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    24 April 1996, Volume 17 Issue 4
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    Articles
    Studies on Heteromacrocyclic Polyether(Ⅻ)──Liquid Membrane Transport Properties of Metal Cations by Oxa-,Thia-,Selena- or TeIlura-Crown Ether
    LI Wei-Ping, GONG Shu-Ling, LIU Xiu-Fang, LU Xue-Ran, XU Han-Sheng
    1996, 17(4):  501-504. 
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    The liquid membrane transport rates of the nitrate saIts of Na+,K+, Ag+ andPb2+ by 10-tellurabenzo-15-crown-5(TeB15C5)were firstly determined, and compared withthose by the corresponding benzo-15-crown-5(B15C5), 10-thiabenzo-15-crown-5(SB15C5)and 10-selenabenzo-15-crown-5(SeB15C5).At the same time,the effects of the concentrations of SeB15C5 in the membrane phase and K+ in the source phase on the transport rates of K+were also investigated.The experimental data indicate that the relationship is linear between the transport rates of K+ and the concentrations of SeBl5C5 and K+ respectively.Thetransport rates of Na+,K+ and Pb2+ by TeB15C5 are larger than those by SB15C5 andSeB15C5,but the transport rates of Ag+ by SB15C5 and SeB15C5,especially by SeB15C5,are much larger than those by TeB15C5.SB15C5 and SeB15C5 show a very high transportselectivity for Ag+ over Na+,K+ and Pb2+,and can be used to separate and recover noblemetals such as silver.
    Expert System RECORES for Classification and Prediction of Resistlvities of Rare Earth Complex Oxides
    LU Wen-Cong, YAN Li-Cheng, LIU Hong-Lin, CHEN Nian-Yi
    1996, 17(4):  505-508. 
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    The relationship between the resistivities of rare earth complex oxides and theircharacteristic parameters was studied by chemical bond parameter-pattern recognitionmethod.An expert system,RECORES,for the classification and prediction of resistivitiesof the compounds has been built on the basis of the classification diagrams and rules found bythe principal component analysis and Fisher method.The expert system posesses the basicproperties of common expert system as well as the pattern recognition package used as a visual and effective tool to save, represent and acquire the knowledges.
    Synthesis, Crystal Structure and Spectral Properties of [Mn2(bzacen)2(MeOH)2(μ-4,4′-bipy)](ClO4)2
    LIU Shi-Xiong, FENG Yun-Long
    1996, 17(4):  509-514. 
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    The title complex[Mn2(bzacen)2(MeOH)2(μ-4,4′-bipy)](ClO4)2 crystallizes themonoclinic system, space group P21/n, with parameters: a=1.3082(3)nm,b=1.2713(3)nm,c=1.8006(5) nm,β=110.91(2)°,V=2.798(2)nm3,Dc=1.45g/cm3,Z=2,F(000)=1268,μ=5.97 cm-1.The final Rvalue is 0.0580 for 2961 observed reflectionswith I≥3σ(I).The complex cation has a bimeric structure with a 4,4′-bipyridine bridgingthe two[Mn(bzacen)(MeOH)]+ moieties.Mn(Ⅲ)ion shows a distorted octahedral coordination with four bonds to N2O2 donor atoms of Schiff base ligand bzacen2- in the basic plane,one Oatom of the MeOHand one Natom of the bridging 4,4′-bipyridine being in the twoopposite sites.The shifts of vC=N,vC=O and vC=C to lower frequencies in IRand Raman spectraindicate that the ligand bzacen2-is coordinated to Mn atom through its nitrogen and oxygenatoms, The lines observed at 463 cm-1 and 401 cm-1 in Raman spectrum are assigned toMn-Oand Mn-Nvibrations, respectively.The obsorption at about 1110 cm-1 shows that ClO4- is not coordinated with Mn atom.There are π-π* transiti On,d-π* chrge-transfer transitlons and d-d* transition in electronic spectrum.The current potential curve in acetonitrileexhbits that Mn(Ⅲ)is in a stable valence state.
    Studies on Extraction of Acetic Acid with TBP in Various Diluents
    YANG Yan-Zhao, YANG Yong-Hui, SUN Guo-Xin, MENG Xiang-Jian, WANG Zhen-Qiao, SUN Si-Xiu
    1996, 17(4):  515-518. 
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    The extraction of acetic acid with TBPin different diluents was studied.The decreasing order of extraction ability of TBPis as follows:toluene,benzene,cyclohexane,kerosene, tetrachloride, chloroform and methyl isobutylketone.The effect of temperatureon the extraction equilibrium was also investigated and the enthalpy of the extraction was obtained.The relationship between the extraction equilibrium constants Kex,and the physicalparameters of diluents can be derived.The extraction mechanism and equilibrium were examined by measurements of IRspectrophotometry.
    Synthesis and Crystal Structure of a Diglycine Dodecaaquo Dierbium Perchlorate
    ZHAO Jian-Jun, JIN Tian-Zhu
    1996, 17(4):  519-522. 
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    The title complex[Er2(Gly)2(H2O)12](ClO4)6.4H2) was synthesized.It's crystal structure was determined by four-circle X-ray diffractometer.The crystal is monoclinic with space group P21/n.The unit cell parameters are as follows:a=1.0571(2)nm,b=1.0837(2)nm,c=1.7728(4)nm,β=90.09(3)°,V=2.0309(7)nm3,Z=2,Dc=2.239 g/cm3.The final deviation Rand Rw is equal to 0.055 and 0.061 respectively.The two erbium ions in[Er2(Gly)2(H2O)12(ClO4)6·4H2Oare connected with two bridging carboxyl groups.Six water molecules are coordinated to each erbium ion, Therefore, there are eight oxygen atoms coordinated to each erbium, forming a distorted square antiprism arrange ment.
    Relationship Between the Structures and Reaction Activity for Hydrothermal Synthesis of MZrO3(M=Ba,Sr,Ca)
    ZHENG Wen-Jun, PANG Wen-Qin
    1996, 17(4):  523-525. 
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    For hydrothermal synthesis of MZrO3(M=Ba,Sr,Ca),the synthetic regularitiesand hydrothermal conditions were investigated, and the reaction process was analyzed on thebasis of the structures and properties of ZrO2·xH2O gelate and MZrO3(M=Ba,Sr,Ca).We proposed that the structure unit formed in the reaction process, in which alkali-earth ioncombined with[Zr4(OH)8(H2O)16]8+ion.When the structure unit continually grew, the reactive activation energy increased with the decreasing of M2+(M=Ba,Sr,Ca)ionic radius,because the incorporation of a smaller A-ion in the perovskite-type structure is accompaniedby rotation of the ZrO6 octahedra.
    Synthesis of Copper(Ⅱ)Complex with meso-Tetra(4-hydroxyphenyl)Porphyrin by Solid State Reaction
    ZHANG Yin-Han, LIU Yun-Ping, NIO Qi-Dao, SONG Zi-Tai
    1996, 17(4):  526-527. 
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    The metalloporphyrin coordination complex(copper with meso-tetra(4-hydroxyphenyl) porphyrin)was synthesized by solid state reaction at room temperature.The molarratio of copper acetate(Cu(Ac)2·H2Oto T(4-HP)Pis 1:1.The reactants are mixed andgrinded in the agate mortar for 15 min.The reaction rate was detected by visible absorptionspectra.The soret band of ligand(422 nm)disappears,after the grinded sample is laid up for10 h at 12℃, and the soret band of complex appears at the 427 nm(the solvent is DMF).The reaction was finished within 1.5 h at 35℃, and was completed within 30 min at 35℃by initiation of ethanol(95%).The composition and conformation of products are characterized by elementary analysis,IR,fluorescence and DTA, Compared with the compound synthesized in liquid state in DMF,the composition and structure of the complex are the same.
    Construction of End-Column Chemiluminescence Detection System for Capillary Electrophoresis
    HUANG Bo, LI Jian-Jun, CHENG Jie-Ke
    1996, 17(4):  528-530. 
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    Aself-constructed end-column chemiluminescence detection system for capillary electrophoresis has been described.Luminol and N-4-aminobutyl-N-ethylisoluminol(ABEI)H2O2 chemiluminescence systems are used to illustrate the feasibility of this instrument.Comparatively sharp and symmetric electrophoretic peaks are obtained with the detection limit of 50 fmol and 290 fmol for luminol and ABEI, respectively, Cr(Ⅲ) and Zn(Ⅱ) ions are separated with rather sharp peaks due to their fast catalytic effect on the luminol-H2O2 reaction.The theoretical plate number reaches 1.51×105 and 1.86 ×105 for Cr(Ⅲ)and Zn(Ⅱ),the detection limits of which are 15 amol and 2.07 fmol,respectively.
    Learning Association by Self-Organization Neural Tree Applied to the Estimation of Formation Condition for Amorphous Phase of Trinal Fluorides
    CAI Yu-Dong, TANG Yun, LU Wen-Cong, YAN Li-Cheng
    1996, 17(4):  531-534. 
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    In this paper,Learning Association by Self-organization neural tree (LASSONT)was applied to the estimation of the formation condition for amorphous phase of trinal fluorides by using the chemical bond parameters,and the intelligential expert systems for computer estimation was established.The classification results show that the performance of theneural tree is good,and therefore LASSONTmight be referred as an effective assistant technique for the investigation of formation condition of amorphous phase of trinal fluorides.
    Determination of Iron(Ⅲ)by Fiber Optic Kinetic Method with Flow Injection Analysis and Fluorescent Probe
    ZHANG Zhu-Jun, WANG Jun-Feng
    1996, 17(4):  535-538. 
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    The properties of anmnonaphthalene-8-sulfonic acid(ANS)as the fluorescentprobe of surface active agent have been studied.The micellar assemblies of ANS-Brij35 hasfirst been used as kinetic indicator of fluorescence.Anew method using flow injection analysis(FIA) and fiber optic to determine iron(Ⅲ)has been developed based upon the fluorescence quenching of ANS-Brij35 by the oxidation of hydrogen peroxide, in which the iron(Ⅲ)is an effective catalyst.The linear calibration curve of iron(Ⅲ)is obtained in the range of 5～300 ng/mL.The limit of detection is 2 ng/mLand the absolute detection limit is 0.2ng.The relative standard deviation is 0.27%(n=11)at the level of 20 ng/mLiron(Ⅲ).Thismethod has been applied to the determination of iron in human hair, aluminum and aluminumalloy without pre-separation.
    A Study on the Reaction Between Fluorescein and Protein
    ZHU Keng, TONG Shen-Yang
    1996, 17(4):  539-542. 
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    The study of the reaction of fluorescein and protein was reported.The bindingsites and binding constant were obtained.According to the thermodynamic parameters,themain sort of binding force can be known.It is proposed that the“Phase Distribution Model”is the proper description of the interaction between fluorescein and protein.
    Determination of Complement Level in Serum by Polarographic Immunoassay
    KANG Xiao-Feng, SONG Jun-Feng, HU Yin-Hua
    1996, 17(4):  543-546. 
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    Anew method for determination of complement level in serum by polarographicimmunoassay was developed in this paper.This method is based on the reaction between ophenylenediamine and hydrogen peroxide catalyzed by hemoglobin from the sensitized cells incomplement-mediate hemolysis, producing an electroactive compound 2,2'-diaminoazobezen(DAA)and determining the DAAby linear-sweep polarography.The linear calibrationcurve is obtained in the range of 0.10 to 1.00 CH50 unit/mLand the limit of detection is 0.08 CH50 unit/mL.The sensitivity of the method is ten times more than that in the spectrophotometric method reported.And 25 samples at a time can be determined.The proposedmethod has been applied to the determination of complement level in healthy human serumand patient serum.
    Simultaneous Determination of Fluoranthene and Chrysene bySynchronous-Derivative-ME-RTP
    YANG Xin, DONG Chuan, JIN Wei-Jun, WEI Yan-Sheiig, LIU Chang-Song
    1996, 17(4):  547-549. 
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    Asynchronous-first-derivative microemulsion stabilized room temperature phosphorimetry is presented for the determination of fluoranthene and chrysene.The selectivityof this method is high with low limit of detection and wide linear range.The LDRs and LODs of synchronous derivative ME-RTP analytical curves are 1×10-7 ~ 1×10-5 mol/L,1.2×10-9 mol/L (fluoranthene);1×10-7 ~ 2×10-5,7.1×10-9 mol/L (chrysene) ,respectively.
    Interaction of Arsenazo Ⅲ with Serum Albumin
    WEI Yong-Ju, LI Ke-An, TONG Shen-Yang
    1996, 17(4):  550-552. 
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    The interaction of arsenazo Ⅲ(AAⅢ) with bovine serum albumin(BSA) in acidicsolution was investigated by a spectrophotometric method.It was considered that the electrostatic force between AAⅢ and BSAis the main binding force,and that the color changeduring the reaction is because of the transformation of AAⅢspecies from free H6L2- form into bound H5L3- form.The apparent binding constant and the maximum binding number under the conditions of PH2.0, with 0.5% NaCl and without NaCl, were estimated respectively by using a linear regression method proposed previously by the authors.The sensitivity ofdetection for BSAwas found to be about the same as that of the bromocresol green method.
    Electrochemical Reduction of NAD+ at Benzimidazole Modified Silver Electrode
    LI Gen-Xi, CHEN Hong-Yuan, ZHU De-Xu
    1996, 17(4):  553-554. 
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    Benzimidazole modified silver electrode which was prepared by a surface complexinduced reaction was not only stable,long-lived, but also could be used for the electrochemical reduction of NAD+.The anodic and cathodic peaks of the modified electrode were at 0.25Vand 0.10 Vrespectively.After addition of NAD+ to the test solution, the cathodic peak ofthe reductive process of NAD+ could be observed at about-0.03 Vand the peak currentwas dependent directly on the NAD+ concentration.
    Separation and Enrichment for Multi-trace Rare Earth Elements onOxine Cellulose Coupled to Inductively Coupled PlasmaAtomic Emission Spectrometry
    GUO Yi-Hang, LIU Chun-Ming, ZHAO Xiao-Liang, WANG Wei-Ling
    1996, 17(4):  555-557. 
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    The filler of microcolumn,oxine cellulose was prepared to separate and enrichmulti-trace rare earth elements(REEs) in geochemical samples.REEs were determined withinductively coupled plasma atomic emission spectrometry.Matrix effects were also studiedthoroughly.
    Studics on the Oxidation of μ-Oxo-bis (manganese(Ⅲ)porphyrin)Complexes and Substituted Effect
    GUO Can-Cheng, DING Liang-Zhong, LIANG Ben-Xi, CHEN Xin-Bin
    1996, 17(4):  558-561. 
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    The oxidation of μ-oxo-bis(tetraphenylporphinatomanganese) [TPPMn (Ⅲ)]2O with the oxidants such as PhIO.H2OO and air is studied.The amounts of [TPPMn(Ⅲ)]2O in the reaction system is shown by monitoring the reaction with UV-Vis spectrum instrument.The different mechanisms may be presented when [TPPMn(Ⅲ)]2Oreacted with different oxidants.The substituent effect and solvent effect in the reactions of the substitutedμ-oxo-bis (manganeseporphyrin)[TXPPMn (Ⅲ)]2O (X=p-(i-Pr),P-CH3,p-Cl, P-F,P-OCH3,H,m-Cl,o-Cl) with H2O2 are also studied.The research results show that abovereaction is accelerated by both electrondrawing substituents on porphyrin ring and nucleophilicity of solvents.
    A Study on Fluorescence Quenching of Dicyanoanthracene by Acenaphthenone via Electron Transfer──Formation Machanism of Exciplex and Its Kinetics
    WU Shu-Ping, JIANG Zhi-Qin, YE Jian-Ping
    1996, 17(4):  562-565. 
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    The kinetics and mechanism of exciplex formation of 9,10-dicyanoanthracene(DCA)by acenaphthenone(ANO) have been studied.The photokinetics of exciplex(ANO/DCA) was determined with transient single-photon counting technique.The measured rateconstants based on biexponential decay reveal that the forward electron transfer(ET) proceeds much faster than the reverse ETand other decay processes while ANOacts as an electron donor.In addition, the diffusion-controlled steady-state fluorescence quenching is mainly caused by ANO/DCAexciplex formation via photoinduced ET.
    Synthesis and Structures of the Complexes of β-Alkoxy-carbonylethyltin Trichlorides with N-Aryl-2-hydroxyacetophenylideneimines
    BAO Ming, HE Qing-Lin, LIU Ji-Hong, LIU Bao-Dian, XING Yan, LIN Yong-Hua
    1996, 17(4):  566-570. 
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    Sixteen novel β-alkoxycarbonylethyltin trichlorides and the corresponding N-aryl-2-hydroxyacetophenylideneimines complexes have been synthesized and characterized.An Xray crystal structure analysis of the complex of β-methyloxycarbonylethyltin trichloride andN4methylphenyl-2-hydroxyacetophe has been performed.The crystal belongs to space group P1 The cell parameters are: a=1.0201 (6) nm, b=1.0822(4) nm, c= 1.3949(6) nm, a=99.88(3)°, β=98.63(4)°, γ=97.86(4)°, Z=2.The ligands coordinate to tin atom via phenolic oxygen atom.Coordination of carbonyl oxygen atom to tin atomstill exists in the complexes.The coordination number of tin atom is 6.
    Synthesis of O-(4-Quinazolinyl)oxime Ethers and Their Antiviral Activity
    HUANG Run-Qiu, LI Hui-Ying, MA Jun-An, QIU De-Wen
    1996, 17(4):  571-574. 
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    The O-(4quinazplinyl)oxime ethers compounds were synthesized by the reactionof 4-chloro quinazoline and substituted aryl oximes under a base.Their structures were confirmed by means of elementary analysis.IR,1H NMRand MS.The preliminary bioassayshows that some compounds have higher antiviral activity against TMV than 1,3,5-triazine-hexahvdro-2,4-dione(DHT);CompoundsⅠ6 and Ⅰ11, at～0.3 mmol/L, results in 60%and 65%inhibition of TMVin nicotiana tabacum leaves respectively, compared to 45% usingDHT,at 0.9mmol/L.
    Development in Study on Reaction of Alkanethiol (Arenethiol)or Their Salts with Iron Carbonyls──Synthesis, Structure and Reaction of Nucleophilic Anionsof the Type [(μ-CO)(μ-RS)Fe2(CO)6]-
    SONG Li-Cheng
    1996, 17(4):  575-585. 
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    The synthesis, structure and reactions of the new type of butterfly-shaped anioniccomplex salts M+[μ-CO) (μ-RS)Fe2(CO)6]-(M+=Et3NH+,Li+,Na+,MgX+) have beenreviewed.The complex salts were usually prepared by the action of alkanethiolates orarenethiolates RS-M+ on Fe3(CO)12 in THFand used in situ for subsequent reactions.Thesingle-crystal X-ray diffraction analysis confirmed that this kind of compsplex salts had a butterfly-shaped framework consisting of Fe2SCatoms.The complex salts are highly reactivetowards diverse electrophilic substrates.Such substrates, generally, include unsaturatedalkyl halides,acid chlorides,alkynes,halides of phosphorus and arsenic,carbon disulfide,sulfur(1) chloride, elemental sulfur and selenium and alkylmercuric chlorides etc..Apparently,such a kind of anionic complex salts has become a very effective reagent and has beenused extensively in the syntheses of novel organometallic and cluster complexes.
    Synthesis of Some Chiral Quaternary Ammonium Salt Porphyrin Compounds
    LIU Yan-Qin, HAN Shi-Tian, QIE Wen-Juan, XIE Hong
    1996, 17(4):  586-588. 
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    Four chiral quaternary ammonium salt porphyrin compounds carrying N-methyle-phedrine or quinine were synthesized.Their structures were demonstrated by elementaryanalysis,IR,UV,1H NMRand MS.
    Peptides Formation of Amino Acids in Water Solution Promoted by Phosphoryl Group
    SHA Yao-Wu, JU Yong, ZHAO Yu-Fen
    1996, 17(4):  589-591. 
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    When N-(O,O-diisopropylphosphoryl)histidine(DIPP His)was incubated at 40℃ in water solutions for 90 h, homo dipeptides,tripeptides even tetra peptides(DIPP-His His His His and His His His His)were detected through FAB-MSand 13 CNMRanalysis.When DIPP-His was incubated with other amino acids in water solution, hetero di and tri peptides (DIPP His pro, DIPP His Asp Asp)were detected.WhenDIPP His was incubated with Gly Glv and Gly GlyOBu, hetero tripeptides(DIPP His Gly Gly and DIPP His Gly GlyOBu)were detected.Apentacoordinated phosphorous intramolecular mixed anhydride may be the activatlng intermediate.
    Analysis of Magnetic Properties of Rare Earth Compound Ho2Co14Fe3
    HUANG Xu-Ri, XIAO Xing-Cai, LI Ze-Sheng, SUN Jia-Zhong
    1996, 17(4):  592-595. 
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    By adding the spin-spin dipole interaction in the convention Hamiltonian,a theoretical analysis of the experimental magnetization of rare earth compound Ho2Co14Fe3 is performed with the aid of parameter-fitting method.It is shown that when the theoretical parameters are adequately fixed,the calculated magnetization curve is in agreement with that ofthe magnetic experiments,and the transition of magnetic moment is explained.
    A Theoretical Study on the Nonlinear Optical Second-order Properties of Azobenzene Series Molecules
    FENG Ji-Kang, WANG Hai-Chuan, XIAO Chang-Yong, SUN Chia-Chong
    1996, 17(4):  596-600. 
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    On the basis of AM1 and INDO/CImethods, we devise the program for the calculation of nonlinear second-order optical susceptibilities βijk and perform systematic theoreticalstudies on the nonlinear optical second-order properties of azobenzene series molecules ,i.e.on the basis of ,we induced different donors on the left sideof phenyl ring, and different acceptors on the right side of phenyl ring,and examined therule of β variation.The regularity summarized from the calculated results has been explainedmicromechanically.Finally,a molecule having a big nonlinear second-order optical susceptibility has been designed.
    Prediction of Salt Effect on Vapor-Liquid Equilibrium in Ethanol-Water System by Scaled Particle Theory
    SUN Ren-Yi, ZHANG Qing-Zhi
    1996, 17(4):  601-606. 
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    The salt effect parameters(from Furter's equation)of three electrolytes (NaCl ,NaBr, KCl) for various ethanol-water mixtures were determined by vapor-liquid equilibriumexperiments.Acalculation method of this parameter(K)by the scaled particle theory wassuggested.The term of hard sphere interactions was calculated by using Masterton-Lee's equation.and that of soft sphere interactions was treated by using Y.Hu's radial distributionfunction method, i.e.taking the first coordination shell as in order,and out of the shell asrandom mixing.The interactions between the charge of ions and dipole or induced dipole ofthe central molecule were considered effectively within the limits of the first coordinationshell,and the ions out of the shell were regarded as L-Jmolecules.In this paper a correlation equation for the located dielectrical constant and liquid concentration was proposed andthe predicted results of the salt effect parameters were in agreement with the experiments bythis equation.
    Analog Thermogram Method(Ⅰ)──Chemical Reactions with Simple Order
    ZENG Xian-Cheng, ZHANG Yuan-Qin, MENG Xiang-Guang, CHEN Min-Zhu, QIN Zi-Ming, HU Qi-Shan
    1996, 17(4):  607-612. 
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    On the foundation of experimental results of thermokinetics, a general analogthermogramequation,△=αte-kβt,which can simulate the thermograms of chemical reactionswith simple order,has been proposed in this paper.Combined with the basic theory ofthermokinetics,a novel studying method of thermokinetics, the analog thermogram method,has been developed.The formulae for calculating kinetic parameter Kn and rate constant kn,which do not involve any instrument constants, have been derived.The expression of thecooling constant of thermokinetic system has been obtained at the same time.The analogthermogram method can be applied not only to studying slow chemical reactions, but also tostudying faster ones.In order to test the validity of this method, the saponifications of ethylpropionate and ethyl benzoate in aqueous ethanol solvent, the saponification of ethyl butyrate in aqueous solution, the substitution of benzyl chloride in aqueous DMSOsolvent, theformation of hexamethylenetetramine in aqueous solution, and the polymerization of acrylamide have been studied.The rate constants calculated with this method are in agreementwith those in the literatures, and therefore the analog thermogram method is believed to be Correct.
    Synthesis,Characterization and Catalytic Activity for H2O2 Decomposition of Tetrabasic Tugstovanadophosphate Heteropoly Rare Earth Element Complexes with Dawson Structure
    SHAN Yong-Kui, XIE Wen-Hua, YE Xing-Kai, WU Yue
    1996, 17(4):  613-617. 
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    Nine tetrabasic tungstovanadophosphate heteropoly rare earth element complexeswith Dawson structure were synthesized.Their general molecular formulas are K15H4[Ln·(P2W16VO61)2]·xH2O(Ln=La3+,Pr3+,Nd3+, Sm3+,Eu3+,Gd3+,Dy3+,Yb3+).Theirstructures and properties were investigated by IR,UV,NMR,ESR,XRD,TG-DTA.Theresults showed that the series of complexes have the same structure asK16[Ce(P2W17O61)2]·50H2O.At the same time, the catalytic activity of the complexes forH2O2-decomposition was also investigated.
    The Exciplex as an Intermediate for Photocycloaddition of 9-Vinyl Anthracene and p-N,N-Dimethylamino Styrene
    GAO Ying, LU Tian-Hong
    1996, 17(4):  618-621. 
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    The appearence of the new fluorescence peak at about 570 nm demonstratesexciplex formation between the singlet states of 9-vinyl anthracene and p-H, M-dimethy-lamino stytene.With increasing the polarity of solvents, the red-shift of the emission wavelength occurs and the fluorescence quantum yield of the exciplex decreases.For example,thefluorescence peak is at 550 nm in totuene and at 595 nm in butanone.The fluorescence qua-tum yields in totuene and in butanone are 0.053 and 0 respectively.Both the relative yield ofthe photocycloaddition dimer and the ratio of the relative yields of the trans and cis dimers decrease with increasing the polarity of solvents.For example,the relative yields of the dimerare 1.0 in totuene and 0.04 in butanone respectively.The ratio of the relative yields of transand cis dimers are 0.54 and 0 in totuene and butanones, respectively.In addition, the exciplex intermediate mechanism was suggested for the photocycloaddition between 9-vinyl anthracene and 9-N,N-dimethylamino styrene.
    ESR Studies of the Effects of Counter Ions on V4+ Ion in Heteropolyacid Salts Catlysts
    ZHENG Ying-Guang, DONG Feng-Xia, WU Tong-Hao, JIA Ji-Fei
    1996, 17(4):  622-625. 
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    The transition metal ions Cu2+ and V4+ in heteropolyacid salts used in one-stepoxidition of isobutyraldehyde(IBL)to produce methacrylic acid(MAA) were studied by ESRmethod.The convolution difference method was applied to the resolution enhancement ofESRspectra of transition metal ions.Spectral parameters of V4+ coordinated to heteropolyanion was detected from complicated and superposed spectra.Furthermore,α2 and Kwerecomputed.We have also discussed the effects of the counter ions Cu2+ and various kinds ofalkali metals on the electron cloud density and delocalization of unpaired electrons and property of V—O bond.
    Laser-Induced Selective Deposition of Nickel on p-Type Silicon
    WANG Jian, YU Zu-Zhan, YU Ning
    1996, 17(4):  626-629. 
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    Selective deposition of thin nickel films on p-type silicon was obtained in a hy drazine-based conventional electroless nickel plating solution at the ambient temperature under laser irradiation.Composition and properties of the deposits were investigated using SEM,AESand RBStechniques.The deposits are in Schottky barrier contact with p-type silicon.The mechanism involved in the deposition process was also discussed.
    An Accurate Ab Initio Calculation on Potential of the Ground States of the He and Li Atoms
    WANGG Yi-Bo
    1996, 17(4):  630-632. 
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    Potential energy curves of the ground state of the He-Li system are determined byusing efficient basis set 6-311++G(3df,3pd)augmented with midbond functions{3s3p3d2f}at the MP4SDTQ,QCISD(T)and CCSD(T)levels.The full counterpoise(FCP)method is applied for the BSSEcorrection.Our calculations indicate a well depth of about(7.0±0.4)×10-6 a.u.at the around re= 11.6 a.u.The results are in very goodagreement with Das and Wahl′s MCSCFvalues, but differ in the experimentally determinedmodel potentials for well.depth deduced by Dehmer and Wharton.
    The Molecular Force Fields and Vibrational Spectra of Intermolecular Hydrogen Bonded Molecules
    SUN Ze-Min, WANG Feng, TANG Zuo-Hua, YAN Guo-Sen
    1996, 17(4):  633-634. 
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    In this paper,we put forward a mixed force field model,and calculated diagonalforce constants by using the model potential function method and the off-diagonal using ab initio method at 6-31Glevel.The force fields obtained in this paper are applied to the analysisof molecular normal vibration and the results are better than those from gradient ab initiomethod.
    Studies on ESR Spectra of Mgo Crystal Treated by Shock Wave and Its Activity for Isomerization of Butene-1
    ZHANG Ju, ZHENG Xiao-Ming, NI Zhe-Min, XU Kang, YANG Ting-Lu, LIU Jian-Jun
    1996, 17(4):  635-637. 
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    After being treated by shock wave,Fcolor centers are formed on MgO crystaland some new signals of free radical(O2-) appear in the ESRspectrum,The results of isomerization of butene-1 showed that the MgO crystal treated by shock wave exhibits a higherconversion of butene-1 and higher yield of cis-butene due to an increase in defects.
    Poly (methylmethacrylate) Langmuir-Blodgett Multilayer Films and Their Application for A Photoreceptor
    ZHANG Cheng, XU You-Yi
    1996, 17(4):  638-641. 
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    In this paper, poly(methylmethacrylate)(PMMA) Langmuir-Blodgett(LB) multilayer films were prepared and applied to the field of a separation functional photoreceptor as a resistant interface layer for the first time.From the π-Acurves.it was found that the PMMA monolayer has anisotropism and relaxation of surface pressure.TEMphotograph showed the orientation and arrangement of PMMA chains in the multilayers.Investigations of transfer ratios, UVand XPSindicated that the deposition of multilayers is uniform.The photoreceptor using PMMA-LBmultilayer films as a resistant interface layer, CuTsPc-LBfilms as a charge generation layer, PVK as a charge transportation layer exhibited surface potential V0=1518 V, percentage of potential discharge after one second exposure △V1s=50.16% and half decay time t1/2=0.93 s.Its photoconductivities are much better than those of the photoreceptor using PMMA coating film.
    Studies on Protein-Resistance of AmphiphilicPolystyrene-g-Poly (ethylene oxide)Copolymers
    SUN Yong-Hong, QIU Yong-Xing, YU Xiao-Jie, FENG Lin-Xian
    1996, 17(4):  642-645. 
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    The adsorption isotherm and kinetics of simple plasma protein (human serum albumin immunoglobulin or fibrinogen)-buffer onto the surfaces of (PS-g-PEO) graft copolymers were investigated by radioiodine labelling technique.The reliability of IC1 labellingmethod was verified.It was discovered that the plateau protein adsorption amount usuallydecreased with surface PEOcontent of PS-g-PEOs increasing;the lowest protein plateau adsorption values were observed <0.25 μg.cm-2.The "comb-like" structure of model materials might be more fit for protein-resistant property of PEO side chains.
    Two-Fluid Polymer Coordination Solution Theory──Equation of State for Pure Components and Its Applications
    JIANG Wen-Hua, LI Hao-Ran, HAN Shi-Jun
    1996, 17(4):  646-650. 
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    A new model named polymer's two-fluid coordination thermodynamic statisticmodel based on Flory's cell theory coupled with local composition is proposed.The holesimilar to that in the Simha-Socmcynsky hole theory is introduced and two concepts of sitefraction and local site fraction in Flory's theory are replaced by coordination fraction and local coordination fraction.Quasi-chemical treatment is applied to calculate the local coordination fraction.An equation of state of pure components based on the new model is derived andthe P-V-Tproperties of three systems [polystyrene, polypropylene and poly (1-betene3)] ,were correlated by the new equation.The results were fine.According to the relation between segment structure of polymer and holes, we predict that if polymers are similar to eachother in structure, their holes and flow properties of melts decrease with the increase of sizeof subgroup of polymer's segment.
    Structures and Properties of the Blend Membrane of Regenerated Silk Fibroin and Poly(vinyl alcohol)and Its Application to Glucose Sensor
    YU Tong-Yin, SHAO Zheng-Zhong, LIU Yong-Cheng, QIAN Jiang-Hong, LIU Hai-Ying, DENG Jia-Qi, HU De-Zhen, ZHAO Hui-Ling
    1996, 17(4):  651-654. 
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    The morphologies and structures of the blend membranes of regenerated silk fibroin and poly(vinyl alcohol) were investigated with scanning electron microscopy,and theirwater absorbility and mechanical properties were measured.The amperometric p-benzo-(quinon mediatingsensor for glucose based on glucose oxidase immobilized in the blend membrane of regenerated silk fibroin and poly(vinyl alcohol) possessed perfect stability and highsensitivity,and its linear range was from 10-5 to 10-2 mol/Lwith the response time less than 20 s.Moreover,its lifetime was over two months.
    Conductivity of Polyoxyethylene/Poly (2-vinyl pyridine)Blend and Compatibilizing Effect of Lithium Perchlorate
    CUI Min-Hui, GUO Jun-Shi, XIE Hong-Quan
    1996, 17(4):  655-658. 
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    Ionic,electronic and mixed(ionic-electronic) conductivities of blends of polyoxyethylene (PEO)poly(2-vinyl pyridine)(P2VP) with different weight ratios after dopingwith LiClO4, TCNQor LiClO4 plus TCNQwere studied.When the weight ratios of PEO/P2V Pare 6/4,5/5 and 4/6, the mixed(ionic-electronic)conductivity of the blends higherthan the total of ionic and electronic conductivity of PEO/P2VP and shows a synergistic effect.LiClO4 in the blend can act as compatibilizer for PEO/P2VP blend
    Studies on Oxygen Enrichment Properties of Poly(cis-butadiene)/Ester-Ether Liquid Crystal Composite Membranes
    ZHANG Zi-Yong, LIN Shang-An
    1996, 17(4):  659-662. 
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    Polymer/liquid crystal composite membranes containing poly(cis-butadiene)(PB)and diethylene glycol bis-4-(4'-ethoxybenzoyloxy) benzoate(DEBEB)with two transitionmesophases were prepared for the first time and their oxygen enrichment properties were investigated.The oxygen permeability of the composite membrane with 10% weight content ofDEBEBliquid crystal exhibited several times greater than that of the PBmembrane at roomtemperature.Relationship between permeability coefficients and temperatures was characterized by N-shape curves,that is,the permeability coefficients first increased,followed by decreasing,and then increased again with increasing temperature continuously.We interpretthis result as effect of phase behavior of the liquid crystal and morphology of the compositemembranes on the permeabilities.
    A Study of Dynamics About the Addition Reaction of n-Dodecyl Alcohol and Ethylene Oxide──Determining the Optimum Reaction Time
    ZHANG Ren-Quan, ZHANG Wei-Bing, LI Kui-Ying, WANG Wan-Xing
    1996, 17(4):  663-665. 
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    In accordence with the reaction mechanism that the reaction of n-dodecyl alcoholethylene oxide(EO)is catalyzed by the strong base,the optimum reaction time expression ofthe relatively highest product containing at the given polymer number of EOis obtained bythe Laplace transform.Our expression was compared with Weibull's and Flory's ones undercertain conditions,and the relationship between the optimum reaction time and the averagepolymer number of EOis discussed.As an example,the conclusion is also proved with theresult that lauryl alcohol reacts with EOunder different catalytic conditions.
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