www.rsc.org/materialsRegistered Charity Number 207890

Showcasing work from a consortium of chemists,

photo-electro-chemists and physical chemists

engaged in polyoxometalates and polymer research at

the Universities of Paris-Sud 11, Versailles

Saint-Quentin and Lehigh University.

Title: Poly(ionic liquid) and macrocyclic polyoxometalate

ionic self-assemblies: new water-insoluble and visible light

photosensitive catalysts

This work introduces a facile synthesis method of water-insoluble

and visible light photosensitive Polyoxometalates and Poly(ionic

liquid) assemblies (POM@PILs). The POM@PILs hybrids open the way

for a variety of effi cient photo-electro-catalysis of multi-electronic

reactions under solar light, including the purifi cation of water.

As featured in:

See R. N. Biboum et al.,

J. Mater. Chem., 2012, 22, 319.

0959-9428(2012)22:2;1-1

ISSN 0959-9428

www.rsc.org/materials Volume 22 | Number 2 | 14 January 2012 | Pages 253–744

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PAPERBin Zhang et al.Synergism of interparticle electrostatic repulsion modulation and heat-induced fusion: a generalized one-step approach to porous network-like noble metals and their alloy nanostructures

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Dynamic Article LinksC<Journal ofMaterials Chemistry

Cite this: J. Mater. Chem., 2012, 22, 319

www.rsc.org/materials COMMUNICATION

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Poly(ionic liquid) and macrocyclic polyoxometalate ionic self-assemblies: newwater-insoluble and visible light photosensitive catalysts†

Rosa Ngo Biboum,a Floriant Doungmene,a Bineta Keita,*a Pedro de Oliveira,a Louis Nadjo,a

B�en�edicte Lepoittevin,*b Philippe Roger,b Francois Brisset,c Pierre Mialane,*d Anne Dolbecq,d

Israel M. Mbomekalle,d C�eline Pichon,e Panchao Yin,e Tianbo Liue and Roland Contant‡

Received 14th September 2011, Accepted 3rd October 2011

DOI: 10.1039/c1jm14573h

Several poly(ionic liquid)s (PILs) were synthesized and assembled

with a multielectronic-process sustaining polyoxometalate (POM)

into new green and water-insoluble nanomaterials (POM@PILs).

They are visible light photosensitive, unlike their two components. A

synergic effect was highlighted for the first time. POM@PILs

achieve complete photodegradation of AO7 in aerobic media. The

photocatalysts were recoverable and recyclable.

The design and synthesis of efficient materials for solar energy

conversion remain a challenging research topic. Among a wide

variety of photocatalysts, polyoxometalates (POMs) have been

actively studied over the past few decades due to their good perfor-

mance under UV light irradiation in homogeneous or heterogeneous

processes.1 POMs are a vast class of green, cheap and stable early

transition metal–oxygen clusters which exhibit semiconductor-like

photochemical behaviors due to analogous electronic characteristics

(band gap transition for semiconductors and HOMO–LUMO

transition for POMs).1a–f However, there are several drawbacks that

restrict their use as efficient photocatalysts in multi-electron reactions

such as fuel formation or degradation of recalcitrant organic

pollutants. First, POMs are very soluble in water and polar solvents.

Second, there is still room for improvement of their photocatalytic

activities under visible light irradiation (l > 400 nm) for efficient

substrate conversion. Third, the kinetics of the photoreduction, in

most cases, decrease dramatically after fixation of one electron.1a

aLaboratoire de Chimie Physique, Groupe d’Electrochimie et dePhoto�electrochimie, UMR 8000, CNRS, Universit�e Universit�e Paris-Sud11, Batiment 350, 91405 Orsay Cedex, France. E-mail: bineta.keita@u-psud.frbLaboratoire de Chimie Organique Multifonctionnelle, Equipe GlycochimieMol�eculaire et Macromol�eculaire Institut de Chimie Mol�eculaire et desMat�eriaux d’Orsay UMR 8182, CNRS Universit�e Paris-Sud 11,Batiment 420, 91405 Orsay Cedex, FrancecInstitut de Chimie Mol�eculaire et des Mat�eriaux d’Orsay, UMR 8182CNRS, Universit�e Paris-Sud XI, 91405 Orsay Cedex, FrancedInstitut Lavoisier de Versailles, UMR 8180, Universit�e de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex,FranceeDepartment of Chemistry Lehigh University, Bethlehem, PA, 18015, USA

† Electronic supplementary information (ESI) available. See DOI:10.1039/c1jm14573h

‡ Retired.

This journal is ª The Royal Society of Chemistry 2012

Although several POM-based heterogeneous photocatalysts have

been investigated,1a–h the development of water-insoluble, recyclable

and environmentally friendly POM-containing multielectronic pho-

tocatalysts remains a challenge. Very recently, we reported the first

examples of fast and reversible photoproduction of four electron-

reduced tungstic POMs but water-soluble systems under visible or

solar light irradiation.1h Following this achievement, it is anticipated

that the ionic self-assembly (ISA) of a POM and a poly(ionic liquid)

(PIL)1j–lwould combine several advantages including a facile route to

the design of hybrids, the transparency of PILs in near UV-vis-NIR

regions and the availability of more binding charges in PILs than in

the corresponding monomers (ILS).

Herein, we report on a green synthesis of visible light induced

multielectronic and water-insoluble photocatalysts based on the ISA

of the macrocyclic POM [H7P8W48O184]33� (1)2 and different imida-

zolium-based PILs. This POM is stable in aqueous media, roughly

from pH ¼ 0 to 8. It undergoes fast and chemically reversible 8-

electron reduction processes at a remarkably favorable potential

without decomposition.2b Such nanohybrid photocatalysts are

unprecedented. They open the way for a variety of photo-electro-

catalyses of multi-electronic reactions under solar light including

water purification applications. In this communication, the activity of

1@PIL hybrids under visible light (l > 400 nm) was evaluated using

the photocatalytic transformation of acid orange 7 (AO7) in aqueous

media with oxygen as an eco-friendly oxidant. AO7 is a highly toxic

azo dye, resistant to biodegradation and UV-vis photo-

degradation.1h,3 Recent studies have reported successful photo-

degradation of AO7 with homogeneous POM-based systems under

UV-near-vis,3 visible1h or solar1h light irradiation. However, to our

knowledge, there is no report on the efficient destruction ofAO7with

water-insoluble POM-based photocatalysts under visible light irra-

diation in aerated or oxygenated aqueous media. The performances

of 1@PIL hybrids towards this reactionwere comparedwith those of

selected Keggin or Dawson-type POM-based hybrids.

Scheme 1 features the different POMs which were prepared

according to literature methods.2,4 All the polyoxometalates consid-

ered in this study have been characterized by single-crystal X-ray

diffraction.2,4 Unless otherwise stated, a pH 1 (HCl) medium was

used for the study of the influence of the nature of the POM because

of the hydrolytic instability of PW12 at pH > 1.2. An oxygen satu-

rated solution is designated as ‘‘oxygenated’’ for short.

J. Mater. Chem., 2012, 22, 319–323 | 319

Scheme 1 Polyhedral representation of the POMs used in this study.

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Monomers (ILs) were prepared in one step by a quaternization

reaction according to previously reported methods with slight

modifications.5 Two styrene-type monomers (ILs) named 1-(4-

vinylbenzyl)-3-butylimidazolium chloride IL2 and 1-(4-vinylbenzyl)-

3-methylimidazolium chloride IL1 were prepared by reaction of

4-vinylbenzylchloride with N-butylimidazole or N-methylimidazole,

respectively (Scheme S1†). Different from styrene-type ILs, the direct

linkage of the imidazolium group to thePIL backbonemay affect the

properties of the resulting PIL. So, a third monomer IL3 was

prepared by reaction of 1-vinylimidazole with bromoethane (Scheme

S2†). PILs (Scheme 2) were synthesised by conventional radical

polymerization in solution using 2,20-azobis(isobutyronitrile) as thethermal initiator.

Upon mixing of aqueous solutions of a selected POM and a PIL

(or IL), a new material precipitates immediately. The insolubility in

water of the hybrids is confirmed by the complete disappearance of all

absorption bands of its components. Fig. S1† features the SEM

images of the as-prepared 1@PIL hybrid powder as a representative

example of photocatalyst morphology. Further details for all the

syntheses are relegated to the ESI†.

The characterization of ILs was carried out by 1H NMR. All the

detected peaks are consistent with the chemical structure of the ILs.1H NMR spectra of the PILs show that the signals of vinyl protons

from the IL at 5–6 ppm disappeared and revealed the presence of

broad peaks at 1–2.5 ppm corresponding to –CH2–CHprotons of the

polymers backbone. The thermal properties of PILs were investi-

gated by thermogravimetric analysis (TGA). The PILs have good

thermal stability in agreement with results obtained by Tang et al.5a

Fig. S2† shows that the association of 1 and PIL1 seems to slightly

increase the thermal stability of PIL1 (see ESI† for NMR and TGA

details).

Scheme 2 Structures of PILs.

320 | J. Mater. Chem., 2012, 22, 319–323

The polymers’ molar masses were determined by static light scat-

tering (SLS). The basis of the SLS data analysis is the Rayleigh–

Gans–Debye equation.6The detailed principle and equations for SLS

can be found in our earlier publications.7The SLS results were treated

by the Zimm plot and from there the weight-average molar mass

(Mw) of the polymers are determined as 36 410, 35 630, and 16 190 g

mol�1 (�5% uncertainty), respectively for PIL2, PIL1 and PIL3 as

shown in Table S1†. Fig. S3† features the Zimm plot of the PILs.

The IR spectra of the POMs, PILs and POM@PIL composites

have been recorded in order to evidence the incorporation of the

polyoxometalates in the PIL matrices but also to check the integrity

of the inorganic complexes after the integration process. Indeed, this

technique is particularly adapted for such purposes as the POM

precursors used here show characteristic vibrations under 1200 cm�1

(Fig. S4A†) while PILs exhibit vibrations in the 1200–1600 cm�1

range (Fig. S4B†). More precisely, we may mention that it is well-

known that theM]O and theM–O–M (M¼W,Mo) vibrations of

POMs are observed in the 930–1000 cm�1 and 750–900 cm�1 ranges

respectively. Additionally, the P–O vibrations are observed in the

1000–1100 cm�1 range and the Si–O ones at ca. 900 cm�1.8For all the

families of compounds studied here (1@PILs (Fig. S4C†),

P2M18@PILs (M ¼ W or Mo) (Fig. S4D†) and XW12@PILs (X ¼H2, P or Si) (Fig. S4E†)), a strict superposition of the POM and the

PIL vibrations is observed in the POM@PILs spectra, proving the

successful formation of the composites reported here. The stability of

the POMs in the POM@PIL hybrids was also confirmed by elec-

trochemical characterization.2b,9

Diffuse reflectance UV-vis-NIR spectroscopy (DRS) was used to

get more insight into the characteristics, in the solid state, of POM-

based hybrids. DRS of POM@IL and POM@PIL hybrids reveal

remarkable behaviors which strongly depend on the nature of the

hybrid components.10 First, the whole spectra are largely red shifted

compared to those of the organic substrate or thePOM alone. Fig. 1

shows an illustrative example with 1@PIL1 as representative.

Second, the 1@PIL1 DRS spectrum (Fig. 1) presents additional

absorption bands which extend through all the visible up toNIR light

domain. These bands are easily identified as those associated with the

first step reduction of 1. For comparison, we used spectroelec-

trochemistry for the determination of the solution absorption spec-

trum characteristics of the products resulting from the reduction of 1

(Fig. S5†). This observation must be unequivocally interpreted as an

electron transfer from PIL1 to 1. It is noteworthy that, in an

Fig. 1 DRS spectra of 1, PIL1 and 1@PIL1.

This journal is ª The Royal Society of Chemistry 2012

Fig. 2 Temporal UV-vis absorption spectral changes observed for an

AO7 (5 � 10�5 M) oxygenated solution as a function of the time in the

presence of 1@PIL1 (2 mg mL�1). l > 400 nm.

Fig. 3 Time profiles of the photodegradation in pH 1 medium under

visible light irradiation of AO7 (5 � 10�5 M): (A) photoactivities of 1 and

PIL1 solutions and dispersions of 1@IL1 and 1@PIL1; (B) photo-

activities in dispersions of 1@PIL1, 1@PIL2 and 1@PIL3.

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environment not kept in the dark, the extent of reduction increases

with the time elapsed before recording the spectra. Altogether, these

phenomena comply with the high photosensitivity of 1@PIL1.

However, hybrids assembled from PIL3 show far less important

photosensitivity than those of the other two PILs. Fig. S6† shows

that 1@IL3 presents also negligible photosensitivity compared to

those of 1@IL1 and 1@IL2. The photosensitivities of the hybrids

depend, as expected, on the redox potentials of the POMs (Fig. S7

and S8†). For example, H2W12 exhibits the most negative redox

potential,2b,9 correlatively, the hybrids obtained with it are the less

photosensitive. Obviously, an intermolecular charge transfer transi-

tion predominates in the high energy region of spectra in this ion-

paired assembly. These observations of intervalence transitions prove

the visible light photosensitivity of our new materials. Such hybrids

open the way for a variety of applications including photocatalysis of

multi-electronic reactions under visible or solar light. The photo-

degradation of AO7 is selected as an illustrative example.

The photocatalytic degradation of AO7 by the POM-based

hybrids was carried out in aqueous aerated, oxygenated or anaerobic

media (pH 1 or 5.6). The 1@PIL1 dispersions in these solutions of

AO7 were irradiated with visible light (l > 400 nm) under magnetic

stirring. At given time intervals of irradiation, an aliquot of the

supernatant liquidwas sampled in order to record theUV-vis spectral

variations of AO7. It is worth noting that the sedimentation of the

hybrid particles at the bottom of the vessel occurs within minutes

after having stopped agitating the solution. This observation is

important because easily recoverable materials are required for large

scale applications. In all these media, blank experiments showed, as

expected,1h,3 that the photodegradation of AO7 alone was negligible.

In anaerobic conditions, the intensity of the characteristic absorp-

tionbandof the azobondofAO7 at 480nmdecreaseswith time. Such

spectral changesare concomitantwith the fadingofAO7orangecolor.

After total bleaching of AO7, a blue color arising from the reduced

formof 1 is observed on the hybrid particles. This is in agreementwith

the known mechanistic scheme1h,3 where the decoloration process is

due to reductive cleavage of the azo bond of AO7 by photoreduced

POM to yield sulfanilic acid and 1-amino-2-naphthol through

4e�/4H+ processes. Thus in anaerobic conditions, AO7 is not miner-

alized as shown by the presence of its high energy bands.

Upon photolysis of 1@PIL1 dispersions in oxygenated solution of

AO7, the intensities of all the AO7 characteristic absorbance peaks

decrease with increasing the irradiation time and simultaneously

agradualdecolorationof thebulk solutionandof the1@PIL1particle

surface is observed. In the presence of 1@PIL1 (2 mg mL�1), total

decomposition ofAO7 (0.05mM) is observed after 60min irradiation

(Fig. 2 and 3A). The rate of the AO7 degradation process increases

with the concentration of 1@PIL1 for concentrations below 2 mg

mL�1. However, even with a concentration as low as 0.5 mg mL�1,

total bleaching of an AO7 (0.05 mM) solution and of the surface of

1@PIL1 particles is observed within 180 min. The comparison of the

time profiles of the decrease in AO7 concentration under other

conditions is also presented in Fig. 3A. Clearly, the photodegradation

efficiencies of 1 and PIL1 are very weak as compared to those of

1@IL1 and 1@PIL1. The photodegradation efficiency of 1@PIL1 is

significantly higher than that of 1@IL1. For example, after irradiation

for 150 min in the presence of 1@IL1, the conversion rate of AO7

reachedonly71.8%while its totaldestruction isobserved in just60min

with 1@PIL1. In the dark, the surface of 1@PIL1 or 1@IL1 particles

gradually turned orange with concomitant fading of the orange color

This journal is ª The Royal Society of Chemistry 2012

of the bulk solution. These observations are attributed to electrostatic

AO7 adsorption onto the hybrid particles. Fig. S9† features the DRS

spectrum of these orange particles that do not fade unless they are

irradiated. The maximum uptake capacity of 1@PIL1 for AO7

(32.3 mg g�1) is ca. 2-fold larger than that of one of the best systems

described in the literature.11Similar observationsweremade inpH¼ 1

solutions thanks to the pH-independent positive charges in PILs.

Thus, the uptake capacity of POM@PILs is pH-independent unlike

J. Mater. Chem., 2012, 22, 319–323 | 321

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those of most of the anionic dye adsorbents which are efficient just in

a narrow pH domain. Whatever the medium, the maximum uptake

capacity of POM@PILs hybrids is roughly three times that of

POM@ILs. Further details for AO7 uptake by the hybrids are rele-

gated to the ESI†.

The influence of the nature of the PIL on the relative extent of

AO7 photodegradation is shown in Fig. 3B. Thus, after 1 h irradia-

tion, the AO7 conversion rates decrease in the sequence: 1@PIL1

(100%) > 1@PIL2 (91%) \ 1@PIL3 (18.4%). Therefore, only

POM@PIL1 hybrids will be considered in the following. The pho-

todegradation efficiencies also strongly depend on the POM nature

(Fig. 4). The AO7 photodegradation with the other selected POMs

proceeds in two steps i.e. after the fading of the coloration of the bulk

solution, significant additional time is needed for the bleaching of the

POM@PIL1 hybrid surface, while with 1@PIL1 these two processes

take place almost simultaneously. In other words, for all POM@

PILs except 1@PIL1, the photodegradation rate is slower than that

of the uptake.

The time needed for the complete photodegradation of AO7 with

POM@PIL1 hybrids decreases in the following order:

H2W12@PIL1 (4 h) > PW12@PIL1 (3 h 30 min) > SiW12@PIL1

(3 h) > P2W18@PIL1 (2 h 30 min) [ 1@PIL1 (1 h).

In the presence of P2Mo18, the decrease in the AO7 concentration

reached only ca. 46.8% in 240 min.

This order is not in close agreement with the redox potentials of

the POMs.2b,9 The influence of other important parameters like the

photosensitivity of the hybrids and the oxidation kinetics of the

reduced POMs by oxygen must be taken into account. For example,

P2Mo18 exhibits themost positive redox potential with a two-electron

process; correlatively, its first reduction species does not possess the

driving force for facile reoxidation by oxygen. It is worth noting that

under all the experimental conditions described above, the POM@

PIL hybrids remain stable and could be reused several times. Even

though the kinetics of the photodegradation process decreases

slightly, complete destruction of the dye is still observed. Despite the

fact that 1@PIL1 is much faster than the other systems, we note that

the observation of total degradation with the Keggin POMs is

important because they are readily available inexpensive commercial

compounds.

Fig. 4 Influence of the nature of the POM on the degradation kinetics of

a 0.05 mM AO7 solution in HCl, pH ¼ 1. The concentration of the

catalyst was 2 mg mL�1.

322 | J. Mater. Chem., 2012, 22, 319–323

To get more insight into the role of oxygen in the photo-

degradation of AO7, experiments were carried out in aerated

solutions in order to reduce the concentration of oxygen. Fig. S10†

shows that in aerated solutions, it was also possible to destroy AO7

by 1@PIL1 albeit with a slower rate than in oxygenated media. For

example, total photodegradation of AO7 (0.05 mM) is observed in

180 min and 400 min, respectively, for oxygenated and aerated

dispersions of 1@PIL1 (0.5 mg mL�1). These results suggest that

dissolved oxygen plays an important role in the photodegradation

of AO7 by the hybrid. To our knowledge, such successful utiliza-

tion of oxygen in visible light induced photodegradation of AO7 by

POM-based catalysts is unprecedented. In short, these materials are

noble-metal free, easily prepared and recoverable. In addition

they perform complete photodegradation in a remarkably short

time.

Mechanistic aspects of AO7 photodegradation follow classical

pathways.1a,g,h,3,12 In the following, the actual charges brought both

by the POM and by AO7 are omitted for convenience. The pho-

todegradation pathways in anaerobic conditions are discussed in the

ESI†. In anaerobic conditions, the main pathway is a reductive

process by the reduced POM@PIL. Following this bleaching, the

blue color of the POM@PIL deepens upon continuous irradiation.

For simplicity, despite the partial reduction of the POM within the

hybrid assembly, the whole complex will be represented by

POM@PIL, instead of (POM, POM(e�)@PIL), where POM(e�) is

the first step reduction of the relevant POM before any deliberate

irradiation.

In the presence of oxygen or air, completemineralization of the dye

is observed, albeit with a faster kinetics in oxygenated than in aerated

media. As both AO7 and the POM@PIL absorb light in our

experimental conditions, we consider first the self-sensitization of

AO7, in agreement with analogous literature results.1g Completing

this scheme by the additional parallel pathway pertaining to

(POM@PIL)* is straightforward.

AO7 / AO7* (l > 400 nm)

AO7*þO2/AO7$þ þO2$�

����!HþHO $

2 /H2O2 ����!hnHO$

HO_+ AO7 / CO2 + H2O

AO7_+ + H2O / AO7 + HO_/ CO2 + H2O

AO7* + POM@PIL / AO7_+ + (POM@PIL)(e�)

This last pathway was not observed when the reactants were not in

the adsorbed state,1h but constitutes an equally preferred route in our

conditions.1g,j–l The electron injected into POM@PIL will be

captured by oxygen molecules dissolved in the suspension, producing

the superoxide anion radical O2_�, its protonated form HO2_ and

finally H2O2. Hydrogen peroxide will be reduced into HO_,

This journal is ª The Royal Society of Chemistry 2012

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a powerful oxidizing agent which will degradeAO7. The hole located

on the excited dye will be captured by H2O molecules adsorbed on

the POM@PIL surface to produce reactive hydroxyl radicals which,

in turn, oxidize the dye.

ðPOM@PILÞðe�Þ þO2/ðPOM@PILÞ þO $�2

������!HþHO $

2 /H2O2 ������!hvHO$

HO_+ AO7 / CO2 + H2O

Followed by:

AO7_+ + H2O / AO7 + HO_/ CO2 + H2O

A complementary route reads: (POM@PIL)(e�) + AO7 /

POM@PIL + sulfanilic acid + amino-1-naphthol-2, followed by

oxidative destruction of these intermediates.

This work introduces a facile synthesis of water-insoluble and

visible light photosensitive POM@PIL catalysts. The PILs and

POM@PILs were characterized by NMR, TGA, SLS, IR, DRS

and electrochemistry. The synergic effect resulting from the

combination of a multielectronic-process sustaining POM and

some PILs was highlighted. The utility of these photocatalytic and

easily recoverable and recyclable materials was exemplified by the

successful fast degradation of AO7 in the presence of dioxygen.

Unlike many adsorbents of anionic dyes, the positive charges in the

PILs are not pH-dependent. Both components of these hybrids

may be considered as green species, thus opening the way for

environmentally friendly applications such as dye removal and

degradation from wastewater and photo(electro)catalytic processes.

Future work to expand the scope of the present discovery will

include further challenging environmental purposes. Fundamental

studies will investigate adsorption kinetics and fast electron transfer

kinetics within the POM@PIL assemblies and their X-ray

characterization.

Note added after first publication

This article replaces the version published on 26th October 2011,

which contained errors in the second equation, following the para-

graph beginning with ‘‘In the presence of oxygen or air...’’, where the

AO7 and oxygen radicals were omitted.

This journal is ª The Royal Society of Chemistry 2012

Acknowledgements

This work was supported by the Centre Nationale de la Recherche

Scientifique (UMR 8000, UMR 8180 and UMR 8182), Universit�e

Paris-Sud 11, Universit�e de Versailles and Lehigh University, Beth-

lehem, Pennsylvania, 18015. Pr Anne Bleuzen and Dr Giulia For-

nasieri from LCI (UMR 8182 ICMMO, Paris-Sud) are greatly

acknowledged for TGA experiments. We are very grateful to Ms

Catherine Tams of Perkin Elmer (LesUlis, France) for her invaluable

help in the DRS experiments.

References

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