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Theoretical study on thermal decomposition of azoisobutyronitrile in ground state

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Science China chemistry 2004年第5期47卷 373-380页

作者： SUN Chengke1,2. ZHAO Hongmei1 & LI Zonghe1 1. Department of chemistry, Beijing {2. university, Beijing 100875, China 2. Department of chemistry, Qujing {2. college, Qujing 655000, China Dept. of Chem. Beijing Normal Univ. Beijing 100875 China Dept. of Chem. Qujing Normal Coll. Qujing 655000 China

The thermal decomposition mechanisms of azoisobutyronitrile (AIBN) in the ground state have been investigated systematically. Based on the potential energy surfaces (PES) of various possible dissociation paths obtained using the semiempirical AM1 method with partial optimization, the density function theory B3LYP/6-311G* method was employed to optimize the geometric parameters of the reactants, the intermediates, the products and the transition states, which were further confirmed by the vibrational analysis. The obtained results show that the re- action process of the two-bond (three-body) simultaneous cleavage Me2.CN)C─ N=N─ C(CN)Me2. 2.e2.CN)C?+N2.is much more favorable than the reaction process of the two one- bond asynchronous cleavage Me2.CN)CN=N─C(CN)Me2.? Me2.CN)CN=N?+ Me2.CN)C?? Me2.CN)C?+ N2. It was suggested that the electron shrinking effect of double bond (─N=N─) in AIBN and the stabilities of the Me2.CN)C?radical as well as N2.molecule are main factors of leading to the reaction proceeding in the former pathway. The calculation results were consistent with all the experimental facts.

关键词： azoisobutyronitrile, radicals, thermal decomposition, density function theory (DFT).

Density functional study on enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine

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Science China chemistry 2006年第4期49卷 296-307页

作者： LI Ming1, ZHENG Wenxu2.& TIAN Anmin2.1. Department of chemistry, Southwest-China {2. university, Chongqing 400715, China 2. Department of chemistry, Sichuan university, Chengdu 610064, China Department of chemistry Southwest-China Normal University Chongqing China Department of chemistry Sichuan University Chengdu China

The enantioselective reduction of keto oxime ether with borane catalyzed by oxazaborolidine is discussed by the density functional theory (DFT) method. The main intermediates and transition states for this reaction are optimized completely at the B3LYP/6-31g(d) level, and the transition states are verified by vibrational modes. As shown, the chirality-controlled steps for this re- action are the hydride transfer from borane to carbonyl carbon and oxime carbon of keto oxime ether, and the chirality for the reduced products is determined in these two reaction steps. In all examined reaction paths, the first hydride is transferred via a six-membered ring and the second hydride via a five-membered ring or a four-membered ring.

关键词： keto oxime ether, oxazaborolidine, enantioselective reduction, DFT.

Approach to synthesis of novel chiral 3-chloro-2.5H)- furanone and its application in asymmetric reactions

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Chinese Science Bulletin 2000年第8期45卷 711-716页

作者： HUANG Hui & CHEN Qinghua1. Department of chemistry, Tonghua Teacher’s {2., Tonghua 134002. China 2. Department of chemistry, Beijing normal university, Beijing 100875, China Department of chemistry Tonghua Teacher’s College Tonghua China Department of chemistry Beijing Normal University Beijing China

The synthetic method of the novel chiral synthon, 5-/-menthyloxy-3-chloro-2.(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucieophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR, H NMR,13 C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(/-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2.3i(4’-/-menthyloxy-5’-/-menthyloxy- butyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex

关键词： new chiral synthon. 5-l-menthyloxy-3-chloro-2.(5H)-furanone absolute configuration spiro-cyclopropane derivative containing multiple chiral centers.

Mathematic Expression of Kinetic Compensation Effect and Relationship between the Exothermic Decomposition Temperature and Critical Temperature of Thermal Explosion of Eighty-six Energetic Materials

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含能材料 2001年第1期9卷 8-9页

作者： HU Rong zu 1, YANG De suo 2. ZHANG Jiao qiang 3 (1. Department of chemistry,Northwest university, Xi′an 710065, China 2. Department of chemistry and Chemical Engineering, Baoji college of Arts and Science, Baoji 72.007, China 3. Department of 西北大学陕西西安 710065 宝鸡文理学院陕西 721007 西北工业大学陕西西安 710072

Two relationships are established using the least squares method,between the kinetic parameters (the apparent activation energy and pre exponential constant),and the exothermic decomposition temperature and ther... 详细信息

关键词： critical temperature of thermal explosion decomposition temperature DSC energetic materials.

Spectral anomalies and spectral switches of partially coherent and polychromatic light diffracted at an aperture

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Science China(Physics,Mechanics & Astronomy) 2004年第1期47卷 24-35页

作者： Lü Baida1, 3 & PAN Liuzhan1, 2.1. Institute of Laser Physics and chemistry, Sichuan university, Chengdu 610064, China 2. Department of Physics, Luoyang {2. college, Luoyang 47102., China 3. State Key Laboratory of Laser Technology, Huazhong university of Science and Technology, Wuhan 430074, China Correspondence should be addressed to L Baida (email: badalu@***) Received July 10, 2.03 Institute of Laser Physics and chemistry Sichuan University Chengdu China State Key Laboratory of Laser Technology Huazhong University of Science and Technology Wuhan China Department of Physics Luoyang Normal College Luoyang China

Based on the propagation theory of partially coherent light in the space-frequency domain, the anomalous spectral behavior and spectral switches in the far field of partially coherent and polychromatic light diffracted at an aperture are studied. It is shown that, as compared with spatially fully coherent and polychromatic light whose spectral anomalies are induced only by aperture diffraction, the spectral anomalies and spectral switches of partially coherent and polychromatic light depend on the aperture diffraction, spatial correlationβ and bandwidth of the original spectrum. Detailed numerical calculations are made to illustrate the behavior of spectral switches of partially coherent and polychromatic light, and the results for spatially fully coherent and polychromatic light are treated as a special case ofβ=1 and included in our theory.

关键词： spectral anomaly spectral switch partially coherent and polychromatic light far field aperture diffraction

Fuzzy controllers based on some fuzzy implication operators and their response functions

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Progress in Natural Science:Materials International 2004年第1期14卷 16-21页

作者： LI Hongxing 1*, YOU Fei 1 and PENG Jiayin 2.1. Department of Mathematics, Beijing {2. university, Beijing 100875, China 2. Department of Mathematics, Neijiang Teacher's college, Neijiang 641112. China) Department of Mathematics Beijing Normal University Beijing 100875 China. Department of Mathematics Neijiang Teacher''s College Neijiang 641112 China

The fuzzy controllers constructed by 2. fuzzy implication operators based on CRI algorithm and their response functions are discussed. The conclusions show that the fuzzy controllers constructed by 9 fuzzy implication operators are universal approximators to continuous functions and can be used in practical fuzzy control systems. And these 9 fuzzy implication operators except for Einstein operator intersection are all the adjoint pairs of some fuzzy implication operators. Besides, there are 3 other fuzzy controllers formed by fuzzy implication operators being regarded approximately as fitted functions.

关键词： fuzzy implication operators CRI algorithm fuzzy controllers response functions universal approximators

Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

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Chemical Research in Chinese Universities 2012年第1期28卷 73-78页

作者： DENG Dong-sheng1,2. WANG Li1, PEI Ya-mei1, FENG Lu2.and LIU Chang-lin1 1. Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, School of chemistry, Central China normal {2., Wuhan 430079, P. R. China 2. college of chemistry and Chemical Engineering, Luoyang normal {2., Luoyang 47102., P. R. China School of chemistry Central China Normal University Key Laboratory of Pesticide & Chemical Biology Ministry of Education Wuhan 430079 college of chemistry and Chemical Engineer{2. Luoyang Normal University Luoyang 471022

Four dinuclear amino acid cadmium（II） complexes [Cd2.tren）2.dl-alaninato）]（ClO4）3·H2.（I）, [Cd2.tren）2. （l-alaninato）]（ClO4）3·H2.（II）, [Cd2.tren）2.dl-phenylalaninato）]（ClO4）3（III） and [Cd2.tren）2.l-phenylalaninato）]· （ClO4）3（IV）, constructed from mixed ligands of tris（2.aminoethyl）amine（tren） and racemic or natural amino ac ids（amino acids=dl or l-alanine, and dl or l-phenylalanine）, have been synthesized and characterized by X-ray crys tallography. The structural analysis of complexes I and III reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual （N,O,O′）-bridged mode, resulting in asymmetric chromo phores of CdN4O and CdN5O in complex I, CdN4O2.and CdN5O in complex III, respectively. The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined. The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield. Moreover, the dias tereoselectivity of the reaction favors the formation of the syn-isomers.

关键词： Dinuclear cadmium(II) complex Amino acid Aldol reaction

Preparation of insoluble β-CD polymer and its application to enantiomers and isomers separation

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Journal of Central South university of Technology 2001年第1期8卷 57-59页

作者： YI Jian ming 1,TANG Kuo wen 2.(1.college of {2. and Chemical Engineering, Central South university, Changsha 410083, China 2.Department of Chemical Engineering, yueyang normal university, yueyang 414000, China) college of chemistry and Chemical Engineer{2. Central South University Changsha China Department of Chemical Engineering Yueyang Normal University Yueyang China

An insoluble β-cyclodextrin polymer cross-linked with epichlorohydrin was prepared, and its structure was identified with infrared spectrum. Colloid stationary phase was prepared by dissolving the polymer in the mixed solvent of diisopropyl ether, methylene dichloride and benzene and treated for 0.5 h by ultrasonication, and then was coated on a fused silica capillary column. The optimun reaction conditions are as follows: the mole ratio of epichlohydrin to β-cyclodextrin is 12.1:1, reacting at 65 °C for 2. h. The Chromatographic performance such as column efficiency, thermal stabilities and polarity were studied, two kinds of disubstituted benzene isomers and eight pairs of enantiomers were separated on the capillary column. The results show that the β-cyclodextrin polymer is suitable for use as a capillary gas chromatographic stationary phase, and possess excellent chromatographic properties in separating enantiomers and position isomers.

关键词： insoluble β cyclodextrin polymer capillary gas chromatography enantiomer position isomer separation

Molecular modeling and spectroscopic studies on the binding of guaiacol to human immunoglobulin

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Science China chemistry 2006年第6期49卷 550-559页

作者： HE Wenying1,2. YAO Xiaojun1, LIU Pengjun2. GAO Zhenxia2.& HU Zhide1 1. Department of chemistry, Lanzhou {2., Lanzhou 730000, China 2. Department of chemistry, Hainan normal {2., Hainan 571158, China Department of chemistry Lanzhou University Lanzhou China Department of chemistry Hainan Normal University Hainan China

The fluorogenic property of guaiacol was exploited for the first time to analyze the interaction with target protein as a probe by molecular modeling, fluorescence, circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. Molecular docking was performed to reveal the possible binding mode or mechanism and suggested that guaiacol can strongly bind to human immu- noglobulin (HIgG). It is considered that guaiacol binds to HIgG mainly by a hydrophobic interaction and there are two hydrogen bond interactions between the drug and the residues LEU 80 and ASP 65, which is in good agreement with the results from the experimental thermodynamic parameters (the enthalpy change △H0 and the entropy change △S0 were calculated to be 65.55 kJ·mol-1 and 132.95 J·mol-1·K-1 according to the Vant’ Hoff equation). Data obtained by the fluorescence spectroscopy indicated that binding of guaiacol with HIgG leads to dramatic enhancement in the fluorescence emission intensity along with significant occurrence of efficient Frster resonance energy transfer (FRET) from the residue of HIgG to the protein bound guaiacol. From the low value of fluorescence anisotropy (r = 0.06), it is argued that the probe molecule is located in the motionally unrestricted environment of the protein. The alterations of protein’s secondary structure in the presence of guaiacol in aqueous solution were quantitatively calculated by the evidences from FT-IR and CD spectroscopes.

关键词： guaiacol, human immunoglobulin, molecular modeling, fluorescence enhancement, Fourier transform infrared (FT-IR) spectroscopy, circular dichroism (CD).