Well‐controlled amphiphilic block glycopolymers and their molecular recognition with lectins

Abstract

The atom transfer radical polymerization of an unprotected glycomonomer, 2‐{[(D‐glucosamin‐2N‐yl)carbonyl]oxy}ethyl methacrylate (HEMAGl) is firstly reported. Controlled polymerizations were performed with the CuBr/N,N,N′,N′,N′‐pentamethyldiethylene triamine catalytic system with ethyl 2‐bromoisobutyrate and 1,2‐bis(bromoisobutyryloxy) ethane as mono and difunctional initiators in DMF solutions (80% w/w) at 40 and 50 °C, respectively. The polymerization of HEMAGl resulted in a controlled polymerization with linear kinetics, molecular weights which increase with conversion and narrow polydispersity indexes. Mono and difunctional PHEMAGl macroinitiators were used to synthesize the amphiphilic di and triblock glycopolymers with n‐butyl acrylate, verifying their living character. The self‐assembly of these glycopolymers in distilled water and in 0.1M NaCl solutions was studied by dynamic light scattering, showing the role of hydrogen bonds and the hydrophobic parts. In addition, their interaction with Concanavalin A lectin was examined, demonstrating the influence of molecular weight and copolymer composition. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3623–3631, 2010

Statistical Glycopolymers Based on 2‐Hydroxyethyl Methacrylate: Copolymerization, Thermal Properties, and Lectin Interaction Studies

“…The synthesis of 2‐{[( D ‐glucosamin‐2‐ N ‐yl)carbonyl]oxy}ethyl methacrylate, HEMAGl, is described elsewhere 26. Methyl acrylate, MA (Merck), was purified by a conventional method 32.…”

“…Despite the considerable progress in glycopolymers synthesis, most synthetic methods require the protection of carbohydrate hydroxyl groups and several purification pathways. Recently, we reported the synthesis of a novel unprotected glycomonomer based on glucosamine and their polymerization via controlled radical polymerization 26…”

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

“…The di-and triblock copolymers containing HEA units were initially activated with p-nitrophenyl carbonate groups and the degree of modification 50 nm was estimated by NMR. Figure 5 shows the 1 H and 13 C-NMR spectra of the diblock PBA 64 Table 2. These degrees are lower than those obtained with HEMA copolymers.…”

“…The binding behavior of these amphiphilic glycopolymers was then compared with that found for PHEAnGl homopolymer at similar degree of modification (degree of polymerization of 132 monomer units and 28 wt% of glucosamine units). Presence of the PBA hydrophobic block favors the binding process as a result of hydrophobic interactions,[29,54,64,65] as deduced from the comparison of the results obtained for the PHEAnGl homopolymer with those determined for the di and triblock glycopolymers, all of them being also represented inFigure 9. This is a consequence of the arrangement of block copolymers to form micelar structures with high amount of saccharide groups at the surface, in concordance with the data obtained by DLS.…”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…Leon et al [138,139] reported the synthesis of amphiphilic block glycopolymers derived from D-glucosamide methacrylate M63. According to one strategy (Entry 121-124, Table 2), M63 was homopolymerized using a monofunctional (A1) or a bifunctional initiator (A27) at 40 and 50 °C respectively (DMF, CuBr(L3)).…”