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Table of Content

    24 June 2001, Volume 22 Issue 6
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    Articles
    Synthesis of Core/Shell Structural CdS/ZnO Nanoparticles by Hydrothermal Method
    SUN Ling-Dong, FU Xue-Feng, QIAN Cheng, LIAO Chun-Sheng, YAN Chun-Hua
    2001, 22(6):  879-882. 
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    CdSand ZnO-capped CdSsemiconductor nanoparticles were synthesized via hydrothermal method by thermal decomposition of the cysteine-cadmium complex precursor. The results of XPSsuggested that CdSand ZnOwas formed. Compared to CdSnanoparticles, the band-gap emission of CdS/ZnOwas greatly improved, which means the shell of ZnOmodified the surface of CdScore and reduced the surface defect. EDconfirmed the formation of hexagon phase CdSand the TEMimage indicated that the size of CdS/ZnOwas about 20 nm.
    Synthesis, Properties and Crystal Structure of [(CH2OH)3CNH<sub>2]2H4SiW12O40·10H2O
    BI Li-Hua, XIN Ming-Hong, WANG En-Bo, HUANG Ru-Dan
    2001, 22(6):  883-886. 
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    Anovel organic-inorganic salt, [(CH2OH)3CNH2]2H4SiW12 O40 ·10H2O, was synthesized and characterized by means of elemental analyses, IRspectrum, cyclic voltammogram and electronic spectrum. The crystal structure of [(CH2OH)3CNH2]2H4SiW12 O40 ·10H2Owas determined belonging to triclinic with space group P1, a=1.2348 (3)nm, b=1.3085 (3)nm, c=1.8404 (4)nm; α=73.88(3)°, β=74.55(3)°, γ=87.40(3)°, Z=2, R=0.0871. Photochromism studies on [(CH2OH)3CNH2]2· H4SiW12 O40 ·10H2Oshow that the electron transfer takes place from the organic cation to the heteropolyanion. The electrochemical behavior of compound(Ⅰ) shows that the redox peak currents are proportional to the scan rate in H2SO4 solution of 2.0 mol/Lwhich indicates the electrode reaction are surface controlled processes.
    Syntheses, Characterization and Crystal Structure of Two Manganese(Ⅲ) Complexes with Ligand N,N'-Ethylenebis(1-phenyl-3-imino-1-butanone)
    FENG Yun-Long, LIU Shi-Xiong
    2001, 22(6):  887-891. 
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    Two manganese(Ⅲ) complexes with the ligand bzacen2- [bzacen2-=N, N' ethylenebis(1-phenyl-3-imino-1-butanone)], Mn(bzacen)(NO2)(EtOH) (1) and Mn(bzacen)(NO2)(MeOH) (2), have been synthesized and characterized by IR, electronic spectra and cyclic voltammetry. Both complexes crystallize in the orthorhombic system, space group Pbca, with parameters for complex 1: a=2.8173(6)nm, b=2.1946(4)nm, c=0.7683(6)nm, V=4.750(5)nm3, Z=8, μ=5.71 cm-1, and with parameters for complex 2: a=2.7641(6)nm, b=2.1832(4)nm, c=0.7705(2)nm, V=4.650(3)nm3, Z=8, μ=5.81 cm-1. The final Rvalues are 0.0540 for complex 1 and 0.0564 for complex 2, respectively. The structure determination of the title complexes reveals an octahedral coordination with an N2O2 equatorial plane composed of the donor atoms from the Schiff base ligand bzacen2-. In these complexes, νC=N, νC=O and νC=C are shifted to lower frequencies in IRspectra; π-π* transitions, d-π* charge transitions and d-d* ligand field transitions are observed in their electronic spectra.
    Racemic Isopropanolamine Templated Synthesis of a 2-Dimensional Layered Compound Al3P4O16· [NH3CH2CH(OH)CH3]2 · [NH4] from Various Non aqueous Solvents
    CHEN Wei, YUAN Hong-Ming, SHI Zhan, ZOU Yong-Cun, CHEN Jie-Sheng, XU Ru-Ren
    2001, 22(6):  892-894. 
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    A 2D layered aluminophosphate Al3P4O16· [NH3CH2 CH(OH)CH3]2· [NH4] containing [NH3CH2CH(OH)CH3]+ and [NH4]+ cations has been synthesized using racemic isopropanolamine as the template from several different non aqueous solvents. The compound has been characterized by single crystal structure analysis. Its space group is P21/m with a=0.89981(6)nm, b=1.47880(10)nm, c=0.97372(7)nm, β=104.790(2)° and V=1.25274(15)nm3. The structure consists of [Al3P4O16]3- macroanionic sheets stacked in an AAAAsequence and two types of cations, racemic [NH3CH2CH(OH)CH3]+ and [NH4]+, are located between the inorganic layers. The individual macroanionic sheet contains AlO4 and PO4 tetrahedral units in the ratio of 3/4 and all the AlO4 vertices are shared, but each PO4 has one terminal POgroup. Additional characterization of the compound by XRD, FTIR, ICPand TGAis also described.
    Studies on Preparation, Crystal Structure and Application of [Mn(CHZ)3](ClO4)2
    ZHANG Jian-Guo, ZHANG Tong-Lai, WEI Zhao-Rong, YU Kai-Bei
    2001, 22(6):  895-897. 
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    The title compound was prepared by mixing the aqueous solution of carbohydrazide and manganese perchlorate. It was characterized by X-ray diffraction. The crystal of the title compound, [Mn(CHZ)3](ClO4)2, belongs to space group P21/n with the crystal parameters a=1.0197(2)nm, b=0.8593(1)nm, c=2.1412(3)nm, β=100.86(1)°; V=1.8426(5)nm3, Z=4. The results show that all carbohydrazides are coordinated as bidentate by the oxygen atom of the carbonyl group and one nitrogen atom of the end group, forming a distorted octahedron. The explosive properties of the title complex were tested, the application in the engineering detonator was investigated.
    Synthesis and Formation Mechanism of PbCl2 Nanowires by Micelle-template Method
    WU Qing-Sheng, ZHENG Neng-Wu, DING Ya-Ping
    2001, 22(6):  898-900. 
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    Polycrystal nanowires of orthorhombic PbCl2, with diameter of 20—30 nm, length up to tens microns, and cell constants of a=0.454 nm, b=0.763 nm, c=0,904 nm, were synthesized by micelle template of polyoxyethylene(9)-dodecyl-ether(C12E9), n-pentanol and cyclohexane when the molar ratio of water to C12E9, R, is 10, the volume ratio of cyclohexane to C12E9 is 8, c(C12E9) is 0.18 mol/Land the concentration of c(Pb 2+) and c(Cl-) are 0.1 mol/L.The middle process and an intermediate were captured. On the basis, the formation mechanism of PbCl2 nanowires were studied. The results indicated that the formation of PbCl2 nanowires was probably via the mechanism of the directional aggregation and orientated growth of the PbCl2 colloidal particles.
    Determination of Nucleic Acids at Nanogram Levels with Tetra-substituted Amino Aluminum Phthalocyanine by a Resonance Light-scattering Technique
    CHEN Xiao-Lan, LI Dong-Hui, ZHU Qing-Zhi, YANG Huang-Hao, ZHENG Hong, XU Jin-Gou
    2001, 22(6):  901-904. 
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    This is the first report of the determination of nucleic acids at nanogram levels based on their enhanced effects on the resonance light-scattering of TAAlPc at 400 nm. Under optimal conditions, the linear ranges of the calibration curves were 0—2500 ng/mLfor Calf thymus DNA(CT DNA), 0—200.0 ng/mLfor Salmon sperm DNA(SM DNA) and 0—4000 ng/mLfor Yeast RNA. The detection limits were 1.4 ng/mLfor both CT DNAand SM DNA, 2.7 ng/mLfor Yeast RNA. The relative standard deviation for the determination of 100.0 ng/mL CT DNAwas 2.1%. The measurement can be made easily on a common spectrofluorimeter. The reaction between TAAlPc and nucleic acids is completed in 2 min and the scattered light signal is stable for at least 1 h. The interference from some interesting co existing substances with the determination of DNAwas also examined. The method was applied to the determination of DNAin golden staphylococcus DNAsample, and the results were satisfactory.
    The Electrochemical Behavior of Soluble Polyimides
    ZHAO Hui, LU Hai-Yan, XING Wei, YANG Hui, DING Meng-Xian, LU Tian-Hong
    2001, 22(6):  905-907. 
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    The effect of organic solvents on the electrochemical behavior of the soluble polyimide(PI) was studied by using cyclic voltammetry. It was found that PIcan undergo electrochemical reaction in some solvents, while the electrochemical response can not be observed in other solvents. The results of IRspectra indicate that the effect of the solvents on the electrochemical behavior of PIis due to the different interactions between PIand the solvent.
    Fourier Transform Infrared Spectroscopic Investigation of Human Blood Cells in Bone Marrow from AML and CML Patients
    GAO Ti-Yu, CI Yun-Xiang, FU Shuang, WANG De-Bing
    2001, 22(6):  908-911. 
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    Eight samples of bone marrow coming from patients affected by acute myeloid leukemia (AML) and nine samples from patients suffered from chronic myeloid leukemia(CML) were studied by FTIRspectroscopy. Obvious differences are observed among the erythrocytes, granulocytes and lymphocytes. No significant differences are found in the granulocytes/lymphocytes between AMLand CMLsamples whereas the spectroscopic differences of leukemic erythrocytes are observed. The ratios of the integrated areas of the band at 1540 cm-1 and 1084 cm-1 in the spectra of erythrocytes from AMLare closer and lower than the corresponding ratios from CMLsamples. Compared to that of CML, the erythrocytes from AMLshow broader amide band Ⅰ and have a higher percentage of α helix in the secondary structures of proteins. These differences indicate the different contributions of red cells in erythrocytic series in the erythropoietic development from proerythroblast to the matured erythrocytes. The results imply the maturation of red cells in bone marrow is related to the proliferation of leukemic cells. The noticeable differences may have important implications for analyzing and evaluating leukemia.
    Analysis of Urinary Nucleosides by Micellar Electrokinetic Chromatography
    ZHENG Yu-Fang, ZHANG Yun, LIU Da-Yu, GUO Xiao-Liang, MEI Su-Rong, XIONG Jian-Hui, KONG Hong-Wei, ZHANG Chao, XU Guo-Wang
    2001, 22(6):  912-915. 
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    Amicellar electrokinetic chromatography method for identification and quantitation of nucleosides in urine has been optimized. After nucleosides were extracted from human urine on phenyl boronic acid affinity chromatography column, the analysis was performed in an uncoated 52 cm×50 μm i.d. capillary tube using a 300 mmol/L SDS-25 mmol/Lborate-50 mmol/Lphosphate buffer (pH=6.96), 0.5 Psi×15 s injection, 7.0 kVvoltage and UVdetection at 254 nm. By using the MEKCmethod developed, 14 normal and modified nucleosides in 28 normal urines were quantified to establish the reference ranges. The result shows that this MEKCmethod is reliable, sensitive, efficient and suitable for clinical application.
    New Typical Ionic Cluster K+(KNO3)n and NO3-(KNO3)m
    SHI Lei, LIU Shu-Ying, LIU Zhi-Qiang, SONG Feng-Rui
    2001, 22(6):  916-918. 
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    New typical ionic clusters with complex anions could be formed directly from the KNO3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO3 being 101 in the full mass spectrometry, of the positive-ion and the negative-ion. The general formula of the ionic clusters belonged to K+(KNO3)n and NO3-(KNO3)m.
    Studies on the Catalytic Spectrophotometry Using SDS-Schiff Cu(Ⅱ) Complex as Mimetic Enzyme
    TANG Bo, LIU Yang, TANG Xiao-Ling
    2001, 22(6):  919-921. 
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    Anew Schiff base, 2-hydroxy-1-napthaldehyde-2-amino thiazole(HNATS) and its Cu(Ⅱ) complex was synthesized. The complex[Cu(Ⅱ)-(HNATS)2] could exhibit an efficient peroxitase like catalytic activity, and catalyze the coupling reaction of 2,4-dichlorophenol and 4-amino antipyrine with hydrogen peroxide. The effect of SDSon the catalytic activity of mimetic enzyme was studied. Based on the reaction, the determination of O2·- by this new spectrophotometric method was developed. The proposed method was used to determine SODactivity of garlic, scallion and onion with satisfactory results.
    Spectroscopic Characteristics of RTP Palladium-porphyrin Probe Interacting with DNA in Aqueous Solution
    YUAN Wen, JIN Wei-Jun, DONG Chuan
    2001, 22(6):  922-924. 
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    The characteristics of absorption, fluorescence, room temperature phosphorescence(RTP) spectra of meso tetrakis(4-N-trimethylaminobenzyl)porphin(TAPP) and Palladium porphyrin(Pd-TAPP) probe in the presence and absence of ct-DNAhas been studied. Pd-TAPP shows a very weak RTPemission in aqueous solution and strong RTP emission in the presence of DNA. Maximum RTPwas observed at pH=7, with maximum excitation and emission wavelengths at 414 nm and 684 nm, respectively. RTPdecay follows a first order exponential equation, RTPlifetime (τ) of probe is (0.72±0.03)ms. The detection limit of ct-DNA may reach 8.8×10-7 mol/L. The relative standard deviation(RSD) is less than ±6.6% in the linear range.
    The Pattern Recognition of Blue Ballpoint Pen Writing Inks by ATR Technique
    WANG Jian, SUN Su-Qin, LUO Guo-An, FENG Ji-Min, WANG Zhi-Qiang, WANG Yan-Ji
    2001, 22(6):  925-927. 
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    Asystematically analytical method for the recongnition of blue ballpoint pen ink has been studied by ATRtechnique of Fourier transform infrared(FTIR) spectrometry. By using this method, a total of 108 blue ink samples have been divided to 18 groups depending on the main component. The spectral characteristics of these inks such as peak location, peak intensity etc. were described by the way of pattern recognition; and the species of inks have been able to be recognized by their correlation coefficient(λ). This system has provided a best reliable and nondestructive method for the determination of ballpoint pen ink.
    Rapid Determination of Albumin of Urine in ΔI Measurement Mode with Portable Spectrophotometer of High Sensitivity
    CHEN Huan-Wen, JIN Qin-Han, Yang-Li-Quan, Luo-Gui-Min
    2001, 22(6):  928-930. 
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    Aportable spectrophotometer developed by Changchun R & D Center for Analytical Instruments, which combines ΔImeasurement mode and a measurement mode together with a high sensitivity, good accuracy and low cost, is employed to replace the traditional spectrophotometer and the sensitivity is enhanced. Therefore, a new rapid method with low cost and simplicity in operation for protein determination is developed. For this method, the linear range is shown to be 0—0.74 μg/mL, the detection limit is 0.01 μg/mL, and the analysis can be completed within 5 min. The albumin in urine is determined and all the results are confirmed by the standard method. Because of the rapid analysis speed, less expenditure, more convenience and simplicity in operation of this method, it is possible to use this method to diagnose glycosuric nephropathy at an early stage, even do it at home.
    Syntheses of Some 17-Heterocyclic Substituted Androstene Derivatives as Inhibitors of Human 17α-Hydroxylase/C17,20-layse(P45017α)
    RU Cheng-Jie, LEI Xiao-Ping, LING Yang-Zhi, ZHANG Li-He, Hundratta-V. , BrodieA. M. H.
    2001, 22(6):  931-935. 
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    172(3'-Pyrazolyl) and 17-(5'-isoxazolyl)androsta-4,16-dien-3-one have been found to be potent inhibitors for human testicular microsomal 17α-hydroxylase/C17,20-layse, which showed potential usage in the treatment of benign prostatic hypertrophy(BPH) and prostatic cancer. In order to further investigate their structure activity relationship, some substituents were introduced at the 5'-position of pyrazole and 3'-position of isoxazole, and eleven derivatives were obtained. The structures of the compounds were confirmed by IR, 1H NMR, elemental analysis or MSmeasurements. Their pharmacological activities are under investigation.
    Synthesis of New Chiral Diphosphine-borane Complex and Its Application to the Catalytic Asymmetric Hydrogenation
    JIANG Ru, NAN Peng-Juan, LIU Wei, LI Xiao-Ye, ZHANG Sheng-Yong
    2001, 22(6):  936-938. 
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    The high enantiomeric pure phenylglycol was synthesized from styrene by Sharpless asymmetric dihydroxylation. The diol was converted to chiral diphosphine-borane complex by esterification and nucleophilic substitution respectively. The complex was superior to free phosphine ligands which are sensitive to atmosphere. It's easy to prepare, purify and reserve. The complex was decomplexated in the presence of HBF4·OMe2 to yield quantitatively the free diphosphine which reacted directly with [Rh(COD)Cl]2 forming in situ catalyst. The asymmetric hydrogenation of methyl z-α-acetamidocinnamate has been accomplished in the presence of catalyst in 100% chemical conversion and 88% e.e..
    Synthesis of Pyrazolyl-heterocycles and Their Fungicidal Activities
    ZHAO WeiGuang, CHEN Han-Song, LI Zheng-Ming, HAN Yu-Fen, YAN Han, LAI Jun-Ying, WANG Su-Hua
    2001, 22(6):  939-942. 
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    Aseries of pyrazolyl heterocycles, including1,3,4thiodiazoles, 1,3,4-oxadiazoles and 1,3,4-triazoles were synthesized from 4-nitro pyrazole formhydrazide. The structures of all new compounds were confirmed by 1H NMRand elementary analysis. Their fungicidal activity was evaluated against Rhizoctonia solani. Structure activity relationships for the screened compounds were evaluated and discussed. It was found that some compounds showed a higher fungicidal activity and systematic activity.
    Studies on the Substituent Effect and Electrochemical Behavior of ⅥB Metal Carbonyl Complexes Containing Bis(pyrazol-1-yl)alkanes
    CHAI Jian-Fang, TANG Liang-Fu, JIA Wen-Li, WANG Zhi-Hong, WANG Ji-Tao
    2001, 22(6):  943-946. 
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    The cyclic voltammetric behavior of ⅥBcarbonyl complexes containing bis(pyrazol-1-yl)alkanes has been investigated. It was found that the redox potentials(E1/2) of metal centers remarkably relate to the ability of electron donating of ligands. Metal centers with electron donating groups on the pyrazolyl rings are easier to be oxidized than those containing electron withdrawing groups.
    Solution Structure of the Imidazole Complex of Cytochrome c
    WU Yi-Bing, LU Jun, YAO Yong, BAI Zhi-Ping, TANG Wen-Xia, ZHU De-Xi, BANCI Lucia, BERTINI Ivano, LIU Gaohua, REDDIG Tim
    2001, 22(6):  947-948. 
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    The solution structure of the imidazole adduct of oxidized horse heart cytochrome c(Im-cyt c) has been determined through 2D NMRspectroscopy. The 35 conformers of the family show the RMSDvalues to the average structure of 0.063±0.007 nm for the backbone and 0.107±0.007 nm for all heavy atoms, respectively. The secondary structure elements and the overall folding of the present structure are substantially similar to those of the solution structure of native protein. However, the replacement of the axial ligand Met 80 with the exogenous imidazole ligand induces significant conformation changes in both backbone and side chains of the residues locating in the distal axial ligand regions. The electron delocalization on the heme moiety and the magnetic susceptibility tensor are consistent with these structural features.
    A Rare Long Conjugated Diterpene Ketene from the Marine Sponge Ircinia selaginea(Lamark)
    YAN Su-Jun, ZHANG Guang-Wen, SU Jing-Yu, ZENG Long-Mei
    2001, 22(6):  949-951. 
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    Anew diterpene, irciniketene, was isolated from the marine sponge Ircinia selaginea(Lamark) collected from the sea around Baihai, Guangxi Province. Its structure was determined by spectroscopic methods. In the structure, a ketene function is connected with a long conjugated system via an allene unit. Irciniketene shows a moderate inhibition toward MGCand HepG2 tumor cell lines.
    Studies on the Conformational Interconversion of Sulfonylurea Molecules in Solution by Molecular Dynamics Simulation Method
    SHEN Rong-Xin, FANG Ya-Yin, MA Yi, SUN Hong-Wei, LAI Cheng-Ming, LI Zheng-Ming
    2001, 22(6):  952-954. 
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    The conformational interconversion of sulfonylurea molecules in solution was studied. The behavior of the compound in non-polar solvent and polar solvent was simulated with molecular dynamics. The variety of conformation which may be provided to the research of structure activity relationship for reference was studied.
    Studies on the Synthesis, Properties and Biological Activities of (9-Carbazoly)-carboxylic Acids
    LAO Wen-Jian, YOU Jing, LU Hao-Jie, CHEN Shu-Lian, SHEN Xue-Jiao, OU Qing-Yu
    2001, 22(6):  955-957. 
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    This paper investigated a rapid one-pot synthesis method of some substituted(9-carbazoly)-carboxylic acids(3a-3m). The reaction was carried out by mixing of the 9H-carbazoles derivatives with bromo-esters and potassium hydroxide using DMFas solvent under microwave irradiation without catalyst. The optimized experiment conditions were 4-8 min irradiation time and 375 Wmicrowave power. The required range of molar ratio of KOHto substituted carbazole was 3-5. The biological activities of some compounds have been tested. They have medium to weak antimicrobial activities.
    Computer Simulations of Hydrogen Adsorption in Single-walled Carbon Nanotubes
    GU Chong, GAO Guang-Hua, YU Yang-Xin, MAO Zong-Qiang
    2001, 22(6):  958-961. 
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    The adsorption of hydrogen gas into single-walled carbon nanotubes (SWNTs) is studied by Grand Canonical Monte Carlo simulation. Hydrogen-hydrogen and hydrogen-carbon interactions are both modeled with Lennard-Jones potential. Hydrogen-carbon interactions are integrated over the whole nanotube to get the molecule-wall interactions. Five adsorption isotherms of different tube diameters at 293 Kand two adsorption curves of different van der Waals (VDW) distances at 293 Kand 5 MPa are displayed. The influence on adsorption of different SWNTs' diameters and VDWdistances are discussed.
    Electrochemical Quartz Crystal Microbalance Study on the Electrochemical Behavior of Guanine, Guansine and Guansine Phosphate at Gold Electrode
    SHEN He-Bai, XIA Jing-Fen, WANG Zhe-Su, ZHANG Zong-Rang
    2001, 22(6):  962-965. 
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    The electrochemical quartz crystal microbalance(EQCM) was used to study the electrochemical behavior of guanine, guanosine and guanosine phosphate on the gold electrode. The results show that the three biological molecules can be oxidized at 1.1 V, which might be caused by the oxidation of C-N bond within three studied molecules. According to the change of electric quantity and mass quantity, we have calculated the number of transferred electron, which is 4. The order of oxidation current is estimated as guanosine phosphate>guanosine>guanine, which might be caused by the different adsorption ability of those molecules.
    Electrocatalytic Oxidation for Formic Acid and Formaldehyde on Platinum Implanted Glassy Carbon Electrode
    ZHANG Cun-Zhong, YANG Jing, WU Zhong-Da
    2001, 22(6):  966-970. 
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    Platinum implanted glassy carbon electrode(Pt/GC) was fabricated and implantation dose is 5×1017ion/cm2. The surface elements composition and the concentration depth profiles of various elements of platinum implanted glassy carbon electrode(Pt/GC) were measured by AES. The chemical state of Pt on Pt/GCelectrode was detected by XPS. The electro-oxidation of HCOOH in 0.5 mol/L HClO4 solution and electro oxidation of HCHOin five kinds of weak basic solutions have been investigated on Pt/GCand smooth Pt electrodes, respectively. The results show that the catalytic activity, according to the real surface area, of Pt/GCelectrode is better than that of pure Pt electrode in electro oxidation of formic acid and formaldehyde. It is possibly related to Pt nanometric clusters formed in bombing. On the same electrode, the currents of oxidation of HCHOin difference weak basic solutions are different. It shows that anion has an obvious effect on the electro oxidation of HCHO.
    Spectroscopy Study on the Photochromism of N,N'-Bis(salicylidene)-1,6-hexanediamine
    ZHAO Jian-Zhang, ZHAO Bing, XU Wei-Qing, LIU Ju-Zheng, WANG Zong-Mu, LI Yao-Xian
    2001, 22(6):  971-975. 
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    The photochromism of N,N' bis(salicylidene)-1,6-hexanediamine was studied by steady state and time-dependent fluorescence spectra, UV-Vis absorption spectra and FTIRmeasurement. The photo product was determined to be the keto form.
    Studies on Microstructure and Crystallization Behavior of Electroless Nickel-High Phosphorus Coatings
    JIANG Tai-Xiang, WU Hui-Huang
    2001, 22(6):  976-979. 
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    The electroless nickel-high phosphorus coatings with 12.8% P(mass fraction) have been deposited from acidic bath containing mixed complexing agents. The microstrucrure and crystallization behavior of the deposits have been characterized by AFM, TEM, DSCand XRD. The results show that the as-plated deposits exhibit a rounded mound topography and have an amorphous structure. The deposits crystallize into metastable phase Ni 5P2 at 343.8 ℃, which are subsequently transformed into stable phases of nickel and Ni3Pcrystallites at 440.4 ℃. This behavior is apparently different from that of the deposits produced from alkaline ethanolamine baths.
    Synthesis of Rutile Tatania by Heterogeneous Nucleation Methods
    YANG Shao-Feng, ZHAO Chun, SONG Li-Zhu, ZHAO Jing-Zhe, WANG Zi-Chen, XU Hui-Fang, LI Bo-Fu
    2001, 22(6):  980-983. 
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    Rutile tatania powders were synthesized in aqueous solutions, avoiding the appearance of TiO2 in anatase form, by heterogeneous nucleation methods with SnCl2·2H2O(method A) and SnCl4·5H2O(method B) as the raw materials respectively. The effects of nuclei and peptizing conditions on the structures of products were investigated. The mechanisms of nucleation were studied by comparing the results of the two different raw materials. The content of SnO2 in the samples with a full rutile structure was 10% and 8%(molar fraction) for the two methods respectively.
    A New Simulation Model for Oxidation of CO on the Catalyst's Surface
    HE Ming-Feng, FENG Tao, KANG Zhe-Wen, HAN Xiao-Jun, ZHAO Li-Zhong
    2001, 22(6):  984-986. 
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    Acellular automation model for the catalytic CO+O2 surface reaction is introduced by means of building oriented two pointed “suprastructure” in lattice. Reactions can only occur in the suprastructures. We use reaction probability as variable to control reactions in suprastructures. The reactions system exhibits three phases: the CO-poisoned, the O-poisoned and the reactive phase, in consistence with the Monte Carlo results.
    Theoretical Study on the Structure and Spectra of C60-TTF Cyclohexene-fused Dyads
    ZHANG Suo-Qin, FENG Ji-Kang, REN Ai-Min, FU Wei-LI, Yao-Xian
    2001, 22(6):  987-990. 
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    Atotal of eight molecules of C60 TTF Cyclohexene Fused Dyads was investigated by ZINDOseries methods. The stable structure and electronic spectra were studied. The results suggested that the calculated electronic spectra the studied molecule were consistent well with those from the experiment. The calculated results have been explained micromechanically.
    Synthesis and Characterization of SAPO-56, a New Member of Silicoaluminophosphate
    TIAN Peng, XU Lei, LIU Zhong-Min, SUN Cheng-Lin, HUANG Tao
    2001, 22(6):  991-994. 
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    The molecular sieve SAPO-56 has been synthesized hydrothermally using N,N,N',N' tetramethyl 1,6-dihexane as template. In the Al2O3-SiO2-P2O5 medium, phase diagram of SAPO-56 was obtained. Pure phase region of SAPO-56 appeared in the range of 0.5<n(SiO2)/n(M)<0.7(M=SiO 2+Al2O+3P2O5), 0.15<n(Al2O3)/n(M)<0.4 and 0.1<n(P2O5)/n(M)<0.3. The effect of template amount on the synthesis of SAPO-56 was also investigated. Provided that other compositions (Si, Al, Pand H2O) was fixed, it presented pure SAPO-56 crystal in the ratios of n(TMHD)/n(P2O5)≥2. The properties of SAPO-56 were characterized by XRD, SEM, TG-DTA, IRand adsorption technique which suggested that SAPO-56 had a good thermal stability and large water adsorption capacity. In the methanol to olefins reaction, SAPO-56 catalyst exhibited a high activity and selectivities to C2, C3 olefins.
    Derivation of Interaction Energy and Force Between Identical Spheres in Linear Superposition Approximation
    CHEN Chong-Jun, CHEN Xiao-Dong, LUO Gen-Xiang, JIN Jun, WANG Hao-Ping
    2001, 22(6):  995-997. 
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    We define an effective surface potential of spherical particle, which can be decomposed as φ(κh)=Y(h)+ΔY(h). First part of the effective surface potential is the unperturbed surface potential which is expressed by equation(6) in the text and other part is a perturbed surface potential of the particle due to the presence of the other particle. Furthermore, a detailed derivation of interaction energy and force between identical spheres in linear superposition approximation is presented. Thus very simple analytic formulas are presented between two identical spherical particles for interaction energy at moderate potential. The agreement with exact numerical results is considerably improved for free energy, but not force. The reason is that the relation of the energy and the force is the relation of integration and differentiation but integration can smooth an integrand and defferentiation exposes singularity of a function. Terefore, the agreement with exact numerical results is better for free energy, but not force.
    Studies of Quantum Chemistry on Fullerene C36 and Their Derivatives C36H2n
    GONG Zhi-Jun, XU Wen-Guo, LI Qian-Shu
    2001, 22(6):  998-1001. 
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    The molecular geometry and electronic structure of fullerene C36 isomers with C2v, D2d, D3h and D6h symmetries and hydrofullerenes C36H2n of D2d, D3h and D6h isomers with different quantum states are studied at the 3-21Glevel of the theory using density functional B3LYPand ab initio HFmethods. The results of calculations show that the effect of electronic correlation have an important influence. Their most stable structures are D6h isomer with a quantum stae 3A2u among C36 and hydrofullerene C36H12 of D3h isomer with a quantum state 1A1' adding hydrogen at C2 position among C36H2n.
    Rheology of Colloidal Dispersions of Positively Charged Al-Mg MMH Particles
    SUN De-Jun, LIU Shang-Ying, YANG Zhi, HOU Wan-Guo, ZHANG Chun-Guang
    2001, 22(6):  1002-1005. 
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    The rheology of aqueous Al Mg MMH(mixed metal hydroxide) dispersions and electrophoretic mobility of MMHcolloidal particles were studied by rheological and electrokinetic measurements as a function of MMHconcentration, pHof dispersion and NaCl concentration. It was found that the suspensions are Newtonian at low MMHconcentrations, while increasing MMHconcentration gives rise to the suspensions with a yielding type of behavior. However, a transition from Newtonian to non-Newtonian flow curves may occur at relatively low MMHconcentration(2%) when suspensions was formulated near the isoelectric point(pHiep) for MMHor with NaCl being added to MMHsuspensions below pHiep. It appears that the rheology of MMHdispersions is closely correlated to the MMHconcentration and the surface charge of MMHparticle. When the recovery experiments with a relatively high vigorous stirring and at a low shear rate were performed on inherent MMHsuspensions consisting of positively charged platelike particles, the evolution of the gel structure is very slow, similar to the result for aqueous Laponite system consisting of negatively charged platelike particles. This result suggests that it is also the long range electrostatic double layer forces that lead to the formation of a repulsive gel in MMHsuspensions, similar to aqueous Laponite system at a high pH.
    Kinetic Studies on State-state Transitions for ·CCl2(X1A1,A1B1,a3B1) Radical and Quenching of ·CCl2(A1B1 and a3B1) with Methane and Chloromethane
    GAO Yi-De, CHEN Yang, PEI Lin-Sen, MA Hua-Qiang, MA Xing-Xiao, CHEN Cong-Xiang
    2001, 22(6):  1006-1009. 
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    CCl2 free radicals were produced by d-c discharge of CCl4(in Ar). The ground electronic state CCl2 radical was electronically excited to pR1 level of A1B1(0,4,0) state by laser exciting at 541.52 nm. Experimental quenching data of·CCl2(A1B1 and a3B1) through methane and chloromethane were obtained by observing time resolved fluorescence from the excited ·CCl2 transition, which showed a superposition of two exponential decay components. The state resolved rate constants kq1, kq2 and kq3 were first time estimated by analyzing and dealing with these data by using three level energy model, which was put forward by us. In combining discharge with free jet LIFthe lifetimes of·CCl2(A→X) and(a→X) transition were measured being(0.83±0.03) μs and(3.12±0.25) μs, respectively.
    Studies on the Surface Photovoltage Property of α-Terthiophene
    CAO Chang-Sheng, WANG Ce, CAO Yaan, SHI Yan-Hui, LI Tie-Jin
    2001, 22(6):  1010-1012. 
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    The behavior of the electron jumping of α-terthiophene under effect of electrical field has been investigated by means of SPSand EFISPS. Combining the result of UV-Vis spectra, the band band transition response peak(HOMO-LUMO) has been assigned and non-band-band transition response peaks have also been assigned according to the conception of polaron. For the SPSand EFISPSof α-3T, near 380 nm, it is band band transition absorption. Near 447, 465 and 600 nm, three different types of electron transitions which are related to energy levels of mono polaron occured. Near 770 and 900 nm, other two types of electron transition which related to bipolaron occured.
    Preparation of Mesoporous Silica MCM-41 from Waterglass with a Convenient Way in an Open vessel
    LI Wen-Jiang, ZHAO Chun, SONG Li-Zhu, ZHAO Jing-Zhe, SHA Xiao-Xiang, ZHOU Bing, WANG Zi-Chen, ZHANG Zong-Tao, ZHAO Mu-Yu
    2001, 22(6):  1013-1015. 
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    Aconvenient and economic method for preparing highly ordered MCM-41 was studied in an open-vessel by using waterglass as the silicon source. XRD, nitrogen adsorption and TEMshow that the product has a highly ordered structure and the hexagonal arrangements of uniformly size pores distribution.
    Theoretical Study on Second-order Nonlinear Optical Properties of Diazadistyrene Derivatives
    LIU Yong-Jun, LIU Ying, ZHAO Xian, LIU Cheng-Bu
    2001, 22(6):  1016-1018. 
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    On the basis of ZINDOprogram, we have designed a program to calculate the nonlinear second-order polarizabilities βijk and βμ according to the SOSequation. The second-order nonlinear optical properties of diazadistyrene derivatives were studied. The calculated results reveal that the introduction of pyrimidine does not influence the transparency but give a rise to large values of β. For the corresponding stilbene derivatives, the effect of the location of pyrimidine on the values of β is greater.
    Electronic Structures and Singlet Electronic Spectra of C76 and C76n
    TENG Qi-Wen, WU Shi
    2001, 22(6):  1019-1021. 
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    The INDOseries of methods were used to optimize the structures of C76n(-4≤n≤6) without any symmetry constriction. It was indicated that there are 30 kinds of bonds and 19 types of unique carbon atoms, but there are not Jahn Teller distortion in C76n, which is different from C76n and C70n .Furthermore, the C76 nions are less stable than C76. Based on the optimized geometries, the electronic spectra were calculated by INDO/SCImethod. It was shown that the NIRabsorptions for C76n singlet will appear beyond 1000 nm. Electronic transition was assigned theoretically and the reason of red shift for absorption peaks of C76n compared with those of C76 was discussed.
    Effect of Desiccation of the Catalyst Precursor on the Performance of Amorphous Ni-B/γ-Al2O3 Catalyst
    LI Jiang, QIAO Ming-Hua, DENG Jing-Fa
    2001, 22(6):  1022-1024. 
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    Amorphous Ni-B/γ-Al2O3 catalyst 1 is prepared with chemical reduction by KBH4 solution after wetness impregnation and desiccation at 70 ℃ first and then at 110 ℃ for thorough water removal. Its higher catalytic activity than amorphous Ni-B/γ-Al2O3 catalyst 2, prepared by conventional one-step desiccation procedure at 110 ℃, is identified in liquid-phase benzene hydrogenation to cyclohexane. Both catalysts are characterized by XRDand SEM, Ni-B/γ-Al2O3 catalyst 1 has a higher active specific surface area and dispersion degree, which can be assigned to more effective distribution of nickel salt over the support during desiccation, thus resulting in its superior activity in benzene hydrogenation.
    Studies on the Kinetic Feature of Orbán Oscillation System from the Role of Cupric Ion
    GAO Qing-Yu, SUN Kang, LI Lan-Ping, CAI Zun-Sheng, ZHAO Xue-Zhuang
    2001, 22(6):  1025-1027. 
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    In the H2O2-KSCN-CuSO4-NaOHreaction system, cupric ion plays an essential role for batch and CSTRoscillation. Since Cu 2+(or Cu+) can be precipitated as CuOH, CuSCNand Cu(OH)2, its concentration has a complex influence on the amplitude and initial high flowrate of oscillation. The pHdrop resulted from the oxidation of KSCNby hydrogen peroxide inhibited the oscillation. The kinetic nature of oscillation should be the H2O2 decomposition catalyzed by cupric and thiocyanate.
    A New Method of the Gibbs-Duhem Equation for Calculating Mixing Free Energy of Polymer Plasticized Systems
    SHAO Zi-Qiang, HAO Hong-Ying, LIAO Shuang-Quan, Yu. M. Lotmentsev, TAN Hui-Min
    2001, 22(6):  1028-1030. 
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    To study method for calculating mixing free energy of polymer solutions. Anew method for treating experimental data on concentrating dependence of chemical potential was advanced. Various methods for calculating mixing free energy through the Flory-Huggins equation were compared. Relations on concentration dependence of chemical potential were gained by various methods. As compared with other known calculating procedures, the new method was shown to provide more precise estimates mixing free energy.
    Synthesis of Multibranched Fullerene Polymer and Studies of Its Thin Film
    QIU Xiao-Yan, HUANG Lan, LUO Guo-Bin, ZHAO Xin-Sheng, YU Ying, SHEN Xian-Feng, Shi-Bing
    2001, 22(6):  1031-1035. 
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    The fullerene reacts with free radicals produced by reaction of 3-chloromethyl-methixy benzene and CuBr to form multisubstituted fullerene derivant. The synthesis of multibranched fullerene polymer was achieved by condensation between 2,2-bis(hydroxymethyl)propionic acid and the fullerene derivant. They were characterized by FTIR, MULDI-TOF MS, TEMand GPC. The thin film was prepared by LBtechnique, and the film morphology was early investigated by AFM.
    Synthesis of the New Type Sulphur-Containing Optical Resin Monomer MPSDMA and Study of the Properties of Its Copolymer Resins
    LU Guang, CUI Zhan-Chen, LÜ Chang-Li, ZHAO Deng-Feng, YANG Bai
    2001, 22(6):  1036-1040. 
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    Benzene ring, groups containing sulphur, and double bond were introduced into the structure of optical resin monomer successfully, and a new kind of optical resin monomer bis[4-(methacryloylthio)phenyl] sulfide(MPSDMA) was synthesized by means of sulfochlorination, reduction, and low temperature phase transfer catalysis reaction. Transparent resins were prepared by copolymerizing MPSDMAwith MMAand St respectively, and the study of the properties of those copolymers showed that this new type of optical resins had a high refractive index and high surface hardness.
    Investigation on Preparation and Property of Macroporous Glycidyl Methacrylate Copolymers
    HANG De-Hua, YUAN Zhi, SUN Jun-Tan, HE Bing-Lin
    2001, 22(6):  1041-1044. 
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    Aseries of macroporous glycidyl methacrylate-triallyl isocyanurate-divinylbenzene(GTD) copolymers were synthesized with toluene and n-heptane as the porogenic agent by suspension copolymerization.Some of them should be used as adsorbents for hemoperfusion.The effects of the amount of crosslinking agent and mixed porogenic agent on structural property, such as specific area, average pore diameter, pore volume and porosity were investigated.
    Synthesis of N-Vinylcarbazole Chromium Tricarbonyl and Its Free Radical Polymerization Reaction
    TIAN Xiao-Hui, LIU Jun, XU Zhong
    2001, 22(6):  1045-1048. 
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    Anovel metal chromium containing organic monomer, N-vinylcarbazole chromium tricarbonyl has been synthesized and the structure has been confirmed by elemental analysis, IRand 1H NMRspectra. N-vinylcarbazole chromium tricarbonyl can undergo free radical polymerization reaction to provide an organometallic polymer which contains equivalent chromium in its structural unit. It was observed that the decrease of polymerizing activity of the monomer caused by the electron withdrawing effect of Cr(CO)3 could be compensated to some extent by the conjugational effect between the benzene ring and nitrogen containing electron donor centers.
    Alternating Copolymerization of Isoprene with Maleic Anhydride by Rare Earth Coordination Catalyst
    HU Zhi-Guo, ZHANG Yi-Feng, SHEN Zhi-Quan
    2001, 22(6):  1049-1052. 
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    Alternating copolymerization of isoprene with maleic anhydride was carried out by rare earth coordination catalyst[Nd(naph)3-AlEt-3] for the first time. The better copolymerization conditions are: [M]total=2.6 mol/L, n(Al)/n(Nd)=10, [Nd]=5×10-3 mol/L, V(toluene)/V(dioxane)=2/5 as solvent, 5 ℃, 2 h. Copolymer yield was 70%. The copolymer was characterized by elemental analysis, IRand 13C NMR.
    The Synthesis and Properties of Fluoropoly(aryl ether ketone)s
    WANG Gui-Bin, WANG Dong, JIANG Zhen-Hua, CHEN Chun-Hai, ZHANG Wan-Jin, WU Zhong-Wen
    2001, 22(6):  1053-1056. 
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    Anovel fluoropoly(ether ether ketone) was synthisized by nucleophilic substitution reactions based on 2-(3'-trifuoromethyl)phenyl hydroquinone(FH) and 4,4'-difluorobenzophenone. Studies on its properties showed that dielectric constant of fluoropoly(ether ether ketone)(FPEEK) was 2.7. FPEEKcould be dissolved in a wide range of organic solvents, such as DMF, DMAc, DMSO, NMP, TMS, dichloromethane, chloroform etc. and thin film of the polymer cast from chloroform was transparent, creasable and tough. Coating film had a strong adhesion force and resistance to impact with surface substrates. Aseries of copolymers of fluoropoly(aryl ether ketone)s were synthesized by nucleophilic substitution reactions based on FH, 4,4'-biphenol(BP) and 4,4'-difluorobenzophenone. Studies on the dielectric constant of copolymers showed that the dielectric constants of fluoropoly(aryl ether ketone)s declined linearly with content of —CF3 increasing in structure units for copolymers.
    Self-assembled Ultrathin FilmsFrom Layered Nanoarchitectures to Functional Assemblies
    WU Tao, ZHANG Xi
    2001, 22(6):  1057-1065. 
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    We have summarized the development of a new type of self assembly technique in fabricating ultrathin filmslayer-by-layer-self ssembly technique, concentrating on some aspects as: driving forces for film fabrication, layered assemblies of biomolecules, inorganic/organic heterostructures, layered assemblies of small organic molecules, ultrathin films for chemically modified electrodes, chemical reaction between layers and layered architecture on nonplanar substrate.
    New Approaches to Polymer Micellization and the Structural Evolution of the Micelles
    LIU Shi-Yong, JIANG Ming
    2001, 22(6):  1066-1072. 
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    The classical micellization behavior of block or graft copolymers in selective solvent was briefle described and a variey of new approaches to polymer micellization caused by specific interactions(hydrogen bonding, ionic interaction, polymer-metal ion coordination interaction), change of termperature and media properties and chemical reactions, etc. was reviewed. Besides, new advances in the further evolution of the micelles leading to core cross linked micelles and shell cross linked micelles are discussed.
    Synthesis and Characterization of Novel Functional Hyperbranched Polyesters
    TANG Li-Ming, HansR. Kricheldorf
    2001, 22(6):  1073-1075. 
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    Aseries of hyperbranched polyesters with controlled inherent viscosities have been prepared by polycondensation of 3,5-bis(trimethylsiloxy) benzoyl chloride with sililated p-methyl aniline under various molar ratios. After reacted with acid chlorides in o-dichlorobenzene, the functionalization of these polyesters was readily accomplished. The end groups of the crude polymers were effectively transferred into vinylic and ethynylic groups in high yields(>85%) as calculated by 1H NMRspectra without any change in their inherent viscosities.
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