Influence of bleaching by ultrasound on fatty acids and minor compounds of olive oil. Qualitative and quantitative analysis of volatile compounds (by SPME coupled to GC/MS)

The effects of bleaching using high power ultrasound (20 kHz) on the quality of olive oil were considered in this study, in order to verify the modifications that can occur in fatty acid composition and minor compounds. During the treatment of olive oil under ultrasonic waves, a rancid odour has been detected. Treated olive oils show no significant changes in their chemical composition but the presence of some volatile compounds, due to ultrasonic treatment. Some off-flavour compounds (hexanal, hept-2-enal and 2(E),4(E)-decadienal) resulting from the sonodegradation of olive oil have been identified. A wide variety of analytical techniques (GLC, HPLC and GC/MS) were used to follow the quality of bleached olive oils with ultrasonic waves by the determination of the amounts of certain minor compounds such as sterols and tocopherols. Steradienes, resulting from the dehydration of sterols, were detected with small quantities especially in severe conditions of sonication. Solid phase micro-extraction (SPME) coupled to gas chromatography was known to be a sensitive technique to follow changes in the oxidative state of vegetable oils by measuring the amount of volatile materials produced during the refining process.     

Electro-optical properties and(E,F) phase diagram of fluorinated chiral smectic liquid crystals

Fluorinated smectic liquid crystals each with a biphenyl benzoate rigid core are investigated. Molecular structures of the studied compounds have difference only in fluorine position and the length of the carbon chain. Dielectric relaxation study and electro-optical measurements are carried out with the classical SSFLC geometry. The field-induced phase transitions are studied and the(E,T) phase diagram is established.     

水溶液中4种杂环化合物的荧光光谱的理论研究

采用量子化学半经验方法RHF/AM1对4种六元杂环化合物进行水溶液中的构型优化, 经振动分析, 未出现虚频率。在此基础上用RHF/CIS方法分别计算了它们的荧光光谱, 并与其气相计算的结果进行了对比, 在水溶液中的计算结果能更好地符合实验值。     

Polyoxaethylene polypodands – powerful reduction catalysts in solid–liquid and liquid–liquid phase transfer systems

The excellent catalytic properties of polypodands, esters of inorganic acids, as phase‐transfer catalysts have been reported previously. Unfortunately, these compounds are unstable under hydrolytic conditions. A group of new, hydrolytically stable podands has been synthesized. Their complex forming abilities towards alkali metal ions have been studied. The podands studied have been used as catalysts in phase transfer catalysis conditions. The kinetics of this process has been determined. All compounds prepared have been found to complex metal ions and are a powerful catalysts in reduction of ketones by borohydrides in solid–liquid and liquid–liquid systems. Copyright © 2013 John Wiley & Sons, Ltd.     

The dipnictenes R-E=E′-R′ (E=P,As, Sb,Bi) revisited: a TDDFT and multi-reference study of some aspects of its electronic spectroscopy

Compounds with double bonds Terp-E=E′-Terp (E, E'=P, As, Sb or Bi; Terp=-C₆H₃-2,6 (C₆H₅)₂) have been studied using DFT. These compounds have been used as a model for other compounds with larger substituents. Some bands of its electronic spectroscopy have been calculated using TDDFT, and the results show high correlation with experimental data, when available. In Bi-containing compounds, the origin of some weak bands in the calculated spectra and also in experimental data is unclear. An assignation of these bands is suggested, wedding the experimental data with calculated and theoretical results. These bands could be weak singlet–triplet transitions, partially allowed by spin-orbit coupling only in Bi-containing compounds. A theoretical estimation of the energy of these bands is achieved using CASSCF and MR-MP2.     

Phase transitions between orthogonal and tilted hexatic phases

Tilt-driven phase transitions between hexatic smectic phases: SmF-HexB and reversed HexB-SmF have been studied in compounds belonging to two enaminoketone derivative homologue series. The tilt angle order parameter has been measured and its temperature dependence near the phase transition point has been described by applying mean-field model. For both phase sequences the tricritical points have been observed on phase transition lines in binary mixtures of respective materials having first and second order phase transitions between hexatic phases. Received 21 June 1999     

Stability,elasticity and electronic structures of Co-Zr binary intermetallic compounds

ABSTRACT

The structural properties, enthalpies of formation and entropic temperatures of five stable Co-Zr intermetallics were systematically investigated by first-principles calculations. The calculated enthalpy of formation was used to measure the phase stability of the Co-Zr intermetallic compounds, and the results reveal that CoZr has the highest phase stability among these Co-Zr compounds. Considering the change of temperature, the entropic temperature T_S was used to illustrate the high-temperature stability of the Co-Zr intermetallic compounds. Additionally, the elastic constants, anisotropy indexes and Debye temperatures have been calculated. According to the calculated anisotropy indexes, CoZr₂ has the highest elastic anisotropy among the Co-Zr binary compounds. Furthermore, the bonding characteristics of these compounds have also been investigated by calculating the electronic structures.     

云南甘草中齐墩果烷型五环三萜化合物的NMR谱的研究

本文研究了云南甘草皂甙元(glyyunnansapogenin)等oleanane类化合物的核磁共振谱。运用PBB,INEPT,DEPT方法,并结合化学位移值规律归属了这些化合物的¹³C-NMR信号。总结出用角甲基的化学位移植范围判定角甲基的取代位置的方法,分析了角甲基被氧取代后对环的化学位移值的影响。按类似olean-12-en,18α-H方式考虑,归属了oleana-11,13(18)-diene化合物的¹³C-NMR信号。讨论了具30→18β内酯或2929→18α内酯类化合物的核磁谱规律。另外,还发现了DE环上有1个OAC取代时,与其偕碳质子的化学位移值规律。     

High pressure behavior of NpSe and NpTe

The high pressure behavior and pressure induced structural phase transition of two neptunium monochalcogenides have been investigated by using a three body potential approach. The calculated compression curves and the values of different high pressure behavior for NpSe and NpTe are presented and have been discussed and compared with the experimental values wherever available. The accuracy of the present approach in reproducing the phase transition pressure and high pressure behavior for these compounds are in general good agreement with the measured data. For NpSe and NpTe, the phase transition pressures for going from NaCl to CsCl phase have been observed at 22.4 and 14.2 GPa, respectively.     

New imine compounds and their copper complexes: synthesis,characterization and comparative investigations of morphologic,mesomorphic, thermotropic,thermo-optical and thermodynamical properties

Investigations of the morphologic, mesomorphic, thermotropic, thermo-optical and thermodynamical properties of new imine compounds and their copper complexes, synthesized by our group, have been carried out. Temperature transformations of typical textures for mesophases, taking place in imine compounds and copper complexes, and the peculiarities of the biphasic regions at the direct and reverse mesophase–isotropic liquid and isotropic liquid–mesophase phase transitions have been investigated.     

Phase transitions of [M(H2O)6](MnO4)2 polycrystalline compounds,where M=Mg2+,Ni2+,Zn2+,Cd2+, studied by DSC

Phase transitions of [M(H₂O)₆](MnO₄)₂, where M=Mg, Ni, Zn and Cd, have been studied at 100–400 K by differential scanning calorimetry (DSC). One solid–solid phase transition for the compounds with M=Mg and Ni and two solid–solid phase transitions for these with M=Zn and Cd have been discovered. Additionally, three phase transitions, connected with three-stage melting process of these compounds, were also found. Thermodynamic parameters of the all detected phase transitions were calculated.     

Electronic structure and structural phase stability of CuAlX2 (X=S, Se, Te) under pressure

The electronic and structural properties of chalcopyrite compounds CuAlX₂ (X=S, Se, Te) have been studied using the first principle self-consistent Tight Binding Linear Muffin-Tin Orbital (TBLMTO) method within the local density approximation. The present study deals with the ground state properties, structural phase transition, equations of state and pressure dependence of band gap of CuAlX₂ (S, Se, Te) compounds.Electronic structure and hence total energies of these compounds have been computed as a function of reduced volume. The calculated lattice parameters are in good agreement with the available experimental results. At high pressures, structural phase transition from bct structure (chalcopyrite) to cubic structure (rock salt) is observed. The pressure induced structural phase transitions for CuAlS₂, CuAlSe₂, and CuAlTe₂ are observed at 18.01, 14.4 and 8.29 GPa, respectively. Band structures at normal as well as for high-pressure phases have been calculated. The energy band gaps for the above compounds have been calculated as a function of pressure, which indicates the metallic character of these compounds at high-pressure fcc phase. There is a large downshift in band gaps due to hybridatization of the noble-metal d levels with p levels of the other atoms.     

Phase transitions as a function of material constants and temperature in intermetallic compounds of the terfenol-D type

A model of magnetic and magnetoelastic properties of intermetallic compounds has been considered with the inclusion of the influence of the “giant” magnetoelastic coupling and the biquadratic exchange interaction. The phase transitions as a function of material constants and temperature have been investigated in the framework of the proposed model. It has been demonstrated that the ferromagnetic and quadrupole phases can be formed in the system under consideration. In this case, the phase transition between these phases is a first-order transition and occurs through the intermediate, i.e., quadrupole-ferromagnetic, state. The dependences of the phase transition temperature on the Heisenberg and biquadratic exchange interaction constants have been obtained for compounds of the terfenol-D type.     

Phase transitions and electrical characteristics of tungsten substituted barium titanate

In the present work, phase transitions and electrical characteristics of tungsten substituted barium titanate are reported. Structural analysis of the prepared samples was carried out to confirm the formation of the compounds in proper phase. Scanning electron micrographs of the compounds have been used to investigate the grain morphology of the material. The dielectric properties of the samples have been studied as a function of temperature and frequency. The variation of dielectric constant (ε_r) with temperature shows a diffuse kind of ferro–paraelectric phase transition. The diffusitivity of the phase transitions has been calculated. Complex impedance spectroscopy analysis was carried out to investigate the electrical characteristics of the specimen.     

Magnetic susceptibility and 119Sn Mössbauer spectroscopy studies of RAuSn compounds (R=La, Ce, Pr)

In this paper the results of bulk magnetic susceptibility measurements and ¹¹⁹Sn Mössbauer spectroscopy measurements of LaAuSn, CeAuSn and PrAuSn intermetallic compounds are presented. New phase transitions in CeAuSn and PrAuSn compounds have been found by both methods employed. Structural and electronic properties are discussed.     

Electro-optical Kerr effect in the isotropic phase of the two antiferroelectric liquid crystal mixtures

We have experimentally studied for the first time the electro-optical Kerr effect and the pre-transitional behavior in the isotropic phase of two antiferroelectric liquid crystal mixtures, W-232 and W-204D, composed of rod-like ester molecules exhibiting the direct smectic-A to isotropic (SmA-I) phase transition. The Kerr law has been confirmed for the two compounds and the variation of inverse Kerr constant with temperature above the smectic–isotropic transition temperatures were determined. Both the mixtures with very broad antiferroelectric phase around room temperature have similar sequence of the phases (i.e., Cr-SmC*A-SmC*-SmA-I). Although, the pre-transitional behavior is usually complex in the isotropic phase of the chiral smectic liquid crystal compounds, the investigated compounds showed a similar behavior compared to that of nematic–isotropic behavior.     

Effect of irradiation on CsNO3, RbNO3., and NaNO2 crystal structure

Studies of the structure changes in heated (20–200°C) and γ –irradiated (10⁹- 5×10⁹ R, E = 1.3 Mev, Tirrad. = 40°C) crystals CsNO₃, RbNO₃ and NaNO₂ have been carried out by means of X-ray diffraction methods. The investigation of temperature effect on the crystal structure has shown that the phase transformation in CsNO₃ and NaNO₂ are of continuous type while that in RbNO₃ is discontinuous. It has been found that crystal structures of CsNO₃ and NaNO₂ change under irradiation in the same way, as they change under heating, No changes of RbNO₃ crystal structure caused by irradiation have been found. Experimental results agree with an assumption that radiation-induced structure changes of high-temperature type can be observed only in the compounds, the phase transition of which is of continuous type.     

High pressure behavior of alkaline earth tellurides

We have predicted high pressure structural behavior and elastic properties of alkaline earth tellurides (AETe; AE = Ca, Sr, Ba) by using two body interionic potential approach with modified ionic charge (Z _m e). This method has been found quite satisfactory in case of the rare earth compounds. The equation of state curve, structural phase transition pressure from NaCl (B1) to CsCl (B2) phase and associated volume collapse at transition pressure of alkaline earth tellurides (AETe) obtained from this approach, so have been compared with experimentally measured data reveal good agreement. We have also investigated bulk modulus, second and third order elastic constants and pressure derivatives of second order elastic constants at ambient pressure which shows predominantly ionic nature of these compounds. First time, we have calculated the Poisson ratio, Young and Shear modulus of these compounds.      

Pressure induced phase transition in rare earth mono-antimonides

Pressure induced structural phase transition of mono-antimonides of lanthanum, cerium, praseodymium and neodymium (LnSb, Ln=La, Ce, Pr and Nd) has been studied theoretically using an inter-ionic potential with modified ionic charge which parametrically includes the effect of Coulomb screening by the delocalized f electrons of rare earth (RE) ion. The anomalous structural properties of these compounds have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Ln ion with the p orbital of neighbouring antimonide ion. All the four compounds are found to undergo from their initial NaCl (B₁) phase to body centered tetragonal (BCT) phase at high pressure and agree well with the experimental results. The body centered tetragonal phase is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82. The transition pressure of LnSb compounds is observed to increase with decreasing lattice constant in NaCl phase. The nature of bonds between the ions is predicted by simulating the ion-ion (Ln-Ln and Ln-Sb) distances at high pressure. The calculated values of elastic constants are also reported.     

Theoretical design of diamondlike superhard structures at high pressure

Diamond, as the hardest known material, has been widely used in industrial applications as abrasives, coatings, and cutting and polishing tools, but it is restricted by several shortcomings, e.g., its low thermal and chemical stability. Considerable efforts have been devoted to designing or synthesizing the diamond-like B–C–N–O compounds, which exhibit excellent mechanical property. In this paper, we review the recent theoretical design of diamond-like superhard structures at high pressure. In particular, the recently designed high symmetric phase of low-energy cubic BC3 meets the experimental observation, and clarifies the actual existence of cubic symmetric phase for the compounds formed by B–C–N–O system,besides the classical example of cubic boron nitride.