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    25 January 2009, Volume 25 Issue 1
    Content
    Content of Chemical Research in Chinese Universities Vol.25 No.1(2009)
    2009, 25(1):  0-0.  doi:
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    Articles
    Hydrothermal Synthesis and Structural Characterization of Three-dimensional Metal-organic Framework [Zn3(C2H2N3)2(C7H5O2)4]
    SONG Zhe, LI Guang-hua, YU Yang, SHI Zhan , FENG Shou-hua
    2009, 25(1):  1-4.  doi:
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    Hydrothermal reaction between mixed ligand(1,2,4-triazole and benzoic acid) and Zn(NO3)2·6H2O afforded a three-dimensional(3D) metal-organic framework Zn3(C2H2N3)2(C7H5O2)4(C2H2N3=1,2,4-triazole, C7H5O2=benzoic acid). The compound was crystallized in the hexagonal system with space group R3: a=2.90234(9) nm, b=2.90234(9) nm, c=1.08597(5) nm, γ=120°, V=7.9222(5) nm3, Mr=816.68, Dc=1.541 g/cm3, Z=9, F(000)=3708, R=0.0636, and wR=0.1777. Its structure consists of ZnN2O2 tetrahedron and ZnN2O4 octahedron, which are connected by 1,2,4-triazole and benzoic acid ligands to form a 3D framework with helical units. This compound forms an interpenetrated NbO topology. The compound was characterized by single-crystal X-ray diffraction, elemental analysis, FTIR spectra, and TGA measurements.

    Synthesis and Luminescence Properties of Three High-dimensional Coordination Polymers: Zn(II) with Imidazole or Benzimidazole Ligand
    ZHANG Zhong-qiang , ZHANG Jing , DONG Lan-jun , ZHU Qin-lei , HUANG Ru-dan
    2009, 25(1):  5-8.  doi:
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    A novel 2D coordination polymer [Zn2(bim)4]n(1)(Hbim=benzimidazole) based on dihydrated- [N,N′-bis(2-aminophenl)-oxalamide](L1·2H2O) with zinc nitrate has been synthesized. Previously we have synthesized complexes [In2Zn3(im)12]n(2)(Him= imidazole) and [Zn(im)2]n(3) successfully. In complex 1, each Zn(II) coordinated with four ligands adopts a distorted tetrahedron coordination mode, and the 2D grid structure is built by the Zn(bim)4 as the secondary building unit(SBU). The luminescence properties of the three complexes were investigated for the first time. The emissions with maxima for complexes 1, 2 and 3 are at 379, 469 and 392 nm, respectively.

    Synthesis and Electrical Properties of New Solid State Electrolyte Materials Ce6-xHoxMoO15(0.0≤x≤1.2)
    ZHOU De-feng , XIA Yan-jie , MENG Jian
    2009, 25(1):  9-12.  doi:
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    Ce6-xHoxMoO15(0.0≤x≤1.2) was synthesized by modified sol-gel method and characterized by differential X-ray diffraction(XRD), Raman, and X-ray photoelectron spectroscopy(XPS) methods. The oxide ionic conductivity of the samples was investigated by AC impedance spectroscopy. It shows that all the samples are single phase with a cubic fluorite structure. The solid solution Ce6-xHoxMoO15(x=0.6) was detected to be the best conducting phase with the highest conductivity(σt=1.05×10-2 S/cm) at 800 ℃ and the lowest activation energy(Ea=1.09 eV). These properties suggest that this kind of material has a potential application in intermediate-low temperature solid oxide fuel cells.

    Synthesis and Characterization of NASICON Nanoparticles by Sol-gel Method
    WANG Biao, LIANG Xi-shuang, LIU Feng-min, ZHONG Tie-gang, ZHAO Chun, LU Ge-yu , QUAN Bao-fu
    2009, 25(1):  13-16.  doi:
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    Na superionic conductor(NASICON) nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800―1000 °C. The performance of the samples was characterized by the analysis methods of X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), and transmission electron microscopy(TEM) as well as conductivity measurement. Compared with those sintered at other temperatures, the NASICON material sintered at 900 °C had the best crystalline structure and higher conductivity.

    Quantitative Model for the Surface-related Electron Transfer in CdS Quantum Dots
    HUANG Chao-biao , WU Chuan-liu , LI Shu-yan , LAI Jin-ping , ZHAO Yi-bing
    2009, 25(1):  17-24.  doi:
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    The influence of surface S2- dangling bonds and surface doped ions(Se2-, Cu2+, and Hg2+) on the photoluminescence of Cd2+-rich CdS QDs was investigated. A quantitative model was proposed to understand the complex transfer processes of excited electrons in CdS QDs. The transfer of excited electrons from either the conduction band or the Cd2+-related trap-state to the surface S2--related shallow hole trap-state is effective. However, the trap of excited electrons by surface doped ion trap-states from the Cd2+-related trap-state is more effective than that from the conduction band. The efficiency of trapping electrons from both the conduction band and the Cd2+-related trap-state can be quantitatively understood with the help of the proposed model. The results show that the transfer efficiency of excited electrons is dependent on the location of the energy-level of the relevant surface-related trap-state. The trap of excited electrons by the surface trap-state with energy-level closer to that of the conduction band is more effective, especially for the trap of excited electrons from Cd2+-related trap-state.

    Simple Method for Simultaneous Quantitation and Fingerprint Analysis of Ginkgo biloba Tablets by High Performance Liquid Chromatography-UV-Evaporative Light Scattering Detector
    WANG Shu-fang, LUO Xiao-ling, SHAO Qing, CHENG Yi-yu , QU Hai-bin
    2009, 25(1):  25-30.  doi:
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    By optimizing the separation and analytical conditions, a reliable, simple and accurate high-performance liquid chromatography(HPLC) method coupled with ultraviolet(UV) and evaporative light scattering detector(ELSD) was developed for the simultaneous determination of lactones and flavonoid, that is, bilobalide, ginkgolide A, ginkgolide B, and rutin, in more than 10 batches of Ginkgo biloba tablets from different pharmaceutical companies. The method could also be applied to fingerprint research, for a more general evaluation of the quality of this preparation. The separation of the components was achieved on a Hanbon C18 column with gradient elution using water and methanol containing 0.1% trifluoroacetic acid(TFA). The column temperature was 30 °C and the flow-rate of the mobile phase was 0.6 mL/min. The drift tube temperature of the ELSD was set at 100 °C, and the nitrogen flow-rate was 2 L/min. Good linear relationships were shown with correlation coefficients for analytes exceeding 0.9913. The limits of detection(LODs, S/N=3) and the limits of quantitation(LOQs, S/N=10) were 0.00887―0.0508 μg/μL and 0.0171― 0.0636 μg/μL, respectively, on the column. The relative standard deviations(RSD) of the analytes were less than 3.61% for intraday and 3.70% for interday, respectively. The average recovery rates obtained were in the range of (97.3±4.3)% to (101.9±3.1)% for all the compounds. The results of quantitative and fingerprint analysis proved that the contents of the components were totally similar in the preparation of Ginkgo biloba tablets from the same pharmaceutical company; whereas, they varied significantly in the preparations of Ginkgo biloba tablets from different companies.

    Measurement of Atrazine Adsorption onto Surficial Sediments (Natural Surface Coatings)—New Evidence for the Importance of Fe Oxides
    LI Yu , WANG Ao, , GAO Qian , WANG Xiao-li
    2009, 25(1):  31-36.  doi:
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    To reveal the relative contribution of the components, Fe, Mn oxides or organic materials(OMs) in the surficial sediments(SSs), and the natural surface coating samples(NSCSs) to adsorbing atrazine(AT), a selective chemical extraction technique was employed, to remove the different components, and the adsorption characteristics of AT on the SSs and the NSCSs were investigated. The observed adsorptions of AT on the original and extracted SSs and NSCSs were analyzed by nonlinear least squares fitting(NLSF) to estimate the relative contribution of the components. The results showed that the maximum adsorption of AT on the NSCSs was greater than that in the SSs, before and after extraction treatments, implying that the NSCSs were more dominant than the SSs for organic pollutant adsorption. It was also found that the Fe oxides, OMs, and residues in SSs(NSCSs) facilitated the adsorption of AT, but Mn oxides directly or indirectly restrained the interaction of AT with SSs(NSCSs) particles. The contribution of the Fe oxides to AT adsorption was more than that of OMs; the greatest contribution to AT adsorption on a molar basis was from the Fe oxides in the nonresidual fractions, indicating that the Fe oxides played an important role in controlling the environmental behavior of AT in an aquatic environment.

    Facile and Convenient One-pot Synthesis of 1,1-Disubstituted Cyclopropanes in Water
    LIU Chun , PAN Wei , YANG Yang , WANG Ke-wei , DONG De-wen
    2009, 25(1):  37-39.  doi:
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    A facile and convenient one-pot synthesis method of substituted cyclopropanes in water has been developed. A series of 1,1-disubstituted cyclopropanes 3 were synthesized from the reaction of β-dicarbonyl compounds 1 with 1,2-dibromoethane 2, in very high yields catalyzed by tetrabutylammonium bromide(TBAB) at 50 ºC in the presence of K2CO3 in water. The catalyst TBAB in the aqueous phase can be reused after the separation of organic products.

    Guanidinium Iodides-based Ionic Liquids: Synthesis and Application for Dye-sensitized Solar Cells(DSSCs)
    ZHENG Ren-feng, WU Mao-cheng, DUAN Hai-feng, ZHANG Yu, WEI Xiao, LUO Xu-yang , LIN Ying-jie
    2009, 25(1):  40-42.  doi:
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    A series of guanidinium ionic liquids(GILs) was designed, synthesized, and used as electrolytes for dye-sensitized solar cells(DSSCs). The effect of electrolytes containing GILs on the photovoltaic performance of DSSCs was investigated. It is demonstrated that these GILs are promising for being used as electrolytes for DSSCs and a conversion efficiency of 4.1% can be obtained under AM 1.5 sun light irradiation.

    Synthesis and Crystal Structure of (R)-4-Hydroxymethyl-2-thioxo Thiazolidine and Its Asymmetric Catalysis
    LI Jing , SHANG Yan-mei , XIAO Chuan , SONG Zhi-guang , LI Ye-zhi, , HUANG Hua-min
    2009, 25(1):  43-46.  doi:
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    (R)-4-Hydroxymethyl-2-thioxo thiazolidine as a new chiral catalyst in the asymmetric addition of diethylzinc to benzaldehyde was synthesized from (R)-4-hydroxymethyl-2-thioxo thiazolidine carboxylic acid and its crystal structure was determined by X-ray diffraction method. The compound was crystallized in the orthorhombic system, space group P212121 with unit cell dimensions a=0.67253(12) nm; b=0.89164(17) nm; c=1.06146(19) nm, volume 0.6365(2) nm3; Z=4, calculated denisity 1.557 Mg/m3; absorption coefficient 0.733 mm-1; F(000)=312. The X-ray crystal structure analysis reveals that the compound has a thione group.

    Characterization and Anti-tumor Activity of Glycopeptides from Ganoderma sinensis
    GAO Yang , JIANG Ru-zhi , CHEN Ying-hong , LUO Hao-ming , XU Duo-duo , GAO Qi-pin
    2009, 25(1):  47-51.  doi:
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    The water-soluble part(GS) of Ganoderma sinense Zhao, Xu et Zhang was divided into high molecular(GS-H) and low molecular(GS-L) parts by Cellulose Super Filtration, and GS was also fractionated into four fractions, GS-1, 2, 3, and 4 by ethanol precipitation according to their molecular weights. Chemical analysis shows that GS and GS-1, 2, 3, 4 were complexes of polysaccharide and peptide. The fractions with molecular weights over 4000, GS-1, 2, 3, and GS-H show anti-tumor activities, however, the fractions with molecular weights lower than 4000, GS-4, and GS-L have no anti-tumor activity, indicating that the anti-tumor activity of Ganoderma Sinensis was caused by glucopeptides with molecular weight ranging from 4000 to 20000. Two purified glucopeptides, GS-6b and GS-7b were obtained from GS-H by ion-exchange and gel-permeation chromatography. Their molecular weights, glycosidic linkages, and configurations were detected by means of IR spectrum, sugar composition analysis, and methylation analysis. The polysaccharide parts of GS-6b and GS-7b had glucan backbone consisting of β-1→3 Glc, and side chain containing glucosyl, mannosyl, fucosyl, xylosyl, galactosyl, and glucuronic acid residues attached on 1-2, 1-4, 1-6 positions of the backbone of GS-6b, or 1-6, 1-4 positions of the backbone of GS-7b. The peptide parts in GS-6b and GS-7b were composed of 10 kinds of amino acids, including Asp, Ser, Arg, Gly, Thr, Pro, Ala, Val, Met, and Lys.

    Synthesis and Biological Activity of Novel 2,3-Dihydro-2-phenylsulfonylhydrazono-3-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyl)thiazoles
    WANG Hao-an, LI Yu-xin, LI Zheng-ming , CHENG Hai-ying, WANG Su-hua , LIU Bin
    2009, 25(1):  52-55.  doi:
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    A series of novel 2,3-dihydro-2-phenylsulfonylhydrazono-3-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyl) thiazoles were designed and synthesized via the reaction of thiosemicarbazide with chloroaldehyde. Their chemical structures were characterized by 1H and 13C NMR spectroscopy and elemental analysis. The bioassay results indicate that some of these compounds exhibit moderate fungicidal and herbicidal activities.

    Components of Volatile Oil from Water-caltrop and Their Anti-tumor Effect in vitro
    ZHAO Wen-jing, NIU Feng-lan , LI Jing, DONG Qing , HUANG Zhan-you
    2009, 25(1):  56-59.  doi:
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    The volatile oil was extracted from water caltrop by steam distillation; it was then analyzed by GC-MS to obtain 16 components, 8 of which were identified. Apocynin was the most abundant one, accounting for 81.41% of the total oil. The in vitro inhibitory effects of the volatile oil on SMMC-7721, MCF-7, Hela, HL-60 cells, and human peripheral blood mononuclear cells(PBMC) were investigated via the MTT method. The morphological changes of the tumor cells were observed and the apoptosis of HL-60 cells was detected by flow cytometry. The proliferation of the tumor cells could be significantly inhibited and the apoptosis of HL-60 cells could be induced by the volatile oil. The proliferation inhibition effect of the volatile oil on HL-60 tumor cells and the induction of the apoptosis of HL-60 cells had dose-dependent feature.

    Adenovirus-mediated HSV-TK Gene Therapy Using hTERT Promoter in CNE Cells in vitro
    ZHANG Yu , YU Xiang-hui , ZHA Xiao, , KONG Wei
    2009, 25(1):  60-63.  doi:
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    Human telomerase reverse transcriptase(hTERT) activity was detected in human nasopharyngeal carcinoma cell(CNE) but not in human normal lung fibroblas t(CCD-11Lu). Recombinant adenoviruses Ad-CMV-TK-enh and Ad-hTERT-TK-enh were constructed and infected into normal fibroblasts and nasopharyngeal carcinoma cells. Ad-CMV-TK-enh with 100 µmol/L of ganciclovir(GCV) caused 87% of CCD-11Lu cells death and 91% of CNE cells death, Ad-hTERT-TK-enh with 100 µmol/L of GCV caused 24% of CCD-11Lu cells death and 79% of CNE cells death. These results indicate that the Ad-hTERT-TK-enh with GCV may be a useful method in suppressing tumor growth in targeted nasopharyngeal carcinoma gene therapy.

    Expression Characterization and Preparation of Human Amyloid Precursor Protein in Escherichia coli
    XU Guang-wei, WANG Jia-peng, HUANG Xue-mei , ZHANG Ying-jiu
    2009, 25(1):  64-68.  doi:
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    To analyze whether expressed amyloid precursor protein(APP) existed in hydrophilic(cytoplasmid) or hydrophobic(lipid bilayer) environment in E. coli and to obtain intact APP for study on its function, we investigated the expression characterization and preparation of the three intact isoforms APP770, APP751, and APP695 in E. coli. The results show that these expressed APPs existed both in hydrophilic cytoplasm region as inclusion bodies and hydrophobic membrane region as membrane-bound state in E. coli. APPs in inclusion bodies were purified on an NTA-Ni2+ agarose column after dissolving in the urea buffer and APPs in membrane-bound state were obtained by ultracentrifugation. The activity analysis indicates that APP770 and APP751 exhibited strong trypsin-inhibitory activity like the natural ones. These results indicate that E. coli cells can be used as host cells for the expression of human integral membrane protein like APP in either soluble or membrane-bound state unless the interest protein undergone post-translational modification is required.

    Effects of Headgroups and Serum on Gene Transfection of Alkaline Amino Acid Based Cationic Lipids
    LI Li, YANG Yang, NIE Yu, HE Bin , GU Zhong-wei
    2009, 25(1):  69-71.  doi:
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    Three cationic lipids with lysylated(1), histidylated(2), and arginylated(3) headgroups and cholesterol hydrophobic moiety were synthesized. The average sizes of liposomes and lipoplexes were around 100 and 160 nm, respectively. The gene transfection efficiency of the three lipoplexes loaded with pGL3 or pORF-LacZ was compared on 293T cells in the presence or the absence of serum. The transfection efficiency of the three lipoplexes in a serum-free medium was 2 to 3-fold higher than that of dioleoyl-trimethylammonium propane(DOTAP). In the presence of serum, however, most of the lipoplexes showed lower transfection activities; only lipoplex 3 retained its high transfection efficiency.

    Rapid Estimation of Enantioselectivity in Lipase-catalyzed Resolution of Glycidyl Butyrate Using pH Indicator
    WANG Ping , WANG Lei , WANG Li-cheng , LI Chun-yuan , WANG Ren , MIAO Qing-hua , YANG Ming , WANG Zhi
    2009, 25(1):  72-75.  doi:
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    A simple method for rapid estimation of the enantioselectivity of lipase in resolution of chiral esters is described. The enantioselectivity of lipase can be estimated rapidly through comparing the difference of hydrolysis rates for the racemic ester and its slow reacting enantiomer under the same condition because the difference mainly depends on the enantioselective ratio(E values). The higher the enantioselectivity of enzyme, the larger the difference of hydrolysis rate. The bromothymol blue(BTB) can be used as pH indicator for microplate reader to monitor the formation of acid in lipase-catalyzed hydrolysis of esters. This method has been successfully used to rapidly estimate the enantioselectivity of several lipases in the resolution of glycidyl butyrate.

    Thermal Behavior, Specific Heat Capacity and Adiabatic Time-to-explosion of GDN
    YANG Xing-kun , XU Kang-zhen, , ZHAO Feng-qi , YANG Xin , WANG Han , SONG Ji-rong , WANG Yao-yu
    2009, 25(1):  76-80.  doi:
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    A new compound, [(NH2)2C=NH2]+N(NO2)2(GDN), was prepared by mixing ammonium dinitramide (ADN) and guanidine hydrochloride in water. The thermal behavior of GDN was studied under the non-isothermal conditions with DSC and TG/DTG methods. The apparent activation energy(E) and pre-exponential constant(A) of the exothermic decomposition stage of GDN were 118.75 kJ/mol and 1010.86 s–1, respectively. The critical temperature of the thermal explosion(Tb) of GDN was 164.09 °C. The specific heat capacity of GDN was determined with the Micro-DSC method and the theoretical calculation method, and the standard molar specific heat capacity was 234.76 J·mol–1·K–1 at 298.15 K. The adiabatic time-to-explosion of GDN was also calculated to be a certain value between 404.80 and 454.95 s.

    Low Temperature Catalytic Combustion of Ethanol over Pt/γ-Al2O3/CexZr1–xO2 Honeycomb Catalysts
    WANG Jian-li, LIU Zhi-min, CAO Hong-yan, GONG Mao-chu, CHEN Yong-dong , CHEN Yao-qiang
    2009, 25(1):  81-85.  doi:
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    It has been found that the catalytic activity toward the decomposition of ethanol in a fix bed reactor can be greatly improved by loading Pt on the surface of CexZr1–xO2. In this study, we have investigated the effects of different x of Pt/γ-Al2O3/CexZr1–xO2 on the catalytic activity of catalysts. The repared catalysts were characterized by BET, XRD, and TPR. The BET surface areas of the catalysts decreased with x decreasing. XRD results reveal that deposited Pt dispersed on the CexZr1–xO2 and γ-Al2O3 matrix. The order of catalytic activities is Pt/γ-Al2O3/Ce0.5Zr0.5O2>Pt/γ-Al2O3/Ce0.25Zr0.75O2>Pt/γ-Al2O3/Ce0.75Zr0.25O2>Pt/γ-Al2O3/CeO2>Pt/γ-Al2O3/ZrO2. Among the catalysts, the reduction peak area of Pt/γ-Al2O3/Ce0.5Zr0.5O2 is the largest and the oxygen mobility is noticeably promoted, which is in good harmony with the catalytic activity. Incorporation of ZrO2 into the CeO2 lattice considerably decreases the destruction temperature for ethanol. Based on these observations, the mechanistic role of oxygen mobility in the oxidation reaction has been suggested.

    Investigation of Microemulsion System for Transdermal Drug Delivery of Amphotericin B
    TIAN Qing-ping , LI Peng , XIE Ke-chang
    2009, 25(1):  86-94.  doi:
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    In order to solve the drawback of poor bioavailability by the oral route and infusion-related side effect for Amphotericin B(AmB), microemulsion vehicles composed of isopropyl myristate(IPM), Tween 80, isopropyl alcohol and water for transdermal delivery of AmB were designed. The pseudo-ternary phase diagrams were constructed by the H2O titration method and the structures of the microemulsion were determined by measuring electrical conducti- vities(σ). The diffusion studies of AmB microemulsion were performed via excised rabbit skin on a drug diffusion apparatus. To obtain a high solubization of AmB, three different methods were tested to incorporate AmB into microemulsion. The result suggests adding AmB in the shape of NaOH solution to the O/W blank microemulsion over the phase inversion temperature(PIT) of the emulsifier obtains the maximum drug content(2.96 mg/mL). The pH value of the system could be adjusted to pH>8.5 or pH<5.2, in this range AmB molecules converts from aqueous to the hydrophilic shell of the microemulsion droplets, drug precipitate is no more than 5%, and the formulations were corresponding to the characterizations of microemulsion. At pH 5.14, AmB microemulsion with Km 1:1, O/SC 1:9(mass ratio of oil phase to surfactant/cosurfactant blend), water content 64.6%, drug content (2.93±0.08) mg/mL, showed the maximum permeation rate (3.255±0.64) μg·cm-2·h-1, which is stable for a long time.

    Preparation and Photocatalytic Property of Porous TiO2 Film with Net-like Framework
    XU Rong-guo , YAO Jian-xi , LAI Xiao-yong , MAO Dan , XING Chao-jian , WANG Dan
    2009, 25(1):  95-97.  doi:
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    By the UV-curing method, a porous TiO2 film with net-like framework has been prepared. The characterization results of the porous TiO2 film by means of SEM, TEM, XRD, and N2 adsorption-desorption analysis show that the net-like framework of the porous TiO2 film is composed of TiO2 nanoparticles, forming three dimensional porous structure. The porous TiO2 film exhibits higher photocatalytic activity for the degradation of methylene blue(MB) dye compared with the conventional dense TiO2 film.

    Theoretical Studies on Adsorption Sites and States of O and N on Ni(311)
    DIAO Zhao-yu, ZHANG yan, ZHANG Xue-na, WANG Ze-xin , WANG Zhong-ni
    2009, 25(1):  98-101.  doi:
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    The adsorption of O and N atoms on the Ni(311) surface was investigated by the 5-parameter Morse potential(5-MP) method in detail. For the O-Ni(311) system, there are three surface adsorption states and the fcc-3-fold site is metastable; the frequency of 75 meV[67 meV in high resolution electron energy loss spectroscopy(HREELS) experiment] is attributed to the vibration at the hcp-3-fold site. For the N-Ni(311) system, however, there are only two surface adsorption states(no surface adsorption state was calculated at fcc-3-fold site). In addition, subsurface states were predicted and all critical characteristics were obtained for the two systems.

    Theoretical Study on the Tautomerization Reaction of Formamide to Formamidic Acid Encapsulated in a Nano-sized Molecular Container
    WANG Xiu-li, YANG Zuo-yin, WANG Ju, ZHANG Jing-chang , CAO Wei-liang
    2009, 25(1):  102-107.  doi:
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    The hybrid calculations with ONIOM(B3LYP/6-31G*:AM1) method were carried out on the tautomerization reaction of formamide to formamidic acid in the microcontainer-encapsulated state. The free-state tautomerization process was also investigated with B3LYP/6-31G**//B3LYP/6-31G* method for the purpose of comparison. Bare tautomerization, H2O-assisted(single-H2O or multiple-H2O) and self-assisted mechanisms were all taken into consideration for the encapsulated state. The results show that only bare tautomerization and single-H2O catalysis mechanisms are possible to the encapsulated for-mamide tautomerization owing to the container's size confinement effect. Geometrical changes in the complexed container and guest molecules are discussed to deeply understand the complex's structural properties. The bare tautomerization barrier in the encapsulated state increases by 23.826 kJ/mol, ac-counting for 12% of the corresponding total energy barrier in the free state, and the increased values for the single-H2O catalysis process are 12.958 kJ/mol, accounting for 16% of the corresponding total energy barrier, respectively. This finding suggests that the encapsulation can make the tautomerization process slightly difficult.

    Rotational Isomeric State Model of Poly(vinylidene chloride) Based Upon ab initio Electronic Structure Calculations
    ZHANG Zhi-jie, LIU Yu-hua, LÜ Zhong-yuan , LI Ze-sheng
    2009, 25(1):  108-111.  doi:
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    The rotational isomeric state(RIS) model was constructed for poly(vinylidene chloride)(PVDC) based on quantum chemistry calculations. The statistical weighted parameters were obtained from RIS representations and ab initio energies of conformers for model molecules 2,2,4,4-tetrachloropentane(TCP) and 2,2,4,4,6, 6-hexachlorohep- tane(HCH). By employing the RIS method, the characteristic ratio C was calculated for PVDC. The calculated characteristic ratio for PVDC is in good agreement with experiment result. Additionally, we studied the influence of the statistical weighted parameters on C by calculating δC/δlnw. According to the values of δC/δlnw, the effects of second-order Cl―CH2 pentane type interaction and Cl―Cl long range interaction on C were found to be important. In contrast, first-order interaction is unimportant.

    Influence of Block Copolymer on Formation and Acid Resistant Properties of Hybrid CaCO3 Particles
    LI Xiao-dong , HU Qiao-ling , ZHAO Shi-fang , SHEN Jia-cong
    2009, 25(1):  112-115.  doi:
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    Block copolymer polystyrene-b-poly(acrylic acid)(PS-b-PAA) was used as structural template for the synthesis of CaCO3 microparticles. Through this procedure, acid resistant hybrid CaCO3 microspheres were obtained. Acid resistant properties of this type of hybrid CaCO3 were studied. Size measurement shows that the acid resistant properties of the hybrid particles are different in different solutions, such as HCl, EDTA, and H2SO4 solutions.

    Letter
    Synthesis of 17-OH-Isosteviol
    LI He-ping , DONG Cheng-min , HOU Yi-min , LIU Hong-min
    2009, 25(1):  116-117.  doi:
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    Research Notes
    Hydrothermal Synthesis, Crystal Structure and Thermal Properties of a Novel Samarium Complex with 1D Nano-chain Structure
    LI Ya-Juan , LIANG Qing , SONG Hui-hua , JIA Mi-ying , SHI Shi-Kao , ZHANG Jian-jun
    2009, 25(1):  118-121.  doi:
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Editor-in-Chief:
Jihong YU
ISSN 1005-9040
CN 22-1183/O6
Special Issue/Column
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