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Anionic ligands tune the structural and catalytic properties of quinoxaline-based copper(II) complexes as mimetics of copper-containing oxidase protein
Faculty
Science
Year:
2022
Type of Publication:
ZU Hosted
Pages:
Authors:
Ahmed Mohamed Fathy Abedulrahman
Staff Zu Site
Abstract In Staff Site
Journal:
Journal of Molecular Structure Elsevier
Volume:
Keywords :
Anionic , ligands , tune , , , structural , , , catalytic , properties
Abstract:
The hexadentate ligand containing quinoxaline backbone along with its Cu(II) -based complexes with various anionic ligands were synthesized and their structures were determined. Molecular formulae were assigned based on the data of both elemental analysis and the electrical conductivity in DMF solutions. Spectroscopic and magnetic measurements were performed to achieve the final structural properties. The exact geometry of the synthesized Cu(II) complexes was demonstrated by processing the PXRD data using a computer program specializing in the structural analysis of metallic complexes. The anionic ligands included in the complex molecule adjust the stereochemistry of the central Cu(II) ion. In this regard, the halogeno ligands direct the octahedral environment while the nitrato, acetato and perchlorato ligands adjust the dsp 3 hybridization of the trigonal bipyramidal stereochemistry. Mimicry of copper oxidase proteins such as catechol oxidase and phenoxazine synthase has been studied. The oxidase biomimetic catalytic activity was tuned by the anionic ligands included in the Cu(II) oxidase mimics. Kinetic measurements allowed the determination of relevant parameters such as V max , k cat , K M and the ratio k cat /K M . The potential catalytic reaction sequences have been suggested based on the results of kinetic investigations. The driving force of the studied catalytic reactions was determined based on the electrochemical data and the impact of the driving force ( λ or –ΔG°) on the catalytic activity was addressed.
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Ahmed Mohamed Fathy Abedulrahman, "Copper (II) complexes based on the mixed ligand system: Study of synthesis, characterization, and stopped-flow kinetics of copper oxidase-mimicking catalytic activity", John Wiley & Sons, 2024
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