Temperature and solvent structure dependence of VO2+ complexes of pyridine-N-oxide derivatives and their interaction with human serum transferrin (Articolo in rivista)

Type
Label
  • Temperature and solvent structure dependence of VO2+ complexes of pyridine-N-oxide derivatives and their interaction with human serum transferrin (Articolo in rivista) (literal)
Anno
  • 2012-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1039/C2DT12503J (literal)
Alternative label
  • D. Sanna; V. Ugone; G. Micera; E. Garribba (2012)
    Temperature and solvent structure dependence of VO2+ complexes of pyridine-N-oxide derivatives and their interaction with human serum transferrin
    in Dalton transactions (2003. Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • D. Sanna; V. Ugone; G. Micera; E. Garribba (literal)
Pagina inizio
  • 7304 (literal)
Pagina fine
  • 7318 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url
  • http://pubs.rsc.org/en/Content/ArticleLanding/2012/DT/c2dt12503j (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 41 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Istituto CNR di Chimica Biomolecolare, Trav. La Crucca 3, I-07040Sassari, Italy Dipartimento di Chimica e Farmacia, and Centro Interdisciplinare per lo Sviluppo della Ricerca Biotecnologica e per lo Studio della Biodiversità della Sardegna, Università di Sassari, Via Vienna 2, I-07100 Sassari, Italy (literal)
Titolo
  • Temperature and solvent structure dependence of VO2+ complexes of pyridine-N-oxide derivatives and their interaction with human serum transferrin (literal)
Abstract
  • The behaviour of the systems formed by VO2+, 2-hydroxypyridine-N-oxide (Hhpo) and 2-mercaptopyridine-N-oxide (Hmpo) was studied both in solution and in the solid state through the combined application of spectroscopic (EPR and UV-Vis spectroscopy) and DFT methods. The geometry of solid bis-chelated complexes [VOL2], with L = hpo and mpo, is square pyramidal, but it can change to cis-[VOL2S], where S is a solvent molecule, when these are dissolved in a coordinating solvent. The equilibrium between the square pyramidal and cis-octahedral forms is strongly affected by solvent and temperature. At room temperature, the predominant species is [VOL2], which gives a pink colour to the solutions; at lower temperatures, the equilibrium is shifted--partially or completely--toward the formation of cis-[VOL2S], which is green. In an acidic environment and in the presence of an excess of ligand, [VOL2] can transform into the tris-chelated complex [VL3]+, in which vanadium loses the oxido ligand and adopts a hexa-coordinated geometry intermediate between octahedral and trigonal prismatic. 1-Methylimidazole (1-MeIm), which represents a model for His-N coordination, forms mixed complexes with stoichiometry cis-[VOL2(1-MeIm)], occupying an equatorial position. In the ternary systems VO2+-Hhpo-hTf and VO2+-Hmpo-hTf at room temperature and pH 7.4, besides (VO)hTf and (VO)2hTf, the mixed species cis-VO(hpo)2(hTf) and VO(mpo)(hTf) are observed, with the equatorial binding of an accessible histidine residue. Finally, the contribution of the N-oxide group to 51V Az and Aiso hyperfine coupling constants, which can be important in the characterisation of similar species, is discussed. (literal)
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