Table of Content

10 May 2009, Volume 30 Issue 5

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Synthesis and Structure Characterization of (C₆H₈N₃)⁺I₃^- and [(Cu₃I₄)(C₈H₁₇N₂)] Based on in situ Ligand Reaction

NING De-Kuan, BI Ming-Hui, LI Guang-Hua, LIU Guo-Zong, SHI Zhan*, FENG Shou-Hua

2009, 30(5):  845-848. 

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Two I-containing compounds, (C₆H₈N₃)⁺I₃^-(1, C₆H₇N₃=2,3-dihydroimidazo[1,2-a]pyrimidine-1-ium) and [(Cu₃I₄)(C₈H₁₇N₂)](2, C₈H₁₇N₂=N-ethyl-1,4-diazabicyclo[2.2.2]octane), were synthesized under solvothermal conditions based on in situ ligand reaction and characterized via elemental analysis, XRD and single crystal X-ray diffraction analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a=0.74281(15) nm, b=0.84241(17) nm, c=0.9993(2) nm, α=82.02(3)°, β=83.30(3)°, γ=82.92(3)°, V=0.6114(2) nm³. Complex 2 crystallizes in the monoclinic system, space group P2₁/c with a=0.68924(14) nm, b=1.0786(2) nm, c=2.2779(5) nm, β=94.84(3)°, V=1.6874(6) nm³. Two kinds of in situ ligand reaction were found in the synthesis of these complexes. (C₆H₈N₃)⁺ ligand was synthesized from 2-aminopyrimidine and ethanol in complex 1, whereas(C₈H₁₇N₂)⁺ ligand was synthesized from 1,4-diazabicyclo[2.2.2]octane and ethanol in complex 2.

Preparation, Characterization and Surface-enhanced Raman Scattering Activities of Cap-shaped Gold Nanostructures

XIAO Gui-Na, MAN Shi-Qing*

2009, 30(5):  849-854. 

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Cap-shaped gold nanostructures, consisting of a SiO₂ core with a Au cap, were prepared with vacuum ion sputtering by depositing Au films onto the surface of self-assembled monolayer arrays of SiO₂ nanoparticles. Their surface morphologies, structures, and optical properties were characterized via TEM, SEM, AFM, XRD, and UV-Vis-NIR spectrophotometer. The surface-enhanced Raman scattering(SERS) activities of gold nanocaps were investigated with methylene blue as a probe molecule. The Raman scattering signal of the adsorbed molecule was found to be enhanced remarkably, and an enhancement factor of the order of 10⁷ was estimated, which indicated that they are potentially useful for ultrasensitive biological and chemical detection.

Synthesis and Electric Field Response Behavior of 4-Chlorophthalate Titanocene Complexes

HE Ling, GAO Ling-Xiang*, Gao Zi-Wei, ZHANG Ying, WU Xiao-Ni, NI Ying-Rui

2009, 30(5):  855-861. 

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4-Chlorophthalate titanocene complexes were synthesized by reacting Cp₂TiCl₂ with 4-chlorophthalic acid in water or in CHCl₃/H₂O medium. The complexes were characterized by TG, IR, ¹H NMR, SEM and EA. The effects of reactive condition on the particle size and the morphology of complexes were investigated. In addition, the electric field response performance of titanocene complexes which were dispersed in the glycerin/gelatin aqueous elastomers were also studied. It was found that there are differences in the structure of the complexes which were synthesized by different methods. The hollow microspheres of complexes with diameter of 05—1 μm and 2—5 μm were obtained by aqueous phase method and two-phase method, respectively. Both of the complexes have obvious response to electric field.

Synthesis, Structure and Catalysis Performance of Complex [Ni(qina)₂(H₂O)₂]·2DMSO

WANG Chuan-Sheng, WU Qiong, ZHU Ming-Chang, GAO En-Jun*

2009, 30(5):  862-865. 

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A single crystal complex [Ni(qina)₂(H₂O)₂]·2DMSO(Hqina＝quinaldinic acid, DMSO=dimethyl sulfoxide) was synthesized at room temperature by the solvent substitution method, which belongs to monoclinic system with space group C₂/m. Two qina ligands chelate a nickel(Ⅱ) ion by O and N atoms and two H₂O coordinate a Ni(Ⅱ) ion by two O atoms at an axis. The complex formed inerratic octahedron configuration, and H bonds, π-π stacking were observed between the molecules. 1-Naphthyl acetate hydrolysis velocity has been remarkably enhanced by the title complex, when the concentration of the title complex was at 1.0×10^-4 mol/L, pH 8.44. The enhancement multiple was 365.

Preparation and Field Emission Capability of Silver Tetracyanoquinodimethane Nanowire Array

TIAN Fei, LI Bao, WANG Chun-Ru*

2009, 30(5):  866-868. 

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The well-aligned silver 7,7,8,8-tetracyanoquinodimethane(AgTCNQ) nanowire array was prepared with the anodic aluminum oxide(AAO) template method. The size, length and morphology of AgTCNQ nanowires were well characterized via scanning electronic microscopy(SEM) and transmission electronic microscopy(TEM). It is revealed that the AgTCNQ nanowires are uniform and both the length and diameter are controllable. The field emission property of the AgTCNQ was studied and the result revealed that the template-synthesized AgTCNQ nanowire array had excellent field emission property. The turn-on electric field of electron emission is 1.51 V/μm, and the F-N enchancement factor is 21.4, which suggest that AgTCNQ nanowires are perfect candidates for field-emitting materials.

Studies on Non-covalent Complexes of Glutathione with L-Aromatic Amino Acids by Electrospray Ionization Mass Spectrometry

CHU Yan-Qiu* , DAI Zhao-Yun, JIANG Gong-Yu, ZHENG Song-Bai, CHEN Xi......

2009, 30(5):  869-875. 

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To explore the non-covalent interaction between reduced tripeptide glutathione and L-aromatic amino acids, a stoichiometry of reduced γ-glutathione and three L-aromatic amino acids, including phenylalanine, tyrosine and tryptophan were mixed respectively, and then incubated at room temperature and physiological pH conditions for 1 h to reach the equilibrium. The electrospray ionization mass spectrometry(ESI-MS) results indicate that glutathione and three L-aromatic amino acids could form non-covalent complexes, respectively. The primary fragment ions of complexes obtained from MS² in a tandem mass spectrometer included aromatic amino acid, glutathione as well as its y₂, b₂, which confirmed the results of ESI-MS. Moreover, in UV spectroscopies, the discrepancy between complexes and reactants also confirmed the formation of complexes in aqueous solution. To avoid distinct ionization efficiency discrepancy and signal suppression in ESI-MS measurements, the interaction between glutathione and L-Tyrosine was evaluated quantitatively, which revealed that the reactant concentration should range from 5×10^-5 to 3.00×10^-4 mol/L. The dissociation constants of three complexes were determined using mass spectrometric titration method, the calculation results revealed that the stabilities of complexes formed by glutathione and three L-aromatic amino acids increased gradually according to the order of tyrosine, tryptophan and phenylalanine.

Research of Cell Concentration and Separation on the Dielectrophoretic Chip with Arrayed Opposite Electrodes

XU Yi*, CAO Qiang, ZENG Xue, WU Yong-Jie, ZHANG Wen-Pin

2009, 30(5):  876-881. 

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A prototype microfluidic dielectrophoretic(DEP) chip for cell separation and concentration based on principle of DEP was presented in this paper. The proposed microfluidic DEP chip was bonded directly with glass substrate deposited Au micro electrodes and polydimethylsiloxane(PDMS) cover plate with designed micro-channels. The effective area of positive DEP was increased by the designed electrode array which composed of several groups of opposite electrodes with different distances on the bottom of glass chip. It also made the DEP chip to capture the target cells from fluid suspension at low AC electric field. Under the condition of 3 V and 3 MHz, the capture efficiency of human red blood cell(RBC) achieved 83%. Furthermore, mixture of RBC and liver cancer cells(HepG2) was separated by capture the HepG2 on the electrode array at 5 V and 400 kHz, and the capture efficiency of HepG2 achieve 86% on the designed DEP chip.

Different Materials Coated Magnetic Nanoparticles Studied by Home-made Surface Plasmon Resonance Sensor

TAO Lei, JIN Wei*, ZHANG Ying, YAN Fei, WANG Lin-Lin, MU Ying, ......

2009, 30(5):  882-885. 

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By means of surface plasmon resonance(SPR) sensor with a light emission diode(LED) as the excitation source, the association degree of the target DNA coupled with different materials coated magnetic nanoparticles with biotinylated DNA probe was investigated. Compared with that of target DNA coupled with magnetic polystyrene microspheres with biotinylated DNA probe, the association of target DNA conjugated with silica-coated magnetic nanoparticles was faster and the RSD was smaller.

Anodic Stripping Voltammetric Immunoassay Based on Coupling Copper-enhanced Nanogold Tags with Magnetic Separation for Highly Sensitive Detection of Proteins

SHEN Guang-Yu*, FENG Hui, HAO Ai-Ping

2009, 30(5):  886-890. 

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A novel and highly sensitive anodic stripping voltammetric immunoassay was proposed on the basis of chemical copper-enhanced gold nanoparticle(nanogold) tags in vitro as the amplification approach with the aid of magnetic separation technique. In a homogeneous bulk solution phase, the human IgG(hIgG) as a model of test system was captured by goat anti-human IgG antibody(anti-hIgG)-conjugated SiO₂@Fe₃O₄ magnetic nanoparticle and anti-hIgG-conjugated nanogold, followed by the copper metal dissolution in diluted nitric acid solution for anodic stripping voltammetry measurement. Comparing with the traditional solid interface reaction-based metal immunoassay, this novel one which introduce homogeneous reaction strategy combined with magnetic separation can provide some advantages, including easy of use, shorter analytical time, and especially amplified capability of detecting hIgG. It can quantitatively determine hIgG in the concentration range of 0.1—1000 ng/mL, with a detection limit about 73 pg/mL.

Optical Detection of Immunoreaction Based on the Orientation Transition of Liquid Crystal

XIONG Xing-Liang*, CAI Shao-Xi, LI Yuan

2009, 30(5):  891-895. 

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The uniform orientation of liquid crystal molecule can be changed easily when exposure to different biological environment and thus lead to the changes of optical images obtained from crossed polarized light with liquid crystal sandwiched between polarizer and analyzer. Based on this principle, we report the uniform planar orientation of thermotropic liquid crystals, 4-biphenyl-4′-pentyl-carbonitrile(5CB), on the films of anti-human serum albumin(anti-HSA) covalently immobilized on the surface of glass microscope slides using(3-aminopropyl)triethoxysilane(3-APTES) and glutaraldehyde(GA) and mechanically rubbed using a rubbing machine. Following immersion of these rubbed films of anti-HSA into aqueous solutions containing different concentrations of HSA, we observed the differences of images and quantificationally analyzed the relationship between gray scale of images and the concentration of HSA using the concept of weighted average of gray-scale value of image. Following immersion of these rubbed films of anti-HSA into solutions containing HSA, BSA, fibrinogen, lysozyme, we compared specific adsorption with nonspecific adsorption on these rubbed films of anti-HSA by observed the differences of images and modulation of polarized light. The result suggests that these types of substrates(rubbed films of proteins) possess high specificity. The provided methods have the potential to be useful in a variety of sensitive, label-free biomolecular detection where specific binding of a target species to its antibody(or antigen) can be imaged through analyze of the optical image of liquid crystal cell placed onto the surface.

Preparation of Novel Mixed Packing Materils and Its Evaluation

YANG Jun-Jiao*

2009, 30(5):  896-898. 

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Novel sulfonic acid and carbon chains of mixed-mode packing materials were synthesized through sulfonating polymer-encapsulated zirconia covered by a porous copolymer of olefinic hydrocarbon and divinylbenzene on its surface. This new packing material was evaluated in CEC, physical properties of these stationary phases were determined with SEM and IR. Chromatographic characteristics were evaluated in CEC.

Novel Method of Protein Detection Based on Cationic Conjugated Polymer and Aptamer Probe

YANG Xiao-Hai, WANG Sheng-Feng, WANG Ke-Min*, LUO Xiao-Ming, TAN Wei-Hong,......

2009, 30(5):  899-902. 

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A novel fluorescence-based method for protein detection was developed based on aptamer probe as the recognized molecule and cationic conjugated polymers(CCP) as the reporter. The quencher-labeled aptamer probe attached to CCP by electrostatic interaction, leading to fluorescence quenching of CCP. When target protein was added, it bonded specifically to aptamer probe, which made the quencher detached from CCP. Then the fluorescence of CCP was resumed. The results show that the fluorescence resuming ratio is proportional to the concentration of target protein. The detection method for thrombin had a linear range of 17—40 nmol/L.

Searching for Novel Lead Compounds of α₁-AR Antagonists: Synthesis, Bioassays and 3D-QSAR of 2-[4-(Aryloxyalkyl)-piperazin-1-yl]benzo[d]oxazole Compounds

LI Jia-Bin, LIU Hai-Chun, ZHANG Li, WANG Tao, JIANG Zhen-Zhou3, XIA Lin*

2009, 30(5):  903-907. 

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Benign prostatic hyperplasia(BPH) is a pathological disorder in the aged men that causes voiding difficulties and thus impacts the quality of life. α₁-AR antagonists are clinically used for the treatment of BPH. Aimed at searching for the novel α₁-adrenoceptor antagonists, eight target compounds bearing 2-(piperazin-1-yl)benzo[d]oxazole scaffold were designed from our lead compound wb5c and synthesized from 5-chloro-2-aminophenol and substituted phenols via condensation, chloration and amination, Williamson ether synthesis and substitution etc.. All target compounds were identified by ESI-MS, IR, ¹H NMR and HRMS. Functional bioassays showed that they had moderate antagonistic activities against α₁-AR. The CoMFA model was constructed for 2-(piperazin-1-yl)benzo[d]oxazole derivertives via SYBYL software package, q²=0.430, r²=0.907, fractions of steric and electrostatic fields were 0.465 and 0.535, respectively. 3D-QSAR analysis leads to insight into further structural optimization.

Synthesis and Biological Activities of 3-Substituent-5-aryloxazolidin-4-ones

YAO Hong-Wei, LI Huan-Huan, SU Na-Na, WANG Hong-Xue, LIU Xing-Hai, ......

2009, 30(5):  908-912. 

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Mandipropamid is the first mandelamide fungicide on the market. Cyclizing open structures in a given structure represents one of the useful methods in the search for biologically active conformations. A series of novel 3-substituentphenethyl-5-aryloxazolidin-4-ones, the ring-closed analogues of mandipropamid, were obtained from the 2-hydroxy-N-(substitutedphenethyl)-2-arylacetamide and aldehydes by refluxing in benzene or toluene with catalytic amount of p-toluenesulphonic acid. Their structures were identified by means of elemental analysis, IR, ¹H NMR and MS spectra. And their structure-activity relationships were discussed.

Influence of DOPC, DOPE and Ceramide on the Organization of Sphingomyelin/Cholesterol Bilayers

HAO Chang-Chun, SUN Run-Guang*, ZHANG Jing

2009, 30(5):  913-918. 

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Lipid rafts are of a dynamic microdomain structure found in recent years, enriched in signal molecules. The change of structure and function of lipid rafts can result in many diseases. LB technique and atomic force microscopy were used to study the effect of 1,2-dioleoy-sn-glycero-3-phosphocholine(DOPC), 1,2-dioleoy-sn-glycero-3-phosphoethanolamine(DOPE) and ceramide on the structure of sphingomyelin(SM)/Cholesterol LB bilayers. We found that each bilayer of lipid mixtures took on uniform distribution bilayer structure when the surface pressure was low. When increasing the surface pressure, great changes were taken place on the bilayers: (1) The bilayers composed of SM/Chol appeared uniform liquid-ordered microdomains structure, with coverage of 80% of mica. (2) In SM/Chol/DOPC bilayers, the liquid-ordered microdomains formed by SM/Chol floated onto the fluid-disordered small DOPC granule, about 30% coverage. (3) When adding DOPE to SM/Chol, the bilayers had changed obviously, meanwhile liquid-disordered, liquid-ordered and gel phases coexisted on the mica. (4) The Ceramide induced the bilayers of SM/Chol rearrangement, the lipids of bilayers occurred flip-flop to form vesicle structure. At the higher surface pressure, all the systems could form specific platform structure. The bond capabilities of molecular groups play an important role in forming structure.

Facile Synthesis of Protected Pentasaccharide Repeat Unit of E.coli O86 O-Antigen

CHENG Shui-Gong, WEI Guo-Hua, DU Yu-Guo

2009, 30(5):  919-922. 

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The protected pentasaccharide repeat unit of E.coli O86 O-antigen was successfully synthesized in seven steps and in 21% overall yield through a combination of HClO₄-SiO₂ solid acid catalytic and inverse procedure. Experimental simplicity, high stereoselectivity, low cost, satisfactory yield are major advantages of our approach. The results of the present exploration should be valuable in the preparation of other oligosaccharides.

Synthesis of Novel β,β-Bridged Porphyrin Dimers and Investigation of Their Photosensitive Activity

HUANG Qi-Mao, XIAO Xin, PAN Zhi-Quan*, LI Zhi-Yuan, DENG Peng-Xing, ZHANG Ying

2009, 30(5):  923-927. 

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Four novel β,β-bridged porphyrin dimers were designed and synthesized. The monomers are 2-(1-hydroxynaphthyl)-5,10,15,20-tetraphenylporphyrin or its Cu(Ⅱ), Ni(Ⅱ), Zn(Ⅱ) complexes. The abilities of singlet oxygen production for the porphyrin dimer and its Ni(Ⅱ), Zn(Ⅱ) complexes under photo irradiation were studied with DPBF as the quencher. The cleavage ability of pBR322 DNA(by gel electrophoresis) and antibacterial activity on Staphylococcus aureus(ATCC 25923) of the novel porphyrin dimers were tested under photo irradiation and in dark. The results show that porphyrin dimers exhibit high photocytotoxicity against Staphylococcus aureus.

Preparation, Characterization and Stability of Neuroglobin Mutant Tyr44Phe

LI Hai-Li, LI Lian-Zhi*, GUO Yu-Jing, TIAN Su-Yan, XUE Ze-Chun, JIANG Yu-Gang

2009, 30(5):  928-933. 

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Neuroglobin(Ngb) is a recently discovered member of the hemoglobin superfamily in nervous system of vertebrates. Tyr44 nearing bis-histidyl ligand His64 contacts with one of the heme propionates by hydrogen bonds, which may involue in the stabilization for the hexacoordinate state of neuroglobin. In order to investigate the role of Tyr44 in structural stabilization of neuroglobin, the neuroglobin mutant Tyr44Phe gene was constructed by site-directed mutagenesis, and the mutant protein was expressed, purified and characterized spectroscopicaly, and its stability was also studied. The electrospray ionization mass spectroscopy result show that the molecular weight of the mutant Tyr44Phe corresponds with the theoretical value. The UV-Visible spectra, fluorescence spectra and circular dichroism(CD) spectra of mutant Tyr44Phe indicated that the mutagenesis doesn′t change neuroglobin’s bis-histidyl heme hexacoordination, but has an effect on heme configuration. Results of stability towards heat and acid show that the mutagenesis decreases the interaction of heme with peptide chain and the heme’s hydrophobic cavity becomes flexible, which proves that Tyr44 plays an important role in neuroglobin structural stability.

Electrochemistry Behavior and Two-photon Absorption Characteristic of C₆₀/C₇₀ Bonded with 1,4-Bis[(carbazole-9-yl)methyl]benzene

TAN Hai-Rong, ZENG He-Ping*

2009, 30(5):  934-937. 

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C₆₀/C₇₀ bonded with 1,4-bis[(carbazole-9-yl)methyl]benzene was synthesized and characterized by FTIR, ¹H NMR and MALDI-TOF. Electrochemical properties of compounds 5 and 6 were studied by cyclic voltammetry. In the meanwhile, two-photon absorption cross-sector values(σ_TPA) of derivatives were also tested by open aperture Z scan experiment.

Design, Synthesis and 5-HT/NE Dual Reuptake Inhibition Activity of Phenylbenzamidine Derivatives

QIN Fang, YANG Jing, WEN Hui, ZHANG Jian-Jun, WANG Ya-Fang, JI Cheng-Xue, ......

2009, 30(5):  938-944. 

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Depression is a kind of common and severe mental illness. Over the past few years, a number of studies have emerged suggesting that treatment with antidepressants which simultaneously enhance both noradrenergic as well as serotonergic neurotransmission including Venlafaxine and Duloxetine may result in higher response or remission rates than treatment with antidepressants which selectively enhance serotonergic neurotransmission. Based on the pharmacophore information and the analysis of structure-activity relationship of SSRIs and SNRIs, a series of substituted phenylbenzamidine derivatives were designed and synthesized in order to search for lead compounds with dual activity. All of them were new compounds, and their structures were confirmed by ¹H NMR and HRMS. Preliminary in vitro pharmacological tests show that all target compounds exhibit 5-HT reuptake inhibition activity and some compounds exhibit NE reuptake inhibition activity. Among the tested, compounds 4b exhibit potent inhibitory activity against 5-HT and NE reuptake in vitro. Compounds 4a and 8a exhibit potent antidepressant activity in vivo. These phenylbenzamidine designed can be further optimized for finding more potent 5-HT/NE dual reuptake inhibitors and antidepressant candidates as well.

Electrical Conductivity Study of Pt/Ce_0.6Zr_0.4O₂ Catalyst in Water-gas Shift Reaction

BI Ya-Dong, XU Heng-Yong*, LI Wen-Zhao

2009, 30(5):  945-948. 

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The catalytic activity for water-gas shift reaction was investigated over Pt catalysts supported on different supports, such as Ce_0.6Zr_0.4O₂, CeO₂ and ZrO₂. The samples were characterized by XRD, temperature-programmed reduction(TPR) and in situ electrical conductivity to evaluate the structure and redox properties. It is concluded that Ce_0.6Zr_0.4O₂ support was a single phase solid solution with high capacity of oxygen transfer, therefore enthanced the catalytic activity of Pt/Ce_0.6Zr_0.4O₂ catalyst, for water-gas shift reaction.

Investigate of Synergistic Effects Mechanism of Mixed Surfactants at the Oil/Water Interface

TAN Jing, CAO Xu-Long, LI Ying*, SONG Xin-Wang, HE Xiu-Juan, CUI Xiao-Hong

2009, 30(5):  949-953. 

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The method of dissipative particle dynamics was adopted to simulate the interfacial orientation of mixed systems between coconut diethanol amide(6501) and dodecyl alpha olefin sulfonate(DAOS),cocoanut amide propyl betaine(CAB), sodium dodecyl benzene sulfonate(SDBS) respectively at the oil/water interface. The effect of salt and molecular structure on the interfacial activity of pure and mixed surfactant systems were investigated. The mechanism of synergistic effects of mixed surfactants is analyzed from the aspects of interfacial efficiency, interfacial density, the array shape of molecules and so on. It was observed that nonionic surfactants have high absorption tendency but low interfacial efficiency, while ionic surfactants have high interfacial efficiency which can be increased with the increase of salinity but low absorption tendency. In the case that ionic or zwitterionic surfactants with higher interface adsorption tendency coexisting with nonionic surfactants, the cavities at the interface layer formed by ionic or zwitterionic surfactants are filled with nonionic surfactant clusters, synergistic effects could be introduced and interface tension could be decreased to ultra low value at low surfactant concentration because of high interfacial efficiency coursed by high interfacial density and high interfacial effectiveness of the mixed surfactants.

Studies on the Kinetics of Thermal Oxidation of Rosin and Abietic Acid on the Polyethylene Film

QIN Rong-Xiu, HUANG Pin-Xian, LIU Xiong-Min*, MA Li, WU Yan-Ling

2009, 30(5):  954-958. 

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The kinetics of thermal oxidation of rosin and abietic acid absorbed on the polyethylene film were respectively studied. The kinetic equation of heat oxidation was determined by UV spectrophotometry. The experimental results show that the thermal oxidation reaction of both rosin and abietic acid are pseudo first order reaction. When the reaction temperatures were 303.15, 308.15, 313.15, 318.15, 323.15 and 328.15 K, respectively, the apparent reaction rate constants of abietic acid were 0.0036, 0.0041, 0.0062, 0.0087, 0.011 and 0.0157 min^-1, respectively. Its reaction activation energy was 50.29 kJ/mol. when the reaction temperatures were 308.15, 313.15 and 318.15 K, respectively, the apparent reaction rate constants of rosin were 0.0009, 0.0015 and 0.0025 min^-1. The reaction activation energy was 80.2 kJ/mol.

Synthesis and Characterization of ZSM-5/Nano-β Core-Shell Composite-Zeolites

TONG Wei-Yi, LIU Zhi-Cheng, KONG De-Jin*, QI Xiao-Lan, GUO Yang-Long*

2009, 30(5):  959-964. 

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ZSM-5/nano-β core-shell composite-zeolites were hydrothermally synthesized by a secondary growth on core ZSM-5 with a uniform size of 1 μm, which was pre-adsorbed with nano-β seeds after pretreated with positive PDDA(poly dimethyldiallylammonium chloride), and then was calcined in air. The obtained products were characterized by XRD, SEM/TEM, and N₂ sorption analysis, which demonstrated the formation of ordered core-shell structure. The results proved the formation of composite-zeolites with a ZSM-5 core(ca.82%) and a poly-nano-β shell(ca.18%). The coverage of shell was tested via S_external measurements of the products, and the core ZSM-5 showed a more compact shell with fumed silica rather than TEOS as the silica source. Moreover, tested by NH₃-TPD and probe reactions on 1,3,5-TMB cracking, it is found that the surface acidity changed after the growth of nano-β layer, and the formed ZSM-5/nano-β has a better catalytic performance(ca.80% conversion) and lower deactivation rate.

Catalytic Activities of MnO_x-CeO₂ Catalysts in Wet Air Oxidation of Pesticide Wastewater

ZHAO Bin-Xia* , ZHANG Xiao-Li, LI Hong-Ya, LIU Lin-Xue, JIN Qi-Ting

2009, 30(5):  965-970. 

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A series of MnO_x-CeO₂ mixed oxide catalysts were prepared by co-precipitation method and used for catalytic wet air oxidation of pesticide wastewater from imidacloprid production. These catalysts were characterized by BET, XRD, XPS. The relationships between the surface structure and catalytic activity, and the effect of the manganese content[i.e. the molar ratio of Mn/(Mn+Ce)] on catalytic activity were researched. BET and XRD data revealed that the particle size of catalyst with n(Mn)/n(Mn+Ce)=0.6 was the smallest, and specific surface area was the biggest in the series of catalysts. XRD and XPS techniques showed that the occurrence of significant interaction between Mn and Ce oxides, resulting in the evolution of textural, structural, oxidation state and the amount of chemisorbed oxygen with manganese content. The highest oxidation state of manganese oxide and the chemisorbed oxygen were present in the surface of MnO_x-CeO₂ mixed oxide catalyst at Mn/(Mn+Ce)=0.7. In the catalytic wet oxidation of pesticide wastewater from imidacloprid production, the most active catalyst was n(Mn)/n(Mn+Ce)=0.7. Using this catalyst, about 89.3%COD removal was attained at catalyst loading of 4 g/L, temperature of 190 ℃, partial pressure of oxygen of 1.6 MPa and influent pH 7.0 for 60 min.

Structure and Electrochemical Performance of Copper Doped Vanadium Oxide Thin Films Deposited by RF Magnetron Sputtering

ZHANG Liang-Tang, SONG Jie, CAI Min-Zhen, XU Fu-Chun, WU Sun-Tao*, ......

2009, 30(5):  971-975. 

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V₂O₅ was used as cathode material for all solid state thin film lithium-ion batteries, so as to improve electrochemical properties of V₂O₅ thin film material. In this paper, copper doped and undoped vanadium oxide films were deposited on silicon substrates by RF magnetron sputtering. The films were characterized by XRD, SEM and XPS. The results show that undoped thin films are polycrystalline-V₂O₅ and copper doped thin films are amorphous copper-vanadium oxide. The Cu ions are at +2 oxidation state, while the V ions are mixed with +4 and +5 oxidation state. With increasing the concentration of doped Cu, the ratio of V⁴⁺/V⁵⁺ increases. The electrochemical tests show that doping copper contribute to increase the capacity of V₂O₅ films. The film with a composition of Cu_2.1VO_4.4 indicate highest capacity among all samples and is observed better cycleability, which is 83.4 μA·h·cm^-2·μm^-1 up to 100 cycles.

Non-Poisson Fluctuation and Non-Nernst Concentration Polarization in Irreversible Electrode Processes with Hysteretic Diffusion-convection Transport

ZHAO Nan-Rong, ZHANG Wen-Hua, LUO Jiu-Li*

2009, 30(5):  976-982. 

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In accordance with the physical picture of boundary layer in the stationary electrode processes with hysteretic diffusion-convection transport we suggest a simple stochastic model to describe this kind of electrode reaction system including the effect of non-equilibrium fluctuations. As a result, a stochastic thermodynamics is established for the concentration polarization arising from hysteresis of the diffusion-convection. Based on it, we further show that the non-Nernst concentration polarization originates in the non-equilibrium fluctuation which departs from the Poisson distributions and even from the central limit theorem, but decreases by the convection companying with diffusion. An example is also given to illustrate the stochastic calculation of the non-Nernst concentration polarization affected by convection.

Effects of Anode Potential on the Electricity Generation Performance of Geobacter sulfurreducens

CAO Xiao-Xin, FAN Ming-Zhi, LIANG Peng, HUANG Xia*

2009, 30(5):  983-987. 

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The anode potential is the critical electrochemical parameter in microbial fuel cells(MFCs), which controls both the energy gain for the microorganisms and the output of MFC. This study aimed at elucidating the effects of anode potentials on the performance of electricigen in MFC. The “H” typed MFCs using Geobacter sulfurreducens as the inoculums were operated at different poised anode potentials. The start-up time, maximum power density and biomass were investigated. The results showed that when operated at anode potentials of -250, -100 and 50 mV versus SCE, MFCs had shorter start-up time and higher power density. The MFC at a potential of -100 mV was proved to have the highest maximum power density of 1.67 W/m³. Also the anode potential affected the biomass.

Direct Experimental Evidence of Ternary Diastereomeric Complexes in Chiral Separations of Phenylglycine Enatiomers with Chiral Mobile Phase by RP-HPLC

YU Qing, CAO Jie*, ZHANG Cheng-Gen

2009, 30(5):  988-991. 

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Chiral separation of D-,L-phenylglycine by RP-HPLC was accomplished by adding a complex of optically active L-Phe-Cu²⁺ to the mobile phase. Chiral separation mechanism was further elucidated in light of unambiguously assigning the structure of the elutents from RP-HPLC by taking advantage of tandem mass spectrometry due to its unique capability of structural identification of the unknows. Mass spectrometry results revealed that the pair of eluents respresented a pair of ternary copper complexes with mixed ligands, providing the first experimental evidence. These complexes are diastereoisomer in nature. The optimized configuration of the diastereoisomer was predicted by theoretical calculation. In addition, the effects of the ratio of Cu²⁺ to L-Phe, pH of chiral mobile phase as well as the concentrations of methanol were investigated.

Theoretical Studies on Electronic Structures and Spectra Properties of Amino 2-(2′-Hydroxyphenyl)benzoxazole Derivatives

YUAN Yan-Jie, HE Rong-Xing, WANG Hui, LI Ming*

2009, 30(5):  992-1000. 

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Density Functional Theory on the Charged Hard-sphere Fluid Confined in Parallel Plates

KANG Yan-Shuang, WANG Hai-Jun

2009, 30(5):  1001-1004. 

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Based on density-functional theory and the modified fundamental measure theory for the classical fluid, the equilibrium density distribution of charged hard-sphere fluid confined in parallel plates was studied. By comparing the density distributions in the case of with and without applied electric field, the effect of the electric field on the molecular density is presented. It is shown that the competition between the Coulomb′s interaction and the field-induced potential energy plays an important role in the aggregated state of charged hard-sphere fluid. The corresponding results can provide helpful clues for understanding quantitatively the properties of plasmas, ionic liquids and electrolyte solutions confined in mesoscopic scale.

Theoritical Studies on the Pyrolysis Mechanism of Pyridazine

HUANG Yu-Cheng, WANG Su-Fan*, JU Xue-Hai, DU Jin-Yan, ZHOU Tao, YE Shi-Yong

2009, 30(5):  1005-1009. 

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The pyrolysis mechanism of nitrogen element in pyridazine as a model compound of coal was investigated by density functional theory(DFT) method. The Mülliken populations, bond dissociation enthalpies and pyrolysis mechanism of title compound were calculated under the(U)B3LYP/6-31G(d,p) level. The single-point energy calculations were performed under the(U)B3LYP/6-311++G(d,p) level for the stationary and transition state structures of pyrolysis processes with the zero-point energy correction. It is shown that the N—N bond has the least population and bond dissociation enthalpy and there is not significant change of the bond dissociation enthalpy for title compound with the temperature increased. The ultimate pyrolysis products are HCN and acetylene according to the calculations. It is proved that NH3 maybe the secondary conversion product of HCN. The rate constants are obtained via Eyring transition-state theory in temperature range of 300—1900 K, the linear relationship between lnk and 1/T is identified.

Theoretical Studies on the Conversion Mechanism Between Double-substituted Ammonium Oxides(R₂HNO) and Double-substituted Hydroxylamines(R₂NOH)——Electronegativity and Steric Effects of Substituents

SHI Guo-Sheng, DING Yi-Hong*

2009, 30(5):  1010-1013. 

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At the B3LYP/6-311++G(d,p) level, we studied the conversion mechanism between the double-substituted ammonium oxides(R₂HNO) and double-substituted hydroxylamines(R₂NOH) with R=NH₂, N(CH₃)₂, N(CH₂CH₃)₂, N[C(CH₃)₃]₂, OH, OCH₃, OCH₂CH₃ and OC(CH₃)₃. It was shown that the thermodynamic and kinetic stability of the double-substituted ammonium oxides R₂HNO are co-controlled by the electronegativity and steric effects. Amongst, the thermodynamic stability of amino-substituted species is dominated by steric effect, whereas that of the alkoxy-substituted species is dominated by electronegativity. The kinetic stability of both amino- and alkoxy-substituted species is mainly influenced by electronegativity.

Theoretical Study on Electronic Properties and Stability of [Mo₆O₁₉]^2- and Tungsten Substituted Complexes Bearing Lindqvist Structure

SHU Xin, ZHOU Xin, PAN Qing-Jiang, LI Ming-Xia, ZHANG Hong-Xing*, ......

2009, 30(5):  1014-1017. 

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In order to understand the effects of substituted W atoms on the Mo Lindqvist-type complexes, the electronic properties and stability of the [Mo₆O₁₉]^2- and its two W substituents were investigated via density functional theory(DFT) method at the BP86 functional level. The results are well consistent with the experimental values. According to the analysis of Mulliken population, bond energy and the frontier orbitals, we concluded that the [4,5-W₂Mo₄O₁₉]^2- is more stable than [4,6-W₂Mo₄O₁₉]^2-, however, the [4,5-W₂Mo₄O₁₉]^2- is more active than [4,6-W₂Mo₄O₁₉]^2-. Our calculations can provide the powerful theoretical support to the experimental investigation of the Lindqvist complexes.

Preparation, Surface Properties and Biological Activity of the Composite of Poly(lactide-co-glycolide) and Bioglass Nanoparticles Surface Grafted with Poly(L-lactide)

DONG Shu-Jun, YU Ting, WEI Jun-Chao, JING Xia-Bin, ZHOU Yan-Min*, ......

2009, 30(5):  1018-1023. 

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SiO₂-CaO-P₂O₅ gel bioglass(BG) nanoparticles with the diameter of 40 nm were synthesized by sol-gel approach. The surface of BG nanoparticles was grafted through the ring-open polymerization of the L-lactide to yield poly(L-lactide)(PLLA) grafted gel particle(PLLA-g-BG). The PLLA-g-BG was further blended with poly(lactide-co-glycolide)(PLGA) to prepare the nanocomposites of PLLA-g-BG/PLGA with the various blend ratios of two phases. PLLA-g-BG accounted 10%, 20% and 40% in the composite, respectively. TGA, ESEM and EDX were used to analyze the graft ratio of PLLA-g-BG, the dispersion of nano-particles and the surface elements of the composites respectively. The rabbit osteoblasts were seeded and cultured on the thin films of composites in vitro. The cell adhesion, spreading and growth of osteoblasts were analyzed with FITC staining, NIH Image J software and MTT assay. The change of cell cycle was monitored by flow cytometry(FCM). The results demonstrated that the surface modification of BG with PLLA could significantly improve the dispersing of the particles in the matrix of PLGA. The nanocomposite with 20%PLLA-g-BG exhibited superior surface properties, including roughness and plenty of silicon, calcium and phosper, to enhance the adhesion, spreading and proliferation of osteoblasts. Our results indicate that the application of PLLA-g-BG with a certain blend ratio can improve the bioactivity and biocompatibility of biodegradable polyester.

Effects of Annealing Condition on the Glass Transition Behavior of PET in R-PET/LLDPE-g-MA Blends

ZHANG Yue, ZHANG Hong-Sheng, GUO Wei-Hong, WU Chi-Fei*

2009, 30(5):  1024-1028. 

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Effects of annealing temperature and annealing time on the glass transition of PET in the Recycle-polycethylene terephatalate(R-PET)/LLDPE-g-MA blends were investigated by DSC. The sub-T_g annealing leads to the enthalpy relaxation in the glass transition region of PET. The T_g of PET shifts to higher temperature with the increase of annealing temperature. The T_g of PET tends to be stable in the blends annealed at 50—70 ℃ for more than 48 h. After above-T_g annealing below 100 ℃, two heat flow transitions of PET appear around the T_g of PET. FTIR results show that molecular conformation of PET begin to change. However, the glass transition of PET disappears in the blend annealed at 100 ℃, and WAXD results show that the crystallinity of PET increases obviously, indicating that the T_cc,on of PET is between 90—100 ℃.

Microstructure and Properties Development of Impact-modified PVC During Photoageing

PI Hong, CHEN Shen-Qing, GUO Shao-Yun*

2009, 30(5):  1029-1034. 

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The effects of acrylonitrile-butadiene-styrene copolymer(ABS), acrylic resin(ACR) and chloride polyethylene(CPE) on photodehydrochlorination, photooxidative degradation and photocrosslinking of poly(vinyl chloride)(PVC) were investigated by UV-Vis, FTIR spectra and DSC. The gel content in exposed sample was estimated gravimetrically. The color change and mechanical properties of PVC during photoageing were also studied. It was found that compared with PVC, the polyene, the carbonyl and the gel content in both PVC/ACR and PVC/CPE blends became much lower after irradiated by UV. The ΔT_g of PVC/ACR blend and PVC/CPE blend were 79% and 24% lower than that of the blank, respectively. However, the reverse phenomena could be found in PVC/ABS blend. Especially, the gel content of PVC/ABS was much higher than that of PVC. These indicate that the addition of ACR and CPE decelerate photodehydrochlorination, photooxidation and photocrosslinking of PVC, while the addition of ABS accelerates the reactions. As a result, the PVC/ACR and PVC/CPE blends have higher color stability and mechanical properties than those of PVC/ABS blend during the photoageing.

Simulation of Banded Spherulite Patterns by Coupled Logistic Map Lattice Model in Three Dimensions

LIU Ying, SUN Zhao-Yan*, AN Li-Jia

2009, 30(5):  1035-1039. 

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Banded spherulite patterns are simulated in three dimensions by means of a coupled Logistic map lattice model. The patterns obtained by numerical calculation are consistent with those in experiments. The simulation results also indicate that the band spacing is decreased with the increase of parameter μ in the Logistic map and increased with the increase of the coupling parameter ε for cube lattices, and increased with the increase of the thickness of the lattice for polymer film, which is quite similar to the results in some experiments. Spiral pattern in three dimensions is also shown in this paper, which helps us understand the form of banded spherulite in polymers.

Preparation of Amylose Crosslinked Poly[(glycino ethyl ester)(alanino ethyl ester) phosphazene] Hybrid Biomaterial

LIN Yi-Jun, LIU Zhi-Ling, DAI Yong-Qiang, CAI Qing*, LI Qi-Fang, JIN Ri-Guang

2009, 30(5):  1040-1045. 

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A kind of novel hybrid material was prepared by crosslinking poly[(glycino ethyl ester)_0.6(alanino ethyl ester)_1.2(chororide)_0.2phosphazene](PAGP₁) with amylose.The results show that the residual P—Cl groups in PAGP₁ can be nucleophilic substituted by hydroxyl groups of amylose in the form of R—ONa. The obtained hybrid polymeric film exhibited no obvious phase separation, which commonly occurred in polymer blends. The crosslinked hybrid material had better mechanical properties than the blended PAGP₂/amylose with similar composition, and was more hydrophilic than pure PAGP₂. This novel material would be a good candidate to be applied for drug-controlled release and tissue engineering applications.

Adsorption of Natural Organic Acids Using Bi-function Resin

WANG Jin-Nan, LI Ai-Min*, XU Li, ZHOU Yang

2009, 30(5):  1046-1051. 

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Natural organic acids are widely existed in dissolved natural organic matter(DOM) in environment, which can form THMs in drinking water disinfection. In this paper, a new kind bi-function resin modified by amine function groups was synthesized to remove these acids from water. Comparing with commercial resin XAD-7, the higher adsorption capacities of fulvic, tannic and gallic acids were observed, such advantages had been explained on the basis of chemical function groups of WJN-07. All the isotherm data for resins in adsorption of three acids can be well fitted by the Freundlich equations, and the equilibrium adsorption capacities of tannic acid are obviously higher than fulvic and gallic acids. Furthermore, values of the enthalpy changes show the adsorption of TA on WJN-07 to be a chemical and endothermic adsorption process. Finally, the changes in the amount of three acids adsorbed on the resin WJN-07 as a function of Pb²⁺ were studied. The capacity of the resin WJN-07 to adsorb these three acids in the presence of Pb²⁺ is significant higher than in the absence of this metal, such changes owing to the interactions of Pb²⁺ with the adsorbed acids and un-adsorbed acids in solution.

Preparation, Structure and Electrochromic Properties of Poly(3,4-ethylenedioxythiophene) Based Conducting Textile

LI Xin*, ZHAO Guo-Liang, QIAN Jing, FU Zhong-Yu

2009, 30(5):  1052-1054. 

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Conductive poly(3,4-ethylenedioxythiophene) coated terylene textile represented by PEDOT/CTT was prepared via in-situ polymerization. It is found that the PEDOT nano-particles with diameter of ~100 nm spread over the surface of terylene fibers resulting in a good conductivity of 2.67×10^-2 S/cm, as measured by a four-probe method. Moreover, the PEDOT/CTT exhibits an electrochromic behavior, which takes a variation of color from pale blue to dark blue when the applied potential changed from -0.42—0 V to 0—1.0 V vs. SCE.