In this report, we describe the synthesis of a molecularly imprinted polymer (MIP) nanotube membrane, using a porous anodic alumina oxide (AAO) membrane by surface-initiated atom transfer radical polymerization (ATRP). The use of a MIP nanotube membrane in chemical separations gives the advantage of high affinity and selectivity. Furthermore, because the molecular imprinting technique can be applied to different kinds of target molecules, ranging from small organic molecules to peptides and proteins, such MIP nanotube membranes will considerably broaden the application of nanotube membranes in chemical separations and sensors. This report also shows that the ATRP route is an efficient procedure for the preparation of molecularly imprinted polymers. Furthermore, the ATRP route works well in its formation of MIP nanotubes within a porous AAO membrane. The controllable nature of ATRP allows the growth of a MIP nanotube with uniform pores and adjustable thickness. Thus, using the same route, it is possible to tailor the synthesis of MIP nanotube membranes with either thicker MIP nanotubes for capacity improvement or thinner nanotubes for efficiency improvement.
In this paper, we present a general protocol for the making of surface-imprinted core-shell nanoparticles via surface reversible addition-fragmentation chain-transfer (RAFT) polymerization using RAFT agent functionalized model silica nanoparticles as the chain-transfer agent. In this protocol, trichloro(4-chloromethylphenyl)silane was immobilized on the surface of SiO2 nanoparticles, forming chloromethylphenyl functionalized silica (silica-Cl). RAFT agent functionalized silica was subsequently produced by substitute reaction of silica-Cl with PhC(S)SMgBr. The grafting copolymerization of 4-vinylpyridine and ethylene glycol dimethacrylate using surface RAFT polymerization and in the presence of 2,4-dichlorophenoxyacetic acid as the template led to the formation of surface-imprinted core-shell nanoparticles. The resulting surface-imprinted core-shell nanoparticles bind the original template 2,4-D with an appreciable selectivity over structurally related compounds. The potential use of the surface-imprinted core-shell nanoparticles as the recognition element in the competitive fluorescent binding assay for 2,4-D was also demonstrated.
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