Microwave-assisted hydrolysis for the physicochemical characterization of functional methacrylic polymers and their bioconjugates.

This study presents a microwave-assisted hydrolysis (MAH) method for accurately determining the molar mass of functional methacrylic polymers and their protein conjugates synthesized via controlled/living polymerization by a grafting from approach. By cleaving ester side chains, MAH converts polymers into linear poly(methacrylic acid) (PMAA), enabling precise molar mass analysis through aqueous size-exclusion chromatography (ASEC). The method is applied to polyglycerol methacrylate (PGMA), polyethylene glycol methacrylate (P(PEGMA)), and lysozyme-PGMA conjugates, with hydrolysis kinetics evaluated under both conventional and microwave heating. Notably, P(PEGMA) exhibits strong resistance to base-catalyzed hydrolysis due to PEG stabilization; however, microwave irradiation significantly improves conversion, achieving results infeasible with standard heating. Characterization by 1H-NMR, FTIR, and SEC confirms successful hydrolysis and accurate molar mass determination. Calibration using PGMA standards further enhances analytical reliability. The MAH-ASEC approach proves robust, scalable, and broadly applicable, offering a valuable tool for the physicochemical characterization of complex polymeric conjugate systems, particularly in biomedical and materials science contexts.