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    10 September 2019, Volume 40 Issue 9
    Cover and Content of Chemical Journal of Chinese Universities Vol.40 No.9(2019)
    2019, 40(9):  0-0. 
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    Non-Aufbau Principle to Achieve High Stability Organic Luminescence Radicals
    TANG Benzhong
    2019, 40(9):  1793-1794.  doi:10.7503/cjcu2019h001
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    To solve the problem of stability of organic luminescence radicals, Li et al. proposed a new kind of organic luminescence radicals with non-Aufbau electronic structure by using donor-acceptor molecular structure. The stability of this kind of radicals was greatly improved and the high luminous efficiency was maintained. Using a non-Aufbau radical as the emission layer of an OLED, the maximum external efficiency of 5.3% has been achieved, which is among the highest efficiencies for pure organic near-infrared electroluminescence. This work has been published online in the Nature Materials in July 22, 2019.

    Articles:Inorganic Chemistry
    Effect of Alkyl Benzene Sulfonate Surfactant on Morphology and Structure of Calcium Silicate Hydrate
    WANG Yue, GUO Xiaohong, ZHOU Guangdong, CHENG Tiexin
    2019, 40(9):  1795-1804.  doi:10.7503/cjcu20190205
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    The effects of the concentrations of SDBS, Ca 2+ and Si O 3 2 - ions, stirring and reaction time on the dispersibility and morphology of calcium silicate hydrate(CSH) using sodium dodecylbenzene sulfonate(SDBS) as template were investigated, the formation mechanism of different CSH spherical shell morphology features was prpposed. The results showed that the crystallinity and polymerization degree of CSH increased and the relative content of Q 2 structure increased with the increase of Na2SiO3 9H2O concentration, SDBS concentration and reaction time, the concentration of Na2SiO3 9H2O and SDBS were the main controlling factors. The spherical micelles formed by SDBS in solution have a strong template action, which effectively changes the crystal growth mode of CSH. By adjusting the concentration of SDBS and the ratio of calcium to silicon and appropriately prolonging the growth time of CSH, the CSH product with complete spherical shell, good disper-sibility and high stability can be obtained.

    Construction of CPO Immobilized Enzyme Reactor Based on Center-radial Dendritic Mesoporous Silica and Its Application
    SONG Yichao, HU Mancheng, LI Shuni, ZHAI Quanguo, JIANG Yucheng
    2019, 40(9):  1805-1812.  doi:10.7503/cjcu20190191
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    The mesoporous silica particles(DSP) with open three-dimensional center-radial dendrimers and uniform particle size were first prepared. Then CPO@DSP immobilized enzyme reactor was prepared by electrostatic interaction with chloroperoxidase(CPO) entrapped into the pore channel. The pore size was regulated by changing the concentrations of tetraethyl orthosilicate(TEOS) and the template agent cetyltrimethylammo-nium chloride(CTAC). The effect of pore size on the catalytic activity of immobilized enzyme reactor was studied. At the same time, the limiting effect of pore channel was discussed based on the kinetic analysis of enzymatic reaction. In addition, sodium alginate(SA) hydrogel film coated on the surface of CPO@DSP was used to improve the leakage of enzyme molecules in the enzyme reactor, and the reusability of the obtained SA-CPO@DSP enzyme reactor was significantly improved. After 10 times of reuse, more than 90% of the catalytic activity was still maintained. When SA-CPO@DSP was applied to the degradation of residual antibiotics in environmental water, the degradation rate of 100 μg/mL substrate in 25 min was over 88%. SA-CPO@DSP was also used for visual colorimetric detection of phenol and 5 μmol/L phenol could be detected by naked eyes. It showed the application prospect of SA-CPO@DSP in environmental protection.

    A Covalent Organic Framework with High Surface Area for Drug Delivery
    LIU Xiaozhou, WANG Yujie, LIU Yaozu, LI Zonglong, LI Hui, FANG Qianrong, JIN Yongri
    2019, 40(9):  1813-1817.  doi:10.7503/cjcu20190087
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    We synthesized a novel 2D covalent organic framework(COF) material with high surface area(1804 m 2/g), denoted as JUC-516, which showed ideal result in the application of drug delivery in simulated body fluid(SBF). Computational simulation by Materials Studio 7.0 software, powder X-ray diffraction(PXRD), N2 adsorption-desorption analysis, scanning electron microscope(SEM) and Fourier transform infrared(FTIR) spectrascopy were carried out to prove the structure and property of JUC-516. JUC-516 was confirmed to be a covalent organic framework with hcb topology based on AA stack, high crystallinity and spherical morphology.

    Growth and Gas Permeation Properties of SIFSIX-3-Ni Membrane
    MU Xin, JIANG Shuangshuang, ZHANG Shuhao, REN Hao, SUN Fuxing
    2019, 40(9):  1818-1824.  doi:10.7503/cjcu20190085
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    Using the macroporous glass-frit disk modified by (NH4)2SiF6 as the substrate, we prepared the SIFSIX-3-Ni membrane by the in situ growth method under solvothermal conditions. The effect of temperature and concentration on the preparation of SIFSIX-3-Ni membrane were investigated in detail. X-Ray photoelectron spectroscopy(XPS) demonstrates that F atom was integrated into the substrate surface. The powder X-ray diffraction(PXRD) patterns were in accordance with the simulated one, indicating that we obtained SIFSIX-3-Ni membranes successfully. Scanning electron microscopy(SEM) showed that the SIFSIX-3-Ni-3 membrane was continuous and uniform with a thickness of about 20 μm. Thermogravimetric analysis(TGA) showed that there was no guest molecules in the membrane before activation. Single gas permeation measurement on SIFSIX-3-Ni-3 membrane demonstrated that the permeability of H2, CO2 and N2 were 6.83×10 -6, 7.42×10 -7 and 8.89×10 -7 mol·m -2·s -1·Pa -1 respectively, and the ideal selectivities of H2/CO2 and H2/N2 were 9.20 and 7.68 respectively. The membrane can retain almost the same permeance of H2, CO2 and N2 after 5 h of continuous testing, indicating that SIFSIX-3-Ni membrane have good stability.

    Analytical Chemistry
    Construction and High Selectivity of Aerolysin Single Molecular Interface for Single Molecule Analysis
    WU Xueyuan, YING Yilun, LONG Yitao
    2019, 40(9):  1825-1831.  doi:10.7503/cjcu20190364
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    As an new conceptual single molecular interface, the biomolecular nanopore can accommodate only a single molecule and contains abundant amino acid residues in the lumen, providing an appropriate confinement for single molecule detection. Herein, a generalized method is proposed for the construct of single molecular interface based on membrane protein. The method is flexible, controllable and repeatable. The characterization of D209R mutation with Poly(dA)4 illustrate that the selectivity of aerolysin single molecular interface is related the electrostatic properties at the entrance of nanopore, which deepens our understanding of aerolysin single molecular interface, providing a paradigm for rational design of functional single molecular interface.

    1H NMR Metabonomic Investigations of N-Benzylhexadecanamide Induced Proliferation and Iestosterone Secretion of Mouse Testicular Leydig Cells
    ZHANG Nanxi, LV Jingwei, JIN Ping, LI Jingfeng, BIAN Xuefeng, ZHANG Hui, SUN Jiaming
    2019, 40(9):  1832-1839.  doi:10.7503/cjcu20190256
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    A metabolomic mechanism was evaluated for inducing proliferation and testosterone secretion of mouse testicular Leydig cells by N-benzylhexadecanamide(NBH) from maca based on 1H NMR metabolism approach. The cell proliferation rate of mouse testicular Leydig cell sbefore and after administration and the testosterone content in the cell culture medium was determined experimentally. Based on principal component analysis(PCA) and orthogonal partial least squares discriminant analysis(OPLS-DA), metabolite differences in mouse testicular Leydig cells before and after administration were studied, and metabolic pathway analysis was performed. The results showed that NBH could increase the proliferation rate and testosterone secretion of mouse testicular Leydig cells. After administration, the profile of the faulty liquid metabolic in mouse testicular Leydig cells was changed significantly, which identified 24distinct metabolites such as leucine, lysine, scyllo-inositol, valine and alanine. Metaboanalyst showed that distinct metabolites mainly involves 10 pathways including alanine, aspartate and glutamate metabolism, glycine, serine and threonine metabolism, glutathione metabolism, pyruvate metabolism, pantothenate and CoA biosynthesis, aminoacyl-tRNA biosynthesis, lysine degradation, Inositol phosphate metabolism, D-glutamine and D-glutamate metabolism as well as glycerophospholipid metabolism. The result indicated that NBH promotes proliferation and secretion of testosterone in mouse Leydig cells by organizing the relevant nodes of the above metabolic pathway.

    Interaction Between Fulvic Acid and Pepsin Investigated by Multispectral and Molecular Docking Simulation
    WANG Xiaoxia, MA Litong, NIE Zhihua, WANG Zhengde, CUI Jinlong, ZHAO Wenyuan, SAI Huazheng
    2019, 40(9):  1840-1846.  doi:10.7503/cjcu20190252
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    The interaction of fulvic acid(FA) with pepsin(PEP) was investigated using fluorescence spectra, UV-Vis absorption spectra, three-dimensional fluorescence spectra, synchronous fluorescence spectra, Fourier transform infrared spectroscopy, circular dichroism and molecular docking simulation method. Fluorescence spectrum analyses shows that the type of fluorescence quenching by FA-PEP is static quenching. According to the Stern-Volmer equation and the static quenching double logarithmic formula, the quenching constants(Ksv) and the number of binding sites(n) were calculated. According to the Vant’t Hoff equation, the thermodynamic parameters were calculated to be ΔH=-59.86 kJ/mol, ΔS=-98.13 J·mol -1·K -1 and ΔG=-30.62 kJ/mol(298 K). Thermodynamic analysis suggests that hydrogen bonds and van der Waal’s forces are the main forces between PEP and FA, and the interaction is spontaneous process. According to the theory of F?rster’s non-radiative energy transfer, the binding distance between PEP and FA was calculated to be 2.436 nm, implying that non-radiative energy transfer occurs between FA. The molecular docking simulation technique displays that the binding force of FA-PEP includes not only hydrogen bonds and van der Waals forces but also hydrophobic interaction forces.

    Investigation on Electrochemical Capture of CO2 by Quinone Derivatives Based on in situ FTIR Spectroelectrochemistry
    FAN Hui, JIN Baokang
    2019, 40(9):  1847-1856.  doi:10.7503/cjcu20190166
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    The electrochemical capture process of CO2 by quinone derivatives, 2,6-dichloro-1,4-benzoquinone(DCBQ) and 2,6-dimethoxy-1,4- benzoquinone(DMOBQ), in acetonitrile solutions were investigated by in situ FTIR spectroelectrochemistry. There are two well-defined couples of redox peaks of both derivatives in acetonitrile solvent in cyclic voltammetry curve(CV), which indicates that the electrochemical reactions undergo two-step one-electron transfer. Due to the different electrophilicity of substituent, the quinone derivatives react with CO2 through different process after the addition of CO2. The CV of DCBQ still presents two couples of redox peaks with the second couple of redox peaks shifts positively; while only one couple of redox peaks appears in the CV of DMOBQ. The results of in situ FTIR experiments further indicated the different mechanisms of capture CO2 by DMOBQ and DCBQ. DCBQ undergoes the EEC mechanism, in which CO2 is captured by the two-step one-electron reduction products dianion DCBQ 2-. However, DMOBQ undergoes ECE mechanism to capture CO2 by the one electron transfer product anion radical DMOBQ ·-. Furthermore, the quantitative analysis of the reduction products of capture CO2 was carried out. The stoichiometric is 1:1 to the two derivatives.

    Preparation of Zirconia Deposited Silica Stationary Phase and Its Application to Hydrophilic-interaction Liquid Chromatography
    YU Qiongwei, ZHENG Feng, FANG Kaimin, FENG Yuqi
    2019, 40(9):  1857-1865.  doi:10.7503/cjcu20190158
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    ZrO2 nanoparticles were deposited on silica by LPD method and the resulting ZrO2/SiO2 was employed as stationary phase in hydrophilic-interaction liquid chromatography. The chromatographic perfor-mance of three columns packed with SiO2, ZrO2/SiO2 and ZrO2 were compared. The results showed that the column packed with ZrO2/SiO2 not only had the advantages of high column efficiency like the SiO2 column, but also the deposited zirconia nanoparticles on the silica surface could shield the silicon hydroxyl group effectively, which benefit for the retention and separation of alkaline substances and showed good hydrophilic-interaction chromatographic performance. Effective separation of 4 deoxynucleosides and 5 basic compounds was achieved on ZrO2/SiO2 column in the hydrophilic-interaction liquid chromatography(HILIC) mode.

    Novel Glutathione Photoelectrochemical Sensor Based on PbS QDs/TiO2 NPs
    ZHENG Shan, LIU Yang, CHEN Piaopiao, XING Yichen, HUANG Chaobiao
    2019, 40(9):  1866-1872.  doi:10.7503/cjcu20190106
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    Firstly, titanium dioxide nanoparticles(TiO2 NPs) was modified to the surface of indium tin oxide(ITO) electrode by high-temperature calcination to prepare TiO2 NPs/ITO electrode. And then sulfide quantum dots(PbS QDs) were modified to the surface of TiO2 NPs/ITO electrode by successive ionic layer adsorption and reaction(SILAR) cycle to prepare the PbS QDs/TiO2 NPs/ITO electrode. And it was used to detect glutathione(GSH). In this sensor, when PbS QDs are excited by 470 nm visible light, it will produce electrons(e) and holes(h +). Immediately after, h + will be captured by GSH in solution, and then GSH is oxidized into GSSH. Therefore, the recombination of electrons and holes were avoided effectively. Thus the photoelectric efficiency has been significantly improved. This sensor had satisfactory sensitivity and selectivity for GSH. what’s more, the detection range is 0.06—1 mmol/L, and the detection limit(LOD) is 4.6×10 -3 mmol/L(S/N=3).

    Organic Chemistry
    Preparation and Immunological Activity Evaluation of Water-soluble β-Glucan from Saccharomyces cerevisiae
    WANG Shanshan, CAI Chao, HAO Jiejie, LI Guoyun, WANG Xueliang, HU Minghua, FAN Luodi, YU Guangli
    2019, 40(9):  1873-1880.  doi:10.7503/cjcu20190195
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    The wasted beer yeast(Saccharomyces cerevisiae) was used as raw material to obtain insoluble β-glucan(SCBG) through acid and alkaline treatment. The water-soluble β-glucan(SCBGs) was prepared by oxidative degradation in the NaOH/urea aqueous solution at low temperature. Four purified components(SCBGs-0-1, SCBGs-1-1, SCBGs-1-2 and SCBGs-1-3) were further obtained by column chromatography. The monosaccharide compositions, molecular weights and chemical structures of four purified components were analyzed by high performance liquid chromatography(HPLC), high performance gel permeation chromatography-multiple angle laser light scattering(HPGPC-MALLS), nuclear magnetic resonance spectroscopy(NMR) and Congo-red test. Their immunological activities, including the effects of phagocytosis and the release of NO and TNF-α, were studied on macrophage RAW 264.7. The results showed that all purified component mainly consisted of glucose. They were kinds of β-1,3/1,6-glucans composed of β-1,3-glucan as backbone with branches at the site of C6 hydroxyl groups. The molecular weights were determined to be 198000, 960000, 270000 and 18700, respectively. All the components still retained their original supercoil structure except SCBGs-1-3. Four purified components could significantly promote the immunological activity of RAW 264.7.

    Synthesis of Macrocyclic Thiacrown Ethers and Their Selective Extraction for Ag(Ⅰ) and Tl(Ⅰ)
    CHENG Xiankun, HOU Xue, TIAN Huan, ZHANG Menglong, WEI Hao, ZHAO Zhuo
    2019, 40(9):  1881-1887.  doi:10.7503/cjcu20190186
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    Based on the crown ether coordination chemistry and soft and hard acid-base(HSAB) theory, two macrocyclic crown ethers of 10,19-dithiabenzo-30-crown-10(DHB30C10) and 10,13,17,20-tetrathiabenzo-3-crown-10(THB31C10) were synthesized, which potentially have excellent complex ability with Ag(Ⅰ) and Tl(Ⅰ). The extraction abilities of the two crown ethers for Ag(Ⅰ) and Tl(Ⅰ) were investigated. The results showed that in the single system, the complexing constants of DHB30C10 and THB31C10 for Ag(Ⅰ) were 9.76 and 13.40, and for Tl(Ⅰ) were 4.769 and 4.35, respectively. In the multi-system, the two crown ethers both exhibit strong selectivity to Ag(Ⅰ). The separation coefficients of DHB30C10 for Ag(Ⅰ) to Cu(Ⅱ) and Ni(Ⅱ) were 194.68 and 142.44, and the corresponding data of THB31C10 were 172.81 and 268.53, respectively. However, the two crown ethers showed poor selectivity to Tl(Ⅰ). The extraction mechanisms of DHB30C10 and THB31C10 for Ag(Ⅰ) and Tl(Ⅰ) were analyzed.

    Efficient Enzyme Immobilization by Combining Adsorption and Cellulose Membrane Coating
    WU Rong, DONG Qihui, SUN Yiyi, SU Erzheng
    2019, 40(9):  1888-1896.  doi:10.7503/cjcu20190185
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    The papain was used as a model enzyme to develop an immobilized enzyme method based on combination of adsorption and cellulose membrane coating. The type of adsorption carries, cellulose category and the solvent type for dissolving cellulose, protectant category and concentration, drying mode and time were systematically optimized. The best adsorption-cellulose coating combined immobilization process was adopting diatomite or HPD-417(macroporous resin) as adsorption carrier, methylcellulose(molecular weight 40000—50000) acetone solution as coating solution, 6%(mass fraction) polyethylene glycol or maltose as the protectant for membrane coating, and drying at 4 ℃ for 9 h. The prepared immobilized papain showed high enzyme activity recovery rate, which attained to 96.50% for diatomite adsorbing-cellulose coating immobilized papain and 93.92% for HPD-417 adsorbing-cellulose coating immobilized papain. Finally, the properties of the immobilized enzyme were investigated. The results showed that the adsorbing-cellulose coating immobilized papain had better thermal stability. After being stored at 80 ℃ for 12 h, the residual activity of the immobilized enzyme remained about 90%. In the range of pH=4.5—9.5, the stability of the immobilized enzyme was better. After being continuously used for 9 batches, the residual activity of the immobilized enzyme remained about 95%.

    Chemical Constituents and Antitumor Activity of Tupistra chinensis
    XIAO Yanhua, ZHANG Guangjie, ZONG Liang, LIU Guohong, REN Lijun, DONG Junxing
    2019, 40(9):  1897-1903.  doi:10.7503/cjcu20190167
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    Tupistra chinensis(Liliaceae), mainly distributed in southwestern China, is a rich source of steroidal sapogenins, saponins and flavans. These components exhibit diverse biological activities such as anti-inflammatory, anti-fungal and anti-tumor properties. As a part of a continuing study for the discovery of novel cytotoxic agents, eight compounds were isolated from the fresh rhizomes of Tupistra chinensis, and their structures were established on the basis of chemical methods and spectral data(MS, IR, NMR), including tupistroside J(1), (25S)-26-O-β-D-glucopyranosyl-furost-1β,3β,22α,26-tetraol-3-O-β-D-glucoside(2), digitoxigenin-3-O-α-L-fucopyranose(3), watti-genin B(4), epiruscogenin(5), epiruscogenin(6), orobol(7), (+)-catechin(8). Compound 1 was a new compound, and compounds 3, 4, 7 and 8 were isolated from Tupistra Ker-Gawl for the first time. All compounds were tested in vitro for their cytotoxic activities against the Human LoVo and BGC-823 cell lines, and compounds 5 and 6 were found to possess significant cytotoxicity against the tested tumor cell lines with half maximal inhibitory concentration(IC50) values of 0.532 and 0.757 μmol/L, respectively.

    β-Stereoselectivity of Glucuronic Acid Analogues Mediated by 2-Cyanobenzyl Group
    ZHANG Yanyan, HAO Kaifeng, ZHANG Guoqiang, ZHAO Wei
    2019, 40(9):  1904-1910.  doi:10.7503/cjcu20190140
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    Heparin(HP) is composed of sulfated disaccharide-repeating units of either L-iduronic acid(IdoA) or D-glucuronic acid(GlcA) linked glucosamine(GlcN) residue. It is well established that heparin plays crucial roles in various physiological processes, such as blood anticoagulation, viral infection, inflammatory response, cell adhesion, cell growth regulation, and tumor metastasis. Since the discovery of the specific AT Ⅲ-binding pentasaccharide domain of heparin, the strategies toward total synthesis of pentasaccharide analogues emerged rapidly. Fondaparinux sodium, as a chemically synthesized ultralow molecular weight(ULMW) heparin pentasaccharide, has been clinically used as an antithrombotic drug for the specific AT Ⅲ-binding property. The chemical synthesis of fondaparinux needed more than 50 steps with an overall yield of ca. 0.1%. And the β-stereospecific synthesis of glucuronic acid has always been a big challenge in the synthetic process of fondaparinux sodium because of the absence of neighbouring group participation effect. Herein, seven glycosyl donors based on glucose and glucuronic acid, in which the 2-OH was protected by 2-cyanobenzyl(BCN) group, were prepared. A series of glycosyl acceptors was utilized to examine the effect of β-stereoselectivity mediated by BCN group in dichloromethane(DCM) and toluene(Tol). The NMR results of these correspon-ding products have indicated that the BCN group participation and solvent effect can efficiently improve the ratio of α/βanomer. The ratio of the glycosylation products was more than 1∶10, and the most was 1∶50. This research has built a set of solid theoretical basis for the synthesis of fondaparinux sodium.

    Physical Chemistry
    Theoretical Study on Mechanism of CO2 Hydrogenation to Formic Acid Catalyzed by Manganese Complex
    ZHANG Lin, ZHANG Wei, YUE Xin, LI Pengjie, YANG Zuoyin, PU Min, LEI Ming
    2019, 40(9):  1911-1917.  doi:10.7503/cjcu20190292
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    Density functional theory(DFT) was used to study the mechanism of carbon dioxide hydrogenation to formic acid catalyzed by manganese complex. The whole catalytic cycle mainly includes two stages of hydrogen activation and carbon dioxide hydrogenation. The calculation results show that the participation of formic acid significantly reduces the reaction energy barrier of hydrogen activation. The hydrogenation process of carbon dioxide follows the outer-sphere mechanism and hydrogen transfer is a stepwise process, in which the hydride transfer is the rate-determining step, with an energy barrier of 21.0 kJ/mol. In addition, the modulation effect of R group on S atom was explored. The results show that when R is an electron-withdrawing group, it can reduce the activation barriers of hydrogen cracking and proton transfer during carbon dioxide hydrogenation. The transfer of hydride is facilitated when the R group is an electron-donating group. When R=CF3, the energy span of the whole reaction is the smallest, which is 80.4 kJ/mol.

    Different Roles of Some Key Residues in the S4 Pocket of Coagulation Factor Xa for Rivaroxaban Binding
    QU Siying, XU Qin
    2019, 40(9):  1918-1925.  doi:10.7503/cjcu20190261
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    The details of the dynamic interaction between rivaroxaban and some key residues in the S4 pocket of Coagulation factor X(FXa) were analyzed by bioinformatics alignment, molecular dynamics simulation and binding free energy calculation. The results indicated that the disruption of the hydrophobic S4 pocket caused by mutations in the key residues directly lower the binding affinity of rivaroxaban to FXa. The hydrophobic effect of the Trp215 side chain is more important in the inhibitor binding, but the effect on the overall structure is relatively minor in the limited time of simulations. Although Tyr99 contributes less in the binding free energy, its mutation may result in an overall conformational change in the domain where the 99 loop is located, thereby affecting the binding specificity of the inhibitor or substrate. The different roles of key residues in the S4 pocket should be fully considered in the drug design of the direct inhibitor of FXa and the development of its antagonists.

    Fabrication of Cu3(BTC)2 Mixed Matrix Membrane and Its Application in Continuous Flow Process
    HOU Junying, HAO Jianjun, WANG Yaya, LIU Jingchun
    2019, 40(9):  1926-1931.  doi:10.7503/cjcu20190250
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    A Cu3(BTC)2@PS mixed matrix membrane(MMM) with 60%(mass fraction) MOF loading was fabricated via solvent evaporation method. The catalyst was characterized by means of SEM, XRD, FTIR and TGA. The results showed that Cu3(BTC)2 MOF uniformly distributed on the MMM and the MMM possessed a good thermal stability. The copper of the Cu-BTC MMM served as the active sites for the flow reaction system. The as-synthesized membranes possess high surface area and excellent hydrophilicity. Cu3(BTC)2 MMM was evaluated as a catalyst for the aldehyde acetalization with ethanol. 99% conversion of benzaldehyde and 99% selectivity of benzaldehyde diethyl acetal was obtained, using Cu3(BTC)2 MMM heterogeneous catalyst for 24 h. It has an excellent practicality to develop this simple mixed matrix membrane for industrial application.

    Synthesis of Functionalized Inverse Opals Photonic Crystals and the Detection of Heparin
    XU Na, LIU Zhonghu, LAN Chengwu, YIN Jianhang, CHENG Kaixuan, MENG Lei
    2019, 40(9):  1932-1936.  doi:10.7503/cjcu20190194
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    Heparin is the primary medicine of anticoagulant that can rapidly prevent from blood clotting, which could generate essential hemorrhage or thrombocytopenia for overusing. By functionalizing inverse opals photonic crystals(IOPCs) with polyethylene imine(PEI), the IOPCs manage to specific detect the presence of heparin via strong electrostatic interaction between them. With the concentration of heparin increasing(0—10 -4 mol/L), maximum peak of Bragg diffraction of functionalized IOPCs shifts about 40 nm. There’s fine Linear relation(R 2=0.99905) between logarithm of concentration of heparin and wave shifts of IOPCs, and the limit of detection is 10 -10 mol/L. The IOPCs obtained perform a well physical and chemical stability, which can be repeatedly used in detection of heparin with prospective practical application.

    Ti-MCM-41 Catalysts for the Ring Opening Reaction of Epoxy Compounds with Amines
    ZHAO Yun, WEI Jinjing, ZHOU Yu, ZHU Jixiu, WANG Houyong, CHEN Aimin
    2019, 40(9):  1937-1948.  doi:10.7503/cjcu20190124
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    The synthesis of β-aminoalcohols by conventional catalysts is limited by a variety of conditions. The mesostructure Ti-MCM-41 molecular sieve catalyst was synthesized from the template cetyltrimethyl ammonium bromide(CTAB) and the isopropyl titanate used as titanium source by hydrothermal synthesis method. All the catalysts were characterized by N2 adsorption-desorption, XRD, SEM/TEM, DR UV-vis, FTIR and NH3-TPD. The XRD and SEM/TEM results indicated that the Ti-MCM-41 catalyst was a mesoporous structure with average pores size of about 2.0—4.0 nm in the sample framework. The catalytic performance of Ti-MCM-41 catalysts for the ring opening reaction of ethylene oxide with dimethylamine was investigated in stainless steel batch reactor under solvent free condition. For the ring opening reaction of ethylene oxide(EO) with dimethylamine(DMA), the synthesized catalyst with the Si/Ti molar ratio of 5∶1 provided the most efficient catalyst performance and the selectivity in the products reaching up to 98.37% and at 86.68% conversion at 145 ℃ and 2.5 MPa. DR UV-Vis, FTIR and NH3-TPD results indicated that the four coordinated Ti in the structure of catalyst makes the surface of molecule sieve catalyst possesses rich Lewis acid site. Moreover, increased the surface acidity is conducive to the improvement of catalytic activity. It revealed that acidic active sites on the catalyst surface might be responsible for promoting the ring opening reaction of epoxy compounds with amines. The mechanism of ring opening reaction of dimethylamine with ethylene oxide catalyzed by Ti-MCM-41 was also discussed.

    Deposition Method Synthesis of Nano-phosphorus/Biomass Carbon Composites and Their High- and Low-temperature Electrochemical Performances as Anode Material in Lithium-ion Batteries
    LI Xiangnan, WANG Qiuxian, FAN Yong, YU Mingming, ZHANG Huishuang, YANG Shuting
    2019, 40(9):  1949-1954.  doi:10.7503/cjcu20190097
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    Using cornstalk core as the carbon source, anode materials P/C with different micro-nano structures were directly synthesized by the deposition method synthesis method. The results show that the CP2[m(P)∶m(C)=4.5∶5.5] assembled lithium-ion battery performed well: the charge capacity of CP2 is 1215.5 mA·h/g at 0.1C(25 ℃), and the reversible capacity is 847.7 mA·h/g after 100 cycles. High- and low-temperature performances were discussed at 0.1C. The results show that the specific capacity of the sample reaches 425.6 mA·h/g at -20 ℃ and 1812.3 mA·h/g at 55 ℃, respectively. An appropriate amount of P distributes uniformly in pores of conductive carbon substrate, so that the lithium-ion battery assembled of this composite show excellent electrical performance.

    Preparation and Quasi-superhydrophobic Properties of the Surface of Mullite Whiskers/Cordierite
    DU Yifan, AI Chaoqian, ZHANG Yaoyao, WANG Wei
    2019, 40(9):  1955-1963.  doi:10.7503/cjcu20190090
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    Silicon-aluminum hybrid gel powders were prepared by sol-gel technology, and the microstructure of mullite whiskers/cordierite was obtained through growth of mullite whiskers on the surface of cordierite ceramic substrate by molten salt reaction. X-Ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy were employed to characterized the structural morphology and phase compositions. The results show that the surface of cordierite ceramic was covered by dense mullite whiskers with nanometer-sized(100—300 nm) diameters and micrometer-sized lengths. The surface modification of mullite whiskers was performed by coupling reaction between n-dodecyltrimethoxysilan and numerous active groups(Si—OH, Al—OH) on the surface of mullite whiskers, and static wetting angle of this sample is 146°. Dynamic wetting studies show that mullite whiskers increase the surface roughness of cordierite ceramics, making the hydrophilic mullite whiskers/cordierite surface more hydrophilic and the surface of the mullite whiskers/cordierite modified by the silane coupling agent change into quasi-superhydrophobic surface

    Treatment of Naphthalene by Microbial Electrochemical System and the Analysis of Microbial Communities
    HUA Tao, LI Shengnan, LI Fengxiang, WANG Haonan
    2019, 40(9):  1964-1971.  doi:10.7503/cjcu20190088
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    Naphthalene of different concentrations(15, 30, 60 mg/L) were adopted as substrate for single-chamber air cathode microbial fuel cell(MFC) reactors. The electricity production performance(power density, polarization curve and cyclic voltammetry curve), naphthalene degradation rate, chemical oxygen demand(COD) and total organic carbon(TOC) degradation rate, and anode and cathode microbial diversity were investigated. The results show that the cyclic voltammetry curve was apparently affected by different concentrations of naphthalene; with the increase in naphthalene concentration, the maximum power density showed a downward trend, and naphthalene had a great influence on the cathode potential of MFC; the maximum power density of naphthalene could reach (645.841±28.08) mW/m 2; the degradation rate of naphthalene by MFC was as high as 100%. Moreover, the degradation rate of COD and TOC by MFC increased with the increase of naphthalene concentration, but the increase rate decreased gradually. On this basis, high-throughput sequencing of MFC anode microbial membranes revealed that Geobacter was a dominant genus with a relative abundance of 81%, while the cathode was mainly based on Aquamicrobium.

    Preparation of V2O3 Hollow Spheres for Lithium Sulfur Batteries
    LI Xin, CHEN Liang, MA Xiaotao, ZHANG Ding, XU Shoudong, ZHOU Xianxian, DUAN Donghong, LIU Shibin
    2019, 40(9):  1972-1978.  doi:10.7503/cjcu20190083
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    The prepared V2O5 hollow spheres were reduced to V2O3 hollow spheres with the assistance of NH3 at high temperature. The morphology and structure of the V2O3 hollow spheres were characterized by transmission electron microscopy(TEM), scanning electron microscopy(SEM), powder X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). The powder of V2O3 hollow spheres and sulfur was mixed directly without further thermal treatment and the mixture was used as the cathode of lithium-sulfur batteries. The electrochemical test show that the initial capacity reaches 1375 mA·h/g and the capacity after 100 cycles is 815 mA·h/g at 0.2C; even at 1C, the initial capacity reaches 710 mA·h/g and the capacity after 500 cycles is 530 mA·h/g. The results indicate that the addition of V2O3 hollow sphere in the lithium sulfur battery can effectively improve the cycle performance.

    Preparation of UIO-66-based Porous Nano-octahedral FeP@PC for Efficient and Durable Hydrogen Evolution
    WANG Wenfeng, QIN Shan, ZHANG Rongrong, ZHOU Panpan, YANG Qinghua, CHEN Tianyun
    2019, 40(9):  1979-1987.  doi:10.7503/cjcu20190047
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    By using UIO-66 as the precursor, porous FeP@PC was prepared by chemical vapor deposition of FeCl3, in-situ carbonization, phosphating and HF etching. The morphology, crystal structure, elemental composition and valence states of FeP@PC were characterized by field emission transmission electron microscopy(FETEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and N2 adsoption-desorption measurements. The results showed that FeP@PC maintained the original porous nano-octahedral structure of UIO-66 and had a high specific surface area of 83 m 2/g. For linear sweep voltammetry and electrochemical impedance spectroscopy measurements, the catalyst FeP@PC only needed overpotential of 156 mV to driven current density of 10 mA/cm 2. Meanwhile, the Tafel slope, the electron-transfer resistance and the electrochemically active surface area of the catalyst were calculated to be 84 mV/dec, 44 Ω and 13.9 mF/cm 2, respectively. In order to evaluate the durability and stability of the catalyst, 12 h-chronoamperometry and 1000-cycle cyclic voltammetry measurements were also conducted and no obvious activity decay was observed.

    Polymer Chemistry
    Study on Photoelectrocatalytic Decolorization Mechanism of Methylene Blue Under the Visible-light Irradiation by Measuring Chemical Oxygen Demand Index
    LIU Fen, ZHOU Min, WANG Suxia, WANG Rong, YANG Ning, MA Yongjun
    2019, 40(9):  1988-1997.  doi:10.7503/cjcu20190030
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    Physical Chemistry
    Preparation of Targeting Nanodiamond-metaminopterone Drug System and Its Interaction with MCF-7 Cells
    LI Lin, XU Xinru, LI Yingqi, ZHANG Caifeng
    2019, 40(9):  1998-2004.  doi:10.7503/cjcu20190247
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    We fabricated a targeted nanodiamond drug system(NPF/G/M) through physical adsorption of methotrexate(MTX) using carboxylated nanodiamonds(ND-COOH) modified with polyethylene glycol diamine(H2N-PEG-NH2), folic acid(FA) and glycidol(GLY) as carriers. The preparation of NPF/G/M was verified by morphological observation, energy dispersive spectroscopy(EDS) of the elemental analysis, zeta potential and particle size. The results showed that NPF/G/M can be effectively released in the tumor site, which is three times than in the physiological environment(pH=7.4). Relying on the high affinity between folate and folate receptors, NPF/G/M was uptaken by tumor cells through energy, temperature, clathrin, caveolin-dependent and folate receptor-mediated endocytosis. Interestingly, toxicity tests showed that NPF/G/M can slowly release the drug into the cells and induce cell apoptosis. The above results indicate that NPF/G/M can be used as a good drug delivery system, which will provide a theoretical reference for clinical application in breast cancer.

    Polymer Chemistry
    In situ Synthesis of Nano-sized Silica Enforced Anionic Polyester Sizing Agent and Its Effect on ILSS of Carbon Fiber Composites
    WANG Zhenyu, LI Jianhua, GUO Huijun, YANG Chuncai
    2019, 40(9):  2005-2011.  doi:10.7503/cjcu20190209
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    Nano-sized silica enforced anionic polyester sizing agent(SEAPs) were synthesized by in situ synthetic technologies. SEAPs was analyzed and characterized by Fourier transform infrared spectroscopy(FTIR), laser particle size analyzer and cryo scanning electron microscope(SEM). The carbon fiber sized by SEAPs was studied with SEM, dynamic contact angle meter and energy dispersive spectroscopy(EDS). The surface morphology, surface energy, surface elements of carbon fibers and interlaminar shear strength(ILSS) of the sized carbon fibers and its reinforced unsaturated polyester composites were tested. The testing results showed that when the mass fraction of TEOS was 5%, the optimal ILSS of carbon fiber reinforced unsaturated polyester composite was obtained, which was 90% higher than that of carbon fibers composites after sizing with commercial epoxy resin sizing agent. In situ synthesized nano-SiO2 formed core-shell micelle with anionic polyester and nano-sized SiO2 is evenly adsorbed on the surface of carbon fibers after sizing, increasing the surface energy of carbon fibers and improving the wettability between carbon fibers and unsaturated polyester, which can effectively enhance the ILSS of carbon fibers composites.

    “One-pot”N-(2-Benzamidophenyl)-salicylaldehyde Imine/TiCl4·2THF for Catalytic Ethylene Polymerization
    ZHANG Danfeng, ZHAO Maoyu, GUO Ning, TANG Songchao, ZHENG Anna
    2019, 40(9):  2012-2019.  doi:10.7503/cjcu20190175
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    Four ligands, N-(2-benzamidophenyl)-salicylaldehyde imine(L1), N-(2-Benzamidophenyl)-3-methylsalicylaldehyde imine(L2), N-(2-benzamidophenyl)-3-tert-butyl-salicylaldehyde imine(L3) and N-(2-benzamidophenyl)-3,5-dibromosalicyl aldehyde imine(L4) were synthesized and characterized by 1H NMR and HRMS. Under activated with methylaluminoxane(MAO), L3/TiCl4·2THF, as model catalytic system, aging conditions of the catalytic system were studied systematically. The optimum conditions are as follows: the aging temperature is 25 ℃, the aging time is 30 min, and the molar ratio of L3/TiCl4·2THF is 3∶1. Based on the optimum conditions, ethylene polymerization by L1—L4/TiCl4·2THF was performed under different polymerization parameters, such as molar ratio of Al/Ni, polymerization time and temperature, pressure. It reveals that the ligand with more bulky frame work exhibits higher catalytic activities and higher molecule weight. L3 reaches the highest activity of 224 kg PE/(mol Ti?h). Besides, the microstructures and thermoal properties of obtained polyethylene samples with L1—L4/TiCl4·2THF were characterized by high temperature 1H NMR, 13C NMR, GPC-IR and DSC. It exhibited that the PE samples are of typical linear high density PE, Mn are between 5.9×10 4 and 11.9×10 4, PDI are around 21.9 to 72.1. The research results help us to understand ethylene polymerization in situ deeply.

    PLG-g-TA/RGD Enzyme-catalyzed Crosslinked Hydrogel for Adhesion and Three-dimensional Culture of Hyaline Chondrocytes
    WEN Jing, XU Zhimin, QI Desheng, WANG Jiayu, YU Shuangjiang, HE Chaoliang, HAN Bing
    2019, 40(9):  2020-2027.  doi:10.7503/cjcu20190148
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    A novel enzyme-catalyzed cross-linking hydrogel based on poly(L-glutamic acid)-g-tyramine/cRGDfk cyclic peptide(PLG-g-TA/RGD) was prepared for the investigation of adhesion and the three-dimensional culture of hyaline chondrocytes. PLG-g-TA/RGD polymers could form a hydrogel by self-crosslinking of the tyrosine group rapidly in the presence of horseradish peroxidase(HRP) and hydrogen peroxide(H2O2). The further research results showed that both the gelation time and gel mechanical strength were significantly enhance with the presence of cRGDfk. More hyaline chondrocytes adhered to the surface of the cRGDfk containing hydrogel compared to the control group after incubation of 3 d. The proliferation efficiency of hyaline chondrocyte in PLG-g-TA/RGD hydrogel was significantly higher than PLG-g-TA formed hydrogel after culture with 1, 4 and 7 d, respectively. The results of the cells indicated that the obtained materials exhibited a good cell compatibility. Above all, the introduction of cRGDfk promotes the adhesion and proliferation of hyaline chondrocytes, and showed the potential application of the original PLG-g-TA/RGD hydrogel in the field of three-dimensional cell culture.

    Development of Novel Polymerizable Antibacterial Monomer and Its Antibacterial Effects on Dental Adhesive
    XU Jiajia, LI Xiaojun, ZHU Weipu, DUAN Zhuhui, MAO Yingjie, LI Xiaodong
    2019, 40(9):  2028-2032.  doi:10.7503/cjcu20190138
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    The object of the present study was to Functionalize adhesive system with antibacterial activity without interfering the bonding effect, to kill bacteria residue on cavity and prevent bacteria from colonization on the margins of bonding. The fluorine-containing imidazolium salt antibacterial monomer was synthesized by the combination reaction of 1-chlorododecane and 1-vinylimidazole, and the replacement reaction to introduce fluoride ion. The synthesized intermediate product and final product were characterized by nuclear magnetic resonance spectroscopy. Fluoride ion was introduced into the bonding system in the form of organic fluorine, and the release behavior of fluoride ion from the functionalized adhesive was studied. The antibacterial experiment showed that the functionalized adhesive was endowed with good antibacterial property, which realized targeted anti-caries ability. The bond strength test indicated that the functionalization with the fluorine-containing imidazolium salt monomer did not affect the bonding performance of the adhesive. These results suggested that adhesive functionalized with the fluorine-containing imidazolium salt monomer had potential for reducing the occurrence of clinical secondary caries.

    Microstructure Regulation of the Reverse Osmosis Membrane to Improve the Boron Removal Performance
    XIE Xin, ZHANG Xiao, LI Ruihan, SONG Xiaoxiao, LIU Lifen, GAO Congjie
    2019, 40(9):  2033-2040.  doi:10.7503/cjcu20190104
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    Thin aromatic polyamide composite reverse osmosis membranes(TFC) were modified by grafting polyethyleneimine(PEI) chains and 4-azidobenzoic acid(ABA) molecules. Attenuated total reflectance Fourier transform infrared spectroscopy(ATR-FTIR) and X-ray photoelectron spectroscopy(XPS) were used to analyze the chemical composition and structure of the active separation layer. Then the hydrophobicity and charge of the reverse osmosis membrane were measured by static water contact angle instrument and Zeta potentiometer, the surface morphology was observed by scanning electron microscopy(SEM) and atomic force microscopy(AFM). Finally, the separation performance of the reverse osmosis membranes was tested in brackish water and seawater condition, respectively. The experimental results show that the separation layers of the reverse osmosis membrane become denser after modifying with PEI and/or ABA, and correspondingly the mass transfer resistance of boron permeation through reverse osmosis membranes is increased. The boron retention rate of the TFC-PEI-ABA membrane modified by both PEI and ABA reach 90.45%, which meets the requirements of World Health Organization(WHO) for water quality.