Abstract
In this research, we explored the synthesis and application of thiolactone acrylamide (TLA) polymers for neutralizing reactive oxygen species (ROS), produced as a result of traumatic brain injury (TBI). We synthesized well-defined TLA polymers using RAFT (reversible addition-fragmentation chain transfer) polymerization across a range of monomer-to-chain transfer agent ([M](0)/[CTA](0)) ratios to achieve a range of molar masses. Polymerizations were carried out using a trithiocarbonate CTA (chain transfer agent) with AIBN (azobisisobutyronitrile) as the initiator in N'N-dimethylacetamide (DMAc) at 60°C. Kinetic studies indicated a linear increase in molar mass with conversion, pseudo-first-order kinetics, and molar mass values that are consistent with theoretical predictions. Furthermore, the polymerizations exhibited a decrease in molar mass dispersity with conversion. We then investigated ring opening of the thiolactone residues with isoserinol (ISOH), which was followed by thiol-ene reactions of the resultant thiol groups with methacrylamide to yield a series of copolymers with different thiol-to-thioether ratios. The resulting polymers demonstrated varying levels of ROS neutralization. Higher thiol concentrations lead to more rapid neutralization while thioether residues provided sustained neutralization activity.