Selective Protein Conjugation of Poly(glycerol monomethacrylate) and Poly(polyethylene glycol methacrylate) with Tunable Topology via Reductive Amination with Multifunctional ATRP Initiators for Activity Preservation

In this study, we compare poly(glycerol monomethacrylate) (PGMA) of different chain lengths and architectures (linear two-arm) with poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) as an alternative polymer platform for the synthesis a new generation protein–polymer conjugates. Mono- two-arm functional atom-transfer radical polymerization (ATRP) initiators were designed selectively attached to lysozyme at N-terminus via reductive amination. Site-specific, grafting from activator regenerated by electron transfer (ARGET) ATRP was carried out in phosphate buffer, reaction parameters optimized obtain conjugates predetermined molar mass topology. The activity preservation under proteolytic high-temperature conditions showed clear dependence on structure repeating unit macromolecular architecture. These results highlighted potential PGMA poly(ethylene (PEG) half-life extension biotherapeutics. Moreover, synthetic approach may inspire design class through optimal combination composition