Loading...

Table of Content

    10 September 2014, Volume 35 Issue 9
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.35 No.9(2014)
    2014, 35(9):  0-0. 
    Asbtract ( )   PDF (16227KB) ( )  
    Related Articles | Metrics
    Review
    Highly Efficient Blue Electroluminescent Materials Based on Phenanthro[9,10-d]imidazole
    LI Weijun, GAO Zhao, WANG Zhiming, YANG Bing, LU Ping, MA Yuguang
    2014, 35(9):  1849-1858.  doi:10.7503/cjcu20140568
    Asbtract ( )   HTML ( )   PDF (3491KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Phenanthro[9,10-d]-imidazole(PI) unit has attracted extensive attentions in organic optoelectro-nic field due to its intrinsic wide band gap, high luminescence efficiency, good thermal stability, balanced charge carrier injection and transport property as well as low fabrication cost. In this manuscript, the recently reported blue electroluminescent PI derivatives were reviewed. The structure characteristics of PI were demonstrated, and the structure-property relationships of some PI derivatives were summarized systemically. At last, all the reported highly efficient nondoped deep blue emitters were summed up in order to comprehensively evaluate the potentials of PI derivatives in organic light emitting diodes(OLEDs) in the future.

    Articles: Inorganic Chemistry
    Ionothermal Syntheses and Characterization of Open-framework Manganese Phosphites (NH4)2Mn3(HPO3)4 and Mn(HPO3)
    HE Yongke, YAN Yan, YANG Fen, WU Junbiao, SONG Xiaowei
    2014, 35(9):  1859-1863.  doi:10.7503/cjcu20140529
    Asbtract ( )   HTML ( )   PDF (1894KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Two open-framework manganese phosphites, (NH4)2Mn3(HPO3)4(1) and Mn(HPO3)(2), were synthesized under ionothermal conditions and characterized by single crystal X-ray diffraction. The two compounds were synthesized under the same conditions, but the structures were different with the use of diffe-rent ionic liquids. The framework structure of compound 1 is built up from MnO6 octahedra and phosphite groups, giving rise to a two-dimensional framework with NH4+ cations filling between the layers; the structure of compound 2 consists of a 3D condensed framework of edge-sharing MnO6 octahedra linking to [HPO3] units via oxygens. The compounds were further characterized by scanning electron microscopy(SEM), powder X-ray diffraction(PXRD) and inductively coupled plasma(ICP), and the magnetic measurements results reveal that strong antiferromagnetic interaction exists in compound 1.

    Morphological Transformation of Mesoporous Silica Using Binary Cationic-anionic Surfactant as Template
    PENG Ce, MU Mingwei, XIE Shihang, CAI Qiang
    2014, 35(9):  1864-1870.  doi:10.7503/cjcu20140371
    Asbtract ( )   HTML ( )   PDF (5481KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Mesoporous silica with various morphologies were obtained using binary cationic-anionic surfactant as template after a facile hydrothermal treatment. Cetyltrimethyl ammonium bromide(CTAB) and sodium dodecyl sulfonate(SDS) were selected as cationic and anionic structure direct agent respectively. Mechanism of morphological control during this process was investigated by regulating the molar ratio of SDS/CTAB. The as-synthesized samples were characterized by scanning electron microscopy(SEM), small angle X-ray diffraction(SXRD), transmission electron microscopy(TEM) and nitrogen adsorption-desorption isotherms measurements. Formation of the different stable morphologies were attributed to the structural transition of SDS/CTAB assembly from micelle to bilayer commitment with the ascending ratio of SDS.

    Influence of Two Different Lead Sources on the Growth of PbSe Nanocrystals
    LI Xiaoteng, WANG Yingnan, LIN Aolei
    2014, 35(9):  1871-1876.  doi:10.7503/cjcu20140311
    Asbtract ( )   HTML ( )   PDF (6052KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Under different reaction temperature and reaction time, we studied the influence of PbO and Pb(Ac)2 as lead sources on the growth of PbSe nanocrystals, respectively. Experimental results indicated that when we used PbO as a lead source, OA as the ligand, monodispersed spherical and truncated octahedral PbSe nanocrystals could be obtained at different reaction temperatures. In contrast, when we used Pb(Ac)2 as the lead source, PbSe nanoflowers and nanostars could be obtained at different reaction temperatures. Different PbSe morphologies could be obtained when we chose different lead sources, which was attributed to different steric hindrance caused by different lengths of capping ligands. However, upon going through a high reaction temperature and a long reaction time, all these diverse morphologies of PbSe nanocrystals could evolve into cubic-like nanocrystals, which is determined by the crystal habit of PbSe.

    Analytical Chemistry
    Studies on Fresh Cervical Cancer Tissues by Raman Spectroscopy
    ZHANG Haipeng, ZHENG Chao, LU Lu, ZOU Yabin, WANG Cuihua, XU Shuping, XU Weiqing, FAN Zhimin, LU Laijin, HAN Bing
    2014, 35(9):  1877-1882.  doi:10.7503/cjcu20140401
    Asbtract ( )   HTML ( )   PDF (1187KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A portable Raman spectrometer was used for distinguishing the characteristics of cervical cancer, cervical intraepithelial neoplasias Ⅲ(CIN Ⅲ) and normal fresh cervical tissues. Based on spectral profiles, the presence of lipids(817, 1127, 1176, 1450, 1769 cm-1) is indicated in normal tissue, and proteins(755, 1003, 1372, 1542, 1577 cm-1) are found in diseased tissues. Between CIN Ⅲ and cervical cancer tissues, proteins(853 and 1542 cm-1) and nucleic acids(1340 cm-1) are found to be good discrimination parameters. These three kinds of tissues have significant differences on the ability of forming hydrogen bond between dihydrogen phosphate ester groups, the relative content of DNA, the disorder of methylene, the deformation of amide I band CO and the formation of carotenoids. These features show that Raman spectroscopy has good clinical application potential which can be used to detect cervical cancer tissues, explore the relationships and differences between cervical cancer and CIN Ⅲ and diagnose cervical cancer early.

    Effects of Huanglian Jiedu Decoction on the Metabolic Features of Brown Adipose Tissue Extracts in Fructose-induced Insulin Resistance Model Based on NMR Metabonomics
    YANG Yongxia, WANG Linlin, ZHENG Lingyun, WANG Shumei, HUANG Rongbo, ZHANG Lei, HUANG Yaoting
    2014, 35(9):  1883-1888.  doi:10.7503/cjcu20140308
    Asbtract ( )   HTML ( )   PDF (1957KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    With the application of 1H nuclear magnetic resonance(1H NMR) spectroscopy, we studied the effect of Huanglian Jiedu decoction(HJD) on the metabonomics of brown adipose tissue extracts in high fructose-induced insulin resistance model. 32 Wistar rats were divided into four groups, i.e., controls, model group, positive drug group and HJD treated group, 8 in each group. The last three groups were given 100 g/L fructose water for 28 d to establish insulin resistance model, normal control group was given the equal volume of pure water at the same time. After 28 d, four groups of rats were given 100 g/L fructose water continuously. Rats in positive drug group were administered orally atorvastain at a dose of 10 mg/(kg·d), and rats in HJD treated group were given by gavage with HJD water. The control and model groups were given by gavage with a certain volume of saline solution, and the experiment lasted 56 d. Brown adipose tissues were obtained and 1H NMR spectra of each sample was performed and analyzed by principal component analysis(PCA)method. Compared with the control group, lactate, alanine, choline, phosphocholine/glycerol phosphocholine(PC/GPC), creatine/creatinine, taurine and inosine increased in the model and lipid decreased. In comparison with model group, the myo-inositol was increased in HJD group, and HJD had reversed the metabolites in the model group. HJD can regulate the body’s energy metabolism and reduce the damaged cell membrances and the injury of liver and kidney. Therefore, this study elucidates the metabolic mechanism of HJD on insulin resistance(IR).

    Quantitative Analysis of Proteins in Human Serum by Species-unspecific Isotope Dilution-gel Electrophoresis-laser Ablation-inductively Coupled Plasma Mass Spectrometry
    ZHANG Dan, FENG Liuxing, WANG Jun, SHEN Dairui, XIONG Jinping
    2014, 35(9):  1889-1895.  doi:10.7503/cjcu20140233
    Asbtract ( )   HTML ( )   PDF (1124KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A methodology based on species-unspecific isotope dilution-gel electrophoresis-laser ablation coupled with inductively coupled plasma mass spectrometry(GE-LA-ID-ICP-MS) was established for the absolute quantification of proteins in human serum by measuring sulfur. The electrophoresis separation condition of human serum were 7.5% separating gel, 4% stacking gel, 100 V until bromophenol blue dye had migrated to the bottom of gel. The average signal intensity of 32S at different concentrations of sulfur enriched gels(1—400 μg/g) showed a good linear relationship. The relative quantitative analysis of transferrin and albumin in human serum was investigated using external standard method. In addition, the created species-unspecific isotope dilution in GE-LA-ICP-MS had added 34S spike signals into gels successfully by mixing sulfur spike with protein strips. According to isotope dilution equation, the method was applied to a fast, accurate absolute quantification of transferrin and albumin in human serum. The methodology was validated by comparing with the quantitative analysis of a serum protein certified reference material(ERM-DA470/IFCC). The results confirmed that determined concentration of transferrin and albumin fitted well with the certified value and the methodology had good accuracy and better measurement precision than external standard method.

    Organic Chemistry
    Synthesis and Evaluation of GnRHa-paclitaxel Tumor-targeting Conjugates
    MA Yongtao, FENG Siliang, WANG Chenhong, ZHOU Ning, LIU Keliang
    2014, 35(9):  1896-1900.  doi:10.7503/cjcu20140451
    Asbtract ( )   HTML ( )   PDF (500KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Tumor targeting can be achieved by combining a chemotherapeutic agent with a targeting moiety, which recognizes tumor-specific or highly expressed receptors on cancer cells. GnRH receptor is over-expressed on various tumor cells but is barely expressed in healthy visceral organs which makes it possible to use GnRH analogues(GnRHa) as the targeting moieties to deliver cytotoxic agents. Two conjugates were synthesized by incorporating paclitaxel(PTX) into GnRH analogue which was synthesized in the solid phase, the conjugation of PTX with GnRH analogs was performed by thio-ether bond and disulfide bond as a linker. The purity of the conjugates was analyzed by high performance liquid chromatography(HPLC) and the structures of the conjugates were confirmed by high resolution mass spectrum(HRMS). The resulting conjugates 1 and 2 both preserved the cytotoxic activity of PTX and also retained the high binding affinity of the peptide hormone portion of the conjugates. The high affinity indicated that the conjugates might be specifically delivered to tumor tissues or cells via endocytosis mediated by GnRH receptor. The results showed that more than 50% prototypes of conjugate 1 remained with incubating in human serum for 24 h which indicating a favorable stability.

    Effect of Different Charged Liposomes on Transmembrane Incorporation Efficiency of the Staphylococcus Aureus Receptor Histidine Kinase AgrC
    XIONG Wen, QUAN Chunshan, WANG Lina, ZHANG Xuning, ZHAO Jing, ZHENG Wei, FAN Shengdi
    2014, 35(9):  1901-1907.  doi:10.7503/cjcu20140057
    Asbtract ( )   HTML ( )   PDF (2304KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    AgrC is a membrane-embedded histidine kinase in Staphylococcus aureus that is thought to act as a sensor for the recognition of environmental signals and the transduction of signals into the cytoplasm so as to regulate and control a series of related pathogenic gene expression. However, for the complexity of cell membrane, it turns to be difficult to study AgrC on bacterial cell membrane directly. Many researches tried to take advantage of proteoliposome which could provide an approximate natural membrane environment and keep the protein activity to study the structure and function of membrane proteins. In order to build a transmembrane protein incorporation system with a relatively high incorporation efficiency, function activity and stability, various factors were considered, such as the impact of different charge polarity head on protein transmembrane incorporation efficiency. Here, four kinds of different charged liposomes were prepared by changing the phospholipid components in liposome and a detergent-mediated method was used to reconstitute truncated AgrC protein(AgrCTM6-7C) into them. The results showed that negatively charged liposomes leaded to a higher incorporation efficiency compared with the positively charged one and about 60%—70% C-terminal cytoplasmic domain of AgrCTM6-7C protein reconstituted into negatively charged liposomes were outside-orientated which remained a highly kinase activity. Furthermore, from circular dichroism detection result, we can draw a conclusion that liposome has certain protective effect on AgrCTM6-7C protein secondary structure and improve the thermal stability of the protein.

    Enantioselective Aldol Reaction of Acetone and Benzofuran-2,3-diones
    LI Xin, HAN Yu, TAN Boxuan, WANG Bin, CHENG Jinpei
    2014, 35(9):  1908-1911.  doi:10.7503/cjcu20140052
    Asbtract ( )   HTML ( )   PDF (1641KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The 3-substituted 3-hydroxybenzofuran-2-one unit is encountered in a large variety of natural pro-ducts with a wide spectrum of biological activities. Therefore, development of new methodologies to the construction of chiral quaternary center at the 3-position of benzofuran-2-one compounds were highly desired. A highly enantioselective Aldol reaction of benzofuran-2,3-ones with ketone catalyzed by N-(2-thiophenesulfonyl)prolinamide through enamine activation strategy was developed. As a result, a number of chiral 3-hydro-xyl substituted benzofuran-2-ones derivatives were synthesized with very good yields(up to 96%) and mode-rate to good enantioselectivities(up to 91% e.e.). This methodology substantially broadens the benzofuranone chemistry and offer functionalized chiral products.

    Mannich Reaction of Aromatic Ketones Based on Acetic Acid as Solvent and Catalyst
    BU Huijuan, ZHANG Jing, MU Boshuai, LI Yuan
    2014, 35(9):  1912-1918.  doi:10.7503/cjcu20131050
    Asbtract ( )   HTML ( )   PDF (1685KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Mannich reaction is one of the most important methods for preparation of β-amino ketones and aldehydes and α,β-unsaturated carbonyl compounds, as well as one of the most important basic reaction types in organic chemistry and it is widely applied as a key step in the synthesis of numerous pharmaceuticals and natural products. However, during the synthesis of 1-aryl acrylic ketone 2 by the Mannich reaction of aromatic ketones, formaldehyde and secondary amine using acetic acid as solvent and catalyst, the Mannich base and expected α,β-unsaturated ketones 2 were not obtained and another kind of compounds 3, 2-aryl formyl allyl acetate were obtained in moderate to good yields(65%—73%). The structure of compounds 3 was confirmed by 1H NMR, 13C NMR, HRMS and IR spectra. The reasons of producing compounds 3 were studied and the results suggested that the special structure of aromatic ketones and excess acetic acid in reaction are responsible for the exceptional Mannich reaction. In addition, the reaction mechanism was postulated.

    Physical Chemistry
    Theoretical Studies on Water Catalysis of Two Esters Interconversion Reaction
    JIANG Juxing, WANG Jiajun, DUAN Yanqing, LIU Ya, WANG Wenyuan, WU Shaohua
    2014, 35(9):  1919-1925.  doi:10.7503/cjcu20140459
    Asbtract ( )   HTML ( )   PDF (455KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Compounds 1 and 2 could interconverse to each other at room temperature when water was encountered. Four possible interconversion mechanisms, A, B, C and D, were put up. At B3LYP/6-311+G(d,p) level in gas phase, the optimized activation energies of TS1 and TS2 in mechanism A were all distinctively more than 120 kJ/mol. But as for mechanism D, the optimized activation energies of TS1 and TS2 were dramatically decreased. Further results showed that the solvation effects of water also reduced the activation energy. Meanwhile, the single point energy were calculated at MP2/6-311++G(2d,2p)//B3LYP/6-311+G(d,p) level. Finally the activation energies of TS1 and TS2 in mechanism D were 106.24 and 107.37 kJ/mol, respectively. Therefore, mechanism D was the most possible pathway for the interconversion between compounds 1 and 2 at room temperature. This preferred mechanism pathway was a special water-catalyzed intramolecular oxoester alcoholysis, which also was a conventional nucleophilic addition, producing a novel tetrahedral alcoholic intermediate.

    Theoretical Studies on the Interaction of CO and CH3O on CuCl(111) Surface for Methanol Oxidative Carbonylation
    ZHENG Huayan, ZHANG Riguang, LI Zhong
    2014, 35(9):  1926-1932.  doi:10.7503/cjcu20140426
    Asbtract ( )   HTML ( )   PDF (3417KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Based on density functional theory method in the generalized gradient approximation, together with the periodic slab model, the single adsorption of CO and CH3O, as well as the co-adsorption of CO and CH3O on CuCl(111) surface involving in methanol oxidative carbonylation to dimethyl carbonate(DMC) were systematically investigated. The reaction mechanisms of CO interaction with CH3O leading to CH3OCO and CH3OCO interaction with CH3O to DMC on CuCl(111) surface were discussed. The calculated results indicate that the interaction between CO and CH3O in the co-adsorption system is stronger than that between free CO and CH3O in gas phase, CO insertion into adsorbed CH3O on CuCl(111) surface to CH3OCO species are the rate-limiting step for the oxidative carbonylation of methanol to DMC, and the corresponding activation barrier is 113.19 kJ/mol, the calculated results are in accordance with the reported experimental facts.

    Preparation, SERS and Catalytic Properties of Au Nano-network Based on Poly(conjugated linoleic acid)
    FAN Ye, FANG Yun, CHEN Hanting, GAO Di
    2014, 35(9):  1933-1940.  doi:10.7503/cjcu20140341
    Asbtract ( )   HTML ( )   PDF (5622KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Networked poly(conjugated linoleic acid)(PCLA) aggregates were prepared from a natural polymerizable monomer, conjugated linoleic acid(CLA), through a simple strategy of molecular self-assembly followed by controlled self-crosslinking. The morphology of the PCLA aggregates by transmission electron micro-scopy(TEM), was a unique network structure with the CLA spherical particles as the junction units that were originated from the CLA micelles. Subsequently, the Au nano-network with core of CLA micelle(20 nm) was synthesized in 2 d through in situ reduction of gold on the surface of the PCLA network. It was found that the Au nano-network based on PCLA could be obtained if and only if PCLA provided both functions of in situ reduction and model. Moreover, the Au nano-network based on PCLA displays better surface-enhanced Raman scattering(SERS) for thiophenol and better catalytic effect on reduction of 4-nitrophenol than the normal spherical Au nanoparticles [(5±1) nm] does.

    Catalytic Properties of Manganese Complex of Cyclic Polyamine Encapsulated in Ethyl Cellulose Microcapsules
    SONG Min, ZHANG Linping, ZHONG Yi, XU Hong, MAO Zhiping
    2014, 35(9):  1941-1947.  doi:10.7503/cjcu20140250
    Asbtract ( )   HTML ( )   PDF (5854KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Manganese complex of cyclic polyamine(MnAcL) was encapsulated within ethyl cellulose(EC) microcapsules via emulsion solvent evaporation technique. The morphology of MnAcL-EC microcapsule was characterized. The results of UV-Vis confirmed the structural integrity of MnAcL in EC microcapsules. The catalytic property of the as-prepared MnAcL-EC microcapsules was evaluated by the oxidation of C.I. Reactive blue 49 with H2O2. It was found that both the particle size and the pores on the surface of the spheres increased after the reaction. However, the amount of MnAcL in EC microcapsules was almost not changed, as measured by the elemental analysis. It was suggested that the oxidation of C.I. Reactive blue 49 was catalyzed successfully by the encapsulated MnAcL inside the microcapsules. What’s more, the as-prepared MnAcL-EC microcapsules could be reused for at least 4 times. These results demonstrated that the MnAcL-EC microcapsule prepared in this paper could be applied as a high efficient catalyst.

    Seed Number Density-controlled Synthesis of Au@SiO2 Nanoparticles
    LUO Chunxiang, CUI Ying, YU Huimin, KONG Gezhi, HU Jiawen
    2014, 35(9):  1948-1953.  doi:10.7503/cjcu20140230
    Asbtract ( )   HTML ( )   PDF (6402KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    In this paper, we systematically investigated the synthesis of Au@SiO2 NPs in isopropanol medium using Frens Au colloids as seeds. It shows that the yield of mononucleate Au@SiO2 NPs is dependent on the amount of the catalyst added, the feeding rate of the silicon source, and especially the number density of the Au seeds introduced. Following these findings, highly monodispersed 200, 320, and 450 nm Au@SiO2 NPs were synthesized, which are ideal building blocks for construction of functional materials.

    Preparation and Visible-light Photocatalytic Performance of Mesoporous Vanadium-doped Titania
    XU Peng, LI Youji, LIU Chen, LI Ming, DENG Ruicheng
    2014, 35(9):  1954-1961.  doi:10.7503/cjcu20140213
    Asbtract ( )   HTML ( )   PDF (3743KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Based on employing the liquid crystal of surfactant cetyltrimethyl ammonium bromide(CTAB), tetrabutyl titanate and ammonium metavanadate as template, titanium source and doping-ion precursor, respectively, vanadium-doped mesoporous titanium dioxide(VMT) was obtained by sol-gel method. The structure of obtained sample was characterized via X-ray diffraction(XRD), nitrogen adsorption-desorption, thermogravimetry-differential thermal analysis(TG-DTA), X-ray photoelectron spectroscopy(XPS), UV-Visible diffuse reflection spectrometry(UV-Vis) and transmission electronic microscopy(TEM). Choosing methylene blue(MB) as the target degradation product, the photocatalytic performance of VMT was discussed under visible light irradiation. The results show that doping vanadium can reduce TiO2 particle size, inhibit photo-electron and hole recombination rate as well as increase specific surface area and the concentration of titanium ion and hydroxyl. Thus VMT exhibits the highest catalytic activity among pure MT, VMT and P25 under UV-light irradiation. In addition, doping vanadium can also lessen MT band-gap energy and improve its catalytic activity under visible light. The optimal photocatalytic condition is as follows: catalyst concentration of 0.83 g/L and MB concentration of 1 mg/L.

    Preparation and Electrocatalytic Properties of Ir0.08Ti0.92O2 and Pt/Ir0.08Ti0.92O2
    WANG Qiang, WANG Rui, XU Haibo
    2014, 35(9):  1962-1967.  doi:10.7503/cjcu20140209
    Asbtract ( )   HTML ( )   PDF (2484KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Ir0.08Ti0.92O2 nanopowder with low Ir loading was prepared by TiN impregnation-thermal decomposition method, and then Pt/Ir0.08Ti0.92O2 electrocatalyst was obtained by microwave assisted hydrothermal synthesis method. X-ray diffractometer(XRD), transmission electron microscope(TEM), energy dispersive spectrometer(EDS) and X-ray photoelectron spectrometer(XPS) were used to analysis the morphologies and composition of the products. Ir0.08Ti0.92O2 showed to be stick-like nanoparticles with the diameter of 15 nm, and IrO2 and TiO2 formed a solid solution with rutile phase, the diameter of Pt nanoparticles on Ir0.08Ti0.92O2 was 5—7 nm. Moreover, Ir/Ti molar ratio in interior support was 0.084∶0.916, whereas that on the support surface was 0.296∶0.704, indicating the surface accumulation of Ir. Polarization curves and linear sweep voltammetry(LSV) were performed to determine their electrocatalytic properties, compared with those of IrO2 by traditional Adams-fusion method and commercial Pt/C. The results showed that the catalytic activity towards the oxygen evolution reaction(OER) was as follows: Ir0.08Ti0.92O2>Pt/Ir0.08Ti0.92O2>IrO2(the former two were almost the same). However, catalytic activity of Pt/Ir0.08Ti0.92O2 towards the oxygen reduction reaction(ORR) was lower than that of Pt/C, showing that a further optimization of Pt particle size was required. Therefore, Ir0.08Ti0.92O2 can be used not only as a low-cost and efficient OER catalyst but also as a suitable support material, which promotes Pt/Ir0.08Ti0.92O2 as a promising dual-functional catalyst with more advantage in cost, catalytic property and stability, as well as an excellent hydrogen evolution reaction(HER) catalyst in acidic medium.

    Fabrication of Superhydrophobic Surfaces with Hierarchical Structures by an Ultrasonic Etch Method
    HUANG Jianye, WANG Fenghui, HOU Shaohang, ZHAO Xiang
    2014, 35(9):  1968-1974.  doi:10.7503/cjcu20140205
    Asbtract ( )   HTML ( )   PDF (6821KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Based on wet etching and ultrasonic cavitation, an ultrasonic etch method was proposed for fabricating micro- and nanoscale hierarchical structures. By ultrasonic etching with isopyknic mixture of nitric acid/ethanol(4%, volume fraction) and hydrogen peroxide(30%, mass fraction) for 2—10 min at room tempe-rature, several hierarchical structures were fabricated on the surfaces of 60Si2Mn, 60#, T10, Cr06, 65Mn and silicon steel. After decorated with fluorosilane, the aforementioned surfaces become superhydrophobic and show water contact angles of 156.0°, 154.8°, 156.4°, 153.9°, 156.6° and 155.8°, respectively, and the corresponding roll angles are 6.5°, 19.2°, 6.1°, 7.8°, 6.7° and 7.2°, respectively. Compared to the regular etching, the chemical corrosion of ultrasonic etching was enhanced and modified by coupling with cavita-tion, and therefore could fabricate hierarchical structures. Due to the differences in microstructure morphologies and wetting states of solid/liquid interfaces, the superhydrophobic surfaces prepared show different wetting behavior. The ultrasonic method proposed is simple, inexpensive and available for other metals, thus having potential values in constructing micro- and nanoscale hierarchical structures and superhydrophobic surfaces.

    Visible Photocatalytic Degradation of Polyvinyl Chloride Film by AgNbO3 Photocatalyst
    WANG Dandan, LIU Junbo, CHANG Haibo, TANG Shanshan
    2014, 35(9):  1975-1981.  doi:10.7503/cjcu20140185
    Asbtract ( )   HTML ( )   PDF (3815KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Pure polyvinyl chloride(PVC) film and PVC-AgNbO3 hybrid films were prepared on glass substrates via a coating method. The photocatalytic degradation experiments were carried out under xenon lamp irradiation. The samples were characterized by X-ray diffractometer(XRD), scanning electron microscope(SEM), and Fourier transform infrared spectrometer(FTIR). The results show that PVC-AgNbO3 hybrid films have much higher photocatalytic degradation activity than pure PVC film. The photodegradation performance of the films can be evaluated directly by their mass loss. The mass loss of the pure PVC film was about 4.09% after irradiation under xenon lamp for 120 min, that of the PVC-3% AgNbO3, PVC-6% AgNbO3, PVC-9% AgNbO3, and PVC-15% AgNbO3 films reached about 20.36%, 23.52%, 27.62% and 33.83% after irra-diation for 120 min, respectively. The mass loss of PVC increased with the increase of the content of AgNbO3. This result prove that the presence of AgNbO3 remarkably promote the photocatalytic degradation rate of PVC film.

    Synthesis of Cucurbitacin Intercalated Hydrotalcite-like Compound Nanohybrids via Delamination-coassembling Method
    WANG Shuang, WU Xiaowen, LI Haiping, ZHANG Renjie, HOU Wanguo
    2014, 35(9):  1982-1987.  doi:10.7503/cjcu20140159
    Asbtract ( )   HTML ( )   PDF (2259KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A nanohybrid of cucurbitacin(CA), a charge-neutral and poorly water-soluble drug, intercalated hydrotalcite-like compounds(HTlc) was synthesized via a delamination-coassembling method. CA molecules were initially incorporated into the micelles of sodium cholate(Ch), and the resulting negatively charged CA-loaded micelles and the positively charged delaminated HTlc nanosheets were then coassembled together into the CA-Ch-HTlc nanohybrid. The so-obtained nanohybrid was characterized by small angle X-ray scattering, Fourier transform infrared, transmission and scanning electron microscopy, zeta potential and elemental analyses. The results showed that the loading of CA in the nanohybrid was 7.06%, indicating that this route could be used to achieve the effective intercalation of charge-neutral and poorly water-soluble drugs into the HTlc gallery. Based on the sizes of Ch and CA, and the gallery heights of the nanohybrid, a possible orientation of Ch anions and CA molecules in the HTlc gallery was proposed. The Ch anions are arranged as a slightly tilted bilayer with their long axis approximately perpendicular to the brucite-like layer, and the CA molecules are encapsulated in the bilayer as a consequence of the hydrophobic interactions. The in vitro release of CA from the nanohybrid was examined, and the results showed that the nanohybrid had a good drug controlled release performance and its drug release process obeyed pseudo-second order kinetics model.

    Improvement Performance of Dye-sensitized Solar Cells with Pt/Ti Counter Electrode Prepared by Electrodeposition-displacement
    WANG Yaoqiong, RAN Xiuzhi, GAO Huanfang, LI Li, WEI Zidong
    2014, 35(9):  1988-1993.  doi:10.7503/cjcu20140135
    Asbtract ( )   HTML ( )   PDF (3275KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A Pt/Ti counter electrode of dye-sensitized solar cell(DSSC) was prepared by displacing electrodeposited Cu on a Ti sheet in H2PtCl6 solution. Morphological characterization of the Pt/Ti electrode shows that the dispersion and size of Pt particles on Ti substrate is significantly improved in contrast to that of the Pt/FTO electrode prepared by pyrolysing Pt salt on a fluorine-doped oxide(FTO) glass substrate. The photocurrent density-voltage(J-V) curves show that the overall energy conversion efficiency of DSSC with the Pt/Ti counter electrode increases by 20.8% relative to that with the Pt/FTO counter electrode. The results also reveal that the improved performance of the DSSC with the Pt/Ti counter electrode is assigned to the higher electrochemical surface area of the Pt/Ti counter electrode than the Pt/FTO, the lower electric resistance and the better reflecting ability of the Ti substrate than the FTO substrate.

    Application of Dimethyl Sulfoxide as Solvent of Electrolyte Solution in Rechargeable Lithium Metal Batteries
    YUAN Zhenshan, XU Qiang, SANG Lin, DING Fei
    2014, 35(9):  1994-1998.  doi:10.7503/cjcu20140126
    Asbtract ( )   HTML ( )   PDF (3838KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Dimethyl sulfoxide(DMSO) was used as the solvent of electrolyte in the rechargeable lithium metal batteries. The lithium deposition morphology and cycling efficiency in DMSO, propylene carbonate(PC) and 1,3-dioxolane(DOL) with lithium hexafluorophosphate(LiPF6) as the solute and in DMSO with lithium hexafluorophosphate(LiPF6), lithium tetrafluoroborate(LiBF4), lithium perchlorate(LiClO4) or lithium bis(trifluoromethane sulfonimide)(LiTFSI)] as the solute respectively were investigated and compared. The resuts show that Li surface deposited in the DMSO solution was smooth and uniform and the lithium cycling efficiency in the DMSO solvent was higher than that in PC solvent in the first ten cyclings.

    Bio-sequestration of CO2 Using Carbonic Anhydrase in situ Encapsulated Inside Electrospun Hollow Fibers
    CUI Jiandong, LI Ying, JI Xiaoyuan, BIAN Hongjie, ZHANG Yufei, SU Zhiguo, MA Guanghui, ZHANG Songping
    2014, 35(9):  1999-2006.  doi:10.7503/cjcu20140059
    Asbtract ( )   HTML ( )   PDF (4831KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Carbonic anhydrase catalyzed bio-sequestration of CO2 to form HCO3-, followed by trapping as solid CaCO3 is one of the most promising technologies for CO2 capturing. The effects of reaction condition on the CO2 hydration using free carbonic anhydrase were systematically investigated. In order to improve the stability of the enzyme and facility its recycling, the carbonic anhydrase was in situ encapsulated inside hollow fibers via a novel co-axial electrospinning technology. Compared with the free enzyme, the immobilized carbonic anhydrase showed much improved thermal stability and suffered much reduced inhibitory effects from cation ions, such as Cu2+ and Fe3+. After 11 reuses, the immobilized enzyme retained about 81.9% of its original activity by comparing the amount of formed CaCO3 precipitation. In the presence of immobilized carbonic anhydrase, both calcite and vaterite CaCO3 solid were formed; while in the absence of enzyme or with free carbonic anhydrase, only calcite CaCO3 was observed.

    Polymer Chemistry
    Synthesis and Characterization of Block Copolymers with PMMA Segment Initiated by Organic Lithium
    CHEN Bo, WANG Jiming, SHU Minze, ZOU bin, GUAN Yong, ZHENG Anna
    2014, 35(9):  2007-2013.  doi:10.7503/cjcu20140468
    Asbtract ( )   HTML ( )   PDF (1149KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Well-defined block copolymers polyisoprene-b-poly(methyl methacrylate)(PI-b-PMMA) and poly(butyl methacrylate)-b-poly(methyl methacrylate)(PBMA-b-PMMA were synthesized in THF initiated by n-BuLi and DPHLi with the addition of P-Complex. The polymerizations were carried out under the conditions which could be achieved in industry through adding monomers by sequence. The conversion of MMA was higher than 90% both in PI-b-PMMA and PBMA-b-PMMA, and the molar ratios of each segment in block copolymers detected by 1H NMR fit to those calculated. The Mn of PI-b-PMMA and PBMA-b-PMMA were 4.0×104 and 1.6×104, respectively. Well-defined triblock polymer PS-b-PI-b-PMMA was synthesized in cyclohexane under the condition which could be achieved in industry. The conversions of monomers were all completed, and the molar ratio in the final triblock polymer was consistent to the one calculated. The final Mn was 7.4×104, and the molecular weight distribution(MWD) was only 1.28.

    Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization
    ZHANG Chunyu, DONG Bo, ZHANG Hexin, CHEN Chunhai, ZHANG Xuequan
    2014, 35(9):  2014-2018.  doi:10.7503/cjcu20140399
    Asbtract ( )   HTML ( )   PDF (1394KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    The spherical MgCl2 supported TiCl4 catalyst(TiCl4/MgCl2/DIBP) was applied to bulk copolymerization of propylene and 1-butene. The influence of comonomer feed ratio on catalyst activity and stereoregularity of the copolymers were studied. The composition and properties of copolymers were investigated by 13C nuclear magnetic resonance(13C NMR), differential scanning calorimetry(DSC), infrared(IR) and gel permeation chromatography(GPC). The results showed that the polymerization activity increased firstly and then decreased with the increasing 1-butene/propylene feed ratio(B/P). The highest polymerization activity was achieved at B/P=0.26. As the 1-butene content in the copolymers increased, the melting point of the copolymers decreased and the molecular weight distribution became narrow. Meanwhile, the mechanical properties of the copolymers were improved significantly, and the transparency was gradually increased.

    Synthesis and Biological Evaluation of Comblike Non-virus Gene Delivery Vector with the Poly(L-glutamic acid) as Backbone
    HE Ning, SUN Hechun, XU Huanxi, SHAO Zhangzhang
    2014, 35(9):  2019-2026.  doi:10.7503/cjcu20140326
    Asbtract ( )   HTML ( )   PDF (3181KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A novelcomblike catiomer, poly(L-glutamic acid)-graft-[polyethylenimine-block-poly(ethylene glycol)][PG-g-(PEI-b-PEG)], was synthesized by coupling of poly(L-glutamic acid)-graft-polyethylenimine(PG-g-PEI) and PEG using isophorone diisocyanate(IPDI). PG-g-PEI was firstly prepared via the ammonolysis of poly(γ-benzyl L-glutamate)(PBLG) with the low molecular weight polyethylenimine. The molecular structural property of PG-g-(PEI-b-PEG) was confirmed by 1H nuclear magnetic resonance spectroscopy(1H NMR) and gel permeation chromatography(GPC). The complexes of PG-g-(PEI-b-PEG)/pDNA were measured by dynamic light scattering and zeta-potential instrument. The results showed that PG-g-(PEI-b-PEG) could efficiently condense pDNA into nanosized particles with positive surface charges. The DNA binding ability of PG-g-(PEI-b-PEG) was further examined by gel retardation assay, and PG-g-(PEI-b-PEG) can retard plasmid DNA completely at N/P ratios above 5 in electrophoresis on agarose gel. The PG-g-(PEI-b-PEG) shows relative lower cytotoxicity against HEK 293T cells even at high N/P ratio demonstrated by MTT assay. The gene transfection evaluation revealed that the higher transfection efficiency for PG-g-(PEI-b-PEG) as a delivery agent was obtained at N/P ratio of 5, which exceeded 20-fold that of PEI 25000. These results suggest that the novel comblike catiomer PG-g-(PEI-b-PEG) might be an excellent biocompatible candidate for gene delivery system.

    Preparation of Antimicrobial Nanofiltration Membrane via Self-polymerization of Dopamine and Surface Grafting of PHGH
    LI Xia, CAO Yiming, KANG Guodong, YU Haijun, LIU Zhongnan
    2014, 35(9):  2026-2030.  doi:10.7503/cjcu20140305
    Asbtract ( )   HTML ( )   PDF (2361KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A novel antimicrobial nanofiltration membrane was fabricated by the self-polymerization of dopamine on polysulfone membrane surface and following surface grafting of polyhexamethylene guanidine hydrochloride(PHGH) in aqueous conditions. The membrane structures, morphologies and hydrophilicity were characterized by attenuated total reflectance-Fourier transform infrared spectroscopy(ATR-FTIR), scanning electron microscopy(SEM) and water contact angle measurement. The concentration of PHGH on grafting degree and filtration performance were investigated. Furthermore, the antibacterial performance of composite membranes was evaluated. The results showed that an active layer with nanofiltration performance was formed on polysulfone membrane surface and the hydrophilicity of membranes was significantly improved by the introduction of dopamine and PHGH. The fluxes decreased while the rejections of inorganic salts and dyes increased with the increasing concentration of PHGH. The composite membranes after grafting exhibited excellent antibacterial performance, when mass fraction of PHGH was 3%, the antibacterial rate reached up to 98.5%.

    Synthesis of 1,4-Bis(chloromethyl)benzene Crosslinked Poly(vinyl imidazolium) and Its Adsorptivity for Phenol from Coal Tar
    XIONG Jiali, MENG Hong, LU Yingzhou, LI Chunxi
    2014, 35(9):  2031-2036.  doi:10.7503/cjcu20140214
    Asbtract ( )   HTML ( )   PDF (1871KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A new poly ionic liquid(PIL) type adsorbent, poly(vinyl-benzyl-imidazolium) chloride(P[VBnim]Cl) was prepared facilely with overall yield above 75% through free radical polymerization of 1-vinylimidazole at 70 ℃ and cross-linking of the resulting polymer with 1,4-bis(chloromethyl) benzene via quaternization reaction in dimethylformamide(DMF) solvent. The as-prepared PIL was analyzed and characterized with respect to composition, structure, morphology and thermal stability by elemental analysis, gel permeation chromatography(GPC), Fourier transform infrared spectroscopy(FTIR), scanning electron microscope(SEM), physical absorption instrument and thermal gravimetric analysis/differential scanning calorimetry(TGA/DSC) technique. The molar ratio of 1,4-bis(chloromethyl) benzene to 1-vinylimidazole is about 1∶3 in P[VBnim]Cl. The P[VBnim]Cl is a beige and fluffy fine powder with primary particle size of 50—80 nm, being mesoporous material with specific surface area 13.86 m2/g and average pore size 9.94 nm. The PIL exhibits good thermal stability with its initial decomposition temperature being about 274 ℃. Adsorptivity for phenol from the model oil of low temperature coal tar was also studied. The P[VBnim]Cl was proved as an excellent adsorbent, being 2 to 10 times superior to the conventional active carbon at fixed other conditions. The excellent adsorptive property is mainly attributed to the chemical adsorption of the IL constituents at dilute phenol concentrations as well as the physical adsorption at higher phenol concentrations due to the porous architecture of P[VBnim]Cl. The used P[VBnim]Cl adsorbent can be regenerated easily with ethyl acetate, and used repeatedly with good adsorptivity.

    Investigation on Thickening Property of the Hydrophobically Associating Polyacrylamides
    CAO Xulong, HU Yue, SONG Xinwang, ZHU Yangwen, HAN Yugui, WANG Kunpeng, GUO Dongsheng, LIU Yu
    2014, 35(9):  2037-2042.  doi:10.7503/cjcu20140179
    Asbtract ( )   HTML ( )   PDF (2031KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    Hydrophobically associating polymers are distinctive water-soluble polymers with a few hydrophobic groups in the hydrophilic macromolecular chain. Because of its unique amphiphilic molecule structure, it has special rheological properties. Six hydrophobically associating polyacrylamide derivatives with different modification monomers were synthesized. Their intramolecular and intermolecular association behavior by internal factors such as the degree of polymerization, the block copolymer content as well as the size of hydrophobic groups and the external factors of the resistance to shear, salt tolerance were investigated. The hydrophobic chain can improved the viscosity and salt resistance of polymers.

    Synthesis and Characterization of Novel Photo- and pH-Responsive Poly[8-1]
    JIANG Hongbo, GONG Chengbin, WANG Qiang, TANG Qian, MA Xuebing
    2014, 35(9):  2043-2049.  doi:10.7503/cjcu20140155
    Asbtract ( )   HTML ( )   PDF (3403KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A photo-responsive functional monomer 4-amino-4'-methylacrylamide azobenzene(AMAB) was synthesized by coupling, reduction, and acylation reaction with 4-nitroaniline as the starting material. A water-soluble cross-linker triethylacrylateamine(TMAEA) was synthesized by acylation reaction with triethanolamine and methacrylic chloride and confirmed by nuclear magnetic resonance(NMR). A novel photo- and pH-responsive polymer: poly[(triethylacrylateamine)8-(triethylacrylateamine)1](T8A1) was successfully prepared by radical polymerization with AMAB and TMAEA using azo bisisobutyronitrile(AIBN) as the initiator. The T8A1 was characterized by thermeagravimetry analysis(TGA), infrared(IR), scanning electromic microscoy(SEM), and ultravidet visible(UV-Vis). The T8A1 exhibited both photo- and pH-response in water, which overcame the shortcoming of conventional azobenzene derivatives that they could only work in organic solvents and lose efficiency in aqueous media. These results made T8A1 amenable for applications in multi-stimuli responsive systems and biotechnology.

    Synthesis, Characterization and Pyrolysis Behavior of ZrB2/SiC Precursor
    GE Kaikai, QIU Wenfeng, HAN Weijian, YE Li, ZHAO Aijun, ZHAO Tong
    2014, 35(9):  2050-2054.  doi:10.7503/cjcu20140152
    Asbtract ( )   HTML ( )   PDF (3113KB) ( )  
    Figures and Tables | References | Related Articles | Metrics

    A novel liquid ZrB2/SiC precursor was prepared by the blend of polyzirconoxane and polyborosilazane, which were used as zirconium, silicon, boron and carbon source. The precursor was transformed into ZrB2/SiC ceramic during the pyrolysis, and its pyrolytic behavior, phase composition and microstructure were studied by TGA, XRD and SEM-EDX. The results indicated that the ceramic sample remained amorphous until t-ZrO2 initially generated at 1500 ℃. Heating to 1600 ℃ led to the formation of ZrC via carbothermal reduction. Further heating to 1700 ℃ led to the formation of ZrB2. During heat treatments, the compact ceramic sample became porous due to formation of CO and NO. The ceramic powder with particle size of 100—300 nm consisted of high crystalline degree ZrB2 and SiC phases, and all the elements were well distributed in ceramic powders.