A self-healable fluorescence active hydrogel based on ionic block copolymers prepared via ring opening polymerization and xanthate mediated RAFT polymerization

In this work we report a facile method to prepare a fluorescence active self-healable hydrogel via incorporation of fluorescence responsive ionic block copolymers (BCPs). Ionic block copolymers were prepared via a combined effect of ring opening polymerization (ROP) of epsilon-caprolactone and xanthate mediated reversible addition-fragmentation chain transfer (RAFT) polymerization. Here polycaprolactone (PCL) was modified with xanthate to prepare a PCL based macro-RAFT agent and then it was utilized to prepare block copolymers with cationic poly(2-(methacryloyloxy) ethyltrimethyl ammonium chloride) (PCL-b-PMTAC) and anionic poly(sodium 4-vinylbenzenesulfonate) (PCL-b-PSS). During the block formation, the cationic segments were randomly copolymerized with a trace amount of fluorescein O-acrylate (FA) (acceptor) whereas the anionic segments were randomly copolymerized with a trace amount of 9-anthryl methylmethacrylate (AMMA) (donor) to make both the segments fluorescent. The block copolymers form micelles in a DMF : water mixture (1 : 4 volume ratio). The ionic interaction of two BCPs was monitored via Forster resonance energy transfer (FRET) and zeta potential measurements. The oppositely charged BCPs were incorporated into a polyacrylamide (PAAm) based hydrogel that demonstrated self-healing behavior and is also highly fluorescent.