Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine.

The anionic complexes [Cu(L(1-))3](1-), L(-)=dopasemiquinone or L-dopasemiquinone, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the nuCC+nuCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g=2.0005 and g=2.0923, and for Cu(II) with g=2.008 and g=2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease.

Simultaneous spectrophotometric determination of Hg2+, Pb2+, and Cu2+ by Zn(dmit) using the multivariate calibration method.

This work investigates the applicability of the anionic complex [NBu4]2[Zn(1,3-dithiol-2-tione-4,5-dithiolate)2] on the simultaneous spectrophotometric determination of transition metals. Principal Component Regression was used in the data analysis. This method was used to determine Hg2+, Cu2+ and Pb2+ in water solution, at t = 0, 20 and 60 min of reaction. The root mean square errors (rms) for Hg2+, Cu2+, Pb2+ were 1.92 x 10(-7), 1.89 x 10(-7) and 9.35 x 10(-8) for t = 0 min, 1.79 x 10(-7), 2.1 x 10(-7) and 2.22 x 10(-7) for t = 20 min and 1.22 x 10(-7), 1.31 x 10(-7) and 1.10 x 10(-7) for t = 60 min, respectively. Results showed the viability of the method in determining concentrations of metallic ions in aqueous medium with high spectral overlap. It is an efficient alternative method for exploring the kinetic behavior of multicomponents systems of interest in physicochemical research.

Interpretation of seasonal variation of metals and abiotic properties in a tropical lake using multivariate analysis and MINTEQA2 program.

The hydrological cycle of Lake Ipê and the principal parameters that could affect its abiotic parameters and its metal (Fe, Mn, and Cd) concentrations were investigated. A detailed study of seasonal variations using Principal Components Analysis (PCA) for the most relevant metals (Fe, Mn and Cd) was performed, assisted by the MINTEQA2 geochemical equilibrium program using 15 water abiotic parameters. The abiotic variables and metals in the lake were governed by the hydrological regimen of the Parana River and by the occurrence of occasional flood pulses and rainfall. The occurrence of cadmium is a concern; its presence could be due to industrial or agricultural activities or even to a natural geochemical process.