Near-infrared (NIR) light offers unparalleled advantages for photocontrolled polymerization, yet its utility is fundamentally limited by low photon energy and reduced efficiency due to catalyst aggregation. Here, we introduce a bioinspired, supramolecular strategy that employs bovine serum albumin (BSA) as a host protein to suppress catalyst aggregation and amplify the catalytic efficiency of NIR dyes in aqueous media. Using zinc tetrasulfonated phthalocyanine (ZnPcS 4 − ) as a model NIR photocatalyst, we show that BSA binding effectively disaggregates ZnPcS 4 − , thereby improving its catalytic efficiency for the generation of hydroxyl radicals. This BSA-ZnPcS 4 − supramolecular complex dramatically accelerates NIR-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization, achieving up to a fivefold increase in apparent rate constant while maintaining precise control over molecular weight and dispersity. Remarkably, the use of endogenous albumin in fetal bovine serum similarly achieves accelerated polymerization rates, and in situ thermal denaturation of the protein leads to construction of high-strength double-network hydrogels. This work establishes a simple, non-covalent, and broadly applicable route to enhance the efficiency of NIR photo-controlled radical polymerization and facilitate the synthesis of protein-polymer hybrid soft materials.
