Molecular dynamics prediction of the mechanism of ester hydrolysis in water.
J Am Chem Soc
; 130(46): 15232-3, 2008 Nov 19.
Article
em En
| MEDLINE
| ID: mdl-18939841
ABSTRACT
Hydrolysis reactions of the basic units of biological polymers with water, or the reverse reaction, the formation of ester, amide, ketal, or phosphate bonds, occur with very high activation barriers in the gas phase but occur much more rapidly in pure water. Car-Parrinello molecular dynamics simulations reported here show that the rate of hydrolysis of methyl formate in pure water is consistent with mechanisms involving cooperative catalysis by autoionization-generated hydroxide and hydronium, a process known to have an activation free energy of 23.8 kcal/mol. In this mechanism, autoionization is followed by rapid simultaneous acid-base catalysis.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Água
/
Ésteres
Tipo de estudo:
Prognostic_studies
/
Risk_factors_studies
Idioma:
En
Ano de publicação:
2008
Tipo de documento:
Article