Unusual kinetic isotope effects of deuterium reinforced polyunsaturated fatty acids in tocopherol-mediated free radical chain oxidations.
J Am Chem Soc
; 136(3): 838-41, 2014 Jan 22.
Article
en En
| MEDLINE
| ID: mdl-24380377
ABSTRACT
Substitution of -CD2- at the reactive centers of linoleic and linolenic acids reduces the rate of abstraction of D by a tocopheryl radical by as much as 36-fold, compared to the abstraction of H from a corresponding -CH2- center. This H atom transfer reaction is the rate-determining step in the tocopherol-mediated peroxidation of lipids in human low-density lipoproteins, a process that has been linked to coronary artery disease. The unanticipated large kinetic isotope effects reported here for the tocopherol-mediated oxidation of linoleic and linolenic acids and esters suggests that tunneling makes this process favorable.
Texto completo:
1
Bases de datos:
MEDLINE
Asunto principal:
Tocoferoles
/
Deuterio
/
Ácidos Grasos Insaturados
Límite:
Humans
Idioma:
En
Revista:
J Am Chem Soc
Año:
2014
Tipo del documento:
Article
País de afiliación:
Estados Unidos