Asymmetric Pauson-Khand reaction with chiral, electron-deficient mono- and bis-phosphine ligands

The intermolecular Pauson-Khand reaction between norbornene and dicobalt carbonyl complexes of phenylacetylene substituted with chiral phosphorus ligands has been investigated. High yields (?98%) and enantiomeric excesses of up to 56% have been observed.     

Stabilization of the unhybridized Sn2+ stannous ion in the BaClF structure and its characterization by119Sn Mössbauer spectroscopy

In divalent tin halides, when the halogen is small and highly electronegative (F, Cl), the tin valence orbitals are hybridized, the tin(II) non-bonded electron pair is located on one of the hybrid orbitals, and the resulting large electric field gradient gives a large quadrupole splitting. The reaction of barium chloride and tin difluoride in aqueous solutions, for large BaCl₂.2H₂O/SnF₂ ratios (>10) results in the precipitation of a white powdered material, which is identified by X-ray diffraction to be BaCIF. However, Tin-119 Mossbauer spectroscopy shows the material contains a fairly large amount of divalent tin in the Sn²⁺ ionic form, with unhybridized orbitals, like in SnCl₂. Using X-ray diffraction, we have established that Sn²⁺ ions substitute 15% of the Ba²⁺ ions at random, and chemical analysis shows the material has the formula Ba_5.66SnCl_7.30F_6.04 and thus is enriched in chlorine.     

Probing the out-of-plane distortion of single point defects in atomically thin hexagonal boron nitride at the picometer scale

Crystalline systems often lower their energy by atom displacements from regular high-symmetry lattice sites. We demonstrate that such symmetry lowering distortions can be visualized by ultrahigh resolution transmission electron microscopy even at single point defects. Experimental investigation of structural distortions at the monovacancy defects in suspended bilayers of hexagonal boron nitride (h-BN) accompanied by first-principles calculations reveals a characteristic charge-induced pm symmetry configuration of boron vacancies. This symmetry breaking is caused by interlayer bond reconstruction across the bilayer h-BN at the negatively charged boron vacancy defects and results in local membrane bending at the defect site. This study confirms that boron vacancies are dominantly present in the h-BN membrane.     

Metabolomic investigation of cholestasis in a rat model using ultra-performance liquid chromatography/tandem mass spectrometry

Metabolomics follows the changes in concentrations of endogenous metabolites, which may reflect various disease states as well as systemic responses to environmental, therapeutic, or genetic interventions. In this study, we applied metabolomic approaches to monitor dynamic changes in plasma and urine metabolites, and compared these metabolite profiles in Eisai hyperbilirubinemic rats (EHBR, an animal model of cholestasis) with those in the parent strain of EHBR - Sprague-Dawley (SD) rats - in order to characterize cholestasis pathophysiologically. Ultra-performance liquid chromatography/tandem mass spectrometry-based analytical methods were used to assay metabolite levels. More than 250 metabolites were detected in both plasma and urine, and metabolite profiles of EHBR differed from those of SD rats. The levels of antioxidative and cytoprotective metabolites, taurine and hypotaurine, were markedly increased in urine of EHBR. The levels of many bile acids were also elevated in plasma and urine of EHBR, but the extent of elevation depended on the particular bile acid. The levels of cytoprotective ursodeoxycholic acid and its conjugates were markedly elevated, while that of cytotoxic chenodeoxycholic acid remained unchanged, suggesting the balance of bile acids had shifted resulting in decreased toxicity. In EHBR, reduced biliary excretion leads to increased systemic exposure to harmful compounds including some endogenous metabolites. Our metabolomic data suggest that mechanisms exist in EHBR that compensate for cholestasis-related damage.     

Oxidation of SnF2 stannous fluoride in aqueous solutions

The rate of oxidation of SnF₂ in aqueous solutions has been studied by redox titrations and Mössbauer spectroscopy on frozen solutions versus the acidity of the solutions and versus time. Tin(II) oxidizes in aqueous solutions; however, the rate of oxidation is much slower than previously reported. Redox titrations show that the amount of tetravalent tin increases continuously with time. Oxygen dissolved in water seems to be the oxidizing species. The oxidation rate is faster in acidic solutions. Mössbauer spectroscopy on frozen solutions shows the slow formation of tetravalent tin; it also indicates that divalent tin in aqueous solutions is similar to that observed in solid SnF₂, except that one water molecule coordinates tin.     

Oxidation of divalent tin in aqueous solutions of SnF2 and 3D transition metals allowed to crystallize slowly in air

Chlorides, nitrates and sulfates of M (M=Mn, Fe, Co, Ni and Zn) were dissolved in aqueous solutions of SnF₂ at M/Sn molar ratios of 0.5 to 3. No HF was used. The solutions were allowed to evaporate in air. Very small amounts of hexagonally shaped crystals of unknown materials were obtained for M=Mn, Co, Ni and Zn. Fe did not yield this phase. X-ray powder diffraction gives identical patterns for the four materials, which are therefore most likely isostructural, and showed that the products are not MSn₂F₆·6H₂O or MSnF₆·6H₂O. Tin-119 Mössbauer spectroscopy gives a single line at negative isomer shift, characteristic of [Sn(IV)F₆]^2– ions.     

Stability and local bifurcation analyses of two-wheeled trailers considering the nonlinear coupling between lateral and vertical motions

Nonlinear Dynamics - Multistability is an area of interest in robotics and locomotion because the ability to achieve multiple configurations or generate multiple gaits allows a single robotic or...     

Sibernitrat als Reagens zum mikrochemischen Nachweis des Sulfat-Ions

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Stability of self-assembled monolayers on titanium and gold

Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.