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    24 July 1995, Volume 16 Issue 7
    Articles
    Interactions of Rare Earth Ions with Bovine Blood Cu(Zn)-Superoxide Dismutase
    FENG Zhi-Xiang, ZHANG Shu-Gong, LIU Qi-Min, YANG Kui-Yue, NI Jia-Zuan, MIAO Jian, YOU Shu-Heng
    1995, 16(7):  993-996. 
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    The interactions of lanthanium trichloride and terbium trichloride with bovine blood Cu (Zn)-superoxide dismutase [Cu(Zn)-SOD] in the aqueous solution of hexam-ethylenetetramine buffer (pH=6. 3) have been'studied by using fluorescece, CDand ESRspectra. The results indicated that rare earth ions were coordinated to the carboxyl groups of acidic amino acid residues which were far from active center of the Cu(Zn)-SOD molecule and only lightly disturbed the secondary structure of the enzyme protien, and made the coordination structure of enzyme-bound Cu2+come from the rhombchedron to the axial shape at 77 K and the activity of Cu(Zn)-SOD enzyme was not nearly changed at room temperature.
    Studies on Rare Earth Complexes of Quaternary Ammonium Salt(Ⅵ)--Synthesis,Characterization and Crystal Structure of Tetrabutylammonium Tetranitrato Diisothiocyanato Neodymate
    ZHANG Ya-Wen, YAN Chun-Hua, LI Biao-Guo, HUANG Chun-Hui, XU Guang-Xian, MA Zhe-Sheng, TANG Chun-Hong
    1995, 16(7):  997-1002. 
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    A new type mixed ligand title complex was synthesized. The general formula was C50H108NdN9O12S2. The infrared spectrum and thermal analysis of the complex were studied. Its molar conductivity shows it to be 3 : 1 type electrolyte and the ionic crystal. The single crystal structure has been determined by a four-circle X-ray diffractometer. The crystal is monoclinic, space group Cc, with unit cell dimensions: a=1. 6578 nm, b=1. 8108 nm, c=2.3962nm, β=91.58°, Z=4. Neodymium is coordinated by 8 oxygen atoms of four biden-tate, nitrate groups, and 2 nitrogen atoms of two thiocyanates, so the coordination number is 10. The average bond length of Nd-O is 0. 2567 nm; the average bond length of Nd-N is 0. 2534 nm. Polyhedron of Nd3+ion is a twist 4,4-bicapped square antiprism.
    Studies on the Complexes of Pr(Ⅲ), Nd(Ⅲ) with 2-[(Substituted phenylamino) carbonyl]benzoic Acids
    SHI Jin-Chao, A Mi-Na, LI Heng-Xin, YANG Bing-Qin
    1995, 16(7):  1003-1006. 
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    Complexes with the general formula Ln(X-P)3·3H2O[X=H, 2-Cl, 4-Br, 2CH3, 3-NO2, 2-OCH3, 2,4-dichloro, 3-OH; P=2-(COO)C6H4CONHC6H5-nXn, n=1,2; Ln=Pr (Ⅲ), Nd(Ⅱ)] have been synthesized and characterized on the basis of elementry analysis, infrared and reflectance electronic spectra and thermogravimetical methods. The results show that the cpordination occurs by means of two oxygen atoms, one is from the amido and the other from the hydroxyl in the carboxylate. Each complex contains three coordination water molecules. The values of Slater-Condon (F2, F4, F6) interelectronic repulsion and Lande parameter (ξ4f) spin-orbit interaction parameters have been computed from the spectral data. The average values of F4/F2and F6/F2have been found to be 0. 137, 0. 0149[Pr (Ⅲ)] and 0.153, 0.0152 [Nd(Ⅲ)], respectively. By using the spectral data, the nephelauxitic ratio (β), average covalency parameters (δ) and average bonding parameters (b1/2) have been evaluated which indicate weak covalent bonding.
    Crystal Structure and Spectra of Ln(p-ABA)3bpy·2H2O Complexes
    ZHENG Xiao-Mei, JIN Lin-Pei, WANG Ming-Zhao, ZHANG Jia-Hua, LU Shao-Zhe
    1995, 16(7):  1007-1011. 
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    Syntheses of Ln(p-ABA)3bpy·2H2O(Ln=Nd, Eu, Yb, p-ABA: p-aminoben-zoate, bpy: bipyridine) and their crystal structure, Raman and fluorescence spectra are re-ported. The crystal belongs to triclinic system with space group P1 The coordination number of the central atom is eight. There are three coordinated modes for carboxylate groups: unidentate, bidentate and bridged. Raman spectra of the complexes indicate that there are more than one coordinated modes for the carboxylate groups. This is in good agreement with the result of X-ray analysis. The high resolution spectra of Eu(p-ABA)3bpy·2H2O show only one Eu(Ⅲ) ion site in the complex. The symmetry for the Eu(Ⅲ) site is C1.
    Syntheses and Characterization of Coenzyme B12Analogues/β-CD Supramolecules
    LUO Lai-Bin, CHEN Hui-Lan, LIU Jun, TANG Wen-Xia, KarlS. Hagen
    1995, 16(7):  1012-1013. 
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    A new kind of supramolecules of coenzyme B12models with β-cyclodextrine, RCo(DMG)2L/β-CD(R=i-C4H9, n-C4H9, n-C5H11, c-C6H11, PhCH2DMG=dimethyl-gly-oxime. L=H2O, NH3), were firstly synthesized and characterized by elementary analysis, FAB-MS and 1HNMR. X-ray structure analysis of i-C4H9Co(DMG)2H2O/β-CD proved that the alkyl group of RCo(DMG)2L was included into the hydrophobic cavity of β-cyclodextrin and the equational DMG was located near the wider opening.
    DNA Cleavage by Organometallic Complex
    GUO Mao-Lin, YANG Pin
    1995, 16(7):  1014-1015. 
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    By using agarose gel electrophoresis technique, DNAcleaving activities of two organometallic complexes, FcT (ferricenium trichloroacetate, bis (trichloroacetic acid) solvate) and TDC(titanocene dichloride), were tested in this paper. The results show that FcTcan cause a single strand cleavage of pBR322 DNA, but TDC can't do under the same condition.
    Oscillographic Flow Injection Analysis
    ZHENG Jian-Bin, LIU Peng, SHI Sheng-Hua
    1995, 16(7):  1016-1019. 
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    Oscillographic flow injection analysis (dynamic oscillographic analysis)means the combination of flow injection technique with oscillographic analysis and oscillographic determination is carried out in continuously flowing solution. Flow-through cell which suited to oscillographic analysis is designed. New technique with feedback voltage is first presented. Reproducibility, detection limit and influences of different factors on peak height of depolarizer are investigated. The method has the characteristics of easy operation, quick analysis, good reproducibility, high sensitivity, saving reagents, and the difficult problems of static oscillographic method have been solved. Therefore, oscillographic determination methods will become a series of really feasible analytical methods.
    High Fidelity Digital Filter Based on Medians
    MIAO Hua-Jian, HU Shang-Xu
    1995, 16(7):  1020-1023. 
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    Anew high fidelity filtering algorithm(HFFA) using medians in moving window is proposed. In case the window width is set to include 2m +1 data points, peaks with widths greater than m points are reserved without distortion, while peaks with widths smaller than m points are completely removed. Compared with other conventional filtering methods, in particular the widely used ones based upon weighted sums, this algorithm has advantages of better filtering effect and less distortion. Ensuring peak height and peak position, which are two major parameters, to be least changed, this new algorithm is especially feasible for filtering physico-chemical spectrum from noises.
    Digital Simulation of Cyclic Voltammetry for Response of Enzyme-Mediator Modified Electrode
    KONG Ji-Lie, DENG Jia-Qi
    1995, 16(7):  1024-1027. 
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    Digital simulation was employed to study the cyclic voltammetry(CV) response of enzyme-mediator modified electrode. The digital model was built and the effect of kinetic parameters on CV curves was discussed. The digital simulation could help to devise or improve the properties of such kind of enzyme-mediator modified electrode.
    Studies on 1:12 Molybdoarsenate Heteroly Anion Film Chemically Modified Electrode
    CHEN Ling-Yin
    1995, 16(7):  1028-1030. 
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    Amonolayer of 1:12 molybdoarsenate acid (AsMo12) was modified on a glassy carbon electrode (GCE) by electrochemical or dip coating method in a solution containing 1. 33×10-5mol/Lmolybdoarsenate, 0.30 mol/L sulfuric acid -20% acetone. Cyclic voltam-metry was used to study the electrochemical behavior of AsMo12and AsMo12film modified electrode. It is confirmed that AsMo12can be strongly adsorbed on the surface of GCE. On the other hand, the autocatalytic reduction of AsMo12and the electrocatalytic reduction of the AsMo12film modified electrode for iodate anion (IO3-) in 0. 30 mol/Lsulfuric acid -20% acetone is described.
    Studies on Improving Selectivity of Microbial-Enzyme Sensor
    WANG Qing, ZHANG Xiao-Hua, DENG Jia-Qi
    1995, 16(7):  1031-1033. 
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    Treated by a special temperature to the microbial sensor and cultured the Es-cherichia Coli in different media, the electrode has improved its selectivity of responses to L-asparagine, L-glutamine and L-asparate. This result is helpful to the further employment of the microbial electrode.
    A Sensor Based on Chemiluminescence for the Determination of Mn2+
    LU Jian-Zhong, ZHANG Zhu-Jun
    1995, 16(7):  1034-1036. 
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    Achemiluminescence sensor for Mn2+combined with flow-injection system is presented in this paper. It was based on the new approach that all of the reagents involved in the chemiluminescence reaction were immobilized electrostatically on Amberlyst A-27 anion-ex-change resin. Mn2+can be sensed directly by the reaction with Luminol and IO4-, which were eluted by Na3PO4from the immobilization column prior to the chemiluminescence reaction. The linear range for Mn2+is 2. 0×10-9-1.0×10-5g/mL. The detection limit is 1.0×10-9g/mL. The column with immobilized chemiluminescence reagents in the resin can be used for 100 times. The sensor has been applied to the determination of Mn2+in water samples.
    Characteristics of a High Current Microsecond Pulsed Hollow Cathode Lamp
    GONG Zhen-Bin, YANG Peng-Yuan, LIN Yue-He, WANG Xiao-Ru, HUANG Ben-Li
    1995, 16(7):  1037-1039. 
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    The voltage-current and spectral characteristics of a high current (up to tens of amperes)microsecond pulsed hollow cathode lamp has been studied. The intensities of the atomic and ionic lines emitted by the pulsed HCLare greatly enhanced as compared with those emitted by the same lamp with DCsupply, and the enhancement factor is much greater for the ionic lines (104) than for the atomic lines. This implies that the HCMSP HCL could be used as a convenient and inexpensive source for ionic fluorescence spectrometry.
    Optical Rotation and Configuration of 5,6-Dimethylidenebicyclo-[2. 2. 1]heptan-2-ol and Its Derivatives
    ZHOU Zhi-Chen, LI Xi-You, GUAN Jing-Qu
    1995, 16(7):  1040-1043. 
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    Some optical pure derivatives, ethers and esters, of 5, 6-dimethylidenebicyclo [2. 2.1]heptan-2-ol were prepared. The relationship between their optical rotation and configuration fits the asymmetric polarizability of multistage sphere model.
    Theoretical Study on Secondary Bond in Organo-metallic Compound (Ⅱ)--Secondary Bonding Between Conjugated Bond of Benzene Ring and Hg
    LAI Cheng-Ming, TANG Jun, YUAN Man-Xue, LUO Hui-Hong
    1995, 16(7):  1044-1046. 
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    According to the experimental material, by Kiefer et al., in order to further discuss the speciality of chemical bond in molecule 3-(p-methoxyphenyl )-2-methyl-2-methoxypropyl mercuric chloride, we have used molecular mechanics method to study the conformation and MNDO semi-empirical molecular orbital method to calculate the electronic structure. The results indicate that in this molecule there is a secondary bonding which consists of conjugated π orbital of benzene ring with the empty 6pxorbital of Hg atom.
    The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(XXII)--Substitution Cycloaromatization Reaction of α-Oxoketene Dithioacetals with Methallyl Grignard Reagent Using Mercaptan as the Nucleophiles
    LIU Qun, XU Bai-Ling, YANG Zhi-Yun, ZHAO Hong-Wu
    1995, 16(7):  1047-1050. 
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    The 1,2-addition of α-oxoketene dithioacetals with methallyl Grignard reagent afforded the carbinols 2. 5 and 6 respectively. Catalyzed by sulfuric acid, 2 and 5 were converted to the same product (such as 3c)3 (or 4) when mercaptan (or phenyl-sulfohydrate) was used as the nucleophile. The above conversion was believed to proceed via a substitution cyclo aromatization mechanism. Under the same condition, compound 6 was converted to the cycloaromatization product 7. Based on the experimental facts, a reactivity order 1,3-propy-lenedithio>1,2-ethylenedithio>dimethylthio was proposed to the substitution cycloaromatization reaction.
    Studies on the Syntheses of Metalloporphyrins and Biomimesis for Cytochrome P-450(XIV)--Catalysis of TPPCo(Ⅱ) for Cyclohexane Monooxygenation
    CHEN Xin-Bin, GUO Can-Cheng, LIANG Ben-Xi, RAO Zong-Hai, YANG Zhi-Guo
    1995, 16(7):  1051-1054. 
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    This paper reports the catalysis of TPPCo(Ⅱ) for cyclohexane monooxygenation with PhIO. The kinetic properties, the temperature effect and the effect of axial ligands of the reactions were studied. The results show that TPPCo(Ⅱ) with axial ligand pyridine can catalyze cyclohexane monooxygenation with PhIO and that the catalytic properties are related to the reaction temperature and the quantity of pyridine. The rates of the reactions can increase with the increase of the reaction temperature. There is Arrhenius relationship between the rate constants of the reactions and the reaction temperature. The yields of the products decrease with the increase of the reaction temperature. The catalytic effect of TPPCo(Ⅱ) is the best when the quantity of pyridine is 50 times that of TPPCo(Ⅱ).
    The Influence of Additive Reagent and Reaction Medium on the Catalytic Characteristics of TPPFeCl in the Biomimetic Oxidation of Cyclohexane with PhIO
    JIANG Du-Xiao, GUI Ming-De, ZHU Shen-Jie
    1995, 16(7):  1055-1058. 
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    The influence of additive isopropyl alcohol, pyridine, hydrochloric acid and sodium hydrate in different quantities on the catalytic characteristics of chloro tetraphenyl-porphinato iron TPPFeCl and (TPPFe)2O in above reaction was studied. It is found that isopropyl alcohol and pyridine in small amounts could increase the yield of oxidation product of cyclohexane. The presence of cyclohexanol could give a longer catalytic lifetime of TPPFeCl. The catalytic oxidation of cyclohexane could be favourable as a small amount of aqueous NaOH was added; but unfavourable as hydrochloride acid was added. This reaction was unfavourable either when the polarity of solvent increased. One of the oxidation products of cyclohexane, cyclohexanone, was verified to be mainly produced by oxidizing cyclohexanol directly by PhIO. The presence of TPPFeCl was unfavourable to form cyclohexanone.
    Synthesis of Two Polynuclear Tetrathiafulvalene Derivatives and Their Behaviour of Cyclic Voltammetry
    SHEN Yong-Jia, DONG Chang-Zheng, NI Cai-Ying
    1995, 16(7):  1059-1063. 
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    Two polynuclear tetrathiafulvalene (TTF) derivatives, which contained three TTFsub-units, were synthesized. Their 1HNMR,13CNMR, MS, and UV absorption spectra as well as cyclic voltammograms (CV) were given. The CV behaviour of the compounds was compared with that of corresponding TTFderivatives containing one or two TTF sub-units. It indicated that the coulombic repulsion in the former was lower than that in the latter, because a conjugation degree in the former was longer than in the latter.
    Molecular Mechanisms of DNA Recognition by RuNi Heterobinuclear Complexes
    BU Xian-He, ZHU Shu-Mei, YANG Ming, WANG Kui
    1995, 16(7):  1064-1065. 
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    The interactions of a new class of intelligent RuNi heterobinuclear complexes, which have been found to be potent inhibitors of HIV-Ireplication, with DNA having been studied. The complexes bind to DNA by intercalation based on increment in viscosity on titration with CT-DNA. The binding strength was further evaluated by spectroscopic measurements. Gel electrophoresis reveals the conversion of supercooled pBR322 DNA to the nicked form and linear form, which is induced by the Ru part of the complexes.
    Electrochemistry of Bridged Dimers of Alkylferrocene
    DING Ting-Zhen, WANG Yan, YANG Yu, WU Yan-Zhong
    1995, 16(7):  1066-1068. 
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    Electrochemistry of nine kinds of bridging dinners of alkylferrocene derivatives was investigated in this article. It was found that CV waves of complexes showed only one reversible oxidation peak when the bridging group was -CH2-. Other complexes give two reversible one-electron oxidation peaks. The only one oxidation potentials of the complexes dependent on the numbers of carbons y in substituent CyH2y+1, and increase with y. But for the complexes of two oxidations peaks, the first potentials Ep1for oxidations were nearly constant when the bridging groups were the same, however, the second potentials Ep2slightly increase with the increase of y. According to the experimental results of burning rate catalytic activity, the smaller Ep2of complex, the larger its catalytic activity.
    Synthesis of Methyl 2,2-dimethylgibberellate A1
    XIE Wen-Ge, CUI Yu-Xin, PAN Xin-Fu
    1995, 16(7):  1069-1071. 
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    Methyl 2,2-dimethylgibberellate A1(9a) and its isomer methyl 2,2-dimethyl-epi-gibberellate A1(9b) were synthesized first by chemical method from gibberellic acid (GA3)3All intermediates were substantiated by MS, IR, 1HNMR. The 1HNMR data of 9awere in agreement with those from literature.
    Studies on Separation of Derivatives of Amino Acid of Enantiomers on Chiral Stationary Phase by High Performance Liquid Chromatography
    SHEN Han-Xi, YANG Guo-Sheng, GAO Ru-Yu, WANG Qin-Sun
    1995, 16(7):  1072-1074. 
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    Eighteen derivatives of six DLamino acid alanine, 2-amino-n-butanoic acid, va-line, leucine, phenylalanine, methionine of enantiomers were separated by L-isoleucine-t-butylamide type chiral bonded stationary phase (CSP) in HPLC. The experimental result showed that the chiral stationary phase had good resolution for the racemic α-amino acid derivatives. The performance of the structure of derivatives and composition of mobile phase for the resolution was examined. The probable mechanism for chiral recognition was proposed.
    The Binding Equilibrium of Mitoxantrone and Deoxyribonuleic Acids
    YANG Pin, WANG Hong-Fei, YANG Bin-Sheng
    1995, 16(7):  1075-1077. 
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    Interaction of mitoxantrone and deoxyribonuleic acids was studied at different phosphate/drug ratios(P/D), and it was found that there are two types of binding processes and interaction models. In a certain range of P/D, one type of model is dominant. At P/D <3, MX leads to condensation of DNA. At higher P/Dratio, MX intercalate into DNA, leading to red-shift of absorption spectra. At P/D>6, MX and DNA are in the binding e-qulibrium, the equilibrium binding constant of MX and calf thymus DNA is 9. 0×105(mol/L)-1at 20℃, and the binding site size n is 5. The results indicate that major groove and minor groove may be the most favorable binding sites in the structures of double stranded nucleic acids. There existed anticooperative effects between the binding sites.
    An ab initio Study on Proton Transfer Reactions of NH3R++NHR2(R=H,CH3)
    FENG Da-Cheng, CAI Zheng-Ting, JU Guan-Zhi, DENG Cong-Hao
    1995, 16(7):  1078-1082. 
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    Proton transfer processes of the system NH4++NH3→NH3+NH4+, NH4++NH2CH3→NH3+NH3CH3+, NH4++NH(CH3)2→NH3+NH2(CH3)2+and NH3CH3++NH2CH3→NH2CH3+NH3CH3+have been studied by ab initio SCF method at RHF/6-31G*level. The results show that: (1) there are two potential wells on each potential surface of these four systems and the proton transfers directly along the line between the two nitrogen atoms; (2) the methyl substitutent in the molecule which accepts proton promotes the proton transfer and that in the molecule which donates proton hinders the proton transfer.
    QSAR Study for the Toxicity of Nitroaromatics to the Fathead Minnow
    LANG Pei-Zhen, LU Guang-Hua
    1995, 16(7):  1083-1087. 
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    The net charges(Qc, QN,Q-NO2) of 50 nitroaromatic compounds were predicted by the quantum chemical method CNDO/2; the energy of the lowest unoccupied molecular orbital (ELUMO) ,the energy of the highest occupied molecular orbital(EHOMO), the difference of heat of formation (△(△Hf)) and the moment of dipole(μ) of 42 nitroaromatics compounds were predicted by MNDO. The relationship of structure-activity was analyzed with the toxicity 96h-LC50of the fathead minnow by using the seven quantum chemical parameters. Through statistical analysis, QSARmodel was yielded as follows:-1gLC50=11. 35-1. 28ELUMO-9.17QN+0. 46EHOMO-0.12μ n=35,r=0.920,s=0.298 The equation and those quantum chemical parameters were used to discuss the toxicity mechanism of the compounds studied here in fish.
    A Theoretical Study of the Structures and Electronic Spectrum of C60O
    FENG Ji-Kang, TENG Qi-Wen, SUN Jia-Zhong
    1995, 16(7):  1088-1092. 
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    The INDO series methods are used to study the two structures of C60O: one is C2v, geometry with a bridging oxygen across the bond between two fused six-membered rings in C60; the othor is C, geometry with a bridging oxygen across the bond betweena five- and a six-membered rings. From the calculated results (including total energy, HOMO-LUMO gap and the spectral character), the most stable isomer of C60O should be the C2vgeometry. Our calculations also showed that this C2visomer has an epoxide-like structure (bridging C15-C30=0. 1518 nm, bond-order=0. 8744). The calculated results of electronic spectrum of the C2vgeometry are in good accordance with experimental results.
    Expressions of Quantum Chaos in the Statistical Characteristics of Eigenvalue-Spectral Fluctuations
    LUO Jiu-Li, Yan Guo-Sen, TAO Chang-Yuan
    1995, 16(7):  1093-1098. 
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    Through studying the quantum counterparts of two kinds of classical conservative systems, such as Henon-Heiles model, Barbains model and the model of the rotating-ball a-long a rigid ring, this title explains the connections of statistical characteristics of the fluctuations in energy spectra with the dynamic behavior of these models. Then, as a result, it reveals that there are two kinds of expressions of quantum chaos in the statistical characteristics of spectral fluctuations. Furthermore, by hamiltonizing the evolution equation of Lotka-Volterra model which belongs to classical dissipative systems in principle, we find that the statistical characteristics of the fluctuations in eigenvalue-spectra of its quantum counterpart go completely beyond the frame of Poisson-GOE(Winger) or GUE distribution. It shows that the fluctuations in eigenvalue-spectra of the quantum counterparts of the classical dissipative and the conservative systems follow different statistical regularities respectively.
    The Catalytic Reduction of NO by CO on Sm2-x,SrxNiO4
    LOU Hui, CHEN Ping, BAO Yun, GE Yu-Ping, MA Fu-Tai, LU Yue-Qing
    1995, 16(7):  1099-1103. 
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    The catalytic activity of perovskite series Sm2-xSrxNiO4(x=0. 4, 0.5, 0. 6, 0. 8, 1.0, 1. 2, 1. 4, 1. 5) has been studied for the reduction of NO by CO. The results indicate that the route at low temperature and low degree of substitution of lanthanum by strontium is different from that at high temperature and high degree of Sr2+substitution, which is closely related to the structure of the compounds, to the sum of the enthalpies of the metal-oxygen bonds in the compounds, to the apparent activation energies for the reduction of NO as well as to the behaviour of oxygen desorption from the compounds.
    The Effects of Alcohols on the Cloud Points of Nonionic Surfactant
    GUO Rong, ZHU Wen-Qing, CHEN Zong-Qi, QI Lin, SHEN Ming
    1995, 16(7):  1104-1108. 
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    The solution of straight chain alcohols made the cloud points of Triton X-100 system increase if the number of alcohol carbon nc<4, and decrease if nc≥4. The longer the chain of straight chain alcohol, the stronger the effect on the cloud point. When the branch chain alcohols were added in the Triton X-100 system, the less the space resistance and the solubility of branch chain alcohols, the lower the cloud points of Tirton X-100 system. The effect of alcohols on the cloud points of Triton X-100 was related to the hydrophilicity and space structure of alcohol and solubilization position in the micelle.
    Kinetics of Anodic Oxidation of Ce3+Ion in Sulfuric Acid at the Lead Dioxide Electrode
    JIN Shi-Xiong, WEN Qing
    1995, 16(7):  1109-1113. 
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    The kinetic data related respectively to Ce4+anodic formation and O2anodic evolution at PbO2electrode in 0. 5 mol/L H2SO4+x mol/L Ce2(SO4)3(x=0. 01-0. 10) and 0. 025 mol/L Ce2(SO4)3+x mol/L H2SO4(x=1. 09-4. 20) solutions were obtained by the method of resolving the steady-state polarization curve. Experiments show that the anodic formation of Ce4+and O2anodic evolution at PbO2electrode in the mixed H2SO4-Ce2(SO4)3solutions can be described by i(O2)=k1aw4expβφ F/RT,i(Ce4+)=k2aw2[Ce3+]expβφF/2RT at the potential region 1.7-1.9V and by i(O2)=k1aw4expβφF/RT, i(Ce4+)=k2aw2[Ce3+]expβφF/RT at the potential region above 1.9V (vs. SCE). On the basis of kinetics data thus obtained the mechanisms are proposed, which can be used to explain many experimental phenomena.
    Methyl Free Radical Beam Generated by Flash Pyrolysis Method
    LIU Zhao-Xiang, LI Run-Jun, LU Jian-Jiang, QIN Qi-Zong
    1995, 16(7):  1114-1115. 
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    The technique of the high-temperatufe flash pyrolysis has been used for the generation of jet-cooled methyl free radical beam. The result shows that Di-tert-butyl peroxide (DTBP) starts to decompose obviously at temperature up to 900 K, and reaches the complete decomposition at 1300 K. Short contact time of the seeded precursor molecules (4% mole DTBP in He) suppresses recombination of the methyl radicals. The major fragments for the flash pyrolysis of DTBP are CH3COCH3and CH3·radical.
    Studies on Thermodynamic Function and Structure Parameters of Tertiary Amine Salt-Alkane-Water Systems
    HU Zheng-Shui, FU Xun, PAN Ying, DING Jiang
    1995, 16(7):  1116-1118. 
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    Four tertiary amine salts, TOA·HCl, N235·HCl, N235·HNO3, N235·HClO4were prepared and their interfacial properties were measured. Thermodynamic function of the systems of tertiary amine salt-alcohol-alkane-water was measured by the dilution method and their structure parameters were calculated by using the model of w/o microemul-sion. The results showed that the "droplet" radii Re<0.5nm. We suggest that the thermo-dynamic stable tetradic system should belong to a kind of reversed micelles contributed by the hydration of alcohol.
    Studies on the Conduction and Catalytic Activity of CaO/La2O3Catalysts
    JI Min, BI Ying-Li, ZHEN Kai-Ji, WEI Quan
    1995, 16(7):  1119-1121. 
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    The C2selectivity of catalyst La2O3for oxidative coupling of methane may be enhanced by doping a small amount of CaO. The studying results by using some experimental techniques, such as determination of ionic conductivity, determination of lattice parameters, Raman spectroscopy and XPS of the catalysts indicated that part of La3+ions was substituted by Ca2+ion(≤3 mol%) in La2O3lattice and C2selectivity in OCM reaction was increased due to the formation of O-ions.
    Studies on Desalination by Pervaporation
    PENG Ping, ZHANG Xiao-Ling, LI Xiao-Dong
    1995, 16(7):  1122-1123. 
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    Desalination by pervaporation was investigated, in which an asymmetric membrane with non-porous layer was used. This kind of membrane was prepared from alloy of PVA and PEG crosslinked by aldehydes and sodium salt. The desalination of 3.5% and 8% NaCl solution with the membrane by pervaporation at 55℃ and 5. 00 kPa(downstream pressure) resulted in the single-stage salt rejection of 99% and the water flux of 14 kg/h·m2. The concentration of NaCl solution has a bit of effect on seperation properties.
    Studies on Synthesis of Poly(2,5-dibutoxy-p-phenylene vinylene) by Phase-Transfer-Catalysis Method
    LIU Cheng-Mei, LIAO Chun-Hua, GUO Jun-Shi, XIE Hong-Quan
    1995, 16(7):  1124-1128. 
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    Poly(2,5-dibutoxy-p-phenylene vinylene) was prepared in "one pot" reaction by the aid of phase-transfer-catalyst (PTC). Effects of sort and amount of PTC, reaction time and temperature, and concentration of NaOH on polymer yield were studied. Properties of the product, such as solubility in different solvents, thermal properties, optical and electrical properties were investigated. The results indicated that the catalytical efficiency of quar-ternary ammonium salts was better than that of poly(ethylene glycol) with different molecular weights. Dimethyl sulfoxide(DMSO), benzene, toluene, could act as the organic phase. The optimum conditions: concentration of NaOH is 50%, reaction temperature is 60℃. The product could readily dissolve in nitrobenzene at its boiling point. The film cast from soluble product could be doped by iodine, ferric chloride, and concentrated sulfuric acid. Its conductivity was about 9. 6×10-2S·cm-1after I2-doping.
    Structure and Properties of Self-Reinforced High Density Polyethylene Prepared by Oscillating Packing Injection Molding Under Low Pressure
    GUAN Qing, SHEN Kai-Zhi
    1995, 16(7):  1129-1133. 
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    This paper has studied the relationship of structure and properties of self-reinforced general grade high density polyethylene (HDPE) prepared by oscillating packing injection molding. The Young's modulus and tensile strength of HDPE have been enhanced greatly from original 1. 0 GPa, 23MPa to 5. 0 GPa, 93 MPa respectively. DSC, TEM and X-ray diffraction investigations indicate the improvement in mechanical properties is ascribed to the production of shish-kebab crystals, the orientation of molecular chains along the flow direction and well developed spherulites. Compared to high pressure injection molding, the method has good perspective in practical application.
    Compatibilization of PDMS/PU Blends(Ⅰ)
    YU Hai-Bin, ZHANG Bang-Hua, SONG Mou-Dao, HAO Guang-Jie, HE Bing-Lin
    1995, 16(7):  1134-1137. 
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    Polydimethylsiloxane-b-(ethylene oxide) block copolymer(DMS-b-OE) was used as compatibilizer for polydimethylsiloxane/polyurethane blends (PDMS/PU) and its effects on morphology, mechanical properties were investigated with SEM, DMA, stress-strain behaviour measurement. The results demonstrated that the compatibility between PDMS and PU was promoted and the mechanical properties were improved.
    Photoluminescence and Electroluminescence of Polymer and Organic Dye Multilayer Films Fabricated by LB Technique
    HUANG Jin-Man, MA Yu-Guang, WU Ying, LI Hong-Bin, SHEN Jia-Cong, YANG Yi, XUE Shan-Hua, LIU Shi-Yong
    1995, 16(7):  1138-1139. 
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    The dye TPB molecules were successfully fabricated into the polymer ESfilms with superlattice structure. The periodical structure of the multilayer films was determined by small angle X-ray diffraction, the period of 5. 8 nm was calculated according to the Bragg equation. It indicated that each periodical structure consists of two layers of LBfilms and the multilayer films have well ordered layer structure. The PLand ELspectra of the polymer/ dye multilayer films showed that the emission peaks of PLand ELshifted to short wave length relative to its bulk material due to the excitons confinement effects.
    Monte Carlo Simulation of Phase Transition of Random Copolymer Systems
    HU Wen-Bing, YU Tong-Yin
    1995, 16(7):  1140-1142. 
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    Three Dimensional Monte Carlo simulation of phase transitions is performed at high density of polymers with limited chain length by introducing intramolecular conforma-tional interaction Ecand intermolecular orientation-dependent interaction Ep, the later is considered as the process of compact pairing of non-bond segments according to our "cooperative pairing model". We prove that at Ep/Ec=1, the phase transition corresponds to polymer crystallization (Fig. 1,2). Then by randomly introducing non-crystallizable segments which do not take part in cooperative pairing process, we find that the phase transitions move to lower temperature (Fig. 3) and the depression of melting temperatures follows Flory's prediction for random copolymer, accompanying the loss of lamellar structure which agrees with experiments. These results illustrate that the cooperative pairing model is a special behavior for crystallizable segments.
    Axially Compressed Behavior of Ultra-High Molecular Weight Polyethylene Films
    XIAO Chang-Fa
    1995, 16(7):  1143-1145. 
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    The axial compressional behavior of ultra-high molecular weight polyethylene (UHMW-PE) film is studied by means of polarizing optical microscopy, scanning electron microscopy and X-ray diffraction in this paper. The results show that a lot of kink bands are formed at about 75° and 90°. It is suggested that (110)〈001〉 and (100)〈001〉crystallo-graphic slips play the dominant role in the formation of the 75° kink bands and 90° kink bands.
    Studies on Photoaging Properties of Calcium Carbonate Filled Polyethylene
    SHEN Jing-Wei, LIU Yue-Jian
    1995, 16(7):  1146-1148. 
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    Photoaging properties of calcium carbonate (CaCO3) filled polyethylene(PE) were investigated by means of artificial photoaging test. Photoaging qualities were characterized by the change of carbonyl concentration and double bond optical density with luminous flux with the aid of FTIR. It is showed that the photoaging behavior of CaCO3filled plastics relates to metallic impurities in the filler, filler content, environment temperature etc.. Degradation with photoaging can be restrained by adding a little proper light stabilizer.