Synthesis of non-equilibrium PtxOs1−x Solid solutions. Crystal structure of [Pt(NH3)4][OsCl6]

Several non-equilibrium solid solutions belonging to the platinum-osmium systems Os_0.9Pt_0.1, Os_0.8Pt_0.2, Os_0.5Pt_0.5, Os_0.7Pt_0.3, Os_0.75Pt_0.25 are prepared and studied. The thermal decomposition of [Pt(NH₃)₄][OsCl₆] in the hydrogen and helium atmosphere is investigated. It is found that the Pt_0.5Os_0.5 solid solution develops through the formation of (NH₄)₂[OsCl₆] and a metallic phase based on Pt. The crystal structure of a double complex salt [Pt(NH₃)₄][OsCl₆] is studied (X8-APEX Bruker, 1508 independent reflections, R = 2.04%). Crystal data for PtOsN₄Cl₆H₁₂ are: a = 11.6216(5) Å, b = 11.0016(5) Å, c = 10.3819(5) Å, V = 1327.4(1) ų, space group Cmca, Z = 4, d _x = 3.333 g/cm₃. The coordination polyhedron around Os is octahedral: 〈Os-Cl〉 2.357 Å, ∠Cl-Os-Cl 89.5–90.5°, while around Pt it is square-planar: Pt-N 2.046 Å, ∠ N-Pt-N 89.59° and 90.41°.     

激光引发二氟卡宾与烯烃的反应

近十年来,激光引发一氯二氟甲烷红外多光子解离和激光敏化反应的研究非常活跃,但大部分工作都集中于解离机制及同位素分离,而对CF_2HC(?)多光子解离产生的二氟卡宾     

In-gel deglycosylation of sodiumdodecyl sulfate polyacrylamide gel electrophoresis-separated glycoproteins for carbohydrate estimation by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Mass determination by mass spectrometric methods (electrospray ionization mass spectrometry (ESI-MS), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS)) of sodiumdodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE)-separated proteins is a well known procedure and reliable protocols are available. In our efforts to use the established methods to determine the molecular mass of the disulfide bridged, heterodimeric glycoprotein GP3 and to determine the carbohydrate content of each protein subunit we developed an in-gel chemical deglycosylation method. For this purpose we established experimental conditions that allow maximum extraction of the high molecular mass protein subunits and developed a routine method to apply the HF-pyridine deglycosylation protocol to proteins isolated from polyacrylamide gel pieces. The novel protocol and extraction procedure described can be used to analyze O-glycosylated proteins up to 150 kDa after SDS-PAGE separation.     

Interactions of Pb(II) with particles of a polluted river

Pb(II) interactions with the surface of suspended matter from a polluted river was studied using differential pulse anodic stripping voltammetry (DPASV) technique. Three sampling sites were selected and studies have been done with samples collected in different times of the year (winter, autumn and summer). The values have been compared with those obtained in spring in the same conditions [Sci. Total Environ. 151 (1994) 101].Particles were separated by centrifugation and suspensions of the freeze-dried particles were titrated with Pb(II), being measured the labile metal fraction by DPASV. For comparison, suspensions of river water without any separation have also been titrated.Results show that surface metal complexes are inert, within the time scale of the analytical technique and desorbed organics from surfaces, form labile Pb(II) complexes in solution. For each sample it was determined the capacity for Pb complexation of particles and desorbed organics and the differential function has been estimated. Despite the heterogeneity of ligands, the systems interpreted in a discontinuous way, present one or two kinds of dominant ligands with Pb affinity.     

Structural Investigation of Guest-to-Host and Ligand-Ligand Interactions in Werner Clathrates of [Ni(4-Etpy)4(NCS)2]⋅ nG Type (G = Naphthalene Derivatives). The Crystal Structure of [Ni(4-Etpy)4(NCS)2]⋅1-Methylnaphthalene

The stoichiometry and spectral properties of [Ni(4-Etpy)4(NCS)2]nG clathrates have been studied where n = 2 for G = 1-BrN (N = naphthalene), n = 1 or 2 for G = 1-MeN, and n = 0.5 for 2-MeN and 2-BrN. The complexes under study show electronic absorption spectra typical of an octahedral environment of the Ni(II) central atom. The differences found in IR spectra for the (CN) and (Ni–-NNCS) vibrations are discussed. The crystal structure of [Ni(4-Etpy)4(NCS)2]1-MeN was determined by X-ray diffraction and refined to R = 0.0586. Discrete non-centrosymmetric [Ni(4-Etpy)4(NCS)2] molecules form layers of a host structure and the space between the layers is occupied by 1-MeN. The relationship between interatomic distances in the host complex of similar clathrates are discussed.     

Synchrotron diffraction studies of TiC/FeTi cermets obtained by SHS

TiC/FeTi composites have been obtained in situ by Self-propagating High-temperature Synthesis (SHS) of an intimate mixture of compacted powders of elemental carbon, titanium and iron. The reaction has been followed in real time by X-ray diffraction at the ESRF. The mechanism of the reaction is discussed in terms of the formation of a liquid phase corresponding to the eutectic of the Fe/Ti system prior to the TiC synthesis. Temperatures of reaction have been estimated by correlating thermal expansion coefficients with diffraction peaks shifts. The microstructures obtained by this method, suitable for cutting tools and wear resistant applications, are presented.     

Synthesis, X-ray structure and properties of a new nitrite-bound copper(II) complex with 2-(3,5- dimethylpyrazol-1-ylmethyl)pyridine in a CuN4(O) coordination

Synthesis and characterization of a nitrite-bound copper(II) compound [CuL⁴)₂(ONO)]ClO₄ have been achieved (L⁴ = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L⁴ provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the d_x²−y² orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible Cu^II---Cu^I response [cathodic peak potential, E_pc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible Cu^II---Cu^I redox response [ ].     

Influence of Cycle Temperatures on the Thermochemical Heat Storage Densities in the Systems Water/Microporous and Water/Mesoporous Adsorbents

The adsorption equilibrium of water on microporous adsorbents (zeolites of NaA-, NaY- and NaX-type as well as their ion exchanged forms) and on mesoporous adsorbents (different silica gels and composite material i.e. silica gel + salt hydrate) has been studied experimentally and theoretically. Using the Dubinin theory of pore filling the characteristic curves of the adsorption systems and other relevant dependences such as isotherms, isobars, isosteres and the curve of the differential heat of adsorption were calculated. For all systems investigated the adsorption were calculated. A_ads and the desorption potential A_des of the closed heat storage system were estimated. These values define the working range of the adsorption/desorption cycle and allow to calculate the specific heat storage density Δ h_sp. On the basis of Δ h_sp the different adsorbents were compared in order to select the optimal porous storage material for a given application. The presented experimental and theoretical investigations show that the adsorption systems water-zeolite and water-composites are promising working pairs for thermochemical heat storage processes for hot tap water supply and space heating of single family dwellings. The advantage of the water-composite system is the low desorption temperature (solar energy) the main shortcoming the low temperature lift. The advantage of the water zeolite system is the high temperature lift, the shortcoming are the relative high desorption temperatures.     

Characteristic features of intra- and intermolecular interactions in crystals of pyrrole-2-carbaldehyde isonicotinoylhydrazone and its hydrate

Pyrrole-2-carbaldehyde isonicotinoylhydrazone (1) and its hydrate [1·H₂O] (2) were studied by single-crystal X-ray diffraction analysis. The introduction of the pyrrole substituent into N"-substituted isonicotinic hydrazide (INH) causes the intramolecular redistribution of the electron density compared to those in INHs studied earlier, which increases the basicity of the hydrazone nitrogen atom (N") involved in intermolecular hydrogen bonding. This effect has not been observed in the structures of N"-substituted INHs and benzhydrazides studied previously. Intermolecular hydrogen bonds play a decisive role in the formation of the crystal structures of 1 and 2.     

Crystal structure of 1-hydroxy-1,2,3-benzotriazolium diphenyl phosphate reveals strong NHO and OHO hydrogen bonds

The structure of 1-hydroxy-1,2,3-benzotriazolium diphenyl phosphate (HOBt/DPP) has been investigated by X-ray analysis. The compound crystallizes in the monoclinic space group P2₁/n with Z = 4 and the following lattice parameters: a = 11.711(2), b = 12.727(2) and c = 12.794(3) Å, β = 105.12(2)°, V = 1840.9(6) ų. The structure was solved by direct methods and refined on F² to R values of wR2 = 0.084 and R1 = 0.034 for 1985 observed reflections. HOBt/DPP has an ionic structure with very short OHO and NHO hydrogen bonds linking the different ions. Owing to these hydrogen bonds, infinite screw-shaped chains which are twisted parallel to the y-axis are formed.