title: Oxidized derivatives of Octopus vulgaris and Carcinus aestuarii hemocyanins at pH 7.5 and related models by x-ray absorption spectroscopy.
abstract: The binuclear copper sites of the met and met-azido derivatives of Octopus vulgaris and Carcinus aestuarii hemocyanins at pH 7.5 were characterized by high-resolution x-ray absorption spectroscopy in the low energy region (XANES) and in the higher region (EXAFS). The accuracy of the analysis of the data was tested with two mononuclear and six binuclear copper(II) complexes of the poly(benzimidazole) ligand systems 2-BB, L-5,5 and L-6,6 (Casella et al., 1993, Inorg. Chem. 32:2056-2067; 1996, Inorg. Chem. 35:1101-1113). Their structural and reactivity properties are related to those of the protein's derivatives. The results obtained for those models with resolved x-ray structure (the 2-BB-aquo and azido mononuclear complexes, and the binuclear L-5,5 Cu(II)-bis(hydroxo) (Casella et al., unpublished)), extends the validity of our approach to the other poly(benzimidazole)-containing complexes and to the hemocyanin derivatives. Comparison between the protein's and the complexes' data, support a description of the met-derivatives as a five-coordinated O-bridged binuclear copper(II) center and favors, for both species, a bis(hydroxo) structure with a 3-A Cu-Cu distance. For O. vulgaris met-azido derivative a mu-1,3 bridging mode for the ligand appears the most likely. The structural situation of C. aestuarii met-azido-derivative is less clear: a mu-1,1 mode is favored, but a terminal mode cannot be excluded.
authors.affiliation: Dipartimento di Chimica, Università La Sapienza, I-00185 Roma, Italy. e.borghi@caspur.it
authors.forename: Elena
authors.initials: E
authors.lastname: Borghi
authors.forename: Pier Lorenzo
authors.initials: PL
authors.lastname: Solari
authors.forename: Mariano
authors.initials: M
authors.lastname: Beltramini
authors.forename: Luigi
authors.initials: L
authors.lastname: Bubacco
authors.forename: Paolo
authors.initials: P
authors.lastname: Di Muro
authors.forename: Benedetto
authors.initials: B
authors.lastname: Salvato
mesh_terms: D000818:Animals; D055592:Biophysical Phenomena; D001703:Biophysics; D003300:Copper / Q000737:chemistry; D003445:Crustacea / Q000737:chemistry*; D006433:Hemocyanins / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D049831:Octopodiformes / Q000737:chemistry*; D010084:Oxidation-Reduction; D013045:Species Specificity; D013057:Spectrum Analysis; D014965:X-Rays
chemical_list: D008024:Ligands; D003300:Copper; D006433:Hemocyanins