Lectin Recognizable Biomaterials Synthesized via Nitroxide-Mediated Polymerization of a Methacryloyl Galactose Monomer

Abstract

The preparation of poly(2-(2′,3′,4′,6′-tetra-O-acetyl-β-d-galactosyloxy)ethyl methacrylate-co-styrene) (P(AcGalEMA-co-S)) glycopolymer was performed via nitroxide-mediated polymerization using a methacrylic acid-based alkoxyamine with N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) (SG1) nitroxide as mediating agent. In the presence of a low proportion of styrene, the polymerization of the glycomonomer was conducted in a controlled fashion at 85 °C. The synthesis of the diblock copolymers was investigated via two routes by using either P(AcGalEMA-co-S) or polystyrene macroinitiators capped with SG1 nitroxide to yield P(AcGalEMA-co-S)-b-PS and PS-b-P(AcGalEMA-co-S), respectively. The AcGalEMA moieties on the diblock copolymer were deacetylated to afford carbohydrate-based amphiphilic diblock copolymer, polystyrene-block-poly(2-(β-d-galactosyloxy)ethyl methacrylate-co-styrene) (PS-b-P(GalEMA-co-S)). The self-assembling properties of PS-b-P(GalEMA-co-S) amphiphilic diblock copolymers were thoroughly exploited to obtain micellar structures and porous films. Lectin binding assays were conducted using the UV−vis spectroscopy and dynamic light scattering to test the biofunctionality of the β-galactose moieties with peanut agglutinin (PNA) on the micelles. The polymer was used to prepare honeycomb structured porous films with bioactivity. Fluorescent PNA was eventually conjugated with the sugar moieties on the porous films. Most protein was conjugated to glycopolymer inside the pore, demonstrating that this procedure can be a simple route to pattern proteins onto surfaces.

Synthesis and characterization of sugar-based methacrylates and their random copolymers by ATRP

“…(NMP) [29,30], reversible addition-fragmentation chain transfer (RAFT) [31][32][33][34] and cyanoxyl-mediated radical polymerization [35,36]. In the present study, a series of well-defined random copolymers comprising different sugar-based methacrylates and methyl methacrylates were synthesized by ATRP and their structures were investigated by spectroscopic, chromatographic and thermal analyses.…”

Droplet condensation on polymer surfaces: A review

“…Galactosylated porous films on protein patterning could also be used as a screening device. 191 Xiong et al studied the use of linear PS and star-shaped PS-block-polybutadiene copolymer solutions that have been cast in a static humid environment and investigated the influence of the flow ability of polymer solution and water vapor pressure on the final film structure by using different starting polymer concentrations at 4 to 90 • C. They found that higher solvent vapor pressure would be required for the fabrication of ordered patterns having smaller pores and initial polymer concentration has an important effect on the packing of condensed water droplets since the polymer solution could reach a level of 'solidification' during a reasonable time of solvent evaporation that fixes the droplets and prevents the droplets from coalescing. …”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…A statistical copolymer of M9 with N,N′-di(octadecyl)acrylamide M8 was also prepared under similar conditions and with similar results (p = 55% after 40 h, Đ = 1.2; Entry 14, Table 1). Amphiphilic lipo-glycopolymers were obtained after Ting et al [86] reported the synthesis of an amphiphilic glycopolymer bearing α-galactoside residues (Entry 11-12, Table 1). Initially, methacrylate glycomonomer M11 was copolymerized with styrene in the presence of N9 as the initiator to afford fairly uniform poly(M11 0.9 -stat-St 0.1 ) (1,4-dioxane, 85 °C, 2.7 h).…”