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    10 July 2013, Volume 34 Issue 7
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    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.34 No.7(2013)
    2013, 34(7):  0-0. 
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    Photoluminescent ZnO Quantum Dots Coated by Polymethacrylamide and Their Application in Cell Imaging
    XU Yu-Dong, ZHANG Zheng-Yong, KONG Ji-Lie, LI Guo-Dong, XIONG Huan-Ming
    2013, 34(7):  1565-1570.  doi:10.7503/cjcu20130148
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    ZnO@polymer core-shell nanoparticles with stable luminescence in aqueous solutions and tunable emission were synthesized by sol-gel method, studied in cytotoxicity tests towards HeLa cells and measured by laser confocal scanning microscope. The shell of such luminescent probes is a copolymer connected the ZnO core through coordination bonds, which contains an external hydrophilic layer of polymethacrylamide and an internal hydrophobic layer of polymethacrylate. Such design protected the ZnO cores from decomposition by aqueous solutions on one hand, and assured the highly dispersity and long-term stability in water on the other hand. Cytotoxicity measurements proved this material is biocompatible and suitable for biological labels. The results of the laser confocal imaging showed these nanoparticles could penetrate the membranes of HeLa cells and exhibited stable fluorescence in the cytoplasm.

    Synthesis, Structure and Phase Transition of a New Microporous Aluminophosphate [C4N2H14]2+[H2Al3P3O14]2-
    LU Hui-Ying, TONG Xiao-Qiang, YAN Yan, YAN Wen-Fu, YU Ji-Hong, XU Ru-Ren
    2013, 34(7):  1571-1575.  doi:10.7503/cjcu20130245
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    In the presence of N-methyl-1,3-diaminopropane, a new microporous aluminophosphate compound [C4N2H14]2+[H2Al3P3O14]2-(1) was synthesized under hydrothermal condition. Single-crystal X-ray diffraction structural analysis showed that compound 1 crystallizes in the orthorhombic space group Pbca with a=1.59839(11) nm, b=0.99402(6) nm, c=1.82261(11) nm, V=2.8958(3) nm3. Its framework consists of AlO5/AlO6 and PO4 units forming 10-ring channels along [010] direction, where the templates exists. Compound 1 transformed to AlPO4-25(ATV) upon calcination at 550℃. It was further characterized by powder X-ray diffraction(PXRD), inductively coupled plasma(ICP) analysis, scanning electron microscopy(SEM), thermal gravimetric(TG) analysis, and elemental analysis.

    Synthesis, Characterization and Photocatalytic Oxidation for 1,5-Dihydroxynaphthalene of Tetrasulfophthalocyanine and Its Metallophthalocyanine Complex
    WANG Ying, REN Qi-Zhi, GUO Lin-Tong, HOU Zong-Sheng, JIANG Zong-Run
    2013, 34(7):  1576-1584.  doi:10.7503/cjcu20130147
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    Tetrasulfophthalocyanine(H2PcTS) and its metal complexes(ZnPcTS, FePcTS and CoPcTS) were synthesized using potassium 4-sulfophthalonitrile as precursor. The use of dialysis and column chromatography can efficiently increase the purity of the products. The structural traits and properties were discussed by Fourier transform infrared(FTIR), ultraviolet visible(UV-Vis) and proton nuclear magnetic resonance(1H NMR) spectrometries and cyclic voltammetry(CV) methods. It has been shown that the complex properties have relationship with the substitution by sulfonic groups and coordination with central metal ions. FePcTS and H2PcTS were used as photocatalysts in oxidative degradation of 1,5-dihydroxynaphthalene in the presence of H2O2 as oxidant. It was found that FePcTS in pH=3.7 solution presented the best catalytic activity. Compared with tetrasulfoporphyrins, tetrasulfophthalocyanines may be more promising photocatalysts in practical degradation of phenol contaminants.

    Preparation and Characterization of a ZnO Nanowires-based Cylindrical Hierarchical Structure
    JING Wei-Xuan, NIU Ling-Ling, WANG Bing, CHEN Lu-Jia, QI Han, ZHOU Fan, JIANG Zhuang-De
    2013, 34(7):  1585-1590.  doi:10.7503/cjcu20130045
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    ZnO nanowires were synthesized with hydrothermal method on an optical fiber core, hence generating a cylindrical hierarchical structure. With a rough surface superimposed on a cylindrical substrate, the morphology of this hierarchical structure was simulated and investigated. SEM images along with relative operators of MatLab software were employed to characterize the morphology of the hierarchical structure and the geometric parameters of ZnO nanowires. Characteristic parameters including root mean square(RMS) roughness, skewness and kurtosis of the line edge profile of ZnO nanowires film were extracted respectively as 39.2 nm, 0.1324 and 2.7146, whilst the surface morphology of the cylindrical hierarchical structure with same values of characteristic parameters were simulated. It was concluded that the properties of the line edge profile were in agreement with that of the simulated surface. Also the effects of the synthesizing parameters on the geometric properties of ZnO nanowires were investigated, resulting in a group of ideal synthesizing parameters as 1.0 mmol/L Zn2+ concentration of the seed layer solution, 0.03 mol/L Zn2+ concentration of the growth solution, 1.5 h of the growth time and 90℃ of the growth temperature. The results can be used for not only the batch fabrication of this cylindrical hierarchical structure, but also the construction of related ZnO nanowires-based sensors in medical, biological, electrochemical and gas detection applications.

    Analytical Chemistry
    Rapid Quantification of 13 Pesticides in Vegetables by Atmospheric-Pressure Solids Analysis Probe(ASAP) Coupled to Tandem Mass Spectrometry
    HUANG Bao-Yong, OUYANG Xi-Hui, SUN Jiang, XIAO Zhi-Yong, PAN Can-Ping
    2013, 34(7):  1591-1597.  doi:10.7503/cjcu20130282
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    A rapid direct-analysis method using atmospheric pressure solids analysis probe coupled to tandem mass spectrometry(ASAP-MS/MS) was established for the detection of thirteen commonly used multi-class pesticides in vegetables, without cleanup, concentration or chromatographic separation, and a single run can be done in minutes. To compensate for the poor precision and instability in ambient ionization technique, ASAP source parameters of the corona discharge, desolvation gas temperature, sample solvent and sample-load mode were optimized. The target compound was identified by product ion abundance ratios in multiple reaction monitoring(MRM)mode and semi-quantified through internal standard calibration curves. The matrix effects of celery, leek and rape were analyzed, and had apparent influences. Under the optimal conditions, the linear range was 5.0—500 μg/L with a coefficient of above 0.995. The limit of quantification(LODs) of analytes were 0.04—0.89 μg/kg, with a precision of 5.1%—13.0%(n=7). The real sample determination shows that the results by ASAP-MS/MS were in accordance with those obtained by ultra performance liquid chromatography coupled to tandem mass spectrometry(UPLC-MS/MS). The proposed ASAP-MS/MS technique can be a powerful tool due to its convenience, rapid, reliable, low-cost and eco-friendly for pesticide screening and emergency monitoring.

    Synthesis and Probe Properties of Rhodamine-triazine Derivatives
    CHEN Yi, ZHANG Yan, ZENG Xi, MU Lan, LI Jun, SUN Qiang, ZHANG Jian-Xin, WEI Gang
    2013, 34(7):  1598-1605.  doi:10.7503/cjcu20130173
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    A series of rhodamine-triazine derivatives was synthesized through the substitution of active chlorine of cyanuric chloride step by step with rhodamine hydrazide(or rhodamine ethylenediamine). The recognition performances of derivatives were studied. Different substituted derivatives can recognize Al3+, Cr3+ or Cu2+ with high sensitivity and selectivity. They were a kind of good performance of metal ion fluorescence and color enhanced probes.

    Analysis of Binding Properties Between β-Cyclodextrin Bipyridine-ruthenium Derivative and Vitamins by Their Fluorescence Spectra
    ZHENG Shan-Shan, CHEN Hong, QI Yan-Tao, WANG Xiu-Hua, FAN Hua-Jun, ZHAO Ying-Ying, ZHANG Fan, YANG Fan, TANG Jie, HE Pin-Gang
    2013, 34(7):  1606-1611.  doi:10.7503/cjcu20130077
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    This paper presents a research of the binding interaction of a new synthetized β-cyclodextrin bipyridine-ruthenium derivative[β-CD-Ru(bpy)3] with a series of vitamins using fluorescent spectrometry. The performance of fluorescence emission of β-CD-Ru(bpy)3 was excellent due to the existence of the center of bipyridine-ruthenium. Based on the effect of molecular recognition between β-cyclodextrin and guest molecule, the fluorescence quenching occured because of the energy transfer between the β-CD-Ru(bpy)3 and the vitamin when a kind of vitamin was added. According to the quantitative value of fluorescence quenching, the binding constants of the new derivative with respect to various vitamins were determined by Benesi-Hildebrand Equation. The results show that the binding capacities of the vitamins with β-CD-Ru(bpy)3 were in a descending sequence of VB12>VK3>VC>VA.

    Electrochemical Immunosensor Based on AuNPs/PDDA-GO for Detection of SirT1
    BI Wen-Ji, LU Dan-Qin, FU Ying, HUANG Qi-Lin, XU Zhi-Ai, ZHANG Wen
    2013, 34(7):  1612-1616.  doi:10.7503/cjcu20121164
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    AuNPs/PDDA-GO nanocomposite was produced by combining poly(diallyldimethylammonium chloride)(PDDA) functionalized graphene oxide nanosheets(PDDA-GO) and gold nanoparticles(AuNPs) through self-assembly method, which offered an efficient platform for antibody immobilization with good biocompatibility. A new type of electrochemical immunosensor based on AuNPs/PDDA-GO nanocomposite for the detection of SirT1 was then developed. The immunosensor construction consisted of the immobilization of the hybrid architecture, the immunoreaction of target antigen SirT1 and capture antibody(Ab1), followed by the binding of HRP-Ab2. The designed immunoassay showed an excellent analytical performance, and exhibited a wide dynamic response range for SirT1 from 0.1 ng/mL to 100 ng/mL with a detection limit of 0.029 ng/mL. Overall, this developed strategy is proved as a simple, cost-effective method, and can be easily extended to other protein analysis.

    Synthesis of Dipicolinate Sensitized LaF3∶Tb Nanoparticles and Their Application in the Determination of DNA
    YU Yong-Li, WANG Li-Mei, XU Shu-Kun, ZHANG Xiu-Juan
    2013, 34(7):  1617-1622.  doi:10.7503/cjcu20121051
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    Lanthanide nanoparticles have been used in bioanalysis due to their excellent luminescence properties. Herein, dipicolinate(DPA) sensitized LaF3:Tb(DPA-LaF3:Tb) nanoparticles with good water solubility were synthesized by hydrothermal method, which emit strong and stable luminescence. X-Ray diffraction(XRD) pattern showed that the particles were single-phase LaF3 crystals in hexagonal system, and transmission electron microscopy(TEM) image showed a good dispersion of DPA-LaF3:Tb nanoparticles with nearly uniform size of about 15 nm. The lifetime of the particles in water was measured 2.95 ms. It was found that DNA could quench effectively the luminescence of the particles. Based on the luminescence quench, the determination of DNA was realized with the linear range of 0.083~13.0 μg/mL and the detection limit of 0.02 μg/mL. Moreover, the interference of coexistence substances to the determination of DNA was studied.

    New Method for Identifying the Aromatic Types of Chinese Liquors Based on a 96-well Plate
    HOU Chang-Jun, DAI Bin, HUO Dan-Qun, YANG Ping, XU Yong, LI Jun-Jie, LUO Xiao-Gang, YANG Mei, FA Huan-Bao
    2013, 34(7):  1623-1628.  doi:10.7503/cjcu20121013
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    A cross-response liquid array sensor that simulated the mammalian taste system was developed for the determination of liquor aromatic types. The liquid array sensor was constructed with 8 sensing units which were consisted of 7 chemical dyes and 1 porphyrin compound. It achieved the type identification through the analyte fingerprints constituted by congregating the spectral response signal of 8 sensing units. The data were collected via a 96-well plate microplate reader, and then was further analyzed with principal component analysis(PCA), hierarchical clustering analysis(HCA) and linear discriminant analysis(LDA). We detected 9 different aromatic liquors. PCA results suggested that the mechanism of identification was mainly based on the trace components of Chinese liquor. Thereamong, the acids of Chinese liquor were the maximum contribution for the identification, because the contribution rate of acids was 54.3% and that of aromatic substances was only 18.6%. Simultaneously, only by 63.4% data rate could distinct liquor aromatic types with satisfaction. HCA dendrogram demonstrated that 9 different aromatic liquors could be correctly classified. LDA further showed the classification accuracy of identification for these 9 different aromatic liquors was 100%. These results showed that this method may provide a simple and efficient way for the rapid identification of liquor.

    Novel Screening Method for Antioxidants Based on the Fructose Autoxidation
    JIA Man, CHEN Hua, ZHAO Rong-Hua, CHEN Ji-Da, XIA Zhi-Ning
    2013, 34(7):  1629-1634.  doi:10.7503/cjcu20121000
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    The fructose in organisms can occur autoxidation reaction to produce kinds of free radicals, which transform to hydroxyl radical(·OH) finally. While ·OH can be captured by sodium benzoate to yield salicylate, which has strong fluroscence emission. The effects of fructose autoxidation were investigated and optimized using fluorescence method. A total of 19.27 μmol/L ·OH were produced under the conditions of pH=7.4, 37℃, reaction time 24 h and the concentrations of fructose, CuSO4 and sodium benzoate of 8.00 mmol/L, 20.0 μmol/L and 24.0 mmol/L, respectively. Antioxidants can scavenge free radicals produced by fructose autoxidation, which resulted in less ·OH product. From these process and principle, a novel screening method for antioxidants were developed based on fructrose autoxidation system. The antioxidative capacity of berberine hydrochloride and ferulic acid were estimated using developed method. The antioxidative capacity of berberine hydrochloride is stronger than that of ferulic acid, their IC50 values are 0.023 and 0.036 mmol/L, respectively.

    Screening and Structures Characterization of Human Serum Albumin Ligands from Radix Aconiti Alkaloids Extract by Ultrafiltration LC-MSn
    ZHU Hong-Bin, LIU Shu, WANG Chun-Yan, LIU Zhi-Qiang, SONG Feng-Rui
    2013, 34(7):  1635-1639.  doi:10.7503/cjcu20120962
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    A ultrafiltration LC-MS screening assay was developed for the screening and structures characterization of human serum albumin(HSA) ligands from the alkaloids extract of Radix aconiti. As a result, 9 compounds that can bind to HSA were found and were identified as 14-benzoylmesaconine, 14-benzoylaconine, 10-OH-mesaconitine, mesaconitine, 10-OH-aconitine, aconitine, hypaconitine, deoxyaconitine and 3,13-deoxyaconitine by ESI-MSn data.

    Organic Chemistry
    Network Gold Nanoparticle Aggregates Mediated by C60
    LI Liang, ZHANG Heng-Yi, ZHAO Jin, LIU Yu
    2013, 34(7):  1640-1645.  doi:10.7503/cjcu20130283
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    Metal nanoassemblies have attracted considerable attention in the fields of nanotechnology and biotechnology, due to their unique chemical/optical, electronic and magnetic properties. The "Click chemistry" reaction of permethyl-β-cyclodextrin with porphyrin units led to the formation of a new asymmetric cyclodextrin-modified porphyrin derivative, which was characterized by 1H NMR spectroscopy and electrospray ionization mass spectrometry(ESI-MS). After reaction of the derivative with chloroauric acid, the water-soluble gold nanoparticles(AuNPs) were obtained. The average particle size of AuNPs determined via transmission electron microscopy(TEM) was (5.0±0.8) nm. Then upon interaction with C60, the network aggregates were formed, and their structures were confirmed by UV-Vis absorption spectroscopy and TEM. The results showed that the fullerenes acted as a sort of "molecular glue", leading to the formation of soluble network aggregates, which may provide a new potential application in bioactive nanoscale materials.

    Synthesis, Characterization and Antitumor Activities of 5-Benzyl-4-tert-butyl-N-arylthiazol-2-amine Hydrobromide
    PENG Jun-Mei, LI Wan, SHEN Kun, HUO Su-Fang, YE Jiao, HU Ai-Xi
    2013, 34(7):  1646-1652.  doi:10.7503/cjcu20121077
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    Recently, more and more thiazole compounds were reported to exhibit antitumor activities. Twenty-nine new 5-benzyl-4-tert-butyl-N-arylthiazol-2-amine hydrobromides were synthesized from arylamino and 2-bromo-4,4-dimethyl-1-arylpentan-3-one. Their structures were confirmed by 1H NMR spectra and elemental analysis. The data of antitomor activities in vitro indicated that the IC50 values of compounds A4, A5, A12 and A29 against A549 cells were 0.016, 0.019, 0.019 and 0.026 μmol/mL, respectively, similar to Taxinol(IC50value was 0.022 μmol/mL). The IC50 values of compounds A5, A7, A13, A14 and A19 against Bel7402 were 0.021, 0.021, 0.026, 0.014 and 0.029 μmol/mL, respectively, similar to Taxinol(IC50 value was 0.030 μmol/mL). The shape changes of A549 cells were observed by inverted microscope and flourescence microscope after staining with Hoechst 33342-PI.

    Synthesis and Properties of 5-Ferrocenyl-pyrazoline Derivatives
    LI Heng-Dong, SU Xiao-Long, CHEN Ping-Hua, XIE Li-Li, YUAN Yao-Feng
    2013, 34(7):  1653-1659.  doi:10.7503/cjcu20121076
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    Recently, great interest has been generated in the synthesis and study of heterocyclic derivatives containing one or more ferrocenes, since these derivatives have potential applications as new functional materials in several areas. As a stable and readily oxidizable organometallic complex, ferrocne has been widely employed in multifunctional systems, which have exhibited potential utilizations in electrochemical sensors, molecular recognition and ethylene oligomerization catalysts. Combining the considerations above, we designed a simple and general approach to synthesis three 5-ferrocenyl-pyrazoline derivatives(3—5). The structures of all the products were determined by IR, MS, 1H NMR, 13C NMR and elemental analysis. The crystal structure of compound 4 was proved by single crystal X-ray analyses. Moreover, compounds 3—5 were characte-rized by CV, UV-Vis absorption and fluorescence spectrometry. Density functional theory(DFT) calculation was adopted to explain these phenomena. These compounds will be used as electrochemical sensors and ethylene oligomerization catalysts.

    Synthesis and Hepatoprotective Activity of Glycoside Conjugates of Ursolic Acid
    ZHU Jian-Qin, CHEN Hui, WANG Shao-Rong, LI Yan, FANG Wei-Shuo
    2013, 34(7):  1660-1666.  doi:10.7503/cjcu20121020
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    Ursolic acid was reported that it could be used for liver protection. However, its usage is restricted by its poor solubility in water. To improve the hepatoprotective activity of ursolic acid, some novel derivatives of ursolic were designed and synthesized. By modified Koenigs-knorr method, six glycoside conjugates of ursolic acid with modification at C3 and/or C28 were synthesized. It was found that compounds 12b and 12e could obviously increase the survival rate of WB-F344 rat hepatic stem-like epithelial cells evaluated through MTT method at cellular level. In vivo, however, it was not found that compounds 12b, 12d and 12f could obviously prevent the rise of the level of serum transaminases induced by ConA in a mice acute immunity liver damage model except that compound 12d could reduce the level of aspartate aminotransferase(AST) to some extent. By the introduction of galactose moieties, the liver protection potency of ursolic acid was improved.

    Physical Chemistry
    Computer Simulation of Vesicle Structure from Self-assembly of Miktoarm Star-like Block Copolymers in Dilute Solution
    LI Bin, ZHU You-Liang, XU Dan, PEI Han-Wen, LIU Hong
    2013, 34(7):  1667-1672.  doi:10.7503/cjcu20130058
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    The self-assembly of miktoarm star-like block copolymers in dilute solution was studied with dissipative particle dynamics(DPD) simulations. The pathway of self-assembly, as well as the influence of molecular architecture of the block copolymers on the self-assembly structures were studied in this paper. The miktoarm star-like block copolymers aggregate into disk-like micelles, then the micelles can close to form a vesicle. For the system with short hydrophilic branch, it is easy to form the vesicle, and the thickness of the bilayer membrane of vesicle is larger since the hydrophobic branches of the miktoarm star-like block copolymers are longer. The results show that it is easier for the miktoarm star-like block copolymers to assemble into vesicles than for the corresponding linear diblock copolymers.

    Theoretical Studies on Adsorption of PFOS on Anatase TiO2 Surfaces
    XUE Qian-Qian, HE Guang-Zhi, XIA Shu-Wei, PAN Gang
    2013, 34(7):  1673-1678.  doi:10.7503/cjcu20130024
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    Adsorption behavior of perfluorooctane sulfonate(PFOS) on anatase TiO2 surfaces was studied with DFT-B3LYP method. Physisorption including hydrogen-bond interaction and chemi-adsorption including bidentate binuclear(BB) and monodentate mononuclear(MM) complexes were investigated in the study. Calculations of adsorption energy(Eads) and Gibbs free energy(ΔGads) showed that physisorption was easier tooccur. Chemi-adsorption surface complexes were produced by reaction between PFOS and surface water(H2O) or hydroxyl(-OH), and the reaction to replace H2O was easier than that to replace -OH group. MM1(reacted with one H2O of surface) surface complex was the most thermodynamically favorable chemi-adsorption mode. The thermodynamically favorable and stability order of PFOS adsorbed on anatase TiO2 surfaces was H-bonded(hydrogen bonded adsorption)>MM1(reacted with one H2O of surface)>BB1(reacted with two H2O of surface)>MM2(reacted with one -OH of surface)>BB2(reacted with one H2O and one -OH of surface). Results of bond length analysis indicated that the interaction between H2O/-OH function group on TiO2 surface and sulfonate group in PFOS resulted in the formation of moderate intensity hydrogen bond. Charges transferred from PFOS molecule to TiO2 surface during chemi-adsorption process, leading to the formation of Ti—O—S bond, and transfered electrons in the process were mainly from strong electronegative atoms O and F.

    Asymmetric Hydrogenation of Acetophenone and Its derivatives Catalyzed by (1S,2S)-DPEN Modified Ir/γ-Al2O3
    YANG Jun, ZHAO Wen-Bo, YANG Chao-Fen, SUN Xiao-Dong, WANG Qi, ZHU Yan-Qing, CHEN Hua
    2013, 34(7):  1679-1684.  doi:10.7503/cjcu20130013
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    Under the basic conditions, an efficient catalyst without any stabilizer was prepared and applied in the asymmetric hydrogenation of acetophenone and its derivatives. The effects of different base, concentration of (1S,2S)-diphenylethylenediamine[(1S,2S)-DPEN] and base, reaction temperature and pressure of hydrogen on the asymmetric hydrogenation of acetophenone were investigated in detail. The results showed that this catalytic system had high activity and moderate enantioselectivity for the asymmetric hydrogenation of acetophenone and its derivatives. Under the optimum conditions, a good enantiomeric excess(e.e.) value of 80.3% was obtained for asymmetric hydrogenation of isobutyrophenone. Especially, the catalyst preparation is simple and no stabilizer was applied. The catalyst performance is steady and the catalyst can be reused several times through the facilitative separation of the catalyst from the reaction medium.

    Studies of Quantum Chemistry of Structure and Properties of 3,7-Bis(nitroimino)-2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3.3.0]octane
    JIN Xing-Hui, HU Bing-Cheng, JIA Huan-Qing, LV Chun-Xu
    2013, 34(7):  1685-1690.  doi:10.7503/cjcu20130011
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    A novel high energetic density compound of 3,7-bis(nitroimino)-2,4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3.3.0]octane(HNGG) was designed. The stable geometry of the compound was completely optimized at the B3LYP/6-31G(d,p) theoretical level of density functional theory(DFT) and the IR spectrum was obtained. The bond dissociation energy(BDE) of the thermolysis initiation bond N7—N22 was calculated and BDE value was 91.47 kJ/mol. The heat of formation of 1219.94 kJ/mol and theoretical density of 2.16 g/cm3 were obtained via isodesmic reaction and Monte-Carlo method, respectively. Based on the theoretical density, the formula of Kamlet-Jacobs was used to predict the detonation properties. The results show that HNGG meets the requirements of high energetic materials with detonation velocity of 10.43 km/s, detonation pressure of 53.44 GPa and detonation heat of 7407.84 J/g. In addition, synthetic route of HNGG was also designed.

    Preparation and Particle Size Controllability of Mg-Al Layered Double Hydroxides via Coprecipitation Method Using T-type Microchannel Reactor
    SUN Mei-Yu, PANG Xiu-Jiang, MA Xiu-Ming, HOU Wan-Guo
    2013, 34(7):  1691-1696.  doi:10.7503/cjcu20121169
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    A T-type microchannel reactor was used to prepare Mg-Al layered double hydroxides(LDHs) via the coprecipitation method. The effects of flow rate of reactant solutions, concentration of mixed salt solution and temperature on the particle size and the particle size distribution of the LDH samples were examined. The results show that the morphology and crystal structure of the LDH samples obtained using the T-type microchannel reactor are similar to those of the materials synthesized by the conventional coprecipitation method. However, the T-type microchannel reactor route could afford smaller particle size and very narrow distribution of particle size for the materials. The flow rate, concentration of mixed salt solution and temperature have an important influence on the particle size and the particle size distribution of the obtained LDH samples. With the increases of the flow rate and temperature, the particle size and the particle size distribution of the obtained LDH samples decreased, while with the increase of the concentration of mixed salt solution, those increased. A major advantage of the T-type microchannel reactor route is that the particle size and the particle size distribution of the as-obtained samples can be simply and effectively controlled by the flow rates of the reactant solutions.

    Properties and Application of Dual Function Pyridinium-based Ionic Liquid in Dye-sensitized Solar Cell
    CAI Mo-Lang, PAN Xu, LIU Wei-Qing, HUO Zhi-Peng, CHEN Hai-Wei, ZHANG Chang-Neng, DAI Song-Yuan
    2013, 34(7):  1697-1702.  doi:10.7503/cjcu20121097
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    1-Ethyl-4-tert-butyl pyridinium iodide(TBEPI) was synthesized under solvent-free condition in the autoclave. The adsorption of TBEPI on the TiO2 surface was measured by the attenuated total reflection.Fourier thansform infrared spectroscopy(FTIR) analysis. The influence of TBEPI and 1,2-di-methyl-3-propylimidazolium iodide(DMPII) on redox behavior and the electron recombination in the dyed-TiO2/electrolyte interface were investigated by cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) in the dark. It is found that TBEPI can be used as the iodine resource and effectively forms the blocking layer to restrain the electron recombination. The performance of dye-sensitized solar cell is improved by modification of TBEPI as a result. This study will provide a perspective to the low cost and high efficiency of DSC by electrolyte optimization.

    Synthesis of cis-Dioxomolybdenum(Ⅵ)-tridentate Schiff Base Complexes and Its Catalytic Activity on the Epoxidation of Soybean Oil
    ZHANG Shu-Yuan, JIANG Ping-Ping, LENG Yan, XU Yu-Cheng, MO Guan-Tian, BIAN Gang
    2013, 34(7):  1703-1708.  doi:10.7503/cjcu20121093
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    The tridentate Schiff base ligand salicylaldehyde-2-hydroxyanil(H2SAP) was obtained via a Schiff base condensation reaction between salicylaldehyde and o-aminophenol in ethanol medium. cis-Dioxomolybdenum(Ⅵ)-tridentate Schiff base complex MoO2(SAP)(EtOH) was synthesized by mixing H2SAP with a solution of MoO2(acac)2 in ethanol. MoO2(SAP)(EtOH) was characterized and its catalytic activity was examined for epoxidation of soybean oil(SBO). The effects of types of oxidants, reaction temperature, time, solvent and additives on the epoxidation of SBO were discussed in detail. The conversion and selectivity of epoxidized soybean oil(ESO) reach 43.0% and 67.2%, respectively, at 80℃ for 4 h, with tert-butyl hydroperoxide(65% TBHP, mass fraction) as oxidant. Meanwhile, the epoxide yield was related to the nature of additives. The yield of ESO reduced dramatically by adding strong coordinating ligands such as imidazole. The mechanism of interaction between the catalyst and oxidant was also investigated.

    Preparation and Electrochemical Performance of Li2MnSiO4/CNTs Composite Cathode Material for Lithium Ion Batteries
    GAO Wei, BAO Li-Ying, SU Yue-Feng, TIAN Jun, LIU Wei, CHEN Shi, WU Feng
    2013, 34(7):  1709-1713.  doi:10.7503/cjcu20121057
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    Li2MnSiO4/CNTs composite cathode material for lithium ion batteries was in situ synthesized by the sol-gel process assisted with hydrothermal method. The crystalline structure and morphology of the obtained samples containing 0, 5, 10, 20 and 30 g carbon nanotubes(CNTs) in 1 mol Li2MnSiO4, respectively, were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and their electrochemical performances were evaluated by different electrochemical test. The results show that the grains of samples have narrow size distribution and their dimension is about 100 nm. They are easy to be an agglomerate mass and the agglomeration of the samples is gradually reduced with the increase of the contents of CNTs. The XRD patterns reveal that the well-crystallized Li2MnSiO4/CNTs materials are orthorhombic with space group Pmn21. The sample with 20 g CNTs in 1 mol Li2MnSiO4(the carbon content is 16.74%) demonstrates the best electrochemical performance, showing an initial discharge capacity of 150 mA·h/g and a discharge capacity of 80 mA·h/g after 20 cycles at 10 mA/g current density. The in situ composite of CNTs could improve the overall conductivity and the electrochemical performance of Li2MnSiO4 cathode materials.

    Systematic Reduction and Analysis of Kinetic Mechanism for High-temperature Combustion of Methyl Heptanoate
    LI Shu-Hao, FANG Ya-Mei, WANG Fan, LI Ping, LI Xiang-Yuan
    2013, 34(7):  1714-1722.  doi:10.7503/cjcu20121047
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    The detailed chemical kinetic mechanism for high-temperature combustion of methyl heptanoate was systematically reduced via integrated mechanism reduction methods. The skeletal mechanism including 108 species and 547 elementary reactions was derived via two-step directed relation graph method(DRG) combined with the principle component analysis(PCA) method from the detailed mechanism consisting of 1087 species and 4592 elementary reactions. The skeletal mechanism was further reduced through time-scale analysis. The computational singular perturbation method(CSP) was used for the selection of quasi-steady state(QSS) species, and 30 species were chosen as good candidates for QSS species. Finally, based on the quasi-steady state approximation(QSSA) method, a reduced mechanism including 78 species and 74 global reactions was obtained. Both the skeletal mechanism and the 78 species reduced mechanism could reproduce combustion characteristics of the detailed mechanism such as the ignition delay, extinction, and distribution of species concentration over a wide range of simulation conditions. Furthermore, based on the skeletal mechanism, reaction path and elementary reactions which are important for high temperature combustion of methyl heptanoate were clarified. Compared with the detailed mechanism, the skeletal mechanism is able to provide a reliable description on high temperature combustion characteristics of methyl heptanoate, which could be helpful in understanding the combustion process of biodiesel.

    Preparation of ZnO/Co-MCM-41 Molecular Sieves and Their Catalytic Performance for Isoamyl Alcohol Oxidation
    GAO Hu-Fei, ZHAO Bin-Xia, LIU Wei-Juan, LIU Lin-Xue, YE Wei, GAO Han, ZHANG Yi, ZHANG Xiao-Li
    2013, 34(7):  1723-1730.  doi:10.7503/cjcu20121041
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    Co-doped MCM-41 supported catalysts 5%ZnO/xCo-MCM-41 were prepared by impregnation method, and applied in the synthesis of isovaleric aldehyde from isoamyl alcohol with dioxygen. The samples were characterized via X-ray diffraction(XRD), fourier transform-infrared spectroscopy(FTIR), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), scanning electron microscopy(SEM), NH-3 temperature programmed desorption(NH-3-TPD), H-2 temperature programmed reduction(H-2-TPR) and N-2 adsorption-desorption. The effects of Co-doping amount on the structure and catalytic performance of molecular sieves were investigated. The results showed that the specific area and pore volume of samples decreased gradually with the increase of Co-doping amount, while median pore diameter first increased and then decreased. 5% ZnO/Co-MCM-41 molecular sieves still remained ordered hexagonal mesopore structure of MCM-41 and had high speci-fic surface area(989 m2/g), pore size(2.88 nm) and larger pore volume(0.88 cm3/g) when Co-doping amount was 0.05. The cobalt introduced into Co-MCM-41 existed mainly as single-site Co(Ⅱ) ions, which improved the effective dispersion of ZnO and moderately reduced the acidity of 5% ZnO/MCM-41 mole-cular sieves. At the same time, it improved the oxidation-reduction potential of 5% ZnO/MCM-41. Compared with 5%ZnO/MCM-41, The selectivity of isovaleric aldehyde increased 28.3% with 5% ZnO/0.05Co-MCM-41.

    Theoretical Study on Antitumor Activities of Naphthoquinone Derivatives
    FAN Wen-Hai, ZHANG Li-Hong, ZHANG Zi-Long, GUO Jing-Fu, REN Ai-Min, GE Peng-Fei
    2013, 34(7):  1731-1738.  doi:10.7503/cjcu20120985
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    A systematic theoretical investigation included 39 kinds natural alkannin derivatives were performed by means of quantum chemical computation method. The ionization potential(IP), electronic affinity(EA) and bond disassociation energy(BDE) of the hydrogen atom in the hydroxyl(O—H) were calculated. The relationship between these physical quantities and the hydroxyl-free radical scavenging activities were analyzed, including the spin density of 5-, 7-, 9-site carbon in the compounds and O14, O16 oxygen, and the effect of EA of molecules on the antitumor activity. The research proves that introducing side chain and unsaturated bond will lead to the decrease of BDE, IP and EA values. All these changes will result in the increase of free radical scavenging activities, which shows that the effect of antineoplastic activity will become more obvious. While introducing large volume group into branch of side chain groups will increase of BDE and IP of the compounds.

    Electrochemical Catalytic Chlorination of Bergenin by Chloroperoxidase Modified Electrode
    WANG Ke, WU Xia-Qin, LI Lin, TIAN Hai-Tao, LU Zhong-Qing
    2013, 34(7):  1739-1742.  doi:10.7503/cjcu20120965
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    A chloroperoxidase(CPO) modified electrode was fabricated by drop-coating the mixture solution of CPO and didodecyldimethylammonium bromide(DDAB) onto the glassy carbon electrode surface. Direct electron transfer of immobilized CPO was observed from cyclic voltammogram. The CPO modified electrode was further used as the working electrode for electrocatalytic chlorination of bergenin in O2-saturated bergenin solution containing potassium chloride. The chlorinated product was confirmed by HPLC-MS. The total turnover number(TTN) of the reaction is estimated to be 13600.

    Electrochemical Quartz Crystal Microbalance Studies on the Storage Behavior of Ions at Activated Carbon Electrodes in NaClO4 Aqueous Solutions
    GAO Ji-Chao, YIN Jiao, QI Li, WANG Hong-Yu
    2013, 34(7):  1743-1747.  doi:10.7503/cjcu20120955
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    Electrochemical quartz crystal microbalance(EQCM) was used to study the mass changes on activated carbon electrodes in various NaClO4 aqueous solutions during the course of ions adsorption into the pores of the electrode. For each electrolyte solution, the hydration numbers of Na+ in the bulk solutions and at the electrode/solution interface were calculated from Raman and EQCM data, respectively. These two sets of hydration numbers of Na+ were compared and the desolvation effect of Na+ was investigated. Results indicate that the desolvation effect of Na+ is suppressed by increasing the concentrations of NaClO4 aqueous solutions, which may be one of the main reasons for the improvement of the supercapacitors' power density. At the same time, results also prove that EQCM is an excellent tool for studies on ions' adsorption.

    Effect of Ethylenediamine-tetramethylene Phosphonic Acid in Electrolyte on Electrocatalytic Performance of Carbon Supported Pd Catalyst for Formic Acid Oxidation
    LU Liang, TANG Ya-Wen, CHEN Yu, CHEN Ting-Ting, GE Cun-Wang, LU Tian-Hong
    2013, 34(7):  1748-1752.  doi:10.7503/cjcu20120866
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    In order to improve the electrocatalytic performance of carbon supported Pd(Pd/C) anodic catalyst for formic acid oxidation in the direct formic acid fuel cell(DFAFC), the effect of ethylenediamine-tetramethylene phosphonic acid(EDTMP) added into the electrolyte on the electrocatalytic performance of Pd/C catalyst for formic acid oxidation was investigated using the energy dispersive X-ray spectroscopy(EDS), X-ray diffraction(XRD) pattern, transmission electron microscopy(TEM) and electrochemical techniques. The Pd/C catalyst electrode in the electrolyte with 0.5 mmol/L EDTMP displays the best electrocatalytic activity and stability for formic acid oxidation. This result is attributed to that the adsorbed EDTMP on the surface of Pd not only decreases the amount of adsorbed CO at the Pd/C catalyst electrode by the ensemble effect but also inhibits the decomposition of formic acid over the Pd/C catalyst to decrease the CO poisoning. However, when the concentration of EDTMP is higher than 0.5 mmol/L, overfull adsorbed EDTMP would occupy the active sites of Pd to decrease the electrocatalytic performance.

    Polymer Chemistry
    Synthesis and Properties of Novel Poly(amic acid) Bearing Oligoaniline Pendants
    CHAO Dan-Ming, WANG Shu-Tao, CHI Mao-Qiang, YANG Rui, WANG Ce
    2013, 34(7):  1753-1757.  doi:10.7503/cjcu20130297
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    A novel poly(amic acid) bearing oligoaniline pendants was designed and prepared. Fourier transform infrared spectroscopy(FTIR), 1H nuclear magnetic resonance spectroscopy(1H NMR) and gel permeation chromatography(GPC) were used to characterize its structure. The prepared polymer displayed an interesting spectroscopic property and reversible electrochemical activity. The material shows satisfactory electrochromic properties with high contrast value, acceptable switching times and excellent coloration efficiency.

    Preparation of Amidoxime Modified Polyacrylonitrile Nanofibers and Its Application in Metal-ion Containing Waste Water Treatment
    DING Yao-Ying, WANG Cheng-Zhi, WEN Xian-Fang, ZHANG Xin-Peng, YE Lin, ZHANG Ai-Ying, FENG Zeng-Guo
    2013, 34(7):  1758-1764.  doi:10.7503/cjcu20130145
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    Polyacrylonitrile non-woven mat with nanofibers was fabricated by electrospinning, and amidoxime modified polyacrylonitrile nanofibers which can be used to absorb and recover metal ion from metal ion containing waste water were prepared via in situ amidoxime modification in aqueous solution. The copper chloride solution was used to simulate metal ion containing waste water and the adsorption behavior of amidoxime modified polyacrylonitrile nanofibers with different oximation time was evaluated. The nanofibers after 8 h oximation were calculated to possess the highest adsorption capacity of 56.5 mg/g according to Langmuir equation, and the concentration of metal ion containing waste water can be reduced from 100 mg/L to 13 μg/L after treating with amidoxime nanofibers, which not only reach but also highly exceed the national standard for metal ion containing waste water treatment(<0.5 mg/L, GB8978-1996). On the other side, the metal ions were desorbed from nanofibers in dilute acid solution, and the desorption ratio was more than 98% after 100 min desorption in 1 mol/L HNO3 solution. Furthermore, the amidoxime nanofibers remain more than 50% of its original adsorption capacity after four adsorption-desorption circles, which showed relative recycling ability of amidoxime nanofiber.

    Fabrication of Electrically Conductive Adhesive Films of Polyelectrolyte/Carbon Nanotubes by Layer-by-Layer Assembly
    ZHANG Jian-Fu, LI Yang, LI Zhi-Cheng, WANG Li-Feng, SUN Jun-Qi
    2013, 34(7):  1765-1769.  doi:10.7503/cjcu20130180
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    Water-based highly adhesive films with satisfactory electrical conductivity were constructed by Layer-by-Layer(LbL) assembly technique. Poly(allylamine hydrochloride) and carbon nanotube(CNT) complexes(PAH-CNT) were assembled with a blend of poly(acrylic acid) and CNT(PAA-CNT) to produce PAH-CNT/PAA-CNT films. Strong adhesion as high as 7 MPa can be achieved when glass substrates deposited with LbL assembled PAH-CNT/PAA-CNT films are slightly pressed together, which means that the glued conductive adhesive films with an area of 1 cm2 can hold a weight of approximate 70 kg. The thin nature of the adhesive films and the incorporated carbon nanotubes endow the adhesive films with satisfactory electrical conductivity.

    One-pot Synthesis and Characterization of Diblock Copolymer via Combining Enzymatic and ATRP
    SA Zong-Peng, LIU Yan-Jing, LI Ya-Peng, ZHU Ming, LI Yu-Xiang, WANG Jing-Yuan
    2013, 34(7):  1770-1775.  doi:10.7503/cjcu20130078
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    Diblock copolymer poly(n-butyl methacrylate)-block-poly(10-hydroxydecanoate)(PnBA-b-PHD) was prepared by one pot strategy via combination of enzymatic polymerization of 10-hydroxydecanoate(HD) and atom transfer radical polymerization(ATRP) of n-butyl methacrylate(nBA). The obtained copolymer was characterized by 1H NMR, FTIR and gel permeation chromatography(GPC). The solution properties of diblock copolymer into water in dry state were examined by atom force microscopy(AFM), in which well-dispersed spherical micellar structure in mono-modal pattern was clearly observed with a size value around 135 nm. Whereas the hydrodynamic diameter of the aggregates surrounded in tetrahydrofuran(THF) was determined by dynamic light scattering(DLS) instrument.

    Preparation and Behavior of Sulfonated Poly(aryle ether ketone sulfone) Containing Amino Proton Exchange Membrane
    XU Jing-Mei, CHENG Hai-Long, MA Li, BAI Hong-Wei, REN Chun-Li, ZHANG Hui-Xuan, WANG Zhe
    2013, 34(7):  1776-1781.  doi:10.7503/cjcu20130066
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    The sulfonated poly(aryle ether ketone sulfone) with different sulfonation degree containing amino copolymers were prepared by polycondensation method. The FTIR and 1H NMR spectra of amino membrane-sulfonated poly(aryle ether ketone sulfone)(Am-SPAEKS) show that the amino groups are introduced into SPAEKS copolymers. The measured results show that the thermal stability, dimensional stability, resistance methanol performance and proton conductivities of Am-SPAEKS membranes are improved due to the introduction of amino groups. The proton conductivity of Am-SPAEKS-1 membrane reaches 0.0894 S/cm at 80℃. The methanol permeability coefficient of Am-SPAEKS-1 membrane is only 0.24×10-6 cm2/s, which is lower than that of pure SPAEKS(0.87×10-6 cm2/s) membrane and Nafion(2×10-6 cm2/s) membrane. All the results indicate that the Am-SPAEKS membranes are promising as proton exchange membranes for middle-high temperature proton exchange membrane fuel cells applications and direct methanol fuel cells(DMFCs).

    Preparation and Properties of Bioactivite Coating on Poly(ether ether ketone) Composite
    YAN Peng-Tao, LI Wen-Ke, WANG Yong-Peng, ZHU Ye, ZHANG Hai-Bo, JIANG Zhen-Hua
    2013, 34(7):  1782-1787.  doi:10.7503/cjcu20130048
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    By the linkage of silane coupling agent, light cured coating was formed on poly(ether ether ketone)/barium-containing glass filler(PEEK-BGF) composite surface. The coating was composed of bioactive nano hydroxyapatite(nHA) and methacrylate light cure resin. Scanning electron microscope(SEM) and X-ray photoelectron spectroscopy(XPS) were used to analyze the topography and elements distribution feature of the sample surface, and the bonding strength was tested by the universal testing machine. Rat osteoblasts cells were cultured on the material surface. The total protein concentration test and alkaline phosphatase(ALP) assay of osteoblasts were performed to examine the bioactivity of new type light cured nano hydroxyapatite/polymethacrylate(nHA/PMMA)hybrid coating. The results show that the nHA hybrid coating can form a rough morphology on the composite surface. With the increase of nHA content, the bioactivity of the coating is enhanced.

    Preparation of Polyaniline/Polystyrene Janus Composite Particles
    CHEN Qin-Hui, CHEN Bao-Ling, ZHENG Long-Hui, LIN Jin-Huo
    2013, 34(7):  1788-1793.  doi:10.7503/cjcu201152
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    A general approach of swelling was used to synthesize the TiO2/PS Janus composite particles. The TiO2/PS Janus composite particles were modified at the knob of TiO2 with aniline to synthesize the PANi/PS Janus composite particles. The surface morphology, component and properties of Janus particles were characterized by scanning electron microscope(SEM), energy dispersive spectrometer(EDS), elemental analysis, transmission electron microscope(TEM), Fourier transform infrared spectrometer(FTIR), thermogravimetric analysis(TGA), ultraviolet spectrophotometer(UV) and four-probe measurement. The results showed that the snowman-like PANi/PS composite particles were dark green. The average diameter of the knob of PS was about 228 nm and that of PANi knob increased from 258 nm which was the average diameter of TiO2 knob in TiO2/PS Janus composite particles to 295 nm. Ti elements could not observed by EDS which was replaced by N element. The mass fraction of PANi in PANi/PS Janus composite particles was about 23.7%. Compared with that of the TiO2/PS Janus composite particles, the conductive properties of PANi/PS Janus particles which was redoped by p-toluenesulfonic acid increased obviously and the conductivity was 0.247 S/cm.

    Synthesis of 6-Methyl-3-methacryloxyethyl-3,4-dihydro-2H-benzo[e][1,3]oxazine and Its Copolymer
    ZHANG Wen-Li, ZHU Chun-Li, WANG Deng-Xia, YAO Bing-Jian, LI Xiao-Na, LU Zai-Jun
    2013, 34(7):  1794-1800.  doi:10.7503/cjcu20120981
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    6-Methyl-3-methacryloxyethyl-3,4-dihydro-2H-benzo[e][1,3]oxazine(MEBM) was synthesized by simple esterification reaction of 2-(6-methyl-4H-benzo[e][1,3]oxazin-3-yl)-ethanol(MB-OH) with methacryloyl chloride. MBEM/N-Phenylmaleimide copolymer[P(MBEM-co-NPMI)] was synthesized with N-phenylmaleimide(NPMI) and MBEM by free radical solution polymerization using azodiisobutyronitrile(AIBN) as initiator and toluene as solvent. The corresponding polymers of PMB-OH, PMBEM and P[P(MBEM-co-NPMI)] were obtained by thermal cross-linking of MB-OH, MBEM and P(MBEM-co-NPMI), respectively. The molecular weight of the resulting copolymer was determined by gel permeation chromatography(GPC). The structure and chemical composition of MBEM and P(MBEM-co-NPMI) were characterized by Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance spectroscopy(1H NMR, 13C NMR). The curing behavior of all substances was also studied by differential scanning calorimetry(DSC) and FTIR. Thermal properties of the cross-linking polymers of PMB-OH, PMBEM and P[P(MBEM-co-NPMI)] were investigated by dynamic mechanical analysis(DMA) and thermal gravime-tric analysis(TGA). The results show that the temperatures in maximum loss factor of the cross-linking polymers of PMB-OH, PMBEM, and P[P(MBEM-co-NPMI)] are 92, 129, and 181℃, respectively. The temperatures in maximum loss modulus of the cross-linking polymers of PMB-OH, PMBEM and P[P(MBEM-co-NPMI)] are 56, 91 and 156℃, respectively. Under N2, the temperatures of the cross-linking polymers of PMB-OH, PMBEM and P[P(MBEM-co-NPMI)] at 5% mass loss are 257, 244 and 260℃, respectively, and the temperatures at 10% mass loss are 280, 266, 284℃, respectively. Their ultimate char yields are 23.2%, 17.8% and 14.0% at 800℃, respectively. These results suggest that P[P(MBEM-co-NPMI)] has excellent heat resistant performance.

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