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    24 April 1994, Volume 15 Issue 4
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    Articles
    Synthesis and Characterization of V-ZSM-5 Zeolites in Weak Acidic Medium
    DU Hong-Bin, TU Kun-Gang, ZHOU Qun, ZHOU Fen-Qi, PANG Wen-Qin
    1994, 15(4):  473-477. 
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    The V-ZSM-5 type molecular sieve was synthesized in a weak acid medium in the presence of F- ions, and with tetrapropylammonium as a template agent, NH4VO3 and VO2+species as vanadium sources.Investigation on the structure was performed by means of XRD, SEM,IR,XPS and ESR.The results indicated that the majority of vanadium was V4+ species, which was introduced into the framework of zeolites.
    Phase Diagram of Ternary System LaCl3-SrCl2-MgCl2
    ZHENG Chao-Gui, ZHENG Yan-Ke
    1994, 15(4):  478-480. 
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    Three surfaces corresponding to the primary crystallization of LaCl3 , SrCl2 and MgCl2, respectively, 3 univariant curves related to the secondary crystallization and a ternary eutectic (15.0wt% LaCl3,49.5wt% SrCl2, 35.5 wt% MgCl2; 545℃) were found in LaCl3-SrCl2-MgCl2 system by means of DTA and X-ray diffraction analysis, Areaction occurs in this system : L=LaCl3+ SrCl2+ MgCl2.An unstable compound has been found in the solid which decomposed at about 500℃.
    Studies on the Synthesis of ZSM-35 Molecular Sieve and Its Templating Effect
    SONG Tian-You, XU Jia-Ning, TONG Yao-Cai, XU Ru-Ren
    1994, 15(4):  481-484. 
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    ZSM-35, ZSM-5 and mordenite are gained from the systems with 1,6-hexanediamine and ethylenediamine as templating agents, respectively.The templating effect during the formation of zeolite ZSM-35, ZSM-5 and mordenite were studied with the chemical analysis, thermal analysis and 13C NMR technique.The experimental results show that 1,6-hexanediamine and ethylenediamine have better templating effect for ZSM-35 molecular sieve than that for mordenite,and 1,6-hexanediamine is an excellent templating agent for ZSM-5 molecular sieve.
    Synthesis,Crystal Strudure and Thermolysis of the Complex [Cu{(CH3O(O)C6H3CH=NC6H4CO(O)H2(O)}]2·H2O
    WANG Hong, LI Shu-Lan, LIU De-Xin, CUI Xue-Gui, LI Xiao-Yan, YANG Zhao-He
    1994, 15(4):  485-489. 
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    The complex [Cu(L)(H2O)]2·H2O (L=3-methoxysalicylideneimino benzoate)was synthesized.The complex crystallizes in an orthorhombic system.space group is Pcan,cell parameters: a=1.0347(4) nm,b=1.5493(7) nm, c=1.7441(3) nm,Z=4,with R=0.047,Rw=0.049.The kinetic parameters were obtained from the analysis of the TG-DTG curves by integral and differential method.The possible reaction mechanism is suggested by comparison of the kinetic parameters.The kinetic eqution may be exprested as dα/dt=A·e-E/RT·3(1-α)2/3 The mathematical expression of the kinetic compensation effect of the thermal decomposition reaction has also been obtained.
    Preparation of Silica-Pillared Layered Titanate
    HOU Wen-Hua, YAN Qi-Jie, FU Xian-Cai
    1994, 15(4):  490-491. 
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    Silica-pillared layered titanate was first prepared by using a new method proposed in this paper.It entails first intercalating H2Ti4O9 with n-hexylamine and then the reaction of the intercalated titanate with APSaqueous solution, and finally calcinating the reaction product in air sequently.The resultant silica-pillared layered titanate has a high surface area of 137.9 m2/g (550℃) and good thermal stability above 550℃.The N2 adsorption-desorption isotherm of this new material demonstrates that it is porous, with an average pore diameter of 3.5 nm.
    Synthesis and Properties of Substituted Nicotinic Acid Chromium (Ⅲ) Salen Complexes
    ZHOU Bao-Xue, SHANG Shu-Chuan, ZOU Li-Zhuang, WANG Da-Qing, ZHANG Xiao-Kai, ZHU Li, REN Jian-Cheng
    1994, 15(4):  492-494. 
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    Four kinds of carboxylic acid chromium (Ⅲ) Salen complexes Cr (Salen) L (H2O)n (L=nicotinate, isonicotinate, pyromucate, benzoate;n=1 or 2) have been synthesized and characterized by elemental analysis, molar conductance, IR, UV , TGand electron microscope.Carboxylate oxygen-bound chromium (Ⅲ) complexes have been observed in these complexes.Atransmission electron microscope study of Cr (Salen) (nicotinate) (H2O)2 showed a hexagonal system structure in the crystal.The TGanalysis in nitrogen for four complexes showed a loss of all water molecules corresponding to the first step, the final decomposition leads to Cr2O3.
    Studies on Binary Gas Solid Adsorption(Ⅰ)──A New System for the Rapid Determination of Adsorption Isotherm with Frontal Chromatography
    DAI Min-Guang, YANG Su
    1994, 15(4):  495-498. 
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    A new system for the determination of binary gas solid adsorption isotherm with chromatography was established.The system was composed of the frontal chromatographic adsorption system and the chromatographic quantitative analysis system.After the equilibrium of the adsorbed phase and the gas phase had arrived in the adsorption system,these components were injected into the analysis system with the carrier gas and were determined respectively by turning the switch valves.The major factors which had an effect on the measurement were discussed at full length.
    Preparation of Open Tubular Immobilized Glucose Oxidase Reactor and Its Application in Flow Injection Analysis
    ZOU Gong-Wei, HU Guan-Jiu, WEN Hong-Mei, WANG Yan-Ling, GU Fang-Xiao
    1994, 15(4):  499-502. 
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    Glucose oxidase was chemically bonded on the inner surface of glass capillary.The glucose was determined in the system of open tubular immobilized enzyme reactor-amperometric detector by flow injection analysis.The effect of flow rate on peak current and dispersion in FIAsystem was discussed.The method of measuring the apparent activity of the open tubular immobilized enzyme reactor was suggested.
    Studies on the State of Hematoporphyrin(HP) in Physiological Condition Solution
    HE Xi-WEn, FENG Xi-Zeng, ZHANG Gui-Zhu, YANG Wan-Long, YU Gui-Ying, SHI Hui-Ming
    1994, 15(4):  503-506. 
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    The polymeric state of hematoporphyrin (HP) under physiological conditions and in aqueous solution has been studied by spectrum analysis.From application of Kasha's theory on the difference spectrum between HPmonomer and dimer, we have estimated that the distance between xanthene planes of HPis 0.528 nm and these planes form the cross angle 20°in dimer molecules (Fig.3).The relationship between the energy transmission of HPHSAand the solution state is discussed.The relationship between the photochemical mechanism of curing malignant tumours and the fluorescence character of HP-HSAis discussed.
    A New Surface Acoustic Wave Impedance Sensor and Its Application in Liquid System
    YAO Shou-Zhuo, CHEN Kang, LIU De-Zhong, NIE Li-Hua
    1994, 15(4):  507-508. 
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    A surface acoustic wave (SAW) impedance sensor was constructed by combining a 61 MHz SAWresonator with the conductive electrodes.Responses of such SAWimpedance sensor were investigated for different electrolyte solutions arid nonaqueous solutions.Afrequency shift-electrolytic conductivity equation was presented as △f=aX+b.The sensor was applied to the rapid determination of total salt content in serum and micro-water content in organic solvent.
    Investigation on Double Electrolytic Cell Positive Feedback Oscillographic Chronopotentiometry
    ZHENG Jian-Bin, GAO Hong(H. Kao), ZHU Jun-Jie, HU Juan
    1994, 15(4):  509-511. 
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    A new method named double electrolytic cell positive feedback oscillographic chronopotentiometry was presented in this paper, and its repeatability was studied.The minimum concentration yielding a measurable incision was determined.The major factors affecting the results of positive feedback were also discussed.The experimental results show that the sensitivity of the new method is 1-5 times as high as that of classical method.Therefore, the new method is very useful in microtitration, and it has an important significance to enhance sensitivity of reprocal oscillographic chronopotentiometry as well as other methods based on (dE/dt)-Ecurves.
    Studies on the Catalytic Kinetic Spectrophotometry for Determination of Ultra-Trace Silver
    ZHANG ZHi-Qi, CHEN Shi-Rong, CHEN Dang-Jiao, ZHANG Gen-Xu
    1994, 15(4):  512-514. 
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    In the presence of α,α'-bipyridyl as activator, the reaction between rhodamine Band potassium peroxydisulphate can be catalyzed by silver(Ⅰ) in acetic acid buffer solution (pH 4.9) with the result of decoloration of rhodamine B.The catalytic reaction is pseudo-zero-order in reactant and the apparent activation energy of catalytic reaction is found to be 37.66kJ/mol.A new catalytic spectrophotometry for determination of ultra-trace silver has been developed.The range of determination is 0.38-35 ng/25 mLsilver and the precision is 3.8%obtained from 11 standard solutions each of which contains 20 ng silver.The method has been applied to the determination of trace silver in ores.
    The Determination of Anti-MV Antibody in Serum with CL-ELISA
    ZHANG Zhu-Jun, ZOU Ke-Wei, CHENG Ming-Jie
    1994, 15(4):  515-517. 
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    A method for determination of the anti-MVantibody in serum is established based on chemiluminescence enzyme-linked immunosorbant assay (CL-ELISA).The MV antigen is coated on the polystyrene cup, then reacts with anti-MV serum to form the immunocompound.The anti-HuIgGlabeled by HRPis used as a second antibody.The enzymatic activity on the antibody is determined by p-iodophenol enhanced luminol-H2O2 chemiluminescent system, which has higher sensitivity than current chromogenic reaction.The curve of anti-MV antibody title determined with CL-ELISA and ELISA is established and 30 clinical samples are tested.The results show that the CL-ELISAhas higher positive ratio than ELISA.Two methods have good correlation.The correlation coefficient is 0.992.
    Application of Forgetting Factor Spectrophotometry to the Analysis of Multiple Components
    FANG Hui-Sheng, XIANG Bing-Ren, LI Rui, ZOU Qiao-Gen, AN Deng-Kui
    1994, 15(4):  518-520. 
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    According to the characteristics of forgetting factor algorithm, the wavelength points were selected on the basis of correlation coefficient and it was used by taking the sample simulating injection Antongding as example.The result showed that the greater correlation coefficient is adopted, the more accurate result can be obtained.The satisfactory result was also obtained using the absorptivity computed by forgetting factor spectrophotometry instead of multivariate linear regression.So, it gives the full reins to the potential merit of forgetting factor spectrophotometry and provides a better approach to the analysis of multiple Components.
    A New Norpentacyclic Triterpenoid Auriculatone from Aster auriculatus Franch
    GAO Cheng-Wei, CHEN Yu-Shu, ZHAO Shu-Nian, LU Yang, TIAN Zhi-Yue, ZHENG Qi-Tai
    1994, 15(4):  521-523. 
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    A new norpentacyclic triterpenoid, auriculatone, was isolated from Aster auriculatus Franch.On the basis of physico-chemical constants, spectral data and X-ray diffraction analysis of 3β-acetoxy derivative (Ⅱ), its structure was determined as 3β-hydroxy-17α-H,18β-H-28-norolean-12-ene-16-one (Ⅰ).
    Syntheses of Phosphaspirocyclic Complunds──3,9-2H-2,4,8,10-Tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-disulfide and Its Addition Reaction with α-Aryl-β-Nitrostyrenes
    LI Yu-Cui, LI Jian-Min, ZHU Xue-Feng, LI Jian-Hua, TAO Zun-Wei
    1994, 15(4):  524-527. 
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    Five new compounds with the general formula:  in which Xis H, p-MeO-, m-PhO-, p-Me2N-, have been prepared through the addition.of 3,9-2H-2,4,8,10-tetraoxa-3, 9-disulfide 2 to α-aryl-β-nitrostyrenes in the presence of NaH and DMA.The reaction mechanism and the 1H NMR of 2 and adducts 3a-e were studied.All the synthesized compounds were also confirmed by IR and elemental analysis.
    Studies on Solid State Photochemical Syntheses and Inclusion Ability of New Host Compounds of Indoles
    MENG Ji-Ben, DU Da-Ming, WANG Wen-Guang, WANG Yong-Mei
    1994, 15(4):  528-531. 
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    The photoreaction of terephthalicaldehyde, methyl p-formylbenzoate, and o-nitrobenzaldehyde with indole in the solid state gave five new products.Four of these products have a good inclusion ability.Products 1,2, 3 and 4 can form 1 : 1,1:2 or.2:1 inclusion complexes 1a, 2a, 3a, 4a and 4b with acetone, ethyl acetate, carbon tetrachloride, and chloroform respectively.The structures of products or inclusion complexes were identified by IR,1H NMR, MS and elemental analysis.X-ray diffraction analyses of inclusion complexes 1a,2a and 3a were carried out to obtain more information about the structures.
    Studies on UV-Vis Spectra of [5,10,15,20]-Substituted Tetrakisphenyl Porphyrin Chlorated Manganese Complexes
    LI Song-Lan, LIAO Dai-Zheng, LIANG Shu-Sen, ZHOU Yi-Ming, ZHU Shen-Jie
    1994, 15(4):  532-535. 
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    The UV-Vis spectra of eighteen [5, 10, 15, 20]-Substituted tetrakisphenyl porphyrin manganese chlorated complexes have been measured and their main bands were assigned.The concentration and solvent effects have also been studied which indicate that the Pπ(Cl)→π* bands undergo a gradual red shift as the concentration of the solution increases and a blue shift as the polarity of the solvent increases.Based on the dipole-dipole interaction with polar solvent, these effects can be understood by realizing that in Pπ(Cl)-π* transitions the ground state is more polar than the excited state.In addition, the linear relation between the λmax values of p-substituted phenyl porphyrints and Hammett constant has been observed.
    Reactions of a Series of Alkyl-p-dialkoxybenzenes with Various Nitrating Agents
    GONG Yue-Fa, ZHAO Cheng-Xue, JIANG Xi-Kui
    1994, 15(4):  536-539. 
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    2-Alkyl-1,4-dimethoxybenzenes (1a-d) react with both concentrated HNO3 and NH4NO3 in glacial acetic acid to form only simple nitrated products,2-alkyl-5-nitro-1,4dimethoxybenzenes (4a-d).However, in the case of 2-alkyl-5-t-butyl-1,4-dimethoxvbenzenes (2a-d) or 2,5-di-t-butyl-1, 4-dibenzoxybenzene (3), the formation of products greatly depends upon both the properties of the employed nitrating agents and the structures of these reactants.According to the observed resultsk, two possibilities for the reactions mechanism are proposed.
    Five New Compounds from Elsholtzia Densa
    SHEN Xu-Wei, ZHENG Shang-Zhen, YIN Zuo-Dong, SONG Zhan-Wu, WANG Lai
    1994, 15(4):  540-542. 
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    Five new compounds were isolated from Elsholtzia densa.By means of chemical and spectroscopic methods, their structures were identified as 3″,4″,5″- trimethoxyfuranoflavone(3), 3″-hydroxy-4″,5″-dimethoxyfuranoflavone (4), 5-(3″-methylbutyl)-8-methoxyfuranocoumarin (5), 5-(3″-hydroxy-3-methylbutyl)-8-methoxyfuranocoumarin (6) and 5-(3″,3″-dimethylallyl)-8-methoxyfuranocoumarin(7).
    The Structure of a New Monoterpenoid Acid from Aster Farreri
    WANG Ming-An, CHEN Yao-Zu
    1994, 15(4):  543-544. 
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    A new monoterpenoid acid (1) with head to head of isoprene was isolated from Aster farreri W.W.Smith et J.F.Jeffery.The structure of 1 was elucidated as (E)-3,6-dihydroxymethyl-4,5-dihydroxy-2-ene-octanic acid on the basis of spectral data.
    Synthesis and Antitumor Activity of Peptidyl-N1-Hydroxymethyl-5-Fluorouracil
    LUO Yi, ZHUO Ren-Xi, FAN Chang-Lie
    1994, 15(4):  545-547. 
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    Six hydrophobic peptidyl 5-FUprodrugs and four amino acid derivatives of 5-FU (Val, Leu, Phe, Gly) were synthesized.All of these new compounds were characterized by UV, IR,1H NMR and elementary analysis.The antitumor activity of these compounds were tested against EACcells in vitro.
    In Situ FTIR Reflection Spectroscopic Studies of Adsorption and Oxidation of Ethylene Glycol on Platinum Electrode(Ⅱ)──Alkaline Media
    CHEN Ai-Cheng, SUN Shi-Gang
    1994, 15(4):  548-551. 
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    The electrooxidation of ethylene glycol (EG) in alkaline media has been investigated with in situ FTIRspectroscopy and cyclic voltammetry.The main products such as CO2 and were detected clearly.Besides CH2OHCOO- and -OOC-COO- species, a new intermediate,  (with its IR absorption band at 2027cm-1 in 0.1 mol/Land at 2036 cm-1 in 0.05 mol/L NaOH solution), was determined and a possible mechanism to form this intermediate was proposed.
    Twisted Intramolecular Charge Transfer in Aqueous Solution ──A Comparative Study of TICT or p-Dimethylaminobenzoic Acid in Cationic and Anionic Micelles by Its Dual Fluorescence
    JIANG Yun-Bao, XU Jin-Gou, HUANG Xian-Zhi
    1994, 15(4):  552-556. 
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    In the aqueous solution of cationic surfactant cetyltrimethylammonium bromide (CTMAB), the TICTfluorescence of DMABOAis dramatically shifted to blue upon the micelle formation, accompanied by an enhancement of the fluorescence intensity ratio of TICTband to normal band (Ia/Ib) and of total fluorescence intensity.While the formation of micelle of anionic surfactant sodium lauryl sulfate (SLS) does not induce the variations of the position of TICTband and of Ia/Ib, only causes a relatively minor enhancement of total fluorescence intensity.It is pointed out that the TICTbehavior in the hydrophobic core of micelle is different from that in pure organic solvent,i.e., decrease of polarity results in increased Ia/Ib, and the electrostatic interaction and hydrophobic interaction between DMABOA and CTMAB micelle are synergetic.
    Preparation and Crystal Structure of Adduct Dihydrate of L-Arginine and Maleic Acid
    ZHENG Ji-Min, CHE Yun-Xia, WANG Ru-Ji, WANG Hong-Gen
    1994, 15(4):  557-560. 
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    The title 1: 1:2 adduct has been prepared and a large single crystal with dimensions of 25 mm×40 mm×13 mm was obtained by a slow-cooling method.The crystal gives the green frequency doubling radiation at 532 nm under the irradiation of Nd3+: YAGlaser beam at 1064 nm.The crystal structure of this potential non-linear optical material was studied by X-ray diffraction method.The crystal is triclinic, space group P1, with α=0.5269(1) nm,b=0.8040(1) nm,c=0.9783(2)nm,a=106.14(1)°β=97.27(1)°,r=101.64(1)°,Z=1;R=0.062 for 932 observed reflections, The molecules of L-arginine,maleic acid, and water are connected each other by intermolecular hydrogen bonds to form three-dimensional net-work.
    Corrosion Behaviour of Palladium Implanted Iron Substrstrates
    WU Zhong-Da, WANG Hong-Sen, LIN Wen-Lian, DING Xiao-Ji
    1994, 15(4):  561-564. 
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    The corrosion behavior of Pd+ -implanted iron substrates was investigated.Implantation of Pd+ was performed with doses between 1× 1016-1× 1018 ion·cm-2 at 40 keV.The anodic dissolution process of Pd+ -implanted iron was measured by means of potentiokinetic sweep in a 0.5 mol/L NaAc/HAc buffer solution with pH 5.0. The open circuit corrosion potential as a function of immersion time was used to evaluate the corrosion resistance of the modified materials.The results show that Pd+ -implantation decreases the critical pa sive current of iron and maintains a better passivity in the acetate buffer solution with pH 5.0 However, the active corrosion rate of Pd+ -implanted iron is higher than that of unimplanted iron when the oxide layer has been reduced.The composition and valency states of elements at the surface of the implanted samples were analyzed by AES and XPS.
    Studies on Kinetics of Incorporation of Metal Ion Porpyrin(Ⅳ)──Coordination Reaction of TPyP Derivatives with Cu2+ in Lactic Acid Buffer System
    PAN Zhi-Quan, REN Jian-Guo, QIN Zi-Bin
    1994, 15(4):  565-569. 
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    Kinetics of the coordination reaction of tetrakis(N-carbomethoxymethyl-3-pyridyl) porphyrin(abbr,H2Tβ-N-ACMSPyP) and tetrakis(N-methylcarbonitrile-3-pyridyl) porphyrin(abbr.H2Tβ-N-ECNSPyP)with Cu(Ⅱ) ion has been studied in latic acid buffer solution in the range of pH 3-5 and an ionic strength of 0.5 mol/L(KCI)at 35.0±0.1℃.The reaction is catalyzed by lactic ion.The effect of concentration of the catalyst and metal ion, and pHvalue of solution was discussed.The observed rate constants of the reaction were obtained as kobs=k{(1.0+b1[L]+b2[L]2)/(1.0+K3,4[H+]2)}[Cu2+];k=5.39 mol-1·L·s-1,b1=3.73 ×102 mol-2·L2·s-1,b2=4.76×104 mol-3·L3·s-1 for H2Tβ-N-ECNSPyP; k=1.24 mol-1·L·s-1,b1=4.00×102 mol-2·L2·s-1,b2=2.75×105 mol-3·L3·s-1 for H2Tβ-N-ECNPyP.The mechanism of the reaction was proposed.The deformation of the ring of porphyrins is the general condition in the reaction.
    Determination and Estimation of Solubility of Substituted Aromatic Hydrocarbons
    WANG Lian-Sheng, HE Yi-Bing, GAO Hong, ZHANG Zheng
    1994, 15(4):  570-573. 
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    Solubility of many kinds of organic compounds was correlated with Van der Waals volume, Lewis acidity and Lewis basicity by the linear solvation energy relationship.Good correlation was found between solubility and Van der Waals volume, Lewis acidity and Lewis basicity.The estimated values fit with the observed ones well.
    A Study on Temporarily Water-Soluble Disperse Dyes Containing Carboxymethylsulfonyl Group──The Synthesis or Intermediates and Dyes
    PAN Xin, WANG Mei
    1994, 15(4):  574-579. 
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    Four new intermediates containing carboxymethylsulfonyl group were synthesized by the methods via chlorosulfonation of acetanilides or oxydation of thioethers.Intermediate (1) was synthesized by oxidation of thioether.Intermediates 3 and 4 were synthesized by chlorosulfonation of acetanilides.Intermediate 2 can be prepared by either methods.Intermediates 1 to 4 and other intermediate compounds were analyzed by IRand elementary analysis.Four new and other six temporarily water-soluble azo dyes containing carboxymethylsulfonyl group in diazo component were prepared.Their absorption specra were obtained.
    Studies on the Surface Chemical State of Cu-Zn-O Catalyst for Methanol Synthesis from Carbon Dioxide with Hydrogen
    XU Yong, LU Guan-Zhong, WANG Ren
    1994, 15(4):  580-583. 
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    XRD,ESR,UDRS,XPS and XAES have been used to examine the surface chemical state of Cu-Zn-Ocatalyst for methanol synthesis from carbon dioxide and hydrogen after the reduction and under the reaction conditions.The results show that only Cu0 on surface of the catalyst was found, no stable Cu2+ and Cu+ exist; a part of ZnO is reduced to produce lower valence Zn(2-δ)+(0<δ<2).And Cu0 and Zn(2-δ)+ is thought to be the active center of methanol synthesis reaction from carbon dioxide and hydrogen according to the activity measurement results.
    Thermal Stability and Activity of Catalytic Oxidation of Isobutyraldehyde of Molybdophosphoric Salt with Keggin Structure Containing Different Equilibrium Cations
    WU Tong-Hao, JIA Ji-Fei, ZHU Li, WANG Guo-Jia, YANG Hong-Mao, JIANG Yu-Zi
    1994, 15(4):  584-586. 
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    Molybdophosphoric acid with Keggin structure is an effective catalyst for oxidation reactions.As the central atom, coordinated atom and equilibrium atom in the molydophosphoric acid are displaced in a suitable manner, it exhibits increasing catalytic properties although the structure of the anion keeps unchanging, In this paper a series of Keggin molybdophosphoric acids containing different equilibrium cations were synthesized by a coprecipitation method.The prepared samples were characterized by means of FTIR, XRDand other techniques.Particularly the thermal stability of Li(Na,K, Cs)equilibrium molybdophosphoric salts were investigated.The catalytic acitivity over this series of samplers for one-step oxidation of isobutyraldehyde to produce methacrolic acid was measured as well.The experimental results indicate that Cs+ equilibrium molybdophosphoric salts is the best catalyst for the mentioned reaction.
    A Theoretical Study of the Nonlinear Optical Second-Order Susceptibilities of Push-Pull Polyenes──Carotenoids
    LI Jun, FENG Ji-Kang, LI Tie-Jin, SUN Jia-Zhong
    1994, 15(4):  587-591. 
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    On the basis of INDO/CI method,using sum-over-state formula, the nonlinear optical second-order susceptibilities βijk,βμ,β0 of push-pull polyenes──carotenoids have been calculated.The conjugated molecular chain length dependence of β0 has been studied,in the range of our research β0 varies as the 2.2 power of the length.Two kinds of substituent series have been studied too, the calculated results illustrate that the acceptor (这里有图片19940432-584-4.gif) is superior to (这里有图片19940432-587-5.gif).
    Studies of the Nature of the Surface Oxygen Species and the Catalytic Activities of V2O5 and V2O5 with the Additive Ag or Ag,Ni
    ZHANG Hui-Liang, SHANG-GUAN Rong-Chang, GE Xin, ZHANG Qi
    1994, 15(4):  592-595. 
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    The TPD-MS technique and the measurement of catalytic activity for toluene selective oxidation were used to study the thermal desorption properties of surface and lattice oxygen of V2O5 and V2O5 with additive Ag or Ag, Ni.The results showed that on the surfaces of the three samples the surface O- and O2- species were detected.With Ag or Ag, Ni added, the activation energy values(Ed)of the desorption of surface oxygen species(O- and O2-)decreased explicitly, and this shows that the Ed value of the sample containing Ag, Ni was the lowest, while the selectivity of benzaldehyde was the highest.In addition, for the samples of V2O5 and V2O5 with the additive Ag, Ni, a desorption peak which was mainly the lattice oxygen(O2-)appeared at 968 and 734℃, respectively, and the Ed value for the sample containing Ag and Ni was also the lowest.
    Determination of the Molecular Mechanical Parameters in Sulfonamide Changrolin Compounds
    WANG Qin-Mi, FAN Yu-Guo, LI Shu-Shen, CHENK Kai-Xian
    1994, 15(4):  596-599. 
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    Using quantum mechanics MNDO program and molecular mechanics MMP2 program, we determined some unknown molecular mechanical parameters in sulfonamide compounds.Using these parameters, we calculated a few sulfonamide Changrolin compounds whose crystal structures are known.We compared the calculated structures with the real structures and the result is satisfactory.All above proves that the obtained parameters are right and usable, and provides a powerful reference for calculating this kind of structures.
    Studies on Interaction of Electronically Excited Water-Soluble Copper-Porphyrins with DNA by Resonance Raman Spectroscopy
    ZHAO Xiao-Jie, JIANG Shan, LU Dong-Sheng, LU Lin, MAO Ci-Bo, AN Cheng-Wu, FAN Yong-Chang, LI Zai-Guang
    1994, 15(4):  600-602. 
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    The resonance Raman spectra of water-soluble porphyrin Cu(NACN)[Cu-tetrakis(4-N-acetonitrilepyridyl)porphyrin], Cu(NEAE) and Ni(NEAE)[Cu or Ni-tetrakis (4-N-ethylacetatepyridyl) porphyrin] and their complexes with calf thymus DNAat different laser pulse powers were measured with 445 nm pulse laser excitation; The analysis results indicate that both of the copper-porphyrins formed electronic exciplex with DNAbut the Ni(NEAE)did not form, In this experiment, besides copper-porphyrin Raman bands Ⅵ (near 1370 cm-1)and Ⅷ(near 1570 cm-1).band Ⅶ(near 1470 cm-1) also show extra band which symbolizes the formation of exciplex.The triplet of copper-porphyrin with a long life time is quenched by DNAand the exciplex may be formed by charge transfer from triplet of Cu-porphyrin to DNA.
    Characterization of Crosslinked Poly (ether urethane)and Study of Its Transitions and Free-Volume Properties with Positron Annihilation
    LIU Hao, GUO Jun-Shi, XIE Hong-Quan, WANG Bo, LI Shi-Qing, WANG Shao-Jie
    1994, 15(4):  603-607. 
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    The structure of crosslinked poly(ether urethane)was characterized by ATR-IR,and its conductivity of the polymer complex with LiClO4 is in close relationship with free-volume of the polymer, In the temperature range from 110─350K, lifetime spectra of positron annihilation in PEUhave been measured.The result shows that positron lifetime is sensitive to the transitions and free-volume holes in the polymer.From lifetime spectra we get the informations of secondary transition, glass transition and crystal melting transition.The temperature dependences of the size of free-volume in PEUare calculated from the o-Ps annihilation lifetime.
    The Structure and Characteristics of Microcelluar Polytetraflouroethylene Porous Membrances
    TANG Chong-Zheng, XU Lian-Xiang, TANG LI-Cong
    1994, 15(4):  608-611. 
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    The paper expounds the physico-chemical properties of microcellular foams and polytetraflouroethylene, micro-and ultramicro-cellular polytetraflouroethylene porous membrances which were prepared in different ways, and characterized by scanning electron microscope, electron spectroscopy for chemical analysis and blowing bubble method.The results show that the substrate membrance through flow coating combines plasma polymerization with ethylene.The membrance is easy to control and has good characteristics.
    Synthesis and Liquid Crystalline Behavior of Thermotropic Copolyethers with Azoxybenzene Mesogens
    ZHANG Qi-Zhen, LI Xiao-Fang
    1994, 15(4):  612-615. 
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    The monomer having mesogenic moieties based on 4,4'-dihydroxyazoxybenzene has been prepared.There is no evidence for liquid-crystal properties in the monomer,Aseries of copolyethers with azoxybenzene in main chain were synthesized using the condensed comonomers 1,6-dibromohexane(A)and 1, 10-dibromodecane(B)with different mole ratios by phase-transfer-catalysis copolyetherification reaction with 4,4'-dihydroxyazoxybenzene.Their liquid crystal behavior has been investigated by differential scanning calorimetry (DSC), polarized optical microscopy(POM)with a hot stage and X-ray diffraction techniques, All of the polymers exhibit enantiotropic nematic mesomorphism.The melting temperature and clearing points can be influence by variation of the copolyethers composition.As shown by Figure 1, the region of liquid crystalline phase of the copolyethers was the broadest and its melting temperature was the lowest when the A/Bmole ratio is 1.Nematic thread and schlieren textures of polymers were observed.Schlieren textures observed usually by POMfor nematic LCPwere characterized by two or four dark brushed meeting at a dark point.Banded texture of their oriented films, which of copolyether with mesogenic azoxybenzene has not yet been observed, was obtained as shown by Figure 3.This banded texture, as seen by POMbetween crossed polarizers, is an optical effect of slight alternating deviations of the molecular chain direction from a fibre axis normal to the bands.
    Research on the Synthesis of Anion Starch Microspheres and Their Properties
    YU Jiu-Gao, Tian Ru-Chuan, LIU Yan-Qi
    1994, 15(4):  616-619. 
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    The anion starch microspheres(PSM) have been synthesized from starch or starch derivatives by the counter suspension crosslinking polymerization in the presence of POCl3 as the crosslinking agent.Another anion starch microspheres(TSM) are made of neutral starch microspheres by the secondary polymerization and anionization using Na3P3O9 as the crosslinking agent.Their surface morphology, size distribution, characters of swelling and adsorbability for drug carrying have been studied in this paper.
    The Determination of Solubility Parameter of Polymer by Means of Swelling Kinetics
    ZUO Ju, ZHANG Yue, QIAO Feng-Jun, RAN Shao-Feng, JIN Chao
    1994, 15(4):  620-623. 
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    This paper was succeeded in the determination of solubility parameter of both linear and network polymer by means of swelling kinetics, which has the following procedures:(1)determine the swelling rate in the solvents with different solubility parameters(δ1);(2)draw a curve of swelling rate against δ1;(3)take the δ1 at the peak value of the curve as the polymeric solubility parameter δ2.In comparison with the classical methods of maximum intrinsic viscosity(MIV) and swelling equilibrium(Qmethod), the method is much better and worth getting applications widely because of convenience, time and energy-saving.
    The 0th and 1st Radii of Gyration for Aa-Bb Type polycondensation
    BA Xin-Wu, LI Ze-Sheng, PAN Shou-Fu
    1994, 15(4):  624-626. 
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    By means of differential method, the kth radius of gyration with k=0,1 is studied for Aa-Bb type polycondensation reaction.As an illustration, the polycondensation reaction of hexanedioic acid and trimethylol propane is discussed.
    Study of Adsorption Spectroscopy on Iron-Arene Complex Photoinitiator
    CHEN Xu-Dong, HUANG Xin-Hua, CHEN Yong-Lie, LIANG Zhao-Xi
    1994, 15(4):  627-629. 
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    The absorption spectroscopy of cyclopentalienyl-cumene iron hexafluorophosphate (Irgacure 261)in four solvents has been studied, the influence of irradiation on Irgacure 261 has been observed.The results show that the initiator can form complexes with acetonitrile and propylene oxide, The kinetics of photolysis of iron-arene complex has been determined,the photolysis reaction of initiator is the first order reaction, the rate constant of photolysis reaction is 0.391 min-1.
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