Using Click Chemistry To Fabricate Ultrathin Thermoresponsive Microcapsules through Direct Covalent Layer-by-Layer Assembly

被引:90
作者
Huang, Cheng-Jyun [1 ]
Chang, Feng-Chih [1 ]
机构
[1] Natl Chiao Tung Univ, Inst Appl Chem, Hsinchu 30050, Taiwan
关键词
POLY N-ISOPROPYLACRYLAMIDE; POLYELECTROLYTE MICROCAPSULES; HOLLOW SPHERES; MULTILAYER FILMS; IN-SITU; CAPSULES; TEMPERATURE; PH; POLYMERIZATION; MICROSPHERES;
D O I
10.1021/ma900478n
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
We report the syntheses of azido- and acetylene-functionalized poly(N-isopropylacrylamide) (PNIPAm) copolymers and their use in the fabrication of ultrathin thermoresponsive microcapsules through direct covalent layer-by-layer (LbL) assembly using click chemistry. The clickable copolymers poly[N-isopropylacrylamide-co-(trimethylsilyl)propargylacrylamide] and poly(N-isoropylacrylamide-co-3-azideo-propylacrylamide) were prepared through atom transfer radical polymerization (ATRP) at 0 degrees C using a synthesized dansyl-labeled initiator and the CuBr/Me6TREN (hexamethylated tris[2-(dimethylamino)ethyl]amine) catalyst complex in 2-propanol. After removing the protective trimethylsilyl groups, these clickable PNIPAm copolymers assemble alternately onto azido-modified silica particles in aqueous media through click reactions catalyzed by copper sulfate and sodium ascorbate. After removing the template, the microcapsules remained stable because of the presence of the covalently bonded triazole units; the microcapsules exhibited thermoresponsive and thermoreversible swelling/deswelling behaviors upon changing the temperature of the medium. Adjusting the number of clickable functionalities resulted in changes to the degree of cross-linking, thereby allowing control over the surface morphology and thickness of the covalently stabilized PNIPAm multilayer thin films. The microcapsules fabricated close to the lower critical solution temperature of PNIPAm exhibited extremely low surface roughnesses and thick multilayer films as a result of their compact chain conformation in aqueous solution, leading to tighter packing of the PNIPAm structure. We further postfunctionalized the surface of the multilayer thin film through click reactions with an azido-modified lissamine rhodamin dye to demonstrate the feasibility of further modification with potentially useful functionalities. Finally, preliminary study on the permeability of microcapsules was presented by using different molecular weigh tetramethylrhodamine isothiocyanate (TRITC)-labeled dextran and rhodamine 6G as probe molecules, and the results revealed that the microcapsules with tighter packing wall are selectively permeable to molecules and show potential applications for the encapsulation of a variety of materials.
引用
收藏
页码:5155 / 5166
页数:12
相关论文
共 50 条
[21]   Surface enhanced Raman scattering (SERS)-active bacterial detection by Layer-by-Layer (LbL) assembly all-nanoparticle microcapsules [J].
Li, Jie ;
Khalenkow, Dmitry ;
Volodkin, Dmitry ;
Lapanje, Ales ;
Skirtach, Andre G. ;
Parakhonskiy, Bogdan V. .
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, 2022, 650
[22]   Layer-by-Layer Assembly of Polyelectrolyte Multilayers on Thermoresponsive P(NiPAM-co-MAA) Microgel: Effect of Ionic Strength and Molecular Weight [J].
Wong, John E. ;
Diez-Pascual, Ana M. ;
Richtering, Walter .
MACROMOLECULES, 2009, 42 (04) :1229-1238
[23]   Cytocompatible Coating of Yeast Cells with Antimicrobial Chitosan through Layer-by-Layer Assembly [J].
Kim, Beom Jin ;
Choi, Insung S. ;
Yang, Sung Ho .
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2016, 37 (11) :1850-1853
[24]   Layer-by-Layer Assembly Through Weak Interactions and Their Biomedical Applications [J].
Matsusaki, Michiya ;
Ajiro, Hiroharu ;
Kida, Toshiyuki ;
Serizawa, Takeshi ;
Akashi, Mitsuru .
ADVANCED MATERIALS, 2012, 24 (04) :454-474
[25]   Reactive films fabricated using click sulfur(vi)-fluoride exchange reactions via layer-by-layer assembly [J].
Liu, Shengjie ;
Cao, Yanping ;
Wu, Zhaoqiang ;
Chen, Hong .
JOURNAL OF MATERIALS CHEMISTRY B, 2020, 8 (25) :5529-5534
[26]   Preparation and Characterization of Sodium Alginate and Polyquaternium-10 Hollow Microcapsules by a Layer-by-Layer Self-Assembly Technique [J].
Wang, Min ;
Zhang, Huihui ;
Shao, Huili ;
Yang, Gesheng .
CHEMISTRYSELECT, 2020, 5 (42) :13295-13299
[27]   Advances in cellular and tissue engineering using layer-by-layer assembly [J].
Shukla, Anita ;
Almeida, Bethany .
WILEY INTERDISCIPLINARY REVIEWS-NANOMEDICINE AND NANOBIOTECHNOLOGY, 2014, 6 (05) :411-421
[28]   Layer-by-layer assembly for ultrathin energy-harvesting films: Piezoelectric and triboelectric nanocomposite films [J].
Lee, Seokmin ;
Yeom, Bongjun ;
Kim, Younghoon ;
Cho, Jinhan .
NANO ENERGY, 2019, 56 :1-15
[29]   CaCO3-Templated Microcapsules to Carry Heparin via Layer-by-layer Self-assembly [J].
Liu, Xinrong ;
Zhu, Baoqing ;
Shao, Yingya ;
Yang, Xinlin .
2009 3RD INTERNATIONAL CONFERENCE ON BIOINFORMATICS AND BIOMEDICAL ENGINEERING, VOLS 1-11, 2009, :1046-1050
[30]   Enzyme microcapsules with substrate selective permeability constructed via layer-by-layer polyelectrolyte self-assembly [J].
Zhao, Zi-Xia ;
Wang, Xin-Sheng ;
Qin, Xia ;
Chen, Qiang ;
Anzai, Jun-ichi .
MATERIALS SCIENCE & ENGINEERING C-MATERIALS FOR BIOLOGICAL APPLICATIONS, 2012, 32 (03) :569-573