Determination of deuterium oxide content in water based on luminescence quenching.

Water molecules (H2O) often reduce luminescence lifetimes of various luminescence probes. The change of lifetime is usually caused by dynamic luminescence quenching induced by O-H oscillators which effectively take away energy from excited molecule. The process can be described by Stern-Volmer equation. We have studied selected luminescence systems where it is possible to detect considerable changes of lifetime in presence/absence of H2O and D2O in this work for analytical purposes. We have tested both, inorganic (Ln3+) and organic compounds using three different instrumentation in order to find the largest change between τH and τD. The Ln3+ containing systems have shown considerable increase/decrease of lifetimes in the presence/absence of D2O (Eu3+: τD/τH = 34.5) whereas organic systems gave significantly lower values of τD/τH (coumarin 123 lifetime ratio, τD/τH = 1.94). The calculated LOD varied from 0.04 mol l-1 (samarium nitrate) to 6.55 mol l-1 (riboflavin).

Formation and decomplexation kinetics of copper(ii) complexes with cyclen derivatives having mixed carboxylate and phosphonate pendant arms.

The kinetic properties of Cu(ii) complexes of H4dota and its analogues with one (H5do3ap), two in the 1,7-position (trans-H6do2a2p), three (H7doa3p) and four (H8dotp) phosphonic acid pendant arms were investigated. The formation of a Cu(ii) complex with H4dota, trans-H6do2a2p and H8dotp at a slightly acidic pH is faster for the phosphonic acid derivatives than for H4dota, but with no simple dependence on the number of -CH2PO3H2 substituents (trans-H6do2a2p > H8dotp > H4dota; pH 4-6). Relative differences in the reactivity among the differently protonated species (HnL(x-)) of the same ligand are successively decreased with the more phosphonic acid groups in the ligand. The faster complexation is probably caused by the higher ability of phosphonates to bind the metal ion and/or to assist in the transfer of protons from the ring amine groups to the bulk water. The acid-assisted decomplexation kinetics of the complexes was followed in highly acidic solutions ([H(+)] = 0.01-5 M) and at different temperatures (15-70 °C) to determine the activation parameters of the reaction. The kinetic inertness of the Cu(ii) complexes follows the order: H4dota > H5do3ap > trans-H6do2a2p > H7doa3p > H8dotp. To obtain information on the influence of additional pendant arms, analogous data were obtained for trans-H2do2a. The ligand is less reactive than H4dota, but the kinetic inertness of its Cu(ii) complex is similar to that of the H4dota complex. As it was considered that the published thermodynamics data on the Cu(ii)-H8dotp system are probably incorrect, the system was re-investigated. It showed a very high stability for the [Cu(dotp)](6-) species and the easy formation of several Cu2L species in the presence of an excess of the metal ion. Also, the structure of the (H6doa3p)(-) anion in the solid state was determined. These experimental data demonstrate that the substitution of acetic acid pendant arms by methylphosphonic acid ones in H4dota-like ligands increases the rate of complexation but significantly decreases the kinetic inertness of the Cu(ii) complexes.

Simultaneous determination of molybdenum(VI) and tungsten(VI) and its application in elemental analysis of polyoxometalates.

Spectrophotometric determination of molybdenum(VI) and tungsten(VI) with application of Artificial Neural Networks is proposed and it was applied for elemental analysis of solid polyoxometalates. Better results in comparison with previously those achieved by previous published method were demonstrated. MALDI-TOF Mass Spectrometry was tested for possible determination of molecular weight of polyoxometalates utilizing different matrices. Phenomena observed during desorption-ionisation processes are discussed. LDI-TOF MS was found to be suitable for the determination of Mo:W ratio in polyoxometalates as a rapid screening method to follow synthetic procedure.

Potentiometric and spectroscopic study of uranyl complexation with humic acids.

By potentiometric study using a specific uranyl ion-selective electrode, the formation of 1:1 and 1:2 (metal:ligand) complexes of uranyl with various humic acids (HAs) was found. The conditional stability constants were calculated using the LETAGROP-ETITR program. Possible structures of the complexes are proposed. Stability constants were found to be rather high indicating that immobilized HA can be used, for example, to remove traces of uranyl from waste waters.

The acidobasic and complexation properties of humic acids Study of complexation of Czech humic acids with metal ions.

The acid-base and complexation properties of humic acids (HAs) extracted from bohemian brown coals were studied. The acid-base behavior corresponds with the model of HA as a mixture of mono- and diprotic acids. This model was also verified on commercial HA substances (Aldrich and Fluka). HA binds strongly with heavy metal ions and the highest stability constant of HA-metal ion complexes was observed for copper(II). Stability constant values were found to decrease in the order: Cu(2+)>Ba(2+)>Pb(2+)>Cd(2+)>Ca(2+). Both acidobasic models for HA alone and those for HA-metal ion interactions were proposed and the computational methodology for polyelectrolyte equilibria studies demonstrated.

The study of complex equilibria of uranium(VI) with selenate.

Uranyl (M)-selenate (L) complex equilibria in solution were investigated by spectrophotometry in visible range and potentiometry by means of uranyl ion selective electrode. The formation ML and ML(2) species was proved and the corresponding stability constants calculated were: log beta(1) = 1.57(6) +/- 0.01(6), log beta(2) = 2.42(3) +/- 0.01(3) (I = 3.0 mol 1(-1) Na(ClO(4), SeO(4)) (spectrophotometry) at 298.2 K. Using potentiometry the values for infinite dilution (I --> 0 mol 1(-1)) were: log beta(1) = 2.64 +/- 0.01, log beta(2) 3.4 at 298.2 K. Absorption spectra of the complexes were calculated and analysed by deconvolution technique. Derivative spectrophotometry for the chemical model determination has also been successfully applied.