TY - JOUR
T1 - Comparative Studies of Structures and Peroxidase-like Activities of Copper(II) and Iron(III) Complexes with an EDTA-Based Phenylene-Macrocycle and Its Acyclic Analogue
AU - Beltran-Torres, Melissa
AU - Sugich-Miranda, Rocío
AU - Santacruz-Ortega, Hisila
AU - Machi, Lorena
AU - Inoue, Motomichi
AU - Velázquez-Contreras, Enrique F.
AU - Soberanes, Yedith
AU - Höpfl, Herbert
AU - Pérez-González, Refugio
AU - Navarro, Rosa Elena
AU - Salazar-Medina, Alex J.
AU - Sotelo Mundo, Rogerio R.
N1 - Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/12/31
Y1 - 2019/12/31
N2 - With the objective of studying the conformational and macrocyclic effects of selected metal chelates on their peroxidase activities, Cu2+ and Fe3+ complexes were synthesized with a macrocyclic derivative of ethylenediaminetetraacetic acid and o-phenylenediamine (abbreviated as edtaodH2) and its new open-chain analogue (edtabzH2). The Fe3+ complex of edtaodH2 has a peroxidase-like activity, whereas the complex of edtabzH2 does not. The X-ray study of the former shows the formation of a dimeric molecule {[Fe(edtaod)]2O} in which each metal with an octahedral coordination is overposed over the macrocyclic cavity, as a result of rigid macrocyclic frame, to form an Fe-O-Fe bridge; the exposure of the central metal to the environment facilitates the capture of oxygen to drive the biomimetic activity. The peroxidase-inactive Fe3+ complex consists of a mononuclear complex ion [Fe(edtabz)(H2O)]+, the metal ion of which is suited in a distorted pentagonal bipyramid to be protected from environmental oxygen. The copper(II) complexes, which have mononuclear structures with high thermodynamic stability compared with the iron(III) complexes, show no peroxidase activity. The steric effects play a fundamental role in the biomimetic activity.
AB - With the objective of studying the conformational and macrocyclic effects of selected metal chelates on their peroxidase activities, Cu2+ and Fe3+ complexes were synthesized with a macrocyclic derivative of ethylenediaminetetraacetic acid and o-phenylenediamine (abbreviated as edtaodH2) and its new open-chain analogue (edtabzH2). The Fe3+ complex of edtaodH2 has a peroxidase-like activity, whereas the complex of edtabzH2 does not. The X-ray study of the former shows the formation of a dimeric molecule {[Fe(edtaod)]2O} in which each metal with an octahedral coordination is overposed over the macrocyclic cavity, as a result of rigid macrocyclic frame, to form an Fe-O-Fe bridge; the exposure of the central metal to the environment facilitates the capture of oxygen to drive the biomimetic activity. The peroxidase-inactive Fe3+ complex consists of a mononuclear complex ion [Fe(edtabz)(H2O)]+, the metal ion of which is suited in a distorted pentagonal bipyramid to be protected from environmental oxygen. The copper(II) complexes, which have mononuclear structures with high thermodynamic stability compared with the iron(III) complexes, show no peroxidase activity. The steric effects play a fundamental role in the biomimetic activity.
UR - http://www.scopus.com/inward/record.url?scp=85076943337&partnerID=8YFLogxK
U2 - 10.1021/acsomega.9b03164
DO - 10.1021/acsomega.9b03164
M3 - Artículo
C2 - 31909331
AN - SCOPUS:85076943337
SN - 2470-1343
VL - 4
SP - 22487
EP - 22496
JO - ACS Omega
JF - ACS Omega
IS - 27
ER -