超高真空中银表面垂直谐波电流的实验测量

在超高真空的条件下,测量了清洁、自由银表面产生的光学二次谐波随基波电矢量与入射面之间夹角(?)的变化,从而通过理论公式,求得由Rudnick和Stern引入的,用于衡量垂直面电流密度的唯象参数a的值,在入射基频光波长为1.064μm时,被测定为-4.0±0.8.     

A Novel Green Preparation of a, a''''-Bis (substituted benzylidene)-cycloalkanones Promoted by FeCl_3 6H-2O in Ionic Liquid

a, a'-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in [bmim][BF4] by using iron(III) chloride hexahydrate as a catalyst. It is shown that [bmim][BF4] and iron(III) chloride hexahydrate can be quantitatively recovered and be reused effectively for many times. Compared with the known methods, this novel process has the advantage of being an envkonmentally benign process together with good yields and mild reaction conditions.     

Synthesis and structure of novel derivatives of thieno[2,3-b]thiocine. An unusual product of intramolecular cycloaddition of 2-homomethallylthio-5-methyl-3-thiophenecarbonitrile oxide

9-Methyl-3,3a,4,5-tetrahydro-6H-thieno[2,3-b]thiocino[4,5-c]isoxazole and 9-hydroxyimino-2-methyl-7-methylene-6, 7,8,9-tetrahydro-5H-thieno[2,3-b]thiocine have been prepared for the first time by the oxidation of 2--alkenylthio-3-thiophenecarbaldoximes with NaOCl. X-ray structural investigations of thieno[2,3-b]thiocine and 2-homomethallylthio-5-methyl-3-thiophenecarbaldoxime have been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1262–1266, July, 1993.     

Structure-Activity Relationship of Insecticidal Steroids. III. Δ4,7-6-Ketosteroids

The toxicity of steroids 1-11 for colorado beetle (Leptinotarsa decemlineata Say.) larvae was studied by contact-intestinal treatment. Active insect-growth regulators were found among the studied compounds.     

Molecular shape effects and quantum theory

Certain features of the chemist's molecular structure model, viz. size and shape, are retrieved even in the best non-adiabatic variational calculations thus far carried out for ground states of H ₂ ⁺ and H₂. Those features do not conflict with the full symmetry of exact molecular eigenstates, once they are properly understood as correlation effects.     

Synthesis of cationic water-soluble esters of chlorin e6

Two esters of chlorin e₆ have been synthesized by esterification with aminoalcohols via the formation of acid chloride using oxalyl chloride and converted to the corresponding cationic water-soluble esters of chlorin e₆. The visible absorption and circular dichroism spectra have revealed that these two cationic chlorin e₆ esters synthesized are readily soluble in water as a monomer.     

Adsorption of the fluoride ion on the surface of various faces of a single crystal of silver: a quantum-chemical study

The fluoride ion adsorption from a gas phase on various faces of a single crystal of silver is studied by a density functional method within a cluster model for metal. The adsorption bond energy is found to increase in the series Ag(100) < Ag(111) < Ag(311) < Ag(110). A substantial structural and energetic heterogeneity of various adsorption sites is revealed. The results are utilized to simulate the electrochemical interface between individual faces of a single crystal of silver and aqueous solutions containing the fluoride ion. It is assumed that the adsorption potential may be represented as the sum of two contributions, one of which describes the metal–ion interaction and the other, the ion solvation energy. The plotted adsorption terms take into account partial degradation of the fluoride ion when adsorbed from an aqueous solution. Estimates of discreteness of the electrical double layer are presented. A conclusion on the maximum manifestation of specific adsorption of the fluoride ion for the Ag(100) face is made.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 232–238.Original Russian Text Copyright © 2005 by Nazmutdinov, Zinkicheva.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Pattern of separatrices and intrinsic reaction coordinates for degenerate thermal rearrangements

A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations.     

Phosphorylthioacetamides in the synthesis of annulated quinoxalines

Diethoxyphosphorylthioacetamide in the reaction with 2,3-dichloroquinoxaline acted as a thionating reagent, giving diethoxyphosphorylacetonitrile and 2-chloro-3-[(3-chloro-2-quinoxalinyl)thio]quinoxaline. Reactions of phosphorylthioacetamides with N-methylquinoxalinium iodide in alcohol media in the presence of a base proceeded stereoselectively to afford cis-3-phosphoryl-1,3,3a,4,9,9a-hexahydro-2H-pyrrolo[2,3-b]quinoxaline-2-thiones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1010–1013, May, 2007.     

Determination of Utratrace Silver Using Surfactant As Sensitizer by Catalytic Near Field Laser Thermal Lens Spectrometry

Thermal lens spectrometry (TLS) is an excellent tool for trace analysis1. TLS allows the detection of absorbances of 10-7～10-8, concentration of ≈ 10-11 mol稬-1 and the analysis of 10-15 L volumes with ≈10-2 absorbing molecules2. Kinetic analysis is playing an increasingly important part in modern analytical chemistry. Therefore, TLS shows much promise in combination with kinetic analysis. However, there are few data on TLS applications in kinetic analysis method so far3～4. A ne…