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

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.