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    10 October 2017, Volume 38 Issue 10
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.38 No.10(2017)
    2017, 38(10):  0-0. 
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    Articles: Inorganic Chemistry
    Thermal Reduation Preparation of Co2+/Dy3+ Doped Cubic Fe3O4 and Their Magnetic Targeting Retention
    YANG Yuxiang, LIU Yicheng, ZHAO Min, YUAN Hongming, YAO Pingping, HUANG Yan, NI Chaoying
    2017, 38(10):  1709-1718.  doi:10.7503/cjcu20170132
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    Co2+/Dy3+ doped Fe3O4 nanoparticles(MxFe3-xO4) were synthesized by the thermal reduction and co-precipitation methods . The structure, morphology and magnetic properties of MxFe3-xO4 were characterized by means of X-ray diffractometer(XRD), transmission electron microscope(TEM) and vibrating sample magnetometer(VSM). The results show that the dopants did not change the maternal symmetry, and the maternal morphology gradually transformed from cube to sphere. The MxFe3-xO4 cubic magnetic particles have maximum saturation magnetization of 76.65 and 70.21 A·m2·kg-1, respectively, when Co2+ actual doping amount is equal to 0.44 and Dy3+ actual doping amount is equal to 0.05. Compared with the superparamagnetic Fe3O4, the cubic high magnetic doped Fe3O4 nanoparticles showed a high retention rate in the simulated magnetic fluid magnetic targeting experiment in vitro.

    Fabrication of Hierarchical Hemisphere Ag Substrate Using Transfer Imprinting with No Pressure Under Ambient Temperature
    SHI Gang, BAI Huiyu, WANG Likui, SANG Xinxin, YANG Jingguo, NI Caihua, LI Ying
    2017, 38(10):  1719-1723.  doi:10.7503/cjcu20170340
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    PS microsphere arrays with three kinds of particle sizes, which were used to make soft templates, were fabricated by self-assembling. Then, the polymethyl methacrylate(PMMA) hemispherical arrays were transferred from the soft template onto the substrate under ambient temperature with no pressure. Ag nanoparticles were formed by photo-reduction on the surface of hemispherical arrays, which performed surface enhanced Raman scattering. The key to this successful transfer imprinting is that the low surface energy of soft template and the hydrogen bond of the interface between PMMA and the substrate.

    Synthesis and Structure Characterization of Homochiral Helical Coordination Polymers with 4-Connected Net Based on Lactic Acid Derivatives
    XU Zhongxuan
    2017, 38(10):  1724-1729.  doi:10.7503/cjcu20170066
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    Using lactic acid derivatives (R),(S)-4-(1-carboxyethoxy)benzoic acid[(R)-H2CBA and (S)-H2CBA)] and 1,4-di(1H-imidazol-1-yl)benzene(1,4-DIB) ligand to assemble with Ni2+ ions, a pair of novel 4-connected homochiral metal-organic frameworks, [Ni2((R)-CBA)2(1,4-DIB)3(H2O)2xH2O(1-D) and [Ni2((S)-CBA)2(1,4-DIB)3(H2O)2] ·xH2O(1-L) have been synthesized under hydrothermal conditions. Complexes 1-D and 1-L feature 2-fold interpenetration structure, containing two kinds of helical chains constructed by achiral 1, 4-DIB ligands and Ni2+ ions. Moreover, powder X-ray diffraction(PXRD), thermogrtavimetric analysis(TGA) and solid-state circular dichroism(CD) techniques were also applied to investigate the properties of the complexes..

    Analytical Chemistry
    Structure and Pathway Research on Chemical Transformation of Ginsenoside Rb1 via HPLC-HRMS/MSn/QqQ Technique
    LI Xue, ZHAO Huanxi, MIAO Rui, LI Wenying, XIU Yang, LIU Shuying
    2017, 38(10):  1730-1736.  doi:10.7503/cjcu20170216
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    Keggin-type dodeca tungstophosphoric acid(HPW) was used in the chemical transformation of ginsenoside Rb1. The aim of this research is to analyze the structure of the transformed products and transformation pathways based on high-performance liquid chromatography coupled with three kinds of mass spectrometry(HPLC-MS), the potential of which in qualitative and quantitative analysis of natural product was also developed. Q Exactive, a kind of high-resolution MS(HRMS), was used for the rapid structural identification of transformed products. Multistage tandem MS(MSn) was further applied to verifying the identified structure. Ten transformed products, 20(S)-Rg3, 20(R)-Rg3, 20(S)-25-OH-Rg3, 20(R)-25-OH-Rg3, 25-OH-Rk1, 25-OH-Rg5, Rg5, Rk1, (20S,25)-epoxy-Rg3 and(20R,25)-epoxy-Rg3 were rapidly identified in all. In HPW-generated acidic solution, ginsenoside Rb1 was chemically transformed through deglycosylation, epimerization at C20 as well as hydration, elimination and cyclization reactions on the aglycone. Triple quadrupole(QqQ) MS was further used in its SRM mode for the accurately quantitative analysis of the conversion of Rb1 and the yield of 20(S)-Rg3, 20(R)-Rg3, Rk1 and Rg5. Rb1 was completely transformed to rare ginsenosides within 40 min. Based on the quantitative analysis results, HPW exhibited a much higher activity towards the transformation of Rb1 in comparison with biotransformation, and it is a kind of efficient reagent for the chemical transformation of ginsenoside Rb1. What’s more, HPLC-HRMS/MSn/QqQ technique was proved to be effective for the qualitative and quantitative analysis of the natural products such as ginsenosides.

    Cytidine-protected Copper Nanoclusters as a Novel Fluorescent Probe for the Detection of Dichromate Anion
    CHEN Tianxia, ZHANG Zhengtao, WANG Yong, NI Yongnian
    2017, 38(10):  1737-1741.  doi:10.7503/cjcu20170160
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    We constructed a fluorescent sensor for the detection of dichromate anion(Cr2O2-7) on the basis of the quenching effect of Cr2O2-7 on the fluorescence of cytidine-protected copper nanoclusters(CuNCs). The experimental results showed that the Cr2O2-7 sensing system provided a linear range of 0.05—7.0 μmol/L with a low detection limit(S/N=3) of 24 nmol/L. In addition, the sensing system exhibited a good selectivity for Cr2O2-7 detection, and could be applied for Cr2O2-7 detection in lake water samples.

    UPLC-QTOF-MS-based Metabolomics Study on Ischemic Stroke Patients
    HUANG Yu, GU Caiyun, WU Hanzhong, XIA Xiaoshuang, LI Xin
    2017, 38(10):  1742-1750.  doi:10.7503/cjcu20170153
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    Ultra-performance liquid chromatography with quadrupole-time-of-flight mass spectrometry(UPLC-QTOF-MS) based metabolomics was used to study the metabolism profiling of the plasma from the patients with ischemic stroke, aiming to seek the potential biomarkers of ischemic stroke. 30 patients with ischemic stroke and 17 healthy controls were enrolled. Principal component analysis and orthogonal partial least squares discriminate analysis were used to investigate the metabolic variations between the patients with ischemic stroke and healthy controls. Metabolic pathways were analyzed. Seven biomarkers were obtained. The levels of sphinganine and phytosphingosine were increased, and the levels of glutamine, pyroglutamic acid and 2-ketobutyric acid were decreased. The results of the pathway analysis showed that sphingolipid metabolism and amino acid metabolism were perturbed, and the energy metabolism was also disturbed.

    Dicyanostilbene-derived Two-photon Fluorescence Probe for Mercury Ions
    HUANG Chibao, PAN Qi, CHEN Xiaoyuan, ZHAO Guanglian, CHEN Huashi, LIANG Xing, LÜ Guoling
    2017, 38(10):  1751-1756.  doi:10.7503/cjcu20170139
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    A novel water-soluble two-photon fluorescent probe for Hg2+(DHg) derived from dicyanostilbene(DCS) as a two-photon fluorophore and bis[2-(2-hydroxyethyl sulfanyl) ethyl]amino group(HAS) as a novel Hg2+ ligand was developed, and its structure was analyzed and identified. The results of UV-Vis absorption and absorption-titration experiments, one- and two-photon excited fluorescence experiments, as well as cellimaging and tissue-imaging experiments showed that the probe has a very high sensitivity and selectivity for the detection of Hg2+ in water. It can be used to detect trace Hg2+ in neutral or basic aqueous solution(pH=7—12), and its binding constant(lgK) for Hg2+ was determined from the one- and two-photon fluorescence-titration curves to be lgK=5.47±0.02 and lgK=5.34±0.02, respectively. Nitrogen atom property and the sulfur atom number on the ionophore are believed to be responsible of the unique selectivity of probe DHg for Hg2+. The fluorescent quantum yields of DHg in toluene, acetonitrile and water are 0.78, 0.42 and 0.20, respectively, and its two-photon absorption cross-section(δTPA) is as high as 840 GM in aqueous solution. The probe could selectively detect free Hg2+ ions in live cells without interference from other metal ions and the membrane-bound probes. Undoubtedly, the probe is an ideal two-photon excited fluorescence bioimaging candidate.

    Organic Chemistry
    Molecular Conformation and Aggregation Regulation of Bay-substituted Perylene Bismides: ortho-Methyl Steric Hindrance
    ZHANG Wenqiang, ZHOU Jiadong, MA Weitao, ZHU Na, XIE Zengqi, LIU Linlin, MA Yuguang
    2017, 38(10):  1757-1763.  doi:10.7503/cjcu20170387
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    The introduction of optoelectronically inactive long chain alkyl substituents commonly used to improve the solubility and film processing can inhibit intermolecular charge transfer in organic semiconductors. Therefore, to decrease the inactive alkyl substituents is important for next generation semiconductors. Herein, we designed and synthesized two perylene bisimide derivatives (PBI1 and PBI2) and investigated the effect of ortho-methylphenyoxyl substituent in bay area on molecular conformation and packing modes in the solid-state. The single crystal analysis confirmed that introduction of CH3 could significantly affect the molecular conformation of PBI, leading to cross-style four phenoxyl groups. The steric hindrance of CH3 inhibited the intermolecular π-π stacking, increased the solubility and enhanced the film-forming characters. The results show that CH3 at the key positions of π-conjugated skeleton could effectively regulate the molecular aggregation. The strategy provides an excellent method to enhance the film processing and decrease the optoelectronic inactive alkyl substituents, therefore an important step forward for the design of new optoelectronic materials.

    Synthesis and Bioactivities Evaluation of Novel 1-(1,3,5-Triazin-6-yl)-3-methyl-4-(5-phenyl-1,3,4-oxadiazol-2-yl) pyrazole
    ZHANG Chenglu, SUN Xiaona, LI Chuanyin, CAI Jiying, WANG Jing, LI Yizheng, WANG Huayu
    2017, 38(10):  1764-1771.  doi:10.7503/cjcu20170239
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    Eighteen novel multi-heterocyclic molecules[7A(a—f), 7B(a—f), 7C(a—f)] were designed and synthesized by hybrid-linking 1,3,4-oxadiazole and 1,3,5-triazine onto pyrazole. The structures of all the compounds were confirmed by IR, NMR and HRMS. The inhibitory activities of target molecules against protein tyrosine phosphatase 1B(PTP1B) and cell division cycle 25 phosphatase B(Cdc25B) were evaluated. As a result, all of the target molecules behave good inhibitory activities against PTP1B and Cdc25B, in which nine compounds show excellent inhibitory activities, respectively. The inhibitory activities of nine compounds are better than the reference oleanolic acid and Na3VO4, respectively. The nine compounds are expected to become potential inhibitors of PTP1B and Cdc25B.

    Asymmetric Synthesis of (S)-N,N-Dimethyl-3-hydroxy-3-(2-thienyl)-1-propanamine by Cell-free System of Carbonyl Reductase CR2
    SUN Taiqiang, LI Bin, NIE Yao, WANG Dong, XU Yan
    2017, 38(10):  1772-1777.  doi:10.7503/cjcu20170164
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    (S)-N,N-Dimethyl-3-hydroxy-3-(2-thienyl)-1-propanamine[(S)-DHTP] is an important intermediate for the production of (S)-duloxetine, which is a new and effective antidepressant drug. Since the efficiency of biosynthesis of (S)-DHTP is yet limited, development of suitable biocatalytic system is necessary for (S)-DHTP production from asymmetric reduction of N,N-dimethyl-3-keto-3-(2-thienyl)-1-propanamine(DKTP). In this study, the cell-free biocatalytic system involving recombinant carbonyl reductase CR2 was constructed and the corresponding reaction conditions were optimized. (S)-DHTP with high optical purity(e.e. value>99.9%) and the yield of 61.70% was obtained from DKTP(10 g/L) at pH=8.0[0.1 mol/L triethanolamine(TEA) buffer] and 30 ℃ after reaction for 6 h, by employing glucose(120 g/L) as the co-substrate and coenzyme NADP+(0.1 mmol/L) to drive the cofactor regeneration system. During the reaction process, the pH value decreased significantly due to the formation of gluconic acid from glucose for cofactor recycling. Then the yield of (S)-DHTP was increased to 67.73% by controlling the reaction pH. Substrate inhibition was observed when investigating the conversion of DKTP under different concentrations, and the space time yield of 1.33 g·L-1·h-1 was achieved for DKTP(10 g/L).

    Synthesis, Metabolic Stability and Biological Activity in vivo of Lorcaserin Derivatives
    ZHANG Lingzhi, JIANG Minrui, WEI Ping, ZHU Qihua, GONG Guoqing, BIAN Xueguo, XU Yungen
    2017, 38(10):  1778-1787.  doi:10.7503/cjcu20170094
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    To improve oral bioavailability and metabolic stability while maintaining the activity and selectivity, 13 carbamate prodrugs of lorcaserin were designed and synthesized by the structural modification of the secondary amine group. The structure of target compounds were confirmed by 1H NMR, 13C NMR, HRMS and IR. In vitro metabolic stabilities of 13 target compounds were explored by rat liver microsomes incubation experiment, among which compound 6b showed a longer half-life and can generate lorcaserin continuously by metabolism. In high-fat diet rats model, compound 6b exhibited slightly better weight loss effect than lorcaserin at the equimolar daily doses.

    Synthesis and Properties of Novel Isothiocyanatotolane Liquid Crystals with Terminal Difluorovinyl Substitute
    LI Juanli, PENG Zenghui, LI Jian, HU Minggang, AN Zhongwei, ZHANG Lu
    2017, 38(10):  1788-1795.  doi:10.7503/cjcu20170031
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    Four kinds of new isothiocyanate liquid crystals composed of tolane core and difluorovinyl terminal group(A1—A4) were synthesized via five step reactions based on 4-iodobenzaldehyde, and four ethyl analogues B1—B4 as comparison structures were also prepared. The structure characterizations of all related pro-ducts were performed using infrared spectrometer(IR), 1H-nuclear magnetic resonance(1H NMR) and mass spectrometer(MS). The mesomorphic properties were investigated by differential scanning calorimeter(DSC) and hot stage polarizing optical microscope(HS-POM). The birefringence values and rotational viscosity were extrapolated. The results showed that the target compounds A1, A2 and A3 exhibit wider nematic phase range(31—62 ℃). Replacement of ethyl chain by difluorovinyl as terminal group is enabled to not only enlarge the nematic phase temperature range but also increase birefringence(Δn=0.038—0.052) and reduce rotational viscosity. The high birefringence mixtures based new liquid crystals with terminal difluorovinyl substitute have wider nematic phase range, higher birefringence, lower rotational viscosity and larger figure-of-merit(FoM).

    Physical Chemistry
    Theoretical Study on the Second-order Nonlinear Optical Properties of Diaryl Ammonia(Boron)-π-carborane Ternary Compounds
    LI Rongrong, WANG Hongqiang, WANG Li, WU Juan, QIU Yongqing
    2017, 38(10):  1796-1803.  doi:10.7503/cjcu20170267
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    The structures and second order nonlinear optical(NLO) properties of diaryl ammonia(boron)-π-twelve vertex carborane ternary compounds were studied using density functional theory(DFT) methods. The results show that the conjugated bridge length and diaryl ammonia(boron) of compounds have relatively small influence on their dipole moments. Along with the lengthening of the conjugate bridge and the increases of electronic space scope <R2>, polarizability and the first hyperpolarizability increase. From the analysises of electronic spectra and the corresponding molecular orbitals of compounds, it is found that the intramolecular charge transfers within these compounds occur mainly between diaryl ammonia(boron) and the π-bridge, while carborane has less contribution. In addition, the differences of the electron donating ability between diaryl ammonia and diaryl boron can adjust second-order NLO responses of these compounds.

    Molecular Dynamics Simulation on Behavior of Common Surfactants at the Oil/Water Interface in Complex Systems
    JIANG Rongjun, LUO Jianhui, BAI Ruibing, JIANG Bo, ZHOU Ge
    2017, 38(10):  1804-1812.  doi:10.7503/cjcu20170242
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    In order to explore the behavior of common surfactants on oil/water interface in complex systems, five models were designed to study using the molecular simulation method. Except a blank model, four different surfactants were placed in the same complex systems as follows: sodium dodecyl benzene sulfonate(SDBS), dodecyltrimethylammonium bromide(DTAB), nonylphenol ethoxylates(NPE), and betaine. These four surfactants represented the anionic surfactant, the cationic surfactant, the nonionic surfactant, and the zwitterionic surfactant, respectively. For these models, radial distribution function(RDF) of surfactants and the oil molecules, mean square displacement(MSD) along z direction of oil molecules, oil/water interfacial tension(IFT), interaction energy between the oil layer and the mineral stone layer, the distribution of relative concentration of oil molecules along z direction, etc. were analyzed. For the SDBS, NPE, Betaine system, at the beginning, the surfactants arranged regularly at the interface of oil/water, the lipophilic parts of the surfactants were partially inserted into the oil phase, the hydrophilic parts were stretched into the water phase. Then the hydrophilic parts of the surfactants got together and formed to a micelle gradually. The micelle, which of its interior is hydrophilic and its exterior is lipophilic, moved to the oil layer gradually. For DTAB, at first, the surfactants were distributed regularly at the interface of oil/water, they gradually became disorderly as the simulation time increased. But the lipophilic head stretched into oil phase and the hydrophilic head distributed at the oil/water from the beginning to end. The order of the interaction between surfactants and oil molecular were: Betaine≈DTAB<SDBS<NPE; The order of oil displacement efficiency of different surfactants were: Betaine>SDBS>NPE>DTAB>None. Above all, the model systems constructed were rationalized. The results obtained from the simulation were agreement with the experimental data. The research gave partly the illustration of actual oil displacement efficiency of different surfactants at the molecular level.

    Theoretical Analysis of Oxygen Diffusion in the Micro-channels of Quinoline Oxygenase
    ZHOU Chao, SHI Ting, ZHAO Yilei, WANG Xiaolei
    2017, 38(10):  1813-1821.  doi:10.7503/cjcu20170202
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    Oxygen diffusion pathways of quinoline oxygenase(HOD) were investigated by bioinformatics analysis, quantum chemical optimization, CAVER and MD pocket prediction, random accelerated molecular dynamics simulations and umbrella sampling. The results show that the pre-reaction site of oxygen does locate inside the active pocket, and there exists several possible oxygen tunnels in HOD, in which the one with shortest length has the highest priority. Random accelerated molecular dynamics proved that oxygen has the highest probability to exit from this tunnel, and umbrella sampling further verified its free energy for oxygen passing by is the lowest. The tunnel ended at the binding site of oxygen located on the Re-face of the substrate, which is consistent with previous studies. These results better illuminate the kinetics and the stereo-selectivity of the catalytic reaction in HOD, and also provide theoretical guidance to further experimentally improve the efficiency of oxygen usage by enzyme.

    Effect of CeO2 on Cu/Zn-Al Catalysts Derived from Hydrotalcite Precursor for Methanol Steam Reforming
    HE Jianping, ZHANG Lei, CHEN Lin, YANG Zhanxu, TONG Yufei
    2017, 38(10):  1822-1828.  doi:10.7503/cjcu20170158
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    ZnAl-LDHs was synthesized on γ-Al2O3 by in situ synthesis method. Moreover, the Ce/Cu/Zn-Al catalysts were prepared by ordinal wet impregnation method and applied to methanol steam reforming. The effect of cerium content on Cu/Zn-Al catalysts was discussed for methanol steam reforming. The catalysts were studied by XRD, SEM, H2-TPR, N2 adsorption techniques and chemisorption N2O. The results showed that the addition of CeO2 improved the copper dispersion, copper surface area and catalyst reducibility. The catalytic activity and hydrogen production rate was also promoted thereby. When the Ce content was 4%, the catalyst exhibited the best catalytic activity, that was, the methanol conversion was 100% and the molar fraction of CO was 0.39% at 250 ℃ in hydrogen production by methanol steam reforming. Compared to the Cu/ZnAl catalyst, the methanol conversion increased by almost 40%.

    Preparation and Stability of Gemini Surfactant Modified Gold Nanofluids
    LI Dan, WU Qian, LIU Li, SUN Xiaori, GUO Meng, FENG Yimin
    2017, 38(10):  1829-1833.  doi:10.7503/cjcu20170150
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    1,4-Bis(N-tetradecyl-N,N-dimethylammonium) propane bromide(G14-4-14) was used as surface modifying reagents for preparation of gold nanofluids in one-step with ascorbic acid as reducing agent and a mixture of petroleum ether/n-butanol as the solvent. Stable oil- or water-based nanofluids containing gold were prepared at different temperatue. The morphology, size and UV-Vis spectra of gold nanoparticles were characterized. When the pH value was 7—8 and the temperature was 0—4 ℃, the hydrophobic and uniform gold nanoparticles were prepared with good dispersity. The effects of polar organic solvents and heating temperature on the stability of gold nanoparticles were presented. If the amount(volume fraction) of polar solvent added was more than 30%, it had significant influence on the stability of the nanofluid. The thermally stable time of gold nanoparticles was shortened as the heating temperature increased.

    Catalytic Performance of Micro-/micro-mesoporous H-ZSM-5 Zeolites for Alkylation of Toluene with Methanol
    ZHAO Li, YU Dongni, DAI Weili, WU Guangjun, LI Landong, GUAN Naijia
    2017, 38(10):  1834-1840.  doi:10.7503/cjcu20170083
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    The effects of acid or alkali treatments as well as acid-alkali treatment on the physicochemical properties and catalytic performances in the alkylation of toluene with methanol over H-ZSM-5 zeolites with different Si/Al ratios were investigated. The zeolites before and after the treatment were characterized by XRD, NH3-TPD, BET and TEM. The results indicated that the acid and alkali treatment had the great effects on the acidity and pore structure of the zeolites, which can directly influence the catalytic activities of the zeolites. Acid treatment can greatly influence the acidity and catalytic activities of H-ZSM-5 with lower Si/Al ratios, while alkali treatment only had the great effects on H-ZSM-5 with higher Si/Al ratios. The combination of acid and alkali treatment can adjust the acidity and pore structures of the zeolites simultaneously, and then enhance the catalytic activity in the alkylation of toluene with methanol.

    Effect of Y2O3 Supporter on the Catalytic Hydrogen Production from an Aqueous Formaldehyde Solution Catalyzed by Metal Cu Loaded on Y2O3
    TIAN Yi, LI Yuexiang, PENG Shaoqin
    2017, 38(10):  1841-1849.  doi:10.7503/cjcu20170065
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    Nano metal Cu was loaded on Y2O3 by NaBH4 reduction method. The sample was characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM) and adsorption measurement of OH- on Y2O3 and Cu. The results show that there is a thin layer of Y(OH)3 on the surface of Y2O3, which can preferentially adsorb OH-, that is, “enrichment” of OH- on Y2O3; metal Cu was loaded on Y2O3 in the form of nano particles. The performance of Cu supported on Y2O3(Cu/Y2O3) catalyst was investigated in alkaline formaldehyde solution. The results show that under low alkalinity, Cu/Y2O3 exhibits higher activity for hydrogen production than unloaded nano metal Cu. When the concentration of NaOH is 0.050 mol/L, the hydrogen amount produced over Cu/Y2O3 is 7.8 times as high as that over nano Cu under N2 atmosphere, whereas the former is 4.3 times as high as the latter under air atmosphere. The optimal NaOH concentration for hydrogen production over Cu/Y2O3 is 0.25 mol/L under both atmospheres. The results can be attributed to “enrichment” effect of OH- on Y2O3, leading to production of the higher concentration of active CH2(OH)O-(formaldehyde anion) species on Y2O3. The stability of Cu/Y2O3 is improved compared with that of unloaded nano Cu. The reason is that the load of Cu on Y2O3 prevents growth of Cu particles during the reaction.

    Precursors Structural Design and Property of Carbon Membrane for CO2 Capture
    SONG Jing, LI Lin, LU Yunhua, XU Ruisong, JIN Xin, WANG Chunlei, WANG Tonghua
    2017, 38(10):  1850-1856.  doi:10.7503/cjcu20170058
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    A series of novel polyimide precursors with rigidity and high free volume was designed and synthesized for the preparation of carbon membranes. The pyrolytic characteristics of polyimides and chemical structures and microstructures of derived carbon membranes were characterized by means of thermogravimetric analysis(TG), Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM). The gas separation performance of carbon membranes was evaluated using pure gases H2, O2, N2, CO2 and CH4. The results indicated that space configuration and free volume of polyimide precursors significantly affected the microstructures and gas separation performance of derived carbon membranes. The higher the structure rigidity of polyimide was, the higher its fractional free volume(FFV) was, the microstructure of prepared carbon membrane became looser and ultramicropore size became larger, resulting in the higher gas permeability of carbon membrane. Wherein, introduction of rigid groups such as fluorene, phthalide, hexafluoroisopropyl in polyimides could effectively disrupt the packing between the molecular chains and enhance the FFV of polyimides. The derived carbon membranes with looser microstructures exhibited excellent gas separation performance which surpassed the Robeson upper bond. Especially, the carbon membrane prepared from ortho-hydroxyl functionalized polyimide exhibited the highest gas permeability among the seven carbon membranes, that was 24770 Barrer(1 Barrer≈7.5×10-18 m2·s-1·Pa-1) for CO2, showing an attractive application prospect for the CO2 separation and capture.

    Synthesis and Application of New Types of Electrolyte Additives for Lithium Ion Battery
    GUO Mengya, ZONG Chengxing, AI Shujuan, FU Fengzhi, WANG Qi, LIU Jing, SUN Donglan, GUO Yanling, GUO Yeping
    2017, 38(10):  1857-1863.  doi:10.7503/cjcu20160920
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    A series of organic molecules combined with benzene ring and cyclic carbonate as electrolyte additives, including terephthalicacidbis-(2-oxo-[1,3]dioxolan-4-ylmethyl)ester(TABE), benzene-1,3,5-tricarboxylic acid tris-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester(BATE1) and benzene-1,2,4,5-tetracarb-oxylic acid tetrakis-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester(BATE2), was designed and synthesized. The effects of these additives on the electrochemical performance of lithium ion batteries were studied by rate capability, constant current charge-discharge test, electrochemical impedance spectroscopy(EIS) and scanning electron microscopy(SEM). The results showed that the amount of substituents on benzene ring greatly influenced the interface between electrolyte and graphite. Compared with the blank electrolyte, a dense and stable Solid electrolyte interface(SEI) film could be observed on the surface of the graphite electrode with BATE1 or BATE2 after 20 charge-discharge cycles, which could optimize the interface between the electrode and the electrolyte and led to the less increase of battery resistance. The test of the rate capability of the battery showed that the addition of BATE2 could improve the rate performance of the battery; meanwhile TABE could make the battery’s performance worse.

    Au Nanowires-MWCNTs Modified Electrode for Catalyzing the Oxidization of Glucose
    XU Kaige, ZHANG Di, LEI Jie, PENG Yage, PENG Juan, JIN Xiaoyong
    2017, 38(10):  1864-1871.  doi:10.7503/cjcu20160907
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    One-dimensional gold nanowires were prepared using oleylamine as reducing agent, and were assembled with carboxylic multi-walled carbon nanotubes(MWCNTs) through electrostatic adsorption to form a layer-by-layer assembled Au nanowires-MWCNTs on the glassy carbon electrode(GCE) to be used as catalyst for the oxidation of glucose. Electrochemical research results showed that the Au nanowires-MWCNTs/GCE electrode displayed higher catalytic properties than the simple Au nanowires or MWCNTs modified electrode towards the oxidation of glucose. Therefore, a new type of glucose fuel cell was elaborately assembled using Au nanowires-MWCNTs/GCE as the anode and platinum membrane/GCE as the cathod, which showed an open circuit-potential of 0.57 V, a maximum power density of 0.28 mW/cm2 at 0.44 V.

    Polymer Chemistry
    Phosphonium-based Crosslinked Poly(aryl ether ketone) Anion Exchange Membranes with 1,4-Bis(diphenylphosphino)butane as the Crosslinker
    XU Yixin, ZHANG Dengji, YE Niya, YANG Jingshuai, HE Ronghuan
    2017, 38(10):  1872-1879.  doi:10.7503/cjcu20170240
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    Two phosphines, rigid triphenylphosphine(TPP) and flexible tributylphosphine(TBP), were chosen to functionalize tetramethylbiphenyl-contained poly(aryl ether ketone)(PAEK), respectively, to prepare anion exchange membranes(AEMs). 1,4-bis(diphenylphosphino)butane was used as the crosslinker to crosslink PAEK, and the crosslinker was quaternized simultaneously. Thus the amount of functional groups of the crosslinked membranes was as the same as those of the uncrosslinked phosphonium-based PAEK membranes. Moreover, the mechanical properties of the crosslinked membranes were more effectively enhanced. The dimensional stability, conductivity, mechanical property and alkali resistance stability of the AEMs were investigated. As the crosslinking degree increased from 0 to 20%, the tensile stress of TPP and TBP modified AEMs increased from 27 MPa to 45 MPa, and from 18 MPa to 30 MPa, respectively. After exposed to 3 mol/L KOH at 60 ℃ for 120 h, the TPP and TBP modified AEMs maintained the conductivity of 81% and 69%, respectively. The results indicate that the alkaline stability of the crosslinked phosphonium-based PAEK membranes is more effectively improved than that of the uncrosslinked ones. At the same crosslinking degree, the TPP modified AEMs exhibit higher tensile stress and better alkali resistance stability than that the TBP modified ones.

    Preparation and Characterization of Self-cleaning Cotton Fabric
    YANG Ziwei, ZHOU Shunli, WANG Rui, WANG Feng, JIANG Yan, ZHANG Xiuqin
    2017, 38(10):  1880-1887.  doi:10.7503/cjcu20170171
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    Self-cleaning cotton fabric with bared and modified TiO2 nanoparticles on the surface was achieved by ultraviolet radiation and ultrasonic wave. The surface morphology, element distribution, photocatalytic activity, ultraviolet screening performance of original and modified cotton fabric were systematically investigated with scanning electron microscope(SEM), energy dispersive spectrometer(EDS), contact angle, ultraviolet-visible absorption spectrometry and photocatalytic degradation of methyl orange(MO). The results show that the adhesion between cotton fabric and nanoparticles has been enhanced after UV irradiation, as well as loaded stability and wash resistance. Cotton fabric with TiO2 nanoparticles on the surface shows super-hydrophobic behavior, excellent photocatalytic activity and UV screening property. Compared with the bared TiO2 nanoparticles, TiO2 nanoparticles modified by polyvinyl alcohol(PVA) shows 3.9 times higher photocatalytic activity in the visible light regime. In addition, a higher UV-Vis absorption in the region of 290—400 nm wavelength can be observed for the modified TiO2 nanoparticles, thereby exhibiting a better UV screening performance.

    Phase Structure of Aa Type of Patchy Colloids
    LIU Shujing, LI Jiangtao, GU Fang, WANG Haijun
    2017, 38(10):  1888-1896.  doi:10.7503/cjcu20170155
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    Phase structure of Aa type of Patchy colloids was presented under various conditions by the principle of phase equilibrium, where the phases of fluid(F), random close packing(RCP) and face centered cubic(FCC) were investigated to give the corresponding phase diagrams for F-F, F-RCP and F-FCC transitions, as well as for the sol-gel transition. It is shown that the crystallization of the Patchy colloid at a relatively high temperature is subjected to a one-step nucleation mechanism, and at a relatively low temperature it is subjected to a two-step nucleation mechanism companied with a metastable glassy state. An attempt is made to illustrate how the association strength and the number of patches regulate the phase state of Patchy particles, in particular, for glassy and crystal states. As a result, a significant effect of the two factors on the critical temperature, triple point, critical density and phase structure were found. Moreover, a relationship between the sol-gel and F-F transitions was also considered.

    Polymer Coatings for Purification and Long-term Culture of Human Adipose-derived Stem Cells
    QIU Linzi, WANG Guirong, PAN Yan, WANG Yiwen, LI Xinqing, DENG Linhong, Mark Bradley, ZHANG Rong
    2017, 38(10):  1897-1905.  doi:10.7503/cjcu20170121
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    Polymer coating(PC) based on polyacrylate hydrogels was prepared through UV initiated polymerization and characterized with X-ray photoelectron spectroscopy(XPS), water contact angles(WCA) and atomic force microscopy(AFM) respectively to understand their chemistry and surface properties. The biological characteristics of human adipose-derived stem cell(hASC) were evaluated after long-term cultured on PC in vitro for 3 passages. The results indicated that the hASC proliferated successfully on the PC, expressed high percentage of specific membrane markers CD49d, CD73, CD105, and very low percentage of HLA-DR and CD31 by using flow cytometry. The results suggested that the proliferated stem cells had the characteristics of hASC. The hASC were differentiated to adipocytes, osteoblasts and chondrocytes and stained with Oil Red O, Alizarin Red S and Alcian Blue respectively to demonstrate the maintaining of pluripotency of hASC. The results showed that the PC2 based on methacrylatoethyltrimethyl ammonium chloride, cyclohexyl methacrylate and diethyl amino ethyl methacrylate(mass ratio of 3:1:2) was the best in hASC binding and proliferation, improved the purification, maintained the pluripotency among the three coatings and TCP. Relative gene expression of the differentiated cells was analyzed by quantitative real-time polymerase chain reaction(RT-qPCR). The results show that the harvest hASC from PC2 are apt to differentiate to osteoblasts and chondrocytes.

    Curing Kinetics of Flame Retardant Epoxy Resin Promoted by Imidazole Grafting Graphene Oxide
    HU Jianhua, SHAN Jiye, TONG Zhen
    2017, 38(10):  1906-1912.  doi:10.7503/cjcu20170059
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    The curing kinetics of a flame-retardant epoxy resin(1.5P-D-U-EMI) containing 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide(DOPO) with imidazole grafting graphene oxide(GO-IPDI-MZ) was investigated by differential scanning calorimetry. The non-isothermal autocatalysis curing mechanism of 1.5P-D-U-EMI was not changed by adding 1% of GO-IPDI-MZ. Tonset and Tp of the flame-retardant epoxy resin with 1 Phr of GO-IPDI-MZ(1.5P-D-GOM-1) were decreased compared with those of 1.5P-D-U-EMI, and the total curing heat ΔH of 1.5P-D-GOM-1 was higher than that of 1.5P-D-U-EMI. 1% of GO-IPDI-MZ plays a catalytic and co-curing action on the epoxy system. The phenomenon of diffusion control was observed at the later stage of isothermal curing, especially at low temperatures. The Kamal-Sourour model modified with diffusion expressed the observed reaction rate curves fairly well. The curing reaction became steady and uniform by introducing GO-IPDI-MZ.