Negatively Charged Metallacarborane Redox Couples with Both Members Stable to Air

The metallacarborane [3,3′‐Co(1,2‐closo‐C₂B₉H₁₁)₂]^? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E_1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C₂B₉H₇I₄)₂]^? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed.     

Ozone production in oxygen by means of F2-laser irradiation at λ=157.6 nm

Ozone is generated in pure oxygen (p5 kPa), synthetic air (p7 kPa) and oxygen-argon mixtures (p3 kPa) by irradiation of these gases with the VUV light of a repetitively pulsed (f _L15 Hz) F₂-laser at =157.6 nm with maximum about 4 mJ/pulse. An absorption photometer measurement operating at 253.7 nm (Hg line) determines the ozone concentration as a function of oxygen and/or additive gas pressure, the repetition frequency of the laser and the wall temperature of the reaction chamber. The temporal development of the ozone concentration as a function of these parameters is calculated by means of rate equations for the species O(³ P), O₂(X ³ _g ^– ), O₃(¹ A ₁), O(¹ D), O₂(a ¹_g), O₂(b ¹ _g ⁺ ) and vibrationally excited O ₃ ^* (¹ A ₁) and the photon distribution. The maximum concentration of O₃ in the sealed-off chamber reaches 1.6% in pure O₂, 4.1% in air and 1.2% in a 1:5 O₂-Ar mixture at 3 kPa. The annihilation of O₃ by the wall and temperature dependent volume processes (300 KT395 K) is studied and the experimental and theoretical results are compared.     

Structural study of copper-nickel aluminate (CuxNi1−xAl2O4) spinels

CuAl₂O₄, NiAl₂O₄, and three ternary spinels Cu_xNi_1?xAl₂O₃ have been prepared, in polycrystalline form, by solid-state reaction of mixtures of CuO, NiO, and Al₂O₃ at 1223 K. X-Ray powder diffractometry, coupled with adequate computational methods, allowed determination of the unit-cell length, oxygen positional parameter, and cation distribution for each compound. Interdependence of these structural parameters is closely analyzed on the ternary oxide spinels. The one-electron difference between the Cu²⁺ and Ni²⁺ ions was found to be enough to render them distinguishable by X-ray powder diffraction.     

A systematic density functional theory study of the electronic structure of bulk and (001) surface of transition-metals carbides

A systematic study of the bulk and surface geometrical and electronic properties of a series of transition-metal carbides (TMC with TM = Ti, V, Zr, Nb, Mo, Hf, Ta, and W) by first-principles methods is presented. It is shown that in these materials the chemical bonding is strongly covalent, the cohesive energies being directly related to the bonding-antibonding gap although the shift of the center of the C(2s) band related peak in the density of states with respect to diamond indicates that some metal to carbon charge transfer does also take place. The (001) face of these metal carbides exhibits a noticeable surface rumpling which grows along the series. It is shown that neglecting surface relaxation results in very large errors on the surface energy and work function. The surface formation induces a significant shift of electronic energy levels with respect to the corresponding values in the bulk. The extent and nature of the shift can be understood from simple bonding-antibonding arguments and is enhanced by the structural rippling of this surface.     

Symmetry of electronic states in garnets

The paper presents the classification of the electronic empty lattice eigenvalues and the classification of the Bloch sums for the garnet structureIa3d (O _h ¹⁰ ) at the symmetry points, H, P, andN of the Brillouin zone. This provides a starting point for the energy band studies of these technologically important materials.The author thanks Dr. V. Frei for useful comments.     

The modulating possibilities of dicarbollide clusters: optimizing the Kharasch catalysts

exo-Cluster dicarbollides substitution has allowed tuning of the E degrees (Ru(II)/Ru(III)) potential to obtain the best-performing Kharasch catalyst. We postulate that this is possible through the to-and-fro electron movement between the boron cluster and the sulfonium moieties.     

Ground-state properties of benzenoid hydrocarbons by simple bond orbital resonance theory approach

π-electron energies and bond orders of benzenoid hydrocarbons with up to five fused hexagons have been considered by the simple Bond Orbital Resonance Theory (BORT) approach. The corresponding ground states were determined according to four BORT models. In the first three models a diagonalisation of the Hückel-type Hamiltonian was performed in the bases of Kekulé, of Kekulé and mono-Claus and of Kekulé and Claus resonance structures, respectively. In the fourth model a simple BORT ansatz was used. According to this ansatz, the ground state is a linear combination of the positive Kekulé structures, all with equal coefficients. It was shown that π-electron energies and bond orders obtained by these models correlate much better with the PPP energies and bond orders than with the Hückel energies and bond orders. This indicates that a simple BORT approach is quite reliable in predicting the more sophisticated PPP results. Concerning the relative performance of the four BORT models, the best results were obtained with the BORT ansatz. The performance deteriorates with the expansion of the basis set. This is attributed to the fact that in these models the improvement of the basis set is not accompanied with the corresponding improvement of the Hamiltonian. Comparing the BORT-ansatz bond orders with the Pauling bond orders, it was shown that BORT-ansatz bond orders correlate much better with the PPP bond orders. This revised version was published online in July 2006 with corrections to the Cover Date.     

Fast determination of lead and copper in dairy products by graphite furnace atomic absorption spectrometry

A rapid and direct procedure for determining lead and copper in dairy products by electrothermal atomic absorption spectrometry (ETAAS) is described. Samples are slurried in a medium containing 50% v/v hydrogen peroxide, 1% v/v nitric acid, 0.5% w/v dihydrogen phosphate, and 20% v/v ethanol and directly injected into the furnace with no previous mineralization. Calibration is performed with aqueous standards. Limits of determination were 0.4 and 2.4 ng/mL for copper and lead, respectively. The reliability of the procedure was checked by comparison with the acid mineralization procedure and by analyzing 3 certified reference milk samples.     

Analytical applications of the o-dianisidine-persulfate reaction: Kinetic determination of silver and cobalt

A kinetic method for the silver determination based on the catalytic effect of Ag(I) on the oxidation of o-dianisidine by persulfate at pH = 4.5 in the presence of 1,10-phenanthroline is proposed. Ag(I) can be determined by measuring the absorbance of the reaction product at 450 nm, using the fixed time method. Co(II) does not have a catalytic effect in the reaction, but in the simultaneous presence of silver and cobalt the reaction shows an induction period the length of which is related to the Ag/Co molar ratio. As a consequence, two new methods for the determination of cobalt and silver using the induction period method are proposed. The two methods for silver are applied to the determination of silver in lead.     

Liquid chromatography with ultraviolet absorbance detection for the analysis of tetracycline residues in honey

The separation of tetracyclines (TCs) using reversed-phase liquid chromatography (LC) is proposed. The use of an amide-based stationary phase prevents the interaction of tetracyclines with the residual silanol groups and thus avoids the appearance of tailed peaks. Detection was based on using an UV spectrophotometer and gradient elution with acetonitrile-oxalic acid as mobile phase permitted good separation of all the peaks. Specificity was demonstrated by the retention characteristics, UV spectra and peak purity index. Linearity, precision, recovery and sensitivity were satisfactory. The procedure was applied to the analysis of tetracycline residues (tetracycline, oxytetracycline (OTC), chlortetracycline (CTC), doxycycline (DC), minocycline (MINO) and methacycline (MTC)) in honey of different types. Extraction involved using a mild acidic solvent containing EDTA to release protein-bound or sugar-bound tetracyclines. For the clean-up step, solid phase extraction using phenyl cartridges was applied. Detection limits in the honey using the proposed procedure are between 15 and 30 ng g(-1), depending on the tetracycline.