Electrochemical formation and phase control of Mg-Li alloys

The electrochemical formation of Mg-Li alloys was investigated in a molten LiCl-KCl(58-42 mol%)eutectic melt at 723 K. The cyclic voltammogram for a Mo electrode showed that the electroreduction of Li~ proceeds in a single step and the deposition potential of Li metal was -2.40 V(vs.Ag/AgCl).For Mg electrode,the electroreduction of Li~ takes place at less cathodic potential than that at the Mo electrode which was caused by the formation of Mg-Li alloys.Phase of the deposited Mg-Li alloys could be controlled by the electrolysis potential,and the samples were characterized by X-ray diffraction and scanning electron microscopy. The results showed thatα-Mg andβ-Li phases were obtained at -2.35 and -2.55 V,respectively.     

DSC study of phase transition of anhydrous phospholipid DHPC and influence of water content

The phase transition behavior of 1,2-di-n-heptadecanoyl phosphatidylcholme (DHPC)with and without water has been studied by use of differential scanning calorimetry It was found by experiment that the glass transition occurred at first during the first heating of a sample of DHPC without water and then the sample underwent melting as an ordinary crystal.Therefore the sample of DHPC without water was a glassy crystal However,the DHPC sample crystallizing from melt was an ordinary crystal From the relationship between the total melting enthalpy Qf of freezable water and the water content h,it was concluded that the water contained in the DHPC samples might exist in three states recognizable thermodynamically.The water in the first state was an unfreezable water It was the water bound directly with the head groups of the phospholipid,i.e.the primary hydration water Every head group might bind seven such molecules of water.The water in the second state was the secondary hydration water,us melt ing point was     

Diffusion and phase equilibria of binary fluids in mesopores

The formation of adsorption hysteresis in mesoporous material with random pore structure may be interrelated with different distributions of the fluid density attained along different paths of the system preparation. To access microscopic details of these distributions, in addition to the main sorptive liquid, distribution of which along the pore space of Vycor porous glass was of interest, a small amount of a probe liquid with a substantially lower vapor pressure has been added. Molecular diffusivities of both liquids then have been traced using pulsed field gradient NMR. Due to different vapor pressures, the two molecular species explore different spaces occupied by the capillary-condensed (accessible for both species) and gaseous (accessible only for the molecules of the main sorptive) phases. Comparative analysis of the diffusion properties obtained at different states along the adsorption isotherm revealed further insight into peculiarities of the fluid distribution and mass transfer of binary fluids in pores.     

Cure reaction and phase behavior of liquid crystalline epoxides-anhydride systems

A series of novel liquid crystalline epoxides with lateral substituents were cured with anhydrides and the cure kinetics was investigated by non-isothermal DSC technique. The results showed that the lengths of lateral substituents have great effect on the value of Ea. The curing reaction became less active, when the liquid crystalline epoxides have long lateral substituents and were controlled by diffusion at the late stage of cure. A nematic structure was observed by POM and XRD.     

Synthesis and thermal properties of NiSbS–As doped phase

The substitution of Sb with As in the NiSbS intermetallic compound was studied in the framework of evaluating a possible increase of the thermoelectric properties. Different NiSb_1?xAs_xS samples were synthesized with increasing amounts of As (0 < x < 0.66) employing a simple synthetic route using a muffle furnace. Scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy was used to investigate the microstructure. X-ray powder diffraction techniques were employed in order to study the possible existence of a solid solution between NiSbS and NiAsS compounds, as well as to identify the crystal structure and determine the lattice parameters. All compounds were found to crystallise with the NiSbS prototype (cP12-P2₁3), with lattice parameters varying from a = 0.59341(7) nm (x = 0) to a = 0.56849(6) nm (x = 1). Good agreement with Vegard’s law was evidenced. Thermal measurements on NiSb_1?xAs_xS samples were carried out using DTA instruments to evaluate the thermal stability and the melting temperatures.     

Orbital phase control of the conformations of α- and β-substituted enamines and vinyl ethers

The conformational stabilities of the α- and β-substituted enamines and vinyl ethers were predicted by orbital phase theory and confirmed by ab initio molecular orbital calculations. Cyclic interaction significantly occurs among the nonbonding orbital n _Y for the lone pair on the hetero atom Y (N in the enamines or O in the ethers), the π and π* orbitals of the CC bond, and the σ_C-H or σ*_C-X orbitals on the substituent CH₂X. The cyclic -n _Y-π-σ_C-H-π*- interaction is favored by the orbital phase continuity in the α-substituted molecules, while the cyclic -n _Y-π-σ*_C-X-π*- interaction is favored in the β-substituted molecules. The most stable conformation was then predicted to be synperiplanar or (pseudo)equatorial in the α-substituted molecules and anticlinical or (pseudo)axial in the β-substituted molecules. Received: 8 May 1998 / Accepted: 30 July 1998 / Published online: 16 November 1998     

Thermodynamics of the solvation and phase distributions of 2,2′-dipyridyl in acetonitrile-DMSO-hexane and methanol-DMSO-hexane systems

The Gibbs energies of 2,2′-dipyridyl when transferred from dimethyl sulfoxide to its mixtures with acetonitrile and methanol are determined from the distribution of substance between immiscible phases. It is found that moving from dimethyl sulfoxide to acetonitrile and methanol weakens the solvation of 2,2′-dipyridyl due to a change in the solvation of amino groups and the hydrocarbon substituent, which is reflected in a reduction in the entropy component of the Gibbs energy.     

Amplitude and phase fluctuation modes in the smectic Cα* phase of an antiferroelectric compound

Dielectric measurements have been carried out on the chiral smectic C_α (SmC_α*) phase of a MHPOBC analogous compound. Two relaxation modes have been observed in this phase for planar orientation of the molecules. One process has been observed at frequency lower than that of the soft mode of the chiral smectic A (SmA*) phase. This relaxation process is connected with the helicity of the SmC_α* phase. In the high‐frequency region, another relaxation process has been observed in the SmC_α* phase for which bias field dependence is similar to that of the soft mode at the SmA*–SmC* phase transition. The experimental observations are in agreement with a recently proposed dielectric theory for the SmC_α* phase and theoretical dielectric results obtained by numerical simulations. Thus, we report here experimental verification of two theoretically predicted dielectric modes in the SmC_α* phase.     

High-performance liquid chromatography–tandem mass spectrometry in the identification and determination of phase I and phase II drug metabolites

Applications of tandem mass spectrometry (MS/MS) techniques coupled with high-performance liquid chromatography (HPLC) in the identification and determination of phase I and phase II drug metabolites are reviewed with an emphasis on recent papers published predominantly within the last 6 years (2002–2007) reporting the employment of atmospheric pressure ionization techniques as the most promising approach for a sensitive detection, positive identification and quantitation of metabolites in complex biological matrices. This review is devoted to in vitro and in vivo drug biotransformation in humans and animals. The first step preceding an HPLC-MS bioanalysis consists in the choice of suitable sample preparation procedures (biomatrix sampling, homogenization, internal standard addition, deproteination, centrifugation, extraction). The subsequent step is the right optimization of chromatographic conditions providing the required separation selectivity, analysis time and also good compatibility with the MS detection. This is usually not accessible without the employment of the parent drug and synthesized or isolated chemical standards of expected phase I and sometimes also phase II metabolites. The incorporation of additional detectors (photodiode-array UV, fluorescence, polarimetric and others) between the HPLC and MS instruments can result in valuable analytical information supplementing MS results. The relation among the structural changes caused by metabolic reactions and corresponding shifts in the retention behavior in reversed-phase systems is discussed as supporting information for identification of the metabolite. The first and basic step in the interpretation of mass spectra is always the molecular weight (MW) determination based on the presence of protonated molecules [M+H]⁺ and sometimes adducts with ammonium or alkali-metal ions, observed in the positive-ion full-scan mass spectra. The MW determination can be confirmed by the [M-H]^- ion for metabolites providing a signal in negative-ion mass spectra. MS/MS is a worthy tool for further structural characterization because of the occurrence of characteristic fragment ions, either MS ⁿ analysis for studying the fragmentation patterns using trap-based analyzers or high mass accuracy measurements for elemental composition determination using time of flight based or Fourier transform mass analyzers. The correlation between typical functional groups found in phase I and phase II drug metabolites and corresponding neutral losses is generalized and illustrated for selected examples. The choice of a suitable ionization technique and polarity mode in relation to the metabolite structure is discussed as well.     

Specific heat of α' phase VD0.71 and VD0.78

We studied the D-D interaction at high deuterium concentrations in vanadium from specific heat measurements on α' phase VD_0.71 and VD_0.78 samples. Compared with pure vanadium, both samples showed between 50 and 140 °C a weakly temperature-dependent specific heat increase of about 2.1k_B (D atom)⁻¹ (at 100 °C). The increase results mainly from new phonons introduced by the deuterium and from D-D interactions causing a temperature-dependent deuterium distribution and, consequently, a temperature-dependent interaction energy. The phonon-induced contribution to the specific heat calculated from frequencies measured by means of neutron spectroscopy is 1.2k_B (D atom)⁻¹ (at 100 °C) which determines the contribution from the D-D interaction to be about 0.9k_B (D atom)⁻¹. The result is discussed on the basis of lattice gas calculations for D-D interaction energies of essentially elastic origin.     

Vapor phase composition and radical polymerization—how the gas phase influences the kinetics of heterophase polymerization

The outcome of radical styrene heterophase polymerization depends strongly on the composition of the gas phase. Data of a comprehensive experimental study show that the effect of the gas phase is quite a complex one and strongly influenced by the nature of the gas, the homogeneity or heterogeneity of the polymerization system, and the kind of initiator. Evidence is presented that the influence of air goes beyond the simple action of oxygen which can cause deceleration or acceleration of the reaction. The experimental results show that the optimum polymerization conditions are obtained in the absence of any foreign gas.     

Influence of oscillator phase on oscillation frequency and sensitivity of an electrode-separated piezoelectric sensor

Theoretical consideration was proposed for the influences of the oscillator phase on the response nature of an electrode-separated piezoelectric sensor (ESPS) to liquid properties and verified experimentally. For the oscillators with different phases, the oscillation frequency of the ESPS may increase, maintain nearly constant or decrease with increasing conductivity in low conductivity solutions. The sensitivity of response to density and viscosity increases slightly with increasing oscillator phase. The response to permittivity depends hardly on the oscillator phase. In addition, the dependence of the oscillation frequency of the ESPS on the supply voltage of the oscillator was explained. The ESPS was used to determine atropine sulfate with a detection limit of 1.6×10~7 mol/L.     

Kinetics and thermodynamics of liquid phase isomerization of α- and β-pinene over Pd/C catalyst

The kinetics and thermodynamics of the liquid phase isomerization of an α- and β-pinene mixture on a Pd/C catalyst were studied. The effects of pinene concentration, catalyst particle size, stirring rate, reaction temperature (293–423 K) and hydrogen pressure (0.5–11 bar) on the rate of α- and β-pinene isomerization were investigated. The reaction rate of the α-pinene isomerization has the first order with respect to the α-pinene concentration and 0.5 order with respect to the hydrogen pressure. The thermodynamic parameters of the isomerization (Gibbs energy, reaction enthalpy and reaction entropy) and the equilibrium ratio of pinenes under the conditions studied were determined. The general scheme of the reaction mechanism of α- and β-pinene isomerization over the Pd/C catalyst was proposed.     

Enantiomeric separation of α-phenylethylamine and its analogs by mixed chiral and achiral stationary phase

A mixed stationary phase of modified β-cyclodextrin, 2,6-di-O-butyl-3-O-butyryl-β-cyclodextrin (phase A), and SE-54 (phase B) was used for enantiomeric separation of α-phenylethylami-ne, o,m,p-methyl and o,m,p-methoxy-substituted analogs. The composition of mixed phase was selected by comparison of each calculated amin(= (γm,i+1)/(γm,i))> the relative retention values of the most adjacent peaks, and γm,last, the relative retention values of the last eluting peak at each preselected ratio. Values of γm,i,α calculated by derived equations were in good agreement with the experimental results obtained with two specified mixed phases. All solutes investigated were almost baseline separated at a predicted composition of phase A and phase B in a single run within 18 minutes.     

Solid and liquid phase equilibria and solid-hydrate formation in binary mixtures of water with amines

Solid and liquid phase diagrams have been constructed for {water+triethylamine,or+N,N-dimethylformamide(DMF) or+N,N-dimethlacetamide (DMA)} Solid-hydrates form with the empirical formulae N(C2H5)3 3H2O,DMF 3H2O,DMF 2H2O,DMA 3H2O and (DMA)2 3H2O.All are congruently melting except the first which melts incongruently.The solid-hydrate formation is attributed to hydrogen bond.The results are compared with the references     

Ab initio study of tautomerism and hydrogen bonding of β-carbonylamine in the gas phase and in water solution

All the possible conformations of the three tautomeric isomers of simple β-carbonylamine were fully optimized at ab initio MP2/6-31G** and B3LYP/6-31G** levels in order to determine the conformational equilibrium and the energies of the O—H···N and O···H—N hydrogen bridges. For the most interesting conformations, further calculations in water solution were also carried out. It was found that carbonylamine is the most stable tautomer, followed by enolimine and carbonylimine. This order of stability does not change in solution. O—H···N is the strongest hydrogen bridge, but in solution its energy as well as that of the O···H—N one are dramatically lowered. The deprotonation energy was also calculated and discussed. Received: 16 September 1999 / Accepted: 3 February 2000 / Published online: 5 June 2000     

The effect of structure and phase transformation on the mechanical properties of Re₂N and the stability of Mn₂N

First‐principles calculations were carried out on recently synthesized Re₂ and Re₃ as well as hypothetical Tc and Mn nitrides. It is found that structure and covalent bonds play an important role in determining mechanical properties. Under a large strain along (0001)〈101 0〉direction, Re₂N undergoes a phase transformation with a slight increase in ideal shear strength. On the other hand, it is transformed into a phase with weaker mechanical properties, if the strain is along Re₂〈1 21 0〉 direction. Mn₂N can be synthesized under moderate conditions due to its more negative formation energy. Re₂N, Re₃N, and Mn₂N show structure‐related mechanical property under larger strains to ReB₂ but exhibit much lower ideal strengths, which is attributed to the larger ionicity of cation–anion bond. Three‐dimensional framework of strong covalent bonds is thus highly recommended to design superhard materials. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Low-temperature heat capacity of β-glycine and a phase transition at 252 K

Low-temperature heat capacity of unstable -glycine was measured in a temperature range 5.5 to 295 K, and thermodynamic functions were calculated. At very low temperatures, heat capacity fits a sum of cubic (Debye) and linear terms: C_p=aT+bT ³. The linear contribution increases with temperature and disappears at the second-order phase transition near 252 K which was observed for the first time.