不同温度下氨基酸在α-咖啡碱水溶液中的体积、粘度及折光率特性

Measurements of density(ρ), viscosity(η), and refractive index(n), were carried out on α-amino acids, DL-solution at 298.15, 303.15, 308.15, and 313.15 K. These measurements have been carried out to evaluate some important parameters, viz., apparent molar volume (φv), partial molar volume (φv0), transfer volume (φ0v (tr)), viscosity A and B coefficients of Jones-Dole equation, free energies of activation per mole of solvent (△μ0#1) and solute (△μ0#2),enthalpies (△H*) and entropies (△S*) of activation of viscous flow, variation of B with temperature ((a)B/(a)T)P, and molar refractive index (RD). These parameters have been interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.     

SYNTHESIS OF γ-SUBSTITUTED-PROPYLCYCLOTETRASILOXANES AND THEIR EMULSION COPOLYMERIZATION WITH OCTAMETHYLCYCLOTETRASILOXANE*

Four γ-substituted-propylcyclotetrasiloxanes have been synthesized. Emulsion copolymerizations of these cyclosiloxanes with octamethylcyclotetrasiloxane have been carried out both in cationic and anionic emulsion systems. By way of these reactions, stable emulsions of organosilicon polymers which contain carbonfuctional groups such as γ-hydroxypropyl, γ-acetoxypropyl and γ-chloropropyi have been obtained.The effects of temperature, catalyst and the amount of γ-substituted-propylcyclotetrasiloxanes in emulsion copolymerizations have been studied.     

Study of Dehydrocoupling Reactions of Diorganotin Dihydrides R1R2SnH2 with Biuret

phenylmethyltin dihydride (PhMeSnH₂), phenylethyltin dihydride (PhEtSnH₂), phenylbutyltin dihydride (PhBuSnH₂) and butylmethyltin dihydride (BuMeSnH₂) with biuret (H₂L) proceeds via SnH/NH dehydrocoupling to afford the corresponding tetra-coordinate cyclic products. The reactions in the molar ratios of 1∶1, 2∶1 and 1∶2 have been studied. The yellow derivatives so isolated were soluble in polar solvents and insoluble in nonpolar solvents. It was found that 1∶1 reaction went to completion while 2∶1 and 1∶2 did not go to completion. The derivatives had been characterized by elemental analysis and spectroscopic techniques viz. IR, ¹H NMR, ¹³C NMR, ¹¹⁹Sn NMR. DSC and TGA of the reaction products have also been studied. All the derivatives were thermally stable upto (190±10) ℃ and degradation occurred after that.     

Exact quantum and TST-CEQ study of the collinear reaction O+HCl

Exact quantum calculations of reaction probabilities have been carried out using hyperspherical coordinates for the collinearr reaction O+HCl(v <1) -OH(v'<1)+Cl . A generalized LEPS potential energy surface with a barrier height of 8.12 kcal/mol has been used in the calculations. According to the calculated results we found that (1) the reaction probability oscillates with energy, (2) the reaction probability shows vibrational adiabaticity, although it is poorer than that for symmetric reaction Cl + HC1. The analysis of resonance has also been done. The reaction rate constants and average cross sections have been calculated by TST-CEQ method. The rate constants are in agreement with that by QCT and smaller than the experimental one. Finally, the threshold has been estimated and is in good agreement with that of the literature.     

纳米TiO2光催化剂的活性与使用寿命

Titanium dioxide nano-particles (for example， P₂₅， Germany， Degussa) have been internationally used as an effective photo-catalyst for many years. In this paper， characterization of P₂₅， photo-degradation ability as well as its life time has been systematically studied by employing methyl orange as a model pollutant. Many factors such as the pH value， pre-treatment have been investigated. Just like other nanometer-sized or ordinary Anatase TiO₂， the catalyst performs better at an optimal pH value. Pre-treatment of the catalyst also enhances the photo-catalytic a-bility. And the P₂₅ have shown rather good life time. The degradation products have been characterized by UV， mass and Raman spectrum. It is found that although the P₂₅ photo-catalyst has shown excellent decolourization a-bility， it is still difficult to degrade the methyl orange into small molecule， such as CO₂ and H₂O. Low-power ul-traviolet lamps (9W， 254nm) have been used throughout. A comparison experiment has been carried out under natural sunlight， and the results have shown that natural sunlight (With temperature below 10℃) could provide even more energy than that of the adopted ultraviolet lamp， which have proved P₂₅ a rather promising photo-catalyst for practical application in environment field under natural surrounding. The obtained results may serve as a valuable reference for the evaluation and preparation of high quality TiO₂ photo-catalyst.     

Photostability Study of Nanoporous TiO2 Film Electrodes in Basic Solutions

The nanoporous TiO2 film electrodes have been prepared by a sol-gel deposition process The photostability of the electrodes in basic solutions has been studied. The results show that the photostability of the electrodes decreases rapidly in strong basic solutions with or without methanol. The reaction of holes to O^2- produces active O^2- atoms and the products O^2- atomsoxidize Ti^3 to Ti^4 on TiO2 film surface and subsurface. This results in the TiO2 film electrodes unstable in basic solutions both without methanol and with too low concentration.     

MgSO4-NaOH-H2O四元交互体系在180℃水热条件下相互作用的动力学研究

In this paper,the forming and transforming process of the magnesium oxysulfates in a quaternary interaction system of MgSO₄-NaOH-H₂O under the hydrothermal conditions at 180℃ has been investigated by using MgSO₄ and NaOH solutions as starting materials. This transforming process of product phase from unstable phase to stable phase with time has been proved by means of chemical analysis, microphotograph, XRD and IR.     

Volumetric and Refractive Index Behaviour of α-Amino Acids in Aqueous CTAB at Different Temperatures

Densities （ρ） and refractive indices （nD） of glycine （Gly）, DL-alanine （Ala）, DL-valine （Val） （0.02, 0.04, 0.06, 0.08, and 0.10 mol·L^-1） in 0.005 and 0.008 mol·L^-1 aqueous cetyltrimethylammonium bromide （CTAB） have been measured at 298.15, 303.15, 308.15, and 313.15 K. The density data have been utilized to calculate apparent molar volumes （φv）, partial molar volumes （φv^0）, at infinite dilution and partial molar volumes of transfer φv^0 （tr） of amino acids. The refractive index data have been used to calculate molar refractivity （Rr,） of amino acids in aqueous cetyltrimethylammonium bromide. It has been observed that φv^0 varies linearly with increasing number of carbon atoms in the alkyl chain of amino acids, and hence, was split to get contributions from the zwitterionic end groups （NH3^＋ COO^-） and methylene group （CH2） of the amino acids. The behaviour of these parameters has been used to investigate the solute-solute, solute-solvent interactions and the effect of cetyltrimethylammoniuln cation on these interactions,     

氯柱硼镁石在盐酸溶液中溶解及相转化平衡溶液的振动光谱分析

The FT-IR difference spectroscopy and the Raman spectroscopy were used to identify the polyborate ions in saturated aqueous solutions during dissolution and transformation of 2MgO·2B₂O₃·MgCl₂·14H₂O in different HCl solutions at 30℃. The assignments of the recorded IR-Spectroscopic frequencies and Raman shift of the borate aqueous solution are given. The existing forms of polyborate anions in saturated aqueous solution and their inter-action have been discussed. The relationships between the existing forms of polyborate anions and the crystallizing solid phases have been gained.     

Dye-sensitized photo-oxidation of disulfiram

Dye-sensitized photo-oxidation of disulfiram has been carried out under various reaction conditions including change in solvents and sensitizers. The product has been isolated and characterized by its physical, chemical and spectral data. To confirm the participation of singlet-oxygen in the reaction, the experiment has also been carried out in the presence of various singlet oxygen scavengers.     

不同温度下α-氨基酸在咖啡碱水溶液中的体积、粘度及折光率特性

Measurements of density(ρ), viscosity(η), and refractive index(n), were carried out on α-amino acids, DL-solution at 298.15, 303.15, 308.15, and 313.15 K. These measurements have been carried out to evaluate some important parameters, viz., apparent molar volume (φv), partial molar volume (φv0), transfer volume (φ0v (tr)), viscosity A and B coefficients of Jones-Dole equation, free energies of activation per mole of solvent (△μ0#1) and solute (△μ0#2),enthalpies (△H*) and entropies (△S*) of activation of viscous flow, variation of B with temperature ((a)B/(a)T)P, and molar refractive index (RD). These parameters have been interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.     

Volumetric Properties of Tetra-n-butyl ammonium bromide in Aqueous Solutions of Magnesium sulphate in the Temperature Range 298.15 to 318.15K and under the Atmospheric Pressure

Density and sound speed measurements have been carried out for the ternary systems consisting of tetra-n-butyl ammonium bromide (TBAB) in 0.1 m aqueous magnesium sulphate heptahydrate (MgSO₄.7H₂O)-water over the full range of composition from T = 293.15 to 318.15 K by using volumetric method. Using this experimental data, various physical and thermodynamical parameters such as adiabatic compressibility, apparent molal compressibility, apparent molal volume, apparent and limiting partial molar volumes of the electrolytes and ions in these mixtures have been evaluated and split into respective ionic contributions. The results have been discussed in terms of ion–ion and ion–solvent interactions occurring between TBAB and aqueous MgSO₄ solutions. Further, structure making/breaking behaviour of MgSO4 has been reported in terms of sign of the partial molar expansibility at infinite dilution.     

Hydrogen and higher shell contributions in Zn2+, Ni2+, and Co2+ aqueous solutions: an X-ray absorption fine structure and molecular dynamics study

A detailed investigation of the hydration structure of Zn2+, Ni2+, and Co2+ in water solutions has been carried out combining X-ray absorption fine structure (EXAFS) spectroscopy and Molecular Dynamics (MD) simulations. The first quantitative analysis of EXAFS from hydrogen atoms in 3d transition metal ions in aqueous solutions has been carried out and the ion-hydrogen interactions have been found to provide a detectable contribution to the EXAFS spectra. An accurate determination of the structural parameters associated with the first hydration shell has been performed and compared with previous experimental results. No evidence of significant contributions from the second hydration shell to the EXAFS signal has been found for these solutions, while the inclusion of the hydrogen signal has been found to be important in performing a quantitative analysis of the experimental data. The high-frequency contribution present in the EXAFS spectra has been found to be due to multiple scattering (MS) effects inside the ion-oxygen first coordination shell. MD has been used to generate three-body distribution functions from which a reliable analysis of the MS contributions to the EXAFS spectra of these systems has been carried out.     

Study of molecular interactions in solutions of azomethines of sulfamethoxazole in N,N-dymethylformamide and tetrahydrofuran

Density, ultrasonic velocity and viscosity of azomethines containing sulfamethoxazole nucleus have been measured in N,N-dimethylformamide and tetrahydrofuran solutions over a wide concentration range at temperature 308.15 K. From these experimental data, acoustical parameters such as intermolecular free path length, isentropic compressibility and relaxation strength have been evaluated, that help understanding the molecular interactions occurring in these solutions. Furthermore, compressibility solvation number, the apparent molar compressibility and apparent molar volume of the solutions have been determined and discussed.     

Thermodynamics of Diglycine and Triglycine in Aqueous NaCl Solutions: Apparent Molar Volume, Isentropic Compressibility, and Refractive Index

New experimental data for the density, speed of sound, and refractive index of aqueous solutions of diglycine + NaCl and triglycine + NaCl have been reported. The apparent molar volume and apparent molar isentropic compressibility of these peptides at various NaCl concentrations have been calculated from the measured properties. The results show that both peptides exhibit a positive volume transfer to solutions with higher NaCl concentrations and a negative apparent isentropic compressibility in the presence of NaCl. These effects indicate that the apparent volumes of the peptide molecules are larger in solutions with higher NaCl concentrations and that the water molecules around the peptide molecules are less compressible than the water molecules in the bulk solvent. These effects are attributed to the doubly charged nature of the peptides and the interactions between the charged groups and hydrocarbon backbone of peptides with the ions.     

Suppression of matrix ions in ultraviolet laser desorption: Scanning electron microscopy and raman spectroscopy of the solid samples

Suppression of low-mass ion peaks in matrix-assisted ultraviolet laser desorption has been found to occur at low matrix-to-analyte molar ratios when using nicotinic acid as matrix, independent of the angle of illumination. Microscopic Raman scattering spectroscopy has been employed to investigate the matrix–analyte solid-state composition. The matrix-to-analyte molar ratios employed in preparing the solutions are reliable guides to the relative amounts of matrix and analyte molecules in the solid crystals, given the method of sample preparation employed involving drying under a stream of nitrogen. A qualitative model based on the proton supply-and-demand argument is tentatively proposed to explain the suppression phenomenon.     

Influence of ultraviolet light on some copper chelates of β-dicarbonyl compounds : Spectral evidence for a photoactivated metallotropy

The influence of ultraviolet light on heptane solutions of the copper chelates of several β-dicarbonyl compounds has been followed by spectroscopy. Reversible transformations are apparent, leading us to assume the presence of a photoactivated metalotropy.     

The volumetric and thermochemical properties of YCl3(aq), YbCl3(aq), DyCl3(aq), SmCl3(aq), and GdCl3(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

Relative densities and massic heat capacities have been measured for acidified aqueous solutions of YCl₃(aq), YbCl₃(aq), DyCl₃(aq), SmCl₃(aq), and GdCl₃(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa. These measurements have been used to calculate experimental apparent molar volumes and heat capacities which, when used in conjunction with Young’s rule, were used to calculate the apparent molar properties of the aqueous chloride salt solutions. The latter calculations required the use of volumetric and thermochemical data for aqueous solutions of hydrochloric acid that have been previously reported in the literature. The concentration dependences of the apparent molar properties have been modeled using Pitzer ion interaction equations to yield apparent molar volumes and heat capacities at infinite dilution. The temperature and concentration dependences of the apparent molar volumes and heat capacities of each trivalent salt system were modeled using modified Pitzer ion interaction equations. These equations utilized the revised Helgeson, Kirkham, and Flowers equations of state to model the temperature dependences of apparent molar volumes and heat capacities at infinite dilution. Calculated apparent molar volumes and heat capacities at infinite dilution have been used to calculate single ion properties for the investigated trivalent metal cations. These values have been compared to those previously reported in the literature. The differences between single ion values calculated in this study and those values calculated from thermodynamic data for aqueous perchlorate salts are also discussed.     

Temperature dependence of density, viscosity, ultrasonic velocity, and other properties of substituted pyrazoles in acetone-water mixtures

The density, viscosity and ultrasonic velocity of some substituted pyrazoles viz. 5-(2-hydroxyphenyl)-3-(pyridin-3-yl)-4-benzoylpyrazol, 5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-(3-pyridinoyl)-pyrazol, 5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-benzoylpyrazol and 5-(2-hydroxyphenyl)-3-phenyl-4-(3-pyridinoyl)-pyrazole have been measured in 70: 30 (vol/vol) acetone-water mixture at 298, 303, 308, and 313 K for 0.01 mol dm^?3 concentration of pyrazoles. The acoustical parameters such as adiabatic compressibility (??_s), relative association (R _A), specific acoustic impedance (Z), apparent molar volume (?_v), apparent molar adiabatic compressibility (?_K), and intermolecular free length (L _f) were calculated from the experimental densities and velocities. The changes in acoustical properties have been used to interpret the molecular interactions in solutions. The activation energies of viscous flow of pyrazole solutions were determined from the data of viscosity at different temperature.