http://www.cnr.it/ontology/cnr/individuo/prodotto/ID40332
The catalytic effect of water on the ketoenol tautomerism. Pyruvate and acetylacetone: a computational challenge (Articolo in rivista)
- Type
- Label
- The catalytic effect of water on the ketoenol tautomerism. Pyruvate and acetylacetone: a computational challenge (Articolo in rivista) (literal)
- Anno
- 2010-01-01T00:00:00+01:00 (literal)
- Alternative label
Alagona* G., Ghio C., Nagy P.I. (2010)
The catalytic effect of water on the ketoenol tautomerism. Pyruvate and acetylacetone: a computational challenge
in PCCP. Physical chemistry chemical physics (Print)
(literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
- Alagona* G., Ghio C., Nagy P.I. (literal)
- Pagina inizio
- Pagina fine
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
- Rivista
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#note
- Invited paper published as part of the themed section \"Water in Biological Systems\" - Published online: Aug. 2, 2010 - Electronic supplementary information available: Two additional tables, two figures related to the dihydrated pyruvate structures, three figures comparing potential energy profiles for the pyruvate tautomerism, and twelve figures related to the dihydrated acetylacetone tautomerism as detailed within the text. See DOI: 10.1039/c003999c (literal)
- Note
- ISI Web of Science (WOS) (literal)
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
- A.G.: IPCF-CNR, MML, Pisa;
G.C.: IPCF-CNR, MML, Pisa;
N.P.I.: \"Center for Drug Design and Development\" and \"the Department of Medicinal and Biological Chemistry\", The University of Toledo, Toledo, OH, USA; (literal)
- Titolo
- The catalytic effect of water on the ketoenol tautomerism. Pyruvate and acetylacetone: a computational challenge (literal)
- Abstract
- The catalytic effect of explicit water molecules on the keto-enol tautomerism in a system of biological interest (enolpyruvate) has been investigated at the B3LYP/6-31++G** level by exploring the potential energy surface in the presence of 1 or 2 water molecules and comparing the energy profiles to the direct tautomerisation one. The water-assisted mechamisms turned out to be more favourable than the direct ones, in agreement with what occurred for the acetylacetone tautomerism in the presence of a single water molecules. To compare the behaviour of water in pyruvate and in acetylacetone, the two-water-assisted mechanism has been also examined for the latter at the B3LYP/6-31G* level. A number of stationary points for both compounds in vacuo and in the presence of explicit water molecules have been computed with DFT coupled to larger basis sets and at the MP2 level. Two diketo forms more stable than any of the ketoenol tautomers have been located, while for pyruvate the keto form is always more favourable than the enol one. The equilibrium constant for acetylacetone tautomerisation has been computed with high accuracy, performing complete basis set extrapolation for the relative internal energy, to determine whether the quality of the method/basis set is responsible for the earlier modest agreement with the experimental value. Monte Carlo and molecular dynamics simulations helped characterize the solution structure and association features in the 0.03-0.22 molar concentration range. (literal)
- Prodotto di
- Autore CNR
- Insieme di parole chiave
Incoming links:
- Prodotto
- Autore CNR di
- Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#rivistaDi
- Insieme di parole chiave di