|244. Muthukrishnan, S.; Mori, H.; Müller, A.H.E.: Synthesis and Characterization of Methacrylate-Type Glycopolymers with Branched Architectures in: Controlled/Living Radical Polymerization, K. Matyjaszewski, Ed., ACS Symp. Ser. 944, 214 (2006)|
We report the synthesis and characterization of glycopolymers of different topologies via atom transfer radical polymerization (ATRP) of a sugar-carrying methacrylate monomer, 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (MAIGlc). Hyperbranched glycopolymers were obtained by self-condensing vinyl copolymerization (SCVCP) of the methacrylic AB* inimer, 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM) with MAIGlc via ATRP, followed by deprotection of the isopropylidene protecting groups. The branched structures were confirmed by 1H NMR, elemental analyses, GPC and GPC/viscosity measurements. Then the monomer, MAIGlc and the polyinitiator, poly(2-(2-bromoisobutyryloxy)ethyl methacrylate), (PBIEM) were used to obtain glycocylindrical brushes (molecular sugar sticks) with PMAGlc side chains, using the grafting from approach via ATRP. The initiating efficency of the initiating sites of the polyinitiator, PBIEM was determined to be in the range of 0.23 < f < 0.38 by cleaving the side chains from the backbone. The morphology of the resulting glycocylindrical brushes was found to be worm-like inspite of low grafting efficiency using scanning force microscopy (SFM). After deprotection, the water-soluble brushes were investigated using SFM and Cryo-TEM measurements.