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Table of Content

    10 August 2011, Volume 32 Issue 8
    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.8(2011)
    2011, 32(8):  0. 
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    Letters
    New Buffer Interlayer for Improving Device Performances of Organic Photovoltaics
    LIANG Li-Zhi, WU Ying, SHI Jing-Long, KANG Bo-Nan*
    2011, 32(8):  1661-1663. 
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    The effects of polytetrafluoroethylene(PTFE) on poly(3\|hexylthiophene)∶phenyl-C61-butyric acid methyl ester(P3HT∶PCBM) based organic photovoltaic(OPV) devices were investigated by inserting thermally evaporated PTFE films between indium-tin-oxide(ITO) and poly(3,4-ethylenedioxythiophene)∶poly(styrene-sulfonate)(PEDOT∶PSS) layers. Significant improvement in terms of open-circuit voltage, short-circuit current, and thereby in its commensurate power conversion efficiency is  compared to devices without a PTFE layer. The OPVs performance enhancement is attributed to the formation of an artificial dipole layer forming  from the rich, negatively charged fluorine that facilitates the hole extraction process.
    Synthesis and Characterization of Novel Electroactive Polyamide with Azo Groups in the Backbone
    HE Li-Bing, BIAN Xiu-Jie, CHAO Dan-Ming, LI Zhi-Liang, LI Ye, WANG Ce, LIU Xin-Cai*
    2011, 32(8):  1664-1666. 
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    An alternating copolymer, electroactive azo polyamide was prepared by oxidative coupling polymerization and its characteristics were systematically studied. The polyamide showed both electroactivity and photoactivity. A large enhancement in the dielectric constant of the polymer was achieved utilizing the method of doping the conjugated oligoaniline segments with hydrochloric acid.
    Synthesis and Characterization of Novel Multi\|temperature Responsive Glycopolymers
    LI Fan, PEI Dan-Feng, SHI Tong-Fei*, ZHANG Guo*
    2011, 32(8):  1667-1669. 
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    Since the existence of sugar groups, glycopolymers can mimic the biological functions of glycolipids and glycoproteins. Recent developments in precision polymerization have made it possible to design glycopolymers of controlled structure and chemical composition. Glycopolymers exhibit sophisticated functions have attracted more and more attentions. Novel glycopolymers containing polyelectrolyte were successfully synthesized by atom transfer radical polymerization. The architectures of the glycopolymers were confirmed by 1H NMR and GPC. DLS and zeta-potential tests were also performed to investigate the solution properties of the glycopolymers. We found that the novel glycopolymers exhibit multi\|temperature responsive property.
    Preparation and Properties of the POSS-containing Composites as Proton Exchange Membranes
    LI Xue-Feng, SONG Yang, ZHU Ming, LIU Bai-Jun*, JIANG Zhen-Hua
    2011, 32(8):  1670-1672. 
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    A naphthylene-containing sulfonated polyaryletherketone(SPAEK) was synthesized as a matrix. A polyazomethine having naphthylene, ether and ketone linkages(PAM) was selected as a molecular-enhanced component. Aimed at improving the properties, a ternary-composite membrane was constructed by incorporating sulfonic acid-functionalized polysilsesquioxane through a sol-gel processing. The morphology of the membranes was studied by SEM. Compared with plain SPAEK and SPAEK/PAM blend, the ternary\|composite membranes show higher proton conductivity and selectivity.
    Articles
    Synthesis and Formation Mechanism of NiO@Al2O3@TiO2 Coaxial Trilayered Submicrocables by Electrospinning
    SONG Chao, DONG Xiang-Ting*, WANG Jin-Xian, LIU Gui-Xia
    2011, 32(8):  1673-1679. 
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    [Ni(CH3COO)2+PVP]@[Al(NO3)3+PVP]@[Ti(OC4H9)4+CH3COOH+PVP] composite cables have been fabricated through modified electrospinning equipment via electrospinning technique. NiO@Al2O3@TiO2 coaxial trilayered nanocables were obtained by calcination of the relevant composite cables. The samples were characterized by thermogravimetric-differential thermal analysis (TG-DTA), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM). Results showed that the samples are NiO@Al2O3@TiO2 coaxial trilayered nanocables. The core layer is NiO, and its diameter is ca. 137.83±8.85 nm. The middle layer is Al2O3, and its thickness is ca. 215.11±8.66 nm. The outer layer is TiO2, the thickness is ca. 156.26±16.50 nm. Formation mechanism of NiO@Al2O3@TiO2 coaxial trilayered nanocables was preliminarily proposed.
    Synthesis and Luminescent Properties of  CaF2 and CaF2∶Yb3+ Mulberry-like Nanostructures
    LIU Ji-Hong, HOU Su-Ying, XU Wei, LIU Xian-Chun, YU Xiao-Dan, LIU Bo, SUN Xiu-Juan, XING Yan*
    2011, 32(8):  1680-1683. 
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    Highly uniform and well-dispersed mulberry-like nanostructures of CaF2 were synthesized by a hydrothermal method without the assistance of any templates or surfactants. The 3D hierarchical CaF2 mulberry-like nanostructures with size about 450nm are assembled by numerous nanocrystals. X-Ray diffraction, scanning electron microscopy and transmission electron microscopy were used to characterize the samples. The formation process of the nanostructures was investigated by time dependent experiments. In addition, the luminescence of Yb3+-doped CaF2 nanostructures were discussed and of particular interest for various photonic applications in ionic crystals and glasses.
    Synthesis and Characterization of   Lamellar Aluminosilicate MAS-20
    XU Di-Ou, WANG Run-Wei, FU Wei-Wei, WANG Ying, ZHANG Zong-Tao*, QIU Shi-Lun
    2011, 32(8):  1684-1687. 
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    High ordered nano-lamellar molecular sieves have been prepared by a co-assembly process of surfactant and structure-directing agent in an hydrothermal system. Experimental data have demonstrated that CTAB can form lamellar micelle by the self-assembly when its concentration in aqueous solution achieves CMC level, leading to the formation of nano-lamellar molecular sieves. The products have homogeneous flaky morphology with a dimension of about 20 nm and possess high ordered microporous structures.
    Synthesis of Monodisperse Fe3O4 Magnetite Schistic Hexagonal Nanocrystals by Polyol Reduction Method
    LI Fang, DU Xue-Yan*, YANG Rui-Cheng
    2011, 32(8):  1688-1694. 
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    Based on the cooperation of surfactants, metal precuesor and liquid environment, monodisperse nanoparticles of hexagonal Fe3O4 magnetite were prepared by 1,2-dodecanediol reduction of iron acetylacetonate[Fe(acac)3] in the presence of oleic acid and oleylamine. The effects of surfactants   reductant on the particles' size and morphology were examined. TEM results show that the use of oleic acid and oleylamine suppressed the growth of magnetite nanoparticles and made the particles size reduced from 24.2 nm to 7.6 nm; a variety of particles morphology arose and schistic hexagonal Fe3O4 nanoparticles were achieved. Magnetic properties show that the as-synthesized Fe3O4 nanoparticles possess features of high saturation magnetization Ms(88 A·m2/kg) and zero remanent magnetization Mr, facilitating their use as magnetic tags for biomedical applications.
    Solvothermal Synthesis and White Up\|conversion Luminescence Properties of La0.789Yb0.20Ho0.001Tm0.01F3 Nanocubes
    DE Gejihu1,2*, SI Qin1, MENG Genlabuqi1
    2011, 32(8):  1692-1696. 
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    La0.789Yb0.20Ho0.001Tm0.01F3 nanocube was synthesized through a hydrothermal method. The crystal structure, composition and morphology of the sample were characterized using X-ray powder diffraction, electron microscopy, high-resolution transmission and energy dispersive X-ray spectroscopy measurements. At the same time, the up-conversion spectra of the sample were measured using F-4600 fluorescence spectrophotometer with single-wavelength diode laser (980 nm) at room temperature. The results show that emissions of red, green and blue were observed for the synthesized sample. The red, green and blue emissions were attributable to 1G4 → 3F4 (or 5F5 → 5I8), 5F5 → 5I8, and 1G4 → 3H6 transitions, respectively, the combination of which resulted in a white emission. The calculated color coordinates demonstrate that white the light can be achieved in a wide range of pumping powers. The sample obtained in the present work is believed to have potential applications in the field of displays, lasers, photonics, and biomedicine.
    Effects of Heat-treatment Condition on Structure and Magnetic Properties of BaSm0.3Fe11.7O19 Ferrite Fibers
    MENG Xian-Feng*, WANG Yun-Long, SHEN Xiang-Qian
    2011, 32(8):  1697-1702. 
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    The BaSm0.3Fe11.7O19 ferrite fibers with diameters below 1μm were successfully fabricated by sol-gel method from starting reagents of metal salts and citric acid. The precursor and calcined products were characterized by means of thermogravimetric and differential thermal analysis (TG-DSC), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometer (VSM). The results showed that the pure BaSm0.3Fe11.7O19 ferrite phase was basically formed after calcined at 750 ℃ for 1 h. With the increase of calcination temperature and holding time, the grain growth take place, the fiber surface became much rougher and plate structure become more and more obvious. At the same time, the saturation magnetization (Ms) of BaSm0.3Fe11.7O19 ferrite fibers monotonously increased, while the coercivity (Hc) initially increased, reached a maximum value of 459.2 kA/m at grain size of 58.4 nm, and then decreased with further grain growth, indicating that the single-domain critical size of BaSm0.3Fe11.7O19 ferrite fibers may be around 60 nm. The difference of Ms and Hc measured at 300K and 77K are attributed to the surface spin order nanocrystalline BaSm0.3Fe11.7O19 ferrite.
    Hydrothermal Synthesis of ZnO Crystallite with Multi-morphology on Zinc Foil and Crystal Growth Mechanism
    XU Xiao-Hong*, ZHANG Min, WU Jian-Feng, LIU Shu-Jie, FANG Bin-Zheng, LENG Guang-Hui
    2011, 32(8):  1703-1708. 
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    Zinc pieces were adopted as raw material to provide nourishment for ZnO crystal growth, ZnO crystal has synthesized on the zinc foils through hydrothermal method. Distilled water, NH3?H2O, NaOH and butyl amine were used as mineralizer to keep hydrothermal environment as alkaline. The results show that ZnO crystal growth habit affect by concentration; molecular structure and solvent saturated vapor pressure of mineralizer remarkably, make the final crystal morphology difference. In the study, the author also speculated on the feature of crystal morphology by XRD data of diffraction intensity of crystal plane and validated by scanning electron microscope (SEM). Moreover, crystal growth mechanisms of ZnO crystallite on the zinc foil were discussed in detail.
    Kinetics Study of Chiral Recognition Between Protein and Amino Acid Enantiomers by Surface Plasmon Resonance
    SHEN Gang-Yi*, GAO Yan, DAI Dong-Sheng*, CUI Jian, LIU Yu-Ming, PEI Ling-Peng
    2011, 32(8):  1709-1713. 
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    Based on surface plasmon resonance technique, a new method has been developed for efficiently recognizing the chiral discrimination between the small molecule L- and D-amino acid enantiomers without any labeling. Bovine serum albumin and lysozyme were selected as chiral recognition probes, and phenylalanine and tryptophan including L-, D- four enantiomers were used as analytes. While six different concentrations of each amino acid enantiomers interacted with two proteins probes at the same time, the binding kinetics informations of them were obtained in real time. The results showed that proteins had excellent chiral recognition capability to L- and D- enantiomers. The chiral discrimination between each of amino acid enantiomers could be recognized obviously by comparison either their binding kinetics parameters or sensorgram. The results also indicated that the affinity of protein and L-amino acid was bigger than that of protein and D-amino acid.
    Extrative Electrospray Ionization Tandem Mass Spectrometry of Apigenin
    DING Jian-Hua, WANG Xing-Xiang, ZHANG Hui, PAN Su-Su, LUO Ming-Biao, LI Jian-Qiang, CHEN Huan-Wen*
    2011, 32(8):  1714-1719. 
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    The extractive electrospray ionization tandem mass spectrometry (EESI-MSn) of apigenin was studied using both positive and negative ion modes. The mechanism of the fragmentation of apigenin was discussed in detail based on the experimental collision-induced dissociation (CID) data recorded in these experiments, and was confirmed by the ESI-MS. The study is useful for the rapid determination of trace amount of apigenin in complex matrix by EESI-MS.
    Determination of Schizandrin A in Body Fluids and Cell Culture Media by Excitation-emission Matrix Fluorescence Coupled with Second-order Calibration
    ZHANG Xiao-Hua, WU Hai-Long*, WANG Jian-Yao, YU Ru-Qin
    2011, 32(8):  1720-1726. 
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    Schizandrin A, which has been shown to have anticarcinogenic activity and hepatoprotective effect is the active schisandra lignan from a traditional chinese medicine schisandra chinensis (wuweizi). A novel method for quantitative analysis of schizandrin A in human plasma samples, urine samples and cell culture media was proposed by combining excitation-emission matrix fluorescence spectra with second-order calibration method based on self-weighted alternating trilinear decomposition algorithm (SWATLD). Satisfactory results have been achieved, fully exploiting “second-order advantage”. The average recoveries of schizandrin A in human plasma samples, urine samples and cell culture media obtained by using SWATLD with N=2 are (100.4±1.6)%,(100.5±6.3)% and(103.6±4.5)%, respectively. It proved that SWATLD based second-order calibration methodologies can be feasible to directly quantify the content of schizandrin A in human plasma samples, urine samples and cell culture media. It could be applied to quantitative analysis of schizandrin A even in the presence of unknown interferences, without time-consuming and complicated pretreatment.
    Preparation and Binding Properties in Aqueous Media of Cholic Acid Imprinted Polymers
    XU Zhi-Feng*, KUANG Dai-Zhi, WEN Ge, ZHANG Fu-Xing, WANG Jian-Qiu, LI Jun-Hua
    2011, 32(8):  1727-1732. 
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    In order to achieve effective imprinting in aqueous media, a cholic acid imprinted polymer (MIP1) was prepared by the combined use of bismethacryloyl-β-cyclodextrin (BMA-β-CD) and 2-(diethylamino) ethylmethacrylate (DEAEM) as functional monomers. The recognition ability of MIP1 for the template in aqueous media was evaluated by equilibrium binding experiments. The results indicated that the imprinted polymer MIP1 obviously exhibited a higher selectivity for cholic acid than the cholic acid imprinted polymers (MIP2 and MIP3) using only BMA-β-CD or DEAEM as a functional monomer. The specific binding capacity (ΔCP) and imprinting factor (IF) of MIP1 were 38.81 μmol/g and 2.46, respectively. It demonstrated that the combination of hydrophobic effect and electrostatic interaction in molecular imprinting was essential for the improvement of the selective ability of the imprinted polymer in aqueous media. In addition, hydrophobic effect was confirmed to be the important force for driving the template molecules into the cavities created by the imprinting process.
    Analysis of Pigments by Nano\|particle Modified Paper Chromatography
    ZHOU Cong, YUAN Ping, CHEN Bo*, YAO Shou-Zhuo
    2011, 32(8):  1733-1736. 
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    Rhodamine B, Sudan I, and Sudan IV were used as model compounds to investigate the different separation characteristics of filter paper which had been modified by silica nanoparticles and silylation reagents. The effects of different nanoparticles size, carbon chains length of silylation reagents and treated methods on the separation characteristics of modified filter paper has been studied. The results showed that, the paper modified by smaller silica nanoparticles size, longer carbon chains length, owned better separation performance. The modified filter paper has the similar retention behavior with reversed-phase column chromatography.
    Determination of Sequence-specific DNA Related to the Avian Influenza H1N1 Virus by Fluorescent Probe Ru(phen)2(dppx)2+
    ZENG Guo-Ping, XIANG Dong-Shan, CAI Jin-Zhang, HE Zhi-Ke*
    2011, 32(8):  1737-1743. 
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    The determination of sequence-specific DNA related to the avian influenza H1N1 virus was realized with the molecular 'Light Switch' complex of Ru(phen)2dppx2+. There is no or weak fluorescence between the Fluorescent Probe Ru(phen)2dppx2+ and ssDNA probe. However, the luminescent enhancement was observed in presence of target DNA resulted from the intercalation of the complex into the hybrids between probe DNA and target DNA. Under the optimum conditions, the linear range of the DNA related to the avian influenza H1N1 virus is 9.3×10-10~7.4×10-8 mol/L, the calibration curve is y = 3.3829x + 8.3948, R2 =0.9982, and the detection limit is 5.3×10-10 mol/L. This method is simple, rapid, sensitive and selective.
    Synthesis and Magnetic Properties of Novel Nickel(Ⅱ) and Terbium(Ⅲ)-Dipyridyl Coordination Bridged Polysilsesquioxane
    WU Lian-Bin, Lü Zhi-Qing, CHEN Qiu, CHEN Li-Min, JIANG Jian-Xiong*
    2011, 32(8):  1744-1749. 
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    A novel bipyridine-bridged polysilsesquioxane was synthesized and its metal-coordination polymers were prepared by sol-gel technology from bipyridine-bridged silsesquioxane and the nickle salt (Nickel acetate) or terbium salt (Terbium chloride) under the catalysis of diluted hydrochloric acid. The structures of polymer and metal-coordination polymer were verified with infrared ray spectrometry, ultraviolet spectrometry and elemental analysis. Meanwhile, the scanning electron microscope (SEM) results suggested that the homogeneous and spherical particles were formed. Finally, The magnetic properties of the two coordinated polymers were tested. The results show that both exhibited ferromagnetism in low temperature. Ni2+-coordination polymer was a hard-ferromagnet due to its large values of coercive force, remanent magnetization and area of magnetic hysteresis loop. However, Tb3+-coordination polymer was a soft-ferromagnet ascribed to its small values of coercive force, remanent magnetization and area of magnetic hysteresis loop.
    Design, Synthesis and Biological Activities of Novel Anthranilic Isophthaloyl Amide
    YAN Tao, YU Guan-Ping, XIONG Li-Xia, YU Shu-Jing, WANG Su-Hua, LI Zheng-Ming*
    2011, 32(8):  1750-1754. 
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    Chlorantraniliprole has been widely studied in the agrochemical field, which is significant in the field of crop protection, particularly important in light of the ability of insects to rapidly developresistance and the need for safe and effective pesticides that act at Ryanodine receptor. A series of novel anthranilic isophthaloyl amides developed from the structure of Chlorantraniliprole was designed and synthesized. Their structures were characterized by 1HNMR and HRMS. The preliminary results of biological activity experiment showed that compound 8d exhibited 60% insecticidal activity against Mythimna separata Walker at 200 mg?L-1; compound 8d exhibited 41.7% fungicidal activity against Physalospora piricola and compound 8a exhibited 41.2% fungicidal activityagainst Gibberella sanbinetti at 50 mg?L-1.
    Synthesis, Structure and Optical Properties of a D-π-A Type 2,2'∶6',2"-Terpyridine Derivative
    GAO Yuan-Hao*, TIAN Yu-Peng*, YANG Jia-Xiang, YANG Feng-Ling, LI Jing, ZHENG Zhi
    2011, 32(8):  1755-1760. 
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    A D-π-A type 2, 2′: 6′, 2?-terpyridine derivative with two-photon properties was synthesized by using 2, 2′: 6′, 2?-terpyridine as an acceptor (A) and other functional group as a donor (D). For the D-π-A type 2, 2′: 6′, 2?-terpyridine derivative, we investigated its crystal structure, linear absorption, single- and two-photon properties.
    Synthesis and Biological Activities of Ifosfamide Mustards Porphyrin Dimers
    WANG Zhi-Wei, GUO Can-Cheng*, TIAN Mi, GUO Lin, SUN Teng-Fei, GUO Qing-Hu
    2011, 32(8):  1761-1767. 
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    Ifosfamide is one of the most important clinical alkylating agent due to its frequent use in cancer chemotherapy. It does not exhibit any cytotoxic activities in vitro, and requires hepatic oxidative metabolism in vivo to generate an alkylating ifosfamide mustard, which is regarded as the ultimate intracellular alkylating metabolite. However, its clinical uses are restricted due to they can not distinguish tumor cells from normal cells. Porphyrins could selectively accumulate in tumor tissues than in normal tissues. Based on these facts, an efficient one-pot method for the synthesis of ifosfamide mustards porphyrin dimers was achieved by treating hydroxyl substituted porphyrin first with POCl3 then with primary amine. The selective synthesis of ifosfamide mustards porphyrin dimers were achieved simply by controlling the ratio of POCl3 vis hydroxyl porphyrin and the reaction condition during the phosphonation step. Five ifosfamide mustards porphyrin dimers were synthesized accordingly by this one-pot procedure and their structures were affirmed by MS, 1H NMR, 31P NMR and elemental analysis. The MTT tests and the uptake tests showed that ifosfamide mustards porphyrin dimers could selectively accumulate and kill cancer cell. The interaction between ifosfamide mustards porphyrin dimers and bovine serum albumin (BSA) was investigated by fluorescence spectrum. The results showed that the ifosfamide mustards porphyrin dimers own a powerful ability of quenching the fluorescence of BSA via static quenching occurring in the non-covalent porphyrin-BSA complex.
    Prediction and Identification of Structural Proteins of Chinese Sacbrood Virus LN Isolate
    MA Ming-Xiao*, MA Chen, CHENG Jian, XIE Zhen-Sheng, LI Ming, FEI Dong-Liang
    2011, 32(8):  1768-1773. 
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    Abstract:Chinese sacbrood virus (CSBV) was purified from diseased insects, and its genome was cloned and sequenced. The genomic RNA of CSBV is 8863 nucleotides in length and contains a single large open reading frame encoding a 319.614kDa polyprotein. The coding sequence is flanked by a 178-nucleotide 5' nontranslated leader sequence and a 142-nucleotide 3' nontranslated region, followed a poly(A) tail. Four major structural proteins, VP1,VP2, VP3 and VP4, were estimated, and mapped to the N-terminal section of the polyprotein of which the genes were predicted. Phylogenetic analysis using RdRp of selected picorna-like viruses shows that CSBV/SBV and Deformed Wing Virus (DWV) tend to group together, which possesses an RNA of similar size and gene order. The results predicted the probable size and gene order of CSBV/SBV. Structural proteins, VP1, VP3 and VP0, were identified after four proteins was analysed by mass spectrographic.
    Self-assembly and Mechanism of Surfactant-like  Peptide A6KA6K
    MA Xin, MENG Qing-Bin, KOU Ying-Ying, LIANG Yuan-Jun, GUO Lei, NI Cai-Hua*, LIU Ke-Liang*
    2011, 32(8):  1774-1778. 
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    A diploid A6KA6K of surfactant-like peptide A6K was designed to study the influence on the length and ratio of the hydrophilic and hydrophobic segments in the peptide self-assembly. The secondary structure of the A6KA6K was mainly random coil and minor α-helix, which characterized by circular dichroism. The results observed by transmission electron microscopy and dynamic light scattering revealed that the peptide could self-assemble to form nanovesicles in aqueous solution. Pyrene probe fluorescence analysis indicated this peptide could form hydrophobic domains in which pyrene molecules were imbedded and undergo self-assembly in the form of micelles. The critical micelle concentration of the peptide was also calculated. Compared with the surfactant peptide A6K reported previously, the longer peptide A6KA6K containing 14 amino acids could formed nanovesicles through self-assembly, because the introduction of a hydrophilic amino acid into the hydrophobic segment of the peptide influenced the hydrophobic interaction of the peptide.
    Discovery of a Novel Dopamine D3 Receptor Inhibitor
    DENG Xin-Xian, SHEN Qing, XU Li-Li, XIONG Zi-Jun, ZHAO Wei-Li, ZHEN Xue-Chu, FU Wei*
    2011, 32(8):  1779-1784. 
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    Dopamine D3 receptor regulates the synthesis and release of dopamine in brain. It is implicated in many neurological processes, including motivation, pleasure, cognition, memory, learning, and fine motor control. It is involved in the pathology of psychotic diseases, such as schizophrenia, Parkinson's disease and drug addiction. It is of great significance to discover novel D3 inhibitors through pharmacophore-based virtual screening for the development of anti-psychotic drugs. In this study, we employed the latest discovered high-resolution crystal structure of human D3 receptor to conduct active-site-analysis, build the receptor-based pharmacophore model and screen the Asinex GOLD Collection database. 7 hits were purchased and tested by pharmacological experiments. A novel inhibitor 04932482 with a high activity against D3 receptor was obtained[Ki=(806.75±34.58) nmol/L]. The structure analysis was conducted and the ligand-receptor interaction was further investigated by docking to guide the structure modification and optimization of compound 04932482.
    Photoelectric Properties of Zr0.5Ti0.5O2 Nano Thin Films
    ZHANG Hai-Feng, ZHANG Min, RUAN Sheng-Ping, MENG Fan-Xu, Feng Cai-Hui, XU Yang, CHEN Wei-You, ZHANG Xin-Dong*
    2011, 32(8):  1785-1788. 
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    Zr0.5Ti0.5O2 thin films were prepared by a sol-gel method and characterized by means of XRD, SEM, XPS and UV-visible absorption spectra. XPS analysis indicated that the atom ratio between Zr and Ti is 1:1. SEM shows that the surface of Zr0.5Ti0.5O2 film is flat and not chapped, which is better than that of pure ZrO2 and TiO2 film. In addition, the film’s abortion edge shows obvious blue shift with the Zr doping. Based on the Zr0.5Ti0.5O2 thin film, planar interdigitated electrodes were prepared and then tested. At 5 V bias, the sample was insensitive to visible light but exhibit significant response under the irradiation of 260 nm UV light.
    Surface Enhanced Raman Scattering on Cu2O/Ag Composite
    WANG Yun-Xin, SONG Wei, YANG Jing-Xiu, XU Wei-Qing, ZHAO Bing*
    2011, 32(8):  1789-1793. 
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    Cu2O/Ag composite was prepared by using a very simple chemical reduction method. The SEM images indicated that Ag nanoparticles are deposited on the surface of octahedral Cu2O particles which were smooth and symmetrical. The surface of bare Cu2O particles is surrounded by large quantities of Ag nanoparticles, but is not form a compact shell. 4-Mpy molecules can be adsorbed not only on the surface of Ag nanoparticles, but also on the surface of Cu2O particles. The SERS enhancement on silver nanoparticles can be attributed to electromagnetic enhancement and chemical enhancement. On the other hand, Ag nanoparticles would also excite localized surface plasmon resaonace under the irradiation with suitable laser light, further enhancing the SERS signals of 4-MPy adsorbed on the near Cu2O particles. This method is exhibites some information on the catalatic properties of the surface of the octahedral Cu2O particles and provides a new kind of materials for SERS applications.
    Absorbent of CuCl/NaY Prepared by Glucose Direct Reduction and the Application for Adsorption of CO and Separation for CO/H2 Mixture Gas
    SUN Si, WU Yong-Yong, LUO Shi-Zhong, CHU Wei*, NI Hong-Zhi
    2011, 32(8):  1794-1798. 
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    The CuCl/NaY sorbents were prepared by impregnation method with copper chloride as metal precursor and glucose as reducing agent. The efficient amount of CO and the separation factor of CO/H2 were measured on sorbents. The microstructures of these sorbents were characterized by XRD 、XPS and TPR techniques. The results showed that the sorbents prepared using glucose as reducing agent had a higher amounts of Cu+ than those without glucose, which results in a better adsorption capability of CO and separation performance for CO/H2
    First-principles Investigation on the Structures and Properties of Pd-substituted Mg2Ni Alloys and Their Hydrides
    HUO Liang, SHI Hong-Cun, XU Bao-En, LI Xiao-Yan, MENG Ling-Peng*
    2011, 32(8):  1799-1806. 
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    The crystal and electronic structures of magnesium-based hydrogen storage alloy Mg2Ni, palladium substituted alloys Mg12Ni6-xPdx(x=1, 2, 3), and their hydrides H2-Mg12Ni6-xPdx (x=0, 1, 2, 3) have been calculated from first-principles density functional theory. Results show that the sizes of primitive cell of the intermetallic alloys and hydrides were increased by substitution of Ni with Pd. Also, the interactions of Mg-Ni and Ni-Ni were affected by the substitution, but the influence is not so much. There are greater deformation and volume increase of the crystal cell after the alloy hydrogenation, which favor the hydrogen diffusion in the bulk. The substitution of Ni located in 3d with Pd atom leads Pd-H bonding interaction to be weaker than the original Ni-H bond, and also leads to the weakening of the neighboring Ni-H bond located in 3b. So the substitution can make hydrogen release more easily and reduce the dehydrogenation temperature.
    Effects of the Distribution of Micropapillae with Nanofolds on the Adhesive Property of Artificial Red Rose Petals
    WANG Jing-Ming*, WANG Chun, WANG Ming-Chao, JIANG Lei*
    2011, 32(8):  1807-1811. 
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    Many biological organism surfaces exhibit amazing characters. An intriguing example is the red rose petals, which is famous with its “petal effect” (i.e. the water droplet adhesion effect). Numerous studies have revealed that these interesting characters of the biological surfaces are attributed to their special wettabilities with the combination of unusual micro/nano- hierarchical structures and chemical composition. In this article, the “petal effect”was reproduce on an “artificial red rose petal”— a superhydrophobic PDMS film with the same hierarchical rough structures of red rose petals. The surface adhesive effect was characterized by the high-sensitivity microelectromechanical balance system, and the effects of micro- and nanostructure on the adhesive property of “artificial red rose petals” was investigated by altering the stretch stage. The morphology of the “artificial red rose petals” at different stage were observed by environmental scanning electron microscope (ESEM), and the wettability was characterized by the apparent contact angle. The experimental results show that surface hydrophobicity can be enhanced by the nano-scaled structure and the high adhesive force is mainly caused by the micro- and nano-scaled structure. It is believed that this work will provide us a new avenue to further understand the wettablilty of solid surface and to design novel microfluidic devices in a wide range of applications.
    Photocatalytic Reductive Degradation of Acid Red 3R by Posphotungstic Acid
    LI Ke-Bin*, ZHAO Feng, WEI Hong, ZHANG Tao, WANG Qin-Qin
    2011, 32(8):  1812-1818. 
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    A strategy for reductive degradation of azo dye Acid Red 3R (AR3R) by using the in-situ generated heteropoly blue (PW12O404-) was investigated. Heteropoly blue was produced by UV irradiation on aqueous solutions containing posphotungstic acid (photocatalyst) and isopropanol (electron donor). The reduction potential of AR3R was measured by cyclic voltammetry and used to assess the thermodynamic feasibility of reduction of AR3R by heteropoly blue. A dark reaction between AR3R and heteropoly blue was carried out to further confirm and reinforce reductive degradation of AR3R by heteropoly blue. In addition, the effects of various factors such as the photocatalyst amount, isopropanol dosage, dye concentrations, and ionic strength on photodegradation of AR3R were evaluated. The results showed that increase of posphotungstic acid and/or isopropanol concentration accelerated photodegradation of AR3R till a saturation value. The initial rates of photodegradation of AR3R increased with increasing in dye concentration, which could be described by the Langmuir-Hinshelwood equation. However, salt concentration displayed a negative effect on photocatalytic degradation of dye. It was assumed that the charge-transfer within a precomplex formed by photoreduced heteropoly blue and AR3R lead to the reductive degradation of dye and oxidative regeneration of catalyst. This study also indicates that POM/isopropanol/UV system provides a green route for reductive decolorization of azo dyes.
    Theoretical Discussion for Influence of Introduction of Gold Atom on Carrier Transport Property of Pentacene
    GENG Yun, WU Shui-Xing, LI Hai-Bin, DUAN Yu-Ai, YANG Guo-Chun, SU Zhong-Min*, LIAO Yi*, SUN Guang-Yan
    2011, 32(8):  1819-1824. 
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    As a well-known hole-transporting material, pentacene has been widely and intensively investigated. Here, the influence of introduction of gold atom on the hole transport property of pentacene was investigated by combining DFT with Marcus theory, focusing on intramolecular reorganization energy, intermolecular transfer integral and hole hopping rate. The results show that the main contributions to λ transits from the stretching of C-C bonds to the stretching of Au-Pentacene with Au introduced, and that this transition becomes increasingly intense when the Au atom is near the edge of pentacene. As for transfer integral, the introduction of Au atom results in the decrease of its value arising from the effect of both the geometries and character of frontier orbitals.
    Correlation of Structure and Sorption Behavior of Modified Bentonite
    SUN Hong-Liang*, ZHU Li-Zhong, ZHU Jian-Xi
    2011, 32(8):  1825-1831. 
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    Bentonite, composed primarily of montmorillonite, is a natural adsorbent material. A novel sorbent with specific structure and property, identified by MEA-HDTMA-IMB, was prepared by modifying Ca-bentonite (IMB) obtained from Inner Mongolia of China with both 2-mercaptoethylamine hydrochloride (MEA) and hexadecyltrimethylammonium bromide (HDTMA). The sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermal analysis (TG-DTA), and specific surface area (N2-BET). The results indicated that both specific surface area and basal spacing of MEA-HDTMA-IMB were increased significantly. The performance of this sorbent showed that MEA-HDTMA-IMB could sorb p-nitrophenol and copper simultaneously from the mixed solution. The sorption of organic pollutant onto MEA-HDTMA-IMB was better than HDTMA-IMB and controlled by a partition process. The sorption of heavy metal onto MEA-HDTMA-IMB was dominated by the formation of complexes and in close proximity to MEA-IMB.
    Combustion Mechanism and Kinetic Modeling Study of Methyl Cyclohexane at High Temperature
    TAN Ning-Xin, WANG Jing-Bo, HUA Xiao-Xiao, LI Ze-Rong, LI Xiang-Yuan*
    2011, 32(8):  1832-1837. 
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    At first, relevant discussions on combustion reaction rules at high temperature of alkanes and naphthenes were presented in this study. According to these rules, a program named ReaxGen was developed for automatic generation of the detailed mechanisms for large hydrocarbons. Secondly, the detailed combustion mechanism of methyl cyclohexane at high temperature was constructed using this program. Then, the influence of ignition temperature, ignition pressure, mole fraction of fuel and equivalence ratios upon the ignition delay time for methyl cyclohexane combustion at high temperature were investigated by a kinetics simulation method using shock tube. In addition, equilibrium calculations were also performed in order to obtain the concentration of product and adiabatic flame temperature. Finally, these calculated results from our mechanism were compared with the literature experimental results and those from other mechanisms available.
    Novel Rapid  Molecular Modeling Method Based on Evolutional Tree for Human Adenovirus Hexon Proteins Family
    YUAN Xiao-Hui, WANG Ying-Chen, QU Zhang-Yi*, REN Jia-Yi, WANG Jing-Fei, GUO Ying-Ying, WANG Ya-Xian, HUA Dong, WU Xiao-Min, YANG Zhi-Wei, GAO Hong
    2011, 32(8):  1838-1844. 
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    Human Adenoviruses (HAdVs) are responsible for many infectious diseases. 54 different serotypes of HAdVs have been identified so far, and the diversity of HAdVs has brought some difficulties to clinical diagnosis and therapy. In this study a novel rapid modeling method for proteins family has been developed on the basis of evolutionary tree, and by this method 7 hexon homologous proteins from D sub-specie Human Adenoviruses (HAdVs) were modeled. An evolutionary tree of these 7 hexon protein amino acid sequences was constructed by neighbor-joining (NJ) algorithm; Based on the information from the evolutional tree, an optimal modeling route was determined to accelerate the modeling of these hexons; And then, rapid modeling of hexons was automatically completed using homology modeling method within MODELER and CHARMM program; and the sturcures were proved to be acceptable by two assessment methods. Compared with the traditional scheme, this novel method can significantly reduce the amount of calculation. Every hexon structure model produced by this novel rapid modelling method could be reliably superimposed to the corresponding model produced by the traditional method. The rapid modeling of HAdVs hexon protein is very important to the molecular designing of HAdVs vaccines and the development of rapid HAdVs diagnostic typing agents.
    Dissipative Particle Dynamics Study of Homopolymer Adsorb on Micelle in Non-equilibrium State
    LI Yan-Chun, LIU Hong, HUANG Xu-Ri*, SUN Chia-Chung
    2011, 32(8):  1845-1848. 
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    We use equilibrium dissipative particle dynamics method to investigate the micelle formed by self-assembly of block copolymer, where a homopolymer chain adsorbed on the surface. Under shear flow, we use non-equilibrium dissipative particle dynamics method to investigate the processes of the homopolymer desorption and micelle fission. The results reveal the qualitative between shear rate and desorption time.
    Synthesis and Thermal Decomposition of Tetracyclo[9.2.1.02,10.13,8]Tetradecane as a High Density Hydrocarbon Fuel
    DU Yong-Mei*, WANG Wei, KANG Jian-Ping, LI Chun-Ying, YANG Jian-Ming, ZHANG Wei, Lü Jian
    2011, 32(8):  1849-1853. 
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    As a high density hydrocarbon fuel, tetracyclo[9.2.1.02,10.13,8]tetradecane was synthesized from dicyclopentadiene and indene by D-A reaction and hydrogenation. Thermal decomposition of tetracyclo[9.2.1.02,10.13,8]tetradecane was studied in a decomposition reactor, and the products were detected by gas chromatography-mass spectroscopy. The conversion of tetracyclo[9.2.1.02,10.13,8]tetradecane at different temperature and time was investigated. The results indicated that the effect of temperature was superior to other factors in this reaction. A primary mechanism was also presumed according to the main products of the reaction. Finally, the kinetic equation of thermal decomposition was obtained. The activation energy derived from kinetic data indicated that tetracyclo[9.2.1.02,10.13,8]tetradecane can decompose more easily than JP-10 fuel.
    Interaction Between Methylene Blue and ctDNA by Time-resolved Spectroscopy
    LIU Tao, ZHANG Chong-Lei, CHEN Ping, TANG Guo-Qing, LIN Lie*
    2011, 32(8):  1854-1859. 
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    In this paper, the singlet oxygen(1O2) kinetics process of MB-ctDNA mixed solutions in D2O was studied by time-resolved spectroscopy, which helped to further investigate the interaction of MB and DNA. The results showed that 1O2 phosphorescence kinetic curves of MB-ctDNA solutions at low concentrations ctDNA and high concentrations ctDNA had obvious differences, these differences were ascribed to change of MB and DNA binding mode and interaction mechanism. At low ctDNA concentration, ionic conjugate formed between MB molecules and ctDNA, significant hypochromic effect was observed in MB absorption band, and 1O2 production dropped sharply with ctDNA concentration increasing, but there were no obvious interaction between ctDNA and 1O2; at high ctDNA concentration, interaction mode between MB molecules and ctDNA changed to intercalative binding, energy transfer between the excited state MB molecules and ctDNA as well as the effect of medium viscosity changed property of the 1O2 dynamics, which greatly decreased the production of 1O2, but ctDNA did not quench the 1O2 apparently. These results indicated that type II photosensitization of 1O2 damaging DNA was not major mechanism of PDT action in MB-DNA solutions.
    Thermodynamic Properties of a Series of Closely Related Ionic Liquids Based on 1-Alkyl-3-methylimidazolium Hydrosulfate
    XU Zhi-Ce, WANG Jian-Ying, WANG Xiao-Ling, HU Yong-Qi*
    2011, 32(8):  1860-1864. 
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    The densities of a series of ionic liquids [C4mim]HSO4 (1-butyl-3-methylimdazolium hydrosulfate), [C6mim]HSO4 (1-hexyl-3-methylimdazolium hydrosulfate), [C8mim]HSO4 (1-octyl-3-methylimdazolium hydrosulfate) and [C10mim]HSO4 (1-decyl-3-methylimdazolium hydrosulfate) were determined from T = (293.15 to 343.15) K. The coefficients of thermal expansion and molecular volume of the ionic liquids were calculated from the density results. Standard entropies and lattice energy of the IL were calculated from the experimental density values using Glasser’s equation. The thermodynamic properties of the ionic liquid were further discussed.
    In-situ Surface Enhanced Raman Spectroscopic Investigation of Photocatalysis at Au@TiO2 Surface
    LIU Wei, GUO Qing-Hua, QIN Wei, YAO Jian-Lin*, GU Ren-Ao
    2011, 32(8):  1865-1869. 
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    Based on the polyelectrolyte-mediated electrostatic adsorption (layer by layer method), Au@TiO2 core shell nanoparticles were prepared through the modification of the different layers of TALH on Au nanoparticles followed with a calcination. By using thiophenol as probe, the surface enhanced Raman scattering (SERS) effect was observed from Au nanoparticles attached with the TiO2 precursor. The SERS effect was dependent on the shell thickness. After coated with three layers of TALH, SERS effect from the Au nanoparticles core disappeared. The photocatalytic processes of methylene blue (MB) was investigated on Au@TiO2 by in situ SERS under UV illumination. The observation of C-N-C skeleton deformation vibrational mode at 450 cm-1 and 504 cm-1 indicated that MB adsorbed on the Au@TiO2 surface in a dimmer or polymer formation at the initial stage. With the increase of the UV illumination time, the band at 481cm-1 assigned to the monomer of MB was enhanced and the bands at 1180 cm-1 and 1073 cm-1 assigned to the C-H relevant vibrational modes disappeared. It indicated that the photocatalytic degradation of MB on Au@TiO2 underwent the transformation of dimmer or polymer to the monomer initially, followed with the degradation of methyl group. The in situ SERS technique combined with UV illumination might be developed as one of powerful tools for monitoring the photocatalytic reactions.
    Crystal Structure, Thermal Properties, Sensitivity Test and Catalytic Activity of  Energetic Compound[Cu(tza)2]n
    TANG Zhan, ZHANG Guo-Tao, ZHANG Tong-Lai*, LI Zhi-Min, YANG Li, ZHANG Jian-Guo, QIAO Xiao-Jing
    2011, 32(8):  1870-1875. 
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    Copper based on tetrazole-1-acetate acid (Htza) was synthesized with tetrazole-1-acetate acid and cupric carbonate basic, a new component method in aqueous solution and obtained its single crystal. The molecular formula and structure of the title complex was characterized by using the elemental analysis and FT-IR techniques, which is [Cu(tza)2]n, and the result is in accordance with the X-ray single crystal diffraction data. The thermal decomposition process of [Cu(tza)2]n was investigated by using differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG), which indicated the thermal decomposition of the title compound displayed three exothermic decompositions and the first exothermic decomposition kinetic parameters Ea and A of these compounds were calculated by the Kissinger method and Ozawa-Doyle method. According to the standard test method GJB 770A-97, the friction sensitivity, impact sensitivity, flame sensitivity and 5 seconds ignition point of the compound were measured, which demonstrated the compound had a certain degree sensitivity and [Cu(tza)2]n could be applied in potential energetic material. Thermal decomposition data of mixture of [Cu(tza)2]n and RDX demonstrates: the addition of the title complex makes the onset temperature and peak temperature of RDX shift downwards, and the thermal decomposition of RDX is accelerated due to the catalyst of the [Cu(tza)2], which can provide theoretical support to further performance study as the title complex is added to the propellant formulations to regulate the burning rate.
    Preparation and Electrochemical Properties of Pt-catalysts Supported on Mesoporous Carbon Nanofibers
    YANG Hua*, SUN De-Hui, REN Hui-Juan, CUI Zhen-Feng
    2011, 32(8):  1876-1880. 
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    Ordered mesoporous carbon nanofibers were prepared by combining the soft template synthesis method of mesoporous carbons with the confinement of channels of anode alumina membranes. The ordered mesoporous carbon nanofibers as supports for loading Pt nanoparticles were obtained using a noncovalent method and ethylene glycol reduction. The results indicate that the mild functionalization method is beneficial for conservation of mesostructure of supports and distribution of Pt nanoparticles. Moreover, the condition of reduction is very important for the load of Pt nanoparticles. The electrochemical properties were studied by cyclic voltammogram and the results show that the Pt-catalysts possess excellent methanol electrocatalytic activity and stability.
    Controlled Ring\|opening Polymerization of ε-Caprolactone Initiated by in situ Formed Yttrium Tribenzyloxide Complex
    LIANG Zhen-Hua, NI Xu-Feng*, SHEN Zhi-Quan
    2011, 32(8):  1881-1883. 
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    Yttrium tribenzyloxide complex in situ formed by the reaction of yittrium trialkyl complex [Y(CH2SiMe3)3(THF)2] with 3 equivalent benzyl alcohol were used as initiator for the controlled ring-opening polymerization (ROP) of ε-caprolactone (CL). 1H-NMR studies indicated that the PCLs obtained were caped by a benzyloxyl group at one end and an alcohol at the other. The number average molecular weight measured by 1H-NMR and GPC both increase linearly with the monomer/yttrium molar ratio with narrow melecular weight distribution (MWD). Moreover, the Mn measured by 1H-NMR agrees with the value of the calculated Mn, suggesting that the ROP of CL undergo a living manner.
    Preparation and Behaviors of Sulfonated Poly (arylene ether ketone Sulfone)s /ZrO2 Composite Proton Exchange Membranes
    WANG Zhe*, GAO Hong-Cheng, ZHAO Cheng-Ji, CHANG Hong, ZHANG Hui-Xuan, NA Hui
    2011, 32(8):  1884-1888. 
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    In order to enhance operating temperature of proton exchange membrane fuel cell (PEMFC), sulfonated poly(aryle ether ketone sulfone)/ZrO2 composite membranes with different contents of ZrO2 were prepared by sol-blend mixed method in this paper. Infrared spectra showed that the Zr-O-Zr absorption peaks existed in composite membrane. SEM photos show ZrO2 nano-inorganic particles uniformly dispersed in SPAEKS polymer matrix. It was found that the introduction of nano-particles ZrO2 improved the thermal stability, water uptake and proton conductivity. The methanol permeability coefficient (5.6×10-7cm2/s) of SPAEKS/ZrO2-10% composite membrane was lower than that of SPAEKS film (6.7×10-7 cm2/s) at 80 oC. The proton conductivities of all composite membrane exceeded 0.08 S/cm at 80 oC, which meet with the requirement of PEMFC at elevated temperature operation. The SPAEKS/ZrO2 composite membranes showed good potential for the usage in high temperature PEMFC.
    Self-assembly and Properties of Multi-sensitive Amphiphilic P(DM-co-AA-co-CA) Copolymer
    GU Xin-Yan, YI Cheng-Lin, LU Yang-Bin, FAN Cun-Hua, JIANG Jin-Qiang*, LIU Xiao-Ya*
    2011, 32(8):  1889-1895. 
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    Coumarin-containing acrylic acid monomer(CA) was designed and synthesized,which could be used together with dimethylaminoethyl methacrylate(DM) and acrylic acid(AA) to synthesize the multi-sensitive amphiphilic copolymer P(DM-co-AA-co-CA) via free radical copolymerization. Its structure was characterized by Fourier transform Infrared Spectroscopic (FTIR)、Magnetic Resonance Spectrometer (1H-NMR), Gel Permeation Chromatography (GPC) and Differential Scanning Calorimeter (DSC). The copolymer could self-assemble into steady spherical micelles in the selective solvent THF/water with suitable initial copolymer concentration and water content. The self-assembly process and characteristic of P(DM-co-AA-co-CA) micelles were studied by UV spectrophotometer、fluorescence spectrophotometer、Zeta Potential、Dynamic laser light Scattering(DLS) and Transmission Electron Microscope(TEM). The results show that in the range of pH=2.13-8.54, the UV absorbance and fluorescence emission intensity of micellar solutions increased with increasing of pH, and in the range of 8.54-12.46, both of them decreased with increasing of pH value. Depending on the solution pH, these micelles can exist in two different micellar charge states and also exhibits an isoelectric point at around pH 9.70, around which the diameter of micelle particles became the smallest, and then it increased either with the pH increasing or decreasing. In basic solution, LCST of micelles decreased with increasing of pH value, and such amphiphilic micelles are of efficient emulsification properties in pH 1.16 and 12.62.
    Construct of Nano Micelles Based on Miktoarm Star Copolymer with a Cyclodextrin Core and Their Inclusion Properties
    MU Cheng-Guang, FAN Xiao-Dong*, TIAN Wei*, BAI Yang, NAN Jiang-Kun, MA Tuo-Mei, YANG Guang
    2011, 32(8):  1896-1903. 
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    A star-shaped polymer, MPEG-CD-PNIPAMx, which possesses the lower critical solution temperature (LCST), was designed and synthesised. MPEG-CD-PNIPAMx was composed of a β-cyclodextrin(β-CD) moiety as the core,one Methoxypolyethylene glycol (MPEG) chain and 2~4 poly(N-isopropylacrylamide)(PNIPAM) chains as double hydrophilic arms. The structure of MPEG-CD-PNIPAMx was characterized by 1H NMR, 13C NMR and the molecular weight and molecular weight distribution were measured by size exclusion chromatography/multi-angle laser light scattering(SEC/MALLS) technology. The number of PNIPAM arm was determined by integrating the peaks of 1H NMR spectrum. When the temperature of aqueous solution of MPEG-CD-PNIPAMx raises over the LCST, the star shaped molecule becomes amphiphilic, and then self-assemble into micelles with PNIPAM as the core layer, β-CD and MPEG as the shell layer. The fluorescence spectroscopy of MPEG-CD-PNIPAMx and its micelles in pyrene aqueous solution revealed that the micells can include hydrophobic guest molecule at two sites: the cavity of β-CD and the hydrophobic core of the micelle.
    Synthesis, Characterization and Properties of a Novel Fluorine-contained Poly(arylene ether) Containing Phenylphosphine Oxide
    LI Qing-Ming, ZHAO Xiao-Gang, ZHANG Nan, WANG Da-Ming, WANG Wei, CHEN Chun-Hai*
    2011, 32(8):  1904-1907. 
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    A novel fluorine-contained poly(arylene ether) containing phenylphosphine oxide (6F-PAEPO) was synthesized by the nucleophilic substitution between bis(4-chlorophenyl)phenyl phosphine oxide (BFPPO) and 4,4'-(Hexafluoroisopropylidene)diphenol (Bis AF). BFPPO was prepared from dichlorophenylphosphine oxide and 4-bromofluorobenzene through Grignard reaction. The structure of the polymer was confirmed by FTIR, 1H NMR, 31P NMR, and 16F NMR. The polymer exhibited excellent thermal stability, mechanical property and solubility. The glass transition temperature of 6F-PAEPO was 211℃, the temperature for 5% weight loss of 6F-PAEPO in N2 and air were 512 and 523℃, respectively. The maximum trasmittance of the polymer film is above of 80%. Especially, the polymer exhibited an outstanding flame retardancy property due to the existence of triphenylphosphine-oxide moities in the main chain. LOI of the polymer was up to 39.9%.
    Synthesis and Characterization of New Poly(bisbenzothiazole)s Containing 4-tert-Butylcyclohexylidene and Alkene Units
    HUANG Wei*, DU Chun-Ping, XIE Mei-Ran, ZHANG Yi-Qun, ZHANG Jun-Mei
    2011, 32(8):  1908-1912. 
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    A new series of poly(bisbenzothiazole)s (PBTs III1,2) containing 4-tert-butylcyclohexylidene and alkene units were prepared from 1,1-bis(4-amino-3-mercaptophenyl)-4-tert-butylcyclohexane dihydrochloride (BAMPBCH?2HCl) and alkene dicarboxylic acids by direct polycondensation. Their chemical structures were characterized by IR, 1H NMR and EA. These polymers exhibited improved solubility due to the introduction of 4-tert-butylcyclohexene group into their structures. They also maintained good thermal stability. The decomposition temperatures at 10 % weight loss of them were above 419 oC. In comparison with poly(p-phenylene-6,6’-(4-tert-butylcyclohexene)bisbenzothiazole) (PBT), the UV absorption spectra of PBTs III1,2 showed the λmax were red shifted. And compared with poly(p-phenylene benzobisthiazole) (PBZT), the λmax were blue shifted. The bandgaps of PBTs III1,2 were 2.56 eV and 2.53eV. The introduction of 4-tert-butylcyclohexene and alkene units widened the optical bandgap range of the benzothiazole polymers. The emission wavelengths of PBTs III1,2 were red shifted in contrast to PBT. The bulky pendant group decreased the aggregation degree of polymer chains. The results of EPR studies showed the intrinsic paramagnetic defects in PBTs III1,2.