Functional and reactive polymethacrylates suitable for preparation of peptide/protein–polymer conjugates

Three reactive polymers, poly(para-nitrophenoxycarbonyloxyethyl methacrylate- co -methyl methacrylate) P( p -NPCEMA- co -MMA) [ rCoP1 ], poly(methyl methacrylate- co -butyl methacrylate- co -allyl methacrylate- co -phenoxycarbonyloxyethyl methacrylate) P(MMA- co -BMA- co -AMA- co -PCEMA) [ rCoP2 ] and poly(methyl methacrylate- co -dimethylaminopropyl methacrylate- co -dodecyl methacrylate- co -phenoxycarbonyloxyethyl methacrylate) P(MMA- co -DMAPMA- co -DMA- co -PCEMA) [ rCoP3 ], respectively, were prepared following two synthetic concepts. Following the first concept, p -NPCEMA and PCEMA were prepared starting with commercially available HEMA and were copolymerized via ATRP with MMA, BMA and AMA. According to the second concept phenoxycarbonyloxy decorated polymethacrylates were obtained via polymer analogous reaction of a HEMA containing functional polymethacrylate, P(MMA- co -DMAPMA- co -DMA- co -HEMA) [ fCoP ], obtained via a cascade reaction of enzymatic transacylation and free radical polymerization. The highly reactive poly(methacrylate)s and silk peptides, hen egg-white lysozyme and Candida antarctica lipase B were used for the preparation of protein/peptide-poly(methacrylate) bioconjugates.