Combination of chemometrically assisted voltammetry, calorimetry, and circular dichroism as a new method for the study of bioinorganic substances: application to selenocystine metal complexes.
Selenium-containing compounds play an important role in antioxidant defense systems, binding to toxic metals, preventing their uptake into cells, and thus protecting cells from metal-induced formation of reactive oxygen species. Here, we present a proposal for a relatively new method as a complement to the more usual methods used in selenium studies. A systematic study of the metal-binding properties of selenocystine (SeCyst) in the presence of divalent metal cations (Cd, Co, Hg, Ni, and Zn) is reported. Isothermal titration calorimetry provides thermodynamic parameters of the systems. Titrations produced curves that could be fit reasonably well to the one set of sites model. The data clearly demonstrate that one M(2+) binds one SeCyst molecule, and the stable M(SeCyst) complex is formed under these conditions. The order of the SeCyst binding constant for the metal ions is Hg(2+) > Cd(2+) ~ Zn(2+) > Ni(2+)> Co(2+). Cadmium ion was selected as a modulator for the behavior of SeCyst in the presence of a nonessential metal, and zinc was selected for the case of an essential element. These interactions of SeCyst with Cd(2+) and Zn(2+), either individually or combined, were studied in aqueous buffered solutions at physiological pH by differential pulse polarography and circular dichroism spectroscopy. Furthermore, recently developed chemometric tools were applied to differential pulse polarography data obtained in mixtures of SeCyst and glutathione in the presence of Cd(2+) at physiological pH.
Departament de Química Analítica, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.
Rui
R
Gusmão
Rafel
R
Prohens
José Manuel
JM
Díaz-Cruz
Cristina
C
Ariño
Miquel
M
Esteban
D001665:Binding Sites; D002151:Calorimetry; D002413:Cations, Divalent / Q000737:chemistry*; D002942:Circular Dichroism; D056831:Coordination Complexes / Q000737:chemistry*; D003553:Cystine / Q000031:analogs & derivatives* / Q000737:chemistry; D055664:Electrochemical Techniques; D008670:Metals / Q000737:chemistry*; D016566:Organoselenium Compounds / Q000737:chemistry*
D002413:Cations, Divalent; D056831:Coordination Complexes; D008670:Metals; D016566:Organoselenium Compounds; C009226:selenocystine; D003553:Cystine