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    24 November 2002, Volume 23 Issue 11
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    Articles
    Synthesis and Crystal Structure of Two New Nickel(Ⅱ) and Copper(Ⅱ) Tetraaza Complexes
    HE Yi, KOU Hui-Zhong, ZHOU Bei-Chuan, WANG Ru-Ji, LI Ya-Dong, WANG Hong-Gen
    2002, 23(11):  2017-2020. 
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    The crystal structures of[NiL]I·0.5H2O (L=12,14-dimethyl-1,4,8,11-tetraazacyclotetradecane-11,13-diene) and[Cu(2,3,2-tet)I2] [2,3,2-tet=N,N′-bis(2-aminoethyl)-1,3-propanediamine] have been determined by single-crystal X-ray diffraction analysis[NiL]I·0.5H2O crystallizes in space group Pbca with Z=16, a=1.806 5(6) nm, b=1.801 7(6) nm, c= 1.972 3(7) nm, R=0.042 6, wR=0.085 7. The asymmetric unit consists of two independent[NiL]+ cations, two iodide anions and one water molecule. The nickel(Ⅱ) ion is coordinated by four nitrogen atoms of the macrocyclic ligand with the Ni-N bond distances ranging from 0.184 8(6)-0.193 0(6) nm. Crystal data for [Cu(2,3,2-tet)I2]: space group P2(1)/n, Z=4, a=0.796 4(2) nm, b=1.114 7(2) nm, c=1.644 2(3) nm, β=91.42(3)°, R=0.034 2, wR=0.085 2. The structure consists of [Cu(2,3,2-tet)I2] monomers with characteristic N4I2 donor sets.
    Synthesis of LiMnO2 by Solid State Reaction in Air and the Influence of Ion Exchange Conditions on Its Structure
    LU Yan-Luo, WEI Min, YANG Wen-Sheng, Evans D.G., DUAN Xue
    2002, 23(11):  2021-2025. 
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    Layered sodium manganese bronze NaMnO2 with a monoclinic structure has been synthesized in air. Its structure is similar to the bronze synthesized in argon. The precursor was used to prepare layered LiMnO2 by ion exchange of Na+ by Li+ under different ion exchange conditions: in a LiCl/LiNO3 eutectic at 300 ℃, in n-hexanol at 145 ℃, in water at 105 ℃, and in ethanol at 95 ℃. X-ray diffraction indicates that the precursor and ion exchange products have a layered structure with the monoclinic space group C2/m. Both XRD and ICP analysis demonstrate that temperature influences the rate of the ion exchange reaction and the crystal structure of LiMnO2 in each case. The higher the temperature, the faster the reaction, and the more severe the distortion of the products. SEM micrographs show that LiMnO2 possesses a needle-like morphology.
    A Study of Abstraction of Hemoglobin by Non-organic Solvent Liquid-solid Extraction System
    EN Jing-Ru, QIN Xiao-Rong, SUN Xiao-Mei, LEI Zhuo-Lin, LI Bu-Hai
    2002, 23(11):  2026-2029. 
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    Polymer-salt-aqueous liquid-solid extraction system is newly developed in 1990′s. The system has been successfully used for extraction of metal ions and bioactive substances such as malic dehydrogenase. The separation and extraction of hemoglobin by modified PEG 8000 mixed with Tween 80 and aqueous K3PO4 system is seldom reported. The easy phase formation by this method can make solid and liquid phases separated without any treatment, so that the imperfection of liquid biphasic technology can be eliminated. The method mentioned in this paper has the features of high capacity, cost effectiveness, convenience. Meanwhile the polymer and salt comprising the extraction system can stabilize and protect the bioactive substances. So the new technology is very suitable for the practical use in large scale. In the research, extraction efficiency from the solid phase is >99% and reversed extraction efficiency can reach 75%. The purity of hemoglobin is 99% after reversed extraction. Highly purified hemoglobin powder can be produced through dialysis and freeze drying treatment.
    Synthesis of Bifunctionalized Organo-MSU-X Silicas
    GONG Yan-Jun, LI Zhi-Hong, Pu Min, WU Dong, SUN Yu-Han, DONG Bao-Zhong, DENG Feng, LUO Qing
    2002, 23(11):  2030-2034. 
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    Organically bifunctionalized-MSU-X silicates were prepared by one-pot synthesis methodology. The solids were characterized by XRD, FTIR, 29Si MAS NMR, TG, N2 physisorption techniques and small angle X-ray scattering(SAXS). The surface morphology and textural properties of such materials varied with synthesis mechanism and various kinds of groups in the channels. SAXS results showed that the binary organic groups uniformly distributed in MSU-X and so-produced materials displayed the fractal characteristics.
    Preparation and Characterization of Three-dimensional Ordered Macroporous Hybrid SiW11O398--SiO2 and γ-SiW10O368--SiO2 Composites
    GUO Yi-Hang, YANG Yu, HU Chang-Wen, WANG En-Bo
    2002, 23(11):  2035-2039. 
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    Three-dimensional ordered macroporous hybrid silica materials based on lacunary Keggin anions such as SiW 11O398- and γ-SiW 10O368- were prepared via sol-gel method as well as polystyrene templating technique. The structures of as-synthesized composites were characterized by UV diffuse reflectance spectra, FTIR, and solid-state MAS NMR. The results indicate that the primary Keggin structures remain intact in the hybrid materials, and chemical interaction exists between POM molecules and silica matrix. The porous structures of the composites were characterized by SEM and TEM, and their average pore diameters were (335±50) nm. The microporosity of the wall structure was evaluated by the nitrogen adsorption determination. The composites exhibit a photocatalytic activity to degrade aqueous malic acid under irradiation in the near-UV areas, and the leakages of the POMs from the hybrid materials are hardly observed during the process of photocatalysis.
    Synthesis and Structure of a Novel Inorganic-organic Hybrid Framework Microporous Material Cd3（BDC）0.5（BTC）2（DMF）（H2O）·3DMF·H3O·H2O
    SHI Xin, FANG Qian-Rong, XIN Ming-Hong, WU Gang, TIAN Ge, ZHU Guang-Shan, LI Ya-Feng, WANG Li-Feng, WANG Chun-Lei, SHANG Tie-Cun, QIU Shi-Lun
    2002, 23(11):  2040-2042. 
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    A new inorganic-organic hybrid framework microporous material Cd3(BDC)0.5(BTC)2·(DMF)(H2O)·3DMF·H3O·H2O, in which two kinds of carboxylate ligands coordinate with cadmium ions synchronously, was obtained under a mild synthesis condition. The titled compound is crystallized in a monoclinic system, space group P2(1)/c with a=1.584 7(7) nm, b=1.426 7(6) nm, c=1.936 3(6) nm, β=113.186(7)°, V=4.024 6(3) nm3, Z=4, D X=1.947 mg/m3, M r=1 179.92, μ=1.662 mm-1, F(000)=2 344, R=0.074 8, wR=0.215 1. Three cadmium centers link with each other through BDC or BTC ligand to form a 3-D open framework.
    A Nanocrystalline NiO Thin Film Prepared by Pulsed Laser Ablation
    WANG Ying, QIN Qi-Zong
    2002, 23(11):  2043-2045. 
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    The NiO thin film electrodes were prepared by reactive pulsed laser ablation of a metallic Ni target in an oxygen ambient at different temperatures. X-ray diffraction and scanning electron microscopy measurements demonstrated that the films deposited at 600 ℃ exhibited nanocrystalline structure with an average particle size of～30 nm. Electrochemical properties of NiO films were examined by charge-discharge measurements. Excellent electrochemical performance, a high capacity retention compared to the amorphous NiO, could be achieved with nanocrystalline NiO films. The improved specific capacity, discharge rate and cycling performance might be related to nano-sized character of the thin film electrode of NiO. This NiO thin film could be used as a promising electrode material for all-solid-state thin film rechargeable Li-ion batteries.
    Hydrothermal Synthesis and Structural Characterization of a Novel P-V-O Layered Compound [H2en]2[H3O]6[Co（H2O）2（VO）8（OH）4（PO4）8]
    ZENG Qing-Xin, CHEN Xu, LI Ya-Feng, YANG Guo-Yu, XU Ji-Qing
    2002, 23(11):  2046-2048. 
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    A new compound [H2en]2[H3O]6[Co（H2O）2（VO）8（OH）4（PO4）8] has been hydrothermally synthesized. Single crystal X-ray analysis indicates that this compound crystallizes in a monoclinic system, space group P21/n with a=1.438 5(3) nm, b=1.012 2(2) nm, c=1.832 5(4) nm, β=90.21°, V=2.668 2(9) nm3, Z=2, Dc=2.112 g/cm3, R=0.055, wR=0.149 7, S=1.037. The structure of [H2en]2[H3O]6[Co（H2O）2（VO）8（OH）4（PO4）8] is characterized by P-V-O layers constructed by [(VO)4(OH)2(PO4)4]6- non-symmetric units. The P-V-O layers are pillared by [Co(H2O)2]2+ group, resulting in the channels within which the protonated diaminoethane and H3O+ are located.
    Investigation on the Interaction of Ruthenated Porphyrin [Ru（bpy）2（MPyTPP）Cl]+ with Calf Thymus DNA
    MEI Wen-Jie, LIU Jie, LI An-Xing, HUANG Qi-Wen, JI Liang-Nian
    2002, 23(11):  2049-2051. 
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    The interaction of ruthenated porphyrin [Ru(bpy)2(MPyTPP)Cl]+ with CT-DNA was investigated with UV-Vis and fluorescent spectrum. It is found that [Ru(bpy)2(MPyTPP)Cl]+ binds to CT-DNA with a high affinity.
    Syntheses and Crystal Structures of K3[GdⅢ（nta）2（H2O）]·5H2O and （NH4）·[GdⅢ（Cydta）（H2O）2]·5H2O
    WANG Jun, LIU Zhen-Rong, ZHANG Xiang-Dong, JIA Wei-Guo
    2002, 23(11):  2052-2054. 
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    Two new GdⅢ complexes with nitrilotriacetic acid(nta) and trans-1,2-cyclohexanediaminetetraacetic acid(Cydta) ligands were synthesized. Their crystal structures were determined by single-crystal X-ray structure analyses. The crystal data are as follows: K3[GdⅢ(nta)2·(H2O)]·6H2O, monoclinic system, C2/c space group, a=1.534 81(15) nm, b=1.292 05(12) nm, c=2.610 8(3) nm, β=96.244(2)°, V=5.146 7(9) nm3, Z=8, M=776.87, Dc=2.005 g/cm3, μ= 3.149 mm-1 and F(000)=3 080, R=0.024 5, wR=0.064 3 for 4 455 unique reflections and R= 0.028 9, wR=0.067 2 for all 10 305 reflections. The GdⅢN2O7 part in the [GdⅢ(nta)2(H2O)]3- anion is a pseudo-monocapped square antiprismatic nine-coordination structure.(NH4)[GdⅢ(Cydta)(H2O)2]·5H2O, triclinic system, P1 space group, a=0.866 2(3) nm, b=1.006 7(3) nm, c= 1.444 8(5) nm, α= 88.282(5)°, β=75.190(5)°, γ=88.317(4)°, V=1.217 2(7) nm3, Z=2, M=643.69, Dc=1.756 g/cm3, μ=2.798 mm-1 and F(000)=650, R=0.030 3, wR=0.080 9 for 4 273 unique reflections and R=0.033 2, wR=0.082 5 for all 5 062 reflections. The GdⅢN2O6 part in the [GdⅢ(Cydta)(H2O)2]- anion has a pseudo-square antiprismatic eight-coordination structure.
    Fabrication of Ordered and Multilayer Film Electrode Containing Iron（Ⅲ） Porphyrin Based on Covalently Attached Interaction and Its Electrocatalytic Reduction to H2O2
    FU Ya-Qin, LI Xiao-Fang, SUN Chang-Qing
    2002, 23(11):  2055-2059. 
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    Construction of a highly stable covalently attached multilayer film electrode containing iron(Ⅲ) porphyrin was achieved by UV irradiation of ionic self-assembled multilayer films of diazo-resins(DAR) and Fe(Ⅲ) tetrakis(p-sulfonatophenyl) porphyrin(FeTSPP). The fabricated processes of the multilayer film electrode were characterized by UV and IR spectra. The modified electrode has an excellent stability and a good catalytic activity toward electroreduction of H2O2.
    A Study on Vegetal Process of Caragana Korshinskii Treated by Polymer Plant Regulator
    LU Xiao-Quan, CAO Wen-Xia, WANG Lan-Zhou ZHU Kai-Mei, ZHANG Min, KANG Jing-Wan
    2002, 23(11):  2060-2062. 
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    The interaction between Co(en)33+ and DNA of C. Korshinskii treated by polymer plant regulator was probed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) for the first time in this paper. Adding DNA into Co(en)33+ solution, the i p value of Co(en)33+ decreased and the peak potential shifted negatively, which showed that Co(en)33+ had the ability to bind into DNA. It was of great importance to analyze vegetal growth prowth precess and study the mechamism of polymer plant regulator.
    Studies on the Electrochemilluminescence of 10-(Carboxylethyl)- acridinium-9-carboxyl-phenyl-ester Iodinate
    YANG Min-Li, LIU Chuan-Zhi, HE Pin-Gang, FANG Yu-Zhi
    2002, 23(11):  2063-2066. 
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    A study of the electrochemilluminescence(ECL) of 10-(carboxylethyl)-acridinium-9-carboxyl-phenyl-ester iodinate(CACPEI) in a neutral solution was carried out. It was found that CACPEI gives a strong ECL in KNO3 solution when an appropriate voltage was applied on Pt electrode. The ECL signal was greatly influenced by the electrochemical parameters and the ECL reaction conditions. All the affecting factors were investigated in detail. Under the optimum conditions, the ECL intensity exhibited a good linear relationship with the concentration of CACPEI in the range of 5.0×10-10-1.2×10-7 g/mL. The detection limit of CACPEI was 2.4×10-10 g/mL(S/N=3). The proposed ECL mechanism was discussed.
    Selective Determination of Dopamine in the Presence of High Concentration Ascorbic Acid and Uric Acid Using Carbon Nanotube Modified Glassy Carbon Electrode
    SUN Yan-Yi, WU Kang-Bing, HU Sheng-Shui
    2002, 23(11):  2067-2069. 
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    A homogeneous dispersion of multiwall carbon nanotubes(MWNT) was achieved by dispersing MWNT into 0.1% Nafion ethanol solution, and a uniform cast film at a glassy carbon electrode(GCE) was obtained via solvent evaporation of the MWNT dispersion. A reversible two-electron redox reaction of dopamine was observed at the MWNT-Nafion modified GCE. In comparison with a bare GCE and a Nafion-modified GCE, MWNT-Nafion modified GCE has a higher sensitivity for dopamine. This modified GCE has an excellent selectivity towards dopamine even in the presence of high concentration ascorbic acid(AA) and uric acid(UA) since AA and UA have no observable electrochemical responses at the modified GCE. The electrochemical behavior of dopamine was closely related to the pH of the buffer solution. The oxidation peak current was proportional to the concentration of dopamine over the range from 5×10-8 to 1×10-6 mol/L, and a detection limit of 2.5×10-9 mol/L was obtained after 3 min open-circuit accumulation. The dispersion and morphology of MWNT-Nafion film were investigated by transmission electron microscopy(TEM).
    Preparation and Characterization of Protein A Immobilized on Monolithic Capillary Column for Affinity Chromatography
    PAN Zai-Fa, MO Wei-Min, WU Ren-An, LUO Quan-Zhou, YE Ming-Liang, ZOU Han-Fa
    2002, 23(11):  2070-2072. 
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    An assay technique for the determination of the human IgG in human plasma has been developed by utilizing protein A immobilized monolithic capillary column. The affinity chromatography experiment was performed on a capillary electrophoresis instrument by using its pressure system as the driving force. Reactive monolithic capillary columns have been prepared by in-situ copolymerization of the monomers in the presence of porogenic dilute, and protein A was immobilized on the monolithic rods directly or through a 11 carbon atom space arm with molded synthetic methods. The non-specific adsorption of two kinds of media has been studied and the results showed that the medium without space arm gives very low non-specific adsorption of BSA. The affinity column without space arm was used to determine the human immunoglobulin G(HIgG) in human serum. The correlative coefficient of the calibration curve reaches 0.998 7. The total time of rapid analysis was less than 0.7 min. The consumption of eluent buffer and sample is much low than by conventional HPLC.
    Chiral Separation on Naproxen and Determination of Chromatography Equilibrium Constant Using Molecular Imprinting
    LEI Jian-Du, TAN Tian-Wei
    2002, 23(11):  2073-2075. 
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    A chiral stationary phase for naproxen separation was prepared by means of molecular imprinting, in which acrylamide and ethylene glycol dimethacrylate were copolymerized in the presence of template. Racemic naproxen was efficiently resolved on the molecular imprinting polymer. The concentration of acetic acid in the mobile phase was optimized. A new affinity chromatography model using molecular imprinting was established by which the agreement between the simulated and experimental results was obtained. The results suggested that affinity chromatography mechanism controled the retention in this system.
    Synthesis of a Family of Ferrocene-bearing Cyclo-pseudo-peptides by Liquid Method and Molecular Recognition
    HAN Qian-Wei, ZHU Xiao-Qing, HU Xu-Bo, CHENG Jin-Pei
    2002, 23(11):  2076-2079. 
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    Two series of new ferrocene-bearing cyclo-pseudo-peptides, including three 1+1 type and three 2+2 type compounds, were designed and synthesized by liquid method. The interactions of the 1+1 type cyclo-pseudo-peptides as the host compounds with some anions were investigated by cyclic voltammetry(CV) and 1H NMR methods. The results show that the 1+1 type hosts can selectively interact with the guest anions by intermolecular hydrogen bond. A reasonable interaction model of the 1+1 type cyclo-pseudo-peptides with anions was proposed.
    SRN1 Reaction of 2,2,2-Trifluoroethyl Halides with Carbanion
    XU Yong-Jun, YANG Xiao-Xi, CHEN Qing-Yun, LIN Yuan-Bin, YE Guo-Xing, DING Jing
    2002, 23(11):  2080-2083. 
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    In organic chemistry, the radical nucleophilic substitution of alkyl halides or S RN1 mechanism is one of the most important parts of single electron-transfer (SET) reaction 2,2,2-trifluoroethyl iodide, bromide, chloride except fluoride reacted with carbanion in DMF under laboratory illumination at a specified temperature for 12 h to give the 2,2,2-trifluoroehtyl derivatives and coupling products of two R1R2R3C-. The acceleration by UV irradiation, suppression by p-dinitrobenzene or hydro-quinone showed that the reactions occurred by SRN1 mechanism. The initiation step may be spontaneous or thermal electron transfer between carbanion and halides because the reactions could occur in dark.
    Studies on Structure of Ecdysterones from Rhaponticum Uniflorum
    CHENG Jie-Kai, ZHANG Yong-Hong, ZHANG Zi-Yi, CHENG Dong-Liang, ZHANG Guo-Lin
    2002, 23(11):  2084-2088. 
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    Seven phytoecdysteroids were isolated from the root of Rhaponticum uniflorum. Their structures, by means of spectroscopic techniques and chemical properties, were identified as ajugasterone C-2,3;20,22-diacetonide(1); 25-deoxy-9(11)-dehydro-20-hydroxyecdysone-20,22-amonocetonide(2); ajugasterone C-20,22-monoacetonide (3); ajugasterone C (4); rhapontisterone C (5); ecdysterone(6); 11α-hydroxyecdysterone ecdysterone(7). Compounds 1 and 2 were new compounds. Compound 3 was obtained from Rhaponticum uniflorum for the first time.
    Synthesis and Application in Ethylene Polymerization of p-Biphenylene-bridged Dinuclear Zirconocenes
    DENG Xiao-Bin, XU Shan-Sheng, WANG Bai-Quan, ZHOU Xiu-Zhong, YANG Ling, LI Yu-Fei, HU You-Liang
    2002, 23(11):  2089-2092. 
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    ?Dibromobiphenyl reacted with n-BuLi to form 4,4′-dilithiobiphenyl, which further reacted with 2,3,4,5-tetramethylcyclopent-2-enone following the elimination of water to give the ligand 4-(C5Me4H)C6H4—C6H4(C5Me4H)-4(1). Ligand 1 reacted with n-BuLi and ZrCl4 to form the p-biphenylene-bridged dinuclear tetramethylcyclopentadienyl zirconium trichlorides 4-(C5Me4ZrCl3)·C6H4—C6H4(C5Me4ZrCl3)-4, which reacted in situ with cyclopentadienyl lithium(CpLi) or indenyl lithium(IndLi) to give the corresponding p-biphenylene-bridged dinuclear zirconocenes 4-(C5Me4ZrCl2Cp′)C6H4-C6H4(C5Me4ZrCl2Cp′)-4 [Cp′= Cp(2), Ind(3)]. The zirconocenes 2 and 3 were characterized by 1H NMR, MS spectra and elemental analysis, and were studied for ethylene polymerization with methyl aluminoxane(MAO) as cocatalyst. Both 3 and 4 show very high activities and reach the maximum at a higher temperature, indicating that the introduction of the p-biphenylene-bridge increased the catalytic activity and thermal stability of the dinuclear zirconocene catalysts.
    Synthesis of Novel Polysubstituted Diethyl 2,7-Naphthalene Dicarboxylates
    YU Zhi-Fang, TIAN Zhong-Zhen, SHI Ji-Xian
    2002, 23(11):  2093-2096. 
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    Substituted 2,7-naphthalene dicarboxylates, possessing heat-resistant property, and giving print ink with good a abrasion resistance and adhesion to various papers, have been found to be extremely useful in polymer industry. Herein, we report a straightforward synthesis of polysubstituted diethyl 2,7-naphthalenedicarboxylates from the readily prepared diethyl 2-methoxy-4,6-dimethyl-1,3-benzene dicarboxylate(1). The tandem Micheal addition-cyclization of benzene diester yielded the substituted 1,2,3,4-tetrahydro-nathtalene-1-one(2). This is a novel and efficient route for the cyclization of aromatic ester onto cyclohexanone or phenolic ring. Substituted 1-naphthols(4) were obtained by a sequential bromination and deprotonation of the compound(2). The aromatization of compound(3) couldn′t be executed by the general route. Herein, the use of DBU is extremely efficient. The methylation of the naphtol(4) generated a symmetric substituted naphthalene dicarboxylate(5b). The structures of all compounds(2a-5b) were characterized by 1H NMR, 13C NMR, IR, MS and elemental analysis. They are unknown compounds.
    Synthesis of New 1,2,4-Oxadiazolo[4,5-d][1,5]benzothiazepine Derivatives Containing 2-Phenyl-1,2,3-triazole Through 1,3-Dipolar Cycloaddition Reaction
    LIU Fang-Ming, WANG Bao-Lei, LI Yan-Ping
    2002, 23(11):  2097-2101. 
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    Benzothiazepines containing 2-phenyl-1,2,3-triazole(2a-2e) which have potentially useful pharmacological properties were synthesized from α,β- unsaturated ketones(1a-1e) and 2-aminothiophenol, and then underwent 1,3-dipolar cycloaddition reaction with aryl nitrile oxides "in situ" and a series of 1,2,4-oxadiazolo benzothiazepine derivatives containing 2-phenyl-1,2,3-triazole(3a-3j) were obtained. The experimental results show that if the substituent R1 or R2 at phenyl of 1,5-benzothiazepine is electron-donated, it will facilitate the 1,3-dipolar cycloaddition reaction. The structures of the products were confirmed by IR, 1H NMR, MS and elementary analyses, and their spectrum characters were also discussed.
    Synthesis and Steric Structure of α-Amino-β-lactam Derivatives of 1,5-Benzothiazepines
    ZHANG Ping, HAO Zhen-Fang, LI Yuan
    2002, 23(11):  2102-2105. 
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    Benzothiazepines reacted with a new N-protected agent of glycine to give the title compounds. The configuration and conformation of the products were determined by X-ray crystal analysis. The results also revealed that the reaction was stereospecific. The two substituents at β-lactam were on the same side, the seven-membered ring was in chair-like conformation.
    CO2 Reforming of CH4 over Ni Supported on Nano-ZrO2（Ⅱ）── Effect of Catalyst Composition and Reaction Conditions on Catalytic Reactivity
    WEI Jun-Mei, XU Bo-Qing, SUN Ke-Qiang, LI Jin-Lu, ZHU Qi-Ming
    2002, 23(11):  2106-2111. 
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    Ni "supported" nano-zirconia catalyst(named as Ni/ZrO2-AS) was extremely stable for CO2 reforming of CH4 to syngas. In the present work, the effects of the Ni loading(5%-32%), reaction temperature(923-1 123 K) and space velocity[GHSV=104-105 mL/(h·g-cat)] were extensively studied. While the catalytic stability of Ni/ZrO2-AS catalysts seemed not significantly affected by the Ni loading, the increase of the loading up to 10% improved effectively the catalyst activity at 1 030 K. In the reactions over the catalysts with higher Ni loadings, the conversions of the reactants approached their values for thermodynamic equilibrium. The increase of the feed space velocity led to a decrease of the reactant conversions, but to an increase of the space time yield of syngas product. TPO measurement of the carbon deposition showed that every nickel atoms in the catalysts survived dynamically two carbon atoms on the average. TPR/TPD and TEM characterizations revealed that Ni/ZiOr2-AS catalysts were different in structure from conventional metal catalysts supported on porous oxides; they were nano-composites of size-comparable metallic Ni and ZrO2 nanocrystals( 10-20 nm). The catalytic stability of Ni catalysts in Ni/ZrO2-AS system is most probably connected with the nature of the nanoacomposite structures.
    Studies on Property of Carbon Deposition on Ni/CeO2-Al2O3 Catalyst for CH4-CO2 Reforming Reaction
    YANG Yong-Lai, XU Heng-Yong, LI Wen-Zhao
    2002, 23(11):  2112-2116. 
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    The influence of the addition of n-type semiconductor oxide CeO2 to Ni-based catalyst on carbon deposition from CH4 and carbon elimination by CO2 was studied by using a pulse microreaction technique. The catalysts were characterized by TPR, XPS and hydrogen chemisorption. It was found that there was an interaction between active metal Ni and semiconductor oxide CeO2. The XPS data indicated that the addition of CeO2 could increase the d-electron density of active atom Ni, which would inhibit the migration of C-H σ-electron from CH4 molecule to d-orbital of Ni atom, therefore, the carbon deposition activity of CH4 decreases. Meanwhile, the migration of d-electron from Ni atom to empty antibond π-orbital of CO2 could be strengthened due to the addition of n-type semiconductor CeO2, thereby, carbon elimination activity of CO2 increases. As a result, the Ni/CeO2-Al2O 3 catalyst has an excellent resistance to carbon deposition. In addition, the influence of the synergetic effect between SMSI and MScI on the resistance to carbon deposition of the catalysts calcined at various temperatures was investigated. It was discovered that, only in the presence of relatively weak metal-support interaction, it could exhibit the metal-semiconductor interaction(MScI).
    Studies on the Dynamic Surface Tension of Dynol-604
    LI Gan-Zuo, CHEN Wen-Jun, GU Qiang, LI Ying, GE Shang-Zheng
    2002, 23(11):  2117-2120. 
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    The dynamic surface tension(DST) of Dynol-604 was measured by using the maximum bubble pressure method. At first the curves of DST with lgt were obtained, then the parameters(ti, t*, tm, γm) were obtained from the curves above and R1/2 can be calculated out. The effects of the concentration of Dynol-604 and temperature on the dynamic surface tension of Dynol-604 have been investigated. The results showed that the dynamic surface activity and adsorption energy of Dynol-604 increased with the increase of temperature and their concentration, and the diffusion energy decreased with the increasing of temperature and Dynol-604 concentration. In a word, the transient and equilibrium surface activities of Dynol-604 are very high.
    XRD, SEM and EDAX Studies of the Preparation Process of Novel Raney-Ni Catalyst
    LEI Hao, SONG Zhen, TAN Da-Li, BAO Xin-He, MU Xu-Hong, ZONG Bao-Ning, MIN En-Ze
    2002, 23(11):  2121-2124. 
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    The preparation of the novel Raney-Ni by leaching Ni-Al starting alloys which prepared by melt-quenching and pretreatment was studied by XRD, SEM and EDAX. The existence of particles with the smaller size of crystallite and more contents of Ni2Al3 phase in the melt-quenched starting alloys result in the structure in which more Ni2Al3 phase exist in the bulk and less NiAl3 on the top layer, thus the migration of Al component from bulk to top layer become the rate-controlling step in the leaching process, leaving more Ni2Al3 residue and making the active nickel disperse on the residual Ni2Al3 uniformly.
    Applications of the Method of Three-dimensional Projection of a Molecule in Quantitative Structure-activity Relationship of Phenol Derivatives
    ZHANG Qing-You, XU Lu
    2002, 23(11):  2125-2128. 
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    Five variables for phenol derivatives were calculated by molecular projection in three-dimensional space, which were combined with eight quantum-chemical parameters and three Am indices. These variables were selected by using leaps-and-bounds regression analysis. Multiple linear regression analysis and artificial neural networks were performed, and the results obtained by using artificial neural networks are superior than that obtained by using multiple linear regression.
    The Reaction Mechanism Between ClONO2 and H
    SUN Ren-An, TAO Zhan-Liang, SUN Yan-Bo, JIN Fei, HAN Ke-Li
    2002, 23(11):  2129-2132. 
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    The reaction mechanisms of reactions ClONO2+H→HONO2+Cl(a), ClONO2+H→OH+ClONO (cis) (b) and ClONO 2+H→OH+ClONO (trans) (c) have been studied with Gaussian 98 program and B3LYP/6-31G* method. The transition states of various possible reaction pathways were obtained and were verified by internal reaction coordinate (IRC) analysis. The results show that the activation energy of the three reactions are almost the same and are 19.5, 20.0 and 23.2 kJ·mol-1 respectively. In the dynamic way, considering the activation energy, we conclude that the three reactions can occur simultaneously. Reaction (a) gives so more energy than reaction (b) and (c) that it is more likely to occur.
    VB-MP2: A Hybrid Method Combining Valence Bond Theory and Many-body Perturbation Theory
    SONG Ling-Chun, LU Lan-Yuan, WU Wei , CAO Ze-Xing, ZHANG Qian-Er
    2002, 23(11):  2133-2136. 
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    A practical valence bond method, called VB-MP2, is presented. The method combines valence bond method and many-body perturbation theory by using MP2 method to get the electronic correlation of inactive electrons. The bond energies of some molecules, such as F2, Cl2, Br2, CH3Lietc., are computed by using the VB-MP2 method. Testing calculations show that VB-MP2 method has the qualities of a VB method along with a quantitative advantage over VB-only method in comparison with traditional core-valence separation.
    Ab initio Potential Energy Surface and Rovibrational Spectra of He-N2O
    ZHU Hua, LI Jiang, XIE Dai-Qian, YAN Guo-Sen
    2002, 23(11):  2137-2141. 
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    The intermolecular potential energy surface for He-N2O has been calculated by using the fourth-order M φller-Plesset(MP4) perturbation theory with a large basis set containing bond functions. The MP4 potential is found to have three minima corresponding to the T-shaped and the linear He-ONN and He-NNO structures. The ro-vibrational energy levels are calculated. The calculated results show that the MP4 potential supports five vibrational bound states
    Preparation and Characterization for a Co-deposited Hybrid Coating of Calcium Phosphate/Chitosan on Ti Alloy Surface
    HU Ren, HU Hao-Bing, LIN Chang-Jian 
    2002, 23(11):  2142-2146. 
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    In this work, a novel electrodeposition has been developed to prepare a hybrid coating of calcium phosphate/chitosan on the surface of Ti alloy. The surface morphologies, chemical compositions and crystalline structures of the hybrid coatings are characterized by using various spectroscopic techniques, such as SEM, XPS, FTIR and XRD etc.. The results indicate that a hybrid coating of calcium phosphate/chitosan is formed on the metal surface when adding minor of chitosan to the electrolyte of calcium phosphate under the electrodeposition condition. The morphology of the hybrid coating is significantly different with that of the pure calcium phosphate. It is also shown that the bonding strength of the hybrid coating to the metal substrate has been increased as high as 2.6 MPa because of the incorporation of chitosan in the coating. Meanwhile, the chitosan is a natural polymer compound with good biological-properties, it is proposed to be of a high biocompatibility and an excellent biocompatibility when forming a hybrid coating of calcium phosphate/chitosan on a metal substrate. It means that the electrodeposited hybrid coating of calcium phosphate/chitosan developed in our lab may become a new promising implant biological material.
    Formation and Photodissociation of Copper-selenium Clusters
    CHEN Yun-Qing, XING Xiao-Peng, GAO Zhen, ZHU Qi-He
    2002, 23(11):  2147-2150. 
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    The formation and photodissociation of Cu/Se binary clusters were studied on the laser ablation tandem time-of-flight mass spectrometer. It was found that the cations [Cu(Cu2Se)n]+ and [(Cu2Se)n]+, the anions [CuSe(Cu2Se)]-, [(Cu2Se)nSe]- were the main products. In the photodissociation experiment of CunSem+, [Cu(Cu2Se)n]+ and [(Cu2Se)n]+ were the main products. The structures and photodissociation channels of Cu3Se+, Cu5Se2+ were studied by using a kind of "DFT" method, in which the LANL2DZ basis was used.
    AC Impedance Studies on Multi-walled Carbon Nanotubes Air Electrode
    HUANG Hui, ZHANG Wen-Kui, MA Chun-An, GE Zhong-Hua, LU Huan-Ming, ZHANG Xiao-Bin
    2002, 23(11):  2151-2154. 
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    The AC impedance properties of the air electrodes using multi-walled carbon nanotubes, active carbon and graphite particles as catalyst layer material were investigated. The results showed that the AC impedance diagram of carbon nanotubes consisted of two semi-circles, in which the high frequency zone was ascribed to the ohmic process within porous structure and the low frequency zone to the kinetic impedance of electrochemical reaction. The Pt nanoparticles deposited on the exterior surface of carbon nanotubes decreased greatly ohmic and electrochemical impedance, so increased electro-catalytic activity of oxygen reduction. However, for the air electrode prepared by active carbon, the thin film diffusion impedance was appreciably observed in addition to ohmic impedance. The low catalytic activity in the graphite air electrode appeared as a consequence of the decreased thin film reaction sites and the mass transport process was dominated by Warburg diffusion. Finally, the equivalent circuit of air electrode was proposed and the simulated kinetic data were also discussed.
    Investigation on Properties of Nano-sized 3Y-TZP Aqueous Suspensions
    LIU Yang-Qiao, GAO Lian
    2002, 23(11):  2155-2158. 
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    Stable suspensions of nano-sized 3Y-TZP were prepared by using a small-molecule anionic dispersant. The influence of the dispersant on the suspension properties was characterized by means of ζ potential, adsorption study and rheological measurements. The interaction between particles was simulated by using DLVO theory and the simulated results showed a good agreement with the experimental results. The stabilizing mechanism of the dispersant was also discussed.
    Dispersion of CuCl2 into NaY Zeolite Studied by Positrons
    ZHU Jun, WANG Shao-Jie, LUO Xi-Hui
    2002, 23(11):  2159-2162. 
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    A series of samples, prepared from mechanical mixtures of CuCl2 with NaY zeolite and resulting in the dispersion of CuCl2, was studied by positron annihilation spectroscopy. We measured the positron lifetime spectroscopy as a function of the weight ratio of the CuCl2-NaY zeolite heated at 140 ℃ for 1 h as well as at 450 ℃ for 4 h, respectively. We also measured it as a function of the heated temperature of 1 h, and as a function of the time heated at 300 ℃ for CuCl2-NaY(mass ratio 0.01). All lifetime spectras were resolved into five(or four) components, in which the third, the fourth and the fifth components were related to the annihilation in β cage, supercage and interface void, respectively. The experimental results showed that positron annihilation spectroscopy was sensitive to probe the change of the dispersion of a few of CuCl2 in NaY zeolite, and there was much CuCl2 remained on the outside surface of NaY after heated at high temperature for a long time even for a few of CuCl2.
    The Dehydrogenation of 2-Butanol on Cu-ZnO Nano-Catalyst
    WANG Zhen-Lü, MA Hong-Chao, ZHU Wan-Chun, YU Jian-Feng, WANG Guo-Jia
    2002, 23(11):  2163-2165. 
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    In this paper, the Cu and ZnO nanoparticles were mixed by the ultrasonic dispersion method. The catalysts were used for dehydrogenation of 2-butanol. Comparing to the Cu and ZnO catalysts, the Cu-ZnO catalyst showed a high catalytic activity and stability. The fresh and reacted catalysts were characterized by XRD, BET and EPR, which showed that the nano-scaled Cu and ZnO catalysts were deactivated during the reaction because of sintering and carbon deposition, respectively. In Cu-ZnO catalyst, the gathering of Cu particles was restrained by adding ZnO, and carbon deposition was avoided due to some interactions between Cu and ZnO.
    Studies on Supported Fe-based Perovskite-like Oxide Catalyst
    HU Da-Wei, QIN Yong-Ning, MA Zhi, HE Fei
    2002, 23(11):  2166-2168. 
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    In this research a technique for the process of ABO3 supported on γ-Al2O3 was proposed, in which the modified carrier was adopted and the citric acid complexing sol-gel method was used. By means of this technique, the activity for SO2 reduction over LaFeO3/γ-Al2O3 is as high as that over non-supported catalyst. The substitution of Sr for La and Cu, Co for Fe decreased the activity of the catalyst, especially when the reaction temperature was low.
    Silver Nanoparticles Assembled on Mica and Its Surface-enhanced Raman Scattering Effect
    WANG Lian-Ying, JI Xiao-Hui, ZHANG Xin-Tong, BAI Yu-Bai, LI Tie-Jin, ZHI Zhuang-Zhi, KONG Xiang-Gui, LIU Yi-Chun
    2002, 23(11):  2169-2171. 
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    We present our work on direct assembly of Ag nanoparticulate film onto mica substrates without coupling agent, and investigate the potential application of this kind of assembly to SERS. Colloidal Ag is assembled onto mica substrates treated with MnCl2 solution by electrostatic interaction, which forms a two-dimensional submonolayer. As shown by AFM study, the assembled process is size-selective, e.g., Ag particles assembled onto mica are more uniform than the mother colloid. The as-prepared Ag nanoparticulate films were shown to be active for surface-enhanced Raman scattering(SERS), as evidenced by the strongly enhanced Raman scattering from the self-assembled films(SAMs) of p-mercaptoaniline(p-MA).
    Monte Carlo Simulation on the Correlations Between Shape and Size of Polymer Chains
    QIAN Chang-Ji, LUO Meng-Bo, XU Jian-Min
    2002, 23(11):  2172-2176. 
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    The configurations of linear lattice polymer chain model were simulated by using Monte Carlo method. The correlation between chain size(measured by the square end-to-end distance R2 and the square radius of gyration S2) and shape(measured by the asphericity parameter A) was studied. A positive correlation is found for any chain length, indicating that a chain configuration of small size is usually more spherical than that of a large one, vice versa. The correlation coefficients CA,R2 and CA,S2 decrease with the increase of chain length, approximately in proportional to the reciprocal of chain length n-1. The results show that the limits of CA,R2 and CA,S2 at a large chain length are independent of the lattice model and chain sampling method, but they become large when the excluded volume among chain segments is considered.
    Fluorescence Studies of the Conformational Behavior of Poly(vinyl-pyrrolydone) in Dilute Aqueous Solution
    GAO Gai-Ling, FANG Yu, ZHU Xing-Hua, HU Dao-Dao, LIU Shou-Xin, CUI Ya-Li
    2002, 23(11):  2177-2181. 
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    Fluorescence anisotropy, fluorescence quenching and non-radiative energy transfer studies via the acenaphthylene(ACE) label and 8-anilino-naphthylene sulfornic acid(ANS) probe have demonstrated that poly(vinyl pyrrolydone)(PVP) adopts loose coiled conformation within a wide pH range. Unlike other water-soluble polymers, PVP tends to combine other polymers and/or small molecules with active hydrogen in their structures. This property may be employed to modify the conformational behavior of some water-soluble polymers with hydrophobic microstructures. The nature of the combination may be attributed to hydrogen bond formation, which makes it be easily adsorbed by metal oxide, including SiO2, Fe3O4 etc. Fluorescence studies have also indicated that the aqueous solution of PVP is stable at least within one week if the pH of the solution is greater than 7.
    Kinetics and Molecular Weight Models and Simulation for Methyl Methacrylate Polymerization
    SHAN Guo-Rong, Gilles Fevotte, Yann LE Gorrec
    2002, 23(11):  2182-2187. 
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    The volume contraction, changing of reactant and resultant, and the effects of gel, glass and cage effects on the rate constants and physical properties in the methyl methacrylate polymerization process are considered. On the basis of the elementary reactions and the species mass balance, novel kinetic and molecular weight models for methyl methacrylate semi-batch polymerization with the participation of chain transfer agent and new materials addition flow rate are presented. Using the presented models, the effects of temperature, initiator concentration and type, monomer or solvent concentration and type, and chain transfer agent concentration and type on the kinetics of methyl methacrylate polymerization and molecular weight of polymer are simulated. Experimental and literature data of kinetics and molecular weight are compared with the simulation results to examine the presented models.
    Comparison of Dynamic Curing Behavior of Polybenzoxazine and Polybenzoxazine/Montmorillonite Hybrid
    YU Ding-Sheng, SHI Zi-Xing, XU Ri-Wei, WANG Yi-Zhong
    2002, 23(11):  2188-2191. 
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    The dynamic curing behavior of two curing systems which include pristine polybenzoxazine monomer(BZ) system and polybenzoxazine monomer insertion montmorillonite(BZ/MMT) system was compared. It was found that the organically treated played a vital role in curing behavior of BZ/MMT system and two types of curing reactions occurred in BZ/MMT system which includes: catalyzed polymerization and thermal polymerization, as a result, big difference in the two systems occurred at the characteristic curing temperature, curing rate, the heat of reaction, reaction order, as well as apparent activation energy.
    Studies on Kinetics of Ultrasonic Induced Microemulsion Polymerization of MMA
    LIAO Yong-Qin, WANG Qi, WANG Liang-Wen
    2002, 23(11):  2192-2195. 
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    In this paper, the radical scavenger DPPH was used to study the kinetics of ultrasonic induced microemulsion polymerization of MMA. Rate constants and apparent activation energy were obtained under various temperatures and power outputs. Compared with the results of ultrasonic induced bulk polymerization of MMA, the rate constants in this study were much higher, indicating that there was higher initiation efficiency of ultrasonic irradiation in emulsion system than in pure monomers. The kinetics results of ultrasonic induced microemulsion polymerization were expected to be suitable for the ultrasonic induced emulsion polymerization for their similar initiation mechanism. The kinetics during the polymerization was also investigated, and the result proved that there was an extended region of constant rate when the concentration of radicals was lower. Therefore, the results of the study on the kinetics of ultrasonic induced microemulsion polymerization of MMA provided a theoretical foundation for deeply understanding the mechanism of ultrasonic induced microemulsion and emulsion polymerization.
    In-situ Albumin Binding Material for Biomedical Application(Ⅰ)──Molecular Design and Surface Characterization
    JI Jian, FENG Lin-Xian, SHEN Jia-Cong
    2002, 23(11):  2196-2201. 
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    Poly(methyl methacrylate)-graft-[ω-stearyl-poly(ethylene oxide)] (PMMA-g-SPEO) and poly(methyl methacrylate)-graft-[ω-ethyl-poly(ethylene oxide)](PMMA-g-EPEO) were synthesized by free radical copolymerization of methyl methacrylate monomer with α-methacryloyl-ω-stearyl poly(ethylene oxide) macromonomer or α-methacryloyl-ω-ethyl poly(ethylene oxide) macromonomer. X-ray photoelectron spectroscopy(XPS) analysis indicates the substantial surface enrichment of the stearyl poly(ethylene oxide)(SPEO). In an aqueous environment, the surface rearrangement is limited, as proved by dynamic contact angle tests. The comb-like copolymer presents a special hydrophobic surface with a high SPEO surface density, which may be due to the "tail like" SPEO architecture on the copolymer/water interface.
    Preparation of Hyperbranched Poly（urea-urethane） with Hydroxyl End-groups from A2 and CB2 Type Monomers
    GAO Chao, YAN De-Yue
    2002, 23(11):  2202-2204. 
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    Hyperbranched polymer with alternating ureido and urethano units was prepared by direct polymerizarion of isophorone diisocyanate(IPDI, A2) with diethanolamine(DEOA, CB2) in the absence of catalyst. In the reaction, one isocyanato group of IPDI reacts fast with amino group of DEOA, generating an intermediate with one isocyanato group and two hydroxyl groups. Now the intermediate formed is a new kind of AB2 type monomer. Further self-condensation of this AB2 species leads to hyperbranched poly(urea-urethane). The reaction mechanism was characterized with in situ FTIR. Temperature and concentration have great influence on the polymerization process. When the feed ratio of IPDI to DEOA is equal to 1∶1, no gelation is observed if the reaction temperature within initial several hours is lower than 20 ℃. Cross-linking would occur if the reaction temperature during initial period is high. The degree of branching(DB) of the resulting hyperbranched poly(urea-urethane) is 46.5%-48.5%.
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