Model investigations for vanadium-protein interactions: vanadium(III) compounds with dipeptides and their oxovanadium(IV) analogues

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dc.contributor.authorTasiopoulos, A. J.en
dc.contributor.authorTolis, E. J.en
dc.contributor.authorTsangaris, J. M.en
dc.contributor.authorEvangelou, A.en
dc.contributor.authorWoollins, D.en
dc.contributor.authorSlawin, A. M.en
dc.contributor.authorPessoa, C.en
dc.contributor.authorCorreia, I.en
dc.contributor.authorKabanos, T. A.en
dc.date.accessioned2015-11-24T19:04:16Z
dc.date.available2015-11-24T19:04:16Z
dc.identifier.issn0949-8257-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/20005
dc.rightsDefault Licence-
dc.subjectCircular Dichroismen
dc.subjectCrystallography, X-Rayen
dc.subjectElectrochemistry/methodsen
dc.subjectElectron Spin Resonance Spectroscopyen
dc.subjectHydrolysisen
dc.subjectMagneticsen
dc.subjectMolecular Structureen
dc.subjectPeptides/*chemistry/*metabolismen
dc.subjectSpectrophotometry, Infrareden
dc.subjectSpectrophotometry, Ultravioleten
dc.subjectVanadates/chemistry/metabolismen
dc.subjectVanadium Compounds/chemical synthesis/*chemistry/*metabolismen
dc.titleModel investigations for vanadium-protein interactions: vanadium(III) compounds with dipeptides and their oxovanadium(IV) analoguesen
heal.abstractThe reaction of VCl(3) with 1,10-phenanthroline and a series of dipeptides (H(2)dip), having aliphatic as well as aromatic side chains, in methyl alcohol and in the presence of triethylamine affords vanadium(III) compounds of the general formula [V(III)(dip)(MeOH)(phen)]Cl. Aerial oxidation/hydrolysis of the vanadium(III) species gives their oxovanadium(IV) analogues of the general formula [V(IV)O(dip)(phen)]. X-ray crystallographic characterization of the [V(IV)O(dip)(phen)] compounds (where dip(2-)=Gly- L-Ala, Gly- L-Val and Gly- L-Phe) revealed that the vanadium atom possesses a severely distorted octahedral coordination and is ligated to a tridentate dip(2-) ligand at the N(amine) atom, the deprotonated N(peptide) atom and one of the O(carboxylate) atoms, as well as an oxo group and two phenanthroline nitrogen atoms. Circular dichroism characterization of the V(III)/V(IV)O(2+)-dipeptide compounds revealed a strong signal for the V(IV)O(2+) species in the visible range of the spectrum, with a characteristic pattern which may be exploited to identify the N(am), N(pep) and O(car) ligation of a peptide or a protein to V(IV)O(2+) center, and a weak Cotton effect of opposite sign to their vanadium(III) analogues. The visible spectra of the V(III)-dipeptide compounds revealed two d-d bands with high intensity, thus indicating that the covalency of the metal-donor atoms is significant, i.e. the vanadium d orbitals are significantly mixed with the ligand orbitals, and this is confirmed by the low values of their Racah B parameters. The high-intensity band of the V(IV)O(2+)-dipeptide compounds at approximately 460 nm implies also a strong covalency of the metal with the equatorial donor atoms and this was supported by the EPR spectra of these compounds. Moreover, the V(III)/V(IV)O(2+)-dipeptide complexes were characterized by EPR and IR spectroscopies as well as conductivity and magnetic susceptibility measurements.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primary10.1007/s00775-001-0308-0-
heal.identifier.secondaryhttp://www.ncbi.nlm.nih.gov/pubmed/11941494-
heal.identifier.secondaryhttp://www.springerlink.com/content/te6xektmf6hyg4j8/fulltext.pdf-
heal.journalNameJ Biol Inorg Chemen
heal.journalTypepeer-reviewed-
heal.languageen-
heal.publicationDate2002-
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Επιστημών Υγείας. Τμήμα Ιατρικήςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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