An Electrostatic Bond Energy Model for Enthalpies of Formation of Chloroalkanes in Gaseous States

An electrostatic bond energy model is formulated to fit the enthalpies of formation and dipole moments of the alkanes and chloroalkanes. In this model, the charge distributions are calculated by an electrostatic approach similar to the "MSE" method, and the enthalpy of formation of a molecule is the sum of the bond energy terms plus the electrostatic energy of the interactions between the charges on all atoms. All parameters of this model are obtained by parameterization. The calculated dipole moments for 13 chloroalkanes and enthalpies of formation for 19 alkanes and non-geminal chloroalkanes agree with the determined values very well. To calculate the enthalpies of formation of geminal chloroalkanes, a correction mainly attributed to the van der Waals interactions in the geminal substituted group, about 24 kJ/mol per pair of geminal chlorine atoms, is introduced.     

First total synthesis of leucamide A

The first total synthesis of marine bioactive cyclic heptapeptide Leucamide A has been accomplished, including a simple method for construction of the 4,2-bisheterocycle tandem pair substructure that employs a DAST-mediated cyclization of beta-hydroxy amide and final HBTU-promoted ring closing.     

Design and Synthesis of 1-Benzyl-3-(a-hydroxy-(un)substituted benzylidene)pyrrolidine-2,4-diones as Potential Herbicides

The inhibitors of 4-hydroxyphenylpyruvate dioxygenase (HPPD, EC 1.13.11.27) are an new kind of herbicides.[1]Generally, in structure, potent herbicides of this kind must possess: (1) a tricarbonyl methane structure and one of the three carbonyl groups must be a subustituted benzoyl group; (2) the compound must be able to enolise so that the enolate is capable of inhibiting HPPD enzyme by competitive combination with Fe2+, the reaction center of HPPD enzyme.[2]Recently, we noticed that the 3-acyltetramic acids form an expanding group of antibiotics and pigments from micro-organisms,[3] they display a range of biological activities[4] and all of this kind compounds possess all of the characters mentioned above. Tests of their antimicrobial activities indicated that the structure of the acyl substituent at the 3-position was important to many typical antibiotics.[4～6] These characters stimulated us to study this kind of compounds so as to discover new herbicides. In this report, we synthesized a series of compounds 3 and tested their herbicidal activities to investigate their structure-activity relationships.     

A Facile Three-Component One-Pot Synthesis of Structurally Constrained Tetrahydrofurans, Which Are t-RNA Synthetase Inhibitor Analogues

A one-pot procedure for the efficient synthesis of a small library of t-RNA inhibitor analogues was developed. Thus,Rh2(OAc)4 catalyzed three-component 1,3-dipolar cycloaddition reactions of carbonyl ylides derived from diazoindan-1,3-dione and aldehydes with other dipolarophiles in 1,1,2,2-tetrachloroethane at 80 ℃ gave ring fused tetrahydrofurans having three stereocenters in good yield.     

Synthesis and stereochemical assignment of 7-arylidene and 7-heteroarylidene morphinan-6-ones

A number of (E)-7-arylidenenaltrexones were synthesized by azeotropic distillation of water from a benzene solution of naltrexone and an aromatic aldehyde (benzaldehyde, 4-chloro- and 4-fluorobenzaldehyde, 3-and 4-pyridinecarboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde) using piperidine as a catalyst. In addition, (E)-7-benzylidenenaloxone was prepared by the previously published Claisen-Schmidt condensation using sodium hydroxide in methanol. The stereochemistry of these arylidene derivatives 3–9 was determined to be (E) by means of nuclear Overhauser enhancement experiments. The ¹³C nmr spectra of (E)- 3–9 are recorded in deuteriochloroform and those of the hydrochlorides in deuteriodimethyl sulfoxide.     

Quantitative volatilization of tin as mixed halides and its application in metal analysis

Proposed in this paper is an improved method for removal of tin as the matrix element by volatilization in an anhydrous medium as mixed halides of different composition. Any one of them boils at a lower temperature than SnBr₄. This ternary system enhances the eventual recombination of temporarily dissociated species to volatile ones, thus making the process quicker and more efficient. The presence of 2 mg of Pb(II) suffices to prevent Bi(III) from loss due to volatilization.     

热处理过程中聚酯长丝的形态变化

在自制的红外三因素处理机上~[1],用红外加热在定张力下对聚对苯二甲酸乙二酯(PET)成品长丝进行热处理(二次定型)。用X-光衍射(WAXS)、X-光小角散射(DAXS)、红外光谱(IR)和双折射方法,测定样品的热收缩、结晶度、晶粒尺寸和取向、非晶取向、长周期和链折叠带强度。所得形态参数的变化表明,处理温度在200℃以上时,张力不再阻碍链折叠。不同定张力样品的形态研究表明,存在阻碍链折叠的某个张力转折值。本文条件下,这个张力值为f_(critical)=0.066g/dtex 。张力大于此值,链折叠过程受阻。     

Electronic conduction properties of silver particles in cesium oxide

The electronic conductivity of a particular metallic particles/semiconductor system, i.e. Ag particles in cesium-oxide thin film, has been studied. The experimental results show a transition from a polycrystalline semiconductor to metallic behavior as characterized by the conductivity-temperature curve (log bs 1/T), and a five order of magnitude increase in the room temperature value of the conductivity with surface Ag content increasing from an equivalent thickness of 2Å to 20Å. It was observed by TEM that the deposited Ag was mainly in the form of dispersed particles with the particle size varying from 20 to 200Å and their separations varying from hundreds to tens of angstroms over the Ag content range. These results can hardly be explained with the model of direct electron tunneling through the Schottky barrier at the Ag-particle/cesium-oxide interface. A microstructure model with two conduction layers is presented, and an analogy to the hopping conduction mechanism is proposed to explain the electronic conduction behavior. This model predicts that the attenuation length for electronic wavefunctions localized at Ag particles falls in the range 20–50Å.     

Copper(II)-catalyzed aerobic oxidation of primary alcohols to aldehydes in ionic liquid [bmpy]PF6

A room-temperature aerobic oxidation of primary alcohols to aldehydes catalyzed by the three-component system acetamido-TEMPO/Cu(ClO(4))(2)/DMAP in the ionic liquid [bmpy]PF(6) has been developed, and the catalysts can be recycled and reused for five runs without any significant loss of catalytic activity. [reaction: see text]     

一种用于版权保护的随机相位量化编码方法

基于传统的随机相位编码技术，提出了一种新的相息图量化编码方法。该方法采用条码编码技术和数制转换原理，将编码得到相息图的高阶量化信息映射为二值矩阵，并进一步打印制作成二值的防伪标签，不但可以实现文本内容的自动录入，同时也提高了传统随机相位编码技术解码图像的信噪比。计算机仿真与光学扫描实验表明，该方法具有认证过程相对简单、解码图像信噪比高、成本低和防伪性能好等优点。