RESUMO
The Zn(II)-cyclen-dipeptide ternary systems (where cyclen is abbreviated as L and dipeptide is glycylglycine (HL(1)) or glycyl-(S)-alanine (HL(2))) were investigated by potentiometry applying both "out-of-cell" and direct titrations and by (1) H NMR spectroscopy. Especially, the (1)H NMR study was found to be very efficient to estimate speciation in the systems. The results obtained under full equilibria indicated two main species, [Zn(L)(HL(1,2))](2+) and [Zn(L)(L(1,2))](+), in both the systems. In the [Zn(L)(HL(1,2))](2+) complex, presence of carbonyl-carboxylate chelate was confirmed, and in the [Zn(L)(L(1,2))](+) species, the peptide coordination is re-organized to carbonyl-amine chelate or only terminal amino group is coordinated. Equilibrium constants describing [Zn(L)](2+)-dipeptide interaction are relatively low, log K = 3.4 for Gly-Gly and 4.1 for Gly-(S)-Ala, respectively. Nevertheless, the values are slightly higher than stability constants for interaction of Zn(II) with the dipeptides (i.e. [Zn(L(1,2))](+) species) where a chelate formation is expected. It indicates that interaction between Zn(II) ion in [Zn(L)](2+) and the dipeptides should be supported by some additional interactions. Potentiometry carried out under non-equilibrum condition showed different species where these additional stabilizing forces play more important role.
Assuntos
Dipeptídeos/química , Compostos Heterocíclicos/química , Modelos Moleculares , Zinco/química , Ciclamos , Espectroscopia de Ressonância MagnéticaRESUMO
Potentiometric titrations and (1) H NMR spectroscopic studies of amino acids binding to the [ZnL](2+) -complex where L=cyclen in aqueous solution provide information concerning complexing species identity, their stability, and coordination mode declaration. The amino acids form stable ternary [ZnL(HL(n))](2+) and [ZnL(L(n))](+) complexes. The observations indicate bidentate coordination mode of the deprotonated amino acids, involving both the amine and the carboxylate functions to the [ZnL](2+) complex in pH region of about 7.5-9.5. The determined stability constants indicate that [ZnL](2+) complex is a very efficient receptor for simple amino acids such as glycine and alanine.
Assuntos
Aminoácidos/metabolismo , Compostos Heterocíclicos/metabolismo , Zinco/metabolismo , Ciclamos , Concentração de Íons de Hidrogênio , Cinética , Espectroscopia de Ressonância Magnética , Prótons , Soluções , TitulometriaRESUMO
Core-shell nanoparticles consisting of La(0.75)Sr(0.25)MnO(3) cores covered by silica were synthesized by a procedure consisting of several steps, including the sol-gel method in the presence of citric acid and ethylene glycol, thermal and mechanical treatment, encapsulation employing tetraethoxysilane and final separation by centrifugation in order to get the required size fraction. Morphological studies revealed well-separated particles that form a stable water suspension. Magnetic studies include magnetization measurements and investigation of the ferromagnetic-superparamagnetic-paramagnetic transition. Magnetic heating experiments in 'calorimetric mode' were used to determine the heating efficiency of the particles in water suspension and further employed for biological studies of extracellular and intracellular effects analysed by tests of viability.