Theoretical modeling of the nonenzymatic solvolysis of CMP-NeuAc in an acidic environment
- 作者：Bartosz Trzaskowski ; Andrzej Leś ; Abraham F. Jalbout ; Ludwik Adamowicz ; Per E.M. Siegbahn
- 关键词：CMP-NeuAc ; Solvolysis ; Sialic acid ; Sialyltransferase ; DFT
- 刊名：Journal of Molecular Structure ; THEOCHEM
- 出版年：2007
- 期刊代码：63_01661280
- 类别：ch
- 出版时间：15 October 2007
- 卷：820
- 期：1-3
- 页码：90-97
- 文件大小：549 K
摘要
A density-functional-theory investigation of the nonenzymatic solvolysis of the cytydine 5′-monophosphate N-acetylneuraminic acid and its derivatives in the acidic environment is presented. The theoretical calculations of the second stage of the reaction mechanism are in agreement with the hypothesis of a dissociative oxocarbenium-like transition state with proton transfer as a key part of the reaction. The geometries of the transition states of the reactions yielding α-methyl and β-methyl glycosides are essentially different. This study provides new theoretical data that can be helpful in elucidating the mechanism of the carbohydrates hydrolysis as well as other reactions catalyzed by the glycosyltransferases.