(Mn1−xPbx)Pb10+ySb12−yS26−yCl4+yO, a new oxy-chloro-sulfide with ∼2 nm-spaced (Mn,Pb)Cl4 single chains within a waffle-type crystal structure

The new oxy-chloro-sulfide (Mn_1−xPb_x)Pb_10+ySb_12−yS_26−yCl_4+yO (x ∈ [0.2-0.3]; y ∈ [0.3-1.6]) was synthesized by dry way at 500-600 °C. A single crystal ∼Mn_0.7Pb_11.0Sb_11.3S_25.3Cl_4.7O indicates a monoclinic symmetry, space group C2/m, with a = 37.480(8), b = 4.1178(8), c = 18.167(4) Å, β = 106.37(3)°, V = 2690.2(9) Å³, Z = 2. Its crystal structure was determined by X-ray single crystal diffraction, with a final R = 5.11%. Modular analysis of the crystal structure reveals a “waffle” architecture, where complex rods with lozenge section delimitate an internal channel filled by a single chain of (Mn_0.7Pb_0.3)Cl₆ octahedra connected by opposite edges. Minimal inter-chain distances are close to 18 Å. The rod wall, two-atom thick, presents, in alternation with S atoms, Pb or (Pb,Sb) cations with prismatic coordination in the internal atom layer, while the external atom layer is constituted exclusively by Sb cations with dissymmetric square pyramidal coordination. A (Pb,Sb)₂S₂ fragment connects two successive rods along (2 0 1) to form a waffle-type palissadic layer. The unique O position, half filled, presents the same environment than the isolated O positions in the oxy-sulfide Pb₁₄Sb₃₀S₅₄O₅, or oxy-chloro-sulfides Pb₁₈Sb₂₀S₄₆Cl₂O and (Cu,Ag)₂Pb₂₁Sb₂₃S₅₅ClO. This compound belongs to a pseudo-homologous series of chalcogenides with waffle structure, ordered according to the size of their lozenge shape channel. Such a complex senary compound of the oxy-chloro-sulfide type illustrates the structural competition between three cations, on one hand, and, on the other hand, three anions. This compound is of special interest regarding the 1D distribution of magnetic Mn²⁺ atoms at the ∼2 nm scale.     

A correlation study of Li ground state by the MCHF procedure

Results are reported for multiconfiguration Hartree–Fock studies of correlation in the lithium ground state, which maintain orthogonality of orbitals within a configuration. It is shown that when the 1s- and 2s-orbitals are fixed at their Hartree–Fock value, configurations for which Brillouin's theorem holds may be important, particularly for atomic properties other than energy. The Fermi contact term is considered as an example.     

Sulfonamides as novel terminators of cationic cyclisations

Trifluoromethanesulfonic (triflic) acid is an excellent catalyst for inducing overall 5-endo cyclisation of homoallylic sulfonamides [e.g. 4] to give pyrrolidines [e.g. 5]. In competitive experiments, pyrrolidines or homopiperidines are formed in preference to piperidines, even when the latter would be obtained by trapping a tertiary carbocation. Cationic cascades terminated by a sulfonamide group are viable for the efficient formation of polycyclic systems.     

Transparent conducting oxides: texture and microstructure effects on charge carrier mobility in MOCVD-derived CdO thin films grown with a thermally stable, low-melting precursor

A series of low-melting, thermally stable cadmium metal-organic chemical vapor deposition (MOCVD) precursors have been synthesized, structurally and spectroscopically characterized, and implemented in growth of highly conductive and transparent CdO thin films. One member of the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N-diethyl-N',N'-dimethyl-ethylenediamine)cadmium(II), Cd(hfa)(2)()(N,N-DE-N',N'-DMEDA), represents a particularly significant improvement over previously available Cd precursors, owing to the low melting point and robust thermal stability. High-quality CdO films were grown by MOCVD on glass and single-crystal MgO(100) between 300 and 412 degrees C. Film growth parameters and substrate surface have large effects on microstructure and electron carrier transport properties. Enhanced mobilities observed for highly biaxially textured films grown on MgO(100) vs glass are attributed, on the basis of DC charge transport and microstructure analysis, to a reduction in neutral impurity scattering and/or to a more densely packed grain microstructure. Although single-grained films grown on MgO(100) exhibit greater mobilities than analogues with discrete approximately 100 nm grains and similar texture, this effect is attributed, on the basis of charge transport and Hall effect measurements as well as optical reflectivity analysis, to differences in carrier concentration rather than to reduced grain boundary scattering. Unprecedented conductivities and mobilities as high as 11,000 S/cm and 307 cm(2)/V.s, respectively, are obtained for epitaxial single-grained films (X-ray diffraction parameters: fwhm(omega) = 0.30 degrees, fwhm(phi) = 0.27 degrees ) grown in situ on MgO(100) at a relatively low temperature (400 degrees C).     

Novel metal-linked face-to-face porphyrazine dimer

We report the synthesis and physical studies of a novel porphyrazine (pz) dimer [1[Ni,Cu]]2, which has Ni(II) ions incorporated into the pz cores and is linked by two Cu(II) ions coordinated to bis(picolinamide) chelates attached to the pz periphery. [1[Ni,Cu]]2 was prepared from precursor pz 2 with a selenodiazole ring fused to the pz core. This ring was deprotected to form the diamino-pz 3, which reacted with 2 mol of picolinoyl chloride hydrochloride to form pz 1[2H,2H], with peripheral bis(picolinamide) chelates; this was metalated to form [1[Ni,Cu]]2. The crystal structures of 1[2H,2H] and [1[Ni,Cu]]2 are presented. The latter is a dimer in which parallel, face-to-face pz's with an average separation of 3.30 angstroms are linked through the peripheral picolinamide ligands by a pair of peripheral Cu(II) ions. Each Cu(II) is coordinated with distorted square-planar geometry by a picolinamide from each pz. In this report, we focus on the interaction of these two peripheral Cu(II) ions. We discuss the preparation and magnetic properties of the pz dimer complex [1[Ni,Cu]]2 with two Cu(II) ions in the peripheral chelate but a diamagnetic metal ion Ni(II) in the pz core. Although [1[Ni,Cu]]2 contains two Cu(II) ions (S = 1/2), we could detect no electron paramagnetic resonance signal, which suggests very strong antiferromagnetic exchange between those two Cu(II) ions. Temperature-dependent magnetic susceptibility measurement gives an exchange splitting between the S = 0 ground state and the excited triplet state of delta = 660 cm(-1).     

Determination of albendazole and its main metabolites in ovine plasma by liquid chromatography with dialysis as an integrated sample preparation technique

Albendazole is a benzimidazole derivative with a broad-spectrum activity against human and animal helminth parasites. In order to determine the main pharmacokinetic parameters in sheep after oral and intravenous administration of a new formulation of albendazole (an aqueous solution), a fully automated method was developed for the determination of this drug and its main metabolites, albendazole sulfoxide (active metabolite) and sulfone in ovine plasma. This method involves dialysis as purification step, followed by enrichment of the dialysate on a precolumn and liquid chromatography (LC). All sample handling operations were executed automatically by means of an ASTED XL system. After conditioning of the trace enrichment column (TEC) packed with octadecyl silica with pH 6.0 phosphate buffer containing sodium azide, the plasma sample, in which a protein releasing reagent (1 M HCl) containing Triton X-100 was automatically added, was loaded in the donor channel and dialysed on a cellulose acetate membrane in the static-pulsed mode. The dialysis liquid consisted of pH 2.5 phosphate buffer. By rotation of a switching valve, the analytes were eluted from the TEC in the back-flush mode by the LC mobile phase and transferred to the analytical column, packed with octyl silica. The chromatographic separation was performed at 35°C and the analytes were monitored photometrically at 295 nm. Due to the differences in hydrophobic character between albendazole and its metabolites, a gradient elution was applied. The mobile phase consisted of a mixture of acetonitrile and pH 6.0 phosphate buffer. The proportion of organic modifier was increased from 10.0 to 50.1% in 12.30 min, then from 50.1 to 66.9% in 1.70 min. First, the gradient conditions and the temperature were optimised for the LC separation using the DryLab software. Then, the influence of some parameters of the dialysis process on analyte recovery was investigated. Finally, the method developed was validated. The mean recoveries for albendazole and its metabolites were about 70 and 65%, respectively. The limits of quantification for albendazole and its metabolites were 10 and 7.5 ng/ml, respectively.     

Contribution of cyclodextrins in the development of different pharmaceutical formulations of a new matrix metalloproteinase inhibitor

Ro 28-2653 is a new synthetic inhibitor of matrix metalloproteinases. The ability of these enzymes to degrade various components of the extracellular matrix seems to play a major role in tumors progression and is potentially effective against bronchial remodeling in asthma and BPCO. Ro 28-2653 is very poorly soluble in water. This low solubility estimated at about 0.56 μg/ml in water at 25 °C gives rise to difficulties in pharmaceutical formulation of oral, injectable or nebulizable solutions. The purpose of our study is to prepare and to characterize inclusion complexes between Ro 28-2653 and cyclodextrins and to investigate the biopharmaceutical repercussion of the inclusion of the active substance. The complex formation was investigated by phase solubility studies. ¹H-NMR spectroscopy and molecular modeling studies were carried out to elucidate the structure of the inclusion complex between Ro 28-2653 and cyclodextrin. Oral, intravenous and nebulizable solutions of Ro 28-2653 were developed with cyclodextrin. The in vivo studies were performed on healthy sheep for the pharmacokinetic evaluation of the oral and intravenous formulations while the nebulization of the complex solution was studied by using an asthma model in mouse.     

First observation of aS C * -S A-TGBA multicritical point in a pure compound

High pressure experiments have been performed by thermobarometric analysis on two homologous (n=10 and 11) of the [3-fluoro-4((R) or (S)-methylheptyloxy) 4′-(4″-alkoxy-3″-fluorobenzoyloxy) tolans series, which both exhibit the TΓB_A phase. The character (first or/and second order) of the transitions involving the TGB_A phase are determined from thermobarograms. The pressure-temperature phase diagrams show that the TGB_A phase is stabilized under high pressure for the two compounds. Forn=11 an inducedS _A phase is observed under high pressures leading to the first experimental observation, on pressure-temperature phase diagram of pure compounds, of aS _C ^* -S _A-TGB_A multicritical point, previously predicted by the Renn-Lubensky theory.     

Synthesis and structure of BaKFeO3: a new quaternary oxide with 1-D ferrate chains

Amber-colored single crystals of the quaternary oxide BaKFeO₃ were synthesized from a mixture of Fe₂O₃, KOH and Ba(OH)₂ heated at 750°C for 5 h then cooled slowly. The structure was determined by single-crystal X-ray diffraction (space group Cmca; a=5.804(1) Å, b=11.528(1) Å, c=12.776(1) Å; Z=8, R₁=0.0376, wR₂=0.0996). The structure is comprised of [FeO₃³⁻]^∞ chains of corner-sharing iron-oxo tetrahedra that are isolated from one another by interspersed Ba and K cations. The iron coordination environment is moderately distorted from perfect tetrahedral symmetry and the Fe-O-Fe bond angles are 152.8°. Magnetic susceptibility data show a pronounced zero-field cooling effect that suggests strong coupling from 5 K to above room temperature.     

Ultraviolet emission spectra of sunbeds

It is well known that UV radiation contributes to the development of skin cancer. Exposure to solar radiation is predominantly responsible for the high incidence rate of skin cancer, but there are also indications that sunbeds are involved. The aim of the present investigation was to determine the UV emission spectra of sunbeds. It included the most common sunbed models, which cover more than 50% of the Swiss market. The UV emission spectra of sunbeds have special characteristics and are different from the sun spectrum, which can be seen in high-resolution spectral measurements. Sunbed emission spectra are similar to the sun spectrum in the UVB (280-320 nm) range but reach values 10 to 15 times higher in the UVA (320-400 nm) range. An average erythema-effective irradiance of 0.33 W/m2 was determined for sunbeds. This corresponds to a UV index of 13, which is significantly higher than the UV index of 8.5 of the high summer sun at noon at intermediate latitudes. The measurements were spread over the whole effective area of the sunbeds, and an inhomogeneous distribution of the irradiances with variations of up to 30% from the average value was found.