Nitroxide-controlled free radical polymerization of a sugar-carrying acryloyl monomer

Abstract

SUMMARY: Controlled free radical polymerization of a sugar-carrying acrylate, 3-O-acryloyl-1,2 : 5,6-di-Oisopropylidene-a-D-glucofuranoside (AIpGlc), was achieved in p-xylene at 100 8C by using a di-tert-butyl nitroxide (DBN)-based alkoxyamine as an initiator and dicumyl peroxide (DCP) as an accelerator. The polymerization gave low-polydispersity (1.2 a M -w /M -n a 1.6) polymers with predicted molecular weights. The same approach with a DBN-capped polystyrene (PS-DBN) as an initiator afforded block copolymers of the type PS-b-PAIpGlc. The acidolysis of the homopolymers and block copolymers gave well-defined glucosecarrying polymers PAGlc and PS-b-PAGlc, respectively. These amphiphilic PS-b-PAGlc block copolymers were observed to exhibit microdomain surface morphologies that differ for different copolymer compositions. This success opens up a new, simple route to the synthesis of well-defined sugar-carrying polymers of various architectures.

Glycopolymer‐Grafted Polystyrene Nanospheres

“…In this case, controlled/''living'' radical polymerizations have been reported as a very facile approach for well-defined and controlled synthesis of glycopolymers. [19][20][21][22][23] In this paper, we describe the synthesis of sugarcontaining colloidal spherical polymer brushes by two different polymerization approaches. Photopolymerization of the functional monomer 3-O-methacryloyl-D-glucose (MAGlc) was used to attach glycopolymer chains to colloidal polystyrene (PS) spheres by a ''grafting from'' technique.…”

Thermoresponsive Glycopolymers via Controlled Radical Polymerization

“…[15,16] Therefore, many research groups started to synthesize glycopolymers. [17,18] Ohno and Fukuda [19,20] have pioneered the synthesis of glycopolymers via both nitroxide-mediated (NMRP) and atom transfer radical polymerization (ATRP) of the corresponding glycomonomers. Recently, various polymerization techniques were used to synthesize glycopolymers aiming for well-defined structures.…”

“…Dry dimethylformamide (DMF), anisole and dioxane were distilled and purged with nitrogen before using them as reaction solvent. 3-O-Acryloyl-1,2: 5,6-di-O-isopropylidene-a-D-glucofuranoside (AIpGlc) was synthesized according to the method reported by Ohno et al [20] 3-O-Methacryloyl-1,2:5,6-di-O-isopropylidene-a-D-glucofuranoside (MAIpGlc) was prepared by the method described by Ohno et al [19] For both monomers, the measured NMR data agreed well with the published values confirming the structure.…”

“…The structures of the glycomonomers are shown in Figure 1 indicating also the abbreviations used: AIpGlc and MAIpGlc for the protected acrylate and methacrylate monomers without spacers, and MAIpGlcC 5/10 for the protected methacrylamides with 5 or 10 methylene spacer units. AIpGlc and MAIpGlc were prepared according to the literature, [19,20] whereas the two methacrylamide monomers MAIpGlcC 5/10 were synthesized for the first time by reacting first methacrylic acid anhydride with the corresponding a,v-amino acid and then attaching the protected sugar unit 1 0 ,2 0 :5 0 ,6 0 -di-O-isopropylidene-D-glucofuranose by applying coupling agents as shown in Scheme 1. The hydrophobic spacers have been chosen to investigate the potential influence of that hydrophobic part on the final thermoresponsive behavior in random and block copolymers with NiPAAm, as well as in future studies of cell/protein interactions.…”

Immobilized Hyperbranched Glycoacrylate Films as Bioactive Supports

“…Controlled/''living'' radical polymerization has allowed well-defined and controlled synthesis of glycopolymers by a very facile approach. [18][19][20][21][22][23][24][25] We have recently reported the synthesis of glycopolymers of various branched architectures via atom transfer radical polymerization (ATRP). [26][27][28][29] Thus, the synthesis of hyperbranched glycopolymers of sugar-carrying acrylates by self-condensing vinyl copolymerization (SCVCP) of an acrylic AB * inimer, 2-(2-bromopropionyloxy)ethyl acrylate (BPEA) with 3-O-acryloyl-1,2:5,6-di-O-isopropylidene-a-D-glucofuranoside (AIGlc) via atom transfer radical polymerization (ATRP), followed by deprotection of the isopropylidene protecting groups, as shown in Scheme 1, has been reported.…”