Synthesis, Kinetic Study, and Spectroscopic Analysis of Peroxidase-like Pinch-Porphyrin Fe(III) Complexes

Hugo Vazquez-Lima; Uriel Arroyo Abad; Aarón Pérez Benítez; Daniel Ramírez Rosales; Rafael Zamorano Ulloa; Yasmi Reyes Ortega; Samuel Hernández Anzaldo

doi:10.1021/acsomega.9b03186

Synthesis, Kinetic Study, and Spectroscopic Analysis of Peroxidase-like Pinch-Porphyrin Fe(III) Complexes

ACS Omega. 2019 Dec 19;4(27):22521-22529. doi: 10.1021/acsomega.9b03186. eCollection 2019 Dec 31.

Authors

Hugo Vazquez-Lima¹, Uriel Arroyo Abad¹, Aarón Pérez Benítez², Daniel Ramírez Rosales³, Rafael Zamorano Ulloa³, Yasmi Reyes Ortega¹, Samuel Hernández Anzaldo¹

Affiliations

¹ Centro de Química Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Edificio IC9, Ciudad Universitaria, Col. Jardines de San Manuel, Puebla Pue. 72570, Mexico.
² Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, Edificio FCQ9, Ciudad Universitaria, Col. Jardines de San Manuel, Puebla Pue. 72570, Mexico.
³ Instituto Politécnico Nacional, ESFM, Ave. Instituto Politécnico Nacional S/N, Edif. 9 U.P. Zacatenco, Col. San Pedro Zacatenco, México City 07738, Mexico.

Abstract

In the present manuscript, we report the kinetic and spectroscopic analysis of six new pinch-porphyrins: protoporphyrin-picpenta 1, mesoporphyrin-picpenta 2, deuteroporphyrin-picpenta 3, protoporphyrin-picocta 4, mesoporphyrin-picocta 5, and deuteroporphyrin-picocta 6. The Michaelis-Menten enzymatic pathway and the guaiacol test confirmed the ability of the compounds to function like new peroxidase models. UV-vis, ¹H NMR, and electron spin resonance studies are in accordance with porphyrin-Fe(III) molecules with the quantum phenomena called quantum mixed spin (qms, s = 3/2, s = 5/2). Importantly, the influence of the presence of the s = 3/2 spin state in the compounds and its critical role for the catalytic capacity is proven here, which was the original hypothesis in our research group. The compounds with higher populations of the s = 3/2 spin state have increased peroxidase activity.