Synthesis of Multifunctional Protein‐Polymer Conjugates via Oxygen‐tolerant, Aqueous Copper‐Mediated Polymerization, and Bioorthogonal Click Chemistry.

Oxygen‐tolerant, aqueous copper‐mediated polymerization approaches are combined with click chemistry in either a sequential or a simultaneous manner, to enable the synthesis of multifunctional protein‐polymer conjugates. Propargyl acrylate (PgA) and propargyl methacrylate (PgMA) grafting from a bovine serum albumin (BSA) macroinitiator is thoroughly optimized to synthesize chemically addressable BSA‐poly(propargyl acrylate) and BSA‐poly(propargyl methacrylate) respectively. The produced multifunctional bioconjugates bear pendant terminal 1‐alkynes which can be readily post‐functionalized via both [3+2] Huisgen cycloaddition and thiol‐yne click chemistry under mild reaction conditions. Simultaneous oxygen‐tolerant, aqueous copper‐catalyzed polymerization, and click chemistry mediate the in situ multiple chemical tailoring of biomacromolecules in excellent yields. [ABSTRACT FROM AUTHOR]