Amphiphilic block glycopolymers via atom transfer radical polymerization: Synthesis, self‐assembly and biomolecular recognition

Abstract

In this work the synthesis of poly(butyl acrylate)‐b‐poly(2‐{[(D‐glucosamin‐2‐N‐yl)carbonyl]oxy}ethyl methacrylate) (PBA‐b‐PHEMAGl) diblock glycopolymer and poly(2‐{[(D‐glucosamin‐2‐N‐yl)carbonyl]oxy}ethyl methacrylate)‐b‐poly(butyl acrylate)‐b‐poly(2‐{[(D‐glucosamin‐2‐N‐yl)carbonyl]oxy}ethyl methacrylate) (PHEMAGl‐b‐PBA‐b‐PHEMAGl) was performed via atom transfer radical polymerization. Monofunctional and difunctional poly(butyl acrylate) macroinitiators were used to synthesize the well‐defined diblock and triblock glycopolymers by chain extension reaction with the glycomonomer HEMAGl. The self‐assembly of these glycopolymers in aqueous solution was studied by dynamic light scattering and transmission electron microcopy, showing the coexistence of spherical micelles and polymeric vesicles. In addition, the biomolecular recognition capacity of these micelles and vesicles, containing glucose moieties in their coronas, was investigated using the lectin Concanavalin A, Canavalia Ensiformis, which specifically interacts with glucose groups. The binding capacity of Concanavalin A with glycopolymer is influenced by the copolymer composition, increasing with the length of HEMAGl glycopolymer segment in the block copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Controlled block glycopolymers able to bind specific proteins

“…The monofunctional and difunctional macroinitiators of poly( n ‐butyl acrylate), PBA‐Br ( M n , SEC =8200 g/mol; M w / M n =1.16) and Br‐PBA‐Br ( M n , SEC =11,600 g/mol; M w / M n =1.16), respectively, were synthesized via atom transfer radical polymerization (ATRP) as previously reported 29, 54, 55. The amphiphilic di‐ and triblock glycopolymers were synthesized via chain extension reaction of HEAGl from PBA macroinitiators.…”

“…Accordingly and mimicking the Nature, a variety of glycopolymers has been synthesized for different applications in biomedicine and biomaterials as tools for investigating carbohydrate‐based interactions, therapeutics and drug delivery systems 5, 7–10. This kind of polymeric material is prepared by different approaches:8, 11–14 (i) conventional2, 15–18 or controlled17, 19–31 polymerization techniques using protected or unprotected glycomonomers; (ii) chemical post‐modification using “classical”32–39 or “click” chemistry21, 40–44 methodologies.…”

“…In previous articles, the syntheses of amphiphilic block glycopolymers based on 2‐([( D ‐glucosamin‐2 N ‐yl)carbonyl]oxy)ethyl methacrylate have been described 28, 29. These works pointed out the feasibility of preparing directly glycopolymers without the deprotection steps.…”

Stereoisomerism effect on sugar–lectin binding of self-assembled glyco-nanoparticles of linear and brush copolymers

“…Considering the fact that many of the currently known CRDs only bind to the terminal oligosaccharides of glycans, glycopolymers with repeating pendent units show their great advantage in mimicking these terminal oligosaccharides [9][10][11][12], which is important to further exploration on both of the known and unknown carbohydrate-protein interactions. Meanwhile, the artificial glycopolymers and glyco-nanoparticles have show enhancement multivalent binding behavior of carbohydrate and lectins [13][14][15][16][17][18][19].…”

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)).…”