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Table of Content

    24 December 2000, Volume 21 Issue 12
    Articles
    Synthesis, Properties and Antiviral Activity of Keggin Molybdogemnium Heteropoly Blues
    LIU Jie, ZHANG Qian-Ling, WANG Li-Jun-WANG En-Bo, HUANG Jin-Wang, JI Liang-Nian
    2000, 21(12):  1791-1796. 
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    Rare earth molybodogemanium 2e, 4e heteropoly blues, LnH3[GeMo10Mo2O40]·8H2Oand LnH5[GeMo8Mo4ⅤO40]·8H2O(Ln=La, Ce, Nd, Sm, Gd), have been prepared and characterized by IR, UV, TG DTA, XPS, ESR.It is found that the structures of the heteropoly blues still retain the Keggin structure with a slight difference compared with their un reduced compounds.The in vivo activity of Pr(2) against influenza virus(FM1) in the mice was investigated.Pr(2) was administrated perorally(po) and intraperitoneally(i.p) to 14-16 g Kunming mice infected with FM1.The results show that in contrast to the positive ribavirin, the curative effect of Pr(2) proved to be better and i.padministration was more effective than poadministration
    Synthesis of Mesoporous Zirconia with Crystalline Framework in Super-critical Ethanol
    ZHAO Jun-Ping, WANG Shu-Guo, GONG Yan-Jun, WU Dong, SUN Yu-Han
    2000, 21(12):  1797-1800. 
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    By using nonionic polyethylene oxide surface(PEO) as a template, mesoporous zirconia was synthesized in super critical ethanol under different conditions(wide pH, various types of PEOand different chelates).XRD, N2adsorption desorption isotherm, TEMand selected area electron diffraction confirmed that the as synthesized powder was mesoporous zirconia with tetragonal walls.Similar to MSUsilica, mesoporous zirconia showed single XRDin small angle, spongy like pore arrangement and non monotonic relation between the pore size and the surfactant length.Thus, the analogous assembly mechanism most likely took place for PEOas the template by forming micelles in thermal ethanol.BETsurface area and pore size could be modified by varying PEO, pHand chelate.The as synthesized mesoporous zirconia had poor thermal stability.It might be because the calcination caused further crystallization and the deformation of crystalline framework, thus losing the meaoporous structure.It is well known that some oxides such as SiO2, Al2O3or TiO2can effectively stabilize totragonal zirconia.Therefore, incorporation with SiO2, Al2O3or TiO2, the meso structure of zirconia successfully retained on the calcination at673 K, or even up to723 Kin some cases.The related work will be published later
    In-Situ Synthesis of SAPO-34 Molecular Sieves on Monolithic Cordierite Substrates
    WANG Ai-Qin, LIANG Dong-Bai, TANG Jun-Wang, XU Chang-Hai, SUN Xiao-Ying, ZHANG Tao
    2000, 21(12):  1801-1804. 
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    SAPO-34 molecular sieves have been successfully synthesized onto the cordierite substrates by hydrothermal technique, and characterized by XRDand SEMmethods.The results show that SAPO-34 layers with the thickness about30μm are evenly distributed onto the inner walls of the cordierite substrate, which results in a weight increase of15%_25% of the substrate.The molar ratio of Et3N/Al2O3had an important effect on the nature of the molecular sieve product crystallized on the substrate.When n SAPO-34 was crystallized on the cordierite substrate; whereas when n (Et3N)/n (Al2O3)=2.5 , a mixture product of SAPO-34 and SAPO5was formed on the substrate.In order to explore the mechanism of SAPO-34 formation on the cordierite substrate, the changes of the crystallization process on the substrate as well as in the solution has also been investigated
    Hydrothermal Synthesis and Spectral Properties of the Eu Doped KZnF3
    LI Hong, JIA Zhi-Hong, FENG Shou-Hua, SHI Chun-Shan
    2000, 21(12):  1805-1808. 
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    The polycrystals of KZnF3:Eu have been synthesized by hydrothermal method at 220℃. The product was characterized by XRD, XPSand SEM.The emission and excitation spectra of europium ion were measured.The existence of Eu 2+ion was confirmed by ESRand spectroscopy.The sites were possibly occupied by Eu 2+ions, charge compensation in this crystal were also discussed
    Far Infrared Shift of Lithium Perchlorate Complex with4-tert-Butylbenzo-15-crown-5
    TAI Xi-Shi, FANG Sheng-Qiang
    2000, 21(12):  1809-1811. 
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    The solid complex of lithium perchlorate with4-tert butylbenzo-15-crown-5(4-t-BB15C5) has been prepared in iodobenzene.The composition of the solid was determined as Li(4-t-BB15C5)ClO4and its melting point was119_121 ℃. The far IRshift of the complex is obvious.The far IRabsorption band of the complex containing100% 6Li can be found by extrapolation, resolving the difficulty in obtaining a sample of100% 6Li up to now.Arelative reduced partition function ratio, [( s/s′)f ] org, being1.045 is calculated.Since the [ (s/s′)f ] aqof lithium perchlorate in solid state had been obtained as1.025and may act as that in aqueous phase, the phase equilibrium separation factor α may be obtained as 1.019 by the quotient of 1.045/1.025 for the extractive system of (4-t-BB15C5) C6H5I/LiClO4H2oThe value of α is just equal to the value of intrinsic separation factor (1+εp) described previously
    Synthesis of High Permeances of ZSM-5 Zeolite Membranes
    LI Yong-Sheng, WANG Jin-Qu, GUO Shu-Cai
    2000, 21(12):  1812-1814. 
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    Zeolite ZSM-5 membrane, whose permeance was up to10-6mol/(m2·s·Pa) and a magnitude higher than that of other groups, was prepared on α Al2O3support by multi in situ hydrothermal treatments, using optimized sol prescription and cheap n butane as the structure directing agent.The membrane was characterized by means of XRD, SEMand single gas permeances measurements, which showed that it was dense and integral without large intercrystal pores and cracks.The permeance of H2, N2, C3H8 and n C4H10was up to2.35×10-6, 1.0×10-6, 1.13×10-7and4.9×10-8mol/(m2·s·Pa), respectively.Ideal selectivity of H2/N2, H2/C3H8and H2/ n C4H10was2.45, 20.8 and48, respectively
    Chemiluminescence Determination of N-Tetrahydrobenzothiazolyl Imine Schiff Base
    ZHANG Si-Chun, LI Hua, GAO Hong
    2000, 21(12):  1815-1819. 
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    Five newly synthesized Ntetrahydrobenzothiazolyl imines show weak chemiluminescence(CL) when oxidized by Ce(Ⅳ) in sulfuric acid, which is significantly enhanced when quinine is present as sensitizer.The possible mechanism is proposed based on CLspectrum, fluorescent spectrum and absorbent spectrum of Schiff base.The relationship between the CLintensity and the concentration of Schiff base is linear in the range of2.0×10-7-8.0×10-5mol/L, and the detection limit is8.0×10-8mol/L.The relative standard deviation(RSD) for7independent determinations of2.0×10-6mol/L Schiff base is 2.4%. Common excipient starch was used in pharmaceutical preparation and most of metal ions do not interfere with the determination of Schiff base, except Mn(Ⅱ), Fe(Ⅲ), Fe(Ⅱ), Bi(Ⅲ), Ti(Ⅰ).The method has been successfully used in analysis of synthesized samples
    Structure Determination of a Novel Ether-linkaged Bisalkaloid Acutiaporberine
    LIN Cui-Wu, SU Jing-Yu, ZENG Long-Mei, LI Hong-PENG, Wen-Lie, XU An-Long
    2000, 21(12):  1820-1823. 
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    Anovel ether linkaged bisalkaloid, acutiaporberine(Ⅰ) , was isolated from the root of Thalictrum acutifolium (Hand.Mazz.) Boivin.Its structure was determined by IR, MS, 1H NMR, 13C NMR, and2D NMR( 1H1HCOSY, 13C1H COSY, NOESY, and HMBC).Ether linkaged bisalkaloids, such as aporphine benzylisoguinoline type and bisbenzylisoquinoline type, have been found.Herein a novel type bisalkaloid composed of an aporphine and a protobebertine is reported for the first time.Compound Ⅰ can inhibit the growth of tumor cells and apoptosis can be seen.However, compound Ⅰ shows only slight toxic effects on normal soma cell lines
    Studies on Cation Recognition Properties of 7-Methoxy-4-methene-coumarin-monoaza-18-crown-6
    LI Long-Di, WU Ying-Guang, ZHANG Zhong-Xiao, TONG Ai-Jun
    2000, 21(12):  1824-1827. 
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    The cation recognition properties of the title luminescent ionophore MMC-MAC(O5) in acetonitrile and aqueous solution by the normal fluorescence or delayed fluorescence methods were studied and the corresponding association constants of complexes and the recognition sensitive factors were determined by the modified H Bequation.The recognition mechanism between MMC-MAC(O5) and metal ion was discussed based on the chemical structure of MMC-MAC(O5) and the fluorescence enhancement effect.Because the carbonyl group of the coumarin participates to the recognition process between the crown ether and the cation, the association constants of the complexes with alkali cations were increased obviously
    Directly Resolution of Enantiomeric 〆,β-Biphenyl Dialkyl Dicarboxylates by HPLC on a Cellulose-Based Chiral Stationary Phase --Mobile Phase Modifier Effects on Retention and Stereoselectivity
    LIU Yue-Qi, GE Yong-Hui, CAI Qing-Song, JIANG Sheng-Xiang, CHEN Li-Ren
    2000, 21(12):  1828-1831. 
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    Achiral stationary phase(CSP) was prepared by coating cellulose tris(3,5-dimethylphenylcarbamate) onto aminopropylated spherical silica gel.The enantioselective separation of a series of biphenyl dialkyl dicarboxylates(DDBs) with antihepatitis activity was chromatographed for the first time on the CSpOf the six DDBs investigated, five could be directly resolved via normal phase mode HPLC.The effect of alcohol modifiers in mobile phase was investigated.The mobile phases used in the study were composed of hexane modified with two homologous series of alcohols: methanol ethanol mixtures(1:1, molar ratio), ethanol, 1-propanol, 1-butanol, 1-pentanol and 2-propanol,2-butanol,2-pentanol, and tert butanol.It was found that the retention time and the separation factors of DDBs on the CSPwere dramatically influenced by the kinds of alcohols in mobile phase.The results of the study indicate that alcohol in the mobile phase not only competes for chiral bondings sites with chiral solutes but can also alter the steric environment of the chiral cavities on the CSPby binding to achiral sites at or near the chiral cavity.The purpose of this paper is to demonstrate that better chiral resolution can be obtained via a change of alcohol modifiers in mobile phase
    The Investigation of a New Recording Mode for Capillary Zone Electrophoresis
    ZHANG Hong-Yi, LI Qian-Feng, LIU Hui-Tao, CHEN Xing-Guo-HU Zhi-De, WANG Rui
    2000, 21(12):  1832-1836. 
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    Since capillary zone electrophoresis emerged as a powerful separation tool, it has been a common practice to record the electropherogram in terms of the time domain.In this recording mode, the migration time often has a considerable change as the potential gradient and temperature inside the capillary do not remain constant in different runs.In this paper, attempt is made to solve the problem in a new way.The electric flux, defined as the amount of electric charge following a cross section of the capillary in a time interval, takes the place of the time as the domain in an electropherogram.At first, it is theoretically demonstrated that as regards to the reproducibility of separation result the use of the electric flux domain is superior to that of the time domain.Then the performances of electric flux domain and time domain are compared in two typical background electrolyte systems, 20 mmol/L Na2B4O7(pH=9.18) and 10mmol/Lphosphate (pH=8.28).When 10mmol/Lphosphate is used as the background electrolyte and applied voltage varies from10to25 kV(the corresponding temperatures at different voltages are also calculated from our method.), the reproducibility in migration time for berberine hydrochloride, antipyrine, sulfadimidine and sulfadiazine is41.7%, 41.8%, 41.5% and42.2%, respectively.In contrast, the reproducibility in electric flux for the above analytes is1.05%, 0.89%, 0.55% and0.84%, respectively.The reproducibilities in peak areas obtained from the two recording modes under the same experimental conditions are also compared.The relative standard deviation in area obtained from time mode for berberine hydrochloride, antipyrine, sulfadimidine and sulfadiazine is 42.5%, 44.5%, 42.9%, 45.0%, respectively.In contrast, the reproducibility in electric flux for the above analytes is3.79%, 2.83%, 3.02% and5.19%, respectively.Besides, the relative standard deviations in migration time and electric flux are compared in 12runs made consecutively at a fixed voltage.The relative standard deviation in electric flux (<0.7%) is lower than that in migration time (>1.8%)
    Synthesis of Silver Nanoparticles by Electrochemical Method
    LIAO Xue-Hong, ZHU Jun-Jie, ZHAO Xiao-Ning, CHEN Hong-Yuan
    2000, 21(12):  1837-1839. 
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    Spherical or dendritic silver nanoparticles have been synthesized by an electrochemical technique in an aqueous solution containing L-cysteine or citric acid.The silver nanoparticles are characterized by powder X-ray diffraction(XRD), transmission electron microscope(TEM) and UV-Vis absorption spectrum.Atypical XRDpattern of the as prepared silver nanoparticles shows the presence of the diffraction peaks corresponding to the (111), (200), (220), (311) planes.All the peaks in the XRDpattern can be indexed as a fcc structure(JCPDS, No.4-0783).The TEMimage in the presence of Lcysteine shows spherical nanoparticles.But the TEMimage in the presence of citric acid shows dendritic nanoparticles
    Synthesis and QSAR of Herbicidal 3-Alkoxy-6-(substituted)phenoxypyridazines
    REN Kang-Tai, SONG Hong-Hai, YANG Xiu-Feng, YANG Hua-Zheng 
    2000, 21(12):  1840-1843. 
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    Aseries of3-alkoxyl-6-(substituted)phenoxypyridazines were synthesized in good yields by a novel synthetic approach, the nucleophilic reaction of3,6-bis (substituted)phenoxypyridazines with alkoxides.Their pI50value against barnyard grass and greenhouse activity against barnyard grass, common crabgrass, rape, amaranth were tested.The results showed that some of them exhibited a higher activity than MH.The primary quantitative sturcture activity relationship(QSAR) was discussed
    Studies on Semisynthesis and Antibacterial Activity of7β-Heterocyclocamido-3-heterothiomethyl Cephalosporins
    HUI Xin-Ping, HAO Lan, ZHANG Zi-Yi, WANG Qin, WANG Fang, GUAN Zuo-Wu
    2000, 21(12):  1844-1847. 
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    New cephalosporin derivatives5a_5b and6a_6h were prepared by condensation of2a_2f with aminothiazoleoxime active ester3 and1-ryl-5-methyl1-H-1,2,3 triazol3-formyl chloride4a_4e, respectively.The intermediate2a_2f were synthesized by reaction of2-substituted-1,3,4 oxadiazol-5-thiols1a-1f with 7-ACA.The structures of the compounds synthesized were confirmed by IR, 1H NMRand MSspectra.The preliminary results of antibacterial activities revealed that5a_5b showed significant antibacterial activities against both Gram-positive and Gram-negative bacteria, and6a_6h had moderate antibacterial activities against these bacteria
    Coupling of DNA to Bead Type Cellulose as Immunoadsorbent
    KONG De-Ling, DAI Jun, CHEN Chang-Zhi, YU Yao-Ting
    2000, 21(12):  1848-1851. 
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    In order to remove the anti DNAantibody from the blood of patients with systematic lupus erythematosus(SLE), DNAimmunoadsorbent was prepared by coupling calf thymus DNAto epichlorohydrin activated cellulose beads.The methods and conditions for activation of carrier beads, DNAcoupling and adsorption with patient's plasma were investigated.The activation level was found to be dependent on the NaOHconcentration, amount of offered epichlorohydrin and the molar ratio between NaOHand epichlorohydrin.One milliliter of cellulose beads was activated by incubation with0.5 mLof epichlorohydrin and2.0 mLof2.0-3.0 mol/L NaOHsolution at40 ℃ for2 h, and the activation level was60_100 μmol/mLbeads.DNAcoupling was found to be strongly dependent on temperature and pH.The optimal coupling conditions were0.1 mol/L Tris HCl buffer, pH7.9-8.0 and70-90 ℃. High activation level, high DNAconcentration and long reaction time were also required.Under the optimal condition, 2.0-3.0 mg of DNAcould be coupled to1.0 mLof cellulose beads.In vitro adsorption tests showed that incubation of1.0 mLof adsorbent with3.0 mLof plasma could remove40%-70% of anti DNAantibody from the plasma
    Preparation of Zirconia by PICA Method for HPLC
    YANG Jun-Jiao, ZUO Yu-Min 
    2000, 21(12):  1852-1854. 
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    The methods for producing inorganic particles with a narrow particle size distribution, which are useful as chromatographic packing materials for high performance liquid chromatography(HPLC), are provided.These methods are based on improvements in the polymerization induced colloid aggregation(PICA) process described.These improved methods involved both synthesis of zirconium oxide colloid and sintering method.Colloid is an important factor in the PICAprocess.The reaction factors of the aqueous sol colloid of zirconium oxide are studied.We use sintering procedure to sinter zirconium oxide colloid, the average particle size is 5μm.Owing to different sintering procdure, the average pore size is between7.0_32 nm and the average surface area is between44_87 m2/g
    Studies on Bio-rational Molecular Design of Photosystem II Inhibitors——(Ⅵ) Synthesis and Hill Inhibitory Activity of Ethyl2-Cyano-3-methylthio-alkyl(benzyl)acrylates
    LIU Hua-Yin, TAN Hui-Fen, YANG Hua-Zheng 
    2000, 21(12):  1855-1857. 
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    Based on targets structure and bio rational molecular design, the title compounds have been synthesized, all compounds have been confirmed by1H NMRand elemental analysis.The Hill reaction inhibitory activity of all the title compounds was tested and the bioassay results indicate that some of them show a good inhibitory activity, the relationship between the structure and inhibitory was analyzed
    Molecular Design of Crown Ethers(ⅩⅩ)-- Syntheses and Cation Selectivities of Benzo-15-crown-5 Derivatives Containing Thiocycle and Selenacycle
    ZHANG Heng-Yi, YANG Ying-Wei, LIU Yu 
    2000, 21(12):  1858-1860. 
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    Two novel benzo-15-crown-5 derivatives containing thiocycle(3) and selenacycle(4) have been synthesized in the presence of Na2S·9H2Oor Na2Se2and characterized by elemental analysis and mass, IR, UVand1H NMRspectroscopy.The cation binding abilities and selectivities of parent benzo-15-crown5(1) and its derivatives3 and4 with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates.The results obtained indicated that novel selera3cyclopentene[3,4 d]benzo-15-crown-5(4) showed moderate extractability and selectivity for Ag+over any other alkali and heavy metal ions
    Synthesis and Crystal Structure of (±)-1-[(2-Hydroxy-5-methylphenyl) (phenyl)methyl]-2-pyridylbenzimidazole
    WANG Jin-Yi, ZHOU Jing, CHENG Dong-Liang, JIAN Pan-Ming
    2000, 21(12):  1861-1863. 
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    (±)-1-[(2-Hydroxy-5-methylphenyl) (phenyl)methyl]-2-pyridylbenzimidazole was synthesized and its crystal structure was determined by Xray four cycle diffraction method.The crystal belongs to monoclinic, space group P21/c , with the crystal cell parameters: a =1.3514(5) nm, b =0.9659(6) nm, c =1.6740(3) nm, β =110.27(2)°, V =2.0497(14) nm3, Z=4, Dc=1.269 g/cm3, R1= 0.0575 . The analyses of crystal structure show that the chain structure is formed by intermolecular Hbond
    Seryl-histidine Dipeptide Side Chains Effects on Its DNA Cleavage Reaction
    WAN Rong, WANG Ning, ZHAO Gang, ZHAO Yu-Fen 
    2000, 21(12):  1864-1866. 
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    The effects of the amino, hydroxyl, imidazole and carboxyl groups of Ser-His on DNAcleavage reaction were studied.It was found that the amino and hydroxyl groups were essential for the DNAcleavage activity of Ser-His, and that anyone of them blocked would result into the loss of cleavage activity.The carboxyl group was not the necessary groupThe presence of the imidazole group would enhance the cleavage activity.However, the histidyl-serine dipeptide, as the formula isomer of Ser-His with the inverse peptide sequence, could not cleave DNAat all.Based on the above experimental results, a presumed cleavage mechanism of Ser-His on DNAwas proposed
    One Pot Synthesis of3-Substituted-(1H)-pyrimidin[1,2-a] quinoline-1-ones Under Microwave Irradiation
    WU Lu-Ling, XU Wei-Ming, HUANG Xian 
    2000, 21(12):  1867-1869. 
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    2-Aminoquinoline reacted with5-bismethylthiomethylene or5-methylthioalkylidene isopropylidene malonates under microwave irradiation as one pot reaction to afford a new convenient synthesis of3-substituted-1(1H)- pyrimidine [1,2-a] quinoline-1-ones
    Density Functional Study on the Structures of the SiOM (M=Li, Be, B, Na, Mg, Al) Complexes
    SUN Ren-An, LIU Yong-Dong, WANG Chang-Sheng
    2000, 21(12):  1870-1874. 
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    The geometrical structures of SiOM (M=Li, Be, B, Na, Mg, Al) complexes have been optimized by using Gaussian94program, B3LYPmethod and the6-311+G( 2d)6d basis set.The calculated results show that Matom can attach to both the silicon atom and oxygen atom in the silicon monooxide molecule.All SiOMcomplexes except SiOAl have more than one stable structures.Furthermore, the most stable geometries of SiOM (M=Li, Be, Na, Mg) complexes are the bent structures, while SiOBand SiOAl complexes have nearly linear or linear structures in their most stable geometries.By the analysis of the Si-Oseparation, force constants of Si-Oand the natural bond orbital analysis, it has been shown that there are highly ionic fractions between the alkali atom and SiOin the most stable structures of the SiOLi and SiONa complexes.These structures, therefore, can be seen as ionic bondings.On the other hand, there are lowly ionic fractions between Matom and SiOin the geometries whose centers are silicon atoms ( i.e., SiOLi configuration Ⅱ, SiOBe configuration Ⅱ, SiOBconfiguration Ⅲ, SiOMg configuration Ⅱ).Thus, these structures can be seen as a kind of weak bonding interactions, not as ionic bondings.
    Prediction of Vapor-liquid Equilibria for Multi-component Systems at High Pressure with Binary Interaction Function
    LIU Guang-Heng, DAI Shu-Shan
    2000, 21(12):  1875-1879. 
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    The mixing rule recently developed by using the binary interaction function Lij(T, x) depending on the thermodynamic state of a given system, coupled with FRKSequation of state, had been successfully used for calculating the excess properties of wide variety of complex systems.In this work, we further indicated that this mixing rule satisfies the invariance condition and tested the capability of this approach for correlating and predicting vapor-liquid equilibria of highly non-ideal systems at high pressure.Fifteen ternary mixtures and their constituent binaries were selected to do the test.The systems selected cover the range from almost ideal to highly non-ideal mixtures.The correlation results of the binary VLEshow that for highly non-ideal systems, instead of the single optimum Lijvalue, Lijfunction has to be used for correlating their VLEquantitatively.The ternary VLEwere predicted by using parameters of constituent binaries only.The results show that, in the case of simple systems, both single optimum Lijvalue and Lijfunction methods predict the VLEwith nearly the same accuracy; nevertheless, the Lijfunction method shows a slight edge over the single optimum Lijvalue method.For the complex systems containing hydrogen, polar and associated components, while the single Lijmethod fails to represent their VLE, the Lijfunction approach can predict the VLEfor all of these complex systems accurately.The predicted results are in good agreement with the experimental data。
    Physical Chemical Processes of Acetone Triplet with Aromatic Amino Acid-containing Peptides
    SONG Qin-Hua, CHU Gao-Sheng, LIN WeiZhen, YAO SiDe
    2000, 21(12):  1880-1883. 
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    The photochemical processes of triplet acetone with aromatic amino acid containing peptides were investigated in neutral aqueous solution using KrF(248 nm) laser flash photolysis.In the presence of acetone, the formation of excited triplet states of tryptophan residues and radicals(Trp/N·) via a-triplet-triplet( T-T ) energy transfer and an electron transfer respectively, was observed in case of Trp Phe, Trp Gly and n-formyl-Met-Trp, while only phenolic hydroxy radical(Tyr/O·), via an electron transfer, was observed in case of Phe Tyr.Furthermore, triplet acetone induced radical transformation: Trp/N· Tyr→-Trp Tyr/O· was observed directly, and the transformation resulting from intramolecular electron transfer was suggested
    Theoretical Studies on the Potential Energy Surface and Rovibrational States for the Electronic Ground State of SO2
    XU Ding-Guo, LU Yu-Hui, XIE Dai-Qian, YAN Guo-Sen
    2000, 21(12):  1884-1887. 
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    Apotential energy surface for the electronic ground state of sulfur dioxide was optimized by using a variational procedure with the exact vibrational Hamiltonian in the bond length-bond angle coordinates.In the optimization, the ab initio force field of Martin is taken as the starting point, and the observed vibrational band origins up to6 500 cm-1are involved.The root mean square error of this fit for the38observed vibrational energy levels is0.93 cm-1. In order to test the refined potential, the vibrational energy levels for the isotopomer34 SO2were calculated and compared with the observed values and other theoretical results.The rovibrational energy levels up to J =6 were also calculated and compared with the observed values
    Quantum Chemical Study on the Structure-odor Relationships of Nitro-containing Musk Ordorant Compounds
    FANG Ya-Yin, CHEN Yong, CAO Yu-Rong, HU Zhong, WANG Yan-Zhong, LIU Jing-Jiang
    2000, 21(12):  1888-1891. 
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    Based on the energy minimization by AM1 method the stable structures of the four nitro containing musk compounds(1-4) are obtained and compared with their crystal structures.It is confirmed that the stable structures are accordant with their crystal structures.According to the study on the stable structures the typical characteristics in the four musk-compounds were proposed.The musk odor activity of the four compounds and a compound(5) with similar structure but odorless are explained reasonably by using the co-
    Theoretical Study on Design Molecules with First Hyperpolarizabilities on a Serials of Babituric Acid and Its Derivatives
    FU Wei, FENG Ji-Kang, REN Ai-Min, SUN Chia-Cung
    2000, 21(12):  1892-1895. 
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    On the basis of ZINDO, according to the sum over state expression, we designed the program for calculating the first hyperpolarizability β . The structures, electron spectra and β (-2ω,ω,ω), β (0,0,0) of a series of babituric acid derivative molecules have been studied.The influence of donor, π-conjugated bridge, acceptor, D-π-A, D-A, D-A-Dstructures on the β was examined.At last, we designed some molecules with excellent NLOproperties and good thermal stability, which have a prospect of practical applications
    Microcalorimetric Studies of Adsorption on the Surface of Pd-Cu/SiO2
    LI MingShi, GE Xin, ZOU Hu, SHEN JianYi
    2000, 21(12):  1896-1899. 
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    Adsorption of H-2, CO, O-2and C-2H-4on m(Pd)/m(SiO-2)=2%, m(Pd,Cu)/m(SiO-2)[n(Pd)/n(Cu)}=1/1]=2%, m(Pd,Cu)/m(SiO-2)[n(Pd)/n(Cu)=1/4]=2% and m(Cu)/m(SiO-2)=8%, catalysts was investigated by using the techniques of microcalorimetric adsorption at room temperature.The effect of O-2on adsorption of C-2H-4on the surface of the catalysts was also studied.It is found that the number of sites for H-2adsorption on PdCu/SiO-2is close to that on Pd/SiO-2. Addition of Cu decreases the sites of stronger adsorption and increases the sites of weaker adsorption of H-2and COon Pd.On the other hand, Pd can promote the dispersion of Cu on SiO-2and accelerate the rate of O-2adsorption on Cu/SiO-2. These results suggest that Pd and Cu atoms are well mixed and Pd atoms are well dispersed in the PdCu/SiO-2catalysts.Ethylene adsorbed on Pd/SiO-2produces ethylidyne and σ and di-π species.The addition of Cu inhibits the formation of the dissociatively adsorbed species--ethylidyne but promotes the formation of undissociatively adsorbed species--π and di-σ species for ethylene adsorption on Pd-Cu/SiO-2catalysts.Ethylene may react with O-2adsorbed on Pd/SiO-2at room temperature.Cu decreases the activity of adsorbed O-2on Pd-Cu/SiO-2. Hence, ethylene may be activated effectively on PdCu catalysts.
    Heterogeneous Asymmetric Hydrogenation of Ethyl Pyruvate on Chirally Modified Pt/Al2O3Catalyst with Fixed-bed Reactor
    LI Xiao-Hong, YOU Xin, LIANG Chang-Hai, ZHANG Sui-Zhi, WEI Zhao-Bin, LI Xu-Yuan, LI Can
    2000, 21(12):  1900-1903. 
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    The enantioselective hydrogenation of ethyl pyruvate on the cinchonidine modified Pt/Al2O3catalyst was investigated using a high pressure reaction system with a fixed bed reactor for the purpose to produce the chiral product without separating the catalyst from the reaction system.The reaction was also investigated in a batch reactor for comparison.About 60% e.e. and90% e.e. were obtained with the fixed bed reactor and the batch reactor respectively, demonstrating the possibility for the heterogeneous asymmetric hydrogenation in the fixed bed reactor.Some adsorbed chiral modifier, cinchonidine, can be slowly removed from the surface of Pt/Al2O3under the continuous flow reaction, as a result, the e.e. values drops with the reaction time in the fixed bed reactor.The enantio selectivity is higher in the fixed bed reactor, but lower in the batch reactor when ethanol was used as solvent than that when acetic acid as solvent.COwas used as molecular probe to characterize the adsorption of cinchonidine on the catalyst surface by IRspectroscopy.Ared shift observed in IRspectra of coadsorbed COwith cinchonidine suggests that the cinchonidine adsorption is mainly through the π interaction with platinum surface and donating electron to the platinum surface.
    Adsorption of Tyrosine on Active Carbon/Water Interface
    ZHAO Zhen-Guo, JIN Ming-Zhong, LIU Ying-Qing
    2000, 21(12):  1904-1907. 
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    The adsorption of tyrosine from aqueous solution on the active carbon at varying pHvalues has been studied.The results indicate that: (1) the adsorption found to be pHdependent,within pH2-4 it increases with pH, within pH6-12 it decreases with pH, at pH4.2-6.1 the adsorption reaches its maximum; (2) the tyrosine is adsorbed mainly in the form of zwitterion; (3) a certain amount of ions of tyrosine is also adsorbed with van der Waals interaction.These probably suggest that the solubility of tyrosine at IEPhas minimum,and the ions and undissociated groups of tyrosine can be adsorbed on the surface of active carbon through van der Waals interaction.
    An ab initio Study of the Luminescence and the Pt(Ⅱ)…Pt(Ⅱ) Interaction in the Compound Pt2(CN)4(CNC4H9)4
    YANG Guang-Hui, ZHANG Hong-Xing, WANG Yue, TANG Au-Qing
    2000, 21(12):  1908-1912. 
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    The Optimizations on the ground state structures were performed under the MP2calculations for Pt(CN)2(CNCH3)2, Pt(CN)2(CNCH3)2-(NCCH3)2and [Pt(CN)2(CNCH3)2]2. Based on these calculations, single excitation configuration interaction (CIS) calculations were carried out to optimize the molecular structures of the excited states and to reveal the excited state electronic structures.The MP2calculations showed that the Pt(Ⅱ)…NCCH3distance are0.405 2 nm in ground state 1Agof Pt(CN)2(CNCH3)2-(NCCH3)2, indicating that CH3CNmolecule is weakly interactive with Pt in the ground state.However, the distance became0.028 10 nm in the excited state, suggestion of a rather strong interaction between Pt(CN)2(CNCH3)2and the solvent molecule in the NCCH3solution.The complex is a linear chain structure at solid state with the Pt(Ⅱ)…Pt(Ⅱ) distance of0.033 25 nm, which illustrated a typical d8-d8attraction in Pt(Ⅱ) complexes.Therefore, the solvation and the metal-metal interaction significantly affect the luminescence of the Pt(CN)2(CNC4H9)2complex in the NCCH3solution and in solid state respectively
    Application of Resonance Raman Spectroscopy to Study the Effect of Rare-earth Ion Er3+on Myoglobin
    ZHAO Yu, XU Jin-Ze, ZHAO Da-Qing, XI Shi-Quan, ZHAO Bing, XU Wei-Qing
    2000, 21(12):  1913-1915. 
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    The effect of rare earth ion Er3+on myoglobin(Mb) was studied by using Resonance Raman spectroscopy.The results show that with the variation of Er3+concentrations, both the oxidation state and spin state of Mb are sensitive to the perturbation of Er3+. Er3+added to Mb affects the oxidation and spin state synchronously.The structure sensitive groups of Mb are more accessible to the Er3+than other groups.According to the fluorometry and CDspectra studied and our results as mentioned above, we considered that Er3+does not interact with heme directly, and Er3+probably leads to the conformational changes of Mb due to the change of oxidation and spin state of Heme
    Synthesis of Phenyl and Phenylsulphonic Acid Functionalized-MSU and Their Catalytic Performance
    GONG Yan-Jun, LI Ying, WANG Shu-Guo, WU Dong, SUN Yu-Han, DENG Feng, YUE Yong
    2000, 21(12):  1916-1918. 
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    Aseries of phenyl-functionalized-MSUmesoporous molecular sieves were synthesized under neutral condition in the presence of biodegradable non-ionic polyethylene oxide(AEO9).By subsequent sulphonation of the phenyl rings attached to the silica framework, the phenylsulphonic acid functionalized MSUderivatives could be obtained.Their structure and property of the organo-modified mesoporous molecular sieves were studied by means of XRD, FT IR, TEM, HRTEM, 13C MAS NMR, 29Si MAS NMR, N2adsorption/desorption and probe reaction techniques.The results showed that the so-produced organo modified mesoporous molecular sieves featured bimodal pore size distribution and the pore channel was similar to those in the MSU(worm-like). The organo modified mesoporous molecular sieves containing phenylsulphonic acid active sites, used as solid acid catalyst, showed a much higher catalytic activity for the formation of2,2-pentamethylene1,3-dioxolane(cyclic ketal) from ethylene glycol and cyclohexanone
    Studies on Structure of TC16PyP(4)/AnQ LB Films
    HE Xue-Zhong, ZHOU Ya-Lin, WANG Ling-Xuang, LI Tian-Kai, ZHANG Man-Hua, SHEN Tao
    2000, 21(12):  1919-1921. 
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    Using n [TC16PyP(4)]/ n (anthraquinone)(1:1) mixture as film-forming material, the film-forming property of TC16PyP(4)/AnQmixture on the air/water interface was studied.The structure of mixed TC16PyP(4)/AnQ LBfilms was characterized by π-Aisotherms, UV-Vis absorption spectra and low-angle X-ray diffraction(LAXD).The experimental results indicate that the TC16PyP(4)/AnQmixture can form a stable monolayer on the air/water interface.Most AnQmolecules are incorporated into the cavities between the long alkyl chains of TC16PyP(4) molecules in the mixed monolayer and LBfilms.Mixed TC16PyP(4)/AnQmonolayer can be transferred to the substrates.TC16PyP(4)/AnQ LBfilms have a good stability and periodicity
    Theoretical Studies on the C——H Bond Insertion Reaction of Carbenes with Ethers(Ⅳ) ——Insertion Reaction of CX2(X=H, F, Cl) with Benzyl Methyl Ether
    LIN Qi-Jun, FENG Da-Cheng, QI Chuan-Song
    2000, 21(12):  1922-1924. 
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    The C——Hbond insertion reactions between benzyl methyl ether and CX2(X=H, F, Cl) have been studied by using density functional theory at B3LYP/631G*level.The potential barriers for the C——Hbond insertions in methyl group of benzyl methyl ether are123.3 kJ/mol(X=Cl) and240.4 kJ/mol(X=F), and those in benzyl group are37.5 kJ/mol(X=Cl) and112.2 kJ/mol(X=F) respectively.No potential barriers are present in both the insertion reactions with methylene groupThe C——Hbond insertion reactions between benzyl methyl ether and CX2(X=H,F,Cl) take place primarily at α carbon of the benzyl group and the phenyl group promotes the C-Hbond insertion by carbene at its neighboring α-carbon more easily
    Rigid Polymer Particle Toughened Polystyrene with no Effect on Its Transparency
    TANG Jun, LIU Feng-Qi, JIN Mei-Hua, YANG Bai 
    2000, 21(12):  1925-1927. 
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    Akind of rigid polymer microsphere with core shell structure was synthesized by multi step composite emulsion polymerization technique.The polystyrene(PS) composite with different particle sizes, concentration and core layer crosslinking agent of core shell particles were prepared.The impact strength and the transparency were studied which indicated that the best condition for toughening PSwas that the particle size was above 100nm, the particle content in PScomposite was in the range of2%-5% and the appropriate crosslinking density in core layer.The material toughness was improved two times higher than that of pure PSwhile the PStransparency was not affected
    Kinetic Model of Vinyl Chloride Suspension Polymerization with Peroxide Mixture as Initiator and Its Application
    SHAN Guo-Rong, WENG Zhi-Xue, HUANG Zhi-Ming, PAN Zu-Ren
    2000, 21(12):  1928-1931. 
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    On the basis of the decomposition kinetic model of peroxide mixture, a kinetic model of vinyl chloride suspension polymerization with peroxide mixture as initiator was derived and can be used to predict the kinetics of vinyl chloride polymerization in good agreement with the experimental data.The initiator efficiency of TxEHP, Tx99, Tx23 and Tx36 at51 or57 ℃ was obtained from the kinetic data of VCpolymerization initiated by single initiator
    Living Cationic Polymerization of β-Pinene with1-Phenylethyl Chloride/TiCl4/Ti(OiPr)4
    LU Jiang, LIANG Hui, ZHANG Rong-Fu
    2000, 21(12):  1932-1935. 
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    The cationic polymerization of β-pinene was carried out with1phenylethyl chloride as an initiator and the mixture of TiCl4and tetraisopropoxytitanium[Ti(OiPr)4] as a Lewis acid activator in CH2Cl2at -40 ℃. The polymerization with strong Lewis acid TiCl4alone completed instantaneously and gave the polymers with broad molecular weight distributions.The addition of weak Lewis acid Ti(OiPr)4, which alone had no catalytic activity for β pinene, retarded the polymerization by TiCl4and led to polymers with narrower molecular weight distributions.When [Ti(OiPr)4]0/[TiCl4]0=1/3, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, and the molecular weight distribution of the polymers was narrow.The living nature of the polymerization was further demonstrated by monomer-addition experiments.1H NMRanalysis of the polymers obtained at [Ti(OiPr)4]0/[TiCl4]0=1/3 showed that1-phenylethyl chloride served as an initiator and generated poly( β-pinene) chains with the CH3CH(C6H5) head group and a tert-Cl tail group
    Polymerization of1,3-Butadiene with Novel Calixarene Rare Earth Complex Based Homogeneous Catalysts
    NI Xu-Feng, LI Wei-Shi, ZHANG Yi-Feng, SHEN Zhi-Quan, ZHANG Tian-Xu
    2000, 21(12):  1936-1938. 
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    Neodymium based homogeneous catalysts for the polymerization of1,3-butadiene, calixarene neodymium(C[n]NdxCly)/Al(i-Bu)3and C[n]Nd/Al(i-Bu)3/Al(i-Bu)2Cl were examined.The binary systems based on C[n]NdxClywere found to be active even in the absence of halogen source, while adding Al(i-Bu)2Cl as the third component, the catalytic activity was improved.Polymer obtained has Mvabout1×105~2×105and cis-1,4 content90%. The ternary systems based on C[n]Nd also had an activity of butadiene polymerization, the effect of different calixarenes on the catalytic activity of ternary system is in the order of C6>C4>C8
    Synthesis of Aromatic Diaminospirodilactone
    QU Jian-Qiang, WANG De-Qiu, HAN Fu-She, DING Meng-Xian, GAO Lian-Xun 
    2000, 21(12):  1939-1943. 
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    Anew kind of aromatic diaminospirodilactone, i.e. 6,6′-diamino-3,3′-spirobiphthalide, was synthesized through multistep reactions from p nitrotoulene and paraformaldehyde.It was found that dinitrospirolactone could be synthesized directly in the acid system through oxidation reaction with a high yield.The increase of solvent polarity leads to an increase of reduction yield of dinitrolactone.The resulting intermediates6,6′- dihydroxylamino-3,3′ spirobiphthalide and6-amino-6′-hydroxylanimo-3,3′ spirobiphthalide were steady aromatic hydroxylamine.The structures of6,6′-diamino-3,3′-spirobiphthalide and its intermediates were confirmed by1H NMR, 13C NMR, MS, IRand elemental analyses
    Synthesis and Characterization of High TgOrgano-Soluble Side-Chain Copolyimides Containing a Triazine-Azo Chromophore
    SUI Yu, GUO Xiao-Xia, YIN Jie, LIU Yan-Gang, GAO Jian-ZHU, Zi-Kang, HUANG De-Yin, WANG Zong-Guang
    2000, 21(12):  1944-1947. 
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    Two series of copolyimides, OPI( x ) and PPI( x ), containing a triazine azo chromophore were prepared by a two step process, which includes a solution polycondensation followed by a chemical imidization.The copolyimides obtained were characterized by FTIRspectroscopy, UV-Vis spectroscopy, DSCand TGA.The obtained copolyimides are soluble in aprotic organic solvents such as N-methyl-2-pyrrolidone(NMP), N,N-dimethyl acetamide(DMAc), N,N-dimethyl formamide(DMF), dimethylsulfone (DMSO) and1,4-butyrolactone.They are almost completely transparent at wavelengths greater than500 nm.The intrinsic viscosities of OPI( x ) and PPI( x ) are in the range0.25-0.50 dL/g.All copolyimides possess high Tg and thermal stability.Tgs are about573 Kfor copolyimides based on pyromellitic dianhydride(PMDA) and533-543 Kfor those based on 3,3′,4,4′ diphenylethertetracarboxylic dianhydride(OPDA) and are almost independent of the chromophore loading level.The5% weight loss temperatures of the copolyimides are more than100 Khigher than the corresponding Tgs and this high thermal stability would ensure high temperature poling of the copolyimides
    Crystal Structure of a Noval Poly(aryl ether ketone) Containing Meta-phenyl Linkage
    QIU Zhao-Bin, WANG Ji-Ku, SHENG Shou-Ri, SONG Cai-Sheng, ZHOU En-Le, MO Zhi-Shen
    2000, 21(12):  1948-1949. 
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    Crystal structure of a novel aryl ether ketone polymer poly(aryl ether ketone ether ketone ketone containing meta-phenyl linkage)(PEKEKm K)} was determined by means of WAXDand ED.An orthorhombic unit cell is proposed containing two chains with a= 0.772 nm, b =0.604 nm and c =2.572 nm.According to the orthorhombic system, the10 reflections of this polymer were indexed
    Studies on Modification of End Groups of Aliphatic Hyperbranched Polyester
    TANG Li-Ming, ZHANG Xiao-Long, LI Wei, LIU De-Shan
    2000, 21(12):  1950-1952. 
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    Anew process was designed to modify the hydroxy capped aliphatic hyperbranched polyester, derived from2,2 bis(methylol) propionic acid and trimethylopropane in which the crude polyester reacted directly with maleic anhydride in bulk to transfer the hydroxy end groups to4-carboxy-2- butante end groups.The modified polyester was characterized by IR, 1H NMR, DSCand viscosity measurement.The results indicated that no side reaction took place during the modifying step and the conversion for the reaction was calculated to be88.9% based on the 1H NMRspectra.The Tgvalue shifted from320.3 Kfor the crude polymer to288.4 Kfor the modified polymer.Moreover, the UVcuring coating of the midified polyester showed high performances in hardness, adhensive and water resistance
    Two-photon Absorption Photoinitiated Polymerization
    YU Xiao-Qiang, WANG Chun, ZHAO Xian, WANG Xiao-Mei, YAN Yun-Xing-FANG Qi, SHAO Zong-Shu, JIANG Min-Hua, SUN Yu
    2000, 21(12):  1953-1955. 
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    Anovel two-photon photoninitiated polymerization is reported.The results of the study show that the two photon polymerization of TMPTMAcan be initiated by means of4,4-bis(di-n-butylamino)-E-stiebene(BDBAS) under600 nm strong laser.The light source that we used for the two photon polymerization is a YAGpumped dye laser whose oscillating wavelength repetition rate and single pulse energy are600nm, 10 ns and15 mJ, respectively.The peak power density of radiation light tight-focused by means of bojective lens is3.8 GW/cm2. The relative mechanism of the polymerization is discussed