TY - JOUR
T1 - Substrate ionization energy influences the epoxidation of m-substituted styrenes catalyzed by chloroperoxidase from Caldariomyces fumago
AU - Muñoz-Guerrero, Fabio A.
AU - Águila, Sergio
AU - Vazquez-Duhalt, Rafael
AU - Campos, Cristian H.
AU - Torres, Cecilia C.
AU - Alderete, Joel B.
N1 - Funding Information:
F. A. Muñoz-Guerrero thanks to CONICYT for a graduate fellowship (number 63105502). Authors are grateful for the support of CONACYT-CONICYT International Cooperation Program (Number PCCI130043 ) México — Chile governments and Red Doctoral REDOC MINEDUC Project UCO 1202 .
PY - 2016/3/5
Y1 - 2016/3/5
N2 - Chloroperoxidase from the fungus Caldariomyces fumago is a versatile heme-peroxidase, which is able to catalyze olefin epoxidation. In this report, the epoxidation of m-substituted styrene catalyzed by chloroperoxidase was studied. The catalytic data fit the Hill's model, and the activity rate (kcat) constants were strongly dependent of nature of substituents. The epoxidation kcat values varied as follows: m-aminostyrene > styrene > m-methylstyrene > m-chlorostyrene > m-nitrostyrene. The catalytic rate constant for m-aminostyrene, an electron-releasing substituent, was 298 times higher than these for m-nitrostyrene, an electron-withdrawing compound. These results were quantitatively analyzed and a good linear correlation between the experimental catalytic constants of m-substituted styrenes and their ionization energies, calculated at B3LYP level of theory, was demonstrated.
AB - Chloroperoxidase from the fungus Caldariomyces fumago is a versatile heme-peroxidase, which is able to catalyze olefin epoxidation. In this report, the epoxidation of m-substituted styrene catalyzed by chloroperoxidase was studied. The catalytic data fit the Hill's model, and the activity rate (kcat) constants were strongly dependent of nature of substituents. The epoxidation kcat values varied as follows: m-aminostyrene > styrene > m-methylstyrene > m-chlorostyrene > m-nitrostyrene. The catalytic rate constant for m-aminostyrene, an electron-releasing substituent, was 298 times higher than these for m-nitrostyrene, an electron-withdrawing compound. These results were quantitatively analyzed and a good linear correlation between the experimental catalytic constants of m-substituted styrenes and their ionization energies, calculated at B3LYP level of theory, was demonstrated.
KW - Chloroperoxidase
KW - Epoxidation
KW - Ionization energies
KW - m-Substituted styrene
UR - http://www.scopus.com/inward/record.url?scp=84955480357&partnerID=8YFLogxK
U2 - 10.1016/j.catcom.2016.01.017
DO - 10.1016/j.catcom.2016.01.017
M3 - Article
AN - SCOPUS:84955480357
SN - 1566-7367
VL - 77
SP - 52
EP - 54
JO - Catalysis Communications
JF - Catalysis Communications
ER -