Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies

Interactions between sinefungin and copper(II) ions were investigated. Stoichiometry and stability constants of the metal-free system and two mononuclear complexes present in solution were determined on the basis of potentiometric data analysis. The results were compared to the Cu(II)-ornithine sys...

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Main Authors: Maria Jaworska, Piotr Lodowski, Ariel Mucha, Wojciech Szczepanik, Gianni Valensin, Massimo Cappannelli, Malgorzata Jezowska-Bojczuk
Format: Article
Language:English
Published: Wiley 2007-01-01
Series:Bioinorganic Chemistry and Applications
Online Access:http://dx.doi.org/10.1155/2007/53521
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author Maria Jaworska
Piotr Lodowski
Ariel Mucha
Wojciech Szczepanik
Gianni Valensin
Massimo Cappannelli
Malgorzata Jezowska-Bojczuk
author_facet Maria Jaworska
Piotr Lodowski
Ariel Mucha
Wojciech Szczepanik
Gianni Valensin
Massimo Cappannelli
Malgorzata Jezowska-Bojczuk
author_sort Maria Jaworska
collection DOAJ
description Interactions between sinefungin and copper(II) ions were investigated. Stoichiometry and stability constants of the metal-free system and two mononuclear complexes present in solution were determined on the basis of potentiometric data analysis. The results were compared to the Cu(II)-ornithine system due to structural similarities between both molecules. Combined spectroscopic and theoretical studies allowed for determination of coordination pattern for the Cu(II)-sinefungin complexes. At acidic pH, copper is bound in “glycine-like” coordination mode, identical with that of ornithine. This involves α-amino group and the carboxyl oxygen. At higher pH, a “bis-complex” is formed by two sinefungin molecules. The second ligand binds in equatorial position displacing two water molecules, what results in the stable {2N,2O} coordination. Both axial positions are supposed to be occupied by N1 nitrogen donors of adenine moiety, what is confirmed by DFT calculations. They interact indirectly with copper(II) through water molecules as the result of dominant syn conformation of purine.
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institution OA Journals
issn 1565-3633
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publishDate 2007-01-01
publisher Wiley
record_format Article
series Bioinorganic Chemistry and Applications
spelling doaj-art-155c521619924de19e084de5cbfd249a2025-08-20T02:02:40ZengWileyBioinorganic Chemistry and Applications1565-36331687-479X2007-01-01200710.1155/2007/5352153521Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT StudiesMaria Jaworska0Piotr Lodowski1Ariel Mucha2Wojciech Szczepanik3Gianni Valensin4Massimo Cappannelli5Malgorzata Jezowska-Bojczuk6Department of Theoretical Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, 14 Bankowa St., Katowice 40-007, PolandDepartment of Theoretical Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, 14 Bankowa St., Katowice 40-007, PolandDepartment of Bioinorganic and Biomedicinal Chemistry, Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wrocław 50-383, PolandDepartment of Bioinorganic and Biomedicinal Chemistry, Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wrocław 50-383, PolandDepartment of Chemistry, Faculty of Mathematical, Physical, and Natural Sciences, University of Siena, Via Aldo Moro, Siena I-53100, ItalyDepartment of Chemistry, Faculty of Mathematical, Physical, and Natural Sciences, University of Siena, Via Aldo Moro, Siena I-53100, ItalyDepartment of Bioinorganic and Biomedicinal Chemistry, Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, Wrocław 50-383, PolandInteractions between sinefungin and copper(II) ions were investigated. Stoichiometry and stability constants of the metal-free system and two mononuclear complexes present in solution were determined on the basis of potentiometric data analysis. The results were compared to the Cu(II)-ornithine system due to structural similarities between both molecules. Combined spectroscopic and theoretical studies allowed for determination of coordination pattern for the Cu(II)-sinefungin complexes. At acidic pH, copper is bound in “glycine-like” coordination mode, identical with that of ornithine. This involves α-amino group and the carboxyl oxygen. At higher pH, a “bis-complex” is formed by two sinefungin molecules. The second ligand binds in equatorial position displacing two water molecules, what results in the stable {2N,2O} coordination. Both axial positions are supposed to be occupied by N1 nitrogen donors of adenine moiety, what is confirmed by DFT calculations. They interact indirectly with copper(II) through water molecules as the result of dominant syn conformation of purine.http://dx.doi.org/10.1155/2007/53521
spellingShingle Maria Jaworska
Piotr Lodowski
Ariel Mucha
Wojciech Szczepanik
Gianni Valensin
Massimo Cappannelli
Malgorzata Jezowska-Bojczuk
Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies
Bioinorganic Chemistry and Applications
title Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies
title_full Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies
title_fullStr Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies
title_full_unstemmed Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies
title_short Characterization of Copper(II) Interactions with Sinefungin, a Nucleoside Antibiotic: Combined Potentiometric, Spectroscopic and DFT Studies
title_sort characterization of copper ii interactions with sinefungin a nucleoside antibiotic combined potentiometric spectroscopic and dft studies
url http://dx.doi.org/10.1155/2007/53521
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