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Table of Content

    10 July 2007, Volume 28 Issue 7
    目次
    高等学校化学学报2007年第28卷第7期目次
    2007, 28(7):  0.  doi:
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    下期目次预览
    2007, 28(7):  0.  doi:
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    研究论文
    Synthesis, Crystal Structure and Photoluminescence Property of a Novel Coordination Polymer [Zn6(bta)4(2,2'-bipy)3]
    LIU Guang-Xiang1, CHU Qian1, KAWAGUCHI Hiroyuki2, SUN Wei-Yin1*, LIANG Hong3*
    2007, 28(7):  1203-1207.  doi:
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    A novel coordination polymer [Zn6(bta)4(2,2'-bipy)3], with three-dimensional structure, was obtained via assembly of flexible tripodal ligand 1,3,5-benzenetriacetic acid(H3bta) with 2,2'-bipy, Zn(NO3)3·6H2O under the hydrothermal condition. The X-ray single crystal diffraction analysis reveals that the complex is monoclinic with space group Cc, a=1.7714(4) nm, b=2.4391(5) nm, c=1.7120(3) nm, β=104.39(3)°, Z=4, V=7.165(2) nm3, Dc=1.722 g/cm3, μ=2.065 mm-1, F(000)=3768, R1=0.0645, wR2=0.1424 for 8019 observed reflections with goodness-of-fit 1.050. The photoluminescence property of the complex in the solid state was studied at room temperature and strong blue emission was observed.
    Preparation and Properties of 5,10,15,20-Tetra(4-myristylimidophenyl) Porphyrin and Its Zn and Mn Complexes
    SUN Er-Jun, WANG Dong, CHENG Xiu-Li, SHI Yu-Hua*, SHI Tong-Shun*
    2007, 28(7):  1208-1213.  doi:
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    A new porphyrin 5,10,15,20-tetra(4-myristylimidophenyl)porphyrin(TMPPH2) and its complexes TMPPMnCl and TMPPZn were synthesized and their structures were confirmed by means of elemental analyses, UV-Vis spectra, infrared spectra and 1H NMR spectra. Raman spectra, fluorescence spectra and X-ray photoelectron spectroscopy spectra of the porphyrin and its complexes were investigated. The electrochemistry of the ligand and the complexes was also studied. The results show that there are much difference between the ligand and the complexes in the UV-Vis spectra, infrared spectra, Raman spectra, fluorescence spectra and XPS spectra. The cyclic voltammetry of TMPPMnCl is different from those of the ligand and TMPPZn, which showed not only the redox of the porphyrin ring, but also the redox of the metal ion Mn3+.
    Supramolecular Structure, Thermal Stability and Release Property of New Drug-inorganic Composites Norfloxacin-intercalated Mg-Al-layered Double Hydroxides
    NI Zhe-Ming*, XIA Sheng-Jie, WANG Li-Geng, XING Fang-Fang, PAN Guo-Xiang, HU Jun
    2007, 28(7):  1214-1219.  doi:
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    A new drug-inorganic composite involving an antibiotic compound norfloxacin(Nor) intercalated Mg-Al layered double hydroxides(Nor-LDHs) was assembled with coprecipitation and ion-exchange methods. The samples thereby obtained were characterized via XRD, FTIR, UV-Vis, TG-DTA and ICP measurements. The results show that the original interlayer nitrate anions of the hydrotalcite can be replaced by norfloxacin anions, and norfloxacin intercalated Mg-Al layered double hydroxides were obtained with a good crystallinity. XRD analyses indicates that the interlayer spaces of as-synthesized Nor-LDHs were 1.29 nm to 1.33 nm, and compared with three-dimensional molecular size of Nor ion calculated from the PM3 semi-empirical molecular orbital method. The norfloxacin guests were arranged alternately with monolayer vertical(along the short axis orientation) between layers. It is found that the interaction of the host layers and the guests is through hydrogen bonding and electrostatic attraction, confirming that the intercalated hydrotalcite has a supramolecular structure. The thermal stability, acid resistance and sustained-release of norfloxacin anion-pillared hydrotalcite were enhanced to a considerable extent, comparing with that of norfloxacin. The release profiles were fitted by Bhaskar equation and the first-order equation, the fitting data primarily follow the experimental results.
    Preparation of Polycrystalline SrTiO3 Ultrafine Fibers via Electrospinning
    ZHOU Xian-Feng1,2, ZHAO Yong2, CAO Xin-Yu2, XUE Yan-Feng1, XU Da-Peng1*, JIANG Lei2, SU Wen-Hui1
    2007, 28(7):  1220-1222.  doi:
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    Perorskite strueture SrTiO3 ultrafine fibers were successfully fabricated via electrospinning combined with Sol-gel technology. Polycrystalline SrTiO3 fibers with a diameter range of 50—400 nm were obtained with calcination of the inorganic/organic hybrid fibers at 900 ℃ for 1 h. The morphology, microstructure, crystal structure and thermal analysis were investigated via SEM, TEM, XRD and TG-DSC, respectively. The results show that the crystalline phase and morphology of SrTiO3 fibers were greatly influenced by the calcination temperature.

    Hydrothermal Preparation of Nanostructured MnO2 and Morphological and Crystalline Evolution
    LI Ying-Pin, ZHOU Xiao-Quan, ZHOU Hui-Jing, SHEN Zhu-Rui, CHEN Tie-Hong*
    2007, 28(7):  1223-1226.  doi:
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    Manganese dioxides with various morphologies were prepared with a common hydrothermal method without any templates or additives. The morphological evolution was accompanied with the conversion of the polymorphic forms, gradually from γ-type to β-type. Meanwhile, MnO2 microspheres, urchinlike nanostructures and nanowires were successfully synthesized. The products were characterized via X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscope. The process can be explained with Ostwald-Ripening mechanism.

    Hydrothermal Synthesis and Structure Characterization of a Piperazine-templated Two-dimenisional Cerium Sulfate, [C4N2H12]3[Ce2(SO4)6(H2O)2
    XIN Ming-Hong, WANG Ying, ZHU Guang-Shan, SUN Jin-Yu, FANG Qian-Rong, XUE Ming, TIAN Ge, QIU Shi-Lun*
    2007, 28(7):  1227-1231.  doi:
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    A cerium sulfate hydrate, [C4N2H12]3[Ce2(SO4)6(H2O)2]·H2O, was synthesized via the hydrothermal method with piperazine as a template and characterized by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with cell parameters a=0.66335(10) nm, b=2.8088(4) nm, c=1.02212(15) nm, β=96.160(2)°, final R indices [I>2σ(I)], R1=0.0466 and wR2=0.1226. The compound exhibits a corrugated layer structure, which is constructed from inorganic anionic sheets of cerium sulfates with diprotonated piperazine cations and water molecules locating between the layers. An eight-membered ring is created in the layer with a diprotonated piperazine molecule locating in it. The thermal behavior of the compound was also examined.

    Preparation and Characterization of Hexagonal Close Packed Ni Nanoparticles
    GONG Jie1,2*, LIU Yang2, WANG Li-Li1, YANG Jing-Hai2, ZONG Zhan-Guo1
    2007, 28(7):  1232-1234.  doi:
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    The hexagonal close packed Ni nanoparticles were prepared by using heat-treating technique with the precursors prepared by sol-gel method. The synthesis condition, structural and morphology of the samples were analysed by using thermogravimetric analysis(TG), differential thermal analysis(DTA), X-ray diffraction(XRD) and transmission electron microscopy(TEM). The results indicate that hexagonal close packed Ni nanoparticles were synthesized at heat-treating temperature of 300 ℃. The cell constants is calculated of a= 0.2652 nm, c= 0.4334 nm. The average grain size of the hexagonal close packed Ni particles is evaluated by Scherrer equation is about 12 nm. The phase transformation from hexagonal close packed Ni to face center cubic Ni structural occured with increasing the heat treating temperature.

    Synthesis, Structure and Electrochemical Property of Calixarene Potassium Polyoxometalates
    LIU Ju-Tao1,2*, LIU Xiao-Wei1, FAN Sheng-Di1, LI De-Qian2
    2007, 28(7):  1235-1239.  doi:
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    One inorganic-organic hybrid and two host-guest complexes were synthesized from calix arene tetra acetic ether derivative(C60H80O12, L) and potassium polyoxometalates. The structures of the complexes were characterized with the elemental analysis, IR, TG-DTA and X-crystallographic. X-ray crystallographic studies reveal the formation of an ionic crystal, which contains a calix-cluster and calix-cluster-calix line array, and belongs to a typical inorganic-organic hybrid(complex 1) or has a host-guest structure(complex 2 and 3) . The results of cyclic voltammograms at different scanning rates showed that the anode peak current of complex 1 was proportional to the square root of the scanning rate and the charge transfer process was controlled by pervasion. The anode peak current of complexes 2 and 3 was proportional to the scanning rate and the charge transfer process was controlled by the surface. The results suggest that there are consanguineous relationship between the anode reaction and the structure.

    Design and Application of Membrane Inlet-Time-of-Flight Mass Spectrometer for Rapid Analysis of Volatile Organic Compounds
    HOU Ke-Yong1,3, CHEN Xin-Hua1,3, DONG Can1,3, LI Jing-Hua1, YAO Lian2, WANG Hai-Long1, WANG Jun-De1, LI Hai-Yang1*
    2007, 28(7):  1240-1245.  doi:
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    This article describes a membrane inlet-miniature time-of-flight mass spectrometer. Double silicone sheet membranes with a thickness of 50 μm was used as interface for the atmospheric pressure direct sample inlet. The experimental result indicates that the enrichment factor of membrane is increased with the increase of the flow speed of the sample, and the signal intensity is almost linear with the gas flow. There is a vacuum differential system between the double membranes and the enriched sample is pulled out quickly, there is almost no memory effect in the membrane inlet system. The response time for benzene, toluene and o-xylene is about 100 s, but it only takes 10 s to get the steady condition after opening the vacuum valve. Comparing with the capillary sample inlet, the enrichment of double membrane is quite effective, the signal intensity for 10×10-6(volume fraction) benzene, toluene and o-xylene is enhanced 280, 370 and 600 times, when the membrane inlet was used under the same experimental conditions. Combining with vacuum ultraviolet soft ionization, the detection limit of the membrane inlet mass spectrometer is 25×10-9 (volume fraction) for benzene, and the linear dynamic range is about three orders of magnitude. The soft ionization is fragment free and qualitative analysis quickly according to the molecular weight of compounds. The instrument was used to on-line analyze volatile organic compounds (VOCs) in mainstream cigarette smoke, more than fifty compounds of VOCs on a mass spectrum were observed. The results indicate that the membrane inlet-time-of-flight mass spectrometer will be useful for a wide range of field application, particularly for environmental monitoring.

    An Improved Ion Chromatography Method for Determination of Trace Level Perchlorate in Environmental Water
    ZHANG Ping, SHI Ya-Li, CAI Ya-Qi*, MOU Shi-Fen
    2007, 28(7):  1246-1250.  doi:
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    An improved ion chromatography(IC) method was developed to determine trace level perchlorate in environmental water samples by using hydroxide selective column IonPac AS16. Perchorate was separated with NaOH eluent added organic modifier. To eliminate the coelution of perchlorate and 4-chlorobenzene sulfonate(4-CBS), organic solvents as the modifier was added into the eluent. The effects of four kinds of organic solvents on the retention time of perchlorate and 4-CBS were studied, and acetonitrile was selected. To improve the method sensitivity, the concentrator column(AG19) was used to concentrate perchlorate online in this work. With the adoption of preconcentration technique, the sensitivity of this method was improved obviously and the method detection limit(MDL) is 0.1 μg/L. The linear range is 0.2—200 μg/L with a linear correlation coefficient of 0.9989, and the relative standard deviation(RSD) of peak area for the eleven successive injections of 0.5 μg/L perchlorate is 4.2%. The method was applied to the determination of perchlorate in some real environmental water samples and the spiked recoveries were in the range of 93%—113%.

    Glucose Biosensor Based on Pt Nanoparticles Modified Aligned Carbon Nanotubes Electrode
    ZHAO Kun, SONG Hai-Yan, CHANG Zhu, ZHUANG Shu-Qi, HE Pin-Gang, FANG Yu-Zhi
    2007, 28(7):  1251-1254. 
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    A sensitive amperometric glucose biosensor based on Platinum(Pt) nanoparticles modified aligned carbon nanotubes(ACNTs)electrode was investigated.Pt nanoparticles which could enhance the electrocataly-tic activity of the electrode for electrooxidating hydrogen peroxide produced with enzymatic reactions were electrocrystallized on 4-aminobenzene monolayer-grafted aligned carbon nanotubes electrode with a potential-step method.These Pt nanoparticles modified ACNTs surfaces were characterized with scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The nano-scale Pt particles dispersed highly on ACNTs can be obtained.The enzyme electrode exhibitsan excellent response performance to glucose with a linear range from 1×10-5 to 7×10-3 mol/L and fast response time within 5 s.Furthermore,this glucose biosensor also has a good reproducibility.

    Flow Injection On-line Oxidizing Fluorometry Coupled to Dialysis Sampling for Studying Thioridazine Hydrochloride-Bovine Serum Albumin Binding
    MA Jian, ZHANG Zhi-Qi*
    2007, 28(7):  1255-1259.  doi:
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    A new flow injection on-line oxidization fluorometry coupled to the technique of dialysis sampling was established for the determination of free thioridazine hydrochloride in serum, and applied to the investigation of binding action of thioridazine hydrochloride with bovine serum albumin(BSA). The thioridazine hydrochloride and BSA were mixed in different molar ratios in 0.050 mol/L phosphate buffer(containing 0.9% NaCl, pH=7.4), and incubated at (37±0.5) ℃ in a water bath. The dialysis sampler was utilized to sample free thioridazine hydrochloride from mixed solution with a relative dialytic efficiency of 8.3%. Then the thioridazine hydrochloride in dialysis solution was injected into carrier and on-line oxidized by lead dioxide solid-phase reactor into fluorescent product with a maximum excitation wavelength of 349 nm and a maximum emission wavelength of 429 nm. The fluorescence intensity measured was linear proportional with the concentration of free thioridazine hydrochloride in mixed solution over the range from 1×10-5 to 2×10-4 mol/L with the detection limit of 6×10-6 mol/L. According to the fluorescence measurement results from mixed solution, the association constant(K) estimated for thioridazine hydrochloride-BSA binding and the number of the binding site(n) with Scatchard analysis were 1.2×104 L/mol and 0.98, respectively. The acting force was suggested to be mainly hydrophobic and the distance between the acceptor and donor was 3.27 nm.

    Stationary Phase Containing Ionic Liquid in Gas Chromatography
    ZOU Qiao-Li1, CHEN Zhi-Yao1, ZHENG Jing-Jing2, XING Jun1*, WU Cai-Ying1
    2007, 28(7):  1260-1262.  doi:
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    Room-temperature ionic liquids were used as the stationary phases in gas chromatography, but many of them suffered from low thermal stability and possessed an unfavorable retention behavior for some classes of molecules. The Geminal dicationic ionic liquid(GDIL)was synthesized and it was mixed with FFAP in the mass ratio of 1∶2 to produce the stationary phase. The column efficiency was 3500 p/m after being conditioned at 220 ℃ and the average polarity was 435.2, significantly deceased compared to the FFAP column. Despite of this, the selectivity of the novel column for both polar aromatic positional isomers and weak polar ones was improved. In addition, it was found that this novel kind of stationary phase had unique selectivity for the mixtures of polycyclic aromatic hydrocarbons, the homologous series of alcohols, esters, carboxylic acids and alkanes.

    Amino Acid Structural Descriptions Based on Random Sampling of Pseudo Atomic Probe and Its QSAR Study
    ZHOU Yuan1,3,4, MEI Hu2,3, YANG Li3, ZHOU Peng2, YANG Shan-Bin3,4, LI Zhi-Liang2,3,4*
    2007, 28(7):  1263-1266.  doi:
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    Considering the three types of non-bonding interactions between drug molecules and protein receptor molecules and using Monte Carlo's randomly sampling technology with eight pseudo atomic probes, a novel set amino acid descriptors for amino acid side chain surface electrostatic, steric and hydrophobic interaction potential field were developed successfully. By using these parameters, the QSAR study was performed for bitter tasting dipeptides(BT) and bradykinin potentiating pentapeptides(BPP) analogues, with R2 and QLOOCV2 being 0.8457, 0.851, 0.7688 and 0.7952, respectively. The effects of the type of amino acid side chain and its position in sequence of peptide were analyzed, and the results show that the ASSPF could describe the structure of peptide analogues, and an unambiguous meaning and high correlation for their activity.

    Preparation of Open-tubular Capillary Electrochromatography Column with the BSA-Poly(amidoamine)(PAMAM) Dendrimer as Bonded Stationary Phase
    GUO Bao-Jing, YANG Yi*, SU Ping
    2007, 28(7):  1267-1269.  doi:
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    Poly(amidoamine)(PAMAM) dendrimer has a large number of terminal groups which can be functionalized by different kinds of ligands. A novel open-tubular CEC(OT-CEC) column in which BSA was bonded to inner wall of capillary as stationary phase through different generations of PAMAM dendrimer was developed. The obtained columns were characterized via labelling BSA with fluorescein isothiocyanate(FITC). Under the optimized condition, the resolution of D,L-Trp was gradually improved with the increase of PAMAM generation. By OT-CEC column modified with BSA-G3.0-PAMAM, the baseline separation of D,L-Trp can be obtained.

    Determination of Vancomycin in Injection via Enzyme Catalysis-Fluorescence Quenching Method
    FENG Xia-Guang, ZHANG Min, ZHAO Hu, WANG Huai-You*
    2007, 28(7):  1270-1272.  doi:
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    A new method for determining vancomycin was established based on the principle of fluorescence quenching. The mechanism of the fluorescence quenching was discussed. A linear relationship is obtained between F0/F and the concentration of vancomycin in the range of 40.0—450.0 μg/mL with the correlation coefficiency 0.9991.The detection limit was 10.91 μg/mL and the relative standard derivative was 0.70%. The effects of pH, foreign ions, standing time on the determination of vancomycin were examined. The results obtained by this method were agreed with those by the official method.

    Method Measuring of Hydrophobic Parameter of Organic Compounds via a Novel Liposome Capillary Electrophoresis
    DONG Zhi-Qiang1, XIA Zhi-Ning1,2*, JIANG Xue-Mei2
    2007, 28(7):  1273-1275.  doi:
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    Liposome capillary electrophoresis(LCE) provides a novel and facile approach for determining hydrophobic parameters(lgP) of organic compounds. In order to avoid the error of the migration time of liposome phase(tl) on determination, a novel technique was developed in this paper, in which the tl was obtained via non-linearity fitting with lgP values from literatures and migration time(tm) of a series of standard compounds. lgP values of the six benzene derivatives determined by this LCE method were compared with literature values and the ones obtained by directly determined tl and MEEKC. The average error between lgP values determined by two LCE methods was 0.07 logarithm units. The LCE method was simple and rapid, which can provide a new way to determine lgP of organic compounds.

    Synthesis of Novel and Highlyactive Nonlinear Chromophores in High Yields and Their Linear and Nonlinear Optical Properties
    GUO Kun-Peng, ZHANG Tao, ZU Feng-Hua, QIU Ling, ZHEN Zhen, LIU Xin-Hou, SHEN Yu-Quan*
    2007, 28(7):  1276-1279.  doi:
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    Two kinds of novel second-order nonlinear optical(NLO) active chromophores based on diazo with TCF(tricyanofuran) as the acceptors and 3,4-disubstituted thiophene as the bridges were designed and prepared. Improvements in the nitration and diazo coupling reactions increased the total yields of the chromophores from 7% to 20%. The structures of the products were fully characterized via IR, UV, MS and 1H NMR. A loading study was carried out by doping the chromophore in polycarbonate(PC) with different mass fractions. The polymer films were prepared and the glass transition temperatures(Tg), refractive indices(n), propagation optical loss(OL) and electro-optical coefficient values(γ33) of the films were determined. The γ33 of 16 pm/V was obtained and higher value is expected if poling conditions are further improved. The decomposition temperatures of the chromophores are above 239 ℃, and the optical losses of the films at 1310 nm and 1550 nm is low. These results indicate that the chromophores are very promising candidates for practical applications in the field of electro-optics and photonics.

    Molecular Design, Synthesis and Biological Activity Evaluation of Novel AHAS Inhibitors Basedon Receptor Structure
    XIAO Yong-Jun, WANG Jian-Guo, LIU Xing-Hai, LI Yong-Hong, LI Zheng-Ming*
    2007, 28(7):  1280-1282.  doi:
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    Based on the crystal structure of AHAS/sulfonylurea complex, 296 molecules were obtained with low binding energy towards AHAS from MDL/ACD 3D database via virtual screening with program Dock 4.0, from which some compounds were synthesized. The biological activities of the synthesized compounds were measured in vitro and in vivo. The preliminary bioassay indicates some compounds displayed a good herbicidal activity on rape and barnygrass and had AHAS inhibition to some extent. These studies indicate the rationality of molecular design based on the crystal structure of AHAS complex.

    Correlation Between Catalytic Characteristics of Papain and Components and Solvent Properties of Ionic Liquids
    LOU Wen-Yong*, ZONG Min-Hua
    2007, 28(7):  1283-1287.  doi:
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    The components and solvent properties of ionic liquids(ILs) show an important impact on papain-catalyzed asymmetric hydrolysis of D,L-p-hydroxyphenylglycine methyl ester(D,L-HPGME). The enzyme was more active, enantioselective and stable in the CnMIm·BF4(n=2—6)-based systems, while it was less active, enantioselective and stable in the systems involving C4MIm·HSO4, C4MIm·Cl, C4MIm·NO3 or C4MIm·CH3COO. Papain's activity increased with increasing the polarity of the ILs CnMIm·BF4(n=2—6) and, conversely, decreased with increasing the polarity of the ILs C4MIm·HSO4, C4MIm·Cl, C4MIm·NO3 or C4MIm·CH3COO. Also, the more hydrophobic the IL was, the more enantioselective and stable the papain was. Fluorescence spectroscopic analysis demonstrates that ILs had an obvious effect on papain's conformation. In the CnMIm·BF4(n=2—6)-containing systems, a blue-shift of the maximal emission(λmax) of papain occurred, while a red-shift of λmax took place in the systems involving C4MIm·HSO4, C4MIm·Cl, C4MIm·NO3 or C4MIm·CH3COO. Papain's conformation changed greatly when the enzyme was placed in C4MIm·HSO4, C4MIm·Cl, C4MIm·NO3 or C4MIm·CH3COO-based systems compared to those with CnMIm·BF4(n=2—6), resulting in more exposure of hydrophobic regions of the enzyme.

    Studies on the Bioactivity of Osteoblasts on the Surfaces of Nano-TiO2 Ceramics
    QU Yang, LI Zhen-Sheng, YANG Bang-Cheng*, ZHANG Xing-Dong
    2007, 28(7):  1288-1291.  doi:
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    Traditional TiO2 is bioinert, which could just form mechanical connection with the surrounding bone-tissue without bioactivity. Because of the nano-effect of nano-materials, the properties of nano-material is always better than the traditional ones, which made it logical to assume that nano-technology is a potential method to improve the bioactivity of ceramics. In this paper, the bioactivities of nano-TiO2 ceramics prepared via normal sintering method by adding hydroxyapatite(HA) or MgO as the crystal growth inhibitors were studied with cell culture method, in which Ros17/28(osteoblast) was cultured on nano-ceramics in vitro. The bioactivity and biocompatibility of nano-TiO2 ceramics were evaluated by investigating the cell extrinsic shape, integrality of cell, cell activity and proliferation by SEM observation and cell toxicity tests including fluorescence coloration observation and MTT, respectively. The result shows that nano-TiO2 ceramics with HA as the crystal growth inhibitor had a good biocompatibility. Its bioactivity is better than pure HA and TiO2 ceramics with MgO as the crystal growth inhibitor.

    Total Synthesis of 6-Oxodendrolasinolide
    LI Yi1, ZHANG Tao2, LI Yu-Lin1*
    2007, 28(7):  1292-1296.  doi:
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    An efficient total synthesis of 6-oxodendrolasinolide(1), a new farnesane-type sesquiterpene lactone, was described. The synthetic route was completed from geraniol 2 and 3-methylbut-2-en-1-ol(5) through twelve steps in 5.6% overall yield. The key steps were regioselective alkylation of the anion of vinyldithian 7 with allylic chloride 4a to generate compound 8, followed by hydrolyzation of the dithiane to afford compound 9. The reduction of enone 9 gave alcohol 10, which was protected as a p-methoxylbenzylether 11. Subsequently, tetrahydropyranyl protective group was removed and oxidized to give the key intermediate aldehyde 13. Then after Corey's oxidative lactionization reaction followed by deprotection of the PMB group compound 15 was formed, which underwent Dess-Martin oxidation to afford the title compound 1.

    Synthesis and Biological Activities of Novel Guanidinoglucosides
    LIAN Zhao-Bin1, TIAN Xiao-Hong1, CAO Ling-Hua1,2*
    2007, 28(7):  1297-1303.  doi:
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    The reaction of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate 1 with 2-amino-4/6-substituted benzothiazoles 2a—2b gave glucosylthioureas(3a—3b), which then reacted with alkyl/aryl amine in the presence of HgCl2 to afford a series of new poly-acetyl guanidinoglucosides(4a—4d, 5a—5d, 6a—6d and 7a—7d). Deacetylation of glycosyl was carried in the CH3OH/CH3ONa solution. The structures of the new compounds were established on the basis of elemental analyses, IR, 1H NMR and mass spectral data and all compounds took β-configuration. The biological activities of these compounds have been evaluated. Compounds 4c, 6c, 8b and 8c showed anti-HIV-1 PR activity, compound 7c showed anti-influenza activity and compounds 5e, 7c and 7d showed inhibitory activity against angiotensin-converting enzyme(ACE) activity.

    Synthesis, Crystal Structure and Glucosidase Inhibitory Activities of (8R,13R)-8, 12,13,17-Tetrahydroandrographolide
    HUANG Li-Hua, XU Hai-Wei, LIU Gai-Zhi, DAI Gui-Fu, LIU Hong-Min*
    2007, 28(7):  1304-1306.  doi:
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    Some glucosidase inhibitors show antitumor metastasis and anti-HIV activities and are also clinically useful for the treatment of diabetes, besides andrographolide derivative have been proven to be potent an α-glucosidase inhibitor. In order to investigate the double effect of glucosidase inhibition activity, a new diterpene lactone derivative 2 was synthesized via reduction of compound 1 which was one of the constitutions of Andrographis Pamicutate (Brum) Nees. The structure of compound 2 was confirmed with X-ray diffraction analysis, NMR, IR, HR-MS and so on. Compound 2 shows a selective α-glucosidase inhibitory activity with inhibition of 49.6% at 100 μmol/L, and the mother 1 has no inhibition activity(100 μmol/L). The results indicate that the double bond can affect the α-glucosidase inhibition activity of andrographolide.

    Facile Total Synthesis of 3-Oxo-11,12,13-trihydroxyeudesm-4-ene
    GUAN Yu-Kun1,2*, FANG Li-Jing2, TANG Zhi-Yong2, LI Yu-Lin2
    2007, 28(7):  1307-1309.  doi:
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    3-Oxo-11,12,13-trihydroxyeudesm-4-ene(1) was a highly oxygenated natural eudesmane isolated from traditional herbal medicine with an antiphlogostic and spasmolytic activity. For the purpose of pharmacological activity research on natural product 1 and its derivatives, a facile total synthesis of compound 1 starting from (+)-dihydrocarvone(2) was completed in an overall yield of 24%. The structures of all intermediates and product 1 were confirmed via 1H NMR, 13C NMR, MS and IR techniques. The NMR data of compound 1 are in agreement with those of natural products.

    Syntheses of Capsaicin and (E)-4-Hydroxy-3-methoxybenzyl-8-methylnon-6-enoate
    YANG Yan, JIN Yong-Sheng, DONG Zhen-Xiu, HU Hong-Gang, YU Shi-Chong, WU Qiu-Ye*
    2007, 28(7):  1310-1312.  doi:
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    Capsaicin and (E)-4-hydroxy-3-methoxybenzyl-8-methylnon-6-enoate were important intermediate of medicine. This research proposed a new method for synthesizing them from 6-bromohexanoic ester by Wittig reaction to give (Z)-8-methyl-6-nonenoic acid(4), then treated by nitrous acid and NaNO2 to induce Z→E isomerization reaction of the carbon-carbon double bond, then followed by condensation reaction to give product in an overall yield of 31%. The method is more convenient than traditional methods.

    Separation and Structural Identification of Hericium Erinaceur Oligosaccharide
    JIANG Rui-Zhi1, WANG Ying2, CHEN Ying-Hong1, GAO Yang1, HUANG En-Xi1, GAO Qi-Pin3*
    2007, 28(7):  1313-1315.  doi:
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    It has been reported that the polysaccharide is the main active constituent of Hericium erinaceur. A series of oligosaccharide(mixtures of disaccharide and heptasaccharide of Hericium erinaceur) were separated from Hericium erinaceur by empty-fibrin filtration. Disaccharide and trisaccharide were purified via HPLC with NH2 column. Component sugars and glycosidic linkage ways were analysed via GC and GC-MS. Electrospray ionization tandem mass spectrometry(MSn) was used for the oligosaccharides structure study and the result shows that the disaccharide has two kind of structural styles and trisaccharide has one kind of structural style.

    Isolation and Structure Characterization of Malonyl-notoginsenoside-R4 from the Root of Panax ginseng
    SUN Guang-Zhi1, LI Xiang-Gao2, LIU Zhi1, WANG Ji-Yan3, ZHENG Yi-Nan2, YANG Xiu-Wei4*
    2007, 28(7):  1316-1318.  doi:
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    A new malonylated dammarane-type triterpene oligoglycoside, named malonyl-notoginsenoside-R4(1), was isolated from the fresh root of Panax ginseng C. A. Mey. The structure of malonyl-notoginsenoside-R4 was determined as 3-O-[6-O-malonyl-β-D-glucopyranosyl(1→2)-β-D-glucopyranosyl]-20-O-[β-D-xylopyranosyl(1→6)-β-D-glucopyranosyl(1→6)-β-D-glucopyranosyl]-20(S) protopanaxadiol on the basis of physicochemical properties and spectral analysis.

    Structure, Acid Properties and Catalysis Performance of Dealuminated MCM-49 Zeolites for the Alkylation of Benzene with Propylene
    ZHANG Yu1,2, WU Shu-Jie1, YANG Xu-Wei1, JIA Ming-Jun1, WANG Li-Xia1, ZHANG Zuo-Wang1, WU Tong-Hao1*, SUN Chia-Chong3
    2007, 28(7):  1319-1324.  doi:
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    Nano MCM-49 zeolite was synthesized and dealuminated by acid reflux and hydrothermal treatment, respectively. The resulting solids were characterized via XRD, N2 adsorption-desorption, NH3-TPD, FTIR and 27Al NMR. The amounts of total acid sites on dealuminated MCM-49 samples were decreased. For the acid reflux samples, the acid strength is not modified. For the hydrothermally dealuminated zeolite at 600 ℃, the acid strength is weaker as observed by NH3-TPD studies. 27Al NMR reveals that the acid dealumination at room temperature for 5 h results in a decrease of the amounts of aluminum atoms in framework of zeolite. After dealumination under acid reflux for 10 h, the spectrum becomes broader, and the shape of the peak corresponding to the tetrahedral aluminum atoms was modified. After hydrothermal dealumination at 600 ℃ for 3 h the broadening of the peaks increased and a new peak at δ 30 appeared, due to extraframework aluminum in a tetra- or pentacoordinate. Nano MCM-49 zeolite shows an excellent catalytic activity and selectivity in the liquid-phase alkylation of benzene with propylene. The conversion of propylene reaches 99.5%, and the selectivity to IPB is 73.6%. The propylene conversion can be decreased by dealumination. Comparision of the product distribution between MCM-49 and dealuminated MCM-49 suggests that dealumination could improve the selectivity to monoalkylation. For D-25-5 zeolite, the conversion of propylene is parallel to that of MCM-49 zeolite, while the yield to IPB increases 5.3%.

    Synthesis and Characterization of TiO2 Nanoparticles and Nanotubes and Their Photocatalytic Property for Nitrobenzene Degradation
    SHI Jin-E, YAN Ji-Chang*, SHANG Shu-Xia, CHEN Da-Wei, WANG Yue-Hong, YAN Fu-Cheng, XUE Jing, CHU Li-Wei, SU Li-Min
    2007, 28(7):  1325-1328.  doi:
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    By changing the parameters of reaction and controlling the conditions of reaction, the spheres TiO2 nanoparticles whose particles size can be controlled and nanotubes whose aspect ratio and surface areas are larger were synthesized via the hydrothermal method. The products were characterized with XRD, TEM, SAED and BET. For testing the photocatalysis performance of the products, we took the nitrobenzene solution with a high concentration as the water sample, completed a series of optimizing experiments for enhancing efficiency of the degradation and comparable experiments of photocatalysis degradation. By reviewing these parameters: the original concentration of the nitrobenzene solution, TiO2 loading, pH of the solution, we found that the effect of degradation was the best when the concentration of the nitrobenzene solution was 300 mg/L, TiO2 loading was 0.4 g/L, the pH of the solution was 6—7. By comparable experiments, we found that the photocatalysis performance of nanotubes is better than spheres titania nanoparticles because of the specific surface areas of nanotubes is larger. After 3 h irradiation by artificial ultraviolet light, the rate of degradation could reach over 90%, About 3.5 h irradiation by artificial ultraviolet light, nitrobenzene almost could be degraded completely.

    研究论文
    Theoretical Study of Potential Energy Surface for Reaction O+HCNO
    WANG Song1, YU Jian-Kang1,2*, DING Da-Jun2, SUN Chia-Chong1
    2007, 28(7):  1329-1332.  doi:
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    It is known that, for the reaction O+HCNO, there were three products P1(HCO+NO), P2(HNO+CO) and P3(NCO+OH) observed by experiments. In the present work, by means of the computational method at the level as CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPVE, the potential energy surface for reaction O+HCNO was built up to give the multi-channel mechanism in which the H or O-migration is involved. It is shown that the product P1 is the major one and the other two products P2 and P3 the minor.
    Synthesis, Characterization and Catalytic Performance of Copper(Ⅱ)-8-quinolinol Functionalized SBA-15
    WANG Hong-Su, HUANG Jia-Hui, XU Chen, XU Ling, SONG Ke, XU Hai-Yan, WANG Zhu-Qian, KAN Qiu-Bin*
    2007, 28(7):  1333-1336.  doi:
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    Firstly, copper(Ⅱ)-8-quinolinol ligands were introduced into the channels of 3-aminopropyl functionalized mesoporous SBA-15(denoted as APS-SBA-15). Then, the obtained copper(Ⅱ)-8-quinolinol functionalized SBA-15 materials[named as Cu(Ⅱ)-Q-APS-SBA-15] were tested as the catalysts for phenol hydroxylation by using H2O2(30%, mass fraction) as an oxidant. The reaction results indicate that Cu(Ⅱ)-Q-APS-SBA-15 was an excellent catalyst for this reaction, and over it a high conversion of phenol and a high selectivity to diphenol could be obtained.
    Internal Mixture of NaCl and Fe2O3 Serving as an Efficient Scavenger for Sulfur Dioxide
    YIN Yong, CHEN Hai-Han, KONG Ling-Dong, CHEN Jian-Min*
    2007, 28(7):  1337-1341.  doi:
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    Internal mixing of sea-salt and mineral dust is often observed in coastal regions and the adjacent marine boundary layer, but the influence on atmospheric chemistry is not well known. In this paper the investigation of the reaction of SO2 on the surface of mixed particles composed of Fe2O3 and NaCl was made by means of DRIFTS and XPS and the corresponding reactive uptake coefficients were calculated. The main products were sulfate/bisulfate and the minor product was sulfite/bisulfite. It was shown that the reaction rates with SO2 are correlated with zero order kinetis. The reactive uptake coefficient for SO2 oxidation by O2 was determined. Different proportions of NaCl resulted in distinct reaction abilities. With increasing the proportion of NaCl, the BET uptake coefficient increased at first and decreased afterwards. When NaCl accounted for 70% of the mixture, the BET uptake coefficient accounted to 4.62×10-6, which is 8.07 times as much as that of pure α-Fe2O3(5.72×10-7). The FeCl2-SO3- formed and served as a temporal reservoir of sulfur species, which can be used to explain the experiment results. The mixture shows a significant capacity to scavenge SO2, it is important to implicate the heterogeneous gas-to-particle conversion mechanism of atmospheric SO2, reevaluate the impact involving mineral dust mixed with sea salt and the influence of the aerosol radiative forcing and the sulfate cooling effect.
    Preparation of Organic White Light-emitting Devices via Exciplex Emission
    XIE Wei-Jie1,2, LI Yu-Peng1,2, SUN Cheng-Lin3, LI Feng1*, FEI Teng1, MA Yu-Guang1*
    2007, 28(7):  1342-1344.  doi:
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    Colour stable organic white light-emitting devices(LEDs) were prepared with N,N-diphenyl-N,N″-bis(1-naphthyl)-(1,1-biphenyl)-4,4'-diamine(NPB) as the hole-transporting layer, cyano substituted oligo(p-phenylene vinylene)(CNDPDSB) as the emitting layer, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline(BCP) as the hole-blocking layer, tris-(8-hydroxyquinoline) aluminum lq as electron-transporting layer. This type of device has a simple structure. The white light comes from the mixing of red exciplex emission at the solid-state interface between CNDPDSB and NPB and blue emissions from NPB and CNDPDSB, respectively. The white LEDs exhibit a maximum luminescence of 1200 cd/m2 and efficiency of 0.2 cd/A, and the Commission International De L'Eclairage(CIE) coordinates of emission vary from (0.33, 0.34) to (0.31, 0.37) with increasing the bias from 6 V to 13 V.
    Energy Transfer and Luminescent Properties in PVK and Novel Donor-acceptor Molecular Materials Blend System
    ZHAO Yi-Xin, PENG Ping, ZHOU Yin-Hua, WU Wei-Cai, TIAN Wen-Jing*
    2007, 28(7):  1345-1349.  doi:
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    The energy transfer and the luminescent properties of PVK and four novel donor-π-acceptor(D-π-A) molecules(CKD, TKD, PKD, NKD) doped systems were investigated with the analysis of UV-Vis absorption spectra, photoluminescent excitation(PLE) spectra and photoluminescent(PL)spectra.The electroluminescence(EL) properties of the blend system were studied via the characterization of the devices ITO/PEDOT/PVK∶D-π-A ω/Alq3/Al. The results demonstrate that by changing the donor moieties of D-π-A molecule, the band gap of D-π-A molecules can be adjusted. Meanwhile the fluorescence quantum efficiency varies significantly with the stereostructure of donor moieties of D-π-A molecules. Both the PL and EL spectra show that the energy transfer between PVK and D-π-A molecules occurs effectively. The emission performance of the blend system could be improved with changing the dopant ratio of PVK and D-π-A molecules. The power efficiency of the device is up to 1.75 cd/A at 729.1 cd/m2, when the dopant mass fraction between PVK and TKD is 6.0%.
    Steady-state and Time-resolved Spectroscopic Studies on the Interaction Between TMPyP4 and Nucleic Acids
    WANG Xue-Fei1,2, ZHANG Hui-Juan3, WU Yi-Shi1,2, WANG Peng2, AI Xi-Cheng2*, ZHANG Jian-Ping1,2
    2007, 28(7):  1350-1355.  doi:
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    Steady-state absorption and fluorescence, circular dichroism and picosecond time-resolved fluorescence spectroscopies were used to investigate the interaction between 5,10,15,20-tetrakis(4-N-methylpyridine)porphyrin (TMPyP4) and nucleic acid molecules, i.e. bases (A, G, T, C), deoxynucleosides (dA, dG, dT, dC), deoxynucleotides (dAMP, dGMP, dTMP, dCMP) and oligonucleotides (dA6, dG6, dT6, dC6). The results show that the interactions between TMPyP4 and the purine species were stronger than that between TMPyP4 and the pyrimidine species. For a certain series of species, such as A, dA, dAMP and dA6, the interaction strength follows the order: base-nucleoside
    Effect of Annealing Temperature on Structure and Gaschromic Properties of WO3 Thin Films
    SHI Ji-Chao2, WU Guang-Ming1*, CHEN Shi-Wen1, SHEN Jun1, ZHOU Bin1, NI Xing-Yuan1
    2007, 28(7):  1356-1360.  doi:
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    WO3 sol(600 mL) was prepared with tungsten powder and 37% H2O2 through the sol-gel method in this paper. WO3 thin films were prepared on silicon chips and ordinary slide glasses via Dip Master method and annealed in ambient air at temperatures of 50, 150, 250, 350 and 450 ℃, respectively. Thickness and refractive index of the WO3 thin films were researched by Spectroscopic Ellipsometer. Surface morphology and microstructure of the films were analyzed with AFM, IR and XRD respectively. The annealing temperature have an important effect on the structure and gaschromic properties of WO3 thin films. At low annealing temperature, WO3 thin films is amorphous and porous structure, and the water of WO3 thin films is appropriate, then this kind of WO3 thin films have a good gaschromic properties.
    Electronic Structures and Second-order Nonlinear Optical Properties of Zinc(Ⅱ) Complexes with Bis(salicylaldiminatio) Schiff Bases and Pyridine Ligands
    SU Tan1, ZHU Dong-Xia1,2, QIU Yong-Qing2*, CHEN Hui2, WANG Yue1,2
    2007, 28(7):  1361-1364.  doi:
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    Based on the crystal structure measured experimentally, the density functional theory(DFT) B3LYP method was employed to calculate the electronic structures of four zinc(Ⅱ) complexes with double schiff bases ligands containing salicylaldehyde with aniline and pyridine ligands at 6-31G(d) level. Moreover, the finite field(FF) method was combined to investigate second-order nonlinear optical coefficient. The results indicate that the double schiff bases ligands have a lower conjugation degree. And the introduction of tert-butyl to Schiff bases and the bridge connecting the double Schiff bases ligands affect the complex structures slightly. Meanwhile, the coordinate bonds, atomic charge distributions, energy levels of frontal molecule orbital and the other properties of the four complexes have similar trends. However, the introduction of tert-butyl changed compositions of the frontal molecule orbital of complexes, which enforced the polarity of Zn—O coordinate bonds. As a result, the linear and second-order nonlinear optical(NLO) coefficients are increased. However, the bridge connecting the double Schiff bases ligands have less influence to the second-order NLO properties.
    Synthesis of AB2 Star-shaped Miktoarms Copolymers and Their Crystallization Behavior
    WANG Kang-Cheng1, HUANG Wei2*, ZHOU Yong-Feng2, YAN De-Yue2*
    2007, 28(7):  1365-1370.  doi:
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    A small molecule (GMS-SA2) with one alkyl chain and two terminal carboxyl groups was synthesized successfully via the reaction of glyceryl monostearate with excessive succinic anhydride. Then, the small molecule was used as a coupling agent to condensate with polyethylene glycols (PEG) with different molecular weights or polyethylene glycol monomethyl ether (PEGm) in the presence of stannous octoate as the catalyst and diphenyl ether the as azeotropic agent to remove water. Thus, the AB2 star-shaped miktoarms copolymers were obtained successfully, and were characterized via 1H NMR, DSC, GPC, XRD, FTIR and micropolariscope, etc. DSC and XRD measurements indicate that the crystallizing temperature and the melting temperature of the AB2 star-shaped miktoarms copolymers were different from those of the corresponding linear PEGs because the existing of GMS-SA2 altered its crystallizing velocity and the perfect degree of crystal. It is very important to control the crystal shape of the star-shaped copolymers through introducing the miktoarms into the copolymers and changing its content in copolymers.

    Studies on an Affinity Sorbent with Polyvinylimidazole as Ligand for Removing Endotoxin
    ZHANG Yuan-Yuan1, ZHOU Kang2, PING Zheng-Hua1*
    2007, 28(7):  1371-1376.  doi:
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    A novel composite affinity adsorption material bearing polyvinylimidazole(PVI) as the ligand for selective removal of endotoxin(ET) was prepared by graft polymerization of vinylimidazole onto silica gel particles in DMF(N,N-dimethyl-formamide). The characteristic bands of imidazole ring at 1500 cm-1 and 665 cm-1 were detected via FTIR and the grafting degree(GD) of PVI was measured with TGA according to the weight loss of the sample. The ET adsorption capacity of the sorbents shows dependence on GD of PVI on the sorbent, and the maximum ET adsorption capacity was attained with GD of 2.5%. The effects of ionic strength and pH values of the testing solution on the sorbent performance were also studied. At pH=7 and ionic strength lower than 1 mol/L the sorbent had the best adsorption ability toward ET even in presence of BSA. The sorbent shows a good blood compatibility. The adsorption kinetics and the isotherm of the sorbent were well accorded with the second order equation and Freundlich equation, respectively. The results reveal the applicability of PVI or other compounds with imidazole group to serve for good ligand in ET removal.

    Synthesis and Characterization of a Novel Water-soluble Conjugated-block Copolymer Containing Carbohydrate
    WANG Yun-Yun1, FAN Qu-Li2, WANG Pei1, MA Zhun1, WANG Lian-Hui1*, HUANG Wei2*
    2007, 28(7):  1377-1382.  doi:
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    A novel well-defined amphiphilic copolymer was prepared via atom transfer radical polymerization(ATRP) with 2-bromoisobutyrate-capped poly(9,9-dihexylfluorene) as macroinitiator and CuCl/HMTETA(1,1,4,7,10,10-hexamethyltriethylenetetramine) as the catalyst. The molecular weight and molecular distribution were well controlled, implying well-defined block structure of the prepared block copolymer. The chemical structure of the copolymer of PMaIpGa-PF-PMaIpGa was confirmed via 1H NMR, FTIR and GPC. The copolymer could be successfully deprotected, and the final conjugated-carbohydrate block was found to be soluble in water. UV and PL spectra were also studied.

    Energy Transmission Mechanism of Electrons in Epoxy Resin During Electron Beam Curing Process
    LI Yu-Bin1,2*, ZHANG Zuo-Guang1, YANG Jia-Ling2
    2007, 28(7):  1383-1387.  doi:
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    A method was proposed to study the energy transmission mechanism of electrons in epoxy resin system during the electron beam (EB) curing. The energy deposition curves were simulated with a Monte Carlo method before radiation curing. The temperature of points in epoxy resin were monitored during the EB curing, and the distribution of cure degree in EB-cured epoxy resin was investigated. The results from the calculation and measurement were combined to discuss the energy transmission mechanism during the radiation curing. At the beginning of radiation, the electron energy deposition in the resin in polypropylene mould coincides with the ion implantation theory, the maximum energy deposits at a certain depth in the resin systems, and then the energy deposition decreases with the increase of the distance from the radiation surface. But in glass mould, the maximum energy deposits at the radiation surface, and then the energy deposition also decreases with the increase of the distance from the radiation surface. The location where the electron concentration is the maximum changes with the radiation cure reaction. Finally, it appears near the zone in which the calculated electron deposition is the maximum, and it is more farther from the radiation surface. The elevated temperature from absorbing energy and in the exothermal reaction has nothing to do with the value of cure degree, but will affect the distribution of cure degree.

    Preparation of Ordered and Porous Honeycomb Structure Film of Poly(lactic acid) with Pluronics® as the Second Component
    SUN Wei, TANG Yue-Chao, JI Jian*
    2007, 28(7):  1388-1392.  doi:
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    A porous poly(lactic acid) film with a well-ordered honeycomb structure was prepared via the breath-figure method. The addition of amphiphilic Pluronics® was proved to be able to benefit a lot to fabricate the well-ordered honeycomb-patterned film. Several influencing factors including atmosphere humidity, solution concentration and the molecular weight were investigated. The fluorescein isothiocyanate labelled bovine serum albumin(FITC-BSA) was used as the probes to investigate the protein absorption onto the pattern film. Fluorescence images showed the corresponding honeycomb patterns, indicating that the honeycomb-patterned films with protein-resistant pores could be successfully constructed with Pluronics® as the second component.

    Synthesis and Properties of Optically Active Polyurethanes Containing 1,1'-Binaphthyl Unit
    NAN Qiu-Li, ZHOU Yu-Ming*, CHEN Jing, GUO Ling-Xiang, WANG Zhi-Qiang
    2007, 28(7):  1393-1397.  doi:
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    A new type of optically active polyurethanes (R-BPU and S-BPU) containing 1,1'-binaphthyl were prepared from chiral 1,1'-binaphthol(BINOL) and 2,4-toluene diisocyanate(TDI) by the hydrogen transfer addition polymerization. The polymers obtained were characterized with FTIR, 1H NMR, UV-Vis, CD, DSC/TGA and so on. The results showed that in the polymeric process, the intrinsic viscosity and the [α]25D of the optically active polyurethanes obtained increased with the enhancement of the optical purity of the BINOL. And the polymers showed an optical stability, the optically rotation of both of the S-BPU and R-BPU could reach -78.0° and +54.6°(DMF, L=10 cm, c=0.25 g/100 mL). The glass transformation temperatures(Tg) of S-BPU and R-BPU reached 258.4 and 286.6 ℃ respectively, meanwhile the thermal decomposition temperatures(Td) got to 305.6 and 323.6 ℃ and both of whose thermal decomposition temperatures improved more than 100 ℃ according to general PUs. Therefore, the target polymers exhibited good thermal properties, the infrared emissivity reached 0.618 and 0.682, and they displayed a low infrared emissivity.

    Synthesis and Characterization of Polyacetals and NMR Study on Its Degradation Kinetics
    SHU Jie1, PENG Min1, YU Jia-Hui2*, LUO Shu-Fang2, YU Lei2, CHEN Qun1
    2007, 28(7):  1398-1402.  doi:
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    With p-TSA as catalyst, four different types of polyacetals(PA1, PA2, PA3, PA4) were synthesized with amino-protected serinol, tri(ethylene glycol) divinyl ether and PEG2000 in different molar ratios. The structure of the resultant polyacetal was characterized with 1H NMR.The degradation process of the copolymers was monitored via 1H NMR in pH=7.4, 6.5, 5.7 PBS and pH=4.7, 4.1, 3.8 acetic buffer, respectively. It was found that the degradation reaction in acidic buffer of PA3 obeyed the first order kinetics equation. With decreasing pH values of the buffer solution, the degradation rate constant increases and the half-life decreases.

    Charge Transport Study of a Series of Monosilanylene-oligothienylene Copolymer Films
    JIANG Xiao-Qing1*, HARIMA Yutaka2
    2007, 28(7):  1403-1407.  doi:
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    Mobilities of charge carriers in thin films of a series of copolymers with repeat units consisting of monosilanylene and oligothienylene(PSnT, n denotes the ring number of an oligothienylene unit) are measured over a wide range of doping levels. Mobilities of charge carriers in these polymer films coincide well with each other in the very low doping regions below a doping level of 0.2%. The mobilities for these copolymer films increase as the doping level increases. Mobilities for the polymers with larger n start to rise at lower doping levels. The mobility enhancement follows an increasing order of the π-conjugation length. For PS14T, the enhancement exceeds 104, close to that observed for electrochemically synthesized polythiophene, implying that the π-conjugation length in this polymer is almost sufficient to reproduce charge transport properties of polythiophenes.

    Synthesis and Properties of Sulfonated Polyimide for Proton Exchange Membrane
    WANG Lei1*, MENG Yue-Zhong2, WANG Shuan-Jin2, ZHU Guang-Ming1
    2007, 28(7):  1408-1410.  doi:
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    A novel sulfonated polyimide containing triphenyl methane as the polymer electrolytes for fuel cell appliaction was successfully synthesized. The sulfonic acid function was only attached at the para positions on the pendant phenyl rings due to the novel sulfonated diamine structures designed. The sulfonated polymers are very soluble in common organic solvents, such as dimethyl sulfoxide, N,N'-dimethylacetamide, and can be readily cast into tough and smooth films from solutions. The membranes show excellent hydrolytic and oxidative stabilities and can be potentially used as the proton-exchange membranes for fuel-cells.