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    24 November 1994, Volume 15 Issue 11
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    Articles
    Synthesis and Crystal Structure of Ferrocenyl n-Heptyl β-Diketone
    LIU Zhan-Mei, LIAN Xi-Shan, LIU Qi-Wang, HAN Li-Min, SU Ning
    1994, 15(11):  1579-1582. 
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    The title compound, C5H5FeC5H4COCH2COC7H15 was synthesized by Claisen condensation of acetylferrocene with ethyl octoate, and it was characterized by elementary analysis, UV-Vis, IR, 1H NMRand MSspectra, Its crystal and molecular structure was determined by X-ray diffraction. Compound C20H26FeO2, M=354.26, belongs to monoclinic system with a space group P21/n, a=0.5790(1) nm, b=4.1634(4)nm, c=0.7635(1) nm, β=101.39(1)°, V=1.8042(4)nm3, z=4.D=1.30 g/cm3, F(000)=752, μ=8.40 cm-1.The final R=0.050 and Rw=0.059. The results of the structure analysis indicate that the β-diketone exists only in the enol form, and a six membered ring is formed through the intramolecular hydrogen bond.The hydrogen-bonded H Odistance is 0.146 nm.
    Interfacial Properties of HDEHP and HEHEHP and the Effect of Additives on Interfacial Properties
    SUN Si-Xiu, HAO Jing-Cheng, CUI Yan, YANG Qi-Mei, GAO Zi-Li, SHEN Jing-Lan
    1994, 15(11):  1583-1587. 
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    The interfacial properties of surface active agents, HDEHP, HEHEHP, TOPO, TBP.SDS.CTMAB.were investigated at 298 K.The interfacial adsorption parameters, Cmin, A1 and Langmuir's adsorption constant Kwere calculated respectively.The effect of additives on the interfacial tensions were discussed.The causes of the additives for the increase and/or decrease of extraction rate were also explained.
    Studies on the Extraction Mechanism of Molybdenum by Primary Amine N1923 in Kerosene
    ZENG Ping, HU Jing-Yu
    1994, 15(11):  1588-1591. 
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    The extraction of Mo(Ⅵ)by primary amine(abbreviated as N1923 or RNH2)in kerosene has been investigated.The effects of pHof the aqueous phase and temperature on this extraction process have been examined. The composition of extracted compound has been determined by equimolar series method, molar ratio method and saturation experiment.The infra-red spectra of the organic phase have also been studied.The mechanism of extraction is discussed.
    Novel Mixing Oxidation State Rare Earth Fluoride KEuCeF6
    GUAN Jun, TANG Zhong-Jia, WU Guo-Qing
    1994, 15(11):  1592-1596. 
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    Novel mixed oxidation state rare earth fluoride KEuCeF6 was synthesized by reducing tysonite structure type mixed rare earth trifluoride with metallic potassium vapor.The new compound was characterized by chemical analysis. X-ray powder diffraction, XPSand fluorescence spectra.The new compound has a stuffed structure of UCl3, related to NaNdF4 and gagarinite.Crystal system:Trigonal;space group: P3 ;Bravais lattice type hPwith lattice parameters a=645.4(2)pm, c=373. 0(1)pm, c/a=0.578. V=134. 65(12)×106pm6, Z=1, Dx=5.49g·cm-3, Dpyc=5.42g·cm-3.
    Synthesis, Crystal Structure and Thermal Decomposition of[Cu(NBOCTB)](ClO4)2·2DMF
    Ll Xiao-Yan
    1994, 15(11):  1597-1601. 
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    The complex of Cu(Ⅱ)with N, N, N'N'-tetra[1'-benzyl-2'-benzimidazol)methyl]-trans-1, 2-diaminocyclohexane(NBOCTB), [Cu(NBOCTB)](ClO4)2·2DMF, wasprepared. The crystal of the complex belongs to triclinic system and P1 space group with a=1.1851(5)nm, b=1.2255(3)nm, c=2.5237(5)nm;a=92.37(2)°, β=98.01(2)°, γ=107.82(3)°;V=3.442(4)nm3, M=1043.93, Z=2, Dx=1.36g/cm3, μ=4.60 cm-1, F(000)=1470. The thermal decompostion of the complex was studied by TG-DTGtechniques.The process of the decomposition can be divided into four stages:(19941106-1597-1.jpg)
    Digital Simulation of Neutral Carrier Cation Selective Electrode Membrane Electrochemical Properties
    WANG Ke-Min, HUO Xi-Qin, YU Ru-Qin
    1994, 15(11):  1602-1606. 
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    Digital simulation techniques are applied to investigate the electrochemical properties of neutral carrier cation selective electrode membranes with a particular attention bening paid to three possible transport mechnisms. The effects of mobilities, concentrations, complex formation constants and hydrophilic anions on potention response are studied.The simulation results provide useful information for exploring the response mechanism of this type of electroded, explaining some experimental phenomena and designing new neutral carrier electrodes.
    Kinetic Study on Electrochemical Oxidation of Alkyl Cobalt Schiff Base Complexes RCo(Salen)
    ZHU Shi-Min, ZHANG Tian-Yi
    1994, 15(11):  1607-1610. 
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    In this paper, the behavior of electrooxidative kinetic process of RCo(Salen)in DMF-TBAPsolution has been studied by cyclic voltammetry, chronoamperometry, linear sweep voltammetry, and lgi-Etechniques on micro gold wheel electrode. The kinetic parameters ks, n1, n2, D, a and kf have been obtained. The results showed that the oxidation of RCo(Salen) is an one electron transfer process coupled with chemical dissociation in which the dissociative product undergoes a second one electron transfer oxidation at the same potential to the initial electron transfer reaction. So, the overall oxidative process can best be described as ECEmechanism, The effect of alkyl group Ron E0 and kf is remarkable. E0 decreases in the order of CH3→C2H5→n-C4H9→i-C4H9. In the meantime, kf changes just in the opposite way.
    A Simple Approach to Resolve Information Lost in Convolution
    SHEN Wei-Yang, ZHUO Zong-Liang
    1994, 15(11):  1611-1614. 
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    Asimple approach to resolve the information lost in convolution has been suggested.Theoretical deduction showed that convolute integers for non-central point evaluation of derivatives can be expressed by the linear combination of those for central point evaluation of derivatives, while the latter was available in the revised Savitzky-Golay tables. This method offers a quick access to generating convolute integers for any point evaluation.The tables are arranged in an easy-to-refer format.
    Studies on Fluorescence Enhancement of Rare Earths──The Fluorescence Enhancement of Europium-2-(2-diphenylacetyl) indan-1,3-dione-cetyltrimethylammonium Bromide System by Ln3+
    SI Zhi-Kun, ZHU Gui-Yun, ZHANG Bin, JIANG Wei
    1994, 15(11):  1615-1619. 
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    Afluorescence enhancenient phenomenon shown by adding La, Gd, Tb, Lu, Y, or Sc ion to Eu-2-(2-diphenylacetyl)indan-1, 3-dione (DPN)-cetyltrimethylammonium bromide(CTMAB) system was observed. In the presence of above enhancing ions, the fluorescence intensity of the system can be increased about 10, 130, 30, 50, 52 or 20-fold, respectively than that of the system containing no enhancing ion, and it was a linear function of theconcentration of europium in the range 1.0×10-10 6.0×10-7mol/L.The detection limitwas 6.0×10-12mol/L.The system was used for the spectrofluorimetric determination of europium in the rare earth oxides and gave satisfactory results.
    Rapid Detection of Carcinogenicity of Metal Ions by Using O2 Electrode with Bacillus Subtilis Rec-assay Strains
    LI Hui, Diliber, DENG Jia-Qi, CHEN Zhong-Fu
    1994, 15(11):  1620-1622. 
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    Asimplified, efficient method has been constructed by combining O2 electrode andBacillus subtilis rec-assay strains to detect genetoxicity of various metal ions. The resultsshow that this method can be used to detect genotoxic metal compounds with a high sensitivity and fidelity, and the carcinogenicity of Cr6+, Co2+, Cd2+, Mn2+ ions are confirmed. Themanipulations are very simple, and reproducible responses was gained within half an hour.So this method can be applied to the screening of environmental metal compounds.
    Synthesis of Lipophilic Metal Phthalocyanines and Application for Carriers of PVC Membrane Electrode
    LI Jun-Zhong, PANG Xin-Yu, LU Shu, GAO De, YU Ru-Qin
    1994, 15(11):  1623-1625. 
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    Lipophilic 4, 4', 4", 4-tetra-tert-butylphthalocyanine cobalt(Ⅱ) and copper(Ⅱ)were synthesized using 4-tert-butylphthalic acid as the starting material.The followingproducts were ascertained through elemental analysis, IRand UV/Vis spectra.Thelipophilic compounds were used as carriers of PVCmembrane electrode, and it was foundthat the PVCmembrane electrode based on 4, 4', 4", 4-tetra-tert-butylphthalocyanine cobaltresponsed linearly to nitrite in a wide range with a high selectivety toward nitrite under theconditions.
    Studies on the Determination of Trace Nitrite with K4Fe(CN)6-NO2-Luminol Chemiluminescence System
    TANG Hong-Wu, LUO Qing-Yao, YU Xi-Mao, HE Zhi-Ke, ZENG Yun-E
    1994, 15(11):  1626-1628. 
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    Anew chemiluminescence method for the determination of trace nitrite based on its oxidation of K4Fe(CN)6 is studied. The chemiluminescence signal arises from the reaction of luminol-K3Fe(CN)6.The detection limit is 3.6×10-9g/mLfor nitrite, the calibration curve is rectilinear from 1×10-8 to 6×10-6g/mLof nitrite, and the relative standard deviation is 3.2%, This method has been applied to the analysis of natural waters, saliva and foods with satisfactory results.
    Synthesis and Structure of Tetramethyldisilandiyl Bis(3-trimethylsilylcyclopentadienyl)Tetracarbonyl Di-Iron and Its Related Compounds
    KONG Chui-Hua, XU Shan-Sheng, ZHOU Xiu-Zhong
    1994, 15(11):  1629-1633. 
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    Asmall amount of the title compound 5(5%)and a desilylated complex(Me2SiSiMe2)[C5H4Fe(CO)]2(μ-CO)2(1)(3%)and its rearrangement isomer[Me2SiC5H4Fe(CO)2]2(2)(16%) were obtained from the reaction of 1, 2-bis(3-trimethylsilylcyclopentadienyl)tetramethyldisilane with Fe (CO)5 at 105110℃.When a xylene solution of 5 was refluxed for 18h, compound [Me2Si(3-Me3Si-C5H3)Fe(CO)2]2(6), as a rearrangement isomer of 5 was obtained in58% yield.It was proved that desilylation of Me3Sioccured in the process of preparing5 and desilylation is related to the(Me2SiSiMe2)-bridge of the reactant.The crystal structure of 5 was determined by X-ray diffraction, The crystal is monoclinic, space group P21/m with a=0.6780(1)nm, b=2.2303(9)nm, c=0.9988(1)nm, β=98.96(1)°, V=1.496 nm3, 2=2, Dc=1.36 g/cm3.The final deviation factor Ris0.044.
    Studies on O-Alkyl, O-arylphosphoro(thioureido)thioates and O-Alkylphosphoro-bis-(thioureido)thioates
    HU Shi-Zian, JIANG Heng, WANG Ping
    1994, 15(11):  1634-1638. 
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    From thiopliosphorylchloride and potassium thiocyanate, series of phosphoro(isothiocyanatido)thioates and phosphoro-bis(isothiocyanatido)thioates were prepared, andthen through the reactions of these componds with amines two series of new oganic phosphorus compounds(RO)(ArO)P(S)NHC(S)NR1R2 and(RO)P(S)[NHC(S)NR1R2]2 were prepared.The structures of these compounds have been confirmed by IR, NMR, and elementary analysis.The results from the preliminary bioassay showed that compound PD-1 has fairlygood bactericidal activity.
    A Mechanistic Study on Reactions of Alkyl 2,5-Dimethoxyphenyl Ketones with t-Butylmagnesium Chloride
    GONG Yue-Fa, ZHAO Cheng-Xue, JIANG Xi-Kui
    1994, 15(11):  1639-1642. 
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    Reactions of alkyl 2, 5-dimethoxyphenyl ketones with t-butylmagnesium chloride were shown to yield the 1, 2-adducts, 1, 6-adducts, and the corresponding alcohols as the major products.The product distributions were found largely dependent on the alkyl group of the ketone and the solvent used. The bulkier the alkyl group . the more favoured the formation of the 1.6-adduct or the alcohol. On the other hand, the formation of the 1, 6adducts became a more important pathway when the reactions were carried out in tetrahydrofuran than in ether.In addition. the trace amount of transition metals in magnesium alsoshowed a little effect on the product distribution. Based on the experimental observations, we suggested that the above reactions, initiated by a single electron transfer, would possiblyundergo via the intermediates, radical ion pairs and radical pair, and the final product distributions greatly depended on the nature of the generated intermediates in each of the reactions.
    Synthesis of N-Isopropyl-O-aryl-O'-galatopyranosyl thiophosphoramidates and Their Biological Activity
    CHEN Ru-Yu, CHEN Xiao-Ru
    1994, 15(11):  1643-1646. 
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    The synthesis of novel N-isopropyl-O-aryl-O'-galactopyranosyl thiophosphoramidates was reported, and the conditions of the reactions were discussed.Apure isomer of N-isopropyl-O-(p-chlorophenyl)-O'-galactopyranosyl thiophosphoramidate 3d, 3d' , was obtained by recrystallization from diethyl ether-petroleum ether. The result of X-ray diffraction analysis showed that the configuration of the chiral phosphorus atom of 3d' was of R-form.The herbicidal and antidisease activities of the title compounds were tested.
    The Condensation of Rhodanine or N-Phenylrhodanine with Aromatic Aldehyde Under Microwave,Solid Base as a Supporter
    ZHANG Ming, WANG Cun-De, YU Shi-Long, TIAN Zhao-Bin, ZHANG Lin, CHEN Zhong-Jun, LI Ji-Guo
    1994, 15(11):  1647-1650. 
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    The condensation reaction of rhodanine or N-phenylrhodanine with aromatic aldehyde was catalyzed by microwave irradiation and with solid base as a supporter. The effects of basic supporter, microwave power and time on the reaction were investigated. Compared with conventional method without solvent or microwave. this method has better the advantage in yields, shorter reaction time and milder reaction conditions. Using 450 Wmicrowave and K2CO3/Al2O3 as basic supporter makes the condensation reaction speed above 102 time faster.Fourteen rhodanine derivatives are obtained.
    Low-Valent Titanium Induced Reductive Coupling Reactions of Aromatic 1,2-Diketones and a-Hydroxy Ketones
    HOU Zi-Jie, LIU Li-Jun, ZHANG Jian-Hua, LI Yu-Lin
    1994, 15(11):  1651-1653. 
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    Treatment of aromatic 1 , 2-diketones or aromatic a-hydroxy ketones with an activated low-valent titanium reagent, prepared by reduction of TiCl3·1/3AlCl3 with a Zn-Cu reagent, gave an intermolecular coupling reaction leading to the (Z)-1, 2.3.4-tetraaryl-2-butenes. Apossible coupling reaction process was proposed for the aromatic a-hydroxy ketones.
    Reaction of Halonaphthalenes with SO3
    LIN Jing, ZOU You-Si
    1994, 15(11):  1654-1656. 
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    The sulfonation of the six halonaphthalenes with SO3 in dichloromethane as the solvent was studied by using 1H NMRas method of analysis of the resulting mixure of sulfo derivatives. Monosulfonation of 1-fluoronaphthalene yields only the 4-S, where the other three 1-halonaphthalenes yielded in addition to some 5-S. Further sulfonation of any of the four 1-halonaphthalenes-4-S's yields a mixtures of the 2, 4-S2, and 4, 7-S2, and eventually also some 2, 4, 7-S3. Sulfonation of 2-chloro-and 2-bromonaphthalenes with 1. 0 mole of SO3 yields a mixture containing predominantly 8-S(～85%) with small amount of 4-S(～15%).The eventual products on using>4. 0 mole of SO3 are 4, 7-S2, and 6, 8-S2.
    Electrochemical and Spectroelectrochemical Behaviour of Porphyrin Compounds Containing Several Redox Centres(Ⅰ)
    TAO Jian-Zhong, SUN Hao-Ran, SHI Tong-Shun, CAO Xi-Zhang
    1994, 15(11):  1657-1661. 
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    The redox behaviour of porphyrin compounds containing several redox centres(where the porphyrin compound is meso-tetrakis (4-nitrophenyl)-porphyrinatocobalt(Ⅱ), [TNPPCo(Ⅱ)]) was investigated by cyclic voltammetry, in-situ UV-visible and FT-IRspectroelectrochemistry in dimethylformamide(DMF)and dimethylsulfoxide(DMSO).The first oxidation or reduction of TNPPCo(Ⅱ)is that centre metal cobalt(Ⅱ)loses or obtains one electron and leads to the formation of[TNPPCo(Ⅲ)]+ or [TNPPCo(I)]-.The secondreduction of TNPPCo(Ⅱ) is that four nitro groups of nitrophenyl on porphyrin ring meso sites respectively obtain one electron at the same potential and lead to the formation of the corresponding radical anions, and in this step overall porphyrin molecule obtains four electrons and leads to the formation of[TNPPCo(I)]5-.The third reduction of TNPPCo(Ⅱ) is that the porphyrin ring obtains one electron, but this reaction is irreversible. It was found that the intermolecular electronic interaction occured between nitro groups and porphyrin ring or centre metal cobalt, but the intermolecular electronic interaction among four nitro groups was not found.
    The Electronic Structure and Spectroscopy of Jahn-Teller Distorted D2h C60-
    FENG Ji-Kang, TENG Qi-Wen, LIJun, SUN Jia-Zhong
    1994, 15(11):  1662-1665. 
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    The geometry optimization of radical anion C60- has been performed by INDOseries of method and the D2h symmetry structure has been obtained. It is illustrated that the JahnTeller distortion has happened for C60- definitely, inducing the single bonds to be shortened and the double bonds to be lengthened, and l5 kinds of bonds and 9 kinds of different atoms have been formed, whereas the extra negative charge distribute near the equator mostly. On the basis of this geometry, the electronic spectrum of C60- has been calculated, the result is in good agreement with the experimental one.The spectrum has been assigned theoretically and the reason of red shift has been discussed.
    Studies on the Existence and Stability of Hexagonal Structure Nickel in Electrodeposited Ni
    GE Fu-Yun, YAO Shi-Bing, XU Shu-Kai, ZHOU Shao-Min
    1994, 15(11):  1666-1669. 
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    Sulfur-containing Ni and sulfur-free Ni deposits have been studied by means of transmission electron microscopy and selected area electron diffraction.The results showed that sulfur-free Ni deposit is of grainy structure, the grain size is about l00-500 nm and the structure is FCC, and sulfur-containing Ni deposit is of laminated structure, the layer thickness is about 200-300 nm, the gain size is about 20-30 nm. Besides FCC Ni, a hexagonal structure Ni is also found between the layers in the sulfur-containing Ni deposit.The differential scanning calorimetry experiment of the Ni deposits showed that the hexagonal structure Ni would be transfered into more stable FCC Ni at near l80℃.
    Reducibility of Vanadium in Zeolite ZSM-5
    ZHANG Chun-Lei, WU Zhi-Yun
    1994, 15(11):  1670-1674. 
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    The reducibility of V(Ⅳ, )-ZSM-5 and V2O5/ZSM-5(preapred by impregnation (Method I) and mechanical mixing(Method Ⅱ), respectivitly) was studied by TPR, XRD, ESRand XPStechniques, Some singificant information about phase changes during the reduction was obtained. It was found that the reduction temperature of V(v)dispersed on the surface of zeolite was lower than that of V2O5. However, V(v)in the lattice of ZSM-5 was more difficult to be reduced; Its reduction temperature is over l200 K. When the temperature was raised to or over 1370 K, V-ZSM-5 was converted into christobalite-structured phase, In this state, V(v)separated form the frameworks was completely reduced to the lower valence.
    The MS-Xα Studies of Sandwich Compound Ni(C5H5)2
    YU Wei-Zhou, CHANG Yi-De, ZHANG Ming-Yu
    1994, 15(11):  1675-1677. 
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    The calculations of the Xa electron energies and the normalization charges are carried out for Ni(C5H5)2. The bonding essential is discussed. The ionization energies and one electron transition energies calculated by using the transition state procedure are in agreement with the corresponding photoelectron data and UV-visible absorption spectra respectively.
    Electronic Spectroscopy of Anthraquinone Containing Bilayer Membranes
    LIU Chun-Jing, TIAN Yong-Chi, LI Guo-Wen, LIANG Ying-Qiu
    1994, 15(11):  1678-1681. 
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    Asingle-chain ammonium amphiphile(ANQU) which contains the anthraquinone chromophore formed stable bilayer membranes in water.The absorption and fluorescence spectra show the aggregate structure.The absorption spectra of ANQUaqueous sample show a considerable red shift relative to that observed in organic media(ethanol).Large red shift is also observed in the gel state, in contrast to that in liquid-crystalline state.These results indicate that the molecular packing mode in bilayer is J-aggregate, which is explained by the head-to-tail anthraquinone chromophore orientation. Both the fluorescence intensity and the peak location of anthraquinone chromophore are sensitively affected by the change in the bilayer physical state.
    The Steady State Electrochemical Behavior of Homogeneous Catalytic Reactions at Microelectrodes of Any Given Geometry
    SU Lian-Yong, LUO Jin, LIN Zhong-Hua, TIAN Zhao-Wu
    1994, 15(11):  1682-1685. 
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    The steady state electrochemical behavior of the pseudo-first and second order homogeneous catalytic reactions at a microelectrode of any given geometry is discussed in this paper.The mathematical treatment of the microelectrode using the concept of reaction layer is simple and is possible to avoid using complicated mathematical skills, By using these equations, some methods for determining kinetic parameters for the pseudo first order and second order CE'reactions are presented.
    A Study of the Preparation of Monodispersed TiO2 Particles
    YU Wang-Lin, YANG Ping, XU Qiu-Yun, ZHU Ying, XI Zheng-Kai, CHEN Zong-Qi
    1994, 15(11):  1686-1689. 
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    The spherical and ellipsoidal monodispersed TiO2 particles were prepared by using the method of hydrolysis from Ti(SO4)2 at increasing temperature.The effects of the concentration of Ti(SO4)2 and initial pHvalue on the size and morphology of the particles were studied systematically. It was found that the size of the particles increased with increasing Ti(SO4)2 cuncentration and decreasing pHvalue, and the morphology of the particles also changed due to the two factors.The morphology, size, and composition of the particles were studied by electronic microscopy and IR.Based on the change of the conductibility of the solution during the formation of the particles, the formation mechanism of the monodispersed particles was discussed.
    Studies on Renew Hydration of MgO and Two Types of Hydroxyl Groups
    CAI Bing-Xin
    1994, 15(11):  1690-1693. 
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    In this paper, renew hydration of MgOand two types of hydroxyl groups were investigated by the techniques of IR, XRD, TG-DTA, It is found that the hydrolysis of MGO, under the experiment conditions, occured on the surface, the two types of hydroxyl groups of hydration are taken off at 600℃, the hydration hydroxyl group and O- build up free hydroxyl group, the two types of hydroxyl groups of MgOare influenced by Li+ added.
    The Study of Conformational Mechanism of γ-Relaxation in PEEK Chain Molecules
    SHEN Liang-Jun, YE Shi-Yong, LI Qian-Shu
    1994, 15(11):  1694-1697. 
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    In this paper AMl semiempirical quantum mechanics calculation was used to study the conformational mechanism of γ-relaxation in PEEKchain molecules.The results show that the contacted phenyl rings will adjust the relative positions when the chain segments are doing crankshaft type motion, and the activation energy of γ-relaxation is interrelated to the relative rotation barrier of phenyl rings, the barriers of crackshaft motions of chain segments and the intermolecular interactions of chains.The value of each part was estimated in this paper and the further calculation of the relative orientation of phenyl rings in PEEKwas done, a much, better result compared with the experimental data was achieved.
    57Fe Mssbauer Spectra Study on Eu0.5 RE0.5 Fe0.5Mn0.5 O3 Oxides
    LI Li-Ping, Wei Quan, REN Xiao-Lin, ZHENG Da-Feng, SU Wen-Hui
    1994, 15(11):  1698-1701. 
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    The method of solid state reaction was used to synthesize the samples of Eu0.5 RE0.5 Fe0.5Mn0.5O3(RE=La, Pr, Nd, Sm, Eu, Gd, Tb.Dy, Ho, Er, Tm, Yb, Y).XRDand 57Fe Mossbauer spectra were measured It is found that the volumes of unit cell of the samples increase with increasing atomic number of RE; Fe3+ ions are in a high spin state, and the relationship between the quadruple splittings and lattice distortion parameter Dof the samples is linear.
    Surface Structures of APS Cationized Si Substrate and Monolayered Polymer Molecular Deposition Film Observed by Atomic Force Microscopy
    ZHANG Xi, GAO Mang-Lai, WANG Li-Yan, SHEN Jia-Cong
    1994, 15(11):  1702-1703. 
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    The surface structure of aminopropyhlanized(APS)cationized Si substrate and monolayered polymer molecular deposition(MD) film were investigated with atomic force microscopy(AFM).AFMimages of the APS Si substrate showed a close packed and well-ordered arrangement, in which the periodical spacings are 0.359 nm and 0.562 nm in two directions, respectively.As shown in the AFMimage of polymer MDfilm, the surface fluctuation is in the range of nanometer scale and its image has no change after scanning 50-100times, thus it is demonstrated that MDfilm is of higher stablity than that of LBfilms.
    MS-Xα-SCF Study on Transitional State of Dissociative Chemisorptive Reaction System CH4/Ni (Ⅲ)
    MA Chen-Sheng, MA Li, YANG Zhong-Zhi
    1994, 15(11):  1704-1706. 
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    For dissociative reaction system of CH4/Ni7, cluster model is employed for MS-Xα-SCFstudy of its transitional state electronic structure, the characteristics of chemisorption bonding and inter-action picture have been drawn, and the results obtained are in agreement with those of expriments.
    Studies on the Stability of Multiple Emulsion
    LIU Pei-Yan, CHU Ying, WU Zi-Shen, YAN Zhong, KANG Wan-Li
    1994, 15(11):  1707-1709. 
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    In this paper, we have studied the stability of multiple emulsion with three kinds of surfactants by using tracer technique.Two interfaces(W/Oand O/W)of W/O/Wtype multiple emulsion and their stability are discussed.According to the results of the electron micrographys and π-Acurves, we draw out the conditions of the stability of multiple emul sion.
    The Temperature Dependence of Electro-optical Properties and Thermo-optical Properties of UV Cured PDLC Films
    PAN Yi, YANG Yu-Liang, LI Li
    1994, 15(11):  1710-1714. 
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    The temperature dependence of electro-optical and thermo-optical properties of UVcured PDLCfilms have been studied and the stability of PDLCas a kind of display device has been investigated. By studying the thermo-optical properties, we have got a method of determining the usable temperature range.The N-Iphase transition behaviour of liquid crys tals in PDLCfilms has been discussed.The correlation between morphology and N-Itransi tion behaviour have also been discussed in this paper.
    Synthesis and Properties of Oxymethylene-Linked Polyoxyethylene Multiblock Polymer
    LIU Chang-Sheng, GUO Jun-Shi, XIE Hong-Quan
    1994, 15(11):  1715-1718. 
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    Aseries of oxymethylene-linked polyoxyethylene multiblock polymer were synthesized by condensing dichloromethane with poly (ethylene glycol)(PEG) of different mol.wt.in the presence of potassium hydroxide powder. The multiblock polymer exhibited a certain crystallinity, and its LiClO4 complex showed a high room temperature conductivity.Alithium battery has been constructed using LiClO4 complex of the multiblock polymer as the electrolyte and Na1+x V3O8 composite as the cathode.The performance of the battery has been investigated.
    Studies on Molecular Diffusion Behavior Before and After Reaction Between Pb2+ -Containing Microgel and H2S in a Good Solvent
    YANG Yi, GAO Ming-Yuan, MA Rong-Jiu, BIAN Feng-Lan, SHEN Jia-Cong
    1994, 15(11):  1719-1722. 
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    Anew kind of lightly crosslinking microgel containing lead ions was prepared by solution polymerization.The diffusion behavior, before and after reaction between the Pb2+ -containing microgel and H2Sin a good solvent, was measured by means of Dynamic Light Scatttering separately.The diffusion coefficients of the microgels at infinite dilution concentration were obtained by extrapolation and hydrodynamic radii of the microgels were calculated with Stokes-Einstein equation.The results show that the volumes of PbS-containing microgel varied with the initial concentrations of Pb2+ containing microgel in reaction. It shows that H2Sreacted not only within one microgel particle, but also between the microgel particles, The linear relationship range of D-Ccurve decreased because of the connection betweenPbS-containing microgel particles.
    Synthesis of New Liquid Crystal Polymers with T-Shaped Two-Dimensional Mesogenic Units
    LI Zi-Fa, CHEN Zhi-Jun, ZHANG Shu-Yuan, WANG Jing-Wu, ZHOU Qi-Feng
    1994, 15(11):  1723-1726. 
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    Two new kinds of polymers were synthesized by low temperature solution polycondensation by using N-2, 5-dihydroxy benzylidene-4-substitued aniline and diacid chloride with different structures as the monomer. The liquid-crystalline behavior of the polymers was characterized by DSC, polarizing microscopy with a heatlng stage and X-ray diffractometer.It was found that one kind of the polymers was nematic thermotropic liquid crystal polymers, and the other kind of polymers was non-liquid-crystalline. The intrinsic viscosities, Tm and Ti of the polymers changed regularly with the change of the structure of the monomers.
    Ionic Conduction of Polymer Electrolytes Based on an Alternating Maleic Anhydride Copolymer with Oligo-oxyethylene Side Chains
    DING Li-Ming, LIN Yun-Qing, ZNOU Zi-Nan, WANG Fo-Song
    1994, 15(11):  1727-1729. 
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    In this paper, the ionic conductivity of the BM350-LiClO4 complexes was studied as a function of temperature and salt concentration.At high salt concentrations, the more pronounced fall in conductivity in the solid medium has been interpreted as being due to the effect of Tg and bulk viscosity on ion transport. Conductivities which displayed non-Arrhe-nius behviour were analysed using the Vogel-Tammann-Fulcher equation and interpreted on the basis of the configurational entropy model derived by Gibbs and coworkers.
    The Syntheses and Characterization of Polydichlorophosphazene and Poly(β-naphthyloxy)phosphazene
    XU Shi-Bhg, ZHENG Fu-An, YANG Yong-Gang
    1994, 15(11):  1730-1732. 
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    The method of preparing N-dichlorophosphoryl-P-trichloromonophosphazene as monomer from PCl5 and(NH4)2 SO4 in 1, 1, 2, 2-tetrachloroethane was investigated. Polydichlorophosphazene can be obtained from the polycondensation of this monomer and poly (β-naphthyloxy) phosphazen (I) was prepared from polydichlorophosphazene and sodium β-naphthyloxy.At the same time, the IR, 31P NMRof the title polymers were determined.The glass transition and viscous flow temperatures determined by TBAare-83℃ and 19℃respectively. Decomposition temperature measured by TGis 338℃.The Mn of Iestimated by VPOis 4110.
    The Effects of Reaction Medium on BDC Initiating Acrylamide Polymerization
    YANG Wen-Jun, SNEN Jia-Cong
    1994, 15(11):  1733-1735. 
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    The effects of reaction medium (alcohol, dioxane, dioxane/alcohol)on the heterogenous polymerization of acrylamide initiated by BDC (benzyl diethyldiothiocarbate)were studied. The results showed that herterogenous polymerization differed from homogeneous solution polymerization initiated by BDCand did not have the character of living radical polymerization. The polarity of reaction medium affected the enolization of acrylamide obviously, and made the yield of polymer and molecular weight different from each other, behaving obvious solvent effects.The UVspectra of products and polymerization of acrylamide initiated by products, show that iniferter functional groups remained in products.
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