Molar excess heat capacities and volumes for mixtures of alkanoates with cyclohexane at 25°C

Molar excess volumes V ^E at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H _2m+1 C _m COOC _n H _2n+1 )+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C _p ^E at constant pressure at the same temperature. V ^E is positive for all systems and rather symmetric, with V ^E (x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C₄H₈O₂, C₅H₁₀O₂, or C₆H₁₂O₂). The composition dependence of C _p ^E is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane.     

Electron density distribution in molecules of 4-aryl-substituted [2.2]paracyclophanes and regioselectivity of their complexation with Cr(CO)3

Charges on carbon atoms in the molecules of 4-aryl-substituted [2.2]paracyclophanes were estimated and the role of charge control as a kinetic factor in regioselectivity of their complexation with (NH₃)₃Cr(CO)₃ was investigated using electron density distribution analysis by the Bader, Weinhold-Reed (NPA), and Mulliken methods. The most plausible picture of the electron density distribution in substituted [2.2]paracyclophanes was obtained by the Bader method and compared with experimental data on the yields of reaction products. Topological analysis of the electron density distribution in the [2.2]paracyclophane molecule by the Bader method confirmed the existence of a weak antibonding interaction between the stacked benzene rings. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–444, March, 1999.     

Determination of Pharmaceuticals by Dynamic Cell Membrane Chromatography Coupled with High-Performance Liquid Chromatography

As a biological affinity chromatographic method, cell membrane chromatography (CMC) using a silica stationary phase covered with specific cell membrane has been used in screening active components. The innovation of this work is that the bioactive cell membrane and the chromatographic packing are mixed and absorbed for the first time to form the pre-column. The pre-column was placed in front of a C₁₈ column to create dynamic CMC online high-performance liquid chromatography (HPLC) system. The retention behavior and dynamic changes of pharmaceuticals were studied for this system. The results indicate that the retention time of the drug was increased and the symmetry factor reached the analytical level after the addition of the dynamic cell membrane pre-column. Therefore, the dynamic CMC coupled with HPLC system may be a potentially rapid and efficient drug analysis approach for the interaction of drug molecule and receptor on red blood cell membranes.     

A thermodynamic and structural study of the interactions of pyridino- and diketopyridino-18-crown-6 ligands with some primary organic ammonium cations

Equilibrium constant (K), enthalpy change (H), and entropy change (S) values have been determined calorimetrically at 25°C in 90%MeOH 10%H₂O (v/v) for the interactions of pyridino-18-crown-6 (P18C6) and diketopyridino-18-crown-6 (K₂P18C6) with perchlorate salts of ammonium, benzylammonium,-phenylethylammonium,-phenylethylammonium, and-(1-naphthyl)ethyl-ammonium cations. The crystal structure of the complex of P18C6 with benzylammonium perchlorate was determined by X-ray crystallography. The¹H 1D and 2D NMR spectra of some of these complexes were used to elucidate their structural features in solution. The logK values for the interaction of the ammonium cations with P18C6 are larger than those with K₂P18C6, probably due to the higher degree of structural flexibility of P18C6. Ligand K₂P18C6 displays appreciable - interaction with the-(1-naphthyl)ethylammonium cation, but not with the-phenylethylammonium cation.- interaction between ligand and cationSupplementary Data relating to this article are deposited with the British Library as Supplementary Publication No SUP 00000 (22 pages)     

The valuation of convertible bonds with numeraire changes

The changes of numeraire can be used as a very powerful mean in pricing contingent claims in the context of a complete market. We apply the method of nurmeraire changes to evaluate convertible bonds when the instantaneous growth and variance of the value of issuer and those of zero-coupon bonds follow a general adapted stochastic process in this paper. A closed-form solution is derived when the instantaneous growth and variance of the value of issuer and those of zero-coupon bonds are deterministic function of time. We also consider a special case when the asset price follows GBM （Geometric Brownian Motion） and interest rate follows Vasicek＇s model.     

加权季节性指数法及其应用

预测医院季度出院人数季度变动趋势;加权季节性指数法;用加权季节性指数法进行季度变动趋势的定量预测与分析,对历史数据样本数量要求不多,并且计算简便;计算结果更具客观性、真实性.     

Stability of the FID sensitivity during an analysis in capillary GC

The sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects.     

Pressure‐induced phase transitions in palmitic acid: C form

In this article, we report a high‐pressure Raman spectroscopy study of palmitic acid (PA, C form) from ambient pressure up to 21 GPa. The effects of hydrostatic pressure on the vibrational spectrum of PA are reported, and the data show that PA experiences a rich sequence of phase transformations. These changes in the crystal structure occur gradually as the pressure increases and they are related to the highly flexible crystalline structure. Copyright © 2011 John Wiley & Sons, Ltd.     

Phase-ordering dynamics of binary mixtures with field-dependent mobility in shear flow

The effect of shear flow on the phase-ordering dynamics of a binary mixture with field-dependent mobility is investigated. The problem is addressed in the context of the time-dependent Ginzburg-Landau equation with an external velocity term, studied in self-consistent approximation. Assuming a scaling ansatz for the structure factor, the asymptotic behavior of the observables in the scaling regime can be analytically calculated. All the observables show log-time periodic oscillations which we interpret as due to a cyclical mechanism of stretching and break-up of domains. These oscillations are damped as consequence of the vanishing of the mobility in the bulk phase. Received 13 April 1999     

Formation Mechanism of Laser‐Synthesized Iron–Manganese Alloy Nanoparticles,Manganese Oxide Nanosheets and Nanofibers

Laser ablation in liquids (LAL) has emerged as a versatile approach for the synthesis of alloy particles and oxide nanomaterials. However, complex chemical reactions often take place during synthesis due to inevitable atomization and ionization of the target materials and decomposition/hydrolysis of solvent/solution molecules, making it difficult to understand the particle formation mechanisms. In this paper, a possible route for the formation of FeMn alloy nanoparticles as well as MnO_x nanoparticles, ‐sheets, and ‐fibers by LAL is presented. The observed structural, compositional, and morphological variations are clarified by transmission electron microscopy (TEM). The studies suggest that a reaction between Mn atoms and Fe ions followed by surface oxidation result in nonstoichiometric synthesis of Fe‐rich FeMn@FeMn₂O₄ core–shell alloy particles. Interestingly, a phase transformation from Mn₃O₄ to Mn₂O₃ and finally to Ramsdellite γ‐MnO₂ is accompanied by a morphology change from nanosheets to nanofibers in gradually increasing oxidizing environments. High‐resolution TEM images reveal that the particle‐attachment mechanism dominates the growth of different manganese oxides.