Loerbroks, Claudia; Boulanger, Eliot; Thiel, Walter
Solvent Influence on Cellulose 1,4-beta-Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynarnics Study
CHEMISTRY-A EUROPEAN JOURNAL, 21:5477-5487, MAR 27 2015

We explore the influence of two solvents, namely water and the ionic liquid 1-ethyl-3-methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.

DOI:10.1002/chem.201405507

Find full text with Google Scholar.