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Synthesis, characterization and activity of imidazolate-bridged and Schiff-base dinuclear complexes as models of Cu,Zn-SOD. A comparative study.
Daier, Verónica A; Rivière, Eric; Mallet-Ladeira, Sonia; Moreno, Diego M; Hureau, Christelle; Signorella, Sandra R.
Afiliação
  • Daier VA; IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina.
  • Rivière E; Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS, Université Paris Sud, Université Paris Saclay, 91405 Orsay Cedex, France.
  • Mallet-Ladeira S; Institut de Chimie de Toulouse, FR 2599, 118 Route de Narbonne, F-31062 Toulouse, France.
  • Moreno DM; IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina.
  • Hureau C; CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, F-31077 Toulouse, France; UPS, INPT, LCC, Université de Toulouse, 205 route de Narbonne, F-31077 Toulouse, France.
  • Signorella SR; IQUIR (Instituto de Química Rosario), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, S2002LRK Rosario, Argentina. Electronic address: signorella@iquir-conicet.gov.ar.
J Inorg Biochem ; 163: 162-175, 2016 10.
Article em En | MEDLINE | ID: mdl-27426051
Two imidazolate-bridged diCuII and CuIIZnII complexes, [CuZn(dien)2(µ-Im)](ClO4)3·MeOH (1) and [Cu2(dien)2(µ-Im)](ClO4)3 (2) (Im = imidazole, dien=diethylenetriamine), and two complexes formed with Schiff base ligands, [CuZn(salpn)Cl2] (3) and [Cu2(salbutO)ClO4] (4) (H2salpn=1,3-bis(salicylidenamino)propane, H3salbutO=1,4-bis(salicylidenamino)butan-2-ol) have been prepared and characterized. The reaction of [Cu(dien)(ImH)](ClO4)2 with [Zn(dien)(H2O)](ClO4)2 at pH≥11 yields complex 1; at lower pH, the Cu3Zn tetranuclear complex [{(dien)Cu(µ-Im)}3Zn(OH2)(ClO4)2](ClO4)3 (1a) forms as the main reaction product. X-ray diffraction of 1a reveals that the complex contains a metal centered windmill-shaped cation having three blades with a central Zn ion and three peripheral capping Cu(dien) moieties bound to the central Zn ion through three imidazolate bridges. The four complexes are able to disproportionate O2- in aqueous medium at pH7.8, with relative rates 4>1>2≫3. [Cu2(salbutO)]+ (4) is the most easily reducible of the four complexes and exhibits the highest activity among the SOD models reported so far; a fact related to the ligand flexibility to accommodate the copper ion in both CuI and CuII oxidation states and the lability of the fourth coordination position of copper facilitating stereochemical rearrangements.
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Superóxido Dismutase / Superóxidos / Cobre / Imidazóis / Modelos Químicos Idioma: En Revista: J Inorg Biochem Ano de publicação: 2016 Tipo de documento: Article País de afiliação: Argentina País de publicação: Estados Unidos
Texto completo
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Assunto principal: Superóxido Dismutase / Superóxidos / Cobre / Imidazóis / Modelos Químicos Idioma: En Revista: J Inorg Biochem Ano de publicação: 2016 Tipo de documento: Article País de afiliação: Argentina País de publicação: Estados Unidos