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Table of Content

    10 October 2009, Volume 30 Issue 10
    Contents
    Content of Chemical Journal of Chinese Universities Vol.30 No.10(2009)
    2009, 30(10):  0. 
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    下期目次预览
    2009, 30(10):  0. 
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    Review
    Application of Computational Chemistry in Identification for Chiral Compounds
    REN Jie, ZHU Hua-Jie*
    2009, 30(10):  1907-1918. 
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    Study on chiral compounds, especially in natural chemistry, becomes more and more important. One of the major problems that are met in the study is configuration identification. When no crystalline is obtained, or in other case, such as that too much complex correlations in 2D NMR are recorded, computational methods provide a useful tool in the study. Currently, the widely used methods include calculation of optical rotations, or determinant of matrix. By comparing these data with the experimental results, the absolute configuration can be assigned.13C NMR computation is an important method. This review will give introduction about uses of these methods in the configuration determination for compounds with different stereogenic centers.

    Articles
    Synthesis, Structure and Molecular Configuration of a Series of Ionic Salt Compounds of Pyrophosphate Ester of Thiamine
    BAI Feng-Ying, LI Xiao-Tian*, ZHU Guang-Shan, XING Yong-Heng , ZENG Xiao-Qing,..
    2009, 30(10):  1919-1924. 
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    Ionic salt compounds [TPP·ClO4·H2O](1) and [TPP·PF6·CH3OH](2)(TPP as the pyrophosphate ester of thiamine) were prepared in the methanol system under room temperature, and characterized by elemental analysis, IR spectra, and single X-ray diffraction. Structural analysis shown that they are ionic compounds and there are abundant hydrogen bondings in molecular structures. On the basis of the data of quantum chemical calculation, their potential reaction activity and electronic configuration were also discussed.

    Urea-combustion Synthesis and Properties of Ce0.8Sm0.2O1.9
    WANG Hong, XU Qing*, HUANG Duan-Ping, CHEN Wen, CHEN Min, KIM Bok-Hee
    2009, 30(10):  1925-1929. 
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    Samaria-doped ceria(Sm0.2Ce0.8O1.9, SDC) is a promising candidate material for electrolyte of intermediate temperature(600—800 ℃) solid oxide fuel cells(IT-SOFCs). SDC powders were synthesized by a combustion method with urea as a fuel. The phase purity and morphology of the resulting powders were characterized by XRD, TG-DSC, FESEM and BET specific surface area measurement. Moreover, the sinterability and electrical conductivity of the SDC were examined. The results demonstrate that the urea-combustion process is a simple and efficient route to produce high reactive SDC powder. It was found that the SDC powder with a pure cubic fluorite phase could be produced via a short-time combustion process. The SDC powder is composed of uniform and dispersed sphere-like particles in the range of 50—150 nm. This desired morphology effectively enhanced the sinterability of the powder. A gas-tight relative density of 95.1% was obtained in the SDC ceramic sintered at a relative low temperature of 1250 ℃. Furthermore, the ceramic sintered at the temperature presented superior electrical conductivity, reaching 5.4×10-2 and 1.0×10-1 Ω-1·cm-1 at the measuring temperatures of 600 and 800 ℃, respectively.

    Synthesis of Plate-like K0.5Bi0.5TiO3 Particles by Topochemical Method
    ZHANG Yang-Hong, ZENG Jiang-Tao*, LI Guo-Rong, ZHENG Liao-Ying, YIN Qing-Rui
    2009, 30(10):  1930-1934. 
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    Plate-like K0.5Bi0.5TiO3 particles were successfully fabricated by topochemical method from bismuth layer-structured ferroelectric (BLSF) Bi4Ti3O12. Owing to its highly anisotropic structure, plate-like Bi4Ti3O12 was firstly synthesized in the KCl flux. The plate-like Bi4Ti3O12 was reacted with the complementary K2CO3 and TiO2, finally transformed to perovskite K0.5Bi0.5TiO3 particles and maintained its morphology nearly unchanged. Our result suggested the size of the plate-like particles is 15—20 μm in length and 2 μm in thickness. The mechanism of the reaction was analyzed according to the results. The KBT particles prepared in this experiment can be used as the template to prepare textured (Na, K)0.5Bi0.5TiO3 ceramics by (Reactive) Template Grain Growth method, inducing the grain orientation and thus enhance the properties.

    Synthesis, Crystal Structure, Thermal Behavior and Sensitivity Properties of New Energetic Compound [Mn(DAT)6](ClO4)2
    QI Shu-Yuan, ZHANG Jian-Guo, ZHANG Tong-Lai*, CUI Yan, YANG Li, YU Kai-Bei,.....
    2009, 30(10):  1935-1939. 
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    A new energetic coordination compound [Mn(DAT)6](ClO4)2(DAT=1,5-diaminotetrazole) was synthesized by DAT and manganese perchlorate and characterized by elemental analysis, differential scanning calorimetry, thermogravimetry-differential thermogravimetry, and X-ray single crystal diffraction method. The crystal belongs to trigonal system and its crystal structure data are as follows: a=b=1.18435(17) nm, c=1.3081(3) nm, α=β=90°, γ=120°, V=1589.1(5) nm3, Z=2. The molecule of the title compound contains one Mn2+ cation, six DAT molecules and two ClO4- anions. The central manganese(Ⅱ) cation is coordinated by six N atoms from six DAT molecules to form a six-coordinated and distorted octahedral structure. In addition, the sensitivity properties of the title compound were studied. The result shows that the title compound has good sensitivity.

    Sandwich Immunosensing Method for Measuring Cardiac Troponin I with Quantum Dots-coupled Antibody Against Troponin I
    SONG Jian, FAN Jia, SONG Da-Qian, BI Li-Rong, ZHOU Gang-Yu, ZHANG Hao, ...
    2009, 30(10):  1940-1944. 
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    In this study, a novel quantitative sandwich immunoassay for detecting cTn I was developed by using surface plasmon resonance biosensor and quantum dots(QD)-coupled antibody for the first time, which amplified the response of biosensor and so had the sensitivity of this method obviously improved. First quantum dots were coupled to the monoclonal antibody(2F11) against cTn I with N-hydroxysuccinimide(NHS) and 1-ethyl-3-(3-dimethyl-aminopropyl)-carbodimidehydrochloride(EDC), and then the coupled product(QD-2F11) was confirmed by SDS-PAGE and its antibody activity was tested by protein blot. Finally, a sensitive sandwich immunosensing method for measuring cardiac troponin I was developed by surface plasmon resonance biosensor with protein A as an intermediate layer, the specific polyclonal antibody as the first antibody[capture antibody, and QD-labeled-monoclonal antibody as the second antibody(detecting antibody)]. The novel sandwich immunoassay showed the detection range of 0.4 to 15 μg/L and a detection limit of0.4 μg/L, which is higher 2 times than the sandwich immunoassay without using QD-labeled antibody and 10 times than the direct immunoassay for cTn I previously developed, respectively.

    Adsorption and Separation of Cytochrome c on Silk Fibroin
    CHEN Ming-Li, YAN Xiao-Rui, WANG Jian-Hua*
    2009, 30(10):  1945-1950. 
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    Selective adsorption of cytochrome c using silk fibroin as adsorbent was observed under certain experimental conditions. A novel separation and preconcentration approach for cytochrome c was thus developed via a silk fibroin packed micro-column in a sequential injection system. The entire process of separation and elution was monitored by spectrophotometry at 410 nm. At pH 5.6, cytochrome c in 2 mL of aqueous solution at 5 g/mL were quantitatively adsorbed by the silk fibroin micro-column, and a NaCl solution of 1.0 mol/L suffices the complete elution of the adsorbed cytochrome c from the micro-column. An enrichment factor of 10 was achieved by fixing a sample volume of 2 mL and an eluent volume of 200 μL. A linear calibration graph within 1.0—10.0 μg/mL cytochrome c was obtained with a detection limit of 0.33 μg/mL and a precision(RSD) of 2.5%(5 μg/mL, n=9). The practical applicability of this system was demonstrated by processing human whole blood for preconcentration of cytochrome c, and the results were verified by assay with SDS-PAGE.

    Simultaneous Determination of Three Quionlones Residues in Milk by Pyridinium Ionic Liquid-based Aqueous Two-phase Systems Coupled with High Performance Liquid Chromatography
    ZENG Yan-Bo, ZHAO Di-Hai, LI Lei*, WANG Lian, SHEN Bing, XI Qi-Hui, ...
    2009, 30(10):  1956-1959. 
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    A method was developed for the analysis of three quinolones(oxolinic acid, nalidix acid and flumequine) in milk by pyridinium ionic liquid-based aqueous two-phase systems coupled with high performance liquid chromatography. Milk samples were extracted with the mixed solutions consisting of sodium chloride and phosphoric acid. Then extracts were enriched by aqueous two-phase systems composed of the ionic liquid pyridine N-ethyl -2-methyl-pyridine bromide salt([EMPy]Br) and K2HPO4. The separation of the analytes was achieved via 0.1% phosphoric acid and acetonitrile with gradient elution under UV detection. The linear ranges are 0.3—15 μg/mL for oxolinic acid, 0.5—20 μg/mL for nalidixic acid and 0.5—25 μg/mL for flumequine. The correlation coefficient(r) is more than 0.9997. The limits of detection are 8—10 μg/kg. Based on detecting spiked quinolones concentrations in milk samples, the absolute recoveries ranged from 86.4% to 94.8% with relative standard deviation from 3.6% to 8.3%. The proposed method of determinating quinolones residues in milk is simple, rapid, friendly to environment and high sensitive.

    HPLC Optimization for Analysis of Epothilones in Polyangium Cellulosum Fermentation Metabolites
    MENG Fan-Xin, GUO Wei-Liang, LU Jia-Hui, DU Lin-Na, LI You-Xin, TENG Li-Rong*
    2009, 30(10):  1960-1964. 
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    Back-propagation artificial neural network combined with genetic algorithm(BPANN-GA) was applied to optimize the high performance liquid chromatography(HPLC) conditions for the determination of epothilone A(Epo A) and epotholine B(Epo B) simultaneously in Polyangium cellulosun metabolites. The concentration of acetonitrile in mobile phase, column temperature and the pH of mobile phase were selected as casual factors and a three-factor-twelve-level uniform design(U123) was used for experiment design. A two-layer back-propagation artificial neutral network(BPANN) was applied to model for the correlation between the casual factors and chromatography optimization function(COF) values, which was chosen as the criterion. Levenberg-Marquardt algorithm was used for training the BPANN. The BPANN model was optimized by selecting the most suitable numbers of hidden neurons depending on the degree of approximation(Da). The correlation coefficient(R) between the COF values obtained by BPANN model and the experiment values was 0.98165. While the optimum BPANN model was developed, genetic algorithm(GA) was applied to find out global dissolution in modeling range. The optimum HPLC conditions obtained by BPANN-GA were as follows: the concentration of acetonitrile in mobile phase was 29.2%(volume fraction); the column temperature was 34 ℃ and pH of mobile phase was 4.23. The validation experiment at the optimum conditions was performed, and the satisfied chromatogram was obtained.

    Protein Expression Alternations for the HaCaT Proteome in Response to the UVB-irradiation and Chemical-carcinogen
    SUN Ming-Zhong*, LIU Shu-Qing*, Lü Xiao, GUO Yi-Meng, GUO Chun-Mei, XIN Yi,...
    2009, 30(10):  1965-1971. 
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    The keratinocyte cell line, HaCaT, was radiated by UVB-irradiation, induced by the 2,4-dinitrobenzene sulfonic acid(DNBS) and stimulated by the combination of UVB-irradiation and DNBS-stimulation(UD), respectively. The differentially expressed protein candidates in response to those stimulations were se-parated by two-dimensional fluorescent in gel electrophoresis(2D DIGE), and the expression levels were quantified by DeCyder software and identifications of interested proteins were performed by the high perfor-mance liquid chromatography nano electrospray tandem mass spectrometry(HPLC-nESI-MS/MS) analysis. Sixty-five protein spots were found differentially expressed with metastatic significance(P<0.05). Comparing to the HaCaT cell treated either by UVB alone or DNBS alone, forty-one and thirteen protein spots were shown positively cooperatively regulated and negatively cooperatively regulated by the stimulations of UVB plus DNBS, respectively; and there are five and six protein spots show similar expression levels as the cells being treated with UVB alone and stimulated with DNBS alone. Sixty unique proteins were identified from all the sixty-five protein spots by HPLC-nESI-MS/MS analysis. Those protein candidates were systemically categorized by bioinformatics analysis based on their molecular functions, involvements in biological processes and pathways. The results from current study provide the protein candidates directly associated with the UVB irradiation and chemical stimualtion, which helps to investigate the formation mechanisms of skin cancers under different environmental conditions and to prevent and treat skin diseases.

    Synthesis and Bioactivities of Novel Indolocarbazole Derivatives
    JIANG Cheng, CHEN Su-Ting, YOU Qi-Dong*, LI Zhi-Yu, TANG Wei-Juan
    2009, 30(10):  1972-1975. 
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    A series of novel indolocarbazole derivatives was designed and synthesized. The solvent was stu-died and the reaction conditions including solvent choice were optimized via easier operations. The cytotoxicities of the 9 target compounds were tested using MTT methods. The results indicate that compounds 4a, 4b, 4d, 4f and 4i show better in vitro activities against HCT116 and P388 than positive control ED-571 did. Particularly, compound 4f is 10 times more potential against P388 than ED-571.

    Bioassay-guided Isolation of Antitumor Compounds from Derris trifoliate Lour and Their Interaction with DNA
    FANG Yu-Chun, SHAO Chang-Lun, LI Jing, LI Yan-Tuan, JIANG Man, WANG Chang-Yun*
    2009, 30(10):  1976-1979. 
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    Two antitumor compounds, tephrosin(1) and rotenone(2), were acquied by bioassay-guided isolation from Derris trifoliate Lour. Compounds 1 and 2, assayed by SRB(Sulforhodamine B) methods, showed antitumor activities against cell lines of HCT8, BEL7402, BGC823, A549 and A2780 in vitro with IC50 values from 0.1 to 90.0 μmol/L. The interaction of the compounds with HS-DNA was investigated using UV spectra and fluorescent spectra. The absorbance values at the UV max peaks of compounds 1 and 2 were reduced by adding HS-DNA while the intensity of fluorescent spectra of EB-HS-DNA were gradually weaken following the increased amounts of compounds 1 and 2. It indicated that the mode of antitumor activities of compounds 1 and 2 was relative to binding with DNA through intercalation mode.

    Comparison Analysis of Proteome of Both Cerebral and Optic Ganalions in Sepia esculenta
    HUANG Fu-Sheng, CHEN Hai-Bin, HUANG Lin, HUANG He-Qing*
    2009, 30(10):  1980-1986. 
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    Sepia esculenta vests in a cephalopoda animal in mollusca. The differentitation of neural system show not only relative higher level in Cephalopoda animal, but also is easily to separate for studying in the neural sciences. Here, proteomes of both cerebral and optic ganglions in Sepia esculenta were effectively separated by a improved approach of 2D-PAGE. In addition, we used both peptide mass fingerprinting(PMF) and database search to identify protein spots in part in 2D-PAGE gel for establishing maps of molecular anatomic of cerebral and optic ganglions primarily in Sepia esculenta. We used a software of Melanie 4 Trial to analyze those ganglions, indicating approximately 682 and 594 protein spots in cerebral and optic ganglions, respectively, which the spot numbers in front more than that in later. Moreover, the same proteins such as mitochondrial malate dehydrogenase precursor, pre-MDH, SNAP-type proteins can be found by both ganglions. In addition, these spots such as elongation factor G, tubulin, and actin shows high match rate, but most protein identified in the gel are hypothetic and structural proteins.

    Effect of Pretreated Silk Fibroin Films on the Regulation of Hydroxyapatite Crystal Growth
    LIU Lin, KONG Xiang-Dong, LI Yu-Cheng, CAI Yu-Rong, YAO Ju-Ming*
    2009, 30(10):  1987-1991. 
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    The silk fibroin films were used as the organic templates to induce the deposition of hydroxyapatite(HAP) crystals in the simulate body fluid. The effect of deposition time and different pretreatment methods for silk fibroin film on the formation of HAP crystals was investigated via XRD, SEM, HRTEM, AFM, FTIR, etc. The results indicate that the silk fibroin films can regulate effectively the deposition and growth of HAP crystals. Longer deposition time is apt to form more HAP crystals with well crystallinity. Furthermore, diffe-rent pretreatment methods lead to various morphology and growth direction of HAP crystals according to the rearrangement of silk film′s surface groups and activation of carboxyl and amino groups induce by EDC/NHS. The mechanism for the silk fibroin film regulating the HAP crystal growth was discussed. The study on the effect of pretreated silk fibroin films on the regulation of hydroxyapatite crystal growth will be helpful for further understanding the process of silk fibroin biomineralization.

    Preparation, Purification and Structure Identification of Angiotensin Ⅰ Converting Enzyme Inhibitory Peptide with High Activity from Oat Protein
    GUAN Xiao*, LIU Jing, WANG Li, YAO Hui-Yuan
    2009, 30(10):  1992-1997. 
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    Oat protein hydrolysate showing strong angiotensin I converting enzyme(ACE) inhibitory activity was prepared by enzymatic hydrolysis with trypsin. Furthermore, a novel peptide with the IC50 value of 77.3 μmol/L was isolated from the hydrolysate using consecutive chromatographic methods including ion-exchange chromatography, gel filtration chromatography, and reversed-phase high-performance liquid chromatography. The peptide was identified by matrix assisted-laser desorption/ionization time-of-flight tandem mass spectrometry as Glu-Gly-Gly-Tyr-Arg.

    Studies on the Purification, Infrared Spectroscopic Analysis and Antiangiogenesis Effects of Fibrinolyric Protein(EFP) from Eupolyphage sinesis Walker
    LI Sui-Jing, HAN Ya-Li*, ZHANG Dong-Mei, LIU Hao, LI Zi-Wei
    2009, 30(10):  1998-2002. 
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    A novel of fibrinolytic protein(EFP) was separated and purified by homogenate, salting-out, ammonium sulfate fractionation, DEAE-52 cellulose column chromatography from fresh tradional chinese medicine Eupolyphaga sinensis Walker. The molecular weight and purity of EFP were detected by sulfate-polyacry-lamide gel electrophoresis analysis. Thin polyacrylamide fibrin plate assay was used to test the fibrinolysin activity of EFP. The key functional group of EFP was analyzed by infrared spectroscopy. Chicken embryo chorioallantoic membrane(CAM) assay was used to test the inhibited effects of EFP on neovascularization in vivo. The results show that the molecular weight of fibrinolyric proteins from Eupolyphaga sinensis is approximately 41300 on sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis, the infrared spectra of the tablets showed characteristic of protein and glycoprotein. The vascular network of CAM of chicken embryo is inhibited by EFP. The results indicate that EFP possesses anti-angiogenic activity and may be useful for the development of novel anti-cancer therapy.

    New Method of Soybean Seed Ferritin Purification and Comparision of Activity with Pea Seed Ferritin
    HU Ju, LIAO Xia-Yun, DENG Jian-Jun, HU Xiao-Song, ZHAO Guang-Hua*
    2009, 30(10):  2003-2008. 
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    Ferritin is a class of iron storage protein presents in all living organisms and serves the dual function of iron detoxification and iron storage. In this paper, a new method of soybean seed ferritin purification was reported. Crude extracts of soybean were heated at 55 ℃ for 15 min, then adjusted to 500 mmol/L MgCl2, stored for 30 min at 4 ℃. It was followed by addition of sodium citrate to final concentration of 700 mmol/L. The protein was further purified by ion exchange chromatography in DEAE-Sepharose and Sephacryl S-300 gel filtration columns. Native-PAGE purified the molecular weight of soybean ferritin was about 560000 and SDS-PAGE analyzed ferritin subunits were separated as two peptides(28000 and 26500). Subsequently, we compared the iron oxidative deposition and reductive release activities of soybean ferritin with those of pea seed ferritin, and found that their mechanisms of the iron oxidative deposition and iron release are different. Finally, a possible reason was given.

    Letters
    Synthesis and ESR Study of Covalent Connection of EMPO on L-Tyr
    DU Li-Bo, WANG Guang-Qing, HAN Lu, JIA Hong-Ying, TIAN Qiu, LIU Yang*
    2009, 30(10):  2009-2011. 
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    L-Tyr-EMPO, a new EMPO analogue bearing an L-tyrosine methyl ether group, was first synthesized by acylation. Various radicals, including O2, ·OH, ·OR, and ·R, have been efficiently detected and characterized via L-Tyr-EMPO. The half-life of the L-Tyr-EMPO superoxide adduct was estimated to be ca. 6.5 min. More importantly, the present study demonstrated a new synthetic strategy for covalent conjugation between cyclic-nitrone and amino group in peptides or proteins, by which the site-specifically spin trapping can be performed via antibody linked nitrone in the near future. Furthermore, with the help of the covalent link, the targeting for the areas of interest in which the monitored radical species was sitespecially generated.

    Articles
    Interaction of Polyethylene Oxide with Non-equimolarly Mixed Cationic-Anionic Surfactants
    WANG Chen, YAN Peng, XIAO Jin-Xin*
    2009, 30(10):  2012-2016. 
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    The interactions of polyethylene oxide(PEO) with the mixtures of sodium decylsulfonate(C10SO3) and decyltriethylammonium bromide(C10NE) were investigated by viscosity, dynamic light scattering and transmission electron microscopy techniques. It showed that PEO had no significant effects on the aggregate size of the non-equimolarly mixed cationic-anionic surfactants. Striking growth of the aggregates was observed only when the molar ratio of C10NE to C10SO3 closed to equimolar, and those strikingly grown aggregates were still vesicles. Therefore, it can be concluded that PEO has striking effects only on vesicle-involved systems, whereas no significant effect on micellar systems. Around equimolar mixing ratio, PEO exhibited stronger influence on C10NE-excessed systems than on C10SO3-excessed ones when the excess extents of C10SO3 and C10NE are the same. The growth of vesicles induced by PEO could be explained in terms of depletion interaction between PEO and vesicles. The fact that PEO has no significant effect on non-equimolarly mixed micellar systems could be ascribed to the strong electrostatic repulsion between charged micelles. The stronger influence of PEO on C10NE-excessed systems was ascribed to that the aggregates in C10NE-excessed systems were closer to equimolar composition than those in C10SO3-excessed ones.

    Preparation of Mercaptopropyl Bonded Silica by Atomic Layer Deposition and Its Adsorption of Palladium(Ⅱ) Ions
    GUO Zhi-Qiang, CHEN Feng, DENG Yi, WAN Qian-Hong, CHEN Lei*
    2009, 30(10):  2017-2023. 
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    Atomic layer deposition was employed for preparation of thiol-functionalized silica as efficient adsorbent of palladium(Ⅱ) ions. Under reaction conditions of 3—5 kPa and 125—150 ℃, trifunctional γ-mercaptopropyltrimethoxysilane(MPTMS), γ-merecaptopropyltriethoxysilane(MPTES) and bifunctional γ-mercaptopropyldimethoxymethylsilane(MPDMMS) were vaporized in an autoclave, and chemically bonded to po-rous silica, respectively. The bonding mode, morphology and thiol group content of the thiol functional silica were characterized by FTIR, solid state 13C and 29Si nuclear magnetic resonance, elemental analysis, TGA, and nitrogen adsorption-desorption analysis. The behavior of the adsorption of Pd(Ⅱ) ions from aqueous solutions at pH=3.0 onto thiol functionalized silica samples was studied by measuring the changes in concentration of Pd(Ⅱ) solution in contact with the silica using spectrophotometry. The results show that bidentate bonding mode is preferred for all three silane reagents and the thiol contents are determined to be 0.84, 0.77 and 0.82 mmol/g, respectively, for MPTMS, MPTES and MPDMMS modified silica. The adsorption of Pd(Ⅱ) ions on MPTMS, MPTES and MPDMMS modified silica could be described by the Langmuir equation with a saturation adsorption capacity of 1.21, 1.04 and 1.14 mmol/g, respectively. The molar ratios of Pd/S were 1.44, 1.35, and 1.39. Thus, both thiol content and adsorption capacity of the materials prepared by atomic layer deposition are higher than those of the bonded silica made by reaction in organic solvent as generally practiced. The present work has demonstrated that atomic layer deposition, characterized by short reaction time, no consumption of organic solvents and high functional group density, is a cost-effective and eco-friendly approach for preparation of silica based palladium scarvengers.

    Chloride-free Cu2O/AC Catalyst Prepared by Pyrolysis of Copper Acetate and Catalytic Oxycarbonylation
    LI Zhong*, WEN Chun-Mei, WANG Rui-Yu, ZHENG Hua-Yan, XIE Ke-Chang
    2009, 30(10):  2024-2031. 
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    The chloride-free Cu2O/AC catalyst was prepared via pyrolysis of copper acetate supported on active carbon Cu(CH3COO)2/AC and used to catalyze vapor-phase oxycarbonylation of methanol to dimethyl carbonate(DMC). The Cu(CH3COO)2/AC precursor was prepared by the incipient wetness impregnation. When Cu(CH3COO)2·H2O was heated from 30 ℃ to 450 ℃ under inert nitrogen atmosphere, it decomposed successively to Cu(CH3COO)2, Cu2O and Cu, corresponding to three chemical processes. Cu2O was obtained at 150—300 ℃ heating temperature, and Cu was formed at 300—450 ℃. When Cu(CH3COO)2·H2O/AC was heated at 200—350 ℃ for 4 h, Cu2O was gradually formed on the surface of AC. The Cu2O/AC catalyst with predominant Cu2O and only a little Cu was obtained when Cu(CH3COO)2·H2O/AC heated at 350 ℃ for 4 h. It was observed that the Cu2O/AC catalyst heat-treated at 300—350 ℃ for 4 h exhibited very high catalytic activity for methanol oxycarbonylation. On the conditions of n(CO)∶n(MeOH)∶n(O2)=4∶10∶1 and SV=5600 h-1, and in the presence of Cu2O/AC catalyst prepared at 300 ℃ for 4 h, the methanol conversion, the space time yield and the selectivity of DMC was reached 6.21%, 128.16 mg·g-1·h-1 and 64.26%, respectively.

    Interaction at Pt-CeO2 Contact Interface over Pt/CeO2/SBA-15 Catalyst
    BI Ya-Dong, ZHANG Wei, XU Heng-Yong*, LI Wen-Zhao
    2009, 30(10):  2032-2035. 
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    A high dispersion of CeO2 within the pores of an SBA-15 mesoporous silica was achieved via deposition precipitation(DP) method, and Pt/CeO2/SBA-15 catalyst was prepared by further depositing Pt on CeO2-modified SBA-15. UV-Vis diffuse reflectance spectra show that intimate contact is formed at Pt-CeO2 interface, which is in favor of the transfer of electrons from CeO2 to Pt and formation of oxygen vacancies. The CO temperature-programmed reduction(CO-TPR) verified the enhanced reducibility of the surface oxygen on CeO2 over Pt/CeO2/SBA-15-DP catalyst.

    Preparation of Mesoporous TiO2/Single Wall Carbon Nanotubes Thin Film Through Electrophoretic Deposition
    ZHOU Wei, FU Hong-Gang*, PAN Kai, TIAN Chun-Gui, QU Yang, SUN Chia-Chung*
    2009, 30(10):  2036-2039. 
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    Mesoporous TiO2/SWCNTs thin films were successfully prepared through electrophoretic deposition method on FTO/meso-TiO2 substrate. The products were characterized by Raman and SEM. The results reveal that SWCNTs are successfully deposited on the surface of mesoporous TiO2 thin film. The dye-sensitized solar cells are assembled with the films and they are sensitized by TCPP and N719, respectively. The results show that they exhibite enhanced power conversion efficiency. This maybe attribute to the compact contact of mesoprous TiO2 and SWCNTs in favor of the transportation of photogenerating electrons.

    in situ FTIR Spectroscopic Studies of Adsorption and Oxidation of L-Serine on Pt Electrodes in Neutral Solutions
    KONG De-Wen, ZHU Tian-Wei, ZENG Dong-Mei, ZHEN Chun-Hua, CHEN Sheng-Pei, ...
    2009, 30(10):  2040-2044. 
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    The dissociative adsorption and oxidation of L-serine on platinum electrode in neutral solutions were studied via in situ FTIR reflection spectroscopy and electrochemical methods. The FTIRS results demonstrate that the serine can be easily dissociated on Pt surface at potentials below -0.6 V(vs.SCE) to form cyanide(~2100 cm-1) and carbon monoxide(COL, ~2034 cm-1; COB, ~1870 cm-1). The observation of an absorption band at 2343 cm-1 is ascribed to CO2, which implies the cleavage of the C—C bond during the dissociative adsorption of serine. It has determined that the cyanide was strongly adsorbed on electrode surface in a wide potential region below 0.7 V(vs. SCE) and inhibited the oxidation of serine. At higher potentials, the serine molecules could be oxidized directly to yield the main product CO2 species. As the pH decreased in the spectroelectrochemical cell during serine reactions, the acidic serine species also detected. The present study revealed the interaction of serine with Pt electrode surface, and suggested a possible reaction mechanism of serine on Pt electrode surface in neutral solutions.

    Luminescent Properties of White Organic Light-Emitting Devices Based on Rubrene Ultrathin Layer
    LI Lu, YU Jun-Sheng*, LI Yi, JIANG Ya-Dong
    2009, 30(10):  2045-2048. 
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    The development of white organic light-emitting devices(WOLEDs) generated lots of interests in this area, as these devices can be employed not only as illumination light source but also as backlight source candidate for next generation flat-panel displays. To achieve white emission from OLEDs, an additive mixture of three primary colors. i.e., red, green, and blue(RGB) or a complementary color modification is indispensable. Comparing to the undoped device, the performances of doped red OLEDs and blue OLEDs were enhanced. Thereafter doping highly fluorescent dyes in emission layer became an important approach to realize WOLEDs with excellent performance. WOLEDs based on an ultrathin layer of yellow fluorescent dye 5,6,11,12-tetraphenylnaphthacene(Rubrene) were investigated. By changing the thickness of ultrathin dye layer fabricated by thermal vacuum deposition and analyzing electroluminescent(EL) spectra of devices, concentration effect of dye on the performance of the devices was analyzed. The results showed that the balanced intensity of yellow and blue light for white light emission was obtained in the device when the thickness of fluorescent dye Rubrene was 0.3 nm. The blue light emitted from fluorescent material N,N′-bis-(1-naphthyl)-N,N′-biphe-nyl-1,1′-biphenyl-4,4′-diamine(NPB) and the yellow light was from fluorescent Rubrene dye. A maximum luminance of 3700 cd/m2 was obtained. The Commissions International L′Eclairage(CIE) coordinates located at(0.32, 0.33), which is almost consistent with the optimum white CIE of (0.333, 0.333). The high performance of WOLED was ascribed to direct carrier trapping(DCT) effect of Rubrene and efficient energy transfer from NPB to Rubrene.

    Structures and Electron Density Topological Properties of the CH3SH…HOO Hydrogen Bond Complexes
    LIU Yan-Zhi*, SHI Xiao-Ning, LI Zhi-Feng, TANG Hui-An, YUAN Kun, ZHANG Jun-Yan
    2009, 30(10):  2049-2054. 
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    The four optimized stable CH3SH…HOO hydrogen bond complexes(14) were found on the potential energy surface at B3LYP/6-311++G** level. The calculated results showed that the complexes 1 and 2 use the H7 atom of HOO as proton donor and the S5 atom of CH3SH as acceptor, and the obvious red shifts of the H7—O8 stretch vibration in the two hydrogen bond complexes were obtained by frequency analysis, and the red shift values were 330.1 and 320.4 cm-1, respectively. As for complexes 3 and 4, they use the H6 atom of CH3SH as proton donor and the terminal O9 of HOO as acceptor. The hydrogen bond interaction energies in the four complexes were -20.81, -20.10, -4.46 and -4.52 kJ/mol, which were calculated with basis set superposition error(BSSE) correction at MP2 level. Natural bond orbital(NBO) theory analysis showed that two kinds of charge transfer exist in CH3SH…HOO hydrogen bond complexes 1 and 2: (1) lone pair n1(S5)→σ*(H7—O8), (2) lone pair n2(S5)→σ*(H7—O8). Analogous charge transfers existed in complexes 3 and 4, but the orbital interactions are weaker. The topological properties of the hydrogen bond structures were also investigated by the atom-in-molecules(AIM) theory, and the results showed that there exist hydrogen bond critical points in four complexes.

    Theoretical Investigation of Recoverin′s Normal Mode Analysis
    LI Ji-Lai, GENG Cai-Yun, BU Yu-Xiang, CHEN Xiao-Hua, WANG Jun, HUANG Xu-Ri*, ...
    2009, 30(10):  2055-2058. 
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    Recoverin is an important branch of neuronal calcium sensor. It had been shown recently that half of the known protein movements can be modelled by using at most two low-frequency normal modes. Hence, we investigated their normal modes by rotational translational block method in order to give a deep insight into the nature of the Ca2+-myristoyl switch conformational transition. The normal mode perturbed models of reco-verin T-state revealed that the overall motion of the first lowest mode could be described approximately as a converse-rigid-body-swivel around the inter-domain linker. While in the one Ca2+-bound structure, in addition to the converse-rigid-body-swivel motion, an exposure of the myristoyl group is also detected, which was proposed as bidirectional conformational transition across the domain interface and facilitates the allosteric transition in signal-transduction processes. These observations indicate that recoverin is intrinsically dynamic.

    Theoretical Studies on Mechanism and Solvent Effects of Reactions of Nitrosobenzene and 2-Methyl-2-nitrosopropane with Formaldehyde
    ZHENG Tian-Long, LI An-Yong*
    2009, 30(10):  2059-2064. 
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    The DFT method B3LYP/6-311++G(d,p) was used to study mechanism of reactions of nitrosobenzene and 2-methyl-2-nitrosopropane with formaldehyde in gas phase and solvents. In gas phase, there are two reaction paths, the concerted and stepwise mechanisms, both of which produce the experimental product, hydroxamic acid; the stepwise mechanism is predominant. The solvent effects were studied with the conductor-like polarizable continuum model respectively in the solvents acetonitrile and water, and we found that the solvent effects reduce the activation energy, but the reduction is small, these reactions are not sensitive to the solvent polarity.

    Theory Studies of 5,7′-(Iminomethyl)-bis-8-hydroxyquinoline and Its Metal-organic Complexes via DFT, NBO and AIM
    LI Zhi-Feng*, ZHU Yuan-Cheng, Lü Ling-Ling, LI Hong-Yu, KANG Jing-Wan
    2009, 30(10):  2065-2070. 
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    The structures of 5,7′-(iminomethyl)-bis-8-hydroxyquinoline(5,7′-iminomethylq2) and its metal-organic complexes M(5,7′-iminomethylq2)2(M=Zn, Mg, Be) were optimized at B3LYP/6-31G level. The absorption spectra based on the above structure were obtained by the time-dependent density functional theory TD-B3LYP with the 6-31G basis set. At the same time, dihydrogen bond in 5,7′-iminomethylq2 and M(5,7′-iminomethylq2)2 were studied with NBO and AIM analysis. The calculated results of absorption spectrum for 5,7′-iminomethylq2 has good agreement with the experimental data. All complexes are excellent electrontransporting materials, absorption spectrum wave bands of which can be tuned little by different metals on the ligand of 5,7′-(iminomethyl)-bis-8-hydroxyquinoline anion. The absorption of M(5,7′-iminomethylq2)2 have a substance red shift compared with that of 5,7′-iminomethylq2. There are also hydrogen bonds in the molecules, which make the molecules more stable.

    Preparation of CdHgTe Nanocrystal and Poly(vinyl alcohol) Nanofibers with Near Infrared Emission
    SUN Hai-Zhu*, ZHANG Hao, JU Jie, ZHANG Jun-Hu, LI Min-Jie, TANG Yue, YANG Bai*
    2009, 30(10):  2071-2075. 
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    Stable CdHgTe nanocrystals(NCs) were prepared via one-step in water. The nanofibers of CdHgTe NCs and poly(vinyl alcohol)(PVA) were obtained from electrospinning the mixing solution of CdHgTe NC and PVA. The diameter of the nanofibers were tuned from 200—400 nm by varying the mass fraction(4%—12%) of PVA solution. The best morphology of the nanofiber was got in the mass fraction range from 8%—10%. The nanofibers had strong photoluminescence in the range of near infrared(NIR) wavelength. Above all, they maintained the original peak position of the NCs in water, which was very difficult for the NC and polymer composites prepared using other methods. Moreover, the stability of the NCs was further improved. They showed a thermal stability at the temperature of 120 ℃, which was much higher than that(80 ℃) of in water.

    Synthesis, Characterization and Degradability of P(LA-co-ACL) Copolymer Bearing Pendant N-Substituted Acylamine Group
    DAI Wei-Feng, DU Zheng-Zhen, HE Yue-Ying, LANG Mei-Dong*
    2009, 30(10):  2076-2081. 
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    The synthesis, characterization and polymerization of a new cyclic 6-(N-isopropyl acylamine ethylidene)-ε-caprolactone(ACL) were reported. α-Subtituted cyclohexanone was synthesized by Michael reaction of N-isopropylacrylamide and cyclohexanone. Then it was subsequently converted into ACL by the Baeyer-Villi-ger oxidation reaction using of 3-chloroperoxybenzoic acid(m-CPBA) as the oxidant. This new lactone was copolymerized with various contents of L-LA by bulk ring-opening polymerization(ROP) initiated by Sn(Oct)2. All the copolymers were characterized by 1H NMR, SEC and DSC. The copolymer formed flexible films and was used to study its degradability. A phosphate buffer(pH=7.4) with temperature 37 ℃ was adopted to proceed the degrading study all through. The hydrolytic degradation of P(LA-co-ACL) was much faster, which is confirmed by the mass loss and change of intrinsic viscosity.

    Synthesis of Liquid Polybutadiene Having Desired 1,2-Vinyl Content with Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3 Catalyst System
    HAO Xiu-Feng, ZHANG Chun-Yu, CAI Hong-Guang, JIANG Lian-Sheng, NA Li-Hua, ...
    2009, 30(10):  2082-2085. 
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    Liquid polybutadiene with desirable 1,2-units content was synthesized by Co(naph)2-Al2(C2H5)3Cl3-P(OPh)3 catalyst system. It was shown that liquid polybutadiene having adequate 1,2-unit content (vinyl=35%—40%), molecular weight(Mn=700—3500), and acceptabele conversion(≥55%) can synthesized after optimizing polymerization conditions.

    Preparation of Water-dispersed Polyimides by Spray Drying
    JING Jing, ZHAO Xiao-Gang, ZENG Zhi, HU Nan-Tao, WANG Cheng-Yang, ...
    2009, 30(10):  2086-2089. 
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    We describe a simple method to prepare a novel kind of water-dispersed polyimide. The resulting polymer particles exhibit a good dispersibility in water, and can form flat films after thermal imidization. The morphologies of particles vary with the chemical structures of polymers, while the temperature plays a lesser role. The spray method is proved to be a promising technique to fabricate polyimide micro- and nano-spheres.

    Preparation and Electrical Property of Monodisperse P(St-BA-AN)/PANI Core/Shell Composite Particles
    YAN Jian-Hong, HUANG Li-Yan*, LIU Zheng-Ping*, ZHANG Jun-Gang, HOU Wen-Bo
    2009, 30(10):  2090-2095. 
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    Monodisperse poly(styrene-butyl acrylate-acrylonitrile)[P(St-BA-AN)] latex particles were successfully coated with polyaniline(PANI) by seed emulsion polymerization method. Conductivity of P(St-BA-AN)/PANI composite microspheres can be controlled by changes of the components of seed latex, the amount of oxidant, aniline and other conditions. Proofs for the synthesis of core/shell composite particles were obtained via scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared(FTIR) spectroscopy and diffuse reflectance spectroscopy. It was found that the electrical conductivity of core/shell composites significantly increased by introducing of acrylonitrile into the copolymer latex particle. The conductivity for the P(St-BA-AN)/PANI(40%) core/shell composites was 0.71 S/cm by four-probe method. FTIR and IR diffuse reflection analysis confirmed that there is certain interaction between nitrile-group in P(St-BA-AN) and imine-group in PANI for the core/shell composites. The existence of the interaction of composite structure is an intrinsic factor that results in the increase of electrical conductivity. The mechanism of the interaction was proposed.

    Preparation of Super-hydrophobic PS Surface with Ultra-low Adhesive Force by Electro-spinning
    MA Wei, JIN Mei-Hua*, YU Chun-Ling, LIAO Ming-Yi, ZHAO Yong*
    2009, 30(10):  2096-2099. 
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    Electro-spinning is widely accepted as a simple and versatile technique for producing micro- and nano-structures. Using this method, micro-nano structured polystyrene(PS) was prepaired by controlling the concentration of PS/DMF solution. At 5%(mass fraction) PS/DMF solution with PS molecular weight of 250000, the surface shows super-hydrophobicity with water contact angle of about 167° and ultra-low adhesive force to water. Furthermore, molecular weight is also important to the surface morphology of the PS film formed by electro-spinning.

    PAN-based Preoxidative Fiber Cyclized Degree of Strict Quantitative Characterization
    GAO Yu, GAO Zhong-Min*, LI Xiang-Shan, GUO Jian-Qiang, WEN Yue-Fang, ...
    2009, 30(10):  2100-2103. 
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    PAN-based preoxidative fiber was prepared under the conditions of constant temperature and fixed-length. Measurement of the preoxidative fiber needs the method of long-period multi-layer structure of small-angle X-ray scattering. Analysis of patterns show that long period L of the preoxidative fiber gotten by the different preoxidation time is average 11.7 nm; preoxidation time ranges from 20 min to 210 min, the volume fraction X0 /L of the cyclization phase volume fraction increases from 7.9% to 86.5%. However, AI values of cyclization index of the preoxidative fiber sample of the same batch, measured through the wide-angle X-ray scattering method, are much more smaller. It is more exact for using X0/L to characterize the degree of cyclization of pre-oxygen wire quantitatively.

    Letters
    Synthesis and Characterization of a Organosoluble Polynaphthalimide
    HYON Hak-Min, PAEK Chol-Hyok, DANG Guo-Dong, ZHAO Xiao-Gang, ZHOU Hong-Wei, ...
    2009, 30(10):  2104-2106. 
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    4,4′-(Phenylene-phenyl-p-dioxo)-bis(l,8-naphthalenedicarboxylic)dianhydride(PPOBNDA) with a phenyl substituent and two ether linkages was synthesized by nucleophilic substitution from 4-bromo-1,8-naphthalene dicarboxylic anhydride and Phenylhydroquinone. A polynaphthalimide(PNI) was synthesized from PPOBNDA and 4,4′-ODA via one-step polycondensation. The obtained polynaphthalimide show excellent solubility in organic solvents, and its film caste from m-cresol solution exhibited good mechanical property, high thermal stability and hydrolysis stability.