热动力学的研究 X. 一级反应的热谱峰高法

本文根据一级反应的热谱曲线方程、建立了速度常数的一种新算法。这种新方法,只需要热谱曲线在各个特征时刻的峰高,而不需要任何峰面积,即可算得反应体系的无量纲参数和速度常数,称为一级反应的热谱峰高法。     

A statistical thermodynamic supermolecule-continuum study of ion hydration: Cell and shell methods

A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li⁺, Na⁺, K⁺, F^– and Cl^– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties.     

Determination of extremely localized molecular orbitals in the framework of density functional theory

Extremely localized molecular orbitals are rigorously localized on only a preselected set of atoms and do not have any tails outside the localization region. The importance of these orbitals lies in their ability to be transferred from one molecule to another one. A new algorithm to determine extremely localized molecular orbitals in the framework of the density functional theory method is presented. This could also be a valuable tool in the quantum mechanics/molecular mechanics methodology where localized molecular orbitals are used to describe covalent bonds across the frontier region. The present approach is used to build up the electron density of thymopentin, a polypeptide constituted by five residues, starting from extremely localized molecular orbitals determined on a set of model molecules. The results obtained confirm good transferability properties for these orbitals.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail     

Chloromethyl-, dichloromethyl-, and trichloromethyl-1,2,4-triazines and their 4-oxides: method for the synthesis and tele-substitution reactions with C-nucleophiles

A simple procedure was developed for the synthesis of 1,2,4-triazines and their 4-oxides containing the ClCH₂, Cl₂CH, or CCl₃ group at position 3 by cyclization of 2-aryl-2-hydrazono-1-oximinoethanes with the corresponding chloroacetonitriles. The reaction pathway depends on the number of halogen atoms in the acetonitrile used. The reactions with trichloroacetonitrile, monochloroacetonitrile, and dichloroacetonitrile afford 3-trichloromethyl-1,2,4-triazines, 3-chloromethyl-1,2,4-triazine 4-oxides, and a mixture of the corresponding dichloromethyltriazines and their 4-oxides, respectively. The reactions of 3-trichloromethyl-1,2,4-triazines with indoles and phenols are accompanied by tele-substitution with elimination of halogen from the trichloromethyl group to give 5-indolyl- (or 5-hydroxyphenyl)-3-dichloromethyl-1,2,4-triazines.     

Synthesis of calixarene-cyclodextrin coupling products

The coupling of two or four mono-6-amino β-cyclodextrin (amino-CD) units, (unprotected or permethylated hydroxyls), to diisopropoxycalix[4]arene crown-6 (CAL) was realised using the N,N′-succinyldiamide linker. The resulting molecules in two series were characterised with the help of mass and NMR spectroscopies. The yields of all coupling products were improved for permethylated sugar series compared to the hydroxylated CD series or to our previous studies. The two β-cyclodextrin (β-CD) residues coupled to disubstituted CAL were orientated from the same side of the crown ether.     

EDTA—Cu配合物用于还原糖的测定

首次报道了应用ＥＤＴＡ（乙二胺四乙酸二钠盐）－铜配合物（ＥＣ）测定还原糖的分光光度法，结果表明，ｐＨ４～１１时ＥＣ的最大吸收波长为７３２ｎｍ，在ＨＣＯ－３ＣＯ２－３缓冲介质中，配合物ＥＣ的吸光度与还原糖在０７７～１６１ｍｇ（六碳糖）范围内有很好的线性关系，相关系数大于０９９８，样品测定回收率在９５％～１０５％之间。该法试剂易得、性质稳定，操作方便，灵敏度较高，取样量少于５ｍＬ。     

The ion product of H2O,dissociation constants of H2CO3 and pitzer parameters in the system Na+/H+/OH−/HCO 3 − /CO 3 2- /ClO 4 − /H2O at 25°C

The ion product of water and the dissociation constants of carbonic acid have been determined in 0.1, 1.0, 3.0, and 5.0M NaClO₄ at 25°C. The ion product of water K _w ^' has been evaluated by emf measurements with a combined glass electrode in NaClO₄ solutions containing 0.001–0.1M HCLO₄ or NaOH. The product K _H ^' K _l ^' K ₂ ^' of the Henry constant for CO₂ and the dissociation constants for H₂CO₃ have been determined by titration of carbonate solutions equilibrated with pCO₂ =10^–3.52 atm, and K ₂ ^' has been evaluated by potentiometric titration and by measuring the H⁺ concentration at fixed HCO ₃ ^– and CO ₃ ^2- concentrations. The ion interaction (Pitzer) equations are applied to describe the constants K _w ^' , K ₂ ^' and K _H ^' H ₁ ^' K ₂ ^' as a function of the NaClO₄ concentration. The experimental data are used to evaluate the mixing parameters _{i/ClO 4} and _{i/ClO 4} ^-/Na⁺ fori = OH ^-,HCO ₃ ^- andCO ₃ ^2-     

Theoretical studies of molecular conformation. Derivation of an additive procedure for the computation of intramolecular interaction energies. Comparison withab initio SCF computations

An additive procedure (SIBFA) is developed for the rapid computation of conformational energy variations in very large molecules. The macromolecule is built out of constitutive molecular fragments and the intramolecular energy is computed as a sum of interaction energies between the fragments. The electrostatic and the polarization components are calculated using multicenter multipole expansions of theab initio SCF electron density of the fragments. The repulsion component is obtained as a sum of bond and lone pair interactions.Tests of the procedure on a series of model compounds containing ether oxygens and pyridine-like nitrogens are reported and compared with the results of correspondingab initio SCF calculations. The resulting methodology is compatible with the simultaneous computation of intermolecular interactions.     

Thermal conductivity measurements on ferrofluids

The thermal conductivity of a number of ferrofluids consisting of colloidally dispersed Fe₃O₄ particles in diester, hydrocarbon, water and fluorcarbon carriers have been measured at 38°C. The variation in thermal conductivity with particle concentration is well described by Tareef's equation (1940). This has enabled the ratio of the physical to magnetic size to be determined and compared with estimates of the ratio obtained from electron micrographs and magnetic measurements.The fit between theory and experiment is particularly good for hydrocarbon carrier fluids giving the ratio of solid to magnetic radiusR _i/R _m=1.24±0.03 compared with the value obtained from magnetic data and electron micrographs of 1.19±0.07. The corresponding value from the fluids with a diester carrier ranges between 1.1<R _d/R _m<1.3 which is again consistent with microscopy and magnetic data.The application of a magnetic field of 0.1 T had no noticeable effect on the thermal conductivities of ferrofluids.     

气相色谱叠加定量方法的研究

叠加法是由内标法衍生而来的一种气相色谱定量方法。对于较复杂混合物的分析,当选择内标物困难时,用叠加法定量更为方便。本文在大量实验的基础上,提出了叠加法定量过程中应注意的一些问题。