Combining the incompatible: Block copolymers consecutively displaying activated esters and amines and their use as protein-repellent surface modifiers with multivalent biorecognition

Abstract

We present the facile synthesis and orthogonal functionalization of diblock copolymers consisting of two incompatible segments, i.e. primary amines and activated esters, and demonstrate their use as protein-repellent brush layers with multivalent biorecognition.

Preparation of Highly Monodisperse Monopatch Particles with Orthogonal Click-Type Functionalization and Biorecognition

“…This block copolymer is the most advanced ink as it provides spatial separation of binding and multivalent interaction to the surrounding. In earlier investigations focusing on the fundamental protein‐fouling behavior, we could show a superior performance of such block copolymers in comparison with random copolymers in terms of preventing nonspecific protein‐fouling, while at the same time showing specific biorecognition . Printing of the block copolymer yields slightly broader patches (3.5 ± 0.5 μm), yet still retaining a low dispersity.…”

“…Printing this polymer in an analogous way yields patches of comparable quality (1.8 ± 0.4 μm), confirming little impact of the side chain functionalities and demonstrating simple ways to incorporate further functionalities. In a third approach, we print a block copolymer containing one block of PAEA (the acrylate analogue) for adhesion to the surface and another block containing triethylene glycol acrylamide methyl ether (TEGA) and 5% triethylene glycol biotinyl acrylamide (BiotinTEGA) side chains (namely, PAEA‐ b ‐P(TEGA‐ co ‐BiotinTEGA)) for biorecognition . The block copolymer consists of 25 repeating units of AEA in the first block and 33 repeating units (TEGA) in the second block containing 5 mol% biotin (BiotinTEGA).…”

“…Poly(aminoethyl acrylate‐ b ‐poly(triethylene glycol acrylamide methyl ether)‐ co ‐(biotin‐4,7,10‐trioxa‐13‐tridecan acrylamide) (PAEA‐ b ‐P(TEGA‐ co ‐BiotinTEGA)) was synthesized as previously reported, and consists of 25 repeating units of AEA in the first block and 33 repeating units in the second block containing 5 mol% of biotin.…”

“…In earlier investigations focusing on the fundamental protein-fouling behavior, we could show a superior performance of such block copolymers in comparison with random copolymers in terms of preventing nonspecifi c protein-fouling, while at the same time showing specifi c biorecognition. [ 68 ] Printing of the block copolymer yields slightly broader patches (3.5 ± 0.5 µm), yet still retaining a low dispersity. The difference in patch size between the polymers derives from the differences in the polymer properties.…”

Preparation of dual stimuli-responsive block copolymers based on different activated esters with distinct reactivities

“…-methylpropionic acid (DDMAT) possess high chain transfer constant, is more hydrolytically stabile, and causes less retardation, it has been reported as a suitable CTA for the polymerization of acrylates[35].Thus, RAFT polymerization of MSA was explored DDMAT as the chain transfer agent, AIBN as the radical source and dioxane as the solvent (Scheme 1). To confirm that the polymerization reaction conditions result in a first-order monomer conversion, we analyzed the polymerization kinetics via1 H NMR in CDCl 3 and GPC in THF.…”