Enzymatic direct synthesis of acrylic acid esters of mono‐ and disaccharides

Abstract

BACKGROUND: There is an increased need to replace materials derived from fossil sources by renewables. Sugar-cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the preparation of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous preparation of protected sugar derivatives, such as glycosides, or activated acrylates, such as vinyl acrylate. RESULTS: Lipase catalyzed esterification of three mono-and two disaccharides with acrylic acid, in the presence or absence of molecular sieves was investigated. The reactions were monitored by high-performance liquid chromatography (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry. The main products are mono-and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was observed for the D-glucose and D-fructose, followed by D-xylose and D-maltose. Molecular sieves had no pronounced effect on the conversion CONCLUSIONS: A feasible method is described to produce and to characterize sugar acrylates, including those containing more than two acrylate groups. The process for production of these higher esters could potentially be optimized further to produce molecules for cross-linking in acrylate polymerization and other applications. The direct enzymatic esterification of free carbohydrates with acrylic acid is unprecedented.

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

“…Lipase selectivity for (trans)esterification can be determined by the hydroxyl reactivity . Thus, more than one hydroxyl of the carbohydrate can be functionalized, as previously reported …”

“…D‐Glucose presents low solubility in t ‐butanol (2.2 g L ‐1 ) and its conversion reached a maximum of 34 mol% using TFMA and 22 mol% using VMA as the methacrylic donor and Novozym 435 as the enzymatic catalyst, with a high selectivity for GMA (87 and 95 mol%, respectively).…”

“…The sub‐products of esterification/transesterification using TFMA, VMA and MA are 2,2,2‐trifluoroethanol, acetaldehyde and water, respectively. While 2,2,2‐trifluoroethanol and water can be easily removed from the reaction medium, acetaldehyde can poison the enzyme, thereby decreasing enzyme reusability …”

“…Tsukamoto and co‐workers reported the esterification of D‐fructose and D‐glucose with acrylic acid in t ‐butanol catalyzed by Novozym® 435 in a homogeneous medium, with a D‐glucose solubility of 2.2 g L ‐1 and a D‐fructose solubility of 18.4 g L ‐1 . They achieved conversions of 80.3% and 64% for D‐glucose and D‐fructose, respectively, producing mono‐, di‐, tri‐, tetra‐ and pentaacrylate carbohydrates.…”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2007–2008

“…On gold nanoparticles to study speciesspecific cell adhesion TOF (DHB) Xyloglucans Glyco-array for monitoring plant cell wall glycosyltransferase activities (Shipp, et al, 2008) Miscellaneous TOF (DHB) 7-Acetoxy-4-methylcoumarin Methanolysis catalysed by cyclosophorases from Rhizobium meliloti Acrylic acid esters of monoand di-saccharides TOF Esterification of free carbohydrates from sugar cane (Tsukamoto, et al, 2008) N-Alkylated 1-deoxymannojirimycin derivatives R-TOF Fluorescent iminoalditol-amino acid hybrids with glucosidase inhibitory properties. (Steiner, et al, 2007) Amphiphilic cyclic disaccharide analogues TOF Two phosphodiester links, four lipophilic chains (Coppola, et al, 2007) TOF Biotinylated glyconanoparticles Reduction with poly(ethyleneglycol), and HAuCl 4 via a photochemical process gives biotinylated gold nanoparticles.…”