溯源辨析“活化分子”概念在化学教材中的角色定位*

“活化分子”作为国内化学教育领域广为人知的科学概念,在各类相关化学教材中都有介绍。然而在国外多种经典化学教材中却完全没有“活化分子”的概念,反映出国内外化学教育领域对化学反应速率理论相关知识点的处理上存在明显的差异与分歧。通过溯源关键历史文献,回顾了“活化分子”概念的形成及其在化学反应速率理论发展过程中的角色演变,指出“活化分子”概念已经退出反应速率理论的舞台,在教材中应更多地呈现其在科学史方面的价值,而不是科学价值。     

液相色谱/大气压化学电离飞行时间质谱分析氢化可的松中微量杂质

采用液相色谱/大气压化学电离飞行时间质谱测定氢化可的松对照品中微量杂 质，并采用源内碰撞诱导解离质谱进行了结构定性分析。方法简单，可靠，重现性 好。     

Two-beam interference detection of the changes in fibre structural parameters during low drawing process

A Pluta polarizing interference microscope with a fibre stretching device attached was used to detect the changes in molecular structure that occur during the fibre cold drawing process. Fibres drawn with low draw ratios show different types of deformation mechanisms. The interference patterns recorded at different draw ratios are used to relate the deformation mechanisms with the measured structural parameters. Some optical parameters are measured such as; refractive indices nand n birefringence n, the polarizability per unit volume , the orientation distribution function f(θ), the angle θ between the stretching direction and the chain axis, and the angle θ_m which the transition dipole moment of the molecular species makes with the molecular axis (chain axis). Three polymeric fibres (Polyethylene terephthalate PET, Polypropylene PP and Polyamide PA) were used in this study and their interferograms are illustrated.     

Electrospray ionization collision induced dissociation of thiocarbocyanine and selenocarbocyanine dyes

The effect of the properties of sulphur and selenium atoms, the composition and location of substituents (―CH₃, ―OCH₃, ―C₂H₅, and ―C₃H₆―((N⁺Br^?)C₅H₅)), and the charge state on the collision induced dissociation (CID) behaviour of ions generated by electrospray ionization (ESI) of thiocarbocyanine and selenocarbocyanine dyes have been investigated. The results show that, for of all the examined singly charged ions, the main dissociation channel was related to the formation of distonic ions, generated as a result of cleavages within the dimethine bridge. In the case of doubly charged ions (with propyl‐pyridinium substituents), competition between fragmentation processes related to charges located at different nitrogen atoms has been observed. The S/Se replacement also has an impact on the CID behaviour of the examined carbocyanine dyes. On the basis of the performed CID MS/MS experiments, general rules for the CID of thiocarbocyanine and selenocarbocyanine dyes have been proposed.     

Chemical mass shifts in resonance ejection experiments in the quadrupole ion trap

Chemical mass shifts were measured in a Paul ion trap operated in the mass-selective instability scan with resonance ejection using a custom-built instrument. These shifts, which can be as much as 2%, decrease with increasing endcap electrode separation owing to changes in the higher order contributions to the electric field. They also decrease with decreasing helium buffer gas pressure. Both of these effects are analogous to those found with boundary ejection. This suggests that the previously proposed chemical mass shift mechanism based on compound-dependent collisional modification of the ejection delay produced by field faults near the endcap electrode apertures holds true also for resonance ejection. The influence of the resonance frequency on chemical mass shifts was also investigated and it is shown that at certain working points (values of the Mathieu parameter q(z) and a(z)) non-linear resonances greatly reduce the ejection delay for all ions, regardless of their chemical structures, and thus reduce the magnitude of the chemical mass shift. Energetic collisions leading to dissociation can take place at an earlier stage during the ejection process in the mass analysis scan when using resonance ejection compared with boundary ejection. This leads to even larger chemical mass shifts of fragile ions in resonance ejection. Increasing the resonance voltage amplitude can enhance this effect. The chemical mass shifts of fragile ions increase with increase in the resonance voltage amplitude, whereas negligible changes occur for structurally stable ions.     

Direct mercury determination in aqueous slurries of environmental and biological samples by cold vapour generation-electrothermal atomic absorption spectrometry

Direct cold vapour generation from aqueous slurries of environmental (marine sediment, soil, coal) and biological (human hair, seafood) samples have been developed using a batch mode generation system coupled with electrothermal atomic absorption spectroscopy. The effects of several variables affecting the cold vapour generation efficiency from solid particles (hydrochloric acid and sodium tetrahydroborate concentrations, argon flow rate, acid solution volume and mean particle size) have been evaluated using a Plackett-Burman experimental design. In addition, variables affecting cold vapour trapping and atomisation efficiency on Ir-treated graphite tubes (trapping and atomisation temperatures and trapping time) have been also investigated. Atomisation and trapping temperatures, trapping time and hydrochloric acid concentration were the significant variables. The 2²+star and 2³+star central composite designs have been used to obtain optimum values of the variables selected. The accuracy of methods have been verified by using several certified reference materials (PACS-1, GBW-07410, NIST-1632c, CRM-397 and DORM-2). A characteristic mass of 390 pg were achieved. The detection limits of methods were in the range of 40-600 ng g⁻¹. A particle size less than 50 μm is adequate to obtain total cold vapour generation of Hg content in the aqueous slurry particles.     

Cold trap/reinjection interface for two-dimensional gas chromatography

The construction and evaluation of an interface for two-dimensional gas chromatography is described. The interface consists of commercially available components and is attachable to available gas chromatographs without any major modifications. The interface has been constructed so as to permit “heartcutting” as well as solute band concentration. Trapping is performed in a simple cold trap of fused silica. Flow switching is accomplished by Deans switching. Factors of the over-all chromatographic performance are examined.     

Calorimetric and nuclear byproduct measurements in electrochemical confinement of deuterium in palladium

We present the results of a new experiment with our multicell set-up implemented with mass spectrometric measurements of⁴He and a highly improved neutron detector. The excess heat measured is comparable with the results of other laboratories, but no neutrons were found and the tritium excess was lower than expected from the power excess. ⁴He has been measured in the electrolysis gases and a tentative correlation of ⁴He with excess power is presented and discussed.     

Nonadiabatic collision model calculations of ion-pair formation cross sections of Cs+O2→Cs++O

This paper has improved Hickman's nonadiabatic collision model by substituting Hickman's constant velocity classical straight line trajectory approximation with the solution of motion equation mR=?dV(R)/dR, and has calculated the cross sections of ion-pair formation Cs+O₂→Cs⁺+O^?₂ with the improved nonadiabatic collision model (INCM). A comparison of our results with other theoretical and experimental results has been made.     

Theoretical investigation on electron scattering by benzene in the intermediate-energy range

We present a theoretical investigation on electron scattering by benzene (C₆H₆) in the intermediate-energy range. Calculated elastic differential, integral, and momentum-transfer as well as total (elastic + inelastic) and total absorption cross sections are reported for impact energies ranging from 20 to 500 eV. A complex optical potential is used to represent the electron-molecule interaction dynamics. A theoretical method based on the single-center-expansion close-coupling framework and corrected by the Padé approximant [F.A. Gianturco, R.R. Lucchese, N. Sanna, J. Chem. Phys. 102 (1995) 5743] is used to solve the scattering equations. The comparison of our calculated results with the experimental and theoretical data available in the literature is encouraging.