On the pressure-induced phase transformation in the structure II clathrate hydrate of tetrahydrofuran

A high-pressure phase of the clathrate hydrate of tetrahydrofuran was prepared by freezing a liquid phase of overall composition THF · 7 H₂O under a pressure of 3.0 kbar, or by pressurizing the solid structure II THF hydrate of 255K to 3.4 kbar. Unfortunately, the products recovered at 77K were always mixed phase materials as shown by X-ray powder diffraction. A number of diffraction lines could be indexed in terms of the cubic structure I hydrate with a slightly expanded lattice parameter, 12.08 Å, giving some support to Dyadin's idea that the high pressure phase transition involves a conversion of Structure II to Structure I. Other phases observed in the recovered product include Ice IX and amorphous materials. The reversion of the high pressure sample to the structure II hydrate was followed by differential scanning calorimetry. At ambient pressure, the high pressure sample converts slowly back to Structure II hydrate event at 77K.NRCC No. 35786.     

The adsorption of endothelin 1 to phospholipids is governed by electrostatic interactions: A monolayer and fluorescence study

In order to elucidate the influence on the lipidic environment on the recognition process of its membrane associated receptor, the interactions of the vasoconstrictor peptide endothelin 1 with various phospholipids have been investigated using different lipidic model membranes: monolayers at constant surface pressure, vesicles and micelles. A monolayer study of ET1 adsorbed onto the water surface has shown that the C-terminus of the peptide points towards the aqueous phase. Penetration measurements into lipidic monolayers indicate that ET1 adsorbs to phospholipids with an orientation similar to that of the air–water interface and fluorescence measurements are in agreement with such an orientation of the peptide. This adsorption is selective for neutral phospholipids and indicates that the nature of the phospholipid headgroups is of major importance for the approach of the membrane associated receptor.     

Thermodynamic characteristics of thermal dissociation of platinum tetrachloride

The pressure of thermal dissociation of platinum tetrachloride by the first step PtCl₄(s) = PtCl₃(s) + 0.5 Cl₂(g) was measured by the static method with a quartz membrane-gauge zero-pressure manometer. An approximating equation for the dissociation pressure vs. temperature was found. The enthalpy (52160±880 J mol⁻¹) and entropy (72.1±1.6 J mol⁻¹ K⁻¹) of dissociation were calculated. The heat of formation found for platinum tetrachloride (−246.3±1.3 kJ mol⁻¹) at 298.15 K agrees well with the value obtained by the calorimetric method (−245.6±1.9 kJ mol⁻¹).__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2028–2031, October, 2004.     

Zustandsbarogramme — Zustandsdiagramme durch Gesamtdruckmessungen

From phasebarograms it is possible to construct phase diagrams. We show on example of the system Bi/Se/O how follow ternary sections from the total pressure measurements in equilibrium and how we can attribute the barogram of the ternary region Bi₂Se₃/Bi₂O₂Se/Se to the binary system Bi₂Se₃/Se. The knowledge of the ternary system Bi/Se/I and its coexistent pressure courses allow to followT-p-x conditions for the chemical transport of phases from this system.

     

Reactions in a Mixture of CH4 and CO2 under the Aciton of Microwave Discharge at Atmospheric Pressure

Reactions between CH4 and CO2 under the action of continuous microwave discharge at atmospheric pressure were studied in a special homemade reactor,The main products were CO and H2,while acetylene and ethylene were also found in the products.Experimental results show that conversions of CH4 and CO2 could be higher than 90% without the presence of any catalyst,Effects of CO2/CH4 molar ratio and total flow rate of the feed gas on the reaction were also investigated.     

Diamond synthesis by DC thermal plasma CVD at 1 atm

Diamond crystals and films have been success full y synthesized by DC thermal plasma jet CVD at a pressure of I atrn. A novel triple torch plasma reactor has been used to generate a convergent plasma volume to entrain the participating gases. Three coalescing plasma jets produces! by this reactor direct the dissociated and ionized gaseous species onto ( 100) silicon wafer substrates where the diamond grows. In a typical 10-min run, depending on the method of .substrate preparation, either microcrystals with sizes up to 8 m or continuous films with thicknesses of 1–2 m have been obtained. X-ray diffraction, scanning electron microscopy, and Raman spectroscopy have been used for the characterization of the crystals and of the films.     

On the Temperature–Pressure Free‐Energy Landscape of Proteins

We studied the thermodynamic stability of a small monomeric protein, staphylococcal nuclease (Snase), as a function of both temperature and pressure, and expressed it as a 3D free‐energy surface on the p,T‐plane using a second‐order Taylor expansion of the Gibbs free‐energy change ΔG upon unfolding. We took advantage of a series of different techniques (small‐angle Xray scattering, Fourier‐transform infrared spectroscopy, differential thermal analysis, pressure perturbation calorimetry and densitometry) in the evaluation of the conformation of the protein and in evaluating the changes in the thermodynamic parameters upon unfolding, such as the heat capacity, enthalpy, entropy, volume, isothermal compressibility and expansivity. The calculated results of the free‐energy landscape of the protein are in good agreement with experimental data of the p,T‐stability diagram of the protein over a temperature range from 200 to 400 K and at pressures from ambient pressure to 4000 bar. The results demonstrate that combined temperature–pressure‐dependent studies can help delineate the free‐energy landscape of proteins and hence help elucidate which features and thermodynamic parameters are essential in determining the stability of the native conformational state of proteins. The approach presented may also be used for studying other systems with so‐called re‐entrant or Tamman loop‐shaped phase diagrams.     

K3MnH5, das erste salzartige Manganhydrid

K₃MnH₅, the First Salt-like Manganese Hydride K₃MnH₅ and K₃MnD₅ were synthesized by the reaction of potassium hydride (deuteride) with manganese powder under a hydrogen pressure above 3000 bar at 875 K. X-ray investigations on powdered samples and elastic neutron diffraction experiments on the deuterated compound at the time-of-flight spectrometer LAD in the temperature range 5–600 K led to the complete structure determination. The atomic arrangement is isotypic with that of Cs₃[CoCl₄]Cl (space group: 14/mcm, Z = 4). The structure of K₃MnH₅ contains isolated [MnH₄]^2?-tetrahedra and additional hydrogen ions which are exclusively coordinated by potassium cations. The magnetic susceptibilities show Curie-Weiss behaviour. At temperatures below 50 K there are obviously antiferromagnetic interactions.     

液相色谱/大气压化学电离飞行时间质谱分析氢化可的松中微量杂质

采用液相色谱/大气压化学电离飞行时间质谱测定氢化可的松对照品中微量杂 质，并采用源内碰撞诱导解离质谱进行了结构定性分析。方法简单，可靠，重现性 好。