Enzymatic synthesis and structural characterization of methacryloyl‐D‐fructose‐ and methacryloyl‐D‐glucose‐based monomers and poly(methacryloyl‐D‐fructose)‐based hydrogels

• Published in: Journal of chemical technology and biotechnology (1986) Vol. 93; no. 6; pp. 1694 - 1704
• Main Authors: Perin, Giovanni Bortoloni, Felisberti, Maria Isabel
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.06.2018; Wiley Subscription Services, Inc
• Subjects: biocatalysis; biomass; Biomedical materials; Butanol; Carbohydrates; catalysts; characterization; Compression; Crosslinking; Decompression; enzymatic reactions; Enzymatic synthesis; enzymes; esterification; ethylene glycol; Fructose; Glucose; green chemistry; Hydrogels; Lipase; Monomers; Polymerization; Polymers; Raw materials; Solubilization; Structural analysis; Synthesis; triacylglycerol lipase
• ISSN: 0268-2575; 1097-4660
• DOI: 10.1002/jctb.5542

BACKGROUND Carbohydrates are important renewable raw materials and their modification by enzymatic reactions with polymerizable groups is of great importance due the possibility of production of polymers with properties for biomedical applications. In this study, D‐fructose‐ and D‐glucose‐based monomers were prepared by enzymatic reactions and structurally characterized. Moreover, hydrogels based on poly(methacryloyl‐D‐fructose) were also prepared and characterized. RESULTS The conversions of 99% and 34% for D‐fructose and D‐glucose, respectively, were achieved using 2,2,2‐trifluoroethyl methacrylate as the methacrylic donor and commercial lipase Novozyme® 435 (EC 3.1.1.3) as enzymatic catalyst in t‐butanol. The molar ratios of D‐fructose and D‐glucose mono‐ and dimethacrylate were 57/43 and 87/13, respectively. These monomers are an isomeric mixture related to the tautomeric equilibrium of the carbohydrates in solution. Methacryloyl‐D‐fructose was polymerized in the presence of a controlled amount of ethyleneglycol dimethacrylate as crosslinker achieving hydrogels with different crosslinking densities which are mechanically stable when subject to compression–decompression cycles and have a high water swelling capability. CONCLUSION The combination of 2,2,2‐trifluoroethylmethacrylate and Novozym® 435 in a heterogeneous media lead to the continuous carbohydrate solubilization and reaction with the formation of carbohydrates‐based monomers. The control of the monomer functionality enables the synthesis of hydrogels with different crosslinking densities that tune their properties. © 2017 Society of Chemical Industry