Volume 3. Issue 9. Pages 1377-1564. 2008 ISSN 1934-578X (printed); ISSN 1555-9475 (online)

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NPC Natural Product Communications

EDITOR-IN-CHIEF

DR. PAWAN K AGRAWAL Natural Product Inc. 7963, Anderson Park Lane, Westerville, Ohio 43081, USA agrawal@naturalproduct.us EDITORS

PROFESSOR GERALD BLUNDEN The School of Pharmacy & Biomedical Sciences, University of Portsmouth, Portsmouth, PO1 2DT U.K. axuf64@dsl.pipex.com

PROFESSOR ALESSANDRA BRACA Dipartimento di Chimica Bioorganicae Biofarmacia, Universita di Pisa, via Bonanno 33, 56126 Pisa, Italy braca@farm.unipi.it

PROFESSOR DEAN GUO State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing 100083, China gda5958@163.com

PROFESSOR J. ALBERTO MARCO Departamento de Quimica Organica, Universidade de Valencia, E-46100 Burjassot, Valencia, Spain alberto.marco@uv.es

PROFESSOR YOSHIHIRO MIMAKI School of Pharmacy, Tokyo University of Pharmacy and Life Sciences, Horinouchi 1432-1, Hachioji, Tokyo 192-0392, Japan mimakiy@ps.toyaku.ac.jp

PROFESSOR STEPHEN G. PYNE Department of Chemistry University of Wollongong Wollongong, New South Wales, 2522, Australia spyne@uow.edu.au

PROFESSOR MANFRED G. REINECKE Department of Chemistry, Texas Christian University, Forts Worth, TX 76129, USA m.reinecke@tcu.edu

PROFESSOR WILLIAM N. SETZER Department of Chemistry The University of Alabama in Huntsville Huntsville, AL 35809, USA wsetzer@chemistry.uah.edu

PROFESSOR YASUHIRO TEZUKA Institute of Natural Medicine Institute of Natural Medicine, University of Toyama, 2630-Sugitani, Toyama 930-0194, Japan tezuka@inm.u-toyama.ac.jp

ADVISORY BOARD Prof. Viqar Uddin Ahmad Karachi, Pakistan

Prof. Øyvind M. Andersen Bergen, Norway

Prof. Giovanni Appendino Novara, Italy

Prof. Yoshinori Asakawa Tokushima, Japan

Prof. Maurizio Bruno Palermo, Italy

Prof. Carlos Cerda-Garcia-Rojas

Mexico city, Mexico

Prof. Josep Coll Barcelona, Spain

Prof. Geoffrey Cordell Chicago, IL, USA

Prof. Samuel Danishefsky New York, NY, USA

Dr. Biswanath Das Hyderabad, India

Prof. A.A. Leslie Gunatilaka Tucson, AZ, USA

Prof. Stephen Hanessian Montreal, Canada

Prof. Michael Heinrich London, UK

Prof. Kurt Hostettmann Lausanne, Switzerland

Prof. Martin A. Iglesias Arteaga Mexico, D. F, Mexico

Prof. Jerzy Jaroszewski Copenhagen, Denmark

Prof. Teodoro Kaufman Rosario, Argentina

Prof. Norbert De Kimpe Gent, Belgium

Prof. Hartmut Laatsch Gottingen, Germany

Prof. Marie Lacaille-Dubois Dijon, France

Prof. Shoei-Sheng Lee Taipei, Taiwan

Prof. Francisco Macias Cadiz, Spain

Prof. Anita Marsaioli Campinas, Brazil

Prof. Imre Mathe Szeged, Hungary

Prof. Joseph Michael Johannesburg, South Africa

Prof. Ermino Murano Trieste, Italy

Prof. Virinder Parmar Delhi, India

Prof. Luc Pieters Antwerp, Belgium

Prof. Om Prakash Manhattan, KS, USA

Prof. Peter Proksch Düsseldorf, Germany

Prof. William Reynolds Toronto, Canada

Prof. Raffaele Riccio Salerno, Italy

Prof. Ricardo Riguera Santiago de Compostela, Spain

Prof. Satyajit Sarker Coleraine, UK

Prof. Monique Simmonds Richmond, UK

Prof. Valentin Stonik Vladivostok, Russia

Prof. Hermann Stuppner Innsbruck, Austria

Prof. Apichart Suksamrarn Bangkock, Thailand

Prof. Hiromitsu Takayama Chiba, Japan

Prof. Karin Valant-Vetschera Vienna, Austria

Prof. Peter G. Waterman Lismore, Australia

Prof. Paul Wender Stanford, USA

Chemical Composition of Diterpenes from the Brown Alga Canistrocarpus cervicornis (Dictyotaceae, Phaeophyceae) Aline Santos de Oliveiraa, Diana Negrão Cavalcantia, Éverson Miguel Biancob, Joel Campos de Paulac, Renato Crespo Pereiraa, Yocie Yoneshigue-Valentind and Valéria Laneuville Teixeiraa,* aDepartmento de Biologia Marinha, Instituto de Biologia, Universidade Federal Fluminense, P.O. Box 100.644, Niterói, RJ, Brazil, 24001-970 bPrograma de Pós-Graduação em Química Orgânica, Instituto de Química, Universidade Federal Fluminense, Niterói, RJ, Brazil, 24020-015 cDepartamento deBiologia Vegetal, Instituto de Biologia Roberto AlcântaraGomes, Universidade do Estado do Rio de Janeiro, RJ, Brazil, 20550-013 dDepartamento de Botânica, Instituto de Biologia, Universidade Federal do Rio de Janeiro, RJ, Brazil, 21941-590 gbmvalt@vm.uff.br Received: June 11th, 2008; Accepted: June 26th, 2008

Specimens of two populations of Canistrocarpus cervicornis were collected from two different localities on the Brazilian coast about 2000 kilometers apart. The CH2Cl2 extracts were analyzed by 1H NMR and HRGC-MS techniques. A total of fourteen diterpenes were detected, eight dolastanes (1-8) and five secodolastanes (9-13). The results obtained revealed a typical pattern for C. cervicornis, which did not vary according to the geographical region. Keywords: Canistrocarpus cervicornis, diterpenes, dolastane, secodolastane, chemical variation, HRGC-MS, NMR. Brown algae (Phaeophyceae) are generally dominant along the coast of Brazil in terms of biomass, but present a smaller number of species in comparison with the red (Rhodophyceae) and green algae (Chlorophyceae) [1,2]. Two orders in particular are important for Brazilian coasts, the Fucales and Dictyotales (e.g. Dictyota Lamouroux) [2]. The Dictyotales consists of the large family Dictyotaceae Lamouroux, in which some 20 genera are currently recognized, and two small families, Dictyotopsidaceae and Scoresbyellaceae [3]. The Dictyotaceae is subdivided into two tribes, Dictyoteae and Zonarieae. Recently, De Clerck and collaborators [3] published a revised classification of the Dictyoteae based on rbcL and 26S ribosomal DNA sequence analysis. In this study, the authors proposed the separation of Dictyoteae into three genera, Dictyota Lamouroux,

Canistrocarpus De Paula et De Clerck, and Rugulopteryx De Clerck et Coppejans. The genus Canistrocarpus includes the old species Dictyota cervicornis Kützing, D. crispata Kützing and D. magneana De Clerck et Coppejans. As we have a great interest in the diterpenes from algae of the family Dictyotaceae [e.g. 4,5], we examined the chemical variation in these compounds from Canistrocarpus cervicornis collected from two widely different localities along the Brazilian coast by using NMR and HRGC-MS techniques. In previous investigations of this alga (as Dictyota cervicornis Kützing) collected in Brazil, 11 dolastane and 4 secodolastane diterpenes were isolated [6-9]. The populations of C. cervicornis presented dolastane and secodolastane diterpenes as major metabolites, which result from a first cyclization of geranyl-geraniol between positions 1 and 11 [4,10-11]. Many

NPC Natural Product Communications 2008 Vol. 3 No. 9

1469 - 1472

1470 Natural Product Communications Vol. 3 (9) 2008 Oliveira et al.

OH

OH

OH

RO

OH

OH

OH

1 2 R = H 4 R = H 3 R = Ac 5 R = Ac

OH

RO

OH

OH

AcOOAc

O OH

O

R 6 R = H 8 9 R = H 7 R = Ac 10 R = OH 11 R = Oac

O OH

OROO OH

O

OH 12 R = H 14 13 R = Ac of these diterpenes were isolated from other populations of this species and also from populations of C. crispatus (as Dictyota crispata) from Brazil [12]. In this context, the populations named Dictyota divaricata and D. linearis from the Caribbean Sea [13,14] and Japan [15-18], D. dichotoma [19-22] and D. indica from Pakistan [23-24], D. furcellata from Australia [25] and Dictyota sp. from the Canary Islands [26] could be considered as C. cervicornis. The two extracts of C. cervicornis presented similar profiles on TLC analysis on silica gel layers (CH2Cl2/EtOAc 4:1 as eluent). The 1H NMR spectra of the extracts of the two populations revealed the presence of 8 as the major diterpene, followed by the dolastane 6 and the secodolastane diterpene 10. The dolastanes 1, 3 and 5 and secodolastane diterpenes 9, 12 and 14 were either absent or present in the crude extract as either minor or trace components (Table 1). The 1H NMR spectra of the two extracts after filtration on silica gel with CH2Cl2/EtOAc (9:1) revealed the presence of 2 and 3 as major diterpenes, but either the absence or a small amount of 6 and 8. The crude extract of the Bahia population presented the dolastane diterpene 4,7-diacetoxy-14-hydroxydolastane-1(15),8-diene (8) as the major metabolite, forming more than 50% of the crude extract. However, the dolastane diterpene 6, the secodolastane diterpenes isolinearol (10) and isolinearol acetate (13) were also encountered in great quantity.

Table 1: Presence of the diterpenes in two populations in the two treatments.

Bahia Rio de Janeiro Compds crude extract after filtration crude extract after filtration

1 tr nd nd tr 2 nd + + + 3 tr + nd + 4 + nd + tr 5 + nd + nd 6 tr nd + tr 7 tr nd + nd 8 + tr + nd 9 nd nd tr tr 10 + + + + 11 + + + + 12 tr tr + + 13 + + + + 14 tr tr + +

others + + + + + present, tr = trace amounts (<5% of the crude extract), nd = not detected In the crude extract of the population from northern Rio de Janeiro, dolastane 8 was again the major metabolite, present along with dolastanes 2, 4-8 and the six secodolastanes diterpenes 10-14. About ten of the diterpenes identified in this population were related to those of C. cervicornis from Angra dos Reis, Rio de Janeiro [6-8,27]. This similarity confirmed an important role of the diterpenes as taxonomic and biogeographic markers. The HRGC/MS analysis corroborated the NMR results, after filtration (see Supplementary Data). Although the HRGC-MS technique is suitable for the analysis of algal extracts [28], the heating procedure resulted in the formation of artifacts (2 and 3) generated by dehydration of the diterpenes. Therefore, the use of less acid organic solvent in extraction (such as n-hexane), caution in drying the biological material, and NMR qualitative and quantitative analysis indicated that further investigation of the diterpene composition would be of value. Finally, the results obtained revealed that this species has a chemical pattern that suffers little variation resulting from geographic location. Experimental

Algal material: Specimens of C. cervicornis were collected during February 2005 in Praia da Penha, Vera Cruz, Bahia (lat. 12°58’22”S, long. 038°30’45”W) and in Praia do Saco do Céu, Ilha Grande, Rio de Janeiro (lat. 23°00’24”S, long. 044°19’05”W). These places are approximately 2000 km. apart. The algae were collected at depths varying from 2 to 5 meters. Voucher specimens are deposited

Diterpenes from Canistrocarpus cervicornis Natural Product Communications Vol. 3 (9) 2008 1471

in the Herbarium of the Universidade do Estado do Rio de Janeiro (HRJ). Extraction: The air-dried algae were extracted with CH2Cl2 at room temperature (25°C). The solvent was evaporated under reduced pressure yielding brownish residues. Aliquots of the crude extracts (20 mg for each population) were filtered through silica gel with 30 mL of CH2Cl2 /EtOAc (9:1). NMR analysis: 1H NMR (300 MHz) spectra were recorded on a Varian Unity Plus 300 spectrometer using CDCl3 as solvent and TMS as internal standard. Chemical shifts were reported in δ (ppm) and coupling constants (J) in Hz. Gas chromatographic analysis (HRGC): The preliminary HRGC analysis was carried out using an HP 5890 CG equipped with an SE-54 glass capillary column (15 m x 0.25 mm; film thickness 0.25 µm) and a FID detector. HRGC/MS analysis: An aliquot of the extract was diluted with an appropriate volume of ethyl acetate and analysed by HRGC-MS on a HP 6890 series GC system, coupled to a HP 5973 mass selective detector in the electron impact mode (70 eV), equipped with a

HP-1 MS capillary column (30 m x 0.25 mm; film thickness 0.25 µm). Injector and detector temperatures were set at 270oC and 290oC, respectively. The temperature program was kept at 160oC, then programmed to 260oC at a rate of 4o C/min and finally raised at a rate of 15oC/min to 290oC for 15 min. Hydrogen was the carrier gas at a flow rate of 1 mL/min. Diluted sample were injected manually in the split mode (1/10 or 1/20). Data were obtained from Frd area percent data. The chemical components were identified based on comparison of their mass spectra with those of standards and/or literature data, by co-injection technique in HRGC, and with Wiley 275 library data of the HRGC/MS system. Silica gel GF254 (Merck) was used for TLC. Supplementary data: Mass spectral data of isolated diterpenes (1-5, 8-10 and 11) is presented (Table 2). Acknowledgments - We are grateful to CNPq for financial support and for Productivity Fellowships to YYV, RCP and VLT. EMB also thanks CNPq for a Doctor’s degree fellowship. DNC and ASO appreciate CAPES for providing ProDoc and Master degree fellowships, respectively. The authors are also grateful to Dr Claudia Rezende and Angelo Pinto for use of the HRGC and HRGC-MS equipment.

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Constituents of ‘Caincin’, a Bioactive Saponin Fraction from the Root-bark of Chiococca alba (L.) Hitch. Jnanabrata Bhattacharyya, S. K. Srivastava, M. F. Agra and George Majetich 1483

A New Biflavanone from Ochna lanceolata Shaik I. Khalivulla, Nimmanapalli P. Reddy, Bandi A.K. Reddy, Ramireddy V.N. Reddy, Duvvuru Gunasekar, Alain Blond and Bernard Bodo 1487

Isoflavonoids from an Egyptian Collection of Colutea istria Mohamed M. Radwan 1491

A Flavonoid Glycoside from the Leaves of Morinda tinctoria Atish K. Sahoo, Nisha Narayanan, S. Rajan and Pulok K. Mukherjee 1495

New Anthocyanins from Stem Bark of Castor, Ricinus communis Robert Byamukama, Monica Jordheim, Bernard Kiremire and Øyvind M. Andersen 1497

Prenylated Xanthones and a Benzophenone from Baphia kirkii Modest C. Kapingu and Joseph J. Magadula 1501

Phytochemical and Antimicrobial Investigation of Latex from Euphorbia abyssinica Gmel. Fathy EL- Fiky, Kaleab Asres, Simon Gibbons, Hala Hammoda, Jihan Badr and Shemsu Umer 1505

Fenugreek Extract Rich in 4-Hydroxyisoleucine and Trigonelline Activates PPARα and Inhibits LDL Oxidation: Key Mechanisms in Controlling the Metabolic Syndrome Alvin Ibarra, Kan He, Naisheng Bai, Antoine Bily, Marc Roller, Aurélie Coussaert, Nicolas Provost

and Christophe Ripoll 1509

Comparison of Different Techniques for Extraction of Biologically Active Compounds from Achillea Millefolium Proa Antoaneta Trendafilova and Milka Todorova 1515

Extraction Methods Play a Critical Role in Chemical Profile and Biological Activities of Black Cohosh Bei Jiang, Kurt A. Reynertson, Amy C. Keller, Linda S. Einbond, Debra L. Bemis, I. Bernard Weinstein, Fredi Kronenberg and Edward J. Kennelly 1519

Antimicrobial Activity and Chemical Composition of Callistemon pinifolius and C. salignus Leaf Essential Oils from the Northern Plains of India Mohit Saxena, Kunal Shrivastava, Santosh K. Srivastava, Suaib Luqman, Ajai Kumar, Mahendra. P. Darokar, Kodakandla V. Syamsundar, Tota Ram and Suman P. S. Khanuja 1533

Analysis of Chemical Constituents of Tithonia rotundifolia Leaf Essential Oil Found in Nigeria Adebayo A. Gbolade, Vânia Tira-Picos and J.M.F. Nogueira 1537

Sedative Effect of Eucalyptus urophylla and E. brassiana in mice Gisele F.D. Teixeira, Roberto C.P. Lima Júnior, Edilberto R. Silveira, Marinalva O. Freitas and Adriana R. Campos 1539

In Vitro Antifungal Activity of Polysulfides-Rich Essential Oil of Ferula latisecta Fruits against Human Pathogenic Dermatophytes Mehrdad Iranshahi, Abdolmajid Fata, Bahareh Emami, Bibi Mohadeseh Jalalzadeh Shahri and Bibi Sedigheh Fazly Bazzaz 1543

Biological Activity and Composition of the Essential Oil of Dracocephalum moldavica L. Grown in Iran Ali Sonboli, Mehran Mojarrad, Abbas Gholipour, Samad Nejad Ebrahimi and Mitra Arman 1547

Antioxidant Activity and Chemical Composition of Essential Oils from Schinus fasciculata (Griseb.) I.M. Johnst and S. praecox (Griseb.) Speg. Ana P. Murray, Silvana A. Rodriguez and María G. Murray 1551

Essential oil Composition of Dendropanax gonatopodus from Monteverde, Costa Rica. An ab initio Examination of Aromadendrane Sesquiterpenoids William N. Setzer 1557

Natural Product Communications 2008

Volume 3, Number 9

Contents

Page

Anti-tuberculosis Compounds from two Bolivian Medicinal Plants, Senecio mathewsii and Usnea florida Qi Hong, David E. Minter, Scott G. Franzblau and Manfred G. Reinecke 1377

Natural Products from Polygonum perfoliatum and their Diverse Biological Activities Chi-I Chang, Fei-Jane Tsai and Chang-Hung Chou 1385

Phytochemical Characterization of the Australian (Aboriginal) Medicinal Plant Dolichandrone heterophylla and Influence of Selected Isolated Compounds on Human Keratinocytes Thomas Dzeha, Kristian Wende, Manuela Harms, Ju Ju (Burriwee) Wilson, Jim Kohen, Subra Vemulpad, Joanne Jamie and Ulrike Lindequist 1387

Analysis of Saponin Mixtures from Alfalfa (Medicago sativa L.) Roots using Mass Spectrometry with MALDI Techniques H. Ewa Witkowska, Zbigniew Bialy, Marian Jurzysta and George R. Waller 1395

Control of Allantoin Accumulation in Comfrey Paulo Mazzafera, Kátia Viviane Gonçalves and Milton Massao Shimizu 1411

Trigonelline (N-methylnicotinic acid) Biosynthesis and its Biological Role in Plants Hiroshi Ashihara 1423

Biosynthesis and Catabolism of Purine Alkaloids in Camellia Plants Misako Kato and Hiroshi Ashihara 1429

A View on the Active Site of Firefly Luciferase Franklin R. Leach 1437

Study on the Chemical Constituents of Premna integrifolia L. Nguyen Thi Bich Hang, Pham Thanh Ky, Chau Van Minh, Nguyen Xuan Cuong, Nguyen Phuong Thao and Phan Van Kiem 1449

Τ-Cadinol Nerolidol Ether from Schisandra chinensis Asmita V. Patel, Gerald Blunden, Peter D. Cary, Lubomír Opletal, Markéta Beránkova, Kersti Karu, David E. Thurston and Milan Pour 1453

Bioactive Semisynthetic Derivatives of (S)-(+)-Curcuphenol Helena Gaspar, Cristina Moiteiro, João Sardinha and Azucena González-Coloma 1457

Eco-contribution to the Chemistry of Perezone, a Comparative Study, Using Different Modes of Activation and Solventless Conditions Joel Martínez, Benjamín Velasco-Bejarano, Francisco Delgado, Rocío Pozas, Héctor M. Torres Domínguez, José G. Trujillo Ferrara, Gabriel A. Arroyo and René Miranda 1465

Chemical Composition of Diterpenes from the Brown Alga Canistrocarpus cervicornis (Dictyotaceae, Phaeophyceae) Aline Santos de Oliveira, Diana Negrão Cavalcanti, Éverson Miguel Bianco, Joel Campos de Paula, Renato Crespo Pereira, Yocie Yoneshigue-Valentin and Valéria Laneuville Teixeira 1469

Cembranoid Diterpenes from the Soft Corals Sarcophyton sp. and Sarcophyton glaucum Daniela Grote, Kamel H. Shaker, Hesham S. M. Soliman, Muhammmad M. Hegazi and Karlheinz Seifert 1473

Dolabellane Diterpenes from Cleome droserifolia Hoda M. Fathy, Mohamed I. Aboushoer, Fathallah M. Harraz, Abdallah A. Omar, Gilles Goetz and Rafael Tabacchi 1479

(Continued inside back cover)