Tailored Interactions of the Secondary Coordination Sphere Enhance the Hydrolytic Activity of Cross-Linked Microgels

by Sharma, Babloo; Striegler, Susanne

A series of mannose-templated microgels with immobilized catalytic sites and catalysis-supporting co-monomers was synthesized and evaluated for catalytic hydrolyses of glycosidic bonds. Interactions of the secondary coordination sphere around the catalytic center were implemented between the sugar and surrounding monomers by copolymerization of corresponding acrylates. The obtained microgels were evaluated for their ability to enhance the catalytic hydrolysis of glycosidic bonds in neutral and alkaline solution. The catalytic proficiency of the microgels reaches a remarkable value of 1.4 X 10(7) at neutral pH when hydrogen-bond-accepting 2-methoxyethyl acrylate is embedded in 20 mol % as a co-monomer, instead of butyl acrylate. The results indicate a strong influence of hydrogen-bond-accepting co-monomers on the stability of the transition state of glycoside hydrolyses in the designed biomimetic catalysts. The overall performance of all microgels correlates very well with the calculated dipole moments of the implemented co-monomers.

Journal
ACS Catalysis
Volume
9
Issue
3
Year
2019
Start Page
1686-1691
URL
https://dx.doi.org/10.1021/acscatal.8b04740
ISBN/ISSN
2155-5435
DOI
10.1021/acscatal.8b04740