茶籽油油学性质的光谱分析研究

用气相色谱测定了思茅地区普洱茶果油中的脂肪酸的组成,并将其与花生油、菜籽油、油茶籽油、橄榄油中的脂肪酸组成进行了比较,发现普洱茶果油中油酸的质最分数高于花生油、菜籽油,低于油茶籽油、橄榄油,芥酸的质量分数低于花生油、菜籽油及油茶籽油,略高于橄榄油,故普洱茶果是一种理想的油料资源.用气-质联用从普洱茶果油挥发性物质中鉴定出30种化合物,其中大部分为醇、醛、酮、酯类物质,并且多数同时含有不饱和键,国内鲜见报道.     

Magnetic properties of equiatomic rare earth cadmium compounds

The magnetization processes obtained in monocrystalline samples are presented for the ferromagnetic compounds of the equiatomic rare earth cadmium series. They are discussed in terms of crystalline electric field and bilinear and quadrupolar pair interactions. A close similarity appears with the isomorphous series with zinc. The importance of quadrupolar interactions is emphasized. They are, for instance, strong enough in DyCd to enforce the fourfold axis as easy magnetization direction instead of the threefold one which would be driven by the only crystalline electric field. A discussion of the magnetic properties of dysprosium compounds having the CsCl-type structure is then given.     

Azo substituted V-shaped liquid crystalline compounds: synthesis and mesophase characterisation

The first examples of V-shaped liquid crystalline materials made of non-symmetrical molecules are reported. They belong to a homologous series of azo substituted compounds, wherein the two arms attached to the 1,2-positions of the benzene ring are different. The new compounds are characterised by the spectroscopic methods. The liquid crystalline properties are investigated using polarising optical microscopy, differential scanning calorimetry and X-ray diffraction studies. All the compounds synthesised here are found to be liquid crystalline. They exhibit nematic and smectic A mesophases, which are uniaxial in nature. The preliminary qualitative experiments showed that the compounds are photosensitive. Based on the X-ray results, the molecular arrangement of these compounds in their mesophases is illustrated. A relationship between molecular structures to mesomorphic properties in such systems has also been predicted.     

Bentonite-modified electrochemical sensors: a brief overview of features and applications

Bentonites are promising materials for electrochemical sensing because of their unique physicochemical properties. They have relatively high surface area, good adsorption and ion-exchange ability, highly tunable surface and interlayer composition, non-toxic nature, and excellent biocompatibility. Moreover, they are outstanding substrates for stable immobilization of different functional moieties. The primary focus of this review article is to highlight the applications of bentonite-modified electrodes for the analysis of organic and inorganic analytes in different matrices. A brief summary on the necessity of analysis of different compounds is provided. For the first time, features and applications of bentonite-modified electrodes are critically appraised. The key features of bentonite-modified electrodes that enhance their electrocatalytic activity toward detection of certain target analytes are highlighted. At the end, an account of current status of bentonite-modified electrodes along with future research directions is provided.     

表面增强拉曼光谱技术在多环芳烃检测中的应用

多环芳烃(polycyclic aromatic hydrocarbons,PAHs)是一类致癌性很强的环境污染物.由于PAHs分子不含有能与金属配位或键合的官能团,因此很难利用SERS技术对其进行直接检测.本文综述了近年来表面增强拉曼散射(surface-enhanced Raman scattering,SERS)...     

Hydrides of intermetallic compounds

Aspects of the progress over the recent years on hydrides of intermetallic compounds are reviewed with emphasis on structure, stability, solid-state properties, catalysis, and kinetics. Some new routes to an understanding of hydride phenomenology are indicated. Generally speaking hydrides represent but one special aspect of intermetallic compounds. They are, however, unique as model systems for questions concerning the stability of intermetallics in general, as thermodynamic data become more readily available during synthesis than is the case with most other metallic systems. Stability criteria are exemplified on model systems chosen to represen instructive or extreme cases. Hydrides are, moreover, unique with respect to the unusual properties of hydrogen as a “metallic” component, especially concerning such characteristics as mass (light), size (ranging from average to exceedingly small as a proton) and electronegativity (relatively high and comparable to B). This promises a wealth of special solid-state properties concerning magnetism, electrical conductivity or superconductivity. Some selected examples in this direction are discussed with emphasis on questions pertaining to the electronic state and the stability of the hydrides. The kinetics of compound (hydride) formation are often extraordinarily fast around ambient conditions opening this facet of intermetallics to rigorous study. Also intriguing new catalytic activity has been identified with metal hydrides implicating in one way or another the special surface properties of metal hydrides. Finally, metal hydrides are gaining in importance with respect to technological applications within a projected hydrogen economy (H or heat storage, electrochemical cells, etc.). Many of the fundamental aspects of metal hybrides have therefore become of practical relevance. Financial support by the Department of Energy, Division of Basic Energy Sciences, is acknowledged.     

硫钒铜矿化合物电子结构和电致变色特性的第一原理研究

基于密度泛函的第一原理赝势平面波方法,计算晶体结构、电子结构和光学性质,研究硫钒铜矿化合物Cu₃VS₄、Cu₃NbS₄和Cu₃TaS₄的电子输运及电致变色特性,探讨作为透明半导体材料应用于太阳能电池和电致变色器件的可能性.电子结构的计算表明这类化合物是间接带隙半导体,其电子能带的导带底和价带顶分别位于布里渊区的X点和R点.价带顶的电子本征态主要来自于Cu原子的d电子轨道,而导带底电子态主要来源于VB族元素原子的d电子轨道.能带结构、电荷布居分析、电子局域化函数和光吸收及反射谱的计算表明这些硫钒铜矿化合物属于极性共价半导体,具有较高的电荷迁移率和优良的电致变色特性,可应用于高效电致变色器件.     

The photoelectron spectra of some iron tricarbonyl complexes of 4π-electron donor ligands

The photoelectron spectra of eighteen compounds which are dienes or diene—iron tricarbonyl complexes have been investigated. A comparison of the photoelectron spectra of the dienes and corresponding iron carbonyl complexes has yielded the values of the perturbation energies for the two π orbitals of the diene moiety caused by interaction with Fe(CO)₃. These perturbation energies are relatively constant (Δπ₁ = 0.89 ± 0.07 eV, Δπ₂ = 0.22 ± 0.06 eV) throughout the series. They have been employed to estimate the π ionization energies of the organic transient species cyclobutadiene (8.29 and 11.95 eV) and trimethylenemethane (8.36 and 11.79 eV), two novel molecules which have not been studied successfully by photoelectron spectroscopy to date.     

Mineralogy, size, morphology and porosity of aggregates and their relationship with soil susceptibility to water erosion

Soil erosion has been considered as the main process related to losses of soil mass and decrease of productivity in cultivated lands as well as on e of the most important processes in landscape evolution. Attention has been paid to many pedological variables affecting intensity of erosion, but little to the influence of iron compounds on the type, size, shape and porosity of soil aggregates. In the present study, three lithopedodomains which were assumed to be closely related to the dominant lithology of the soil parent material, varying in the degree of water erosion intensity, were selected for further analysis which focused mainly on the influence of iron oxide mineralogy on the soil aggregation. Powder X-ray diffractometry, 80 K Mössbauer data and SEM images are used to correlate all these variables with observed erosion activity in the field. The present data indicate that the more the soil is rich in iron (hematite and/or goethite) or aluminium (gibbsite) (hydr)oxide, the smaller are its aggregates and is porous. Soils derived from metabasic rocks are much more susceptible to collapse under wetting than those from other lithologies. They have the highest iron and clay content. Schist-derived soil is richer in muscovite, has bigger aggregates and porous and are less prone to collapse, while the granite-derived soil presents relatively intermediate resistance, when humid.     

Spectroscopic methods for determination of catecholamines: A mini-review

Catecholamines are biogenic compounds that perform a variety of vital functions, playing a key physiological role in humans and animals. They are important markers in diagnosis of diseases and dysfunctions as well as widespread components of pharmaceutical formulations. Therefore, development of highly sensitive, rapid, and economically efficient methods for the determination of catecholamines is of great interest. The spectroscopic analytical methods have a good potential in this respect. This mini-review summarizes in a concise manner some advances and trends in the determination of catecholamines by spectroscopic methods, including spectrophotometry, fluorescence spectroscopy, immunoassays with spectroscopic detection, Raman spectroscopy, and other methods. Information on mainly determined compounds and analyzed samples is given and discussed. Analytical strategies and performance for the quantitation of catecholamines in various samples are described.     

Deuteron production — an entropy puzzle?

We reconsider the possibility of deducing the entropy attained in energetic heavy-ion reactions by means of the measured abundancies of compounds. In-medium corrections for the effective binding forces are seen to sensitivity influence the balance between nucleons and compounds. They reduce the deuteron production to rates close to the observed values with entropy values in line with conventional expectations.     

Distance measurements in spin-1/2 systems by 13C and 31P solid-state NMR in dense dipolar networks

In this article solid-state NMR methods for the determination of internuclear dipole-dipole couplings between homonuclear spin-1/2 nuclei are presented. They are suitable for relatively dense dipolar networks which are still dominated by 2-spin interactions. C-/R-symmetry theory is applied to create a double-quantum average Hamiltonian using phase-modulated radio-frequency irradiation and magic-angle sample-rotation. Symmetry derived pulse sequences with improved compensation against chemical shift anisotropies were found assuming a small isotropic chemical shift difference and using numerical calculations of the spin dynamics. Moreover it is shown that a constant time procedure can be used to acquire reliable double-quantum build-up curves even in systems in which damping obscures oscillations in their symmetric build-up curve. This technique is demonstrated on four crystalline model compounds with 31P and 13C spin systems typical for inorganic and biological applications. Comparison to crystal structure data indicates that the distances derived this way from 31P and 13C double-quantum NMR carry only small systematic errors caused for example by anisotropic J-coupling, dipolar contributions from adjacent spins and relaxation.     

N-甲酰基化合物的NMR谱的研究

测定了一系列N-甲酰基化合物的NMR波谱,对其一般特征进行了对比、讨论,尤其注意到由于C-N键的双键性而产生的异构体的性质以及氢键对于异构体的稳定作用.对于复杂的N-甲酰基化合物可根据简单的N-甲酰基化合物的谱图进行讨论.     

Non-destructive and in situ analysis of Egyptian wall paintings by X-ray diffraction and X-ray fluorescence portable systems

The concurrence and complementarities of obtained images under various wavelengths and the elemental and structural analyses provided by XRF and XRD, using portable non-invasive systems, have allowed for obtaining accurate data about the employed pictorial technique in two Egyptian wall paintings dating from the New Kingdom. Thus, compounds such as Egyptian blue, Egyptian green, goethite, jarosite, hematite, calcite, anhydrite or huntite have been detected in the paintings. The performance of the measurements by the different techniques and its contribution to the knowledge of the materials are discussed. They notably give a clue on the origin of arsenic compounds, unexpectedly detected in some decors.     

Insights into the interaction and binding mode of a set of antifungal azoles as inhibitors of potential fungal enzyme-based targets

Azole-containing compounds are a kind of chemical entities of natural and synthetic origin having a wide-range of activities. They are therefore considered as important moieties for fungicide development, mostly due to the possible action on several enzyme-based targets. As part of our research on fungicidal agents, the relationship between the ligand-enzyme affinities of several synthetic azole-containing compounds against a set of fungal enzyme-based targets was in silico evaluated through molecular docking. The affinity values of the test compounds were mostly higher than those of the respective test controls. Binding modes between enzymes and test compounds were firstly investigated through Vina scores and ligand–residue interactions. Furthermore, statistically relationships among docking scores were successfully found by multivariate analysis. They were mostly correlated with reported MIC₈₀ values, so it denoted an evident discrimination of the test compounds. Strong electron withdrawing groups on phenylacrylamide moiety were responsible for establishing stronger complexes with the enzyme targets, being trichodiene synthase and α-l-fucosidase the most important ones. Moreover, stability of a set of representative protein/ligand complexes was also analyzed by 10 ns molecular dynamics simulations (MD). Significant differences into the MD runs were detected and directly correlated to docking performances. Finally, docking affinity scores and HOMO–LUMO energy gaps resulted well predicted by comparative molecular field analysis (CoMFA) models, demonstrating the structure type is particularly associated with those calculated properties and these results were thus consistent with the respective validation parameters.     

Vibrational Modes of Photo-Excited in Quasi-One-Dimensional Halogen- Bridged Mixed-Valence Compounds

Vibrational modes of photo-excited in quasi-one-dimensional halogen-bridged mixedvalence compounds are investigated by using tight-binding model for electrons and quasiharmonic approximation for lattice vibration. Pt-halogen compound is taken as a onedimensional two-atom base chain, and the unit cell contains 12 atoms and a 12×12 dynamical matrix D_ij follows. Solving the corresponding determinantal equation numerically, the 12 eigenfrequencies are found. They are more accurate than the ones by harmonic approximation in comparison with the experimental data.     

九里香叶中香豆素类化合物的抗炎镇痛活性

分离九里香叶中具有抗炎镇痛活性的香豆素类化合物.利用小鼠扭体镇痛实验为活性跟踪动物模型,以硅胶色谱柱为分离手段,以波谱学为空间鉴定手段,并以小鼠扭体镇痛实验和二甲苯致耳朵肿胀实验为活性鉴定的动物模型.分离得到了6种香豆素类化合物,分别为蛇床子素、脱水长叶九里香内酯、橙皮内酯、伞形花内酯、东莨菪素、Murracarpin...     

First principle study of LiXS_2(X=Ga,In) as cathode materials for Li ion batteries

From first principle calculations, we demonstrate that LiXS_2(X = Ga, In) compounds have potential applications as cathode materials for Li ion batteries. It is shown that Li can be extracted from the LiXS_2 lattice with relatively small volume change and the XS_4 tetrahedron structure framework remains stable upon delithiation. The theoretical capacity and average intercalation potential of the LiGaS_2(LiInS_2) cathode are 190.4(144._2) m Ah/g and 3.50 V(3.53 V). The electronic structures of the LiXS_2 are insulating with band gaps of _2.88 eV and 1.99 eV for X = Ga and In, respectively.However, Li vacancies, which are formed through delithiation, change the electronic structure substantially from insulating to metallic structure, indicating that the electrical conductivities of the LiXS_2 compounds should be good during cycling.Li ion migration energy barriers are also calculated, and the results show that Li ion diffusions in the LiXS_2 compounds can be as good as those in the currently widely used electrode materials.     

Banana-shaped 1,2,4-oxadiazoles

3,5-Disubstituted 1,2,4-oxadiazoles are a new type of liquid crystalline (LC) compounds with asymmetrical five-membered heterocycle as a central unit. They have a bent shape and are very convenient model-compounds for studying the dependence of the LC properties on the molecular design. We have also synthesized and investigated ‘banana-shaped’ 1,2,4-oxadiazoles using the ester groups as the linkage units. The new compounds exhibit spontaneous polarization in the smectic phase, even if there is no chiral group in the molecules. Preliminary experimental data suggest the presence of spontaneous polarization in the nematic phase as well. In order to study the structural properties of the LC phases, X-ray diffraction (XRD) measurements on powder samples have been carried out. Based on the XRD data, a model of the structural arrangement of the bent molecules in the smectic phase is provided, which accounts for the macroscopic spontaneous polarization as well as the ferroelectric switching behavior.     

Phason Contribution to the Lattice Heat Capacity and Thermoconductivity

The phason contributions to the lattice heat capacity and thermoconductivity are obtained in the low-temperature limit for quasi-one-dimensional compounds. They are concentrated around temperatures related to the pinning frequency and the heat capacity is controlled by the density of states while the thermo,conductivity is governed by the phason velocity.