Improved Alkyl Glycoside Synthesis by trans‐Glycosylation through Tailored Microenvironments of Immobilized β‐Glucosidase

Here, we present for the first time, how the micro‐environment can directly improve biocatalytic selectivity of immobilized ß‐glucosidase. ß‐Glucosidase from Thermotoga neapolitana was immobilized on a variety of functionalized off‐stoichiometric thiol‐ene (OSTE) particles, where highest activities were observed for thiol and imidazole functional particles. Compared to the soluble enzyme, the selectivity (r_s/r_h) between trans‐glycosylation of p‐nitrophenyl ß‐D‐glucopyranoside (pNPG) with 1‐propanol over hydrolysis was increased by a factor of 2‐3 using particles containing imidazole (rs/rh of 6.7) and carboxylic acid moieties (r_s/r_h of 9.2), respectively. These results demonstrate clearly that enzyme selectivity depends directly on the local environment of the enzyme with the support.