Antonio Ranieri

Carlo Augusto Bortolotti

Gianantonio Battistuzzi

Marco Borsari

Marco Sola

Mirco Meglioli

English

Archivio istituzionale della ricerca - Università di Modena e Reggio Emilia

PhD Winter School on Inorganic Materials – Synthesis, Characterization and SustainabilityInoMat2024 – Bressanone (BZ), Italy, 15-18th January 2024AXIAL COORDINATION INFLUENCE ON THE HYDROGENASE-LIKE ACTIVITY AND REDOX PROPERTIES OF COBALT SUBSTITUTED GLOBINSMirco Meglioli a, Gianantonio Battistuzzi a, Marco Borsari a, Antonio Ranieri b, Carlo Augusto Bortolotti b, Marco Sola ba Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia, Via Campi 103, 41125, Modena, Italyb Department of Life Sciences, University of Modena and Reggio Emilia, Via Campi 103, 41125, Modena, Italymirco.meglioli@unimore.itOne of the viable alternatives to fossil fuels is green hydrogen, produced by water electrolysis using electricity from renewable sources. Unfortunately, the high overvoltage required for H2 discharge significantly increases the required energy compared to the theoretical value [1]. Cobalt coordination compounds have been widely studied as catalysts for H2 production, due to their ability to reduce the above mentioned overpotential mainly in non-aqueous solvent and aerobic conditions, but they are barely soluble in neutral water. A possible approach to improve their water solubility and maybe their efficiency is to obtain artificial enzymes by embedding these compounds inside protein scaffolds as non-native cofactors [2-4]. Within this framework, our interest focuses on globins, metallo-proteins that contain a non-covalently bound heme b as prosthetic group. We have replaced the native metal-cofactor with Co(III)-protoporphyrin IX to obtain the corresponding Co-adducts, which were characterized by spectroscopic (UV-Vis, MCD and fluorescence emission) and electrochemical techniques (cyclic and square wave voltammetries with a working pyrolytic graphite electrode). The aim of the work is to understand the influence of axial metal coordination on the electrocatalytic activity of Co-substituted globins towards hydrogen H2 production and on the redox properties of the Co(III)/Co(II) couple inside the protein scaffold. The investigation was carried on Co-myoglobin complexes featuring water, ammonia, imidazole as Co(III) distal axial ligands and on the bis-histidine Co-adducts of human neuroglobin and its C46AC55A mutant, lacking a structurally relevant intramolecular disulfide bridge.  ____[1]	M. El-Shafie, Results in Engineering 2023, 20, 101426.[2]           S. Neya et al., Inorganic Chemistry 2013, 52, 7387-7393.[3]           M. Bacchi et al., Inorganic Chemistry 2014, 53, 8071-8082.[4]           A. Onoda et al., Current Opinion in Chemical Biology 2015, 25, 133-140.	2

AXIAL COORDINATION INFLUENCE ON THE HYDROGENASE-LIKE ACTIVITY AND REDOX PROPERTIES OF COBALT SUBSTITUTED GLOBINS

https://iris.unimore.it/bitstream/11380/1368091/1/Abstract_Meglioli_Mirco_INOMAT2024.docx

AXIAL COORDINATION INFLUENCE ON THE HYDROGENASE-LIKE ACTIVITY AND REDOX PROPERTIES OF COBALT SUBSTITUTED GLOBINS

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