Imbalanced tunneling ready states in alcohol dehydrogenase model reactions: rehybridization lags behind H-tunneling
| Autor: | Yun Lu, Blake A. Hammann, Sadra Kashefolgheta, Mortezaali Razzaghi |
|---|---|
| Rok vydání: | 2012 |
| Předmět: |
Acetonitriles
Alcohol Carbocation Photochemistry Catalysis chemistry.chemical_compound Cations Kinetic isotope effect Materials Chemistry Acetonitrile Alcohol dehydrogenase biology Hydride Metals and Alloys Alcohol Dehydrogenase Hydrogen Bonding General Chemistry Acceptor Surfaces Coatings and Films Electronic Optical and Magnetic Materials Kinetics chemistry Models Chemical Alcohols Ceramics and Composites biology.protein Biocatalysis Heterocyclic Compounds 3-Ring |
| Zdroj: | Chemical communications (Cambridge, England). 48(92) |
| ISSN: | 1364-548X |
| Popis: | The secondary kinetic isotope effects for the hydride transfer reactions from aliphatic alcohols to two carbocations (NAD(+) models) in acetonitrile were determined. The results suggest that the hydride transfer takes place by tunneling and that the rehybridizations of both donor and acceptor carbons lag behind the H-tunneling. This is quite contrary to the observations in alcohol dehydrogenases where the importance of enzyme motions in catalysis is manifested. |
| Databáze: | OpenAIRE |
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