Quantification of trace elements in human serum fractions by liquid chromatography and inductively coupled plasma mass spectrometry

On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO₃ buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd.     

Material tensor parameters of LiNbO3 relevant for electro- and elasto-optics

The complete set of self-consistent parameters of nominally undoped LiNbO₃ crystals of congruent composition that describe the electro-optic, piezoelectric, elasto-optic, elastic, and dielectric response has been determined by numerically evaluating available measurements. The parameters were determined at room temperature and consist of the low-frequency clamped dielectric constants ε^S _ij, elastic stiffness constants at constant electric field C^E _ijkl, piezoelectric stress coefficients e_ijk, elasto-optic constants at constant electric field p^E _ijkl, and clamped electro-optic coefficients r^S _ijk. It is shown that the complete set is required for calculating the effective electro-optic coefficients and dielectric constants in photorefractive applications of LiNbO₃. Received: 4 January 2002 / Revised version: 1 February 2002 / Published online: 14 March 2002     

Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

Crystal structure and vibrational spectra of hydrazinium (2+) tri-μ-fluoro bis[pentafluorozirconate (IV)] fluoride and vibrational spectra of its hafnium analogue

Monoclinic (N₂H₆)₃Zr₂F₁₃·F crystallizes in space group P2₁-C ₂ ² (No. 4) with unit cell dimensionsa=5.670(1),b=10.984(2),c=10.601(2) Å,=93.88(1)°,V=658.7(4) ų andZ=2. Two different types of N₂H₆ ²⁺ ions are present. One is involved in strong H-bonds to F^– ions in infinite chains running along the a axis (the shortest N-F distance is 2.437(5) Å), and the other links the structure through weaker bi- and trifurcated H-bonds to fluorine ligands of the Zr₂F₁₃ ^5– ions. The N-N bond lengths range from 1.430(5) to 1.446(5) Å with apparently no meaningful correlation to the type of N₂H₂ ²⁺ ions. The Zr₂F₁₃ ^5– ions have very nearly C₂ point symmetry and are formed by joining two distorted bicapped trigonal prisms of ZrF₈-units through a common face. Distances of Zr-F terminal bonds range from 2.015(2) to 2.112(2) Å and of bridging bonds from 2.133(2) to 2.212(2) Å. (N₂H₆)₃Hf₂F₁₃·F is isomorphous. The vibrational spectra of the two compounds are nearly identical, with the exception of a strong infrared band, which is assigned to a stretching mode with the moving central atom within the anion. The anion part of the spectrum is simple, showing broad unresolved bands. The cation part shows two types of N₂H₆ ^– ions. H-Bonding is strongly present in the spectra, but no simple correlations with the H-bond strength is evident.     

Electrocatalysis by foreign metal monolayers: Oxidation of formic acid on platinum

It was demonstrated that some foreign metal monolayers formed by underpotential deposition have pronounced catalytic effects on the oxidation of formic acid on platinum. The explanation of these effects was sought within the framewor of existing data on the formic acid oxidation and the underpotential deposition. It was found that the catalytic effect of foreign metal monolayers originates in the decrease of hydrogen adsorption thus preventing the formation of the main poisoning species COH. At the same time these experiments confirm the previously postulated mechanism of formation of the poisoning species involving adsorbed hydrogen.