A Well-Defined Novel Aldehyde-Functionalized Glycopolymer: Synthesis, Micelle Formation, and Its Protein Immobilization

Abstract

A new aldehyde-functionalized glycomonomer, 1,2:3,4-di-O-isopropylidene-6-O-(2′-formyl-4′vinylphenyl)-D-galactopyranose (IVDG), was designed and prepared. The "living"/controlled radical polymerization of IVDG was successfully achieved using 2,2′-azobis(isobutyronitrile) as the initiator and 1-phenylethyl dithiobenzoate as the reversible addition-fragmentation chain transfer (RAFT) agent at 60 °C in tetrahydrofuran. The polymerization followed first-order kinetics, the number-average molecular weight of the obtained polymers increased in direct proportion to the monomer conversion, and the molecular weight distribution was narrow (polydispersity index <1.1). Removal of protective isopropylidene groups from the sugar residue in polyIVDG was carried out quantitatively using 88% formic acid at room temperature, yielding a novel amphiphilic polymer containing both galactopyranose and aldehyde functionalities. These amphiphilic polymers self-assembled into well-defined aldehyde-bearing polymeric micelles in aqueous solution without recourse to any surfactant. The size of the micelles increased almost linearly with the molecular weight of polyIVDG precursor, which could be controlled directly via the aforementioned RAFT polymerization process. Protein-bioconjugated nanoparticles were also successfully prepared by the immobilization of bovine serum albumin (as a model protein) onto the aldehyde-functionalized micelles.

Living Radical Polymerization by the RAFT Process - A Second Update

“…PEGA [204] St [205] 357 [206] 362 [207] St/EVE [208] (St/MAH) [208] 50 [209] NAM [47] 52 [210] S S Si(OCH 3 ) 3 -C 53 [210] E Poly(silsesquioxane) macro-RAFT agent PSSQ S S MMA [210] MA [210] DMAM [210] St [210] MMA/312 [210] 54 [211] NAM [211] (Continued) [165] 56 [211,212] [47,211] NAM/342 [212] …”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2007–2008

“…Emulsion-polymerization of styrene in the presence of dextran (Ladaviere, et al, 2007) 1,2:3,4-di-O-isopropylidene-6-O-(2′-formyl-4′-vinylphenyl)-D-Galp (IVDG) polymer TOF (CHCA) Polymerization of IVDG achieved with 2,2'-azobis(isobutyronitrile) as initiator and 1-PhEt dithiobenzoate as RAFT agent at 60°C (Xiao, et al, 2008) Galactose-functionalized poly-L-glutamic acid-based glycopolymers TOF (sinapinic)…”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…Al-Bagoury et al [177] reported the RAFT polymerization of isopropylidene protected D-glucofuranose methacrylate M13 and D-fructopyranose methacrylate M45 in mini-emulsion. Polymerizations were conducted at 70 °C in a mixture of hexadecane/H 2 O/SDS/NaHCO 3 using three different dithiobenzoate-type RAFT agents (R9, R10 and R11; Entry 190,[201][202][203][204] Table 3). Big deviations of molar masses with respect to their theoretical values were observed in all cases and the best results were obtained using R9 (Đ  1.25, M n /M n,th < 2.7).…”

“…The RAFT polymerization of aldehydo-glycomonomer M50 and the self-organization of the resulting polymer into micelles was the subject of a paper by Xiao et al [201] The reaction was mediated by R11 (THF, 60 °C, 50 h; Entry 238, Table 3) and proceeded with pseudo-first order kinetics and a linear increase of molar mass with conversion. Uniform polymers were thus obtained (Đ d = 0.10) whose molar mass substantially deviated from the theoretical value though (M n /M n,th  0.6).…”