Abstract
This study demonstrates the synthesis of an amphiphilic block copolymer, Ni2+-nitrilotiracetic acid-end-functionalized-poly(poly(ethylene glycol)methyl ether methacrylate)-block-polystyrene (NTA-p(PEGMA-b-St)), morphology control via their self-assembly behavior and reversible bioconjugation of hexahistidine-tagged green fluorescent protein (His6-GFP) onto the surfaces of polymeric vesicles through nitrilotriacetic acid (NTA)-Ni2+-His interaction. First, the t-boc-protected-NTA-p(PEGMA-b-St) was synthesized by atom transfer radical polymerization. After the removal of the t-boc protecting group, the NTA group of the polymer was complexed with Ni2+. To induce self-assembly, water was added as a selective solvent to the solution of the copolymer in tetrahydrofuran (THF). Varying the water content of the solution resulted in various morphologies including spheres, lamellas and vesicles. Finally, polymeric vesicles decorated with green fluorescent protein (GFP) on their surfaces were prepared by the addition of His6-GFP into the vesicles solution. Reversibility of the binding between vesicles and His6-GFP was confirmed with a fluorescent microscope.
Highlights
The self-assembly of amphiphilic block copolymer has been researched intensely during the past few years as a representative method based on bottom-up approaches in the development of nanotechnology [1,2,3,4,5]
We describe the synthesis of Ni2+ -nitrilotriacetic acid (NTA)-end-functionalized-poly(poly(ethylene glycol)methyl ether methacrylate-block-styrene) (Ni2+ -NTA-p(PEGMA-b-St)) by atom transfer radical polymerization (ATRP) and show that the architecture of surface-functionalized aggregates can be controlled by adjusting the solution conditon in the same tendency with common amphiphlic block copolymers such as poly(ethylene oxide-b-styrene)
The initiator was prepared with t-boc protecting groups in order to ensure high solubility of the initiator and prevent protonation of the ligand in the ATRP step (See Scheme S1) [41,42]
Summary
The self-assembly of amphiphilic block copolymer has been researched intensely during the past few years as a representative method based on bottom-up approaches in the development of nanotechnology [1,2,3,4,5]. Among approaches to the development of polymeric assembly systems, structure formation using block copolymers containing special functionalities on their terminus is one of the methods used to prepare surface-functionalized nanostructures and indicates great potential of applications, depending on the functions and properties of the chain end, in diverse fields including medical, cosmetic and catalytic formulations [9,10,11,12,13,14]. In this sense, many studies have been conducted to develop.
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