ESR and magnetic studies of octahedral [Fe(III)(Cl)(pcd)(H2O)(DMSO)] (pcd=pyridine-2,6-dicarboxylato) compound showing Fe(III) species with different spin states in solution

Hernández-Anzaldo, Samuel; Sánchez-Morales, Nailea; Zamorano, R.; Escudero, R.; Hoz, María de Jesús Rosales; Reyes‐Ortega, Yasmi

doi:10.1016/j.molstruc.2013.02.021

Cited by 7 publications

(7 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The typical UV–vis bands for Fe(III) containing qms are identifiable in Figure S2, in the range of 580–550 nm for all the pinch-porphyrin compounds studied herein. 18 Furthermore, the Soret band for 1–6 decreases because the intensity of the transition in the system is lower due to the change in the geometry of the molecule, which becomes axially coordinated to the pinch ligand. 19,20…”

Section: Resultsmentioning

confidence: 99%

“…Thus, experiments at low temperature were needed, Figure S1. The series of spectra show the lineshape of six-coordinated-like porphyrin complexes. − Furthermore, the heme-ethyl groups in these kinds of compounds have been well studied, as well as their influence in the porphyrin’s pyrrole rings protons. The admixture of the spin could be established on the basis of the electronic and magnetic interaction over the longitudinal axis ( d x 2 – y 2 orbital) with the electronic σ-spin delocalization, resulting in different chemical shifts.…”

Section: Resultsmentioning

confidence: 99%

“…To confirm the peroxidase-like behavior, guaiacol tests were performed for 1–6 , followed by UV–vis, resulting in λ max (nm) for the guaiacol oxidation products (Scheme S1), proving their formation. Additionally, the data from UV–vis spectra allowed us to perform a Michaelis–Menten study for each compound, proving that the compounds behave as enzymes ruled by this model. , Complementarily, the guaiacol test proves even further that 1–6 are indeed the peroxidase model.…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

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

et al. 2019

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Enzymes are proteins that act like natural catalysts, producing a huge increase in the reaction rate by lowering the energetic barrier in the transition state of a process [1,2]. Scientists have tried to mimic this power using synthetic products [2,3].…”

Section: Introductionmentioning

confidence: 99%

“…Scientists have tried to mimic this power using synthetic products [2,3]. In this context, peroxidases are among several proteins targeted for replacement by coordination compounds, specifically synthetic metalloporphyrins, due to their similarity to the prosthetic groups found in peroxidases.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2016

View full text Add to dashboard Cite

Abstract:The spectroscopic and kinetic characterization of two intermediates from the H 2 O 2 oxidation of three dimethyl ester [(proto), (meso), (deuteroporphyrinato) (picdien)]Fe(III) complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively) pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III) quantum mixed spin (qms) ground states is described herein. The kinetic study by UV/Vis at λ max = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1-3 + guaiacol + H 2 O 2 Ñ oxidation guaiacol products). The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III) and H 2 O 2 , resulting in only two types of kinetics that were developed during the first 0-4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III) family with the ligand picdien [N,N'-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1 H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

show abstract

Enhanced photocatalytic hydrogen evolution with a Mixed-Valence iron Metal-Organic framework

Zhang

et al. 2023

Chemical Engineering Journal

View full text Add to dashboard Cite

ESR and magnetic studies of octahedral [Fe(III)(Cl)(pcd)(H2O)(DMSO)] (pcd=pyridine-2,6-dicarboxylato) compound showing Fe(III) species with different spin states in solution

Cited by 7 publications

References 31 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

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

Enhanced photocatalytic hydrogen evolution with a Mixed-Valence iron Metal-Organic framework

Contact Info

Product

Resources

About