Preparation of IL-loaded microreactors based on polyelectrolyte microcapsules

Elodie Souron, Annie-Claude Gaumont, Karine Glinel, Isabelle Dez


Encapsulation of ionic liquids (ILs) in crosslinked polyelectrolyte microcapsules, made via layer-by-layer assembly (LbL) was successfully conducted. Two different ILs were studied: 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim]BF4 and 1-butyl-3-methylimidazolium hexafluorophosphate [Bmim]PF6. The polyelectrolyte microcapsules were successfully used as microcages for the synthesis of poly(methylmethacrylate) (PMMA), a non water-soluble polymer, in IL medium. Finally, the behaviour of the IL-loaded microreactors in polar and apolar solvents was evaluated. The strategies described in this study offer new routes for the preparation of microreactors incorporating IL which are of interest for many applications in the field of organic synthesis, catalysis and adsorption of active substances.

Supplementary information


Ionic liquid; Polyelectrolyte capsule; Layer-by-Layer; Microreactor; Radical polymerisation

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Wasserscheid P, Welton T. Ionic liquids in synthesis. Wiley-VCH, Weinheim 2007.

Austen Angell C, Ansari Y, Zhao Z. Ionic Liquids: Past, present and future. Faraday Discuss. 2012;154:9-27.

Martins M, Frizzo C, Moreira D, Zanatta N, Bonacorso H. Ionic Liquids in Heterocyclic Synthesis. Chemical Reviews 2008;108(6):2015-2050.

Singh R, Sharma M, Mamgain R, Rawat D. Ionic liquids: a versatile medium for palladium-catalyzed reactions. J. Braz. Chem. Soc. 2008;19(3):357-379.

Wilhelm R, Winkel A, Reddy P. Recent Advances in the Synthesis and Application of Chiral Ionic Liquids. Synthesis 2008;2008(7):999-1016.

Domínguez de María P. “Nonsolvent” Applications of Ionic Liquids in Biotransformations and Organocatalysis. Angewandte Chemie International Edition 2008;47(37):6960-6968.

Hallett J, Welton T. Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2. Chemical Reviews 2011;111(5):3508-3576.

Han D, Row K. Recent Applications of Ionic Liquids in Separation Technology. Molecules 2010;15(4):2405-2426.

Jastorff B, Störmann R, Ranke J, Mölter K, Stock F, Oberheitmann B, Hoffmann W, Hoffmann J, Nüchter M, Ondruschka B, Filser J. How hazardous are ionic liquids? Structure–activity relationships and biological testing as important elements for sustainability evaluationThis work was presented at the Green Solvents for Catalysis Meeting held in Bruchsal, Germany, 13–16th October 2002.. Green Chemistry 2003;5(2):136-142.

Zhao D, Liao Y, Zhang Z. Toxicity of Ionic Liquids. Clean Soil Air Water 2007;35(1):42-48.

ZHENG Q, TAN Z, WANG D, HAO A, LIU B, LÜ X, SHI Q. Calorimetric Study and Thermal Analysis of 4-(Aminomethyl) Benzoic Acid. Chinese Journal of Chemistry 2009;27(4):672-676.

Stolte S, Abdulkarim S, Arning J, Blomeyer-Nienstedt A, Bottin-Weber U, Matzke M, Ranke J, Jastorff B, Thöming J. Primary biodegradation of ionic liquid cations, identification of degradation products of 1-methyl-3-octylimidazolium chloride and electrochemical wastewater treatment of poorly biodegradable compounds. Green Chem. 2008;10(2):214-224.

Harjani J, Farrell J, Garcia M, Singer R, Scammells P. Further investigation of the biodegradability of imidazolium ionic liquids. Green Chemistry 2009;11(6):821.

Valkenberg M, deCastro C, Hölderich W. Immobilisation of ionic liquids on solid supports. Green Chemistry 2001;4(2):88-93.

Mehnert C. Supported Ionic Liquid Catalysis. Chemistry - A European Journal 2005;11(1):50-56.

Riisagera A, Fehrmanna R, Haumannb M, Wasserscheidb P. Supported ionic liquids: versatile reaction and separation media. Topics in Catalysis 2006;40(1-4):91-102.

Gu Y, Li G. Ionic Liquids-Based Catalysis with Solids: State of the Art. Advanced Synthesis & Catalysis 2009;351(6):817-847.

Hagiwara H, Ko K, Hoshi T, Suzuki T. Supported ionic liquid catalyst (Pd-SILC) for highly efficient and recyclable Suzuki–Miyaura reaction. Chem. Commun. 2007;(27):2838-2840.

Wolfson A, Vankelecom I, Jacobs P. Co-immobilization of transition-metal complexes and ionic liquids in a polymeric support for liquid-phase hydrogenations. Tetrahedron Letters 2003;44(6):1195-1198.

Baudoux J, Perrigaud K, Madec P, Gaumont A, Dez I. Development of new SILP catalysts using chitosan as support. Green Chemistry 2007;9(12):1346.

Moucel R, Perrigaud K, Goupil J, Madec P, Marinel S, Guibal E, Gaumont A, Dez I. Importance of the Conditioning of the Chitosan Support in a Catalyst-Containing Ionic Liquid Phase Immobilised on Chitosan: The Palladium-Catalysed Allylation Reaction Case. Advanced Synthesis & Catalysis 2010;352(2-3):433-439.

Clousier N, Moucel R, Naik P, Madec P, Gaumont A, Dez I. Catalytic materials based on catalysts containing ionic liquid phase supported on chitosan or alginate: Importance of the support. Comptes Rendus Chimie 2011;14(7-8):680-684.

Vincent T, Guibal E. Chitosan-Supported Palladium Catalyst. 5. Nitrophenol Degradation Using Palladium Supported on Hollow Chitosan Fibers. Environmental Science & Technology 2004;38(15):4233-4240.

Guibal E, Vincent T, Jouannin C. Immobilization of extractants in biopolymer capsules for the synthesis of new resins: a focus on the encapsulation of tetraalkyl phosphonium ionic liquids. Journal of Materials Chemistry 2009;19(45):8515.

Jouannin C, Dez I, Gaumont A, Taulemesse J, Vincent T, Guibal E. Palladium supported on alginate/ionic liquid highly porous monoliths: Application to 4-nitroaniline hydrogenation. Applied Catalysis B: Environmental 2011;103(3-4):444-452.

Le Bideau J, Viau L, Vioux A. Ionogels, ionic liquid based hybrid materials. Chem. Soc. Rev. 2011;40(2):907-925.

Earle M, Seddon K. Ionic liquids. Green solvents for the future. Pure and Applied Chemistry 2000;72(7):1391-1398.

Gao H, Li J, Han B, Chen W, Zhang J, Zhang R, Yan D. Microemulsions with ionic liquid polar domains. Phys. Chem. Chem. Phys. 2004;6(11):2914.

Gao Y, Li N, Zheng L, Zhao X, Zhang S, Han B, Hou W, Li G. A cyclic voltammetric technique for the detection of micro-regions of bmimPF6/Tween 20/H 2 O microemulsions and their performance characterization by UV-Visspectroscopy . Green Chem. 2006;8(1):43-49.

Zheng Y, Eli W. Study on the Polarity of bmimPF 6 /Tween80/toluene Microemulsion Characterized by UV-Visible Spectroscopy . Journal of Dispersion Science and Technology 2009;30(5):698-703.

Yang W, Lu Y, Xiang Z, Luo G. Monodispersed microcapsules enclosing ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate. Reactive and Functional Polymers 2007;67(1):81-86.

Gao H, Xing J, Xiong X, Li Y, Li W, Liu Q, Wu Y, Liu H. Immobilization of Ionic Liquid [BMIM][PF 6 ] by Spraying Suspension Dispersion Method . Industrial & Engineering Chemistry Research 2008;47(13):4414-4417.

Xiang Z, Lu Y, Zou Y, Gong X, Luo G. Preparation of microcapsules containing ionic liquids with a new solvent extraction system. Reactive and Functional Polymers 2008;68(8):1260-1265.

Ma H, Dai L. Particle Self-Assembly in Ionic Liquid-in-Water Pickering Emulsions. Langmuir 2011;27(2):508-512.

Binks B, Dyab A, Fletcher P. Novel emulsions of ionic liquids stabilised solely by silica nanoparticles. Chemical Communications 2003;(20):2540.

Bradley L, Gupta M. Encapsulation of Ionic Liquids within Polymer Shells via Vapor Phase Deposition. Langmuir 2012;28(27):10276-10280.

Saito T, Torii S. Microcapsule for adsorption and recovery of cadmium(II) ion. Separation Science and Technology 2002;37(1):77-87.

Shchukin D, Patel A, Sukhorukov G, Lvov Y. Nanoassembly of Biodegradable Microcapsules for DNA Encasing. J. Am. Chem. Soc. 2004;126(11):3374-3375.

Ye S, Wang C, Liu X, Tong Z, Ren B, Zeng F. New loading process and release properties of insulin from polysaccharide microcapsules fabricated through layer-by-layer assembly. Journal of Controlled Release 2006;112(1):79-87.

Sukhorukov G, Fery A, Möhwald H. Intelligent micro- and nanocapsules. Progress in Polymer Science 2005;30(8-9):885-897.

Peyratout C, Dähne L. Tailor-Made Polyelectrolyte Microcapsules: From Multilayers to Smart Containers. Angewandte Chemie International Edition 2004;43(29):3762-3783.

Sukhorukov G, Rogach A, Zebli B, Liedl T, Skirtach A, Köhler K, Antipov A, Gaponik N, Susha A, Winterhalter M, Parak W. Nanoengineered Polymer Capsules: Tools for Detection, Controlled Delivery, and Site-Specific Manipulation. Small 2004;1(2):194-200.

De Koker S, Hoogenboom R, De Geest B. Polymeric multilayer capsules for drug delivery. Chemical Society Reviews 2012;41(7):2867.

Anandhakumar S, Debapriya M, Nagaraja V, Raichur A. Polyelectrolyte microcapsules for sustained delivery of water-soluble drugs. Materials Science and Engineering: C 2011;31(2):342-349.

Shchukina E, Shchukin D. LbL coated microcapsules for delivering lipid-based drugs. Advanced Drug Delivery Reviews 2011;63(9):837-846.

B. Neu, A. Voigt, R. Mitlöhner, S. . Biological cells as templates for hollow microcapsules. Journal of Microencapsulation 2001;18(3):385-395.

Fakhrullin R, Minullina R. Hybrid Cellular−Inorganic Core−Shell Microparticles: Encapsulation of Individual Living Cells in Calcium Carbonate Microshells. Langmuir 2009;25(12):6617-6621.

Zhao Z, Wang X, Qin X, Chen Q, Anzai J. Enzyme microcapsules with substrate selective permeability constructed via layer-by-layer polyelectrolyte self-assembly. Materials Science and Engineering: C 2012;32(3):569-573.

Kazakova L, Shabarchina L, Sukhorukov G. Co-encapsulation of enzyme and sensitive dye as a tool for fabrication of microcapsule based sensor for urea measuring. Phys. Chem. Chem. Phys. 2011;13(23):11110.

Nayak S, McShane M. Encapsulation of Peroxidase by Polymerizing Acrylic Acid Monomers in "Clean" Polyelectrolyte Microcapsules. Journal of Biomedical Nanotechnology 2007;3(2):170-177.

De Temmerman M, Demeester J, De Vos F, De Smedt S. Encapsulation Performance of Layer-by-Layer Microcapsules for Proteins. Biomacromolecules 2011;12(4):1283-1289.

Wang Z, Qian L, Wang X, Yang F, Yang X. Construction of hollow DNA/PLL microcapsule as a dual carrier for controlled delivery of DNA and drug. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2008;326(1-2):29-36.

Moya S, Sukhorukov G, Auch M, Donath E, Möhwald H. Microencapsulation of Organic Solvents in Polyelectrolyte Multilayer Micrometer-Sized Shells. Journal of Colloid and Interface Science 1999;216(2):297-302.

Cordeiro A, Coelho M, Sukhorukov G, Dubreuil F, Möhwald H. Effect of shear stress on adhering polyelectrolyte capsules. Journal of Colloid and Interface Science 2004;280(1):68-75.

Andreeva D, Gorin D, Möhwald H, Sukhorukov G. Novel Type of Self-Assembled Polyamide and Polyimide Nanoengineered ShellsFabrication of Microcontainers with Shielding Properties. Langmuir 2007;23(17):9031-9036.

Wang Z, Zhu H, Li D, Yang X. Preparation and application of single polyelectrolyte microcapsules possessing tunable autofluorescent properties. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2008;329(1-2):58-66.

Volodkin D, Petrov A, Prevot M, Sukhorukov G. Matrix Polyelectrolyte Microcapsules: New System for Macromolecule Encapsulation. Langmuir 2004;20(8):3398-3406.

Richert L, Boulmedais F, Lavalle P, Mutterer J, Ferreux E, Decher G, Schaaf P, Voegel J, Picart C. Improvement of Stability and Cell Adhesion Properties of Polyelectrolyte Multilayer Films by Chemical Cross-Linking. Biomacromolecules 2004;5(2):284-294.

Dähne L, Leporatti S, Donath E, Möhwald H. Fabrication of Micro Reaction Cages with Tailored Properties. J. Am. Chem. Soc. 2001;123(23):5431-5436.

Petrov A, Volodkin D, Sukhorukov G. Protein-Calcium Carbonate Coprecipitation: A Tool for Protein Encapsulation. Biotechnol Progress 2008;21(3):918-925.

Szarpak A, Cui D, Dubreuil F, De Geest B, De Cock L, Picart C, Auzély-Velty R. Designing Hyaluronic Acid-Based Layer-by-Layer Capsules as a Carrier for Intracellular Drug Delivery. Biomacromolecules 2010;11(3):713-720.

Kubisa P. Application of ionic liquids as solvents for polymerization processes. Progress in Polymer Science 2004;29(1):3-12.

Erdmenger T, Guerrero-Sanchez C, Vitz J, Hoogenboom R, Schubert U. Recent developments in the utilization of green solvents in polymer chemistry. Chemical Society Reviews 2010;39(8):3317.

Kubisa P. Ionic liquids as solvents for polymerization processes—Progress and challenges. Progress in Polymer Science 2009;34(12):1333-1347.