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Molecules 2014, 19(1), 980-991; doi:10.3390/molecules19010980
Article

EPR Spectroscopy of a Clinically Active (1:2) Copper(II)-Histidine Complex Used in the Treatment of Menkes Disease: A Fourier Transform Analysis of a Fluid CW-EPR Spectrum

1,†
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1,†
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2
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2
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1
 and
1,*
1 Faculty of Chemical and Food Technology, Slovak Technical University, Bratislava SK-812 37, Slovakia 2 Faculty of Natural Sciences, Constantine The Philosopher University, Nitra SK-949 74, Slovakia These authors contributed equally to this work.
* Author to whom correspondence should be addressed.
Received: 27 November 2013 / Revised: 23 December 2013 / Accepted: 26 December 2013 / Published: 15 January 2014
(This article belongs to the Section Medicinal Chemistry)
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Abstract

Redox active transition metal ions (e.g., iron and copper) have been implicated in the etiology of many oxidative stress-related diseases including also neurodegenerative disorders. Unbound copper can catalyze formation of reactive oxygen species (hydroxyl radicals) via Fenton reaction/Haber–Weiss chemistry and therefore, under physiological conditions, free copper is potentially toxic and very rarely exists inside cells. Copper(II) bound to the aminoacid L-histidine represents a species discovered in blood in the mid 60s and since then extensive research on this complex was carried out. Copper bound to L-histidine represents an exchangeable pool of copper(II) in equilibrium with the most abundant blood plasma protein, human serum albumin. The structure of this complex, in aqueous solution, has been a subject of many studies and reviews, however without convincing success. The significance of the (1:2) copper(II)-L-histidine complex at physiological pH documents its therapeutic applications in the treatment of Menkes disease and more recently in the treatment of infantile hypertrophic cardioencephalomyopathy. While recently the (1:2) Cu(II)-L-His complex has been successfully crystallized and the crystal structure was solved by X-ray diffraction, the structure of the complex in fluid solution at physiological pH is not satisfactorily known. The aim of this paper is to study the (1:2) Cu(II)-L-histidine complex at low temperatures by X-band and S-band EPR spectroscopy and at physiological pH at room temperature by Fourier transform CW-EPR spectroscopy.
Keywords: copper-histidine complex; copper metabolism; Menkes disease; EPR spectroscopy; FT-EPR spectroscopy copper-histidine complex; copper metabolism; Menkes disease; EPR spectroscopy; FT-EPR spectroscopy
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).
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Gala, L.; Lawson, M.; Jomova, K.; Zelenicky, L.; Congradyova, A.; Mazur, M.; Valko, M. EPR Spectroscopy of a Clinically Active (1:2) Copper(II)-Histidine Complex Used in the Treatment of Menkes Disease: A Fourier Transform Analysis of a Fluid CW-EPR Spectrum. Molecules 2014, 19, 980-991.

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