Modification of polysaccharides via thiol‐ene chemistry: A versatile route to functional biomaterials

Abstract

We present herein a mild and rapid method for the modular functionalization of polysaccharides. Several ene‐functional charged and neutral polysaccharides, that is, hyaluronic acid and dextran, were prepared by esterification of the hydroxyl groups with pentenoic anhydride. The modified polysaccharides were then reacted with six model mercaptans under UV light, leading to linear polymers modified with hydrophobic groups, peptides, or oligosaccharides as well as chemical hydrogels. The thiol‐ene coupling reactions were found to proceed with high efficiency in short reaction times and with nearly no degradation of the polysaccharide backbone. Moreover, they were carried out in aqueous media, without the use of any metal catalysts, enhancing the attractive nature of this process. Notably, we investigated whether it is feasible to prepare cell‐responsive hydrogels by sequential bioconjugation and cross‐linking of the polysaccharide backbone with a bioactive peptide and poly(ethylene glycol)‐dithiol, respectively. All together, these results highlight the potential of this coupling strategy for the modular functionalization of polysaccharides under click chemistry‐like conditions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Designing multivalent probes for tunable superselective targeting

“…We used a two-step synthetic procedure based on the esterification of HA hydroxyl groups with pentenoic anhydride followed by the reaction with a β-CD-thiol derivative ( Fig. 1 B, 1) (16,22). This thiol-ene coupling method provides mild and efficient functionalization of polysaccharides, and the DS β-CD can be tuned by varying the HA disaccharide-β-CD-thiol molar ratio (22).…”

“…1 B, 1) (16,22). This thiol-ene coupling method provides mild and efficient functionalization of polysaccharides, and the DS β-CD can be tuned by varying the HA disaccharide-β-CD-thiol molar ratio (22). Thus, using 0.09 and 0.30 molar equivalents of β-CD-thiol with respect to the repeating disaccharide unit of HA, we obtained HA-β-CD derivatives with DS β-CD = 3% and DS β-CD = 21%.…”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

“…Used to reveal critical enzyme-substrate interactions in GlfT2-catalyzed mycobacterial galactan assembly (Poulin et al, 2012) UDP-xylose and UDPgalactose TOF (DHB) Synthesis in Trichomonas vaginalis (Rosenberger et al, 2012) Uridine--O-(2-thiodiphospho)-Nacetylglucosamine TOF/TOF Enzymatic synthesis with MALDI-TOF to assay for glycosyltransferase activities Complex N-glycans TOF Accelerated O-glycosylation under frozen conditions (Ishiwata et al, 2012) Cyclodextrins TOF (DHP) Modification of the secondary face by coppercatalyzed Huisgen 1,3-dipolar cycloaddition (Ward & Ling, 2011) Fucosylated N-glycans TOF Use of 1 3-and 1 6-fucosyltransferases for core fucosylation Functionalized carbohydrates TOF Synthesis via thiol-ene chemistry (Mergy et al, 2012) Galactooligosaccharides TOF Use of -galactosidase inclusion bodies containing Escherichia coli cells (Lee et al, 2011f) Glycopeptides TOF (DHB) Solid-phase synthesis using microwave irradiation (Garcia-Martin et al, 2012) Glycopeptides TOF By ring opening polymerization of Oglycosylated--amino acid N-carboxyanhydride N-Glycopeptides (Nokami et al, 2011) Immunomodulatory disaccharides R-TOF (DHB, CHCA)…”

Organic Modification of Hydroxylated Nanoparticles: Silica, Sepiolite, and Polysaccharides

“…Several pentenoate-modified polysaccharides with various degree of modification were prepared by esterification of hyaluronic acid and dextran using pentenoic anhydride [283].…”