Glycopolymers obtained by chemical modification of well‐defined block copolymers

Abstract

Well‐defined di and triblock copolymers based on 2‐hydroxyethyl methacrylate, HEMA, and n‐butyl acrylate, BA, have been synthesized by atom transfer radical polymerization, ATRP. Two copolymers have been selected to prepare glycopolymers containing D‐(+)‐glucosamine or N‐(4‐aminobutyl)‐D‐gluconamide, NABG, by chemical modification of HEMA units. The chemical modification occurs by activation of the hydroxyl groups of the HEMA units with highly reactive p‐nitrophenyl carbonate groups. The block copolymers structure and self‐assembly have been comprehensively studied in solid state and in solution by differential scanning calorimetry, X‐ray diffraction, atomic force microscopy and dynamic light scattering. The resulting glycopolymers obtained upon chemical modification turned out to be water soluble. Therefore, their carbohydrate‐lectin interactions of have been analyzed by turbidimetry measurements. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Chemical modification of block copolymers based on 2-hydroxyethyl acrylate to obtain amphiphilic glycopolymers

“…[ M w /M n =1.16) and Br-PBA 91 -Br (M n,SEC =11,600 g/mol; M w /M n =1.16), respectively, were synthesized via ATRP as reported in previous works. [54,56] Herein, di-and triblock copolymers were prepared by chain extension reaction of HEA from those PBA macroinitiators using a relation of …”

“…The glass transition temperatures (T g s) of the block copolymers consisting of BA and HEA were determined by differential scanning calorimetry and the values are listed in Table 1. The T g s of mono and difunctional macroinitiators of PBA were previously measured (-50.2 and -49.9 ºC, respectively) [54] and that of PHEA homopolymer (M n sec =15,300 g/mol, M w /M n =1. 19), was determined at -7.9 ºC, which is in good agreement with the values found in the literature, [57] and lower than that exhibited by PHEA synthetized using conventional radical polymerization or other techniques, i.e.…”

“…Currently, there are few approaches to achieve glycopolymers; [24,25] including either polymerization [29][30][31][32][33][34][35][36][37][38][39][40] or chemical modification [19,20,23,24,[41][42][43][44][45]. Our lab has an extensive experience on the incorporation of different carbohydrates onto hydroxylated polymers, i.e., poly(vinyl alcohol), [46] ethylene-vinyl alcohol [47][48][49][50][51][52][53], poly(2-hydroxyethyl methacrylate) [54] and poly(ethyl α-hydroxymethylacrylate). [55] The present research describes a satisfactory combination of those two aforementioned approaches.…”

“…carbohydratelectin interaction with Concanavalin A. Additionaly, these results were compared with those previously reported based on 2-hydroxyethyl methacrylate, HEMA. [54] EXPERIMENTAL SECTION…”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…Muñoz-Bonilla et al [157] described the synthesis of diblock and triblock amphiphilic glycopolymers with pendant D-glucosamine or N-(4-aminobutyl)-D-gluconamide residues. To this end, 2-hydroxyethyl methacrylate M33 polymerized using two poly(butyl acrylate) macroinitiators (polyM47-Br, M n = 8200 Da, Ð = 1.16; or Br-polyM47-Br, M n =11,600 Da, Ð = 1.16) in the presence of CuCl(L2) in DMF at 80 C.…”