Influence of Equatorial CHâ
â
â
O Interactions on Secondary Kinetic Isotope Effects for Methyl Transfer.
Angew Chem Int Ed Engl
; 55(9): 3192-5, 2016 Feb 24.
Article
em En
| MEDLINE
| ID: mdl-26823274
ABSTRACT
DFT calculations for methyl cation complexed within a constrained cage of water molecules permit the controlled manipulation of the "axial" donor/acceptor distance and the "equatorial" distance to hydrogen-bond acceptors. The kinetic isotope effect k(CH3)/k(CT3) for methyl transfer within a cage with a short axial distance becomes less inverse for shorter equatorial Câ
â
â
O distances a decrease of 0.5â
Å results in a 3 % increase at 298â
K. Kinetic isotope effects in AdoMet-dependent methyltransferases may be mâ§odulated by CHâ
â
â
O hydrogen bonding, and factors other than axial compression may contribute, at least partially, to recently reported isotope-effect variations for catechol-O-methyltransferase and its mutant structures.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2016
Tipo de documento:
Article
País de afiliação:
Reino Unido