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    24 November 1995, Volume 16 Issue 11
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    Articles
    Pattern Recognition Applied to MeX-REX3Type Phase Diagrams Investigation
    WANG Xue-Ye, YAO Shu-Wen, CHEN Nian-Yi
    1995, 16(11):  1657-1659. 
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    Pattern recognition or artificial neural network with chemical bond parameters as features or inputs is applied to MeX-REX3type phase diagrams investigation. After training with the data of known phase diagrams,the mathematical models obtained can be used to make computerized prediction of the formability,the chemical stoichiometry, the melting types(congruent or incongruent melting) and melting point of intermediate compounds,with good results.
    Studies on Phase Chemistry of Meyer′s Reaction of Compound Formation in Alkali Metal Bromide/Rare Earth Metal Tribromide Systems (I) ──A Study on Quaternary System CsBr-LaBr3-HBr(12%)-H2O(25℃)
    WANG Hui, RAN Xin-Quan, CHEN Pei-Heng
    1995, 16(11):  1660-1663. 
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    Phase chemistry relation of quaternary system CsBr-LaBr3-HBr (12%)-H2O at 25℃ was studied in this paper for the first time,the corresponding equilibrium diagram was constructed.Akind of new compound is discovered in the system,At the same time,X-ray powder diffraction, thermal analysis (TG and DTA) and polarization-character of the new compound obtained from the system were investigated.Comparing the system with quaternary system CsCl-LaCl3-HCl (13%)-H2O (25℃) ,bromide system and chloride system are very different in numbers,formula types of the compounds,and in phase chemical behavior.
    FTIR Characterization of Extracted Organic Phase in Saponified Organophosphoric Acid System Containing Lanthanide
    YAO Shu-Xin, WANG Du-Jin, WENG Shi-Fu, WU Jin-Guang
    1995, 16(11):  1664-1668. 
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    FTIR spectroscopy was used to investigate the coordination interaction of D2EHPA[di(2-ethylhexyl) phosphoric acid] with lathanide(Ⅲ)series(La3+→Lu3+, except radioactive promethium). P=O band shifts to the lower frequency when D2EHPA is saponified with concentrated basic solutions (NaOH,KOH or NH3· H2O).The coordination sequence of Na+,K+and NH4+with P=O group is NH+>Na+>K+. The frequency of P=O band in the extracted organic phase containing RE-D2EHPA complexes shifts to the lower wavenumbers as the lanthanide(Ⅲ)loading increases in organic phase,and the intensity of P=O band increases. FTIR spectra results show that the coordination ability of lanthanide(Ⅲ)series with P=O group is as follows:La3+<Ce3+<Pr3+<Nd3+<Sm3+>Eu3+>…>Lu3+, namely,the complexation intreaction of Sm3+with P=O is the strongest.In addition,the w/o microemulsion was gradually destructed with the entrance RE3+into the organic phase.
    Theoretical Studies on the Active Conformation for Double-Ring β-Lactam Antibioties
    ZHANG Shi-Guo, LI Hong, YANG Pin
    1995, 16(11):  1669-1671. 
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    The relationship between conformation and activity of three typical double-ring β-lactam antibioties:penicillin,△3-cephalosprins and △2-cephalosprins was studied in this paper. It is found that the configuration of the bridge carbon atom and the atom attached to the side amide is an important structural factor for their activities.
    Synthesis Characterization and Magnetism of μ-Nitronyl Nitroxide Binuclear Nickel (Ⅱ) Complexcs with Irregular Spin States
    SUN Bai-Wang, JIANG Zong-Hui, LIAO Dai-Zheng, HUAN Zhen-Wei, LIU Ai-Jian, WANG Geng-Lin
    1995, 16(11):  1672-1676. 
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    Four complexes of the general formula[Ni(pfpr)2]2NITR·nH2O, where pfpr=pentafluoropropionate, NITR=2-R-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide, and n=2(for R = ph);3(for R = phMe);4(for R = phCl,PhOMe),were synthesized,Thesecomplexes were characterized by elemental analyses,TG-DTA IR,electronic spectra,ESR and molar conductances. The structures of these complexes were discussed.The variable temperature(4-300 K) magnetic susceptibilities of the complexes[Ni(pfpr)2]2NITPHCl·4H2O and [Ni(pfpr)2]2NITPhOMe·4H2O were determined, indicating that the complexes have a magnetic behaviour of trinuclear system Ni(Ⅱ)-Cu(Ⅱ)-Ni(Ⅱ) with irregular spin state. The observed susceptihility data were fitted to those from theoretical magnetic equation,The exchange constants,J,were found to be equal to-152. 8cm-1and-174.6 cm-1,respectively,This indicates a stronger antiferromagnetic spin-exchange interaction between the radical and nickel (Ⅱ) ion.
    Studies on Interfacial Properties of HDEHP in n-Octane
    SUN Guo-Xin, YANG Yong-Hui, SUN Si-Xiu, SHEN Jing-Lan
    1995, 16(11):  1677-1679. 
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    The interfacial activity of HDEHP at n-octane/0.05 mol/L(H2,Na2)SO4interfacewas investigated at 298 K. Different adsorption isotherms such as the Gibbs,Szyzkowski and Polynomial were found as fits well to experimental interfacial tension isotherms. The interfacial adsorption parameters,CAC, Cmin,Aiand the free energy of adsorption △Gadwere calculated,respectively.
    The Electrochemistry of Nicotinamide-adenine Dinucleotide at a β-Naphthochinonsulfonicum Modified Gold Band Electrode
    JU Huang-Xian, MA Wei, CAI Chen-Xin, CHEN Hong-Yuan
    1995, 16(11):  1680-1684. 
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    The preparation of β-naphthochinonsulfon-icum(NQS) modified gold band electrode was studied.The electropolymerization process of NQS/PPy and the effects of experimental conditions on the behaviour of polymer membrane were discussed. The effect of anionic NOS on chronoamperometric curves in electropolymerization process was explained with the nucleation and growth theory. The modified electrode can catalyze the electrochemical reduction of NAD+at a gold electrode. At pH 7.0,the catalytic peak current is proportional to the concentration of NAD+in the range of 4.0× 10-3to 1. 5×10-3mol/L. The electrocatalvtical mechanism was also discussed.
    Synthesis of HIC Packing and Study of Its Chromatographic Characteristics
    LI Hua-Ru, CHEN Guo-Liang
    1995, 16(11):  1685-1689. 
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    A HIC support has been synthesized by using the domestic silica with major pore Diameter. The mixture of six standard proteins,α-Amylase in saliva and rIFN-γ from E. Coli.were separated through gradient elution by high-performance hydrophobic interaction chromatograply respectively.The chromatographic column has less irreversible adsorption,α-Amylase and lysozyme used in this study are almost quantitatively recovered on thiscolumn. The effects of salt concentration in eluent and temperature on retention behaviours of proteins were investigated with packing prepared,and the chromatographic attribution of the support has been demonstrated.
    The Application of Biotinylated Enzyme in Biosensor
    LU Xin, HE Pin-Gang, FANG Yu-Zhi
    1995, 16(11):  1690-1693. 
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    This paper describes the preparation of enzyme electrode with active multilayers glucose oxidase utilizing avidin-biotin technique under +0.6V potential, avidin is adsorbed on Pt electrode,then active multilayers of glucose oxidase can be immobillized with avidin bi-otinylated glucose oxidase complex. The biosensor has the characteristies of high sensitivity,wide response range,fast responding,and it can be repeatedly activized with avidin biotinylated enzyme complex solution. The limit of detection for glucose is 6. 0× 10-6mol/L. The linear relationship between △iand concentration of glucose holds in the range of 1.0× 10-5～1.0× 10-2mol/L.
    Enhancement of the Fluorescence of Zn(Ⅱ)-Morin Complex by Ionic β-Cyclodextrins and Its Analytical Application
    ZHU Li-Zhong, QI Zhi-Hong, JIN Hui, QI Wen-Bin
    1995, 16(11):  1694-1696. 
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    The effects of three ionic chemical modified β-cyclodextrins, hydroxypropyltrimethylamine β-CD(QA-β-CD),diethylaminoethyl β-CD(TA-β-CD)and carboxymethylβ-CD(CM-β-CD)on Zn(Ⅱ)-Morin fluorescence system were studied comparatively with β-cyclodextrin(β-CD).Amechanistic investigation has been conducted by using pyrene as the probe molecule for the media polarity changes in its surrounding microenvironment.The different effects of various CDs or CD-surfactant mixture on Zn(Ⅱ)-Morin system have been interpreted in terms of formation and geometric compatibility of multicomponent complex,fluorescence quantum yield ratio of fluorophoric complex to that of the corresponding fluorophoric reagent.Amethod is described for the fluorimetric determination of zinc based on the formation of Zn(Ⅱ)-Morin complx in the presence of CM-β-CD.
    The Studies of the Adsorption Behaviour of Isoquinoline on a Silver Electrode
    CEHN Jian, ZHAO Wen-Tao, HU Ji-Ming, XU Zhi-San, SHENG Rong-Sheng
    1995, 16(11):  1697-1699. 
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    Adsorption behavior of isoquinoline on silver surface in HCl solution was studied using SERS specta. The results show that isoquinoline is adsorbed silver via Ag-N＜ interaction in a perpendicular orientation. As the applied voltage is shifted to-0.6V, the strength of Ag-N＜ bond declines and the adsorption orientation is tilted.
    The Influence of Cu(Ⅱ)on Bovine Superoxide Dismustase's Activity
    XU Tong-Min, ZHOU Tian-Shu, JIN Li-Tong
    1995, 16(11):  1700-1702. 
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    The relation between the content of the cofactor Cu2+of bovine superoxide dismustase and enzyme's activity is studied.Different amount of Cu2+is added into SOD solution,then Cu2+in SOD reaches new distribution balance.The content of free Cu2+is determined by GFAAS after preconcentration on Nafion modified tungsten coil,and the enzyme's activity is detected by the method of 1,2,3-trihydroxybenzene auto-oxidation.
    Studies on Preconcentration and Separation of Trace Elements with Silica Gel Bonded by Acid Chrome Blue K
    ZHANG Yu-Guo, LIU Feng, LI Ke-An, LI Dong-Mei, WU Yan-Sheng, TONG Shen-Yang
    1995, 16(11):  1703-1705. 
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    This paper reports preconcentration and separation of trace elements with silica gel bonded by acid chrome blue K(ACBK·SG).ACBK·SG is stable in the range of 6 mol/L HCl to pH=8.0 and in common organic solvents such as ethanol or acetone,Maximum adsorption capacity of Pd(Ⅱ)on ACBK·SG is 172 μmol/g,Pd(Ⅱ)and Pt(Ⅳ)of 10-9/g can be separated from transition metal ions on ACBK·SG column and measured by spectrophotometry.
    Studies on Reactions of 6,6-Dialkylfulvenes with Grignard Reagents
    ZHENG Qing-Hui, LIU Yu-Long, HE Zheng-Jie, CHEN Shou-Shan
    1995, 16(11):  1706-1709. 
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    Exocyclic double bond addition and reduction took place when 6,6-dialkylfulvenes reacted with allylmagnesium halide and cyclopentadienyl magnesium bromide,respectively.Some titanium compounds Cp(C5H4)CRR1-CH2CH=CH2)TiCl2and(C5H4CHRR1)2TiCl2have been prepared by the complexation of substituted cyclopentadienyl anions obtained from the above reactions with(CpTiCl2)2O or TiCl4.However,no reaction was observed when 6,6-dialkylfulvenes were treated with ethylmagnesium bromide,n-butylmagnesium bromide,phenylmagnesium bromide,benzylmagnesium chloride, cyclopentadienyllithium and cyclopentadienylsodium,separately.Reaction mechanism of fulvenes with allylmagnesiumhalides and cyclopentadienylmagnesium bromide is discussed.
    Studies on the Derivatives of ω-Aryloxyacetoxy ω-(1H-1,2,4.Triazol-1-yl)acetophenone
    SHI Yan-Nian, LU Yan-Chang, FANG Jian-Xin, HUA Yan-Ling
    1995, 16(11):  1710-1713. 
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    Fifteen new ω-aryloxyacetoxy ω-(1H-1,2,4-triazol-1-yl)acetophenone have been synthesized.Their chemical structures have been confirmed by IR,1HNMR,MS and elemental analysis,The biological tests show that some of these compounds have good herbicidal,fungicidal or growth regulator activities.
    Synthesis of Tetramethyldisilandiyl Dicyclopentadienyl Lanthanide Complexes and Structure of[Me4Si2(C5H4)2Sm(μ-Cl)(THF)]2
    SONG Fu-Quan, LU Guo-Lhng, WANG Zhao-Yu, ZHOU Xiu-Zhong
    1995, 16(11):  1714-1717. 
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    The reaction of Me4Si2(C5H4)2Na2with LnCl3in THF leads to the formation of Me4Si2(C5H4)2LnCl(Ln: Nd(3), Sm(4), Gd(5),Y(6))or Me4Si2(C5H4)2Ln(C5H5)(THF)n Ln: La(1) n=1, Pr(2) n=0); complex 4 was recrystallized in THFto form [Me4Si2·(C5H4)2Sm(μ-Cl)(THF)]2in space group P21/c with a=1. 2982(3) nm,b=1. 2269(3)nm,=1.3681(2) nm,β=96.79(2)°,Z=2,R=0.068.
    Studies on Acylthiosemicarbazides and Related Heterocyclic Derivatives (XXV)──Synthetic and Spectroscopic Studies on1-[5′-Amino-1′- (4′-chloropbenyl)-1′,2′,3′-triazol-4′-acyl]-4-arylthiosemicarbazides
    ZHANG Zi-Yi, DONG Heng-Shan, YANG Shi-Yan, CHEN Mao-Qi
    1995, 16(11):  1718-1722. 
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    We prepared 13 new derivatives 3a-1,of 1-[5′-amino-1′-(4′- chlorophenyl)-1′,2′,3 ′- triazol-4 ′- acyl]-4-arylthiosemicarbazides by reaction of 5-amino-1-(4 ′-chlorophenyl)-4-carbohydrazide-1,2,3-triazole with several arylisothiocyanates; The structures of all compounds were confirmed by elemental analysis, IR,1HNMR and MS.
    Studies on the Syntheses,Crystal structure and Electron Spectra of Chloroethylenebisoxazoles
    ZNANG Wen-Qin, WANG Ming-Zhen, WANG Hong-Gen
    1995, 16(11):  1723-1726. 
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    Two new compounds trans-1,2-bis[2-(5-phenyloxazolyl)]dichloroethene(I) and trans-1,2-bis[2-(5-phenyloxazolyl)]chloroethene(Ⅱ) were synthesized.They were identified by elementary analysis,UV,mand MS.The crystal structure of Iwas determined by x-ray diffraction method.Iis monoclinic,space group P21with a = 0.8450(2)nm,b=0.6994(1)nm,c=1.5432(5)nm,β=102.38(2)°,V=0.8907 nm3,Dx=1.429g/cm3,μ=3.79 cm-1,F(000)=392,Z=2.Because of large chlorine atom attached to double-bond carbon atom,the planarity of Ⅰand Ⅲ became poor. Their UV and FLspectra shifted to the blue,and their fluorescence quantum yields got extremely lower than that of POEOP.
    The Reaction of Deactivated Napthalene Derivatives with Sulfur Trioxide
    ZOU You-Si, LIN Jing
    1995, 16(11):  1727-1730. 
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    The reaction of sulfur trioxide with deactivated naphthalene derivatives containing an electron withdrawing substituent, viz.-CHO,-COPh,-CO2H, and-CO2Me, indichloromethane as the solvent has been studied by analysis of the resulting mixtures of the sulfo derivatives with 1HNMR,Monosulfonation of 1-formylnaphthalene yields 5-S,6-S,7-Sand 8-S, in a 55: 9:6: 30 ratio, that of 1-benzoylnaphthalene 5-S,6-S and 7-S in a ratio of 83: 11: 6, and 1-nitronaphthalene only 5-S. 1-Naphthoic acid and its methyl ester upon SO3sulfonation and aqueous work-up both yield 5-and 8-sulfonaphthoic acid in a ratio of 65: 35 and 77: 21 respectively. The initially formed peri substituted product is the intramolecular anhydride of 8-sulfo-1-naphthoic acid. All the 2-substituted naphthalenes upon SO3sulfonation yield 5-S and 8-S.
    Catalyzed Oxidation by Rhus Vernicifera Laccaxe(X)──The Laccase-catalyzed Oxldation of Cateckols Containing tert-Butyl Group and the Microenvironment Effect of Rhus Laccase
    WANG Guang-Hui, HUA Jian-Li
    1995, 16(11):  1731-1736. 
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    The dissociation and Laccase-catalyzed oxidation of six catechols containing tertbutyl group were investigated spectrophotometrically under pH 6.0～8.0 conditions. The studies show that in the presence of tert-butyl group,not only to bonding of these substrates is improved,but through the influence of the microenvironment effect of laccase,the dissociation of these substrates is promoted and the enzymatic reaction can take place under condition of weak acidity(pH6.0), which is far from the first-order dissociation of these sub-strates. Because of the influence of the characterization of tert-butyl group and the microenvironment effect of laccase, these substrates can be transformed by laccase into corresponding o-quinones at pH6.0,and they have a synthetic value,Moreover,using ESR-spin stabilization technique,the o-semiquinone anion-radicals generated during the enzymatic reaction were trapped in pH6.0,and the superfine structures of the ESRspectra were discussed.The result demonstrate that the Laccase-catalyzed reaction of these substrates underwent the stage of the proton transportation and one-electron oxidation.
    Studies on the New Packings of High Performance Ion Exchange Chromatography for the Separation of Proteins(Ⅳ)──The Synthesis and Application of the Packings of the Strong Anion Exchange Chromatography
    CHANG Jian-Hua
    1995, 16(11):  1737-1739. 
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    The silica with epoxy group reacted with diethylamine or polyethyleneimine, then the product reacted with methyl iodide or benzyl chloride and yielded the packings of strong anion exchange chromatography with quaternary ammonium cation. These packings can be used for separating proteins and biotechnology product, such as IFN-γ,GM-CSF and HCG.
    Syntheses and Biological Activityies of 1-(Substituted Isoxazolyl)-1,2,4-triazoles and 1-(Substituted Pyrimidinyl)-1,2,4-triazoles
    HUANG Zhen-Nian, LI Zheng-Ming
    1995, 16(11):  1740-1743. 
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    α-Oxo-α-(1,2,4-triazol-1-yl)ketene dithioacetals 1 reacted with hydroxylamine hydrochloride in the presence of barium hydrate in refluxing ethanol to give a mixture of isomeric 1-[5-alkylthioisoxazolyl)-1,2,4-triazoles 2 and 1-(3-alkylthioisoxazolyl)-1,2,4-triazoles 2'].Their mass spectral fragmentation was discussed respectively. On treatment with guanidine and thiourea in a refluxing sodium ethoxide, 1 afforded 1-(substitutedpyrimidinyl)-1,2, 4-triazoles 3 and 4. The preliminary biological tests show that isoxazolyltriazoles 2 and 2' have plant-regulatory activities.
    Syntheis and configuration of Dibenzo-Crown Ethers Derived from Salicyl Alcohol
    HUANG Shu, MENG Jie, MAO Zhi-Hua, TIAN Bao-Zhi
    1995, 16(11):  1744-1746. 
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    Two dibenzocrown ethers(1 and 2) were synthesized by the reaction of salicyl alcohol with NaH and di- and triethyleneglycol ditosylates in DMF, Their structures were characterized by elemental analysis, IR,1HNMR and MS. Dibenzo-20-crown ether(1)was confirmed as anti-configuration by the X-ray diffraction analysis of its single crystal.According to the configuration of 1, the reaction mechanism of the synthesis is proposed.
    The Chemical Constituents of Pedicularis Chinensis
    WANG Chang-Zeng, JIA Zhong-Jian
    1995, 16(11):  1747-1748. 
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    Two new compounds, 1 and 2, were obtained from the roots of Pedicularis chinensis Maxim,On the basis of spectral data and chemical evidence,compounds 1 and 2 were elucidated to be rel-(6R, 5R,9R)-(2-oxa-bicyclo[3,3,0]oct-3-one-8-en-9,8-diyl)dimethanol and 3-β-butoxy-3,4-dihydroaucubin, respectively.
    The Disproportionation of Hydroalkoxysilanes Catalyzed by KF
    ZHANG Zeng-You, SHANG Jian, Zhou Xiou-Zhong
    1995, 16(11):  1749-1751. 
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    The disproportionation of(C2H5O)3SiH and CH3SiH(OC2H5)2using DMF or THF as the solvents in the presence of KF(and 18-crown-6)was studied and the effects of catalyst system,temperature and solvent on the disproportionation were discussed. The results showed that KF/18-crown-6 is a good catalytic system for the disproportionation of hydroalkoxysilones, the solvent and temperature affect obviously the reaction.
    Production and Photoionzation of Clusters for CH3CN/C2H3Cl Complex System
    SHENG Liu-Si, QI Fei, LUO Zhi-Yong, GAO Hui, ZHANG Yun-Wu
    1995, 16(11):  1752-1756. 
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    Photoionization of CH3CN/C3H3Cl complex system is proceeded by synchrotron radiation single photon in a diameter 70μm cw supersonic jet with a quaduapole mass spectramer, The cluster ions(CH3CN)m(C2H3Cl)m+are observed. The C2H3ClCN+ion(m/e=88), whose mass peak is high, is produced by ″intramolecular″ion-molecule reactions withinionized clusters, The heat of the exothermic reaction makes the bond H3C&CN broken.The result of ab initio calculation demonstrates that the C2H3ClCN+ion is stable. Photoionization efficiency curves and ionization potentials are obtained.
    DV-XαEmbedded Cluster Studies:Chemisorption of Oxygen Species on NiO(100)Surface
    LU Xin, XU Xin, WANG Nan-Qin, ZHANG Qian-Er
    1995, 16(11):  1757-1760. 
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    Chemisorptions of oxygen species on cation site of NiO(100)surface have been studied by means of DV-Xα embedded cluster model calculations, Calculational results show that: i) Adsorption of molecular O2species results in an adsorption state of O22-, which subsequently faciliates the dissociation of the O-O bond to give rise to an O-adspecies; ii)the adsorptions of all the investigated oxygen species increase the oxide state of the cations.
    Propertis of Poly(o-phenhlenediamine)-Film Coated Electrode and Its Effect on Kinetics of Benzoquinone Reduction
    WEI Dong, WU Hui-Huang
    1995, 16(11):  1761-1766. 
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    The electrochemical behaviour of poly-o-phenylenediamine (PPD)film coated electrode in pH 7. 0 phosphate buffer solution was studied by voltammetry and in-situ IRreflectance spectroscopy. The results showed that PPD exhibits redox activity at the potentials more negative than0.0V (SCE), and the redox process is accompanied by doping and undoping of H2PO4- ions, showing that the polymer is positively charged. The reduction of benzoquinone at the PPD electrode occurs in the electroactive potential range of PPD. RDEexperiments indicated that benzoquinone is able to penetrate into the polymer matrix and exchange electron with the polymer. According to the model of PPD as a conducting polymer,the kinetics of benzoquinone reduction was analyzed and the influencing factors were discussed.
    The Study on Conformation of O,O′-2,2′-Bisbenzo,S-benzyl Dithiophosphate
    GUO Hong-You, REN Xin-Gang, CAO Wei-Liang, WANG Zuo-Xin
    1995, 16(11):  1767-1770. 
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    The energies and conformations of single molecule of the title compound have been investigated by using ASED-MO method.Four stable conformations corresponding to different minima on the potential surface were obtained.The theoretical analysis has been made for the distributions and transformations of the four stable conformations and the relationship between single molecule and that in crystal.
    Studies on the Energy Band Structure and Conducting Mechanism of Reduced-state Polyhalogenoaniline
    LIN Xian-Jie, XU Long-Jun, ZHAO Cheng-Da
    1995, 16(11):  1771-1774. 
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    In this paper,the energy band structure and the conducting machanism of polyhalogenoaniline have been studied by using EHMO-CO method. The result showed that the carrier of polyhalogenoaniline is monopolaron and the polaron lattice is formed on the chains of the polyhalogenoaniline, We find that substitution affects the conductivity of the polymer is due to that the band width of the highest occupied energy band(HOBW) is changed, but the doping raises greatly the conductivity of the polymer because the band gap between the HOBW and the LUBW is markedly lessened.The role of d-orbital in the energy band of polymer is discussed.
    Ab Initio Calculations on Pd2-CO Cluster Model
    XU Xin, WANG Nan-Qin, LU Xin, ZHANG Qian-Er
    1995, 16(11):  1775-1779. 
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    Pd2-CO cluster model has been investigated by means of ab initio calculations with metallic basis set of Pd atom ζ mECP , Based on the Metallic State Principle and Bond-Prepared State Principle,Pd2-CO cluster has been carefully studied in order to model the bridged CO on Pd surface. The calculation results showed that an electron should be excited from the occupied Pd2(5s+5s)orbital to the empty Pd2(5s一5s)orbital to be prepared for the bonding with CO. This excitation not only reduced the repulsion between Pd2(5s+5s) and CO5σ,but also facilitated the interaction between Pd2(5s一5s)and CO2π*.
    Synthesis of Nitrogen-Doped Fullercnes, Carbon Nanotubes and Nanocrystals in Nitrogen Atmosphere
    ZHAN Meng-Xiong, YU Rong-Qing, WANG Yu-Huang, YANG Shi-Yao, CHENG Da-Dian, LIU Chao-Yang, ZHENG Lan-Sun
    1995, 16(11):  1780-1782. 
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    Nitrogen-doped fullerenes,carbon nanotubes and nanocrystals have been synthesized simultaneously for the first time through the arc-discharge of graphite electrodes in a pure nitrogen atmosphere.They were prepared in a reaction chamber filled with pure nitrogen gas at the pressures of 10664-53320 Pa. Apotential of 20-30 Vand a current of 100-140 Aac were applied between two pure graphite rods in the chamber. Nitrogen-doped fullerenes were discovered in soot and characterized by laser desorption mass spectrometry and X-ray photoelectron spectroscopy.Both C60- and C59N-can be observed on laser desorption mass spectrometry. In addition, a series of nitrogen-substituted carbon cluster anions appear on low-mass section of the mass spectrum. The XPS result also confirms the existence of nitrogen-doped fullerenes. Spectral peaks of C(1s)and N(1s) with binding energies of 288.1 eV and 402.8 eV can be distinguished.The latter has a single sharp feature, differing significantly from N2adsorbed on a C60film,which produces a spectral peak near 400.2eV. Carbon nanotubes were observed in deposit.The deposit formed in a nitrogen atmosphere is much richer in carbon nanotubes than that formed in a heliumor argon atmosphere.The carbon nanotubes were investigated by transmission electron microscopy(TEM).Some unusual structural patterns of carbon nanotubes have been observed from the TEM images.In addition, nanocrystals were observed by TEM after the deposit was treated in the corrosive solution. The nanocrystals may be C3N4.
    Carbon Namotube Prepared by Catalytic Pyrolysis of Methane
    CHEN Ping, WANG Pei-Feng, LIN Guo-Dong, ZHANG Hong-Bin, TSAI Khi-Rui
    1995, 16(11):  1783-1784. 
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    Carbon nanotube can be produced by the catalytic pyrolysis methane on Ni catalyst at 450℃, TEM observation reveals that almost all the carbon filament produced by this method was in the form of tubular structure. Outer-diameter, length of the carbon nanotube as well as their productivity are governed by reaction temperature and the performance of the catalyst. The separation and purification of the carbon nanotube produced from the catalyst powder are easily performed by washing with aqueous solution of nitric acid followed by oven-drying at 200℃; nearly all powder of the catalyst can be removed away and comparatively pure carbon nanotube can be obtained.
    A New Algorithm for the Permanent Approach to Valence Bond Theory
    WU Wei, MO Yi-Rong, ZHANG Qian-Er
    1995, 16(11):  1785-1786. 
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    Based on Ryser permanent expansion method, a new algorithm for the so-called permanent approach to valence bond theory is presented. With the new algorithm, Hamiltonian and overlap matrice elements are calculated directly, rather than by the"sequential"Laplace expansion method used in our previous work. The algorithm will be more easily implemented than that based on Laplace expansion method.
    Determination of Interface Size in Multi-Phase System Ushing SAXS Method
    JIN An-Ding, LI Gang, WANG Jia-Liang
    1995, 16(11):  1787-1789. 
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    Anew method for determining the specific interface between different phases in a multi-phase system was recommended and as examples a group of SMSI catalyst Rh/TiO2was tested.The method,which is based on the calculation of correlation function and electron density fluctuations, was started from the intensity data collected on a rotating-anode X-ray diffraction system. The data were used to calculate the correlation function γ(0) value and the specific interface in multi-phase system using formulas given by Brumberger,et al.The results were valuable for chemists to explain the experiments in catalysis research work such as SMSI catalysis study and so on.
    Synthesis of Non-symmetric Octaalkoxy-Substituted Phthalocyaninato-polysiloxane and Its Monomolecular Films
    MU Jin, XIA Qiang, HUA Yu-Jing, ZHOU Wei-Dong, XIAO Tong
    1995, 16(11):  1790-1792. 
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    Poly[(2,3-dimethoxy-9, 10, 16, 17,23,24-hexaoctoxyphthalocyaninato)siloxane] was synthesized.UV-Vis spectra indicate that the strong cofacial interaction occurs between Pc units in the same main chain and the molecular aggregates of the polymer are formed in the LB film, The surface pressure-area isotherm shows the existence of the sharp phase transitions during the compression of the film. The polymer can be deposited on solid substrates to form LB films.
    Studies on Isomerization and Thermal Eliminaton of Dinitrodiazophenol Using AM1 Met Method
    LI Yong-Hong, WANG Sheng, HONG San-Guo, XIAO He-Ming
    1995, 16(11):  1793-1795. 
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    he isomerization and thermal elimination of dinitrodiazophenol (DDNP)were investigated by using the AM1 method.The resuIts showed that the quinoid isomer is more stable than cyclic isomer; the activation energy of the isomerization(quinoid isomer→cyclic isomer)is 181.506 kJ/mol; the activation energies of eliminating NO2on atom C(6)and C(4) of quinoid isomer are 120.361 kJ/mol and 130.273 kJ/mol,respectively; and those ofcyclic isomers are 131. 808 and 122. 708 kJ/mol,respectively.
    Oxidative Coupling of Methane and in situ FTIR Spectra Study of Oxygen Adspecies over SrF2/Nd2O3Catalysts
    LONG Rui-Qiang, WAN Hui-Lin, LAI Hua-Long, KSAI Khi-Rui
    1995, 16(11):  1796-1797. 
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    For oxidative coupling of methane(OCM)at 750℃, the C2selectivity and yield over SrF2/Nd2O3catalyst system were found to be obviously higher than those over Nd2O3.The in situ FTIR spectra were taken at OCM reaction temperature(700℃)and showed that O2-adspecies was observed on 50%SrF2/Nd2O3catalyst, which might be the active and C2selective oxygen species.
    Random Walk on a Circle
    XU Xue-Tong, YANG Yu-Liang
    1995, 16(11):  1798-1801. 
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    We provide a theory about the random walk on a circle with radius R. The analytical form of the probability distribution of the end to end vector after n steps ω(θ,π)and theaveraged square of end to end distance <r2> are given, Our findings are the following: whenR2》nl2,<r2>≈nl2which restores the result of the random walk in a 1Dinfinite space lattice;when R2《nl2,<r2>≈πR2/3.The general expressions for the average end to end distance<|r|> and the kth moment <rk> are given.
    Studies on the Drug Controlled Release Materials of Polyphosphate Containing Tyrosine Ester
    FAN Chang-Lie, HU Bin, ZHUO Ren-Xi
    1995, 16(11):  1802-1805. 
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    Novel polyphosphates containing tyrosine alkyl ester were synthesized by solutionpolycondensation in the presence of catalytic amount of DMAP. The release properties of methotrexate(MXT)from these polyphosphates and their microcapsules including MTX were studied.
    Synthesis of Crosslinked Polystyrene Supported Platinum Complexes and Their Catalytic Properties for Hydrosilylation
    KAN Cheng-You, YUAN Qing, ANG Yong, KONG Xiang-Zheng
    1995, 16(11):  1806-1809. 
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    Mercaptomethylated and crosslinked polystyrene supported platinum complexes were synthesized and used for hydrosilylation as the catalyst, and they have a high activity in hydrosilylation of olefines and acetylenes with dichloromethylsilane(DCMS),particularly for compounds with one conjugated substituent such as styrene, phenyl acetylene and trialkyl vinyl silanes. Hydrosilylation activity is obviously reduced for compounds with electron acceptor groups adjacent to double bond as butyl acrylate, and they have no activity for methyl methacrylate. These catalysts have a good reusability.
    Synthetic Methods of Acrylate Polymer Latexes Modified with Organosilicons and Their Film Properties
    KONG Xiang-Zheng, KAN Cheng-You, LUO Dong, YUAN Qing
    1995, 16(11):  1810-1813. 
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    Acrylate copolymer latexes modified with organosilicons were prepared using monomer emulsion addition process, batch and initiator addition processes, The results of particle morphology and latex stability, obtained from different copolymerization processes,showed that stable latex can be produced only by monomer emulsion addition process.Mechanisms of the emulsion polymerization were discussed.Films were casted from diluted latexes. Hardness, water absorption, solubility in THF of various films were also studied, it was found that polymerization and filmproperties are significantly influenced by organosilicon content.The cross-linking density of copolymers was increased and water absorption decreased with increase in organosilicons. Keeping the total organosilicon content constant (MATS+D4at 10% by weight) and with increasing D4/MATS, latex film hardness was seriously diminished when D4/MATS was below 1, and a slow decrease was observed whenthis ratio was above 1.
    Aggregation Behaviour of Sulfonated Butyl Rubber Ionomers in Solution(I)──ESR Spectra Analysis
    ZENG Zhao-Hua, FENG Ke, LI Zhuo-Mei, ZHANG Jian-Hui
    1995, 16(11):  1814-1817. 
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    Electron Spin Resonance(ESR)measurements on manganese-ionomers of sulfonated butyl rubber(Mn-SIIR)show that polar cosolvents such as alcohols could solvate the ionic groups and then destroy ionic aggregation. The solvation would be weakened and the ionic aggregation increased as temperature increased.These are in agreement with the results from viscosity measurements of ionomer in mixed solvents. But the content of ionicgroups in solution had no significant effect on the degree of ionic aggregation.
    The Synthesis of PDHPV and Its Electroluminescent Characters
    LI Chen-Xi, YIN Chun, HUANH Wen-Qiang, YIN Shou-Gen, ZHANG Hui-Qi, HE Bing-Lin, GAO Jun, HUA Yu-Lin
    1995, 16(11):  1818-1820. 
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    A kind of soluble electroluminescent polymer poly(2,5-diheptoxy-1,4-phenylenevinylene)(PDHPV)was synthesized and its electroluminescence(FL)properties were investigated. Amilder condition in the synthesis of the MeO-precursor was found,i.e.MeOH-H2O mixed solvents can turn the sulfonium precursor into MeO-precursor at ambient temperature, Two kinds of devices were fabricated by drop coating: ITO/PDHPV/AL,ITO/PDHPV/Alq3/Al(Alq3:8-hydroxyquinoline aluminium).The luminescence spectra produced in these devices are essentially the same as that of the photoluminescence(PL)of PDHPV. The Alq3 layer acts as the electron-conducting, hole-blocking layer, The efficiency and brightness of the double-layer device was improved. Compared with the analogous double-layer device fabricated with PPV and Alq3: ITO/PPV/Alq3/Al, a strange phenomenon was observed, Alq3 instead of PPVemits light, this is due to the wider band gap of PPV (2.5 eV)than that of PDHPV(2.1 eV) which blocks the creaticn of the singlet excitons in the polymer layer. The band gap of PDHPV narrower than that of PPV makes the radiative decay occur in the PDHPV layer instead of Alq3 layer. The double-layer device has a betterstability.
    A Study of the Effect of Benzyl Alcohol on Micellar Solution of F127 by Eluent Gel Permeation Chromatography
    WANG Qing-Guo, LIU Bo, CAI Li-Xing, LI Guang-Ya, Phce C. Booth C., CHENG Rong-Shi
    1995, 16(11):  1821-1822. 
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    A chromatographic method for study of effect of alcohol on micelle formation of nonionic surfactant in aqueous solution is described. The method, based on eluent gel permeation chromatography(E-GPC) , can detect critical micelle temperature(CMT) and micellemdlecule equilibrium of the system. The experiment shows the presence of benzyl alcohol decreases CMT of F127 aqueous solution up to 10℃ and makes micelle-molecule equilibrium shift towards micelle formation.
    Kineics and Models of Carbon Fiber Oxidation at High Temperature Atmosphere in Air
    TANG Long-Gui
    1995, 16(11):  1823-1825. 
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    An investigation on the process of carbon fiber oxidation at high temperature atmosphere in air was done by means of the non-isothermal multi-heating rates, The oxidation kinetics and models were given out in the form of the empirical equations. Based on them,it is possible to predicte successfully the weight loss, oxidation rate and life-time of the carbon fiber during the process under different conditions of the temperature (T1,T2) and interval(t).
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