Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III) Reaction Intermediate Models of Peroxidase Enzymes

Anzaldo, Samuel Hernández; Abad, Uriel Arroyo; García, Armando León; Ramı́rez-Rosales, Daniel; Zamorano, R.; Ortega, Y. Reyes

doi:10.3390/molecules21070804

Cited by 4 publications

(2 citation statements)

References 34 publications

(41 reference statements)

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“…The peroxidases belong to the biggest superfamily of biocatalyzers and are evolutionarily related monomeric proteins, usually with a molecular weight ranging from 35 000 to 45 000 Da. − Moreover, peroxidase enzymes at the resting state exhibit a single heme b cofactor with a high-spin s = 5/2 penta-coordinated Fe(III), with axial coordination via the N ε of conserved proximal histidine. The imidazole ring of this histidine is approximately perpendicular to the porphyrin plane, giving the molecule mobility within the plane and allowing the coordination to a possible sixth substituent. − This feature has a key role for O 2 release on Fe(III), and, hence, for life itself…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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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.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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“…Porphyrins and analogues, well known by their impressive applications in several areas such as catalysis [ 25 , 26 , 27 , 28 ], photocatalysis [ 29 , 30 ] electronic materials [ 31 , 32 , 33 ], supramolecular chemistry [ 34 , 35 ], biomimetic models [ 36 , 37 ] , and medicine [ 25 , 38 , 39 , 40 , 41 , 42 , 43 ], are also often used as sensor probes due to their unique photophysical and photochemical properties [ 25 , 35 , 44 , 45 , 46 ]. In fact, porphyrins as free-bases or as metallo complexes have been used to create the so-called artificial noses and tongues for gas, cations, anions, and neutral species detection [ 47 ].…”

Section: Introductionmentioning

confidence: 99%

N-Confused Porphyrin Immobilized on Solid Supports: Synthesis and Metal Ions Sensing Efficacy

et al. 2018

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In this work, the N-confused porphyrin 5,10,15,20-tetraphenyl-2-aza-21-carbaporphyrin (NCTPP) was immobilized on neutral or cationic supports based on silica and on Merrifield resin. The new materials were characterized by appropriate techniques (UV-Vis spectroscopy, SEM, and zeta potential analysis). Piezoelectric quartz crystal gold electrodes were coated with the different hybrids and their ability to interact with heavy metals was evaluated. The preliminary results obtained showed that the new materials can be explored for metal cations detection and the modification of the material surface is a key factor in tuning the metal selectivity.

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Investigating axial ligand impact on pinch-porphyrin peroxidase activity with [bis(o-methylpyridino) (dimethylesterprotoporphyrinato)Fe(III)] chloride

Romero-Morán¹,

Hernandez-Anzaldo²,

Vázquez‐Lima³

et al. 2023

J. Porphyrins Phthalocyanines

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The synthesis and characterization of a novel hexacoordinated compound as a product of the reaction between chlorodimethylesterprotoprphyrin–Fe(III) 1 and 2–methylpiridine (2–CH3Py) was performed. The [bis(o–methylpyridino)(dimethylesterprotoporphyrinato)Fe(III)] chloride 2 is a compound of the family of the pinch–porphyrins, a model of peroxidase enzymes. We analyzed 2 using UV-Vis, 1H NMR, and EPR spectroscopies, as well as kinetic quantifications of its peroxidase activity and computational analysis, to evaluate the presence of the pinch-ligand coordinated to 1 in a series of pinch-ironprotoporphyrin complexes, as previously reported. Our investigation revealed that the oxidant activity of Compound I derived from peroxidase activity determination of 1 and 2, respectively, is better controlled when a heterohydrocarbonated chain is attached to the pyridyl groups that coordinate axially to 1; an effect evidenced by a decrease of the activation energy value associated with Compound 0 formation during the reaction performed by pinch–porphyrin, with the picdien axial ligand and hydrogen peroxide. When correlating the contribution of [Formula: see text]3/2 in the quantum mixed-spin state (qms), [Formula: see text]3/2, [Formula: see text]5/2, of iron(III)-based complexes with their peroxidase activity, we found that when the qms [Formula: see text]3/2, [Formula: see text]5/2, of iron(III) had 80% character [Formula: see text]3/2, the peroxide activity increased significantly. This could be a fundamental trait that could affect the peroxidase activity owing to the distortion of the iron geometry associated with its coordination number when [Formula: see text]methylpyridine is used as an axial ligand.

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Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III) Reaction Intermediate Models of Peroxidase Enzymes

Cited by 4 publications

References 34 publications

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

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

N-Confused Porphyrin Immobilized on Solid Supports: Synthesis and Metal Ions Sensing Efficacy

Investigating axial ligand impact on pinch-porphyrin peroxidase activity with [bis(o-methylpyridino) (dimethylesterprotoporphyrinato)Fe(III)] chloride

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