Table of Content

10 January 2011, Volume 32 Issue 1

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Contents

Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.1(2011)

2011, 32(1):  0. 

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Letters

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LI Xiu-Min, PENG Na, CHEN Shan-Hu, ZHAO Ming, CHEN Yao-Qiang, GONG Mao-Chu*

2011, 32(1):  1-3. 

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CeO2-ZrO2-La2O3-Al2O3（CZLA）samples with different CeO2, ZrO2 and La2O3 contents were prepared by peptizing method. The CZLA samples were characterized by X-ray diffraction (XRD) and N2 adsorption-desorption. The low Pt-Rh content catalysts were prepared by using OSM（Ce0.4Zr0.4Y0.1La0.1O1.9）and CZLA samples as the support, and the catalytic performance was investigated. N2 adsorption-desorption results showed that CZLA sample with 2% La2O3 maintained a highest specific surface area of 97.10 m2?g-1 when aged at 1100℃ for 5 h. After calcination at 1000℃ for 5h, XRD results revealed that both CZLA samples were γ-alumina, lanthanum existed in a dispersed phase, while CZ existed as solid solution in alumina. Activity tests showed that the catalyst which supported by CZLA sample with 2% La2O3 showed an excellent catalytic performance. Its light-off temperature was 249oC, and full conversion temperature was 286oC for C3H8.



Crystallization of Low Molecular Weight Poly(p-phenylenebenzobisthiazole) in Dilute Solution

Kai GUO

2011, 32(1):  4-6. 

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Low molecular weight Poly(p-phenylenebenzobisthiazole) (PBZT) was crystallized in sulfuric acid above and below cloud point temperature respectively, and multi-layer lamellar crystal and fascicular crystal composed of rod-like crystals were obtained. Through transmission electron microscope (TEM) observation and selected area electron diffraction (SAED) study, it was found that, for fascicular crystal, the molecular chains were perpendicular to the direction of long axis of rod-like crystal, and the average width of rod-like crystals was close to the average length of molecular chains. While for lamellar crystal, the molecular chains were perpendicular to the surface of lamellar crystal in the main.



Synthesis of Ether-ketong Linked High-performance PolymersBased on a Naphthylene-containing Diamine

ZHU Ming, LIU Bai-Jun*, LIU Xiao, JIANG Zhen-Hua

2011, 32(1):  7-9. 

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A new naphthylene-containing diamine having a bulky twist structure was synthesized. Under a mild polycondensation reaction, polyazomethine and polyimide containing ether and ketong linkages were readily prepared. The films of two high-performance polymers exhibited high Tg (219 and 274 oC), high moduli, good thermal stability and improved solubility.



Articles

Synthesis of AgCl Nanoparticles in W/O Microemulsion and Study of AgCl/GMA-MMA-AMPS Copolymer Organic-inorganic Hybrid Membranes

JIANG Zeng, WU Li-Guang*, ZHOU Zhi-Jun

2011, 32(1):  10-15. 

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Nanoparticles of AgCl were synthesized in W/O microemulsion using 2-acrylamido-2-methyl propane sulfonic acid (AMPS) as surfactant, glycidyl methacrylate(GMA)/ methacrylate(MMA) mixture as oil phase. And then AgCl/poly(GMA-MMA-AMPS) copolymer organic-inorganic hybrid membranes were prepared by microemulsion polymerization for separation of benzene/cyclohexane mixture by pervaporation. The effect of oncentration of surfactant(CAMPS) and salt (CNaCl 、CAgNO3) on formation and morphology of AgCl nanoparticles were studied by ultraviolet-visible spectrum and transmission electron microscopy(TEM). The results shown that the mean diameters of AgCl nanoparticles are small (10-30nm); the sizes of AgCl nanoparticles increased with ω and concentration of salt (CNaCl、CAgNO3). AgCl nanoparticles maintained well dispersion in AgCl/poly(GMA-MMA-AMPS) copolymer organic-inorganic hybrid membranes. The hybrid membrane demonstrated good separation performance for pervaporation of benzene/cyclohexane mixture, and could overcome the trade-off phenomenon of polymer membranes.



Hydrothermal Synthesis of Ba\|ferrite  in Steady Magnetic Field

XU Bin, ZHONG Yun-Bo*, FU Xiao-Ming, REN Zhong-Ming

2011, 32(1):  16-22. 

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By Using XRD, SEM, TEM, and VSM methods, the shape, micro structure and magnetic property of the barium ferrite powder prepared by hydrothermal synthesized in different magnetic field (reactive temperature: 150℃ and 180℃) were discussed . It was shown that, BaFe2O4 powder can be prepared at the reaction temperature of 150℃ without magnetic field, while at the reactive temperature of 180℃ the powder are composed of BaFe12O19 with sheet shape. While with the magnetic field imposed, all the powder are composed of rod-like BaFe12O19 at the reactive temperature of both 150℃ and 180℃. With the increase of magnetic flux density, the proportion of rod-like BaFe12O19 also increased. When the magnetic flux density reached 10T, single-crystal BaFe12O19 with the diameter of about less than 100nm and length of tens of microns has been obtained. The products obtained by hydrothermal reaction under different magnetic flux are all small size and showed paramagnetic property. Thermodynamic calculation results show that with the application of magnetic field, the magnetic Gibbs free energy of hydrothermal reaction reached hundreds or even thousands of kJ/mol. So it changed the hydrothermal reaction in the thermodynamic aspect, which made the hydrothermal reaction turn to generate the product with higher susceptibility.



Preparation and Properties of GdF3∶Eu3+ Luminescent Nanomaterials with Special Morphology

LI Xia, LIU Gui-Xia*, DONG Xiang-Ting, WANG Jin-Xian

2011, 32(1):  23-27. 

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GdF3:Eu3+ luminescent nanomaterials with the morphologies of flat nanorods、nanoflowers and nanoflakes were prepared by PEG-2000, citrate acid and glycine as surfactant via hydrothermal method, the structure and properties were characterized. XRD results showed that the samples are all orthogonal phase GdF3. FESEM images indicated that morphologies varied from the kinds of surfactants. The effect of the reactant concentration on the morphology of the products using PEG-2000 as surfactant was studied, and the growth mechanism was discussed. Photoluminescence spectra showed that the luminescent intensity is different under different excitation wavelength. The effective energy transfer process occurred between Gd3+ and Eu3+ in GdF3:Eu3+. The strongest emission peak of GdF3:Eu3+ nanocrystal is near 591nm, corresponding to 5D0→7F1 magnetic dipole transition of Eu3+. The emission intensities are different from the samples with various morphologies.



Synthesis, Structure and Gas Adsorption Property of a Novel 2D Layer Nickel Organo-diphosphonate Compound

LI Hua*, REN Ha, ZHANG Wei-Wei, QIU Shi-Lun, ZHU Guang-Shan

2011, 32(1):  28-31. 

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A novel metal organo-diphosphonate compound constructed 2D layers with alkaline gas adsorption property has been synthesized through hydrothermal method. The compound is isomorphous and crystallizes in the Monoclinic, C2/c space group. The metal ions are six-coordinate with four oxygen atoms coming from phosphonate and coordinated aqua molecules and two nitrogen atoms coming from 4, 4’-bpy. The two oxygen atoms of phosphonate are uncoordinated which indicated that the structure could absorb some alkaline gas.



Synthesis, Structure and Gas Adsorption Property of a Novel 2D Layer Nickel Organo\|diphosphonate Compound

REN Yu-Ying ZHOU Ding GUO Jing SHI Ying XIE Jian-Jun XIE Zhi HE Bo

2011, 32(1):  32-37. 

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Local structure of Nd doped ions in Lu2O3 nanopowders and transparent ceramic samples were investigated through X-ray absorption fine structure (EXAFS). EXAFS spectroscopy of Nd L3 edge at about 6215 eV demonstrated that doped Nd atoms has entered Lu2O3 host lattice by substitution solid solution. Fitting results of EXAFS data presented detailed information about species of Nd near-neighborhood coordination atoms，inter-atom distance，coordination number and disorder parameter. Nd ions in Lu2O3 host are mainly six coordinated with the first shell nearest Nd-O distance of 2.25A, which was less than Nd-O first shell distance 2.51A of Nd2O3. The disorder parameter raised from 0.052 to 0.090 with increasing Nd3+ doping concentration from 0.5at.% to 3at.%. Nd:Lu2O3 nanocrystalline powders exhibited a lager first shell nearest Nd-O distance，coordination number and disorder parameters than those of transparent ceramics.



Metabonomics Study on the Acute Toxicity of Toad Venom

LIANG Xiao-Ping, ZHANG Zheng, HU Ping, ZHONG Hong-Fu, GE Zhao-Hui, ZOU Ting-Ting, LIANG Qiong-Lin, WANG Yi-Ming, LUO Guo-An*

2011, 32(1):  38-43. 

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In this study, the metabonomics method coupled with electrocardiogram were applied to the study on the acute toxicity of toad venom. The profiles of serum samples were obtained with ultra performance liquid chromatography coupled with time-of-flight mass spectrometry (UPLC/TOF-MS). The data were firstly processed with the software Markerlynx and then analyzed with the principal components analysis (PCA) and orthogonal partial least squares discriminate analysis (OPLS-DA). The potential biomarkers were screened out according to the VIP (variable importance in projection) value and identified with i-fit, database and corresponding reference standards. The metabolites of significant intergroup differences were finally found to be lipids related to myocardial energy metabolism. According to the biological functions of the obtained potential biomarkers, it was deduced that the heart injury may be induced by disturbing lipid metabolism through hampering the re-acylation of free fatty acid or activating protein kinase pathway. This study provides a new approach to discover the underlying mechanism of toad venom toxicity.



Construction and Evaluation of Continuous Two\|dimensional Open\|tubular Ion Exchange/Reversed Phase Monolithic Column Capillary Electrochromatography System

ZHU Ya-Xian, ZHANG Ling-Yi*, LEI Wen, ZHANG Wei-Bing*

2011, 32(1):  44-49. 

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A continuous two-dimensional open-tubular ion exchange / reversed phase monolithic column capillary electrochromatography system was developed. Reversed phase monolithic column was firstly synthesized in the end part of the capillary, then N-(3-(trimethoxysilyl)-propyl)-ethlenediamine was surface coated to the other part of the capillary. The separation of seven organic acids verified the effect on the separation of ion exchange in the open-tubular capillary. Rhizoma gastrodiae was separated to evaluate the system, and 34 peaks were recognized. In the new electrochromatography system, electroosmotic flow, electrophoresis flow and interaction between solute and stationary phase, which all devote to adjusting the selectivity of the separation. This system is designed for complex samples with highly hydrophobicity components and highly hydrophilicity components simultaneous. This new column system combining advantages of multidimensional separation and adjusted stationary phase selectivity is suitable for the analysis method development of complicated samples.



Liquid Crystal Modified Organic\|inorganic Hybrid Silica Monolithic Column for Capillary Electrochromatography

FENG Rui, SHEN Min, CHEN Hao*, HUANG Zai-Fu, ZENG Zhao-Rui*

2011, 32(1):  50-55. 

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A terminal-vinyl liquid crystal 4’-(ω- undecenyloxyl)-4-xenol was synthesized and used to modify terminal-vinyl organic-inorganic hybrid silica monolithic column by free radical polymerization procedure using AIBN as an initiator. Naphthol, PAHs, phthalate ester and steroids were successfully separated on the column and the separation effects were compared with unmodified column. Mechanism was inferred to hydrophobic interaction, π-π interaction and hydrogen bonding. Reproducibilities of migration times for steroids were reasonable with RSD less than 3.27% for five consecutive within-column runs and were 7.39-9.05% for column-to-column measurements of three columns, respectively.



Highly Selective Colorimetric Fluoride Receptors Based on 2-Hydroxynaphthaldehyde Phenylhydrazone Derivatives

NIE Li* HU Lei, FU Xu-heng

2011, 32(1):  56-61. 

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Three 2-hydroxy naphthaldehyde phenyl hydrazone derivatives were designed and synthesized (1-3; substituent R = p-H, p-NO2, 2, 4-(NO2)2). The interaction between the target compounds and anions was investigated by means of a UV spectrometer, and the effect of the affinity and selectivity of receptors to anions was also studied by changing the N’-substituted groups of benzene ring. The result showed that absorption spectra of receptors were red shifted significantly in acetonitrile solution containing F－and CH3COO－, and a clear color change was observed from yellow to blue or red in acetonitrile solution. The receptor molecule 2 had high selectivity and sensitivity response to F－ and will promise to a good sensing molecule in detection of F－by naked eye. The recognition selectivity of receptor molecule 3 to anion can be changed through adding water in acetonitrile solution, and receptor molecule 3 only recognized F－in 5％H2O-95％ CH3CN(V/V) solution, but had no evident response to other anions. So receptor molecule 3 is expected to be a new sensor which can recognize F－by naked eye in aqueous solution.



Synthesis of Fluorescent Probe Based on Rhodamine and Its Appalication in the  Determination for Cu2+

YUAN Yue-Hua, FENG Feng*, TIAN Mao-Zhong*, MENG Shuang-Ming, BAI Yun-Feng

2011, 32(1):  62-66. 

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In this paper, Cu2+ fluorescence enhancement probe RA based on rhodamine B have been synthesized. It was discovered that the fluorescence intensity of RA increased with the addition of Cu2+ in acetonitrile/water (1/1, V/V) solution, the maximum absorption wavelength was 548 nm. The maximum emission wavelength was 571 nm. Addition of a Cu2+ ion lead to an obvious color change to pink as well as significantly enhanced fluorescence, while other common metal ions such as Na+, K+, Mg2+, Ca2+, Mn2+, Cd2+, Cr3+, Co2+, Ni2+, Ag+, Pb2+, Zn2+, Fe3+, Hg2+ induced no or much smaller color/fluorescent spectral changes. The selective fluorescence enhancement of RA attributed to the spirolactam ring being opened upon the addition of Cu2+ to RA, and a highly delocalized conjugated structure of RA was formed. The sensor was useful for measuring Cu2+ at concentrations ranging from 6.5×10-8 to 2.9×10-6 mol?L-1 with a detection limit of 5.0×10-8 mol?L-1. The recognition of Cu2+ was not reversible, and compound RA was pH-insensitive Cu2+ fluorescent probe, which would detect Cu2+ effectively in a relatively wide range of pH (pH=4.1—10.5) including the significant physiological region.



Enzyme-catalyzed Preparation of 20(S)-Ginsenoside Rg2,20(S)-Ginsenoside Rh1 and 20(S)-PPT

CHENG Le-Qin, KIM Yu-Jin, YANG Deok-Chun*

2011, 32(1):  67-73. 

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Abstract The prosapogenins of ginsenosides have significant phamacological activities such as antitumor, antimetastatic effects. Due to low or non-existent content of the prosapogenins in normal ginseng, it is necessary and meaningful to prepare more active prosapogenin by degradation of major ginsenosides. In this paper, ginsenoside Re and Rg1 were hydrolyzed by crude enzyme of strain Microbacterium esteraromaticum GS514 and the resultant’s structures were determined using 1H NMR and 13C NMR analysis. The experimental results showed that reaction of ginsenoside Re and Rg1 with crude enzymes affected by NaCl treatment. If ginsenoside Re and Rg1 reacted with crude enzymes directly, ginsenoside Re could not be converted other ginsenosides and ginsenoside Rg1 was converted into ginsenoside F1 through selective hydrolysis of β-D-glucopyranosyl moiety connected with C6. But if the reaction were carried out in the presence of NaCl, ginsenoside Re converted into 20（S）-ginsenoside Rg2, ginsenoside Rg1 into 20（S）-ginsenoside Rh1 and 20（S）-protopanaxatriol through selective hydrolysis of β-D-glucopyranosyl moiety connected with C20．These results indicated that C20β-D-glucopyranoside enzyme was activated by NaCl, and it has significant effect on the production of different secondary ginsenosides by high regioselectivity and stereoselectivity.



Design, Synthesis and Biological Activities of Novel Analogues of Chlorantraniliprole Containing Heptafluoroisopropyl Group

FENG Qi, LIU Zhi-Li, WANG Ming-Zhong, XIONG Li-Xia, YU Shu-Jing, LI Zheng-Ming*

2011, 32(1):  74-78. 

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A series of novel analogues of chlorantraniliprole containing heptafluoroisopropyl group, developed from the structures of chlorantraniliprole and flubendiamide , was designed and synthesized according to the substructure link principle. Their structures were characterized by 1H-NMR and HRMS. Their insecticidal and fungicidal activities were also evaluated.



Syntheses and Biological Activities of α-Substitued Phenylethyl Amide Compounds

LI Huan-Huan, WANG Zhen-Jun, WANG Li-Zhong, LI Zheng-Ming, ZHAO Wei-Guang*

2011, 32(1):  79-83. 

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Mandipropamid is the first mandelamide fungicide on the market. Two series of novel N-substitued benzyloxy-α-alkoxy phenylacetamide compounds and α-subsitued benzylamino-phenylacetamide compounds, the bioisosteric analogues of Mandipropamid, have been synthesized from Vanillin and mandelic acid by substitution, reduction and so on. Their structures were characterized and determined by 1H NMR, HRMS. The result of the preliminary biological activity tests showed that some of the compounds exhibited some anti-fungal activities. For example, N-(3-methoxyl-4-ethoxylbenzyloxy)-α-ethoxyl-4-chloride-phenylacetamide had inhibition rate 90% against fungicidal activity at the concentration of 200 ug /mL. N-(3-methoxyl-4-ethoxylbenzyloxy)-α-isopropoxy-4-chloride-phenylacetamide had inhibition rate 80% against phytophthora capsici at the concentration of 20 ug /mL.



Expression and Preliminary Activity Identification of Several Linked Antigen Epitopes of Consensce Genes of Yersinia Pestis, Hantavirus and Leptospira

PU Yun1,2, QI Yan-Fei1, XU Guo-Liang3, XU Hui3, ZHANG Shi-Yao1, MENG Ri-Zeng1,2, SONG Xiu-Ling1, YANG Huai-Ning2, LI Juan1*

2011, 32(1):  84-87. 

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The expression vector pET-rYHL was constructed by inserting the linked gene contained two antigen epitopes of F1 capsule antigen from Yersinia Pestis, six antigen epitopes of Hantavirus and six antigen epitopes of Leptospira into pET-20b and was identified by digestion with restriction enzymes and sequence analysis. Then an expression strain was selected after transformation of the recombined plasmid into E. coli BL21 (DE3), fusion protein with His-tag was efficiently expressed in the form of inclusion body after IPTG induction. The inclusion body was washed, dissolved and purified by Ni2+ chelate chromatography under denatured condition. SDS-PAGE analysis and Western blotting showed that the fusion protein with a molecular weight of about 40 000 was purified and the purity was up to 98%. The results ELISA showed specific reactions with Plague, Epidemic hemorrhagic fever and Leptospirosis positive sera respectively, and no cross-reaction with other positive sera sample(salmonella ) using the expression protein.



Inhibitation and Binding of Rugulosin  with N-Hsp90

CHEN Jun-Jie, YI Yu-Ting, YU Miao, XUE Shao-Long, XIONG Qian-Qian, HE Xiao-Meng, ZHANG Lian-Ru*

2011, 32(1):  88-94. 

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By Docking simulation, We find the combination between Rugulosin and N-terminal of Hsp90 which is the ATPase activity domain. Rugulosin show a strong inhibition to ATPase activity of Hsp90 and the IC50 is 22.27μM in vitro experiment. In this study, we do a research on the interaction mechanism of Rugulosin with NHsp90 protein (N-Terminal of Hsp90)by fluorescence, circular dichroism, UV - visible absorption spectroscopy, and SPR technology. fluorescence spectra experiment results show that Rugulosin cause a strong fluorescence quenching on endogenous fluorescence of Hsp90 by static quenching method. Thermodynamic analysis signify the Binding mechanism is electrostatic forces and dissociation constant is 22.4 ± 0.17μM. Circular dichroism spectra detected the α-helix of NHsp90 reducing as the Rugulosin concentration increased, This study show that Rugulosin can make a combination with NHsp90, thereby inhibiting its ATPase activity. Ruglulosin may be a potential inhibitor of Hsp90.



Construction, Expression and Activities of a Novel Anti-HIV-1 Protein GRFT

LI Chang, LI Xiao, LIU Yu-Sheng, YU Fang, HAN Jia-Li, HU Bo, YE Ming, WANG Jing, DU Shou-Wen, JIN Ning-Yi*

2011, 32(1):  95-99. 

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A DNA sequence encoding GRFT was synthesized according to the deduced amino acid sequence of GRFT, using an E. coli codon preference table, and cloned into the prokaryotic expression vector pET28a (+). Then the recombinant plasmid was transfered into E.coli BL21(DE3). The target protein was obtained after induced by isopropyl-β-D-thiogalactopyranoside (IPTG). The results of SDS-PAGE and Western Blot showed that the protein was well expressed and had antigenic activities. When different parameters were optimized, the highest production could account for 55.84% of total bacterial protein. Gel scan analysis showed that the purity was 94.06% after the target protein refolding and purification with Ni2+-NTA affinity chromatography. The antigenic and cellular biding activities of target protein were identified by Dot-ELISA and IFA methods based on the HIV-1 infection target cell models prepared by our laboratory. The results suggested that the recombinant protein has special recognition and binding activity with target cells. This research will settle solid foundation for further investigate of anti-HIV-1 genetic engineering agents and targeted therapy.



Immobilization of Peptide Aptamer of Specific Indentification of Endothelial Progenitor Cell on Titanium Surface

CHEN Zhuo-Yue, LI Quan-Li, ZHAO Yuan-Cong, CHEN Jia-Long, YOU Tian-Xue, XIONG Kai-Qin, HUANG Nan*

2011, 32(1):  100-104. 

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In vivo spontaneous endothelialization of cardiovascular materials is thought to be a promising approach to prevent the formation of thrombus and restenosis. Capturing endothelial progenitor cells (EPC) from blood and inducing EPC to grow on the surface of stents is a new strategy for this purpose. In this study，we developed a facile and effective approach to construct a surface that possessed a high affinity and specificity to EPCs by binding peptide aptamer. In order to introduce primary amine groups to covalently immobilize biotin，the titanium surface was treated by phosphoric acid solution to obtain the hydroxyl groups which were used to covalently immobilize aminopropyltriethoxysilane. Furthermore，the biotin was grafted onto the amine functionalized titanium surface by carbodiimide (EDC)-mediated. Finally，using layer-by-layer self-assembly method，biotinylated peptide aptamer was fixed on the titanium surface by the biotin-avidin recognition system. The results of fourier transform infrared spectroscopy (FTIR)，fluorescence labeling method and scanning electron microscopy (SEM) demonstrated that peptide aptamer was successfully bond to the titanium surface. This peptide aptamer modified surface shows a promising application for vascular devices.



Heterogenous Degradation of Toxic Organic Pollutants by Hydrophobic Iron(Ⅲ) Schiff Base Complex Under Visible Irradiation

CAO Ting-Ting, ZOU Cai-Qiong, LUO Guang-Fu, CHEN Deng-Xia, ZHAO Xiao-Rong, LI Rui-Ping, HUANG Ying-Ping*

2011, 32(1):  105-112. 

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A hydrophobic Iron(Ⅲ) Schiff Base complex, Fe-Bis-Schiff-base-salicylaldehyde-o- Phenylenediamine (Fe-SPA), was prepared by chemical synthetic method. In a water-soluble medium, the hydrophobic Fe-SPA could be used as a heterogeneous photocatalyst to degradate organic pollutants. The photo-catalytic degradation of Rhodamine B (RhB), Methylene Blue trihydrate(MB) and 2, 4-dichlorophenol (2,4-DCP) under the visible irradiation and neutral condition (at pH 7.2) were used as probe reactions to evaluate the photo-catalytic activities of Fe-SPA. Under the optimal conditions, RhB was decolored completely in 150min, MB was decolored completely in 300min, and DCP was removed more than 65% in 10h. ESR results showed that the highly reactive oxygene species ?OH was produced in the reaction. IR and Uv-Vis results indicated that RhB was degraded to small moleculars, such as amine substances and carbonyl (carboxyl) compounds. In a water-soluble medium, the hydrophobic Fe-SPA which was used as a heterogeneous photocatalyst is stable after 5 recycles.



Influence of Ethylenediamine Tetraacetic Acid on the Hydrodesulfurization Activity of Nano HZSM-5 Supported NiMo Catalyst

JIN Feng-Ying, GUO Xin-Wen, WANG Xiang-Sheng*

2011, 32(1):  113-117. 

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The effects of chelating ligands (nitrilotriacetic acid (NTA), 1,2-ethylenediamine (EN), citric acid (CA), glutamic acid, ethylene-diaminetetraacetic acid (EDTA) or trans-1,2-cyclohexanediamine-N,N,?,?-tetraacetic acid (CyDTA)) during the preparation of CoMo/Al2O3, CoMo/SiO2, NiMo/ SiO2 et al. were reviewed, however, the influence of chelating agent for hydrodesulfurization of catalyst over molecular sieve carrier no reports. In this paper, a new type of EDTA-NiMo/nano-HZSM-5 catalyst for FCC gasoline hydrodesulfurizaiton was prepared. The catalyst showed higher HDS activity and more stable HDS activity for FCC gasoline than the NiMo/nano-HZM-5 catalyst. And they were characterized by XRD, ICP, FT-IR, 27Al NMR, TG-DTA, PyIR, and NH3-TPD. The results indicated that there was a strong interaction between EDTA and nano-HZSM-5, which weakens the interaction between the active metal components and support, improves dispersion of active metal components on the surpport surface. Besides, it is the interantion between EDTA and Ni that promotes the reduction and sulfidation of catalyst. Therefore, the hydrodesulfurization activity of the catalyst is improved.



Effect of Si/Al Ratio on the Performance of Cu-Zn-Si-Al Catalyst Prepared by Complete Liquid\|phase Technology for Dimethyl Ether Synthesis from Syngas

HUANG Wei*, SONG Ya-Jun, FAN Jin-Chuan, YIN Li-Hua

2011, 32(1):  118-123. 

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A series of CuZnAlSi bifunctional catalysts with different Si/Al ratio were prepared by a complete liquid phase method and the catalytic performance was evaluated in a slurry reactor. The catalysts were characterized by means of XRD, NH3-TPD-MS, H2-TPR and XPS. The results showed that Cu species was present as low-valence in the catalysts prepared by complete liquid-phase technology. The grain size of Cu had major impact on the catalytic activity. The change of Si/Al ratio led to the change of acid amount and acid strength, thereby influence the selectivity of catalysts. Adjusting the Si / Al ratio can improve the stability of catalysts. When the Si/Al ratio equaled to 1/2, the catalyst can obtain good performance.



Effect of Anodic Electrodeposition Condition on Composition, Morphology and Structure of Ti/SnO2-Sb2O5/Nano-Co3O4+PbO2 Composite Electrode

DAN Yuan-Yuan, LU Hai-Yan, LIU Xiao-Lei, LIN Hai-Bo*, HUANG Wei-Min, ZHAO Jing-Zhe*

2011, 32(1):  124-128. 

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Ti/SnO2-Sb2O5/PbO2+Nano-Co3O4 composite electrode material was prepared by the anode composite electrodeposition methods on Ti substrate with the intermediate SnO2-Sb2O5 layer. The Influence of preparation conditions on the composition, structure and morphology of the composite material were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy(XPS) and scanning electron microscope (SEM) analyses. The results showed that porosity and roughness of the PbO2 surface were increased because of the embedded Co3O4; the Co3O4 embedding content was effected by the deposition potential, nano particles concentration and the addition of organic reagent.



In situ FTIR Studies on Electrochemical Debromination Reaction of 2-Bromobenzoic Acid

LI Mei-Chao, BAO Dan-Dan, MA Chun-An*

2011, 32(1):  129-133. 

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The electrocatalytic reductive debromination of 2-bromobenzoic acid in aqueous solution on titanium, graphite and copper electrode was investigated by using cyclic voltammogram. Compared with titanium and graphite, copper electrode exhibited a high electrocatalytic activity for the reduction process of 2-bromobenzoic acid. Further studies by in situ FTIR suggested that the mechanism of the reaction was electrochemical hydrodebromination process. 2-bromobenzoic acid was electroreduced to its free radical ion initially after receiving an electron. Then the free radical ion was further debrominated to produce benzoic acid free radical at the more negative potential. Finally, benzoic acid was obtained by receiving another electron and H+, which has been further confirmed by constant current electrolysis experiments.



Electrocatalytic Performance and Formic Acid Tolerance Ability of Macropore Carbon Supported Ir Catalyst for Oxygen Reduction

LIU Chun-Yan, XU Bin, TANG Ya-Wen, CAO Gao-Ping, YANG Yu-Sheng, LU Tian-Hong*

2011, 32(1):  134-138. 

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In this paper, the electrocatalytic performance and formic acid tolerance ability of the Vulcan XC-72 carbon black supported Ir (Ir/XC) catalyst and the macropore carbon supported Ir (Ir/MC) catalyst in the direct formic acid fuel cell were investigated using the energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) spectroscopy, Raman spectroscopy and electrochemical technique. It was found that the electrocatalytic performance of the Ir/MC catalyst for the oxygen reduction is better than that of the Ir/XC catalyst. The onset reduction potential of oxygen at the Ir/MC catalyst is 0.1 V more positive than that at the Ir/XC catalyst. The limiting current density of the oxygen reduction at the Ir/C catalyst is 30% larger than that at the Ir/XC catalyst. This could be only attributed to the large pore diameter and porosity as well as high graphitization extent because the average diameters and relative crystallinity of two catalysts are similar. In addition, both catalysts have the good formic acid tolerance. Therefore, MC is a carbon carrier of the catalyst better than XC.



Surface Charge Characteristics of n-AlGaN/GaN Heterostructures Films in Nano-scale by Kelvin Probe Force Microscopy in Vacuum

WANG LingLing YANG WenSheng WANG DeJun XIE TengFeng

2011, 32(1):  139-142. 

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The surface charges characteristics of n-AlGaN/GaN heterostructures films in nano scale have been studied by means of KFM technique in vaccum conditions. The results showed that all the dislocations of n-AlGaN/GaN heterostructures films were negatively charged, and the maxinum contact potential difference was about 590mV. Moreover the contact potential variations around the dislocations in n-AlGaN/GaN heterostructures films was much larger than that of dislocations in diameter. The photo-generated charges rediscontribution has been observed also under illumination. This result indicates that surface charges of semiconductor in nano-scale can be measured quantitatively by KFM in vacuum condition.



Effect of Different Solvents on Structure and Gas Properties of PPESK Carbon Membranes

PANG Jing, WANG Tong-Hua*, LI Lin, QI Wen-Bo, ZHANG Shou-Hai, JIAN Xi-Gao

2011, 32(1):  143-149. 

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For the investigation of different solvents’ influence on structure and performance of PPESK carbon membranes, PPESK derived films for gas separation were prepared with NMP，CHCl3，DMAc and TCE. The chemical structure, microstructure and gas separation properties of these membranes were characterized by FTIR、TG、XRD and gas permeation tests. The result indicated that the main cause of gas permeation and selectiveity was the different carbon structure，pores and flexility of carbon membranes induced by the variation discipline during preoxidation and carbonization in consequence of solubility, boiling point, volatility and content of solvents.



Effect of Preparation Conditions on the Catalytic Performances of PtRu/CAs Catalysts for Methanol Electro-oxidation

ZOU Yue-Chao, LI Xia, HUANG Yong-Min*, LIU Hong-Lai

2011, 32(1):  150-154. 

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The impregnation method was applied to prepare the platinum – ruthenium (Pt-Ru) catalysts in which the content of Pt was 15%, and the atomic ratio of Pt and Ru was 2:1. The properties of the catalysts prepared with varied impregnated mediums (acetic acid, sodium acetate and water) and different carriers (carbon nanotubes and carbon aerogels) were studied in detail. The X-ray diffractometry(XRD) and transmission electron midroscopy(TEM) were used to observe the surface morphology of above Pt-Ru catalysts. The Energy Dispersive X-ray Spectrum(EDS) was used to analyze the composition of catalysts. The electrochemical performance of the catalysts was examined by cyclic voltammetry with a glassy carbon working electrode in a solution of 1.0 mol/L CH3OH and 0.5 mol/L H2SO4. In above all catalysts, the catalyst prepared with the metal precursor impregnated in CH3COOH and carbon aerogels as a carrier has the highest electrocatalytic activity. The peak current density gets to 38.24 mA/cm2, which is much higher than the rest of the catalysts prepared with other conditions in this paper.



DFT Studies on Electronic Spectra and Second\|order Nonlinear Optical Properties of Schiff Base Ligands Containing Ferrocene and Their Ni(Ⅱ) Complexes

LI Xiao-Juan, SUN Shi-Ling, LIU Yan, ZHAO Hai-Bo, LIU Chun-Guang, QIU Yong-Qing*

2011, 32(1):  155-160. 

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The geomertrical structures of Schiff base ligands containing ferrocene and their Ni(II) complexes were optimized by using density functional theory(DFT) B3LYP method. On the basis of the stable structures, the electronic spectrum of complexes were calculated by TD-B3LYP method. The polarizability and second-order nonlinear optical (NLO) properties of ligands and complexes were investigated by combining with the finite-field (FF) method. The results show that the values do not change significantly from ligands to their Ni(II) complexes, but enhanced by increasing the conjugation bridge and adding withdrawing-electron substituent groups. Moreover, compared with ligands, all complexes have a larger second-order NLO coefficients. The values of the double bond bridge Schiff base ligands are much larger than the single bond bridge ones, but the values of the double bond bridge Schiff base complexes are close to the single bond bridge Schiff base complexes. In addition, ferrocenyl groups have different roles in ligands and complexes, acting as an accepter in ligands but a donor in complexes.



Time\|dependent Density Functional Theory Studies on the Electronic Spectra of Mo2 and W2 Quadruply Bonded Compounds

QIU Yi-Xiang, WANG Shu-Guang*

2011, 32(1):  161-169. 

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The low-lying electronic excited states of M2Cl4(PMe3)4 and M2(O2CCH3)4 (M = Mo, W) have been studied using the time-dependent density functional theory (TDDFT). Furthermore, the applicability of a series of functionals, such as LDA, GGA and hybrid functional, for calculating d-d and charge-transfer (CT) transitions of quadruply bonded metal compounds have been tested. It is found that the LDA and GGA functionals provide accurate description of the d-d transitions, but yields substantial errors for the excitation energies of CT transitions. The electrostatic attraction between the separated charges in long-range excited charge-transfer states originates from the non-local Hartree-Fock exchange potential and is a non-local property. Present-day TDDFT method employing pure exchange-correlation functionals (LDA or GGA) does not capture this effect and therefore fails to describe CT excited states correctly. The hybrid functionals include parts of HF exchange provide accurate results for the CT transition energy, but the errors in the d-d transition energies were much larger than those predicted by the LDA and GGA functionals. In order to simultaneously obtain the accurate descriptions of both d-d and CT transitions of quadruply bonded metal compounds, we will look forward to the strict time-dependent non-local functional is applied to the calculation of TDDFT method.



Facile Synthesis and Self-assembly Behavior of Novel Multihetero-arms Hyperbranched Polyglycerol

ZHOU Li, YIN Hui-Jun, GAO Chao*, XU Wei-Jian*

2011, 32(1):  170-174. 

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A novel multihetero-arms hyperbranched polyglycerol (HPG-h-arm) was synthesized through facile three steps: synthesis of HPG by anionic ring-opening polymerization of glycidol, grafting hydrophobic palmitic acid (PA) chains and reactive Br by N,N’-dicyclohexylcarbodiimide (DCC) coupling reaction, and grafting hydrophilic poly(2-(dimethyl amino)ethyl methacrylate) (PDMAEMA) chains by atom transfer radical polymerization (ATRP). The structure of the HPG-h-arm was characterized by FTIR and 1H NMR. The self-assembled behaviors of the HPG-h-arm in different solvents were detected by DLS, and the morphology of the assembly was examined by TEM and AFM. The results showed that the HPG-h-arm could form spherical micelles with different sizes in different solvents.



Synthesis of a Novel Fullerene End-capped Poly(γ-benzyl L-glutamate)

ZHANG Qing-Huan, FU Ling-Yun, ZHANG Jun, YANG Xin-Lin*

2011, 32(1):  175-179. 

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Fullerene polymers have attracted much attention during the past decade. To explore the synthesis of fullerene polypeptides, a fullerene— γ—benzyl L—glutamate conjugate containing a free amino group was used as an initiator, polymerization of γ—benzyl L—glutamate N—carboxy— anhydride was performed for the first time via ring—opening polymerization, leading to formation of a novel fullerene end—capped poly(γ—benzyl L—glutamate) with a yield of 37.2%. The product was characterized by 1H NMR, FTIR, UV—VIS, MALDI—TOF MS and thermogravimetric analysis. Compared with previously reported method, this route avoids utilization of azides and affords the products with relatively identical structures, highlighting its potential application in fullerene polypeptide synthesis.



Molecular Dynamics Simulation Study on the Reorientation Behavior of Linear Polyethylene Under High Electric Field

YU Xiang, HAN Ming, YANG Xiao-Zhen*

2011, 32(1):  180-184. 

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The charge equilibration (QEq) method was adopted to calculate the charge distribution along the linear polyethylene (PE) chains. It was found that the CH3 and CH2 groups in the non-polar PE chain have non-zero charges. Then the single PE chain was found to be able to reorient in the high electric field by the MD simulation. At last, the QEq method was applied in calculating the charge distribution in the multi-chain PE systems both in vacuum and in bulk condition, and the MD simulation revealed that the PE systems in both conditions can be reoriented. The original reason for this reorientation phenomenon was the asymmetry of the charge distribution along the chains.



Polymorphic Crystals from Different Thermal Treatments and Its Effect on Biodegradation Behavior of Poly(butylene adipate)

ZHAO Li-Fen, JIANG Ni, GAN Zhi-Hua*

2011, 32(1):  185-189. 

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On the basis of characteristic polymorphic crystals of poly(butylene adipate) (PBA), the PBA films with α crystal structure were prepared by two methods of melt crystallization and annealing treatment. The polymorphic crystal structure, crystal size and crystalline morphology of PBA α crystals with different thermal history were studied by wide angle X-ray diffraction (WAXD), atomic force microscope (AFM) and differential scanning calorimeter (DSC). The biodegradation behavior of PBA α crystals from different thermal treatments was investigated by following the weight loss with time. The results of this work indicated that the difference of PBA α crystals in spatial orientation of polymer chains in the same crystal lattice due to the different thermal history is the essential reason which results in the different biodegradation rates.



Emusifier\|free Latex Copolymerziation of 2,2,3,4,4,4-Hexafluorobutyl Acrylate and Styrene by Amphiphilic RAFT Agent

CHEN Yan-Jun*, ZHOU Hui, LUO Wen, LI Ming, ZHANG Chao-Can

2011, 32(1):  190-195. 

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With the presence of the synthesized amphiphilic reversible addition-fragmentation chain transfer (RAFT) agent, poly(2,2,3,4,4,4-Hexafluorobutyl acrylate-co-styrene) latexes were prepared via emulsifier-free emulsion polymerization. The effects of the amphiphilic RAFT agent and polymerization temperature on the polymerization kinetics, controllability of polymerization and latex particle sizes were studied. The chemical structure, Tg, molecular weight，molecular weight distribution of copolymer and surface property of the latex films were characterized by FTIR, 1H NMR, DSC, GPC and surface tension instrument, respectively.



Synthesis and Characterization of Titanium\|containing Styrene Monomer and Polymer

YANG Hong-Ling, ZHANG Sheng, ZANG Yi-Bo, ZHU Fang-Hua, ZHANG Lin, CHEN Xue-Tai*

2011, 32(1):  196-200. 

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A styrenic monomer containing dicylopentadienyltitanium group and 2,6-pyridinedicarboxylate has been synthesized and fully characterized. A stable and soluble copolymer was obtained by the solution copolymerization reaction between the titanium-containing monomer and styrene. This copolymer was found to be soluble in THF, CH2Cl2 and toluene and exhibit a glass transition temperature of 106 oC. This titanium-containing polystyrene could be used in the fabrication of the micro-spheres for the ICF experiments.