Scale‐up of pseudo solid‐phase enzymatic synthesis of α‐methyl glucoside acrylate

Abstract

The successful scale-up of the enzymatic synthesis of alpha-methyl glucoside acrylate from laboratory-scale (milliliter) to pilot-scale (liter) was examined. Specifically, Candida antarctica lipase B (Novozym 435) was used as a biocatalyst to produce alpha-methyl glucoside acrylate via the transesterification of alpha-methyl glucoside (MG) with vinyl acrylate (VA) using acetone as a solvent. This is a pseudo-solid-phase synthesis; only a fraction of the alpha-methyl glucoside and the product are soluble in acetone. Molecular sieves were used to remove traces of water in the reaction medium and to increase enzyme stability by removing the acetaldehyde by-product. A general method was also developed to purify and recover the monoacrylate product from unreacted sugar and undesired diester by a simple crystallization and precipitation process.

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

“…9 Table S1 (available in the Supporting information) summarizes the main results reported in the literature regarding the functionalization of glucose and fructose with polymerizable groups using both the chemical and enzymatic (lipase and protease) routes. In general, the monomer yield/carbohydrate conversion tends to be higher for enzymatic catalysis 12,[23][24][25][26][27][28][29][30][31][32][33][34][35][36] than for the chemical route, 13,[17][18][19][37][38][39][40][41][42] however, high yields in the carbohydrate functionalization can also be achieved using some chemical routes. 13,21,39,42 Moreover, Candida Antarctica lipase B (EC 3.1.1.3), commercially available in a supported form under the name Novozym ® 435, is widely used in the functionalization of carbohydrates in organic media, including the enzymatic-catalyzed carbohydrate (meth)acrylation.…”

“…13,21,39,42 Moreover, Candida Antarctica lipase B (EC 3.1.1.3), commercially available in a supported form under the name Novozym ® 435, is widely used in the functionalization of carbohydrates in organic media, including the enzymatic-catalyzed carbohydrate (meth)acrylation. 12,[25][26][27][28][29]43 Lipase selectivity for (trans)esterification can be determined by the hydroxyl reactivity. 44 Thus, more than one hydroxyl of the carbohydrate can be functionalized, as previously reported.…”

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

“…D ‐glucose appears to be the best substrate, with an overall conversion of 80.3% in the presence of molecular sieves (Table 1), which is lower than the nearly quantitative reaction reported for the transesterification of vinyl acrylate with methyl α‐ D ‐glucoside in acetone21, 23 or with methyl β‐ D ‐glucoside in t ‐butanol 5. In the absence of molecular sieves, the conversion of glucose was lowered to 72.4% (Table 1), which compared favourably with a value of 58% achieved in the condensation esterification of methyl β‐ D ‐glucoside with acrylic acid in t ‐butanol 13.…”

Synthesis of glycomonomers via biocatalytic methods

“…Candida antarctica t-Butanol, 50°C, 1 day 95 a Perin and Felisberti ( 2018) Lipase from Candida antarctica selectively catalyzes the monosubstitution of vinyl groups toward a primary alcohol at the C-6 position of monosaccharides with pyranose structures Granville et al, 2007;Kim et al, 2004;Li & Rethwisch, 2002;Park et al, 2004), at the C-6 position of reduced disaccharides Miura, Ikeda, Wada, et al, 2003), and at C-6 or C-6 00 positions of trisaccharides (P erez-Victoria & Morales, 2007). Mono-and disubstitution of vinyl groups was observed when fructose, sucrose, and trehalose were used as the substrates (Park et al, 2000;Perin & Felisberti, 2018).…”