Probing the Bioinorganic Chemistry of Cu(I) with 111Ag Perturbed Angular Correlation (PAC) Spectroscopy

The two most common oxidation states of copper in biochemistry are Cu(II) and Cu(I), and while Cu(II) lends itself to spectroscopic interrogation, Cu(I) is silent in most techniques. Ag(I) and Cu(I) are both closed-shell d10 monovalent ions, and to some extent share ligand and coordination geometry...

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Bibliographic Details
Main Authors: Karner Victoria
Jancsó Attila
Hemmingsen Lars
Format: Article
Published: 2023
Series:INORGANICS 11 No. 10
Subjects:
doi:10.3390/inorganics11100375

mtmt:34409105
Online Access:http://publicatio.bibl.u-szeged.hu/31946
Description
Summary:The two most common oxidation states of copper in biochemistry are Cu(II) and Cu(I), and while Cu(II) lends itself to spectroscopic interrogation, Cu(I) is silent in most techniques. Ag(I) and Cu(I) are both closed-shell d10 monovalent ions, and to some extent share ligand and coordination geometry preferences. Therefore, Ag(I) may be applied to explore Cu(I) binding sites in biomolecules. Here, we review applications of 111Ag perturbed angular correlation (PAC) of γ-ray spectroscopy aimed to elucidate the chemistry of Cu(I) in biological systems. Examples span from small blue copper proteins such as plastocyanin and azurin (electron transport) over hemocyanin (oxygen transport) to CueR and BxmR (metal-ion-sensing proteins). Finally, possible future applications are discussed. 111Ag is a radionuclide which undergoes β-decay to 111Cd, and it is a γ-γ cascade of the 111Cd daughter nucleus, which is used in PAC measurements. 111Ag PAC spectroscopy may provide information on the coordination environment of Ag(I) and on the structural relaxation occurring upon the essentially instantaneous change from Ag(I) to Cd(II).
Physical Description:13
ISSN:2304-6740