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Table of Content

    10 March 2010, Volume 31 Issue 3
    Contents
    Content of Chemical Journal of Chinese Universities Vol.31 No.3(2010)
    2010, 31(3):  0. 
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    Review
    Advances in Bio-inspired Smart Surfaces with Special Wettability
    DU Chen-Guang, XIA Fan, WANG Shu-Tao, WANG Jing-Xia1, SONG Yan-Lin, JIANG Lei
    2010, 31(3):  421-431. 
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    Bio-inspired surfaces with special wettability have attracted much attention because of their promising applications in daily life and industrial applications. Recently, several bio-inspired intelligent surfaces with special wettability were designed and constructed by modifying chemical compositions and surface roughness. By use of various techniques, researchers were succeeded in controlling micro/nanostructures, responsive materials, and surface wettability, consequently bridging the gap between intelligent surfaces with special wettability and practical applications.

    Letter
    Preparation and Photoresponse of Nonliquid Crystal Poly(amic acid) Containing Azobenzene
    ZHANG Chao-Hui, ZHAO Xiao-Gang, LIU Yan-Mei, WANG Ce, ZHANG Wan-Jin*
    2010, 31(3):  432-434. 
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    A nonliquid crystal azobenzene polymer was prepared. The obtained films exhibit fast bending response at room temperature, which can improve the efficiency of the transformation of energy from light to mechanical energy. The surface structure of the relief gratings was investigated by atomic force microscopy. The depth of surface relief in a typical case is found to be around 94 nm. The product structures were characterize by UV light, 1H NMR, AFM and Fourier transform infrared spectrum.

    Articles
    Synthesis and in vitro Anticancer Activities of  Chiral Ruthenium Complexes and Interaction of the Complex with Bovine Serum Albumin
    LIU Ya-Nan, YANG Fang, MEI Wen-Jie, LIU Jie*, ZHENG Wen-Jie*
    2010, 31(3):  435-441. 
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    Chiral ruthenium(Ⅱ) complexes Δ-[Ru(bpy)2(pyip)]2+ and Λ-[Ru(bpy)2(pyip)]2+ were synthesized and characterized in detail by elemental analysis, 1H NMR, electrospray ionization mass spectrometry(ESI-MS) and circular dichroism(CD). The in vitro anticancer activities of the ruthenium(Ⅱ) complexes were screened by MTT assay. The results show that Δ-[Ru(bpy)2(pyip)]2+ exhibited higher cytotoxic effects against human cancer cells. The quenching mechanism of the fluorescence of bovine serum albumin(BSA) by chiral ruthenium(Ⅱ) complexes was investigated by fluorescence spectroscopy under simulative physiological conditions. The binding constant K and the number of binding sites were determined according to Scatchard equation and the main binding force was discussed via thermodynamic equations. The experimental results show that the quenching mechanism of chiral ruthenium(Ⅱ) complexes to bovine serum albumin was static quenching. The binding constants K were 1.16×105, 5.12×104, 3.64×104 L·mol-1 with one binding site, respectively. The binding force is electrostatic interaction. Chiral ruthenium complexes have nearly no effect on the serum protein conformation.

    Effect of Zn-Chlorophyll Prepared from Silkworm Faeces on DNA Photocleavage
    SI Li-Ping, LIU Jing-Jing, SHI Lei, WANG Xiang-Li, ZHANG Lei, LIU Hai-Yang
    2010, 31(3):  442-446. 
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    Zinc chlorophyll(Zn-CHL) complex was prepared using chlorophyll extacted from silkworm faeces. Relative viscosity, UV-Visible and CD spectra were used to study the interaction between Zn-CHL and ct-DNA. Agarose gel electrophoresis was also carried out to investigate the photocleavage ability of Zn-CHL to pBR 322 DNA. The results suggested that the binding mode of Zn-CHL and ct-DNA was outside binding, the binding constant was 2.32×105 L/mol. Agarose gel electrophoresis picture showed that Zn-CHL could induce DNA cleavage upon irradiation.

    Solvothermal Synthesis and Electromagnetic Properties of Fe3O4 and Its Zn2+-Substituted Zn1-xFe2+xO4 Nanocrystallines
    YAN Ai-Guo, LIU Hao-Mei, LIU Ping-Ting, HAO Xi-Hai, LIU Yue-Jun*
    2010, 31(3):  447-451. 
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    Fe3O4 and Zn1-xFe2+xO4 nanocrystallines were successfully prepared using NaAc as protective reagents via solvothermal method. The structure, size, morphology and chemical composition of the products were investigated in detail by X-ray diffraction(XRD) and scanning electron microscopy(SEM).The results indicate that the monodisperse nanocrystallines are nanospheres and the averaged size of Zn0.07Fe2.93O4(70 nm) is smaller than that of Fe3O4(170 nm). The magnetic properties of the sample were investigated and revealed that the saturation magnetization(54.2 A·m2·kg-1) of Zn0.07Fe2.93O4 nanocrystalline was smaller than that of Fe3O4(81.6 A·m2·kg-1). The electromagnetic performance and microwave adsorption efficiency of both nanocrystallines were measured by a vector network analyzer(VNA) technique in a frequency region 2—18 GHz. The results indicate that Zn0.07Fe2.93O4 nanocrystallines exhibit better microwave adsorption efficiency. For example, the Zn0.07Fe2.93O4 nanocrystalline, the reflection loss maxium is 19.3 dB, almost equal to the double values of Fe3O4 (9.8 dB), and the bandwidth with a reflection loss more than 10 dB is up to 2.5 GHz.

    Growth and Characterization of InGaAs Quantum Dots with High Density and Long Emission Wavelength
    LI Lin*, ZHANG Bin, LI Zhan-Guo, LI Mei, LIU Guo-Jun
    2010, 31(3):  452-455. 
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    InAs quantum dots with high-density(~5×1010 cm-2) were fabricated on GaAs substrate by metal-organic chemical-vapor deposition(MOCVD), the growth parameters were studied at room temperature, the ground state peak wavelength of photoluminescence(PL) spectra and full width at Half-Maximum(FWHM) are 1.346 μm and 24 meV, respectively, when the QDs were finally capped with 5 nm InGaAs(12% In content) strain-reducing layer(SRL). The results of PL measurements showed that the InGaAs SRL with higher In content which was fatricated at lower growth temperature could improve the optical quality of InAs QDs with strong red-shift in the spectra.

    Fabrication of Superhydrophobic Surface on Aluminum Alloy by Sandblasting-anodizing-fluorination
    ZHOU Quan-Hui, YU Xin-Quan, ZHANG You-Fa*, LI Kang-Ning, CHEN Feng1, GU Zhong-Ze
    2010, 31(3):  456-462. 
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    In order to study the influence of main processing parameters of composite method on the surface morphology and superhydrophobicity, sandblasting and anodizing were combined to obtain micro-nano structure on the surface of aluminum alloy. After the treatment of fluorination, the surface showed excellent superhydrophobicity. The results demonstrate that the structure at micron level is fabricated by sandblasting while the structure at nanometer level is prepared by anodizing. However, superhydrophobic surface cannot be achieved just by a rough surface structure or the decoration of polymer with low surface energy, or the combination of the decoration and single microstructure or nanostructre. The combination of the decoration and micro-nano structure is the key to attain superhydrophobicity on aluminum alloy. Gas-trap is intercepted during the contact of the surface with water droplets, which effectively reduces contact area and heat exchange between the surface and water droplets. Condensation of water molecules and corrosion of sea water are therefore slow down, which explains the improvement of frost resistance and corrosion resistance to sea water of the superhydrophobic surface on aluminum alloy.

    Activity Analysis of T4 DNA Ligase Based on Linear Fluorescence Probes
    LIU Bin, YANG Xiao-Hai, WANG Ke-Min*, TAN Wei-Hong
    2010, 31(3):  463-467. 
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    A continuous, simple method with high specificity for analyzing T4 DNA ligase activity is introduced by monitoring the fluorescence change in real time. Linear DNA probes that can occur in fluorescent resonance energy transfer were used as templates and detecting probes in a homogeneous solution. The limit of detection of T4 DNA ligase was 1.2 U/mL, the KM and Kcat were (1.18±0.06) μmol/L and 40 min-1, respectively. In addition, the method was applied to investigate the influence of chemical drugs and metal ions on T4 DNA ligase activity. This method not only overcame the drawbacks of traditional radioactive assays, such as discontinuity and being time-consuming and complicated, but also can be applied to the activity assay, kinetics investigation and drug screening of other ligases.

    Application of Ionic Liquid-non Polar Solvent Microwave Extraction to the Study of the Chemical Constituents from Roots of Panax ginseng C. M. Mey.
    SUN Shuo, ZHAI Yu-Juan, SUN Ye, ZHANG Yu-Pu, LIU He, WANG Xing-Hua*, YU Ai-Min,
    2010, 31(3):  468-472. 
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    The ionic liquids(IL) was used as the microwave absorption medium and an ionic liquid-non polar solvent microwave extraction(ILNPSME) method was developed. The proposed method was applied to the extraction of the chemical constituents from the root of Panax ginseng C.M.Mey. The ILNPSME method was compared with solid microwave absorption medium-non polar solvent microwave extraction(SMMNPSME), polar solvent microwave extraction(PSME) and combined solvent microwave extraction(CSME) methods. PSME method is suitable to the extraction of polar constituents. The main chemical constituents obtained by SMMNPSME and ILNPSME methods are similar, which indicate that the IL can act as a microwave absorption medium and energy translation material. The proposed method has many advantages, such as short extraction time, simple operation and the use of green solvent, and is a suitable method to extract the chemical constituents from plant meterials.

    Determination of Hexabromocyclododecane in Textiles by Isotope Dilution-Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry
    MA Qiang*, BAI Hua, WANG Chao, XI Hai-Wei, MA Wei, ZHOU Xin, DONG Yi-Yang, ...
    2010, 31(3):  473-478. 
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    A comprehensive analytical method based on isotope dilution-ultra performance liquid chromatography-tandem mass spectrometry has been developed for the determination of α-,β-,γ-hexabromocyclododecane in textiles. Various textile samples were extracted under 10.3 MPa and 80 ℃ by accelerated solvent extraction method with two static cycles using hexane-acetone(1∶1, volume ratio) as the extraction solvent. The reconstructed solution was then cleaned up by ENVI-CarbⅡ/PSA solid phase extraction cartridge. Qualitative and quantitative analysis was carried out for the analyte under the MRM mode after the chromatographic separation on Waters ACQUITY UPLC BEH phenyl(50 mm×2.1 mm, 1.7 μm) column with methanol-water gradient elution. The limit of quantitation(LOQs) for α-,β-,γ-hexabromocyclododecane was 0.5 μg/kg. The mean recoveries at the three spiked levels of 0.5—10 μg/kg were 84.2%—93.7%, with the intra-day precision less than 10% and the inter-day precision less than 12%. This method is accurate, rapid, sensitive and adapt to the inspection of hexabromocyclododecane in textiles.

    Analysis of Oversulfated Chondroitin Sulfate in Contaminated Heparin by Precolumn Derivatization High Performance Liquid Chromatography
    ZHAO Xia*, LI Guang-Sheng, YU Guang-Li, WANG Jin-Xia, WANG Hao, SUN Shu-Meng, ZH
    2010, 31(3):  479-483. 
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    Based on the monosaccharide composition difference between heparin and OSCS, a simple and quantitative high performance liquid chromatography method has been established to determine OSCS present in contaminated heparin in this paper. After degradation of contaminated heparin by 3 mol/L trifluoroacetic acid(TFA) at 110 ℃ for 4 h, the monosaccharides were derivatized with 1-phenyl-3-methyl-5-pyrazolone(PMP), and separated on a C18 reversed phase column with a mobile phase of 0.1 mol/L phosphate buffer-acetonitrile(82∶18, volume ratio) at a column temperature of 25 ℃. The flow rate was 1.0 mL/min and the detection wavelength was 245 nm. There is a good separation between the peaks of monosaccharide-PMP derivatives of heparin and OSCS under the chromatographic conditions, and the two lots of contaminated heparin were found to contain 19.6% and 28.3% OSCS, respectively. This method is easy to apply and suitable for the determination of OSCS contaminant in heparin with high accuracy, reproducibility and sensitivity.

    Studies on Gallbladder Tissues, Tissue Plasma Membranes and Cell Lines by FTIR
    WANG Jian-Sheng*, ZHANG Jia, WU Wen-An, DUAN Xiao-Yi, WANG Si-Cen, ...
    2010, 31(3):  484-487. 
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    12 Cancer tissue samples, 14 inflammatory samples and 10 normal samples of gallbladder and their corresponding tissue membranes and gallbladder cancer cell lines were observed via FTIR. Compared to normal gallbladder tissue, the intensities of bands, related to lipids, at 2955, 2920, 2870, 2850 and 1740 cm-1, decreased for gallbladder cancer tissue, the intensity of bands, related to protein, at 1550 cm-1 decreased for gallbladder cancer tissue; the intensities of lipids bands and protein bands increased for gallbladder cancer cell line obviously; the intensities of lipids related bands also increased for gallbladder cancer tissue membrane; the intensity of band related to nucleic acid for gallbladder cancer tissue is similar to that for gallbladder cancer cell line and the band disappeared for gallbladder cancer tissue plasma membrane; the ratio of I1460/I1400 changed uniformity for tissue, cell line and tissue plasma membrane, which is smaller for cancer ones and bigger for normal ones. These results indicate that compared with those of gallbladder cancer tissue, the FTIR spectra changed a lot for gallbladder cancer cell lines and gallbladder cancer tissue plasma membrane. Protein and lipids relatively decreased in gallbladder cancer tissues but increased in gallbladder cancer cell line and gallbladder cancer tissue plasma membrane. The paper expounds FTIR variation for carcinogenesis from tissue, cell line and tissue plasma membrane. The ratio of I1460/I1400 changed uniformity for tissue, cell line and tissue plasma membrane, more studies may get a fine clinical diagnosis index.

    Extraction-oxidation Desulfurization of Fuel with Pyridinium-based Ionic Liquid
    ZHAO Di-Shun*, WANG Ya-Nan, DUAN Er-Hong, ZHANG Juan
    2010, 31(3):  488-491. 
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    The N-butyl-pyridinium-based ionic liquid [BPy]BF4 was prepared. The effect of extraction desulfurization on model oil with thiophene and DBT was investigated. Ionic liquid and hydrogen peroxide were tested in extraction-oxidation desulfurization to model oil. The results show that ionic liquid [BPy]BF4 is effective to remove sulfur content in model oil. The best conditions are V(IL)∶V(Oil)∶V(H2O2)=1∶1∶0.4, 55 ℃ and 30 min. The ratios of desulfurization to thiophene and DBT reached 78.5% and 84.3%, respectively, which were much higher than extraction desulfurization only with ionic liquid. In this condition, effect of desulfurization on FCC gasoline was also investigated, the desulfurization was 56.3%. Regenerate ionic liquid can be used more than 4 times.

    Structure Identification of an Acidic Pectin HAM-3-Ⅱb-Ⅱ from Avicennia Marina (Forsk.) Vierh.
    FANG Xu-Bo*, JIANG Bo, CHEN Xiao-E
    2010, 31(3):  492-496. 
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    Avicennia marina(Forsk.) Vierh. is one of the most widespread mangroves species of the world. The plant is widely used in the treatment of skin disease, ailments and wounds. Researchers have so far focused their attentions on its medicinal functions and chemical constituents. HAM-3-Ⅱb-Ⅱ, an acidic polysaccharides was obtained from Avicennia Marina by a series step of extraction, isolation and purification. The structure was studied by periodate oxidation, Smith degradation, partial hydrolysis and methylation analysis. The results show that HAM-3-Ⅱb-Ⅱ is an acidic pectin-type belong to RGI family, the backbone of main chain contained homogalacturonan fragments as “smooth regions” with 1,4-α-D-GalpA and rhamnogalacturonan segments as “hairy regions” with repeating unit of →4)-α-D-GalpA-(1→2)-α-L-Rhap-(1. T-, 1,6-, 1,3,6-, 1,4-, 1,4,6-D-Galp and T-, 1,2-, 1,3-, 1,5-, 1,2,5-, 1,3,5-Araf are linked as arabinogalactan type Ⅰ, arabinogalactan type Ⅱ, galactan and arabinan at the cite of O4 of Rha in the form of the side chain. Hence, HAM-3-Ⅱb-Ⅱ was considered a new bioactive pectin from Avicennia Marina.

    Multi-walled Carbon Nanotubes Induces Nuclear Factor-κB Activation in A549 Cells
    YE She-Fang*, WEN Wen, WANG Yi-Fang, LIN Cui-Lin, WU Yi-Hui, ZHANG Qi-Qing
    2010, 31(3):  497-501. 
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    The present study was undertaken to examine the effects of multi-walled carbon nanotubes(MWCNTs) on nuclear factor(NF)-κB activation in human A549 lung epithelial cells. Cultured A549 cells were stimulated with various concentrations of MWCNTs in the presence or absence of antioxidants. The intracellular generation of reactive oxygen species(ROS) was detected by means of flow cytometry analysis with a redox-sensitive fluorescent probe 2′,7′-dichlorfluorescein-diacetate. NF-κB activity was measured by electrophoretic mobility shift assay(EMSA). The protein levels of p65 and IκBα were assessed by Western blot analysis. Translocation of p65 into the nucleus was examined by immunofluorescence confocal microscopy. The results showed increased ROS and NF-κB activity in response to treatment of A549 cells with MWCNTs. MWCNTs stimulated nuclear translocation of the p65 subunit of NF-κB, IκBα phosphorylation in A549 cells. Treatment of A549 cells with antioxidants prior to adding MWCNTs resulted in a significant reduction in ROS generation, NF-κB activity, p65 translocation and IκBα phosphorylation in A549 cells. These results indicate that MWCNTs are able to induce NF-κB activation in A549 cells mediated by oxidative stress.

    Substrate-binding Sites of Human Selenium-containing Single Chain Abzyme by Quikchange Site-directed Mutagenesis
    SONG Jian, XU Jun-Jie, WEI Jing-Yan, YU Yang, SUN Wei-Guo, ZHANG Gui-Rong
    2010, 31(3):  502-506. 
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    Ala180 in site 1 and Ala44 in site 2 of human selenium-containing single chain abzyme Se-scFv-B3 were chosen to be mutated to serines, respectively, to study the substrate binding sites and the catalytic group of Se-scFv-B3 and to find the reason why the Se-scFv-B3 has lower catalytic activity based on the theoretical anticipation for the protein. After serine residue was reacted into secystins by chemical modification, the activity of the anterior one is about two times than that of the Se-scFv-B3, but the latter one did not offer a significant improvement. This indicated that site 1 was the predominant binding site for GSH, which was consistent with the foregoing conjecture and the results of energy calculation. In this study, the GPX activity of Se-scFv-B3 was improved and the site 1 preliminarily confirmed to be the substrate binding site based on both theoretical and experimental research. All of these observations will be useful for further work in this area.

    Stress Proteins of Gill Tissue in Patinopecten yessoensis Exposed to Cadmium Salt
    FANG Cai-Wang, HUANG Qing-Yu, LING Xue-Ping, KE Cai-Huan, HUANG He-Qing
    2010, 31(3):  507-513. 
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    The organelle ultrastructure in gill tissue was observed by transmission electron microscope(TEM) in Patinopecten yessoensis(PY), finding the pathological changes of gill filaments, nucleus and mitochondria in the tissue exposed to CdCl2(10 mg/L). The proteome of gill tissue in PY was perfectly separated by two-dimensional polyacrylamide gel electrophoresis(2D-PAGE), obtaining approximately 800 protein spots, and selecting 37 differential spots intimidated with cadmium salt in the gel. In addition, these differential proteins were identified by both matrix-assisted laser desorption/ionization-time of flight mass spectrometry(MALDI-TOF MS) and database searching. The results showed that 7 differential proteins tightly connected with the cadmium toxicity were considered to be up-regulated proteins such as heat shock protein 70 and β-amylase, and down-regulated proteins such as tropomyosin, actin and calcium activated nucleotidase 1. Moreover, transcriptional regulator Crp/Fnr family showed low expression, while ABC transporter showed high expression. We suggest that these differential proteins in part have strong potentials to be utilized as protein biomarkers for monitoring the pollution level of cadmium continuously and evaluating its risk to organisms.

    Tandem Synthesis of 1,3-Disubstituted 2,6-Dioxabicylco-[3.2.1]Octane Derivatives
    JIN Hui-Juan*, LU Jing, ZHENG Ning-Juan, WU Xue
    2010, 31(3):  514-519. 
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    A series of 1,3-disubstituted 2,6-dioxabicyclo[3.2.1]octane derivatives were obtained by a tandem reaction of 2-methyl-4-penten-1,2-diol and various aromatic aldehydes catalyzed by indium trichloride in high yields. These products were generated through sequential acetalization, Prins cyclization and intramolecular nucleophilic addition reactions in one pot. All of the new compounds were confirmed via 1H NMR, 13C NMR and MS analysis, and the configuration of product was determined by the NOESY experiment.

    Relationship of the Esterify Reaction Condition of 2,3,4-Trihydroxybenzophenone and 2,1-Diazonaphthaquinone-5-Sulfonyl Chloride and the Solubility of Its Product
    LIU Lu, ZOU Ying-Quan*
    2010, 31(3):  520-523. 
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    The esterify product of 2,3,4-trihydroxybenzophenone and 2,1-diazonaphthaquinone-5-sulfonyl chloride is widely used as the photoactive compound in photoresist. And its solubility is the critical factor in practical production. In this paper, several 2,3,4-trihydroxybenzophenone esterify 2,1-diazonaphthaquinone-5-sulfonyl chloride photoactive compounds were synthesized at different conditions and their solubility were different. High-pressure liquid chromatography was used to determine the retention time and integral area ratio of every esterified production. And through analyzing the stable configuration of photoactive compounds, the existence of triethylamine salt of diesterified product was thought to be the main factor that affects the solubility. Above all, the optimum synthetic condition of the photoactive compound is that acetone/water(85∶15, volume ratio) is applied as the solvent and Et3N is applied as the catalyst.

    Preparation and Sensing Performance to Formaldehyde Vapor of Quaterthiophene-Based Fluorescent Films
    LIU Tai-Hong, NIE Yun-Xia, HE Gang, ZHANG Yuan, DING Li-Ping, FANG Yu*
    2010, 31(3):  524-529. 
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    A fluorescent film was fabricated by chemical immobilization of 2,2′∶5′,2″∶5″,2″′-quaterthiophene(4T), which was employed as a sensing element, onto an amine-terminated glass wafer surface. It has been demonstrated that the fluorescence emission of the film is not stable in air, and it decreases along with increasing scanning time. However, the emission can be stabilized by treatment of the film under UV light irradiation in air. It was found with interesting that a new emission(λem=464 nm) appears after divulging the film in formaldehyde vapor. The intensity of the emission increases along with increasing the exposure time. Further experiments reveale that the fluorescence sensitization is fully reversible and highly selective. Common acids, ammonia and alcohols have little effect upon the fluorescent emission of the film. Therefore, it is anticipated that the film may be developed into a formaldehyde sensor. In addition, a possible sensing mechanism was proposed according to known photochemistry of oligothiophene and the experimental results from present study.

    Preparation and Characterization of CuPc(COOH)8-SA/CuTAPc-CS Bipolar Membrane
    CHEN Ri-Yao, CHEN Zhen*, ZHENG Xi, CHEN Xiao, NI Shi-Mao, YOU Chun-Man
    2010, 31(3):  530-536. 
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    The sodium alginate(SA) cation layer and the chitosan(CS) anion layer were modified by copper octocarboxyphthalocyanine[CuPc(COOH)8] and copper tetraaminophthalocyanine(CuTAPc) to prepare the CuPc(COOH)8-SA/CuTAPc-CS bipolar membranes(BPM). The ion exchange capacity and hydrogen ion transmigration rate of the CuPc(COOH)8-SA cation exchange membrane, and the ion exchange capacity and hydroxide ion transmigration rate of the CuTAPc-CS anion exchange membrane were increased. The water splitting rate at the interlayer of the CuPc(COOH)8-SA/CuTAPc-CS BPM was promoted. In comparison with the Fe-SA/mCS BPM modified by Fe3+, the membrane impedance, IR drop and swelling degree of the CuPc(COOH)8-SA/CuTAPc-CS BPM all obviously decreased. The IR drop of the CuPc(COOH)8-SA/CuTAPc-CS BPM was 0.9 V at a higher current density of 120 mA/cm2.

    Molecular Dynamics Simulation of the Corrosive Medium Diffusion Behavior Inhibited by the Corrosion Inhibitor Membranes
    LIU Lin-Fa, LIU Jin-Xiang, ZHANG Jun*, YOU Long, YU Li-Jun, QIAO Gui-Min
    2010, 31(3):  537-541. 
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    The diffusion behavior of four corrosive media(H2O, H3O+, HS-, and Cl-) in membranes formed by six 1-(2-hydroxyehtyl)-2-alkyl-imidazoline compounds with various alkyl chain lengths was investigated with molecular dynamics(MD) simulation. The simulation was performed by calculation of diffusion coefficients of corrosive particles in the membranes, fractional free volumes of the membranes, and the interaction energies between particles and membranes. And the microscopic inhibition mechanism of the membranes for diffusion of corrosive particles was explored. The calculated results showed that all the membranes formed by corrosion inhibitor molecules can effectively prevent the corrosive particles from diffusing to the metal surface, and thus inhibit or delay the corrosion process. With the elongation of alkyl chain length, the inhibitor membranes showed increased capacity for prevention of diffusion of corrosive particles. While membranes formed by identical molecules showed more preferable inhibition performance for cations and anions(H3O+, HS-, and Cl-) than that for neutral molecule(H2O).

    Molecular Dynamics Simulation on the Melting Point of Ionic Liquid [emim]Br
    FENG Hai-Jun, ZHOU Jian* , QIAN Yu
    2010, 31(3):  542-547. 
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    The melting point of ionic liquids being around room temperature is the key of applications of ionic liquids. In this work, molecular dynamics simulation is carried out to study the melting point of ionic liquid [emim]Br by the direct heating and NVE ensemble approaches, to find a suitable method in preclicting the melting point of ionic liquids. In the direct heating method, the variations of the Nonbonding energy(E), density(ρ), radial distribution function(RDF), diffusion coefficient(D) and translational order parameter(TOP) of [emim]Br with temperature are analyzed to determine the melting point; whereas in the NVE ensemble method, a co-existing solid-liquid system is achieved to judge the melting point. For these two methods, the direct heating method can cause superheating of the system, while the NVE ensemble method can overcome this problem. In predicting melting points of ionic liquids, the NVE ensemble method should be preferred.

    Catalytic Conversion of Fructose to 5-Hydroxymethylfurfural by Ion-exchange Resin in Ionic Liquid
    DU Fang, QI Xin-Hua*, XU Ying-Zhao, ZHUANG Yuan-Yi
    2010, 31(3):  548-552. 
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    An efficient process for the dehydration of fructose to 5-hydroxymethylfurfural(5-HMF) in ionic liquid 1-butyl-3-methyl-imidazolium chloride([BMIM]Cl) in the presence of ion-exchange resin was deve-loped. A 5-HMF yield of 78.0% was achieved in 10 min at 100 ℃, where the reaction time required was much lower than that reported in previous works for converting fructose to 5-HMF. No remarkably decrease in 5-HMF yield occurred for initial fructose concentrations up to 20%(mass fraction). The ionic liquid and ion-exchange resin could be recycled and exhibited constant activity for 9 successive trials.

    Theoretical Study on Structures and UV-Vis Spectra of Macrocyclic Thiophene Derivatives
    HUANG Shuang, REN Ai-Min*, LI Zhuo, ZHAO Yang, MIN Chun-Gang
    2010, 31(3):  553-558. 
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    The theoretical studies on macrocyclic thiophene derivatives(C[3T_DA]5) in different symmetries(C1, C5, C5v) were carried out with density functional theory(DFT) and Time-depended density functional theory(TDDFT) methods. The stable molecular structures were obtained by DFT. And then the UV-Vis spectra of C[3T_DA]5 derivatives were calculated base on the optimized structures. The results show that C[3T_DA]5-Bu with C5 and C5v symmetries are more stable. The calculated spectra of C[3T_DA]5-Bu with C5 is in well agreement with the experimental values. For macrocyclic thiophene(C[3T_DA]5) derivatives, both molecular symmetry and the substituent with the same property influence the stability of the molecular structure.

    Thermodynamic Characteristics and Direct AFM Observation of Binary Mixtures of PE with Stearic Acid and Octadecanol
    CHANG Yi-Guang, SUN Run-Guang*, HAO Chang-Chun
    2010, 31(3):  559-565. 
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    Thermodynamic characteristics of binary mixtures of phosphatidylethanolamine(PE) with stearic acid(SA), and octadecanol(OD) formed at the air/water were investigated in terms of surface pressure(π)-area(A) relation. On the basis of the data, the thermodynamic parameters of compression modulus(CS-1), excess mean area per molecule(Aex), and surface excess Gibbs energy(ΔGex) were calculated. We can quantitatively analyze the molecular interactions in the mixed monolayers. The experimental results showed that the various molar ratios of the two components, PE and SA, PE and OD, influenced thermodynamic parameters. The thermodynamic analysis indicated that the thermodynamic parameters[excess molecular area(Aex), surface excess Gibbs energy(ΔGex)] of PE/SA and PE/OD were obtained maximum negative deviation from the ideal behavior at XSA=0.2, 0.8 and XOD=0.2, suggesting an attractive interaction between molecules. The other way round, the molar ratios of OD at XOD=0.2, 0.4, 0.6, were found to be conspicuously maximum positive, suggesting an intermolecular repulsion. The AFM images of mixed PE/SA and PE/OD monolayers are in favor of the theoretic analysis of the thermodynamic characteristics.

    Study on Self-assemble of Rod-rod Diblock Copolymers with Self-consistent Field Lattice Model
    HAN Xiang-Gang, ZHANG Cheng-Xiang*
    2010, 31(3):  566-570. 
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    The self-assemble behavior of the rod-rod diblock copolymers was studied by means of self-consistent field lattice model, and the results were compared with the coil-rod diblock copolymers. It is shown that the order-disorder transition point of rod-rod diblock copolymers is lower than that of coil-rod diblock copolymers. Four stable structures are obtained, i.e., overlapping cylinders, cylinders, lamellae and zigzag lamellae. The overlapping cylinders and cylinders occur only in the region near the order-disorder transition curve. Lamellae are observed in the region above the order-disorder transition point. However, the stable zigzag lamella structure occupies a big region corresponding to the strong interaction between two different components of diblock copolymers.

    Preparation and Capacitive Performance of TSA-PANI/PNR Composites by Emulsion Polymerization
    XU Hai-Li, CAO Qi*, WANG Xian-You, CHEN Quan-Qi, LIAO Li
    2010, 31(3):  571-576. 
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    Using paratoluenesulfonic acid(TSA) as dopant and emulsifier, and ammonium persulfate(APS) as initiator, the composites of polyaniline, TSA and neutral red(TSA-PANI/PNR) were synthesized by emulsion polymerization. The structure and morphology of the composites were investigated by X-ray diffraction(XRD) and scanning electron microscopy(SEM). Symmetric redox supercapacitor was assembled with TSA-PANI/PNR as active electrode material and an l mol/L H2SO4 aqueous solution as electrolyte. The electrochemical performances of the supercapacitors were characterized by galvanostatic charge-discharge, cyclic voltammetry and A.C. impedance spectroscopy. The results show that TSA-PANI/PNR composite exhibits outstanding electrochemical capacitor performance compared with TSA/PANI electrode. The specific capacitance measured from cyclic voltammetry is 1350 F/g for TSA-PANI/PNR composite material and 1038 F/g for TSA/PANI at 1 mV/s scan rate; the initial specific capacitance of the TSA-PANI/PNR supercapacitor is about 348 F/g at a constant current of 5 mA. Meanwhile, the retention of the capacitance after 1000 charge-discharge cycles was 87%.

    Computer Simulations of Cross-linking Reactive Mechanism of Polyacrylamide/resol
    NI Tao, HUANG Guang-Su*, ZHENG Jing, GAO Pin, CHEN Meng-Meng
    2010, 31(3):  577-582. 
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    The polyacrylamide gel crosslinked by the prepolymer of phenol and formaldehyde is a kind of chemical flooding agent with excellent temperature and salt resistant properties during the enhanced oil reco-very(EOR). But its cross-linking reactive mechanism is not clear for a long time. In this article, the cross-linking mechanism of polyacrylamide/resol was studied by density-functional theory, molecular mechanic and molecular dynamic methods base on computer simulation. Firstly, propionamide(PA) and 2,4,6-trihydroxy-methylphenol(THP) were looked as model compounds, Gibbs free energy(ΔG) and energy of barrier for transition states involved were calculated by density-functional theory. The results showed that both PA/THP and THP/THP condensation reactions can happen from thermodynamics, while their reaction energies of barrier are different. The energy of barrier for the ortho-position condensation reaction of PA/THP is 64.54 kJ/mol, lowest among the reactions. Secondly, base on the above conclusions, the cross-linking structure of PA/THP was constructed, and found that the reacted —CONH2 is occupied 60% on the total —CONH2 according to the account. At last, the crosslinked products were characterized by X-ray photoelectron spectroscopy. The results show that the numbers ratio of —NH— and —NH2 reached 1.5∶1 in the final products, and validated the results of computer simulation.

    Optical Waveguide Based on Crystalline Organic Nanobelts of 1,3-Diphenyl-2-pyrazoline
    CHEN Wei, FU Hong-Bing*, YAO Jian-Nian
    2010, 31(3):  583-587. 
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    1D single-crystalline 1,3-diphenyl-2-pyrazoline(DP) nanobelts were prepared by the modified repercipication method with mixed poor solvents. The thickness of DP belt can be controlled at 200 nm with the width at 2 μm and the length at tens of microns. XRD and SAED indicate that the DP nanobelt grow along the [100] direction due to the π-π stacking of DP molecule. The steady-state absorption and fluorescence spectra indicate that DP nanobelts have unique optical properties which are different from the monomers and the bulk crystals. Furthermore, we find the belts are able to absorb the excitation light and propagate the PL emission towards the tips. The results presented in this paper provide useful information for the design and fabrication of optical waveguides from molecular materials.

    Hydrothermal-template Route to Carbon Nanotubes and Its Application in Lithium-ion Battery
    FENG Hong-Bin, WEN Zhen-Hai, LI Jing-Hong*
    2010, 31(3):  588-591. 
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    A facile method, combining hydrothermal method with the template technique, was developed to synthesize open-ends carbon nanotubes(CNTs). X-ray diffraction and electron microscopy analysis techniques were used to characterize the samples. The electrochemical properties of the as-prepared CNTs as anode materials for lithium battery were studied by galvanostatic method. Results showed that the as-prepared CNTs displayed higher capacity and superior cycle performance in comparison with the multiwalled carbon nanotubes(MWNTs).

    Synthesis and Characterization of New Organic-inorganic Based Catalyst——Effect of Steric Hindrance on Catalytic Performance
    SHAO Yan-Qiu, WANG Hong-Su, GUAN Jing-Qi, YU Xiao-Fang, LIU Heng, KAN Qiu-Bin*
    2010, 31(3):  592-596. 
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    Two different hybrid secondary amine-functionalized mesoporous SBA-15 silica materials were synthesized by a direct synthesis method. X-ray diffraction(XRD), N2 physisorption and transmission electron micrographs(TEM) showed that the prepared materials possessed similar mesoporous structure to pure siliceous SBA-15. Thermogravimetric analysis(TGA), FTIR and elemental analysis of nitrogen indicated the successful introduction of corresponding organic functional groups into mesoporous materials. In the Aldol condensation of acetone with 4-nitrobenzaldehyde, two different hybrid secondary amine-functionalized mesoporous materials displayed enhanced catalytic performance in comparison to primary amine-functionalized materials. The possible reason is that the presence of organic functional groups with larger steric hindrance led to the enhanced catalytic performance of basic amino groups.

    Water-soluble Light-emitting Nanoparticles Prepared by Non-covalent Bond Self-assembly of Functionalized Poly(p-phenyleneethynylene)s and Poly(acrylic acid)
    LU Xiao-Mei, FAN Qu-Li, ZHANG Guang-Wei, PU Kan-Yi, HUANG Wei*
    2010, 31(3):  597-601. 
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    A series of water-soluble light-emitting nanoparticles were prepared from functionalized poly(p-phenyleneethynylene)s(PPE) and water-soluble poly(acrylic acid)(PAA) by non-covalent bond self-assembly. Their structures and optoelectronic properties were investigated through dynamic light scattering(DLS), UV and PL spectroscopy. These results show a correlation between the size of the nanoparticles so formed and the mass ratio of PAA/PPE used. It was also found that after formation of nanoparticles in aqueous solution, the hydrophobic PPE chains tended to form π-interchain aggregation, just as it did in the solid state.

    Synthesis and Electroluminescent Properties of Novel Hyperbranched Poly(fluorene-co-pyrido[3,2-b]pyrazine)s
    ZHOU Peng*, WANG Jing-Yu, LI Xiao-Dong
    2010, 31(3):  602-606. 
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    Several novel hyperbranched conjugated polymers with pyrido[3,2-b]pyrazine as core and 9,9-dioctylfluorene as branches were synthesized based on a novel tribrominated pyrido[3,2-b]pyrazine. The hyperbranched polymers exhibit good solubility in common organic solvents such as toluene and tetrahydrofuran. The polymer light-emitting devices with architecture of ITO/PEDOT/polymer/Ca/Al were fabricated by utilizing the prepared copolymers as emissive layer. The device with PFPQ-2 as active layer exhibited very efficient blue electroluminescence with the maximal external quantum efficiency of 1.29% and maximal brightness of 1173 cd/m2, with CIE coordinates of (0.16, 0.11).

    Nonisothermal Crystallization Kinetics of P(BHB-CL)
    ZHU Ming, LI Ya-Peng, TANG Jun, WANG Shu-Wei, WANG Jing-Yuan*
    2010, 31(3):  607-611. 
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    The nonisothermal crystallization behavior of biocompatible and biodegradable polyester P(BHB-CL) was investigated via differential scanning calorimetry(DSC). Avrami equation, Ozawa approach, and Mo approach were adopted to study the nonisothermal crystallization of P(BHB-CL), and activation energy value of P(BHB-CL) was determined according to the Kissenger method. The results show that Mo approach can be successfully applied to analyze the nonisothermal crystallization process of P(BHB-CL).

    Effect of Solvent on the Enzyme Catalysis Biodegradation of PBS with High Molecular Weight and Its Modified Copolymer
    ZHANG Min*, DING Ming-Liang, ZHANG Ting, YANG Jin-Ming
    2010, 31(3):  612-615. 
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    PBS and PBS/CHDM copolymers with high molecular weight were degraded via immobilized lipase in different polar solvents, such as toluene, tetrahydrofuran, and mixed solvent of toluene and tetrahydrofuran, respectively. The degradation products were analyzed by mass spectrometry(MS). The chemical structure was characterized by FTIR. And the molecular weight was determined by GPC. Under the function of immobilized lipase, PBS with Mn=100000 can be degraded to Mn=40000 in toluene and to Mn=14000 in tetrahydrofuran system. While in mixed solvent of toluene and tetrahydrofuran, PBS and PBS/CHDM with Mn more than 100000 can be degraded to below Mn=1000. The products almost are monomer, 1—4 cyclic oligomer, liner oligomer and a small amount of linear oligomer. The existence of a small amount of water has a certain impact on enzymatic reaction.

    Preparation of Nanocrystal/Polymer Composite Monolayer for TEM Characterization
    YAO Xi, DONG Feng-Xia, WU Jie, NING Yang, ZHANG Hao*
    2010, 31(3):  616-622. 
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    A facile and feasible method for preparing transmission electron microscope(TEM) specimen was reported by combining the phase transfer of aqueous nanocrystals(NCs) and the formation of polymer-supported free-standing films on water/air interface. In comparison to traditional TEM specimen preparation method-especially for aqueous systems, the quality of TEM images is greatly improved due to better particle dispersion. The TEM images show that through optimizing a few preparation factors, distinct particle dispersion and clear images of individual particles can be observed. In addition, we apply this strategy to other NCs to prove that this method is universal for preparing TEM samples of various NCs, such as Au, Ag, CdS and CdTe.

    Preparation and Characterization of Polymeric Precursor for Boron Nitride Fibers
    DENG Cheng, SONG Yong-Cai*, WANG Ying-De, LI Yi-He, LEI Yong-Peng
    2010, 31(3):  623-628. 
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    Based on B-trichloroborazine(TCB) with boron-nitrogen ring structure, the monomer was synthesized by substitution reaction with different molar ratio of propylamine/isopropylamine, then the corresponding polyborazine was obtained through thermal polymerization. The chemical component and structure of polyborazine were analyzed, and the influence of different propylamine/isopropylamine molar ratio on the polyborazine properties and spinnability were examined. The results indicate that polyborazine precursor prepared at 150 ℃ for 10 h and propylamine/isopropylamine molar ratio 2∶1, could possess nearly linear molecule skeleton and be prone to melt spinnability. When melt at 90 ℃, the precursor fibers are prepared with average diameter 10—20 μm and BC1.27N1.52Hx structure. After curing process and sintered in NH3 at 1200 ℃, the near-stoichiometric BN fibers was obtained, which proved this precursor is apt for preparation of BN fibers.