No document available.
Abstract :
[en] Poly(ethylene glycol) (PEG)-based polymers have been widely employed in anti-fouling coating applications due to their robust bio-relevant properties including water solubility and biocompatibility. However, limited by its poor adhesion towards surfaces, demands an addition modification strategies. Mussel adhesive proteins (MAPs) are potential models for adhesive polymers, which exhibits underwater adhesion towards dissimilar materials under environmentally challenging conditions. Most often experimentally simple, but structurally complex poly(dopamine) has been used as an analogues of MAPs for metal chelation, cross-linking and surface binding purposes. Inspired by MAPs, we have developed catechol-bearing copolymers for surface adhesion of stainless steel.
This study describes the synthesis and reversible addition−fragmentation chain transfer (RAFT) polymerization of mussel-inspired acetonide-protected dopamine (meth)acrylamide monomers (ADA and ADMA). A series of well-defined P(PEGAm-b-ADAn) and P(ADMAn-b-PEGMAm) copolymers across a range of molar masses (13−42 kg/mol) with low molar mass dispersities (Đ = 1.12−1.25) were reported for the first time. Post polymerization TFA treatment yields block copolymers bearing free –catechol units in quantitative yields (>95%). The self-assembling nature of amphiphilic block-copolymers was studied by 1H-NMR, DLS and TEM. Surface functionalization and anti-fouling experiments were performed in real time using quartz crystal microbalance coupled with dissipation (QCM-D). The copolymer upon oxidation yields reactive quinones, which can be exploited to cross-link with chitosan (also, polymers with free –NH2 and –SH groups), thereby producing nano(macro)gels. In general, these novel class of block copolymeric ligand systems can be foreseen as versatile ingredients in material chemistry to obtain biocompatible multifunctional systems, benefited by high water solubility with inherent stealth ability and protein-repellency, as well as effective chelating groups, and may find application for a variety of biomedical fields, of which we have illustrated an important example.
