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    10 August 2018, Volume 39 Issue 8
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.39 No.8(2018)
    2018, 39(8):  0-0. 
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    Articles: Inorganic Chemistry
    Property of Au Nanoshuttles with Arrow-head Prepared via Wet Chemical Synthetic Method
    WU Dan, LI Man, ZHONG Yao, AN Kuisheng, CHEN Yanwei
    2018, 39(8):  1617-1623.  doi:10.7503/cjcu20180301
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    Au nanoshuttles(Au NSs) with arrow-head were synthesized via wet chemical method by adjusting the concentration of chemical precursors in the solution. The crystal structure and optical properties of Au nanoshuttles were researched by different characterization methods including transmission electron microscopy, UV-Vis-NIR absorption spectra and SERS spectra, etc. At the same time, the growth mechanism of Au nanoshuttles was discussed. Au nanoshuttles have good photothermal properties compared with Au nanorods. The anisotropic Au nanoshuttles with arrow ends feature the local surface plasmon resonance optical properties and possess more advantages than the metal materials with other morphology when they are used in the applications about enhanced local electric field and photothermal conversion. In addition, their photothermal conversion efficiency was calculated. The effect of arrow morphology on the photothermal properties of Au nanoshuttles was disscussed.

    Efficient Synthesis of Highly Uniform AlPO4-11 Microcrystalline and Study on the Crystallization Process
    XIA Kun, ZHOU Dan, YANG Yun, YANG Shuijin, XIA Qinghua
    2018, 39(8):  1624-1630.  doi:10.7503/cjcu20180103
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    AlPO4-11 microcrystalline molecular sieve was synthesized rapidly and efficiently in the rotation hydrothermal crystallization mode. In the static hydrothermal crystallization mode, the pure phase of the AlPO4-11 molecular sieve cannot be obtained, and the crystal size is large, which consists of 50—70 μm rod crystals and 5—10 μm spherical crystals. Compared with the static hydrothermal crystallization mode, the rotation hydrothermal crystallization mode(rotational speed: 100 r/min) can greatly shorten the crystallization time of AlPO4-11 molecular sieve(the shortest crystallization time is 40 min) and significantly reduce the grain size with the crystal being 1 μm×0.5 μm microcrystalline. The crystallization process of AlPO4-11 was studied by means of powder XRD, scanning electron microscope(SEM), confocal microscopy Raman spectroscopy and Fourier transform infrared(FTIR) spectroscopy.

    Ionic Liquid Assisted Synthesis of α-Fe2O3 Nanospheres Based on Potassium Acetate Solution and Their Gas-sensing Properties
    PAN Shuai, HU Xiaobing, SONG Runmin, XIE Lili, ZHU Zhigang, ZHENG Liaoying
    2018, 39(8):  1631-1639.  doi:10.7503/cjcu20170804
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    α-Fe2O3 nanospheres with good crystallinity and uniformity, diameter of 10—30 nm were synthesized from FeCl3·6H2O and CH3COOK with 1-butyl-3-methylimidazolium chloride([Bmim]Cl) as ionic liquid structure-based agent and surfactant by hydrothermal method at a constant temperature of 150 ℃ for 8 h. The effects of different amounts of [Bmim]Cl on the formation of iron oxide and its gas sensing properties were investigated. The gas-sensing results show that α-Fe2O3 nanospheres exhibit the best gas-sensing properties to ethanol when the amount of ionic liquid is 12 mmol. When the working temperature is 300 ℃, the sensitivity of as-prepared α-Fe2O3 nanospheres to 50 μL/L ethanol is 7.56, which is 5.6 times that of α-Fe2O3 generated without ionic liquid. There is also a good linear relationship(R=98.8%) in the range of 10—200 μL/L, and the sensor has good selectivity and stability. In addition, the gas-sensing mechanism of α-Fe2O3 nanospheres to ethanol, and the influence of operating temperature on its gas-sensing properties were discussed in detail.

    Analytical Chemistry
    Sepatation of Antipyretic Analgesics by CapillaryElectrochromatography with Block Copolymer Coating
    FENG Wenya, QIAO Juan, QI Li, LI Zhiwei
    2018, 39(8):  1640-1646.  doi:10.7503/cjcu20170853
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    A unique open tubular capillary electrochromatography(OT-CEC) system with block copolymer coating was constructed for separation of antipyretic analgesics. The amphipathic poly(maleic anhydride-co-styrene) was synthesized by reversible addition-fragmentation chain transfer polymerization method. The effects of several key factors on the OT-CEC separation efficiency were investigated. Interestingly, by adding organic solvent to the running buffer, the block copolymer coating could self-assemble to form micelle-like spheres and play the role of surfactants. Comparing with the bare capillary, the coating one could enhance the separation efficiency obviously. Moreover, the results indicated that the coating capillaries had a good stability and repeatability. Under the optimized OT-CEC conditions, the developed OT-CEC assay was used to ananlyze the antipyretic drugs in clinical tables with satisfactory linearity(R2≥0.988). The detection limits obtained from the calculations based on signal-to-noise ratio(S/N=3) were 3.5—4.8 μg/mL for the test drugs.

    Synthesis and Application of Colorimetric Probe for the Simultaneous Detection of Sulphion and Homocysteine/Cysteine in the Serum Samples
    XIA Yuting, JIANG Bo, WU Qing, HU Qinghong, YUAN Zeli
    2018, 39(8):  1647-1655.  doi:10.7503/cjcu20170806
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    A new but versatile probe 1 was developed, which can be used for simultaneous detection and discrimination of sulphion(S2-) and homocysteine(Hcy)/cysteine(Cys). 4-Bromine-1,8-naphthalenedicarboxy-licanhydride was used as the starting material to prepare probe 1 by the reactions of condensation and Williamson ether synthesis. Meanwhile, probe 1 was characterized by means of 1H NMR, 13C NMR, HRMS, elemental analysis and FTIR spectra. The recognition mechanism of the colorimetric probe 1 responses to S2- and Hcy/Cys was verified by high performance liquid chromatography, mass spectrum and 1H NMR titration. A lot of detailed experiment results indicate that the colorimetric probe 1 responses of these three analytes are most likely the result of the thiol nucleophilic reaction. Probe 1 shows rapid, selective and sensitive response for these three analytes with unique absorbance enhancement at 552 nm for S2- and distinct fluorescent turn on signal changes at 552 nm for Hcy/Cys. At the same time, after reaction of probe 1 with S2- or Cys in Tris-HCl(10 mmol/L, pH=7.4, 50% ethanol) buffer solution, the color of solution changed from colorless to purple-red or wine, respectively. Therefore, probe 1 could be used to develop a colorimetric test kit for S2- and cysteine. The detection limits of probe 1 for S2-, Hcy and Cys were respectively determined as 8.83×10-6, 1.26×10-6 and 7.65×10-7 mol/L, indicating that the probe 1 has a good sensitivity for S2- and Hcy/Cys. In addition, the competitive experiments results show that the probe 1 is highly selective for S2- and Hcy/Cys over other competitive. Probe 1 could be used to detect S2- and Hcy/Cys in the serum samples with satisfactory results.

    Determination of Dopamine Based on RO/Gold Nanoparticles-poly(dienedimethylammonium chloride) Modified Carbon Fiber Microelectrode
    LI Yuan, WANG Tingting, LI Mei, CHENG Han
    2018, 39(8):  1656-1661.  doi:10.7503/cjcu20180034
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    Carbon fiber microelectrode(CFME) was modified with oxygen-containing groups(RO) in pure water by potentiostatic method, then with poly(dially dimethyl ammonium chloride)(PDDA) functionalized gold nanoparticles(AuNPs) by electrochemical deposition method, as a result, the RO/AuNPs-PDDA/CFME was fabricated. The surface morphologies of different modified microelectrodes were characterized by means of scanning electron microscope(SEM), and the cyclic voltammetry behaviors of DA were investigated with modified electrodes. The research results showed that in pH 7.0, 20 mmol/L Tris-HCl buffer solution, the RO/AuNPs-PDDA/CFME exhibited excellent electrocatalytic effect toward dopamine(DA). Under the optimal experimental conditions, the oxidation peak current was proportional to the concentration of DA in the range of 1×10-7—5×10-5 mol/L with a correlation coefficient of 0.9912. The detection limit was 3.3×10-8 mol/L(S/N=3). In brief, the RO/AuNPs-PDDA/CFME has the advantages of simple preparation, good reproducibility and high stability, thus, it is suitable for sensitive detection of DA.

    Rapid Detection on Chlortetracycline Residues in Honey by Surface-enhanced Raman Spectroscopy
    ZHANG Lutao, ZHOU Guangming, LUO Dan, CHEN Rong
    2018, 39(8):  1662-1667.  doi:10.7503/cjcu20180016
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    The surface-enhanced Raman spectroscopy(SERS) technique was used to rapidly and non-destructively detect the residues of chlortetracycline(CTC) in honey. The prepared gold nanoparticles were used as Raman signal enhancement module. The influence of volume ratio and interact time between gold nanoparticles and CTC was discussed and optimized. Different concentrations of CTC solution were detected. The linear equation of concentration and Raman signal strength on characteristic peak was drawing. After pretreated, the recovery rate of honey sample was detected by the recovery of standard addition. The results show that the characteristic peak of chlortetracycline in 1450 cm-1 could be used to detecting chlortetracycline(CTC) residues in honey. The best volume ratio of gold nanoparticle to CTC was 1:1 and the best interact time was 1 min. Within the scope of 10—250 mg/L, there was a favorable linearity between the concentration of CTC and SERS characteristic peak in 1450 cm-1. Linear equation was Y=1×10-4X+0.0110, and the coefficient of determination was 0.9948. Recovery rate was from 80% to 120% when detecting chlortetracycline(CTC) residues in honey. This detection method is simple, fast, and accurate which provides a new method for detecting antibiotic residues in foods.

    Organic Chemistry
    Cytotoxic Activity of Trichothecene Compounds and Derivatives from Myrothecium sp.
    JIA Yunjing, SHI Wensi, HU Feiliu, ZHU Huajie, LIU Li, MA Zhengyue
    2018, 39(8):  1668-1675.  doi:10.7503/cjcu20180007
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    Five trichothecene compounds were obtained from Myrothecium sp. KX136897 and their structures were confirmed by means of 1H NMR, 13C NMR and HRMS. Compound 1 was used for the further structural modifications and four new derivatives were synthesized. The structure of compound 6 was different from those of the other derivatives, which was identified via comparing its 13C NMR with the reported structure. Furthermore, compound 6 was confirmed by comparing the calculated data with the experimental data of 13C NMR. Compounds 1—9 were used for antibacterial and cytotoxic activity study, respectively. It was found that if the epoxy ring at positions C12 and C13 was opened and then reformed a new four-membered epoxy ring, the cytotoxic activity of compound 1 would decrease. Besides, the protection of hydroxyl at position C2' by acyl would also cause the decrease of cytotoxic activity.

    Triphenylamine-based Dicyanostilbene Type Two-photon Fluorescence Solvatochromic Probe
    HUANG Chibao, PAN Qi, CHEN Huashi, LIANG Xing, LÜ Guoling
    2018, 39(8):  1676-1682.  doi:10.7503/cjcu20180157
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    Using the diphenylamino group as the electron donor, the cyano group as the electron acceptor, and the dicyanostilbene as a two-photon fluorophore, a novel two-photon fluorescence solvatochromic probe(SP1) was developed by means of the structure-activity relationship of D-π-A(D: electron donor, A: electron acceptor) electron architecture. The structure was characterized and identified by means of nuclear magnetic resonance spectra and element analysis instrument. SP1 showed a wide range of 152 nm in solvent solvatochromism, the maximum emission wavelengths in cyclohexane and dimethylsulfoxide(DMSO) were 452 and 604 nm, respectively. It can be used for the detection of solvent polarity and viscosity. Solvents can also be identified according to maximum emission wavelengths. SP1 had a large two-photon absorption cross section, the maximum two-photon absorption cross-sections in cyclohexane and DMSO were 6670 and 2040 GM, respectively, and also had a large Stokes shift(194 nm). Its photostability, water solubility and cell permeability were excellent. The probe can be used for the measurement and imaging of cell viscosity.

    Synthesis and Antibacterial Activities Evaluation of Chalconesemicarbazone Derivatives Bearing 1,3,4-Thiadiazole Moiety
    WAN Jinlin, WU Shouqun, GAN Yiyuan, MENG Jiao, WANG Zhenchao*, OUYANG Guiping*
    2018, 39(8):  1683-1690.  doi:10.7503/cjcu20180081
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    A series of chalconesemicarbazone derivatives bearing a 1,3,4-thiadiazole moiety was designed and synthesized from benzaldehyde and 1,3,4-thiadiazole. All the target compounds were characterized by means of nuclear magnetic resonance and high resolution mass spectrometer. The preliminary bioassay results indicated that all the title compounds exhibited a certain antibacterial activities in vitro against Xanthomonas oryzae pv. oryzae, Ralstonia solanacearum and Xanthomonas axonopodis pv. citri. Especially, compounds 7j and 7k displayed excellent antibacterial activities(100%) against the above three plant pathogenic bacteria at a concentration of 100 μg/mL. And the corresponding EC50 (50% effective concentration) values were 15.13, 30.90, 24.49 and 21.33, 24.54, 14.79 μg/mL, respectively, which were superior to the commercial antibacterial agent bismerthiazol(92.23, 58.88 and 123.02 μg/mL).

    High Efficiently co-Catalytic Oxidation Bio-guaiacol to Vanillin by Co2+/Ni2+
    MAO Haifang, ZHANG Bo, HU Xiaojun, CAI Jiaoyang, MEI Tiantian, LIU Jibo, ZHANG Xiaoliang
    2018, 39(8):  1691-1698.  doi:10.7503/cjcu20180187
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    A catalytic oxidation system involving transition metals Co2+ and Ni2+ was studied for high-efficiency vanillin preparation under alkaline conditions. The catalytic system could efficiently convert a variety of biomass guaiacol into vanillin rapidly in low O2 pressure. Using the density functional theory(DFT), the molecular model of the reactants was constructed and the reaction activity of the substituent group was verified by analyzing the electron cloud density of α-carbon and β-carbon. Furthermore, considering the reaction taken place in a closed environment with the presence of CH3OH and O2 under high temperature and pressure, the safety experiments were employed to ensure the experiment carrying out under safety condition. It also had important guiding significance to industrial production in the future.
    Synthesis and Electrochromic Properties of Thiophene-carbazol-benzene Derivativies
    QU Xingxing, DAI Yuyu, LI Weijun, OUYANG Mi, ZHANG Cheng
    2018, 39(8):  1699-1706.  doi:10.7503/cjcu20170837
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    The central phenyl and biphenyl groups were introduced into the N-positions of two thiophene-carbazole structures to form the desired 9,9'-(1,4-phenylene)bis[3,6-di-2-thienyl]-9H-carbazole(BTCPh) and 9,9'-[1,1'-biphenyl]-4,4'-diylbis[3,6-di-2-thienyl]-9H-carbazole(BTCBPh), respectively. The obtained BTCPh and BTCBPh were electrochemically polymerized to generate the corresponding polymers, poly 9,9'-(1,4-phenylene)bis[3,6-di-2-thienyl]-9H-carbazole(pBTCPh) and poly 9,9'-[1,1'-biphenyl]-4,4'-diylbis[3,6-di-2-thienyl]-9H-carbazole(pBTCBPh), which might possess the cross-linked structure. The polymers were investigated by different character methods, such as cyclic voltammetry, multi-current step, ultraviolet visible near infrared absorption spectrum, scanning electron microscope and so on. The results showed that both of pBTCPh and pBTCBPh polymers exhibited excellent electrochromic properties with similar color changes, high optical contrast and good electrochemical cycle stability. And pBTCPh polymer film showed the faster color switching speed than pBTCBPh, which was ascribed to the possible more uniform stack structure in pBTCPh film. The uniform stack structure was beneficial to the fast ion inserting/deserting behavior in the electrochromic process.

    Asymmetric [3+2] Annulations of 1,4-Di-thiane-2,5-diol and N-Boc Aldimines Catalyzed by Tertiary-amine Thiourea
    DONG Xu, FENG Boxu, CHEN Li, LI Xin
    2018, 39(8):  1707-1712.  doi:10.7503/cjcu20170847
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    A highly enantioselective asymmetric [3+2] annulation of 1,4-di-thiane-2,5-diol and N-tert-butoxy-carbonyl(N-Boc) aldimines was catalyzed by a bifunctional tertiary-amine thiourea catalyst. The N-Boc aldimine was assumed to be activated and oriented by the hydrogen bonds of the thiourea, meanwhile the tertiary amine of the catalyst would provide suitable basicity to enhance the nucleophilicity of the mercaptoace-taldehyde. This method realized the construction of double chiral center via a one-step synthesis. As a result, a number of chiral thiazolidine scaffolds, which present in bioactive molecules widely, were smoothly synthesized with 10%(molar fraction) chiral catalysts, and achieved up to 95% enantioselectivity and 7:1 diastereoselectivity in good yields.

    Physical Chemistry
    Photofragment Translational Spectroscopy of CF3I at 238 nm:Vibrational Distribution of CF3 Fragments andCurve Crossing Probability
    LIN Dan, CHENG Min, DU Yikui, ZHU Qihe
    2018, 39(8):  1713-1720.  doi:10.7503/cjcu20180152
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    The photodissociation dynamics of CF3I at 238 nm was studied using our high resolution mini-TOF(time of flight) photofragment translational spectrometer. The results indicated the strongest signal comes from the I* channel of the 3Q0 parallel transition[i.e., CF3I(X)→CF3I(3Q0)→CF3(ν)+ I*], and the vibrational peaks of CF3 fragments were resolved. From the peak gap, both the overtone bands (ν1, ν2=0) and the combination bands(ν1, ν2=1) of CF3 fragments were partially resolved(ν1=701 cm-1, the symmetric stretch mode; ν2=1086 cm-1, the umbrella mode). At 238 nm, the ratio of the two band series was found with ∑P(ν1, 1)/∑P(ν1, 0)=0.48/0.52. The vibrational distribution of CF3 fragments were also measured. The branching fractions of the four pathways were 0.664 for X→3Q0 → I*, 0.084 for X→3Q01Q1→I, 0.178 for X→1Q1→I and 0.074 for X→1Q13Q0→I*. The experimental curve crossing probability for 3Q01Q1 was P01=0.112 and that for 1Q13Q0 was P1→0 =0.294. The anisotropy parameter of I* channel was β(I*)=1.70, and that of I channel was β(I)=-0.04.

    Catalysis Theoretical Study on Water Gas Shift Reaction of Au-based Binary Alloy Au12M(M=Cu,Pt,Ni)
    FANG Lei, XIA Shengjie, XUE Jilong, MENG Yue, QIAN Mengdan, LUO Wei, ZHANG Xiaofeng, NI Zheming
    2018, 39(8):  1721-1728.  doi:10.7503/cjcu20180118
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    The structural stability, thermodynamic stability and reactivity of Au12M(M=Cu,Pt,Ni) alloy clusters doped with Cu, Pt and Ni were studied by density functional theory(DFT) calculations. The reaction mechanism of water gas shift reaction(WGSR) in gold-based binary alloy clusters was also discussed. The Au12Ni alloy clusters were found to have the best stability and electron activity. The reaction mechanism of redox mechanism and carboxyl mechanism in gold-based binary alloy clusters was explored. The result shows that the WGSR on the Au12Cu alloy is in accordance with the redox mechanism A, those on Au12Pt and Au12Ni alloy clusters are in accordance with the redox mechanism B. Comparing the optimal reaction path of the three clusters, Au12Cu clusters show the best catalytic activity for WGSR.

    Molecular Dynamics Simulation on the Orientation of Alkane Mixture on Graphene
    LIU Yanfang, YANG Hua, ZHANG Hui
    2018, 39(8):  1729-1733.  doi:10.7503/cjcu20180097
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    The orientation of alkane mixtures on graphene was studied by molecular dynamics simulation. It has been found that the orientation is affected by the simulation temperature. The alkane chains are laid perpendicular to the graphene at low temperature and parallel to the surface at high temperature. As the temperature increases, some of the shorter alkane chains will leave the mixture, and the number of these shorter alkane chains will gradually increase.

    Study on the Decay Dynamic of Excited State and Photodissociation Channel for 2-Nitronaphthalene
    YANG Meng, ZHANG Tengshuo, ZHENG Xuming, XUE Jiadan
    2018, 39(8):  1734-1740.  doi:10.7503/cjcu20170768
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    Density functional theory(DFT) and complete active space self-consistent field(CASSCF) calculation methods, combination with the level of activation space(10,10), and basis set 6-31G(d) were used to obtain structures information of ground state, excited states, intersections and transition states for 2-nitronaphthalene(2NN) and its nitrous acid ester isomer(ISO). Multi-configurational second-order perturbation(CASPT2) method with basis set Aug-cc-PVDZ was adopted in calculating the energy of all the given structures and the Frank-Condon areas. At the same time, the potential energy surface scans along N—O bond were carried out to determine the feasibility of the dissociation for isomers. Finally, the overall picture of decay dynamics for 2NN after being excited to S1-FC(ππ*) was presented based on those calculation results. The results show that the nonradiative decay pathway to T1 state of 2NN originates from S1-FC(ππ*), undergoes intersystem crossing and internal conversion through curve-crossing points of S1T3, S1T2 and T2T1. Thus the efficient decay channel can be: S1-FC-2NN®S1T3-MIN-2NN or S1T2-MIN-2NN®T3-MIN-2NN or T2-MIN-2NN®T2T1-MIN-2NN®T1-MIN-2NN. This pathway is the most important nonradiative decay channel for excited state decay dynamics of 2NN due to the small energy barrier and high efficiency of forming transient species of T1 state. In addition, calculation results on the potential energy surface suggest that isomerization reactions from 2NN to ISO need to overcome big energy barriers in S0, T1 and S1 states, respectively, which results in the pretty low efficiency of ArO· radicals.

    Effect of Structural Ordering on the Performance of Mesoporous Carbon Supported CuCoCe Catalyst in the Synthesis of Higher Alcohols from Syngas
    WEI Junyi, GAO Zhihua, HUANG Wei, AI Peipei, YAN Feifei, YOU Xiangxuan
    2018, 39(8):  1741-1749.  doi:10.7503/cjcu20180207
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    Three kinds of mesoporous carbons were synthesised via soft-templating methods by adjusting the molar ratio of formaldehyde and resorcinol in the carbon source. The CuCoCe catalysts supported on different mesoporous carbons were prepared by co-impregnation method. The effect of structural mesopore ordering to catalytic properties for higher alcohol synthesis from syngas was studied in this passage and the catalysts were characterized by X-ray diffraction(XRD), N2 adsorption-desorption(BET), transmission electron microscopy(TEM) and X-ray photoelectron spectroscopy(XPS), etc. The results show that the catalytic property has been constantly improved with the improvement of mesopore ordering. The catalyst supported on the highly ordered mesoporous carbon has the highest space-time yield(869.14 mg·gcat-1·h-1) and selectivity(50.48%) of higher alcohols, where the mole fraction of C2+OH reached 90.31% in the alcohol products.This study show that the pore structure affects the distribution and presence of active metals on the support. Highly ordered 2D hexagonal straight pore channels are conducive to the uniform dispersion of the active component CuCo and its close association, which promot the electron transfer between the two, thereby effectively inhibiting the continuous growth of the carbon chain, resulting in a significant increase in the activity of the catalyst and narrowing the distribution of the alcohol product.

    Synthesis of Fe2O3/rGO/N-rGO Catalyst and Its Application in Selective Hydrogenation of Nitrobenzene
    WANG Yingyu, ZHAO Huaiyuan, HOU Zhaoyin
    2018, 39(8):  1750-1758.  doi:10.7503/cjcu20170844
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    Iron-based catalysts exhibited excellent performance for ammonia synthesis, production of olefins(via Fischer-Tropsch synthesis), selective catalytic reduction of NOx, and so on. It is of great significance to explore new applications and mechanisms of iron catalysis, which has attracted more attention for its abundance, low price, and nontoxicity. Herein, a convenient and stable iron oxide(Fe2O3)-based catalyst was prepared via the pyrolysis of graphene oxide, aniline and ferrous acetate at varied temperature(denoted as Fe2O3/rGO/N-rGO), in which active Fe2O3 nanoparticles(NPs) were supported on composite carbon films composed of reduced graphene oxide and nitrogen-reduced graphene oxide. The resulting Fe2O3/rGO/N-rGO composites were applied for the selective hydrogenation of nitrobenzene. It was found that Fe2O3/rGO/N-rGO-700 composite was highly active and stable for the direct selective hydrogenation of nitrobenzene to aniline under mild conditions, because of large surface area, micropore-mesopore compound channel and dispersed Fe2O3NPs. At the same time, it was found that the hydrogenation of NB performed mainly in a direct routine, which can depress the formation of those byproducts with high boiling points.

    Electrochemical Behaviour of Gd(Ⅲ) on Bi Electrode and Thermodynamic Data of BixGdy Intermetallic Compounds in LiCl-KCl Molten Salts
    JIANG Tao, WANG Ning, PENG Shuming, LI Mei, HAN Wei, CHEN Yitung
    2018, 39(8):  1759-1767.  doi:10.7503/cjcu20170820
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    Electrochemical behaviours of Gd(Ⅲ) were investigated on liquid Bi pool electrode and Bi film electrode in eutectic LiCl-KCl molten salts in the temperature range of 723—823 K by a series of electrochemical techniques. Moreover, the thermodynamic data, such as activities and relative partial molar Gibbs energies of Gd in the Bi-Gd alloys as well as the Gibbs energies, enthalpies and entropies of formation for Bi2Gd, BiGd, Bi3Gd4 and Bi3Gd5 were calculated using open circuit chronopotentiometry. Galvanostatic and potentiostatic electrolysis were performed to prepare the Bi-Gd alloy on liquid Bi electrode. The alloy samples were characterized by X-ray diffraction(XRD) and scanning electronic microscopy-energy dispersive spectrometry(SEM-EDS). The results indicate that Bi-Gd alloys are comprised of BiGd and Bi3Gd5 phase, respectively.

    Mechanisms and Electrochemical Properties of Different Stabilizers in Stannous Methanesulfonate Solution
    WANG Chaonan, LU Haiyan, HUANG Weimin, LI Xiangzhong, LIN Haibo
    2018, 39(8):  1768-1774.  doi:10.7503/cjcu20180072
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    The effects of hydroquinone, catechol, resorcinol and ascorbic acid on the stability of stannous methanesulfonate plating bath, electrochemical properties and the surface morphology of the tin coating were investigated. And the relationship between the stability of the plating solution and the reducibility and electrochemical activity of the stabilizer was explored by cyclic voltammograms. The influence of stabilizer on the cathodic polarization performance of the bath was investigated by alternating current(AC) impedance and chronopotentiometry. The principle of cyclic application of hydroquinone in electroplating process and the optimal concentration of hydroquinone were studied. The results show that there is an important relationship between the stability of the plating solution and the reduction ability and electrochemical activity of the stabilizer. The stability of the four stabilizers on the bath is in the order of magnitude: hydroquinone>catechol>ascorbic acid>resorcinol, and hydroquinone, the best stabilizer, can double the storage time of the plating solution. Phenolic stabilizers can increase the degree of cathodic polarization of tin deposition and refine the grains, while ascorbic acid has a depolarization effect on the deposition of tin. Hydroquinone plays a role of antioxidant, brightener and leveler in the tin electroplating process. The corrosion resistance of the coating shows that the optimum concentration of hydroquinone is 1.0 g/L.

    Electrochemical In-situ Synthesis and Photocatalytic Properties of BiF3 Thin Films
    ZHAO Zu, LI Rui, ZHANG Xiaochao, ZHANG Changming, LIU Jianxin, WANG Yawen, WANG Yunfang, FAN Caimei
    2018, 39(8):  1775-1781.  doi:10.7503/cjcu20180001
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    BiF3 thin films were prepared by simple in-situ electrochemical method at room temperature. The X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), UV-Vis diffuse reflection spectroscopy(UV-Vis DRS) and density functional theory(DFT) were employed to characterize the crystallinities, structures, morphologies, optical properties and energy band structures of the as-prepared BiF3 thin films. The photocatalytic activity and stability of BiF3 thin films were evaluated by the degradation of Rhodamine B(RhB) under simulated sunlight irradiation. The results show that the BiF3 thin films exhibit the nanosheet structure with high purity, excellent photocatalytic activity and stability. The conduction band minimum and the valence band maximum of BiF3 thin films are mainly contributed by Bi6p and F2p orbital electrons, respectively. It was also found that, with the increase of electrolyte concentration, the structural morphologies of BiF3 thin films changed, resulting in that the photocatalytic activity of BiF3 thin films first enhances and then decreases. When the electrolyte concentration is 1.5%, the BiF3 nano-film is obviously staggered, which is conducive to the transport of reactants and light reflection, thereby increasing the reaction space of catalyst and the utilization efficiency of light. The photocatalytic degradation efficiency of RhB reaches 99.2% after 5 h simulated solar light irradiation, and still remains above 81% after being used 4 times. The possible formation mechanism of BiF3 thin films on Bi plate via novel in-situ electrochemical method was proposed.

    Electrochemical Performance of Hydroxylated Multi-walled Carbon Nanotube Sandwich Separator in Lithium-sulfur Battery
    WANG Jie, SUN Xiaogang, CHEN Wei, LI Xu, HUANG Yapan, WEI Chengcheng, HU Hao, LIANG Guodong
    2018, 39(8):  1782-1789.  doi:10.7503/cjcu20180067
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    Hydroxylated multi-walled carbon nanotube cellulose paper(MWCNTs-OHP) was obtained by vacuum filtration of hydroxylated multi-walled carbon nanotubes(MWCNTs-OH) and paper fibers. A multi-functional PP@MWCNTs-OHP@PP sandwich separator was formed by MWCNTs-OHP cellulose paper sandwiching between two polypropylene(PP) membranes and was used in lithium-sulfur battery. The morphology and structure of PP@MWCNTs-OHP@PP were characterized by transmission electron microscopy(TEM), scanning electron microscopy(SEM), infrared spectroscopy and energy dispersive spectroscopy(EDS). The electrochemical test showed that the initial discharge capacity of Li-S batteries with the PP@MWCNTs-OHP@PP sandwich separator reached to 1532 mA·h/g and the utilization rate of active substances reached 91.5%. The capacity still maintained 516 mA·h/g at 1C after 500 cycles with stabilized coulombic efficiency above 96.4% and slow capacity decay rate of 0.028% per cycle. As the charge-discharge rate decreased from 3C to 0.1C, the discharge capacity recovered from 336 mA·h/g to 820 mA·h/g, showing excellent magnification.

    Preparation of Ni3N Nanosheet Arrays/Carbon Cloth Anode and Its Catalytic Activity for Oxygen Evolution Reaction
    HONG Guohui, WU Weili, WANG Chen, ZHANG Nan, WANG Jiku, ZHAO Lina, YANG Weiqiang
    2018, 39(8):  1790-1796.  doi:10.7503/cjcu20180052
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    Ni(OH)2 nanosheet arrays on carbon cloth[Ni(OH)2 NAs/CC] were synthesised via hydrothermal treatment. Then Ni3N nanosheet arrays on carbon cloth(Ni3N NAs/CC) were prepared through the nitridation of corresponding Ni(OH)2 NAs/CC precursor with NH3, thus polymer binder free three dimensional self-supporting electrode was established. The structure and morphology of the composite electrode materials were investigated by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM) and transmission electron microscopy(TEM) analyses. The results indicate that the porosity, roughness and electrochemical effective area of Ni3N NAs/CC electrode surface are increased. The activities for the oxygen evolution reaction(OER) of the Ni3N NAs/CC were explained by recording linear scanning voltammograms and Tafel plots, the results indicate that the activity for OER is effectively increased and the overpotential for oxygen evolution could be lowered by approximately 280 mV. In the meantime, Ni3N NAs/CC electrode exhibited good durability.

    Polymer Chemistry
    Preparation of Pickering Emulsion of Paraffin Wax and Microspheres Using Polymer Particles as Pickering Stabilizer
    XIAO Zuoxu, CAO Hongyan, JIANG Xubao, KONG Xiangzheng
    2018, 39(8):  1797-1805.  doi:10.7503/cjcu20170848
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    Polymer particles were prepared through precipitation polymerization of trihydroxymethyl propane triacrylate(TMPTA) with 1-dodecene(DC) in binary solvent of ethanol-water(EtOH-H2O) without any surfactant and stabilizer. The particles of P(DC-TMPTA) were used to prepare Pickering emulsion of paraffin wax in a mixture of EtOH-H2O by simple shaking at 70 ℃, above the melting point of the wax. By rapidly cooling down the system to temperature far below the melting point of the wax, wax microspheres with narrow size distribution were obtained. The process was optimized with regard to the composition of EtOH-H2O, shaking rate and the size of P(DC-TMPTA) particles. Morphology of the wax microspheres was examined by SEM, showing the wax spheres were covered by a layer of P(DC-TMPTA) particles. The size of the wax spheres was easily adjustable, from about 50 μm to 480 μm, by changing the shaking rate or the amount and the size of the polymer particles. This process is featured by the absence of any additives except the free radical initiator in the preparation of P(DC-TMPTA) particles. This work provides therefore a novel pathway to the fabrication of uniform and clean wax microspheres.

    Synthesis of TiCl3 Complexes Containing Aryloxy Groups and Application for Ethylene Polymerization and Copolymerization
    WANG Jianwei, REN Yingchun, MI Puke, XU Sheng
    2018, 39(8):  1806-1814.  doi:10.7503/cjcu20170841
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    Novel olefin polymerization catalysts with lower cost and simple synthetic process were developed. ArOTiCl3 complexes[(2-OMeC6H4O)TiCl3(C1), (2,4-Me2C6H3O)TiCl3(C2), TiCl3(1,4-OC6H4O)TiCl3(C3), TiCl3(1,4-OC6H2O-Me2-2,5)TiCl3(C4)] and corresponding (ArO)2TiCl2 complexes [TiCl2·(OC6H4-OMe-2)2(C5) and TiCl2(OC6H3-Me2-2,6)2(C6)] were synthesized and well characterized. When combined with methylaluminoxane(MAO), the ArOTiCl3 /MAO system shows moderate activity for ethylene copolymerization with 1-hexene. The 13C NMR result of polymer indicates that the 1-hexene incorporation in polymer reached up to 6.88%(molar fraction). The polymer was characterized by 13C NMR and the mechanisms of methyl, ethyl and long side chain formation were given. The effects of polymerization temperature, concentration of polymerization monomer and polymerization time on the catalytic activity were investigated.

    Synthesis of Folate-conjugated Stearic Acid Grafted Bletilla striata Polysaccharides Copolymers and Application for Delivering Antitumor Drugs as a Drug Delivery Carrier
    GUAN Qingxiang, JI Danyang, SUN Bo, QIAO Jin, HE Tong, ZHANG Guangyuan, YU Zhenjing, YIN Jianyuan, YANG Wei
    2018, 39(8):  1815-1822.  doi:10.7503/cjcu20180021
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    Folate-conjugated stearic acid-grafted Bletilla striata polysaccharides copolymers(FA-BSPs-SA) were prepared and characterized using 1H nuclear magnetic resonance spectroscopy(1H NMR), ultraviolet visible spectrophotometry(UV) and infrared spectroscopy(IR). Docetaxel-loaded FA-BSPs-SA(DTX-loaded FA-BSPs-SA) micelles were prepared by an emulsion-solvent evaporation method and characterized. The cytotoxicity of copolymers and DTX-loaded micelles was evaluated by MTT assay. The results of 1H NMR and IR demonstrated that stearic acid and folic acid have been grafted on Bletilla striata polysaccharide. Docetaxel could be entrapped into micelles of FA-BSPs-SA copolymer. DTX-loaded BSPs-SA copolymer micelles displayed pH-dependent properties in the respects of in vitro release behavior ranging from pH=5.0 to pH=7.4. The particle sizes of DTX-loaded micelles decreased whereas encapsulation efficiency and loading capacity increased with the substitution degree increase of folic acid. The cell survival rates subjected to FA-BSPs-SA and BSPs-SA were still above 80% at the concentration of 40 μg/mL. The anti-tumor effect in vitro of DTX-loaded FA-BSPs-SA and DTX-loaded BSPs-SA micelles were superior to that of DTX solution at the same concentration. More-over, DTX-loaded FA-BSPs-SA micelles exhibited stronger inhibitory effects on tumor cells with folate receptor expression in comparison to DTX-loaded BSPs-SA micelles. FA-BSPs-SA polymers are expected to be nanoscale materials for hydrophobic antitumor drugs.

    Preparation of Hydrophilic Epoxy Resin and Its Wettability Regulation
    QIAN Yihao, ZHANG Dongjie, CHENG Zhongjun, KANG Hongjun, LIU Yuyan
    2018, 39(8):  1823-1828.  doi:10.7503/cjcu20180174
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    A hydrophilic shape memory epoxy resin was prepared by introducing polyethylene glycol(PEG) into the 4,5-epoxy cyclohexane-1,2-2-phthalate glycidyl ester(TDE-85) epoxy/m-phenylenediamine(MXDA) system, meanwhile, its surface wettability could be controlled by changing its pillar structure under external thermal-stimuli. The result shows that the introduction of PEG effectively increases the hydrophilicity of TDE-85 epoxy resin, and the optimal amount of PEG is 20%(mass fraction). In this condition, the water contact angle is about 54 °, indicating the realization of wetting conversion from the original hydrophobic TDE-85 epoxy resin/MXDA curing system(water contact angle is about 108°) to the hydrophilic TDE-85/MXDA/PEG system. The Tg of the obtained material is 71 ℃, and its shape fixed ratio and recovery ratio are 96.10% and 99.97%, respectively, meaning that the obtained material has a good shape memory property. The micropillars onto the surface by the template method, reversible wetting switching between the hydrophilicity(51°) and the superhydrophilicity(0°) can be realized based on the shape memory ability.

    In situ Initiation, Polymerization and Construction of Cationic Active Sites of Gemini Molecules in Polysulfone Substrates
    YANG Jiarui, WANG Yifu, WANG Jilin, WANG Lulu, FENG Ruijiang
    2018, 39(8):  1829-1837.  doi:10.7503/cjcu20170769
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    Gemini-type polymerizable cationic surfactant monomer(maleate diethyl bis [octyl(dodecyl, hexadecyl)dimethyl chloride/ammonium bromide])(G8-2-8, G12-2-12, G16-2-16) was introduced into a chloroform casting solution of a polysulfone(PSF) polymer, with the help of potassium persulfate(KPS) initiator, in situ initiation of the aforementioned Gemini molecule polymerization, thereby preparing a Gemini/polysulfone anion exchange membrane with an ordered array of cationic active sites. The anion conductive film was subjected to structural characterization and performance testing. The results showed that with the increase of Gemini content, the indexes of water uptake, swelling ratio, ion exchange capacity and electrical conductivity showed an increasing trend. With the growth of hydrophobic carbon chains in the Gemini structured, the water uptake, swelling ratio, ion exchange capacity, conductivity, elongation at break and so on decrease, the tensile strength of the membrane material increased. When the mass fraction of Gemini was 20% and the carbon number of hydrophobic hydrocarbon chain was 8, the water uptake was 12.35%, the swelling ratio was only 10.13%, the ion exchange capacity was 0.61 mmol/g, and the conductivity was 3.776 mS/cm at 80 ℃. Alkali resistance of G8-2-8-PSF series membranes was investigated at 80 ℃ and 6 mol/L KOH alkaline, the results showed that after 240 h of alkali-bubble, the highest decrease in conductivity was only 2.0%, showing a good alkali stability.

    Preparation of Hydrophilic Polypropylene/Polyvinyl Butyral Hollow Fiber Membranes by Melt-spinning-stretching
    LUO Dajun, SHAO Huiju, JIN Jinbo, XIE Gaoyi, CUI Zhenyu, YU Jie, QIN Shuhao
    2018, 39(8):  1838-1845.  doi:10.7503/cjcu20170784
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    Polyvinyl butyral(PVB) as hydrophilic modification agent and polypropylene-g-maleic anhydride(PP-g-MAH) as a compatibilizer were blended with polypropylene(PP) in order to prepare hydrophilic PP/PVB hollow fiber membranes by melt-spinning and stretching(MS-S). The effect of PVB at different mass ratios on crystallization behavior and hydrophilicity of PP/PVB blends was investigated by differential scanning calorimeter(DSC) and water contact angle(WCA). The wide angle X-ray diffraction(WAXD) and small-angle X-ray scattering(SAXS) were used to analyze the effect of PVB at different mass ratios on the crystalline lamellar structure of PP/PVB hollow fiber after annealed. The pore dimensions and distribution of inner surface of PP/PVB hollow fiber membranes were measured using field emission scanning electron microscope(FESEM). In addition, the porosity and pure water flux of PP/PVB hollow fiber membranes were tested. The results showed that the hydrophilicity of PP /PVB blends was improved obviously because of WCA of PP/PVB blends reduced from 103° to 76° with the increase of PVB. At the same time, PVB accelerated the nucleation rate of PP because of PVB acted as heterogeneous nucleation effective. However, the maleic anhydride of PP-g-MAH was chemically bound to hydroxy of PVB, which also delayed the motion of molecular chain and leaded to imperfect crystal structure, especially excessive addition of PVB. The results confirmed WAXD and SAXS analysis. The crystallinity of PP/PVB2.5(2.5%PVB) hollow fiber was better than that of pure PP hollow fiber after annealed. The lamellar orientation, lamellar thickness, and structure of Shish-Kebab of PP/PVB2.5 hollow fiber were better than that of pure PP hollow fiber after annealed. The porosity of corresponding hollow fiber membrane was 66% and pure water flux was 320 L/(m2·h), which increased by 76.8% compared with that of the pure PP hollow fiber membrane.

    Co-immobilized Laccase-Mediator System with Ionic Liquids-regenerated Cellulose Microspheres for Indole Degradation
    2018, 39(8):  1846-1852.  doi:10.7503/cjcu20170799
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    An innovative method of preparing immobilized Laccase-Mediator System (Im-LMS) was established by immobilizing Trametes versicolor laccase and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) on cellulose microspheres simultaneously. The mediator ABTS was mixxed with ionic liquid cellulose solution and was encapsulated during the process of cellulose regeneration. The as-prepared cellulose-ABTS microspheres(Ce/ABTS) with 3D pore structure were characterized by SEM, XRD and FT-IR. Then laccase was immobilized on Ce/ABTS by dopamine self-polymerization to synthesize Ce/ABTS@Do/Lac. The method developed in this work, for the first time, realized the co-immobilization of laccase and mediator facilely and effectively. The Ce/ABTS@Do/Lac were used in the enzymatic degradation of indole, and the degradation rate was up to 99%. As compared with the free laccase, the Ce/ABTS@Do/Lac showed higher pH stability and operational stability.Benefited from the mediation effect of the immobilized ABTS, the Ce/ABTS@Do/Lac still worked after 9 cycling runs, which was 9-fold longer than that of a free laccase-mediator system. The successful recovery of both laccase and mediator is promising to reduce the cost for the application of laccase in wastewater treatment and might be helpful to cut down the secondary pollution from free laccase mediators. The Ce/ABTS@Do/Lac must have a great potential in large-scale application for organic wastewater treatment.
    Copolymerization of Norbornene and 1-Octene Catalyzed by Bis(phenoxy-imine) Titanium Complex
    MENG Jiafeng, NI Xufeng, ZHENG Hao, SHEN Zhiquan
    2018, 39(8):  1853-1858.  doi:10.7503/cjcu20180089
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    The copolymer of norbornene with 1-octene was prepared by the catalysis of the ternary catalytic system consisted of bis(phenoxy-imine) titanium complex(Ti), triisobutyl aluminum(Al) and organoboron compound(B). The obtained copolymer showed a modest molecular weight(Mw: ca. 3.0×104—6.5×104) and broad molecular weight distribution(MWD: ca. 2.0). The influence of copolymerization conditions was explored. The optimal copolymerization conditions are as follows: n(Al)/n(Ti)=5:1, n(B)/n(Ti)=1:1, n(Monomer)/n(Ti)=400:1, n(NBE)/n(OC)=5:5, polymerized at 40 ℃ for 6 h and the copolymer yield reached up to 43.7%. The reactivity ratios of norbornene and 1-octene were 3.01 and 0.08, respectively, tending to form a random copolymer. The copolymer exhibited good thermal stability(Td>300 ℃) and moderate glass transition temperature(Tg=87—174 ℃) controlled by the content of norbornene in the backbone.