Recent progress in fabrication and functionalization of Ca-alginate capsules with ultrathin membranes

doi:10.11949/j.issn.0438-1157.20150663

Abstract

Abstract:

Calcium alginate (Ca-alginate) capsule membranes are widely used in biological and medical fields due to their notable advantages such as good biocompatibility, and mild gelation conditions. Thin capsule membranes are desired to reduce the resistance to the mass transfer across the membranes, and to accelerate the exchange of solutes between the internal space of the capsule and the external environment. Therefore, fabrication and functionalization of Ca-alginate capsules with ultrathin membranes have attracted much attention recently. This paper reviews recent progress in fabrication and functionalization of Ca-alginate capsules with ultrathin membranes, and the controllable fabrication of Ca-alginate capsules with ultrathin membranes via a co-extrusion approach, organic/inorganic hybrid processing via adsorption of protamine molecules and biosilicification as well as functional modification of the Ca-alginate capsules with ultrathin membranes are highlighted. The thicknesses of the resultant Ca-alginate capsule membranes range from 0.6 to 150 μm, and the permeability performance of the capsule membranes could be controllably adjusted. The strategy reported in this paper provides a novel approach to fabricate novel structures of capsule membranes for various applications, particularly as a new tool for screening microorganism survival and growth in three-dimensional environments. Protamine is used to inspire and template silica formation onto the surfaces of the Ca-alginate capsules, which provides a facile and efficient method to prepare the organic/inorganic hybrid capsules with ultrathin membranes. The Ca-alginate/protamine/silica capsules efficiently inhibit the swelling of Ca-alginate capsules, and thus are promising carriers for encapsulation of cells and enzymes. In addition, Ca-alginate capsules membranes blended with poly(N-isopropylacrylamide) (PNIPAM) nanogels exhibit desirable thermo-responsive gating characteristics. pH-Responsive switching functions can be endowed by the electrostatic interactions between Ca-alginate networks and protamine molecules, or by the swelling/shrinking behaviors of the grafted poly(methacrylic acid) (PMAA) brushes on the capsule membranes. These functional capsules with ultrathin membranes have many potential applications in various fields such as enzyme catalytic reactions, immobilizations of cells and foods, and controlled release of chemicals.

Key words: capsule membranes, calcium alginate, ultrathin shells

摘要：

海藻酸钙胶囊膜由于具有制备过程温和环保、材料生物相容性优良等优点,广泛应用于生物医药等领域。薄壁结构的胶囊膜可减小跨膜传质阻力,加速囊膜内外物质的交换,因而备受学术界和工业界的广泛关注。近年来,具有超薄壁结构的海藻酸钙胶囊膜的制备与改性成为一个研究热点。本文综述了超薄壁结构海藻酸钙胶囊膜的制备方法及其功能化的研究新进展,重点介绍了利用共挤出毛细管装置制备超薄壁结构的海藻酸钙胶囊膜、利用精蛋白吸附与仿生硅化技术对超薄壁结构海藻酸钙胶囊膜的有机/无机杂化处理,以及利用复合纳米响应性凝胶颗粒的方法和接枝响应性聚合物高分子的方法实现超薄壁结构海藻酸钙胶囊膜的功能化改性等方面的研究现状。

关键词: 胶囊膜, 海藻酸钙, 超薄壁结构

CLC Number:

TQ316
TB34

HE Fan, XIE Rui, JU Xiaojie, WANG Wei, LIU Zhuang, CHU Liangyin. Recent progress in fabrication and functionalization of Ca-alginate capsules with ultrathin membranes[J]. CIESC Journal, 2015, 66(8): 2817-2823.

何帆, 谢锐, 巨晓洁, 汪伟, 刘壮, 褚良银. 超薄壁结构海藻酸钙胶囊膜制备及其功能化研究新进展[J]. 化工学报, 2015, 66(8): 2817-2823.

References 33

[1]	Lee K Y, Mooney D J. Alginate: properties and biomedical applications [J]. Prog. Polym. Sci., 2012, 37(1): 106-126.
[2]	Lin Y H, Liang H F, Chung C K, Chen M C, Sung H W. Physically crosslinked alginate/N,O-carboxymethyl chitosan hydrogels with calcium for oral delivery of protein drugs [J]. Biomaterials, 2005, 26(14): 2105-2113.
[3]	Jain D, Bar-Shalom D. Alginate drug delivery systems: application in context of pharmaceutical and biomedical research [J]. Drug Dev. Ind. Pharm., 2014, 40(12): 1576-1584.
[4]	de Vos P, Faas M M, Strand B, Calafiore R. Alginate-based microcapsules for immunoisolation of pancreatic islets [J]. Biomaterials, 2006, 27(32): 5603-5617.
[5]	Morch Y A, Donati I, Strand B L, Skjak-Braek G. Effect of Ca2+, Ba2+, and Sr2+ on alginate microbeads [J]. Biomacromolecules, 2006, 7(5): 1471-1480.
[6]	Sugiura S, Oda T, Izumida Y, Aoyagi Y, Satake M, Ochiai A, Ohkohchi N, Nakajima M. Size control of calcium alginate beads containing living cells using micro-nozzle array [J]. Biomaterials, 2005, 26(16): 3327-3331.
[7]	Taqieddin E, Amiji M. Enzyme immobilization in novel alginate-chitosan core-shell microcapsules [J]. Biomaterials, 2004, 25(10): 1937-1945.
[8]	Vandenberg G W, Drolet C, Scott S L, De la Noüe J. Factors affecting protein release from alginate-chitosan coacervate microcapsules during production and gastric/intestinal simulation [J]. J. Control. Release, 2001, 77(3): 297-307.
[9]	Jiang Z Y, Zhang Y F, Li J, Jiang W, Yang D, Wu H. Encapsulation of b-glucuronidase in biomimetic alginate capsules for bioconversion of baicalin to baicalein [J]. Ind. Eng. Chem. Res., 2007, 46(7): 1883-1890.
[10]	Chai Y, Mei L H, Wu G L, Lin D Q, Yao S J. Gelation conditions and transport properties of hollow calcium alginate capsules [J]. Biotechnol. Bioeng., 2004, 87(2): 228-233.
[11]	Zhang Y F, Wu H, Li J, Li L, Jiang Y J, Jiang Y, Jiang Z Y. Protamine-templated biomimetic hybrid capsules: efficient and stable carrier for enzyme encapsulation [J]. Chem. Mater., 2008, 20(3): 1041-1048.
[12]	Chai Y, Mei L H, Lin D Q, Yao S J. Diffusion coefficients in intrahollow calcium alginate microcapsules [J]. Chem. Eng. Data, 2004, 49(3): 475-478.
[13]	Bremond N, Santanach-Carreras E, Chu L Y, Bibette J. Formation of liquid-core capsules having a thin hydrogel membrane: liquid pearls [J]. Soft Matter, 2010, 6(11): 2484-2488.
[14]	Rolland L, Santanach-Carreras E, Delmas T, Bibette J, Bremond N. Physicochemical properties of aqueous core hydrogel capsules [J]. Soft Matter, 2014, 10(48): 9668-9674.
[15]	Liang W G, Yang C, Wen G Q, Wang W, Ju X J, Xie R, Chu L Y. A facile and controllable method to encapsulate phase change materials with non-toxic and biocompatible chemicals [J]. Appl. Therm. Eng., 2014, 70(1): 817-826.
[16]	Wang J Y, Yu H Y, Xie R, Ju X J, Yu Y L, Zhang Z, Chu L Y. Alginate/protamine/silica hybrid capsules with ultrathin membranes for laccase immobilization [J]. AIChE J., 2013, 59(2): 380-389.
[17]	Chu L Y, Li Y, Zhu J H, Chen W M. Negatively thermoresponsive membranes with functional gates driven by zipper-type hydrogen-bonding interactions [J]. Angew. Chem. Int. Ed., 2005, 44(14): 2124-2127.
[18]	Yang M, Chu L Y, Wang H D, Xie R, Song H, Niu C H. A novel thermo-responsive membrane for chiral resolution [J]. Adv. Funct. Mater., 2008, 18(4): 652-663.
[19]	Xie R, Li Y, Chu L Y. Preparation of thermo-responsive gating membranes with controllable response temperature [J]. J. Membr. Sci., 2007, 289(1/2): 76-85.
[20]	Qu J B, Chu L Y, Yang M, Xie R, Hu L, Chen W M. A pH-responsive gating membrane system with pumping effects for improved controlled-release [J]. Adv. Funct. Mater., 2006, 16(14): 1865-1872.
[21]	Wei J, Ju X J, Zou X Y, Xie R, Wang W, Liu Y M, Chu L Y. Multi-stimuli-responsive microcapsules for adjustable controlled-release [J]. Adv. Funct. Mater., 2014, 24(22): 3312-3323.
[22]	Luo T, Lin S, Xie R, Ju X J, Liu Z, Wang W, Mou C L, Zhao C S, Chen Q M, Chu L Y. pH-Responsive poly(ether sulfone) composite membranes blended with amphiphilic polystyrene-block-poly(acrylic acid) copolymers [J]. J. Membr. Sci., 2014, 450: 162-173.
[23]	Chu L Y, Yamaguchi T, Nakao S. A molecular recognition microcapsule for environmental stimuli-responsive controlled-release [J]. Adv. Mater., 2002, 14(5): 386-389.
[24]	Ju Xiaojie(巨晓洁), Xie Rui(谢锐), Wang Wei(汪伟), Chu Liangyin(褚良银). Development of ion-recognition-responsive smart materials based on crown ethers [J]. CIESC Journal(化工学报), 2013, 64(1): 261-267.
[25]	Liu Zhuang(刘壮), Ju Xiaojie(巨晓洁), Xie Rui(谢锐), Wang Wei(汪伟), Chu Liangyin(褚良银). Progress of Pb2+-recognition-responsive smart polymeric functional materials [J]. CIESC Journal(化工学报), 2014, 65(5): 1571-1576.
[26]	Chu L Y, Li Y, Zhu J H, Wang H D, Liang Y J. Control of pore size and permeability of a glucose-responsive gating membrane for insulin delivery [J]. J. Control. Release, 2004, 97(1): 43-53.
[27]	Zhang M J, Wang W, Xie R, Ju X J, Liu L, Gu Y Y, Chu L Y. Microfluidic fabrication of monodisperse microcapsules for glucose-responsive at physiological temperature [J]. Soft Matter, 2013, 9(16): 4150-4159.
[28]	Wang J Y, Jin Y, Xie R, Liu J Y, Ju X J, Meng T, Chu L Y. Novel calcium-alginate capsules with aqueous core and thermo-responsive membrane [J]. J. Colloid Interface Sci., 2011, 353(1): 61-68.
[29]	Mei L, Xie R, Yang C, Ju X J, Wang J Y, Zhang Z, Chu L Y. Bio-inspired mini-eggs with pH-responsive membrane for enzyme immobilization [J]. J. Membr. Sci., 2013, 429: 313-322.
[30]	He F, Mei L, Ju X J, Xie R, Wang W, Liu Z, Wu F, Chu L Y. pH-Responsive controlled release characteristics of solutes with different molecular weights diffusing across membranes of Ca-alginate/protamine/silica hybrid capsules [J]. J. Membr. Sci., 2015, 474: 233-243.
[31]	Mei L, He F, Zhou R Q, Wu C D, Liang R, Xie R, Ju X J, Wang W, Chu L Y. A novel intestinal-targeted Ca-alginate-based carrier for pH-responsive protection and release of lactic acid bacteria [J]. ACS Appl. Mater. Interfaces, 2014, 6(8): 5962-5970.
[32]	Mei L, Xie R, Yang C, Ju X J, Wang W, Wang J Y, Chu L Y. pH-Responsive Ca-alginate-based capsule membranes with grafted poly(methacrylic acid) brushes for controllable enzyme reaction [J]. Chem. Eng. J., 2013, 232: 573-581.
[33]	Alessandri K, Sarangi B R, Gurchenkov V V, Sinha B, Kiessling T R, Fetler L, Rico F, Scheuring S, Lamaze C, Simon A, Geraldo S, Vignjevic D, Domejean H, Rolland L, Funfak A, Bibette J, Bremond N, Nassoy P. Cellular capsules as a tool for multicellular spheroid production and for investigating the mechanics of tumor progression in vitro [J]. Proc. Natl. Acad. Sci. U. S. A., 2013, 110(37): 14843-14848.