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Synthesis,characterization,structures and magnetic property of chiral oxalate-bridged dicopper(Ⅱ) complexes

Science china chemistry 2010年第6期53卷 1255-1260页

作者： WU Ling1,WANG Jun2,ZHU CaiFei1,LIN YiJi1,CHEN LeiQi1,FAN Jun2 & ZHANG Hui1 1State Key Laboratory of Physical chemistry of Solid Surfaces department of chemistry,College of chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,{4. 2School of chemistry and Environment,South china normal University,Guangzhou 510006,{4. 1. State Key Laboratory of Physical chemistry of Solid Surfaces department of chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China2. School of Chemistry and Environment South China Normal University Guangzhou 510006 China

The oxalato-bridged dicopper(II) complexes [Cu2(μ-ox)(LRR)2(H2O)2(ClO4.2] (1),[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4.2](1a),[Cu2(μ-ox)(LSS)2(H2O)2(ClO4.2] (2) and [Cu2(μ-ox)(LRR)(LSS)2(CH3COCH3)2(ClO4.2] (3) [LRR = (8R,10R)-(-)-[4.5]-pineno2,2′-bipyridine,LSS = (8S,10S)-(+)-[4.5]-pineno-2,2′-bipyridine;ox2= oxalate] were first prepared.A possible mechanism for the formation of the chial dicopper(II) complexes was *** on elemental analysis,conductance measurement,UV-Vis spectra,CD spectra and X-ray single-crystal diffraction,the oxalato-bridged structures of 1 and 2 were deduced to adopt two Cu(II) ions and the bridged oxalate lying in the nearly same *** crystal structures of 1a and 3 reveal that the coordination geometry around each Cu(II) ion is an elongated and distorted octahedron and two axial solvent molecules and two perchlorate ions are anti to each other respectively in both binuclear *** solution CD spectra of 1 and 2 in the visible d-d range show very weak Cotton effects with peaks at 588 and 779 nm,which are approximately of mirror image,suggesting the optical activities may be derived from the vicinal effects of the chiragenic centers at the pinene group of LRR and LSS,*** 1 has been characterized by variable-temperature magnetic susceptibility and the data was least-square fitted to the Blenaey-Bowers *** exchange integral J was found to be -338.4.(4. cm-1,indicating a strong antiferromagnetic interaction between two copper(II) ions.

关键词： dicopper(II) complex chiral bipyridine μ-oxalate bridge crystal structure CD spectroscopy magnetic property

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Theoretical studies on ammonia oxide and its unimolecular reactions

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Chinese Journal of chemistry 1990年第5期8卷 405-411页

作者： HAN,Yun-Zhu ZHU,De-Zhong department of chemistry,Liaocheng Teachers Coilege,Liaocheng ShandongZHAO,Cheng-Da department of chemistry,Northeast {4. University,Changchun department of chemistry Liaocheng Teachers College Liaocheng Shandong department of chemistry Northeast Normal University Changchun

The unimolccular reactions of ammonia oxide H_3NO,isomerization and dehydrogenation, are investigated by ab initio MO calculations with the 4.31G basis *** geometries and energies of the reactant,transition states and products have been determined on the singlet potential energy sur- *** reaction ergodography along the intrinsic reaction coordinate(IRC)for the two reactions have been *** vibrational frequency correlation diagram of the two reactions are analyzed along the IRC.

关键词： IRC Theoretical studies on ammonia oxide and its unimolecular reactions mode

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DNA barcoding provides distinction between Radix Astragali and its adulterants

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Science china(Life Sciences) 2010年第8期53卷 992-999页

作者： GUO HaiYan1,2, WANG WeiWei2, YANG Ning2, GUO BaoLin3, ZHANG Sun2, YANG RuiJing2, YUAN Ye2, YU JunLin4. HU SongNian2, SUN QiShi1 & YU Jun2 1School of Traditional Chinese Materia Medica, Shenyang Pharmaceutical University, Shenyang 110016, china 2Key Laboratory of Genome Sciences and Information, Beijing Institute of Genomics, Chinese Academy of Sciences, Beijing 101300, china 3Chinese Academy of Medical Sciences, Peking Union Medical College Institute of Medicinal Plant Development, Beijing 100094. china 4.3} of {4., Tonghua normal College, Tonghua 134.02, china 1. School of Traditional Chinese Materia Medica Shenyang Pharmaceutical University Shenyang 110016 China2. Key Laboratory of Genome Sciences and Information Beijing Institute of Genomics Chinese Academy of Sciences Beijing 101300 China3. Peking Union Medical College Institute of Medicinal Plant Development Chinese Academy of Medical Sciences Beijing 100094 China4. Department of Chemistry Tonghua Normal College Tonghua 134002 China

Based on variable nuclear and/or organellar DNA sequences among vastly divergent species as well as morphologically indistinguishable species, DNA barcoding is widely applicable in species identification, biodiversity studies, forensic analyses, and authentication of medicinal plants. The roots of Astragalus membranaceus and A. membranaceus var. mongholica are commonly used as Radix Astragali in several Asian countries, including china, Japan, and Korea. However, in addition to the two species recorded in the Chinese Pharmacopoeia, there are twenty-three species from different genera including Astragalus, Oxytropis, Hedysarum, and Glycyrrhiza, which have been used as adulterants not only in trading markets but also by the herbal medicine industry. Therefore, a simple, reliable, and accurate classification method is important for distinguishing authentic Radix Astragali from its adulterants. In this study, we acquired data for 37 samples from four related genera within the family Fabaceae. Then we compared four candidate DNA barcoding markers using ITS, matK, rbcL, and coxI sequences from nuclear, chloroplast, and mitochondrial genomes, all commonly used for plants to identify genetic variations among genera, intraspecies, and interspecies. We observed higher divergences among genera and interspecies for ITS, which have the average Kimura 2-parameter distances of 4.5% and 14.1%, respectively, whereas matK was found to have sufficient divergence at the intraspecific level. Moreover, two indels detected in the matK sequence are useful for PCR studies in distinguishing Radix Astragali from its adulterants. This study suggests that the combined barcoding regions of ITS and matK are superior barcodes for Radix Astragali and further studies should focus on evaluating the applicability and accuracy of such combined markers for a wide range of traditional Chinese herbs.

关键词： Radix Astragali DNA barcode Astragalus adulterant identification

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Theoretical studies on the mechanism of the thermal decarboxylation and decarbonylation of a number of α-keto-acids

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Chinese Journal of chemistry 1995年第6期13卷 487-492页

作者： CHEN,Li-Tao CHEN,Guang-Ju FU,Xiao-Yuanchemistry department,Beijing normal University,Beijing 100875,china chemistry department Beijing Normal University Beijing 100875 China

Both processes of decarboxylation and decarbonylation of a number of acids including RCOCO2H,R=H,CH3,CH2F,CF3,CH=CH2,Ph,OH have been studied by semi-empirical MO theory AMI method to verify the reaction mechanism of each process and the effect of different substituents on *** calculated results are consistent with the experimental reports and can be summed up as follows:(1) The decarboxylation of these acids to form aldehydes and carbon dioxide is concerted and takes place through a 4.membered ring transition state in which a partial negative charge develops on the carbon of the α-carbonyl group,so that the inductive effect of some substituents is favourable for this process.(2) Their decarbonylation into carboxylic acids and carbon monoxide however is the attack of the OH on the carbon of the alkyl portion of the acid,forming a 3-membered ring transition state.(3) The activation energy of decarbonylation is lower than that of decarboxylation,since oxygen is more nucleophilic than hydrogen and also the strong OH bond need not to be broken.

关键词： Decarboxylation decarbonylation a-keto-acid

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Electrochemical behavior of C-(60) modified electrode in aqueous solutions

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Chinese Journal of chemistry 1994年第2期12卷 117-122页

作者： SHI, Zhan-Ling MAO, Yi-Ping TONG, Wei JIN, Li-Tongdepartment of chemistry, East china normal University, 3663 Zhong Shan Road (N), Shanghai 200062,{4. department of chemistry East China Normal University 3663 Zhong Shan Road (N) Shanghai 200062 China

The construction of adsorptive type C60 modified electrode and its electrochemical reduction and oxidation behavior in aqueous solutions are described in this report. Four pairs of one-electron transfer reduction and oxidation cyclic voltammetry is obtained in aqueous solution containing 30% CH3CN and 2% (C2H5)4.OH. It is reported in this paper that the C60 modified electrode also catalyzes the electrochemical reduction of dissolved oxygen in 4.% DMF and 2% (C2H5)4.OH aqueous solution and this might open a new field for the potential applications of C60 in electrochemistry and electroaualytical chemistry.

关键词： C60 modified electrode electrochemistry.

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Synthesis and Crystal Structure of Complex {[Cu（N-men）2（cda）2]·[Cu（N-men）2]·（ClO4.2}（N-men=N-Methylethylenediamine,cda=Carbamyldicyanomethanide Anion）

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Chinese Journal of Structural chemistry 2002年第6期 640-642页

作者： SHI Jing-Min XU Wen LU Su-QiaoWU Chang-Ju GE Jie-Chao ZHANG Zhi-De(department of chemistry, Shandong normal University, Jinan 250014. china)(department of chemistry, Taiyuan Education Institute, Taiyuan 030001, china)

Mononuclear complex {[Cu(N-men)2(cda)2]·[Cu(N-men)2]-(ClO4.2} was synthesized by sodium carbamyldicyanomethanide Na(cda), N-methylethylenediamine and hydrate copper perchlorate. The crystal belongs to the triclinic system, space group P 1 with a = 7.229(2), b = 8.114.2), c = 15.936(4. A, α = 80.511(4., β = 78.993(4., r= 72.118(4.°, V = 867.6(3) A3, Z = 1, C20H4.Cl2Cu2N14.10, Mr = 838.68, Dc = 1.605 g/cm3, F(000) = 4.4.and μ = 1.4.9 mm-1. The structure was refined to R = 0.04.0 and wR = 0.1289 for 2503 observed reflections (I > 2σ(I)). In the complex there exist two kinds of coordination models for Cu (II) ions. One is that the Cu (II) ion is coordinated by four nitrogen atoms which are from two N-men molecules, and a slightly distorted square planar coordinate environment is formed around the Cu (II) ion; the other is that the Cu (II) ion is coordinated by six nitrogen atoms, of which four are from two N-men molecules and the left from nitrile groups, resulting in a distorted octahedron around the

关键词： synthesis crystal structure copper complex

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α－OXOKETENE　CYCLIC　DITHIOACETALS　chemistry　──REACTION　OF　α，α－DIOXO（ESTER）KETENE　CYCLIC　DITHIOACETALS　WITH　BUTANONE

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Chinese Chemical Letters 1996年第2期7卷 95-98页

作者： Zai Ming ZHU Yong Ting XU(department of chemistry, Liaoning normal University,Delian, 116029)Qun LIU(department of chemistry,Northeast normal University,Changchun, 130024.Jie Han HU(Dalian Institute of Chemical Physics,Academia Sinica,Dalian, 116001) LIAONING normal UNIV DEPT CHEM DALIAN 116029 PEOPLES R CHINA NE normal UNIV DEPT CHEM CHANGCHUN 130024 PEOPLES R CHINA ACAD SINICA DALIAN INST CHEM PHYS DALIAN 116001 PEOPLES R CHINA

Cyclic dithioacetals of α,α-dioxo (estcr) ketene 3 were reacted with butanone to afford the Michael adducts 4. catalyZed by metal Na. This process provides a new method for the Synthesis of ring-compouds in goob yie... 详细信息

关键词： VERSATILE

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4.羟基-3-甲氧基肉桂酸的二阶非线性光学性质研究

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物理学报 2001年第9期50卷 1699-1702页

作者：赵波祁铁流南京师范大学化学与环境科学学院南京210097 南京军医学院化学教研室南京210099

分析了 4.羟基 3 甲氧基肉桂酸的分子结构特点 ,研究了其二阶非线性光学性质和固体样品的透光性能 .结果表明它具有很强的二次谐波产生和较宽的透光波段 ,截止吸收波长λcut off=4. 0nm ;抗光伤实验表明 ,该化合物具有较高的抗光伤阈值 ... 详细信息

分析了 4.羟基 3 甲氧基肉桂酸的分子结构特点 ,研究了其二阶非线性光学性质和固体样品的透光性能 .结果表明它具有很强的二次谐波产生和较宽的透光波段 ,截止吸收波长λcut off=4. 0nm ;抗光伤实验表明 ,该化合物具有较高的抗光伤阈值 .计算了其分子二阶非线性光学系数 β ,并与相应的衍生物作了比较研究 .

关键词： 4.羟基-3-甲氧基肉桂酸二阶非线性光学性质透光性能光电子学

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Inner Sphere Reorganization Energy for the Electron Transfer Reactions between M-C_6H_6 and M^+-C_6H_6 Complexes in Gaseous phase: An ab initio Computation

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Chinese Chemical Letters 1998年第11期9卷 0-0页

作者： Zheng Yu ZHOU Jian XU Chuan Song ZHANG Xing Ming ZHOU (department of chemistry, Qufu normal University, Qufu, 273165) Qufu normal Univ Dept Chem Qufu 273165 Peoples R China

The complex of sodium perrhenate with ester derivative of calix[4.arene having the stoichiometric formula [NaL]Reo4.H2O, was prepared. The X-ray structure analysis revealed that the sodium ion is coordinated to four ether and four carbonyl oxygen atoms giving a coordination number of eight with a tetragonal antiprism configUration. The complex cation [NaL]+ and anion ReO4.are linked by electrostatic attraction.

关键词： Calix arene sodium perrhenate, crystal structure

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Synthesis and Magnetism of μ-IsophthalatoOxovanadium(Ⅱ) Binuclear Complexes

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Chinese Chemical Letters 1997年第6期8卷 555-556页

作者： Cui Wei YAN Yan Tuan LI Dai Zheng LIAO (department of Biology, Qufu normal University, Qufu Shandong, 273165 Deportment of chemistry, Qufu Mirmal University, Qufu Shandong, 273165 department of chemistry, Minkai University, Tianjin, 300071) department of Biology Qufu Normal University Qufu Shandong 273165 China department of chemistry Qufu Normal University Qufu Shandong 273165 China department of chemistry Nankai University Tianjin 300071 China

Two μ-isophthalato oxovanadium(Ⅱ) binuclear complexes, [(VO)2-(IPHTA) (phen)2] SO4.(1) and [(VO)2 (IPHTA) (NO2-phen)2 ]SO4.(2) were syn thesized and characterized. The magnetism of complex (1) was studied

关键词： Synthesis and Magnetism of IsophthalatoOxovanadium Binuclear Complexes

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