Biohybrid glycopolymer capable of ionotropic gelation

• Main Authors: Ghadban, Ali, Albertin, Luca, Rinaudo, Marguerite, Heyraud, Alain
• Other Authors: School of Materials Science & Engineering
• Format: Article
• Language: English
• Published: 2014
• Subjects: DRNTU::Engineering::Manufacturing::Polymers and plastics
• Online Access: https://hdl.handle.net/10356/101113; http://hdl.handle.net/10220/19539
• Institution: Nanyang Technological University

Ionotropic gelation is particularly appealing for the formation of hydrogels because it takes place under mild conditions, is not thermoreversible, and does not involve toxic chemicals. A well-known example is the gelation of alginate in the presence of calcium ions, which is at the base of numerous applications involving this polymer. In this study, alginate-derived oligosaccharides were converted into acrylamide- and methacrylamide-type macromonomers in two steps without resorting to protective group chemistry. They were then copolymerized with 2-hydroxyethylmethacrylamide in aqueous solution to yield high molar mass biohybrid glycopolymers containing between 25 and 52% by mass of oligosaccharide graft chains. A comparative kinetic study showed that both acrylamide- and methacrylamide-type macromonomers reacted since the early stages of the copolymerization, but that the mole fraction in the polymer was smaller than in the feed up to 50–60% conversion and increased markedly afterward. This effect was slighter for the methacrylamide-type macromonomer though. Copolymers carrying oligosaccharide chains with 16–20 repeating units were synthesized and used for a gelation experiment: When dialyzed against CaCl2 0.5 mol L–1, the polymer carrying (1→4)-α-l-guluronan residues led to a soft isotropic self-standing transparent hydrogel, while the polymer carrying (1→4)-β-d-mannuronan residues gave a loose opaque gel. This study demonstrates that alginate-extracted oligosaccharides and aqueous radical polymerization can be combined for the flexible design of biohybrid glycopolymers capable of ionotropic gelation under very mild conditions.