biomolecules used as a ligand. The world-

leading brands (TermoFisher Nunc, Corning etc.) widely use proprietary

hydrophilization technologies for this purpose [1].

Availability of an independently developed hydrophilization technology

will promote competitiveness of emerging local manufacturers of ELISA-related

products and facilitate access to advanced medical care for all sections of the

population [2].

Results of investigation of the hydrophilized polystyrene surfaces using

FTIR-spectroscopy, scanning probe microscopy, contact angle measurements,

and adsorption properties for selected classes of biomolecules are presented.

Possible mechanisms of hydrophylization are discussed on the ground of

characteristic reactions of the phenil core and formation of polar functional

groups at the polystyrene surface.

O.V. Shynkarenko gratefully acknowledges partial support provided by the Swiss

National Science Foundation (SNSF, Bern) under grant No. IZ73Z0_152661 (SCOPES).

1. Nunc surfaces - for passive adsorption. Nunc No. 69909 - Ver. 1.1 - YNI/CT 01-2005.-

www.nuncbrand.com.

2. Local Production for Access to Medical Products: Developing a Framework to Improve

Public Health. World Health Organization, ISBN 978 92 4 150289 4 -

www.who.int/phi/publications/Local_Production_Policy_Framework.pdf.

163

Influence of photochemical aging on biocidal activity of

Ag-containing silica


1, O.I. Oranska

1, O.M. Zaichenko

2,


2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Zabolotny Institute of Microbiology and Virology, NAS of Ukraine,

154 Acad. Zabolotny Str., Kyiv 03143, Ukraine

Highly dispersed silica composites, containing nanoparticles of metal

silver and its compounds on their surface, are considered to be promising

materials for improving the fungicidal properties of plastics and lacquer coating.

In most cases, silver nitrate is used for synthesis, which decomposes under the

synthesis conditions to metal state and oxide structures. It is known that silver

compounds are photosensitive and under the influence of visible light are

reduced to metal state. During the process of Ag/SiO2 synthesis, a number of

compounds may be formed on the surface, which composition and crystalline

structure may be changed under the action of visible light. Thus, changes in the

Ag/SiO2 were registered using XRD and UV-Vis methods. The intensity of the

reflections of metallic silver for the sample, containing 1.0 mmol of Ag per

gram SiO2, increased by 2.7 times after holding it under light for 30 days.

Changes in the structure of the compounds after photochemical aging was

observed for binary systems Ag-Cu/SiO2 too. The biocidal activity of the

samples towards series of micromycetes is shown in the Table. Biocidal activity

was determined by the wells method in Petri dishes using appropriate agar

medium at 26 ± 1 °C, and efficacy was assessed by the measuring the diameter

of the zones of inhibition of culture growth and expressed in mm as the average

for three experiments.

Samples Diameter of growth inhibition zone of micromycetes, mm

Pa

ecil

om

yce

s

va

rio

ti

Pen

icil

liu

m

fu

nic

ulo

sum

Ap

erg

illu

s

terr

eus

Asp

erg

illu

s

nig

er

Asp

erg

illu

s o

ryza

e

Pen

icil

liu

m

ch

ryso

gen

um

Tri

cho

der

ma

vir

ide

Sta

chyb

otr

ys

ch

art

aru

m

Pen

icil

liu

m

au

ran

tio

-g

rise

um

002 Ag 18 35 32 21 14 40 17 30 30

002 Ag-a* 25 33 24 20 14 30 25 21 29

001 AgCu 19 21 29 25 14 29 23 17 21

001 AgCu-a* 24 16 21 22 14 22 23 24 18

*-a – is aged sample.

Thus, the modified silica showed both increasing and reduction of antifungal

efficiency after photochemical aging, depending on the nature of micromycetes.

164

Synthesis and electrical properties of copper/silica-containing

carbon nanocomposites

V.M. Bogatyrov, S.M. Makhno, M.V. Galaburda, O.I. Oranska,

Yu.I. Gornikov, P.P. Gorbyk

Chuiko Institute of Surface Chemistry, NAS of Ukraine, 17 General Naumov Str., Kyiv 03164, Ukraine, [email protected]

Polymer composites with various electro and thermo-physical

characteristics are in demand in the development of devices of electronic

equipment for various purposes. Adjustment of these characteristics is achieved

not only by nature of the polymer, but also by the use of functional fillers. To

solve the problem of increasing the thermal conductivity of polymeric

composites while reducing electrical conductivity, we have synthesized

composite samples of filler based on the modified nanosized copper powder.

Initial sample of the powder with a crystal size of copper of 50 nm (Cu-1)

was synthesized by pyrolysis of a mixture of copper acetate, pyrogenic silica

and poly(ethylene glycol) (using weight ratio of 15:1:3, respectively), under

inert atmosphere at 700 ° C. Modified sample Cu-2 was obtained via modifying

the initial sample Cu-1 by polysiloxane liquid (PMS-1000) at 300 °C. Cu-3

sample was obtained using additional modification of Cu-2 by silicone lacquer

KO-075. All samples were characterized by X-ray diffraction, FTIR, TG and

DTG analyses. The electrical conductivity measurements were performed at low

frequencies at room temperature two-pin method using immittance meter E7-14.

Thermal conductivity of the samples was measured by thermal conductivity

meter IT-λ-400 in the temperature range 15-200 °C

Table. Thermal and electrical conductivity of the samples

Samples Electrical conductivity

σ, om-1

·cm-1

Thermal conductivity

λ, W/m·.K

Cu-1 0.03572 0.19

Cu-2 0.02030 -

Cu-3 0.00884 0.75

Obtained results indicate the decrease in the electrical conductivity of the

composite powder with increasing of the modifier content. The results of

thermal conductivity measurement are more controversial. Methodological

difficulties in the preparation of the powders, which are associated with the

different nature of the surface of the copper particles, and they do not allow to

uniquely interpret the given value of thermal conductivity due to different

porosity of the samples after pressing at the pressure of 20 MPa.

165

Chitosan-functionalized spherical nanosilica matrix as

drug delivery system

K.O. Filatova1,2

, V. Sedlarik2

, A. Di Martino

2, A. Golovan

1,

T.V. Krupska1, V.V. Turov

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Center of Polymer Systems, University Institute, Tomas Bata University in Zlin,

T. Bati 5678, Zlin 76001, Czech Republic

Since the first report of surfactant-templated synthesis in 1992 [1], silica-

based materials with tuneable structures, high surface areas, large pore volumes

and different functionalized groups have attracted much attention for their

potential applications as drug delivery devices, sorbents and catalysts [2]. Silica-

chitosan based materials could provide additional amenities to encapsulate and

reach control release of different compounds [3].

We performed synthesis of spherical silica using an ammonia-based

catalysis method under highly dilute and low surfactant conditions and TEOS as

a silica source. 3-Aminopropyltriethoxysilane was used to functionalize SS with

next grafting with chitosan (Si-Cs) and chitosan grafted polylactic acid (Si-Cs-g-

PLA). Encapsulation efficiency and release kinetic of doxorubicin were

estimated.

Fig. Release profile of Doxorubicin from Si-Cs (left) and Si-Cs-g-PLA (right) in different dissolution

media at pH 2.0 (1), 7.0 (2) and 8.0 (3). Each data point is the mean of three determinations

1. C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature, 359 (1992) 710.

2. S.Wang, Microp. Mesop. Mater., 117 (2009) 1.

3. W.T. Liu, Y. Yang, P.H. Shen, Express Polymer Letters, 9 (2015) 1068.

166

Stabilization of Enoxil in the polymer matrix

M.V. Galaburda1, V.M. Bogatyrov

1, T. Lupascu

2, N.V. Kokosha

3, I. Povar

2


17 General Naumov Str., Kyiv 03164, Ukraine 2Institute of Chemistry, Academy of Sciences of Moldova,

3 Academiei Str., MD 2028, Chisinau, Republic of Moldova. 3“International Center for Medical Technologies Implementation” ltd.

Enoxil is a complex of biologically active substances obtained by

oxidation of grape seed tannins. It is a mixture of monomeric derivatives of

catechin, epicatechin in the free form and esterified with gallic acid as well as

with peroxidic compounds. Enoxil is characterized by high antioxidant activity

and amplified therapeutic properties. However, because of its high

hygroscopicity, there is a problem for its storage while saving the main

properties of the complex [1].

The aim of this work is to stabilize Enoxil in the matrix of polyacrylamide

(AQUALAN, Ukraine, synthesized for contact lenses). This hydrogel is

obtained by radical co-polymerization of monomers in the presence of

dispersion medium and represents the first type of modified hydrogels in which

the chemical bonds between the macromolecules are formed and the entire

volume of solvent between the cells is kept (up to 99 % of the total mass) so that

determines their thermal irreversibility, chemical inertness, resistance to changes

in pH over a wide range. Such hydrogels have high sorption properties [2].

To achieve the main goal, the polymer

was placed into the aqueous solution of Enoxil

(5 wt. %) for 10 h at 15 °C. The biomolecules

easily penetrated into polymer during adsorption

and were washed out during desorption. The

process of adsorption and the state of

biomolecules before and after adsorption have

been analyzed using spectrophotometric

measurements.

It has been shown that this method is suitable to integrate, stabilize and

provide a prolonged activity of biocomplex.

Acknowledgements


(FP7/2007–2013), Marie Curie International Research Staff Exchange Scheme (IRSES

grant No 612484) for financial support of this project.

1. P. Kuzema, I. Laguta, O. Stavinskaya, O. Kazakova, M. Borysenko, T. Lupaşcu, Nanoscale Research

Letters. (2016) (DOI: 10.1186/s11671-016-1287-y)

2. Patent of Ukraine No 64849 “Biocompatible polyacrylamide hydrogel and method of its preparation”

Fig. Photo of the samples:

1 – initial polyacrylamide,

2 – polymer from aqueous solution,

3 – from aqueous solution of Enoxil

167

Influence of nanosilica powder on winter wheat germination

capacity

А.P. Golovan, T.V. Krupska, I.V. Siora, N.Y. Klymenko, O.А. Novikova,

V.V. Turov

Chuiko Institute of Surface Chemistry, NAS of Ukraine

17 Generala Naumova str., Кyiv 03164, Ukraine, [email protected]

Getting high-quality harvests of agricultural plants is one of the most

important national economy problem. Agricultural plants productivity depends

on the quality of seeds and their preparation for sowing. Nowadays different

treatment technologies of seeds are used which include a dusting as well.

Therefore, the aim of our research was investigation of the nanosilica powders

influence on germination energy and capacity of wheat grains under laboratory

conditions.

Investigations were carried out according to SSTU 4138-2002. Grains

were treated by hydrophilic A-300 and AM-1 hydrophobic silica (with

S = 300 m2/g) and their mixtures before sowing.

0 1 2 3 4 5 6 7 8 9 10

60

70

80

90

100

ge

rmin

atio

n e

ne

rgy, %

samples

Petri dishes

Sand

0 1 2 3 4 5 6 7 8 9 1060

70

80

90

100

ge

rmin

atio

n c

ap

acity,

%

samples

Petry dishes

Soil

Sand

Fig. 1. Energy germination Fig.2. Germination capacity

Fig. 1 shows us that the germination energy values are greater for testing

(sample 4) in Petri dishes in comparison with other samples. However, Fig. 2,

shows that the germination capacity of wheat which was treated by initial silicas

and their mixtures is above the control.

168

A quantum-chemical study of the antioxidant properties of

natural phenolic compounds

O.O. Kazakova



There is a growing interest in the antioxidant properties of silymarin - a

standardized herbal extract of the milk thistle seeds (lat. Silybum marianum)

containing a mixture of flavonolignans (silibinin, isosilibinin, silicristin,

silidianin), flavonoids (quercetin and taxifolin) and other polyphenolic

compounds. Silymarin used as a hepatoprotective drug for the prevention and

treatment of liver diseases of different etiologies. Silica nanocomposites with

silymarin may be more effective for the treatment of, for example, toxic liver

disease.

Molecular structure (Fig.) has been optimized by using Hartree-Fock

theory with the 6-31G (d,p) basis set by means of the GAMESS. The enthalpies

of dissociation of O-H bonds for all OH-groups and ionization potentials of

molecules were calculated using DFT (B3P86/6-31G(d,p)) (GAMESS), and the

solvation model IEF PCM was used to account for the solvent effects.

It was shown

that the OH groups of

the side phenolic ring

(20-OH group for

silibinin and sili-

cristin and 3'-OH,

4'-OH for quercetin

and taxifolin) and

additionally OH-

group in position 16

for silicristin give the

maximum contribu-

tion to the hydrogen

atom transfer mecha-

nism. It was found

that the presence of 2,3-double bond affect the redistribution of charge and

increases the contribution of the 3-OH group to a hydrogen atom transfer

mechanism for the quercetin molecule compared to taxifolin.

The contribution of the electron transfer mechanism to the antioxidant

activity is reduced in a series of quercetin - silicristin - taxifolin - silibinin.

a c

b d

Fig. The three-dimensional optimized structure of silibinin (a),

silicristin (b), taxifolin (c) and quercetin (d) molecules with the

numbers of carbon atoms, which are attached OH group

169

Improvement analysis system of the signal transmission

parameters estimation analysis by the signal reflection from the

thermal albedo deviations surfaces

N.O. Khemych1, S.V. Prokhorenko

1,2, M.G. Popryaga, O.V. Shynkarenko

3,

R. Wojnarowska-Nowak2

1Lviv Polytechnic National University, Ukraine, [email protected]

2Centre for Microelectronics and Nanotechnology,

University of Rzeszow, Rzeszow, Poland, 3Institute of Semiconductor Physics NAS of Ukraine, Kyiv

Recent years there is a growing interest to the dissolved liquid phase

systems research, in particular thin films of colloidal suspensions of

nanoparticles of biomolecules. The important task is a detailed research of the

parameters of the system under the temperature effect, because obtaining the

thermal deviation data can ensure more detailed analysis of the test structures

processes. Mainly, developed research methods of optical and thermal

depending parameters are based on the analog radiation beam transmitting via

the test specimen medium and they are implemented by the double transmission

from the perfect mirror. The improving of data transmission information is

implemented with using the differential equating analysis of the signal

propagation via the test suspense. The system analysis of the test specimen is

carried out using the encoded beam scanning, which provides the higher

probability of the signal transmission via the specimen noise media. Due to this

data transmission type are getting such advantages of digital signal processing as

small instrumentation inaccuracies impact and high noise protection (the

message can be distorted only by the false data receiving occasion, e.g. by very

high contaminating signal). The correlation analysis of informational flows

parameters alterations over the temporal intervals of the incomplete encoded

signal transmitting (in particular thermal depended component of instability) can

ensure obtaining the information about the behavior characteristics that are

transmitting signal impairing. In the studied system the noise protection is

attained by use of signal spectrum spreading (DSSS technology) and removing

the narrow spectrum disturbances. Correspondingly the direct impact to the

signal transmitting accuracy has the optical transmitting channel noise level. The

autocorrelation function (ACF) may be assumed as the signal transmitting

characteristic. ACF is obtained by means of signal convolution operation during

the data occurrence to the input of the detector. Therefore using the above-

described approach can be investigated by digital techniques modify the optical

channel of the researching object (no-homogenous thick-layer, placed at the

ideal mirror, which we consider as variable albedo surface), as well as to

investigate specimen temperature-dependent changes.

http://www.multitran.ru/c/m.exe?t=2409930_1_2&s1=%E4%EE%EF%F3%F1%EA%E0%FE%F9%E8%E9%20%ED%E5%F2%EE%F7%ED%EE%F1%F2%FC

170

Hydroxyapatite self-assembly from simulated body fluid on

carboxylated surface of Ti-containing alloys

Ie.V. Pylypchuk 1, G.V. Khmil

2, S.V. Gorobets

2, P.P. Gorbyk

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National Technical University of Ukraine "Kyiv Polytechnic Institute",

37 Peremohy av., Kyiv 03056, Ukraine

The development of the new biomimetic technologies is essential for

biological mineral deposition on metallic surfaces. This opens the way for

creation of new biomimetic structures and nanostructured composite materials

with desired characteristics and properties.

A deposition of hydroxyapatite (HA) coating onto the metal or alloy

surface is important in accordance to improve the osseointegration between

implants and living bone or tissues. In case of HA, strategy of biomimetic

method consists in a few stages. First, one is the creation of special, negatively

charged nucleation sites on the metal surface by modification with active

functional groups. Next stage is the process of mineralization in the SBF equal

by chemical composition to human plasma. Electrostatic interaction between

negatively charged surface and excess of positively charged calcium ions (from

SBF) provide recharging of the surface to positive sign. This, in turns, induce

adsorption of PO43-

anions, which promotes layer-by-layer hydroxyapatite self-

assembling.

Method of immobilization of 3-APTES derivatives with DTPA onto

surface of Ti-containing alloys was developed. Self-assembly of hydroxyapatite

on carboxylated surfaces was investigated. Samples were characterized by

FTIR, SEM and XPS methods.

171

Nanosilica-yeast cells based system for remediation of water

N.Y. Klymenko, І.V. Siora, E.А. Novikova, А.P. Golovan, Т.V. Krupskaya,

V.V. Turov



Petroleum and petroleum products are recognized as major environmental

pollutants. Since the development of the petroleum industry its negative impact

on the environment could not be completely exclude. There is a necessity to

develop methods and technologies for remediation of soils and water after

pollution by petroleum products. Nowadays the most perspective method is

bioremediation based on the oxidation of petroleum products by

microorganisms. Earlier studies have shown that highly dispersed materials are

able to activate the metabolic activity of microorganisms. Thus the aim of the

work was to study the ability of composite based on the Saccharomyces

cerevisiae yeast cells and mixture of hydrophilic (A-300) silica and hydrophobic

(AM1-300) silica (1:1) to motor oil hydrocarbon oxidation and to affect the

growth of cells colonies.

Ready composite system was added to the flask with water and motor oil.

Suspension of yeast cells in medium with aqua and motor oil without nanosilicas

mixture addition was used as a control. Kinetic of carbon dioxide emission

during fermentation process of yeast cells was measured quantitatively.

Fig. Kinetic curves of emissions of carbon

dioxide by suspension of yeast cells in the

composites consisted of yeasts (0.5 g (1), 1 g (2))

and reference to pure yeasts (0.1 g (3), 0.2 g (4))

The intensive duplication of yeasts

leads to exhaustion of hydrocarbons

reserve, increasing of vital activity

products quantity and death of old cells. It was shown that the presence of the

composite at the amount of 0.5 g and 1 g increases vital activity of the cells in

2.5 times and about 6 times respectively compared with the control. It was found

that increasing of composite concentration leads to rising of carbon dioxide

emissions in almost 2 times. Thus, the composite system based on the mixture of

hydrophobic and hydrophilic silica and yeast cells allows destructing of

hydrocarbons used as nutrients in aqueous medium.

1. Е.А. Tsimberg, L.V. Titova, I.К. Kurdish, J. Microbiol. 53 (1991) 55.

0

50

100

150

200

0 20 40 60 80

, day

m(C

O2),

g/l

1

2

3

4

172

Development of chitosan/carbon nanotubes composites for neural

tissue engineering

R.B. Kozakevych1, Yu.M. Bolbukh

1, V.A. Tertykh

1,

T.I. Petriv2, V.V. Medvedev

2, O.A. Rybachuk

3, R.G. Vasyliev

4


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2Romodanov Institute of Neurosurgery NAMS of Ukraine,

32 Platon Mayboroda Str., Kyiv 04050, Ukraine 3Bogomolets Institute of Physiology NAS of Ukraine,

4 Bogomoletz Str., Kyiv 01024, Ukraine 4State Institute of Genetic and Regenerative Medicine NAMS of Ukraine,

67 Vyshhorodska Str., Kyiv 04114, Ukraine

Creation and implementation of biomaterials that could repair tissue

defects is one of the most important contemporary issues. Recently, natural

biopolymers, especially chitosan, have attracted great interest as a potential

scaffolding biomaterial [1]. However, the poor electrical conductivity of this

polymer has limited their application for neural tissue engineering [2]. Its

electrical conductivity can be improved by using a small amount of conductive

nanofiller, such as carbon nanotubes. Therefore, our efforts have been focused

on the preparation of composites by the incorporation of conductive carbon

nanotubes (CNTs) into a chitosan matrix.

Oxidized CNTs (0.1, 1.0, 10.0 wt. %) were ultrasonicated for 30 min in

the 2 % chitosan solution in acetic acid (2 %). The mixtures were cast as a thin

film onto flat Teflon plates. After drying the films were neutralized in an

aqueous solution of NaOH (1 M) and were cross-linked with glutaraldehyde

(1 %). After that, the obtained composites were washed with distilled water and

dried at 70°C for 4 h.

The chitosan/carbon nanotubes composites were fully characterized by

IR-spectroscopy, AFM, TG/DTA. Culture of mouse cells was used to evaluate

nerve cell affinity to the obtained biomaterials. Synthesized composite materials

have significantly improved nerve cell affinity compared to chitosan.

Acknowledgements



under REA grant agreement n° PIRSES-GA-2013-612484, “NANOBIOMAT”.

1. F. Croisier, C. Jerome., Eur. Polym. J. 49 (2013) 780.

2. J. Huang, Y. Zhang, L. Lu, X. Hu, Z. Luo., Eur. J. Neurosci. 38 (2013) 3691.




http://www.ncbi.nlm.nih.gov/pubmed/?term=Huang%20J%5BAuthor%5D&cauthor=true&cauthor_uid=24118464

http://www.ncbi.nlm.nih.gov/pubmed/?term=Zhang%20Y%5BAuthor%5D&cauthor=true&cauthor_uid=24118464

http://www.ncbi.nlm.nih.gov/pubmed/?term=Zhang%20Y%5BAuthor%5D&cauthor=true&cauthor_uid=24118464

http://www.ncbi.nlm.nih.gov/pubmed/24118464

173

Investigation of cytotoxic activity of magnetocarried

nanocomposites based on doxorubicin

S.P. Turanska1, A.P. Kusyak

1, A.L. Petranovska

1, S.V. Gorobez’

2,

V.V. Turov1, P.P. Gorbyk

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2National Technical University of Ukraine «Kyiv Polytechnic Institute»,

37 Prospekt Peremogy, Kyiv 03056, Ukraine

The new magnetosensitive nanocomposites (NC) Fe3O4/DR,

Fe3O4/SiO2/DR, Fe3O4/TiO2/DR, Fe3O4/hydroxyapatite/DR, containing a

modern antitumor drug doxorubicin (DR) were synthesized [1]. We

investigated biocompatibility and bioactivity of NC. It was shown that in

quantities of 0.6-0.8 mg of doxorubicin per specimen, the nanocomposites had

cytotoxic and antiproliferative activity with respect to model cells

Saccharomyces cerevisiae. Mechanism of cytotoxic action of NC coincides

with corresponding influence of doxorubicin on model cells. A possibility was

shown for using yeast cells as economic test-method to control cytotoxic

activity in development of new forms of antitumor remedies. Prospects were

shown for medico-biological use of nanocomposites. Research into

biocompatibility of nanomaterials was carried out by studying their influence

on cell viability of baker's yeast Saccharomyces cerevisiae. Viability of cells

was determined by a cytochemical method with the help of Goryaev chamber

using optical microscopy and methylene blue dye by registration of

concentration change for cells growing at a temperature ~ 22 °C in suspensions

containing nanocomposites, yeast cells, minimal synthetic nutrient medium,

saline. The data obtained were compared to the results of studying control

samples. Bioactivity of NC was evaluated from their cytotoxic influence on

Saccharomyces cerevisiae cells and decrease in cell proliferation rate. These

effects are due, in particular, to participation of doxorubicin in redox cyclic

reactions and a corresponding increase in quantity of free radical molecules,

induction of oxidative stress, cell cycle delay in G1- and S-phase. Magnetic

liquids containing Fe3O4/HА/DR NC stabilized by sodium oleate and

polyethylene glycol were produced and investigated.

The work was carried out with support of goal complex programs of fundamental

investigations of the National Academy of Sciences of Ukraine “Fine Chemicals” (project

31/16).

1. P.P. Gorbyk, L.B. Lerman, A.L. Petranovska, S.P. Turanska, I.V. Pylypchuk, in: A.

Grumezescu (Ed), Fabrication and self-assembly of nanobiomaterials, applications of

nanobiomaterials, Elsevier, 2016, p. 289–334.

174

Screening the Orchidaceae Juss. family plants for

the antioxidant properties of the leaves extracts

I.V. Laguta1, O.N. Stavinskaya

1, R.V. Ivannikov

2, О.I. Dzyuba

2


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2M.M. Gryshko National Botanic Garden, NAS of Ukraine,

1 Timiryazevska Str., Kyiv 01014, Ukraine

Plants of Orchidaceae Juss. family are known to be widely used in East

medicine. These plants may be a source of such bioactive compounds as

alkaloids, phenanthrenes, terpenoids. In particular, leaf extracts of orchids plants

may contain such valuable antioxidants of nature originals as flavonoids and

possess high antiradical activity.

Using plants grown ex situ and in vitro, extracts from the leaves of

seventeen species of Orchidaceae Juss. family were prepared. Antioxidant

activity of the extracts was studied, the content of flavonoids in the extracts was

estimated.

The plants extracts of ten species were found to possess high antioxidant

properties and/or high flavonoids content, that makes them potentially

interesting raw materials for production of effective antioxidants of nature

originals. In general, the plants cultivated ex situ had higher content of bioactive

compounds as compared to the plants grown in vitro. At the same time, for

several species, the distinctions in the properties of the extracts prepared from

the plants grown ex situ and in vitro were insignificant. Furthermore, the plants

of two species cultivated in vitro were found to contain the highest amounts of

antioxidants and flavonoids.

Five species were found to have high content of bioactive compounds

being cultivated in vitro; these plants may be used in biotechnological processes

of antioxidants production. The following step of the work will be the

preparation of the composite material based on the plants extracts and fumed

silica. Using silica nanoparticles with hydrophilic or modified surface will allow

one to combine in one formulation several active substances with different

mechanism of action, to increase biocompatibility and stability of antioxidants,

to provide the prolonged release of active substances.

Acknowledgements

The research leading to these results has received funding from the target complex

multidisciplinary program of scientific research of Ukraine "Molecular and cellular

biotechnology for medicine, industry and agriculture".

175

A new approach to complex standardization of silica – multi

herbal nanodispersed preparations

N.O. Lipkovska, V.M. Barvinchenko, M.T. Kartel



Number of dietary supplements under the trade name of Phytosils based

on fumed silica as enterosorbent and highly dispersed native medicinal plants in

various combinations and ratio aimed on specific therapeutic action were

developed by the authors. Essential bioactive components of Phytosils are plant

polyphenols known for their antiallergenic, antiatherogenic, antiinflammatory,

antimicrobial, antioxidant, antithrombotic, cardioprotective and vasodilatory

effects which are attributed mainly to their antioxidant activity. Therefore, the

value of antioxidant activity in relation to total phenolic content could be used

for the standardization of these new herbal dietary supplements.

The simple, rapid and sensitive spectrophotometric method for the

determination of total antioxidant activity of herbal products has been developed

and tested on seven Phytosil multi-herbal dietary supplements. The method was

based on the reducing of colored cupric tetrabenzo-[b,f,j,n][1,5,9,13]-

tetraazacyclohexadecine complex by natural antioxidants.

N N

N N

Cu 2+

N N

N N

Cu ++ e_

CuTAAB 2+ CuTAAB +

Жовтий Блакитний

CuTAAB

2+ CuTAAB

+

yellow, ′max=268 nm, max′′=298 nm blue, max = 660–712 nm

It was shown that total antioxidant activity of Phytosil dietary

supplements strongly correlates to their total phenolic content (all R2 values ≥

0.960) confirming that phenolic compounds are dominant antioxidant

components in these preparations. It can be concluded that antioxidant activity

values determined by the proposed CuTAAB2+

reducing method and total

phenolic content determined at optimized wavelength can be used for good

quality assurance and standardization of Phytosil dietary supplements and other

multi-herbal preparations.

176

Effect of microwave low intensity electromagnetic wave on the

vital activity of yeast cells in the presence of graphene

O.M. Lisova, S.N. Makhno, P.P. Gorbik



It is known that the biological response of the cell systems to the impact of

low intensity electromagnetic wave (LEMW) has a resonant character, on the

other hand, a decisive role in the processes of living organisms play surface

phenomena arising from the interaction of fine particles, oxide systems, carbon-

containing compounds. There is no definitive data on the impact of graphene

derivative nanostructures on living organisms, including the dominant trend to

consider graphene as a negative factor.

The aim of the work is to study changes in the vital processes of the yeast

Saccharomyces cerevisiae in nutrient medium containing nanoplate graphene

(NG), after prolonged exposure LEMW cells and also the influence of LEMW

with different frequency in the presence of NG.

The paper studied the influence of NG (obtained by electrochemical

dispergasion) and LEMW on the activity of yeast cells in suspension by the

method of speed gassing control. The dependences of the yeast vital processes

from concentration of NG in suspensions and the impact of emission were

studied, two experimental series were conducted independently: NG were added

to the substrate after the exposure process of dry yeast and subjected to

irradiation of suspension containing NG. The NG aqueous suspension with a

concentration of 0.06 wt. % was used.

Relative speed of gassing concentration is approximately linear and weakly

depends on the content of NG in the investigated range. There is a gain of vital

processes of yeast suspensions containing NG on average by 20-25% compared

to control, but the change of the nature of gassing rate in the presence of NG

from time is not observed. The presence of NG in suspensions containing yeast

after exposure at the dry state is a stimulating factor.

The inhibitory effect LEMW NG compensate not so clearly (10%), as

they enhance the beneficial effect (40%).

Adding the NG in the suspension before the irradiation appears in the vital

activity processes not so definitely.

Thus, the presence of NG in the yeast suspensions is a motivating factor

and it does not cause the negative effects on the vital activity processes at the

cellular level.

177

Synthesis of tryptophan-stabilized Fe3O4/Ag core-shell

nanoparticles

Iu. Mukha, N. Vityuk, G. Eremenko, N. Ostapchuk, Ie. Pylypchuk,

P. Gorbyk



Nanoparticles composed of magnetic core and Ag shell simultaneously

possess both magnetic and plasmonic properties and can be applied for targeted

drug delivery and therapy of cancer. Here we describe the method for Fe3O4/Ag

core-shell nanoparticles synthesis and their physical-chemical properties. As an

approach for preparation of Fe3O4/Ag core-shell complex nanoparticles in

aqueous solution we used method described in [1].

Typical metal plasmon resonance band inherent for individual metal is

present in absorption spectrum of Fe3O4/Ag solution (fig.) indicating the

formation of silver shell. In the presence of iron oxide core the absorption

maxima is shifted in short-wavelength region to λmax = 422 nm accompanied by

band broadening compared to individual silver, reduced stabilized with

tryptophan. Obtained colloidal solutions were stable during several months

maintaining their optical properties.

300 350 400 450 500 550 6000,0

0,5

1,0

Ag NPs

Fe3O

4 / Ag NPs

max

= 429nm

Ab

so

rba

nce

, a

.u.

, nm

max

= 422 nm

Fig. UV-vis spectra of Fe3O4/Ag and Ag nanoparticles solutions

1. Iu. Mukha, N. Vityuk, O. Severynovska, A. Eremenko, N. Smirnova, Nanoscale Research

Letters (2016) 11:101.

178

Influence of technological conditions on the physical and

chemical properties of biogenic hydroxyapatite dopped with

ferromagnetic additions

O. Otychenko1,2

, A. Parkhomey1, T. Babutina

1, I. Uvarova

1,2

1Frantsevich Institute for Problems in Materials Science,

3 Krzhizhanovsky Str., Kyiv 03680, Ukraine, , [email protected] 2National Technical University of Ukraine «Kyiv Polytechnic Institute»,

37 Prosp.Peremohy, Kyiv 03056, Ukraine, [email protected]

The aim of this work is determination an optimal technological conditions

for obtaining alloyed biomaterial with acquired magnetic properties as a result

of using the physical and chemical methods of precipitation of the ferromagnetic

additions on the surface of dispersive biogenic hydroxyapatite (BHA) for

application particularly in the osteoplastic surgery as well as for definition of an

influence of this conditions on the properties of prepared materials.

Foregoing bioactive material for medical application has been obtained by

doping the nanostructured BHA‟s microgranules, prepared according with TУ У

33.1-22965991.002-2001 with ferromagnetic additions by using two sort of

condense physico-chemical methods [1]. Low-temperature thermolysis of

alloyed biomaterial was performed in vacuum and nitrogen-containing medium

for comparison. Phase and chemical composition of prepared compounds have

been controlled by using X-ray (“DRON-3,0”, Co -radiation) and chemical

analyzes. Also controlled the Specific surface area has been determined by the

method of thermal desorbtion of nitrogen (Table).

Table. Physico-chemical parameters of materials

Material Heat treatment

parameters

Specific

surface area,

m2/g

Fe content,

wt. %

N content,

wt. %

C content,

wt. %

BHA+Fe3O4,

chemical method Vacuum medium,

500 ºС, 2 h

8.82 1.01 - 0.57

BHА+Fe3O4,

phys.-mech. method 7.38 1.17 - 0.55

BHA+Fe3O4

chemical method Nitrogen-

containing

medium,

500 ºС, 2 h

7.46 0.98 0.1 0.30

BHA+Fe3O4,

phys.-mech. method 6.28 1.07 0.4 0.30

It was found that the magnetization of the biomaterial and as a result of its

magnetic controllability directly depend on the ferromagnetic phase

homogeneity of alloying additives and influence on a biochemical activity

significantly, especially on the change of their biosolubility.

1. O. Otychenko, A. Parkhomey, T. Babutina, I. Uvarova, HighMathTech–2015: abstracts of 5-th International

Conf., Kiev, October 5–8, 2015, p. 204.

179

The study of physicochemical properties of oxidized enotannins

N. Petrov


3Academiei Str., MD 2028, Chisinau, Republic of Moldova, [email protected]

Biologically active substances of natural origin are often use in medicine

and agriculture for combating different diseases caused by fungi, bacteria and

viruses. The grape seeds are a valuable source for obtaining enotannins, that are

natural compounds with phenolic structures and which possess remarkable

antioxidant properties.The enotannins obtained from grape seeds are natural

compounds with polyphenolic structure, possessing significant antioxidant

properties, but their use is difficult, since most of the enotannins are insoluble in

water. To improve the physicochemical, antioxidant and antibacterial properties

of the enotannins, it was amended their chemical structure. Enotannins were

selected from local sources, from seeds of white (Enotanin 2) and red grapes

(Enotanin 1 and 3). New hydrophilic products (Enoxil I, II and III) were

obtained by depolymerization of the macromolecular chains of the initial

enotannins through the oxidation process by hydrogen peroxide using.

To determine the antioxidant properties of the Enoxil compound it was

used the chemiluminescence method (CL), in the generating luminescence

system- Luminol-H2O2. It was prepared 0.1% solution of Enoxil, Luminol

(1 mM) and H2O2 (0.2 mM) and as a buffer it was used Tris-HCl pH 8.6. The

results of the research for antioxidant activity (AA %) assessment of Enoxil (I, II

and III) have demonstrated that the values are basically the same. They are quite

pronounced and are in the range from 93.16 to 95.58%.

The obtained compounds have to be studied to determine their antifungal,

antibacterial and pharmacological properties.

Acknowledgements

Authors are grateful for the financial support accorded by the European Union's Seventh

Framework Programme (FP7-PEOPLE-IRSES-2013) under the grant agreement no PIRSES-

GA-2013-612484.

1. T. Lupaşcu, G. Duca, G. Lupaşcu, Enoxil - preparat ecologic pentru protecţia plantelor.

Ch: S. n., 2010.

2. L. Packer, The Antioxidant Miracle. New York: Copyright, 1999, 276 p.

3. V. Kulciţki, P. Vlad, Gh. Duca, T. Lupashcu, Chemistry Journal of Moldova. 2(1) (2007)

36.

180

Synthesis and properties of hydroxyapatite/MWCNTs composites

E. Skwarek1

, Y. Bolbukh2, V. Tertykh

2, W. Janusz

1





Hydroxyapatite and its composites are of interests for application in

medicine due to their absorption ability and biocompatibility. Physical and

chemical properties as well as soft indestructible interactions with human tissue

make hydroxyapatite attractive as the object of the in vivo and in vitro research.

Filling such materials with carbon nanotubes has inspired wide interests in

current nanoscience and nanotechnology.

Composites of carbon nanotubes and hydroxyapatite were prepared by the

wet synthesis. The obtained materials were characterized by DSC analysis,

nitrogen adsorption/desorption technique, XRD spectroscopy and scanning

electron microscopy. The hydroxyapatite/nanotubes interface were characterised

and electrochemical properties was studied. The parameters of the electrical

double layer such as density of surface charge, zeta potential as well as pHpzc

and pHIEP., were exterminated.

Obtained results confirm the material structuring in the presence of

pristine MWCNTs and an affect of nanotubes surface nature on the composite

internal structure. As follows from results of the nitrogen ad/desorption method

and scanning electron microscopy the pure hydroxyapatite and composites with

pristine and oxidized multiwalled carbon nanotubes have different porosity and

morphology of aggregates. In depend on the nature of surface active sites of the

filler the structure of composite was changed from crystalline to amorphous and

the oxides composition was differed from native hydroxyapatite. Synthesised

hydroxyapatite reinforced with carbon nanotubes can be a promising material

for high-load-bearing metal implants targeted drug delivery system and other

biomedical fields.

Acknowledgements




181

Obtaining and characterization of enotannins by

physico-chemical methods

T. Lupascu, N. Timbaliuc, A. Gonţa, N. Petrov


3 Academiei Str., MD 2028, Chisinau, Republic of Moldova

Massive pollution of the environment with chemical, biological, physical

and other agents negatively influences the health of the human body, in

particular, through the formation of free radicals. Contemporary medicine

recommends the use of biologically active substances obtained from natural raw

materials, which exhibit remarkable antioxidant properties, as one of the most

harmless methods for health recovery [1]. The class of polyphenols is

considered among the highest potent natural antioxidants, which comprises

phenolic acid, flavonoids, enotannins, and others. The grape seeds represent in

the Republic of Moldova the most important raw material, rich in polyphenols,

which is a valuable natural source of local origin for obtaining enotannins.

These compounds represent a mixture of catechin and epi-catechin oligomers.

The polymeric chain is formed opon condensation of carbon atom at position C4

in C-cycle and carbon atom in C8, in A-cycle. Formation of polyphenol

oligomers by policondensation processes of catechin and epi-catehin have been

studied previously.

In order to obtain high content of enotannins, grape seeds (intact and

crushed forms) have been used as extractable local raw material. Different

concentrations of ethanol solution (10%; 20%; 30%…96%) have been used as

solvent to extract phenolic compounds at the ratio of 1:10 (dry weight seeds/

solvent‟s volume). The total phenolic content was determined using Folin

Ciocalteu method with minor modifications. Based on the obtained data, it have

been established that the total amount of extractable tannins rises with the

increases of ethanol concentration up to 50%. By using this concentration of

ethanol, the resulted amount of tannin was around 10.06 mg /g (crushed seeds)

and 6.49 mg/g for intact seeds. For the characterization of antioxidant activity,

of both intact and crushed seeds enotannin extracts, was used cation ABTS

radical method and DPPH radical test. These compounds of natural origin have

strong antioxidant activities and are of great interest for future microbiological

and pharmacological research, as they have high antioxidant activities.

Acknowledgements

Authors are grateful for the financial support accorded by the European Union's Seventh

Framework Programme (FP7-PEOPLE-IRSES-2013) under the grant agreement no PIRSES-

GA-2013-612484.

1. T. Lupaşcu, Gh. Duca, V. Gonciar. Enoxil preparat ecologic pentru sănătatea omului″,

Monografie, Editura ″Ştiinţa″, Chişinău, 2012, 256 p.

182

Synthesis and biocidal properties of Cu-containing

nanocomposites


1, O.I. Oranska

1, M.V. Borysenko

1,


2, O.M. Zaichenko

2


17 General Naumov Str., Kyiv 03164, Ukraine 2Zabolotny Institute of Microbiology and Virology, NAS of Ukraine,

154 Acad. Zabolotny Str., Kyiv 03143, Ukraine

Copper compounds have been used for centuries as active biocidal

materials. In this study, the effect of the composition “porous carbon-copper” in

various ratios of components on their fungicidal activity was considered.

Nanocomposites were synthesized by pyrolysis of a mixture of copper acetate,

polymers, and fumed silica. Three types of polymers: Phenol-formaldehyde

resin (Cu-1), resorcinol-formaldehyde resin (Cu-2) and polyethylene glycol

(Cu-3) were used in the synthesis. Silica content was varied from 0 to 35 wt. %

while copper content – 9-75 wt. %. Porous carbon is the rest. The samples were

characterized by TG-DTG, XRD and SEM analyses.

The biocidal activity of the Cu-containing composites and test samples

was tasted towards 12 strains of fungi. The most typical results are shown in the

Table.

Samples

Diameter of growth inhibition zone of fungi, mm

Pen

icil

lium

funic

ulo

sum

Asp

ergil

lus

terr

eus

Paec

ilom

yces

vari

oti

i

Pen

icil

lium

urt

icae

Myr

oth

eciu

m

verr

uca

ria

Tri

choder

ma

viri

de

Pen

icil

lium

chry

sogen

um

Asp

ergil

lus

nig

er

Pen

icil

lium

aura

nti

ogri

seum

Cu-1 0 0 0 30 0 27 0 0 30

Cu-2 0 0 0 18 0 0 0 0 24

Cu-3 20 0 0 30 29 19 25 0 24

SiO2 0 0 0 0 0 0 0 0 0

C 0 0 0 0 0 0 0 0 0

Tests have shown that composites are more active against Peniсillium

strains and less active against Aspergillus strains. Besides, the sample with the

highest content of copper (Cu-3) is most active. It may be assumed that the

activity is associated with the influence of metabolic products of fungi and

metallic copper nanoparticles. Due to this reaction, bioactive mobile ions

Cu2+

are formed.

183

Justification enterosorption nanodispersed silica drugs use in

complex treatment of community-acquired pneumonia at patients

with immunosuppression

O.O. Viltsaniuk

Vinnytsya National Pirogov Memorial Medical University,

56 Pirogov Str., Vinnytsya 21021, Ukraine, [email protected]

Community-acquired pneumonia (CAP) treatment is one of the biggest

problem of our time. Introduction of new antibiotics for CAP treatment into

clinical practice doesn‟t solve the problem of high mortality due to the large

number of complications, especially at patients with immunosuppression. One

of the reason for this process severity is endogenous intoxication. We have

developed a method of severe CAP treating at patients with immunosuppression,

which includes use of cationic surface active antiseptic therapies and

enterosorbents based on nanodispersed silica (NDS).The aim of the study is to

prove the effectiveness of the developed method for the treatment of severe CAP

on patients with immunosuppression.

The objects of the study were patients with severe immunosuppression

and CAP, which were divided into two groups: primary, in which treatment was

conducted for the methodology and the comparison group in which treatment

was conducted by conventional methods. Both groups of patients were

representative by age, sex and co-morbidities. To assess the effectiveness of

treatment in both groups of patients commonly used clinical, laboratory,

biochemical, immunological, microbiological methods and parameters of

endogenous intoxication (EI).

Studies have shown that using a developed method at patients with severe

CAP group had a more favorable course than in the comparison group, which

showed a rapid normalization of laboratory and blood biochemical parameters,

indicators of EI and normalization of general clinical parameters. If the main

group of patients were conducted additional Enterosorption used, indexes EI

approached the normal range for 7-9 days from starting treatment and before

discharge were within normal limits, the comparison group general clinical,

laboratory, biochemical indices approached to normal just before discharge and

even before discharge remained elevated. At the same time 17.1% of

comparison group patients had complications in the form of destructive changes

in the lungs, whereas in patients treated with the developed method, the number

of complications was significantly lower and was only 4.1%

Thus developed method of severe CAP treatment whith NIR

enterosorbtion provided more favorable course of the disease, can reduce EI,

reduce complications, diminish the patients hospital stay and reduce mortality.

184

Bimetallic gold/silver alloy nanoparticles prepared in the presence

of tryptophan

N. Vityuk1, Iu. Mukha

1, G. Grodzyuk

2,3, A. Eremenko

1


17 General Naumov Str., Kyiv 03164, Ukraine, [email protected] 2L.V. Pisarzhevskii Institute of the Physical Chemistry, NAS of Ukraine,

31 Nauki Ave., Kyiv 03028, Ukraine, [email protected] 3NanoMedTeсh LLC, 68 Gorkogo Str., Kyiv 03150, Ukraine.

Gold and silver nanoparticles (NPs) can be applied on their own or in

combination with other objects for targeting, imaging and therapeutic [1]. Due

to synergistic effect their bimetallic composition could act more effective in

cancer treatment. Also the toxicity of nanosized metals could be greatly

decreased through the use of essential amino acid as reducing agents [2].

Earlier we described an approach to obtain stable monometallic gold and

silver nanoparticles in aqueous solution in the presence of tryptophan depending

on the pH of the medium [3], and here we used it for synthesis of bimetallic

“alloy” AgAu nanoparticles for further investigation of their antitumor activity.

Optical spectra of NPs contained typical metal LSPR bands with intensive

maxima at 425 and 523 nm. For bimetallic AgAu NPs the only one band

maximum characteristic for “alloy” type NPs is located between the maxima

inherent to the bands of individual metals and depends on the composition of the

particles. It is shifted from silver to gold according to Ag:Au molar ratio,

namely λmax = 434 (3:1), 469 (1:1) and 497 nm (1:3).

Dynamic light scattering data indicate polydispersity in colloidal solution.

Monometallic particles are mainly formed with the average size up to 10 nm

according to number and volume basis, but intensity basis suggests formation of

a wide range of aggregates up to 200 nm. Zeta potential measurements showed

that surface of synthesized nanoparticles carried a negative charge. Metal-amino

acid complex formation competes with the metal reduction process that cause

aggregate formation in Ag(Au)/tryptophan system.

1. J. Conde, G. Doria, P. Baptista, J. Drug Deliv. 2012 (2012), ID 751075, 12 p.

2. I.O. Shmarakov, Iu.P. Mukha, V.V. Karavan, O.Yu. Chunikhin, M.M. Marchenko,

N.P. Smirnova, A.M. Eremenko, Nanobiomedicine, 2014, 1:6

3. Iu. Mukha, N. Vityuk, O. Severynovska, A. Eremenko, N. Smirnova, Nanoscale Research

Letters (2016) 11:101.

185

Amino acid adsorption onto nanocrystalline ceria surface

N.N. Vlasova



The adsorption of aspartic and glutamic acids from aqueous electrolyte

solution onto nanocrystalline ceria surface has been studied as a function of pH

and ionic strength. Acid-base titration and amino acid adsorption data are

interpreted in terms of surface complexation theory with basic Stern model and

GRFIT program including surface ion-pair formation with background

electrolyte ions.

2 3 4 5 6 7 8

0

20

40

60

80

100

2 3 4 5 6 7 80

50

100

150

200

250

Glu = 1 mmol/l

CeO2= 1 g/l

0.01 M NaCl

Adsorption, %

pH

HL-

H2L

H3L

2+

Asp =1 mmol/l

CeO2= 1 g/l

0.1M NaCl

0.01M

pH

Adsorption, mcmol/g

a b

Fig. Adsorption of glutamic (a) and aspartic (b) acid onto ceria surface

Stability constants of surface complex of glutamic and aspartic acid, in which

monoanion is bound with protonated hydroxyl groups of ceria, are calculated.

Structure of surface complexes is confirmed by IR-spectroscopy.

Table. Surface equilibria for proton, electrolyte ion and amino acid adsorption on

the nanocrystalline ceria (SSA = 60 m2/g; particle size 25–30 nm)

Surface reaction logK±0.05

≡CeOH + H+↔ ≡CeOH

2 4.73

≡CeOH ↔ ≡CeO– + H

+ –7.87

≡СеOH + H+ + Cl

- ↔ ≡СеOH

2 Cl- 5.73

≡СеOH + Na+ ↔ ≡СеO

– Na

+ + H

+ –6.87

≡СеOH + H3L+↔ ≡СеOH

2 HL–-

+ Н+ 2.98 (GLu); 3.34 (Asp)

≡СеOH

2 + HL– +↔ ≡СеOH

2 HL–-

4.98 (Glu); 4.62 (Asp)

186

Effect of gold nanoparticles on morphological and functional

characteristics of bone marrow mesenchymal stromal cells

N.A. Volkova, E.V. Pavlovich, M.S. Yukhta, A.N. Goltsev

Laboratory of Biotechnology and Applied Nanotechnology,

Department of Cryopathophysiology and Immunology,

Institute for Problems of Cryobiology and Сryomedicine, NAS of Ukraine,

Kharkov, Ukraine

The gold nanoparticles (AuNPs) as a structural basis of nanocomposites

have been previously applied to deliver molecules into cells with a therapeutic

effect. In all these cases, AuNPs enter inside a human body and contact the cells.

Nanocompounds in high concentrations can have a toxic effect on the cells in

vitro and in vivo. Unfortunately, there are no clear conclusions about the

variability of nanoparticle parameters such as physical and chemical properties

as well as about the conditions of cell studying [1].

The effect of AuNPs on the viability, proliferative capacity and

apoptosis/necrosis processes of bone marrow mesenchymal stromal cells

(MSCs) was investigated.

MSC cultures obtained from rat bone marrow. AuNPs were obtained by

citrate synthesis [2] with an initial metal concentration of 45 μg/ml. The average

size of AuNPs was 15 nm. They were entered into MSCs by a passive diffusion

during 1-h incubation at 37 С in the nutritive medium supplemented with

AuNPs (1.5, 3, 6, 9 μg/ml).The apoptotic/necrotic processes in the cells were

examined with FACSCalibur. The ability to colony formation was assessed by

scoring the individual colonies comprised of at least 30 cells. Proliferative

characteristics were examined by MTT-test. The results were processed with

Student's t-test using Excel software.

The results obtained by flow cytometry suggested that AuNPs at

concentrations of 1.5 and 3 μg/mL on the 7th day of culturing do not cause the

development of necrosis and apoptosis in cells. After 7 day culturing in the

presence of AuNPs at concentration of 6 and 9 μg/mL a decrease in the

percentage of viable cells and an increase of the number of apoptotic cells were

observed compared with the control samples (without AuNPs). The use of

AuNPs at concentrations of 1.5 and 3 μg/mL did not influence morphological

structure and was characterized by normal proliferation and ability to colony

formation.

1. A.M. Alkilany, C.J. Murphy, J Nanopart Res., 12 (2010) 2313.

2. L.A.Dykman, V.A. Bogatyrev, S.Y. Schyogolev, N.G. Khlebtsov Gold nanoparticles.

Synthesis, properties, biomedical applications, Nauka: Moscow, 2008.


http://www.ncbi.nlm.nih.gov/pubmed/?term=Pavlovich%20O%5Bauth%5D

http://www.ncbi.nlm.nih.gov/pubmed/?term=Goltsev%20A%5Bauth%5D

187

Application of temperature-programmed desorption mass

spectrometry to study the interaction of dextran polymeric chains

with fumed silica surface

T. Kulik, B. Palianytsia



Dextran is a complex branched glucan composed of α-1,6-glucopyranose

units. Its biocompatibility makes it attractive as a polymer for the synthesis of

silica-based nanomaterials with potential applications in drug delivery systems.

The work is devoted to the studying of the interaction of dextran with the

fumed silica surface, investigation of adsorbed polymer layer structure and

influence of the silica surface modification by dextran on its thermochemical

properties.

The adsorption/desorption of dextran on the fumed silica surface was

investigated. Thermolysis of dextran and dextran adsorbed on the fumed silica

surface were investigated using desorption mass spectrometry. Stages that

correspond to the thermolysis of non-connected segments of adsorbed dextran

and segments directly connected to the silica surface were determined. Approach

for the estimation of p parameter value based on TPD MS data was suggested.

The correlation of adsorbed dextran amount and p parameter value was

obtained. Segment types of adsorbed polymers are usually referred to as trains,

loops, or tails. Trains are segments directly interacting with the surface. Loops

are areas of polymeric chains with two ends attached to the trains. Tails are so-

called “lost ends” of an adsorbed chain. The p parameter is a ratio of the number

of all train segments (Atrains) to the sum of all segments (Aloops+tails+trains), i.e.,

p=Atrains/Aloops+tails+trains. Obviously, the two pyrolysis stages of the silica-

adsorbed dextran are caused by two types of dextran: those directly bound to the

surface (trains) and those non-silica-bonded (loops and tails). The p parameter

was calculated from the integrated intensities (int) of the I(m/z=110) and II

(m/z=126) peak types: p=int I/(int I + int II).

Acknowledgements

This publication is based on work supported by the Swedish Research Council (VR) under

contract 348-2014-4250.

188

Auothor Index

A

E. Abarca-Morales, 85

N.V. Abramov, 83, 125

J. Adelsberger, 84

S. Alekseev, 117

А.А. Аlexeenko, 133, 134

L.S. Andriyko, 50

D. Aravopoulou, 84

T. Azarova, 69

B

T. Babutina, 178

O.M. Bakalinska, 36, 90

L. Bardash, 106

V.M. Barvinchenko, 175

E.V. Basiuk, 33, 85

V.A. Basiuk, 33, 85

A.A. Beda, 28

G.V. Beketov, 162

A.G. Belous, 23, 151

P.V. Belyaev, 37

L.A. Belyakova, 86, 123, 141, 154

V.A. Bershtein, 99

A. Beshliu, 52

Yu.A. Beznosyk, 48

T.M. Bezugla, 49

O.A. Bieda, 82

A.G. Bilous, 121

A.M. Bivigou-Koumba, 84

M. Blachnio, 31, 91

V.M. Bogatyrov, 87, 163, 164, 166,

182

A.A. Boiko, 133, 134

Yu. Bolbukh, 22, 26, 53, 122, 137,

180

Y.M. Bolbukh, 145, 172

S.B. Bolshanina, 42

M.V. Bondarenko, 88

T.I. Borodinova, 89

N.V. Bortnyk, 90

O.A. Boryak, 68

M.V. Borysenko, 87, 133, 134, 159,

182

M. Borysenko, 153

A. Borzakovskiy, 108

A.V. Brichka, 90

S.Ya. Brichka, 90

Y.O. Budash, 140

T. Budnyak, 53, 91, 92

V.Y. Bulakh, 140

A.F. Burban, 116

M. Burjanagze, 155

N.O. Burkiashvili, 156

T.O. Busko, 96

C

S.V. Camyshan, 88

V.V. Chagovets, 68

V. Chernii, 54

A.Yu. Chernyak, 48

N. Chorna, 24, 93

A. Chrzanowska, 34, 38, 55, 77

Z. Czapla, 104

R. Czerwieniec, 54

D

A. Dąbrowski, 101, 102, 103

T.Ia. Datsko, 56

O.V. Davidova, 133, 134

M.L. Dekhtyar, 57

O.I. Demchyna, 94

E.M. Demianenko, 43

Kh.V. Demydova, 94

А. Derylo-Marczewska, 31, 32, 34,

38, 53, 55, 77, 91, 153

S.M. Desenko, 28

V.Ya. Degoda, 145

A. Di Martino, 165

M. Diaz-Garcia, 27

R.M. Dlubovskiy, 66

O.P. Dmytrenko, 96

N.M. Dolaberidze, 95

Y. Dovbii, 54

N.E. Drobyshevskaya, 133, 134

A.V. Dubenko, 46

I.V. Dubrovin, 83, 96, 114

O.A. Dudarko, 60, 148

I.O. Dulina, 121

189

M.A. Dzagania, 156

O.Ya. Dzhodzhyk, 116

M.O. Dziazko, 141

Yu.S. Dzyazko, 29

L. Dzubenko, 97, 140

О.I. Dzyuba, 174

E

A.M. Eremenko, 131

A. Eremenko, 184

G. Eremenko, 177

L. Eprikashvili, 98

E. Espuche, 108

F

E.N. Fadieiev, 58, 149

A. Fainleib, 105, 106, 108

A.M. Fainleib, 99, 152, 157

G.V. Fedorenko, 100

О.P. Fedorchuk, 151

Y.S. Fetisova, 148

K.O. Filatova, 165

S.S. Fomanyuk, 59

G

V. Gabunia, 155

A.R. Gaidai, 60

A.V. Gaidin, 130

M.V. Galaburda, 87, 163, 164, 166,

182

A.V. Galak, 142

V. Galysh, 44

R.V. Garmash, 48

K. Gdula, 101, 102, 103

I.I. Gerashchenko, 118

O.I. Gichan, 61

I. Ginsari, 69, 72

A. Gładysz-Płaska, 92

A. Golovan, 165, 167, 171

K.O. Golubchik, 66

A.N. Goltsev, 186

O.V. Goncharuk, 74, 139

A. Gonţa, 181

A.M. Gorb, 104

P.P. Gorbyk, 83, 96, 97, 112, 114,

119, 125, 136, 138, 140, 164, 170,

173, 176

P. Gorbyk, 177

T. Goreacioc, 69, 72

B.M. Gorelov, 104

Yu.I. Gornikov, 129, 164

S.V. Gorobets, 170

S.V. Gorobez‟, 173

A.S. Gorohivskiy, 113

F. Gouanve, 108

D. Grande, 105, 108, 157

Yu. Grebel‟na, 144

A.G. Grebenyuk, 43, 45, 48, 64, 128

O. Grigoryeva, 105, 106, 108

O.P. Grigoryeva, 152, 157

L.M. Grishchenko, 49

M. Grochowicz, 107, 124

G. Grodzyuk, 184

T.Yu. Gromovoy, 33, 85

S. Gryn, 117

E.G. Gule, 145

G.M. Gunja, 136

V.M. Gun‟ko, 19, 50, 51, 74, 139,

159

K.G. Gusakova, 99

K. Gusakova, 105, 108

H

D.M. Haliarnyk, 36

I.Yu. Halutskaya, 29

N.A. Havrylyuk, 109

O.O. Havryliuk, 70, 110

L.V. Henao-Holguin, 33

L.A. Honcharova, 111

I

M. Ignatovych. 62

B.A. Imamaliev, 161

O.V. Ischenko, 79, 82

M.G. Ismailova, 161

A. Ivanets, 69

R.V. Ivannikov, 174

J

W. Janusz, 180

http://www.ncbi.nlm.nih.gov/pubmed/?term=Goltsev%20A%5Bauth%5D

190

K

N. Kachalova, 115

O.M. Kamіnskiy, 112

N.N. Kamneva, 30

V.I. Kanevskii, 63

A.L. Kara, 66

L.V. Karabanova, 111

L.A. Karachevtseva, 78

A.V. Karakurkchi, 113

M.T. Kartel, 36, 44, 90, 175

G.N. Kashin, 114

V.N. Kaurkovska, 64

O.O. Kazakova, 168

K.A. Kazdobin, 65

T.A. Khalyavka, 88

O.A. Khaynakova, 27

G.V. Khmil, 170

N.O. Khemych, 169

А. Khodko, 115

M.O. Khodykina, 65

T.O. Kiose, 66

D. Kirilenko, 99

D.V. Kisel, 145

P. Klonos, 22

N.Y. Klymenko, 167, 171

N.G. Kobylinska, 27

S.D. Kobylianska, 121

G.Y. Kolbasov, 59

I.S. Kolesnyk, 116

I.V. Komarov, 92

V. Konovalova, 81

V.V. Konovalova, 116

О.М. Korduban, 138

T. Kordzakhia, 98

S. Korobko, 54

Т.Ye. Korochkova, 67

D. Korytko, 117

G.V. Korzhak, 35

M.V. Kosevich, 68

P.O. Kosorukov, 120

S. Koutsoumpis, 152

R.B. Kozakevych, 26, 44, 172

M.A. Kozhemiak, 76

L.F. Kozin, 71

O.S. Krupennikova, 132

T.V. Krupska, 165, 167, 171

О.S. Кukolevska, 118

T. Kulik, 187

A.P. Kusyak, 119, 173

N.V. Kusyak, 112

V.S. Kuts, 25

V.E. Kutsenko, 89

A.V. Kutsyi, 71

T. Kuznetsova, 69

K. Kyriakos, 84

A. Kyritsis, 84, 158

V.P. Kyslyi, 162

L

I.V. Laguta, 174

A. Laschewsky, 84

N.S. Lavrenyuk, 99

O.M. Lavrynenko, 120

S.H. Lin, 57

O. Linnik, 24, 93

B.O. Linova, 121

N.O. Lipkovska, 175

A.I. Liptuga, 162

A.I. Lisogor, 71

O.M. Lisova, 176

B.V. Lytovchenko, 70

V.V. Lobanov, 43, 48

O. Lomtadze, 155

Ya.Y. Lopatina, 89

T. Lupaşcu, 52, 69, 72, 122, 135,

166, 181

R.A. Lutkovskyi, 37

L. Lutsenko, 153

D.Yu. Lyashenko, 123

V.S. Lysenko, 145

M

M. Maciejewska, 107, 124

M. Majdan, 92

S. Makhno, 144

S.N. Makhno, 125, 136, 164, 176

N.P. Maksymovych, 100, 150

F.D. Manilevich, 71

A.W. Marczewski, 31, 32, 34, 38, 55,

77, 91

Y.S. Marikvas, 131

A.I. Marynin, 30, 50, 51

A.K. Matkovsky, 74, 139

I.S. Matviichuk, 96

I.P. Matushko, 100, 150

R.V. Mazurenko, 125

191

N.O. Mchedlov-Petrossyan, 30

V.V. Medvedev, 172

A. Meier-Koll, 84

I.V. Melnyk, 101, 103, 126

T.G. Meshkova, 81

V. Meza-Laguna, 33, 85

A. Miasnikova, 84

I.N. Mihailescu, 24

N.A. Mirdzveli, 95

O.V. Mischanchuk, 78

Iu. Mukha, 115, 177, 184

O. Мykhailenko, 127

N

D.B. Nasiedkin, 128

R. Nastas, 69, 72

A.N. Nazarov, 145

N.V. Nikolenko, 46

M.O. Nijaradze, 95

L.V. Nosach, 159

O.А. Novikova, 167, 171

V.O. Novotna, 41

O

O.M. Odnovolova, 28

V.M. Ogenko, 132, 146, 147

S.I. Okovytyy, 46

L.P. Oleksenko, 100, 150

L. Oleksenko, 153

O.I. Oranska, 87, 129, 163, 164, 182

V.V. Orlov, 68

S.I. Orysyk, 75

E. Osawa, 30

N. Ostapchuk, 177

J. Osypiuk-Tomasik, 124

O. Otychenko, 178

P

E.M. Pakhlov, 19, 118

B. Palianytsia, 187

N.D. Paliychuk, 47

A. Panagopoulou, 158

Ya.V. Panasiuk, 35

T.M. Panchyshyn, 130

C.M. Papadakis, 84

A. Parkhomey, 178

K.A. Parshyn, 78

O.Yu. Pavlenko, 120

A.V. Pavlenok, 134

E.V. Pavlovich, 186

V.I. Pekhnyo, 75

N.O. Perlova, 29

O.V. Perlova, 29

K.D. Pershina, 65

A.L. Petranovska, 112, 119, 138, 173

I.S. Petrik, 131

T.I. Petriv, 172

N. Petrov, 179, 181

O. Petuhov, 69, 72, 73

N.B. Pirtskhalava, 156

Yu.K. Pirskyy, 130, 132

Yu.P. Piryatinsky, 145

P. Pissis, 22, 158

V. Plavan, 97

Yu.V. Plyuto, 128

D.I. Pobokin, 63

E.N. Poddenezhny, 133, 134

B. Podskościelna, 124

V.O. Pokrovskiy, 78, 79

O.I. Polovina, 104

M.G. Popryaga, 169

L. Postolachi, 69, 72, 135

I. Povar, 122, 166

S.V. Prokhorenko, 169

S.L. Prokopenko, 136

I. Protsak, 137

N.A. Prybora, 60

Ie.V. Pylypchuk, 92, 170

I.V. Pylypchuk, 138

Ie. Pylypchuk, 177

R

V.Z. Radkevich, 49

A.E. Raevskaya, 35

T.L. Rakyts‟ka, 66

I.J. Ramirez-Calera, 85

G.G. Repich, 75

O.S. Remez, 74, 139

N.M. Rezanova, 37, 140

N. Rezanova, 97

O.P. Ripko, 100, 150

S. Rogalsky, 122

S.P. Rogalsky, 122, 157

N.V. Roik, 141, 154

http://www.ncbi.nlm.nih.gov/pubmed/?term=Pavlovich%20O%5Bauth%5D

192

V.M. Rozenbaum, 57, 63, 67

I. Rubashvili, 98

V.P. Ruchko, 150

A.V. Rudenko, 131

G.Ya. Rudko, 145

N.V. Rusakova, 58, 149

V. Rusu, 69, 72, 122, 135

O.A. Rybachuk, 172

V.A. Ryzhov, 99

S

Y.I. Sachanova, 160

N.D. Sakhnenko, 113, 142, 160

V. Sakhno, 108

I.S. Samchileev, 46

T.F. Samoylenko, 94

O. Sapyanenko, 97, 140

D.V. Savchenko, 145

Ya.I. Savchuk, 163, 182

D.P. Savitskyi, 143

V.F. Sazonova, 29, 76

M. Sęczkowska, 32, 34, 38, 55, 77

V. Sedlarik, 165

O.Yu. Semchuk, 70, 110

O. Severynovska, 54

D.V. Shaban, 83

N. Shalvashvili, 155

L.F. Sharanda, 132

T. Sharashenidze, 155, 156

Yu.S. Shchukin, 120

V.S. Shelkovsky, 68

Y.Y. Shlapa, 23

I.A. Shpak, 59

S.V. Shulga, 146, 147

O.V. Shynkarenko, 162, 169

O.V. Severynovska, 75

S.V. Sevostianov, 145

Yu. Sementsov, 144

V.S. Sidorenko, 63

I.V. Siora, 167, 171

G.I. Skolyar, 100

J. Skubiszewska-Zięba, 19, 74, 87,

139

E. Skwarek, 101, 102, 103, 180

V.V. Sliesarenko, 60, 148

N. Smirnova, 21, 24, 93

N.P. Smirnova, 131

O.V. Smirnova, 48

S.S. Smola, 58, 149

S. Snegir, 115

D.S. Sofronov, 28

E.V. Sokovykh, 150

L.M. Soldatkina, 39, 41

S.O. Solopan, 23

E.D. Solovyova, 151

A.K. Soni, 42

M. Souli, 84

A.S. Stanislavov, 42

S.P. Starik, 145

D.L. Starokadomsky, 146

O. Starostenko, 105, 106, 108

O. M. Starostenko, 152, 157

G.M. Starukh, 40

O.N. Stavinskaya, 174

N. Stefan, 24

D. Sternik, 53, 92, 153

N.V. Stolyarchuk, 126

A.V. Strizhak, 92

O.L. Stroyuk, 35

M. Studziński, 26, 137

V.I. Styopkin, 89

I. Sulym, 153

A.V. Sviatogor, 146

T

T.R. Tatarchuk, 47

V. Tertykh, 22, 26, 43, 53, 91, 92,

122, 137, 180

V.A. Tertykh, 145, 172

N. Timbaliuc, 52, 181

V.V. Tkachenko, 30

L.I. Trakhtenberg, 57

I. Tretyakova, 54

I.M. Trofymchuk, 154

G. Tsintskaladze, 155, 156

V.G. Tsitsishvili, 95

О.Ye. Tsomyk, 67

K.S. Tsyganenko, 163, 182

A.S. Tupchienko, 130

S.P. Turanska, 112, 119, 138, 173

V.V. Turov, 165, 167, 171, 173

A.F. Tymchuk, 80


193

U

A.I. Ukrainets, 50, 51

I. Uvarova, 178

V

M. Vaclavikova 126

A.V. Vakaliuk, 49

A.V. Vashchuk, 157

A.A. Vasko, 89

A.V. Vasin, 145

O. Vassiliadi, 158

R.G. Vasyliev, 172

M.V. Ved‟, 113, 142

M.V. Ved, 160

P.Y. Vezdenetskyi, 146, 147

O.A. Viltsaniuk, 37

O.O. Viltsaniuk, 183

N. Vityuk, 177, 184

N.N. Vlasova, 185

N.A. Volkova, 186

V.Y. Volkova, 66

N. Volvach, 117

E.F. Voronin, 159

W

S. Wacke, 104

R. Wojnarowska-Nowak, 169

X

Y

P.N. Yakushev, 99

A.A. Yanovska, 42

I.Yu. Yermolenko, 160

O. Yershova, 81

I.Yu. Yevchuk, 94

M.S. Yukhta, 186

K.G. Yunuskhodjaeva, 161

T.I. Yushchenko, 118

Z

O.M. Zaichenko, 163, 182

V.N. Zaitsev. 27

V.I. Zarko, 19, 50, 51, 74, 139

M. Zautashvili, 98

M.A. Zavrichko, 39

V.I. Zelentsov, 56

M.G. Zhludenko, 82

Yu.L. Zub, 20, 60, 101, 103, 126,

148



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