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Table of Content

    10 July 2011, Volume 32 Issue 7
    Contents
    Cover and Content of Chemical Journal of Chinese Universities Vol.32 No.7(2011)
    2011, 32(7):  0. 
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    Review
    Anodic Pd Catalyst in Direct Formic Acid Fuel Cell and Its  Electrocatalytic Stability
    LI Huan-Zhi, SHEN Juan-Zhang, YANG Gai-Xiu, TANG Ya-Wen, LU Tian-Hong*
    2011, 32(7):  1445-1450. 
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    The electrocatalytic activity of the Pd anodic catalyst in direct formic acid fuel cell(DFAFC) for the formic acid oxidation is excellent, while its electrocatalytic satability is poor. The reason and mechanism of the excellent electrocatalytic activity and the poor electrocatalytic stability of the Pd/C catalyst have become an important investigation area of the anodic Pd catalyst in DFAFC. This paper mainly summarizes the situation of research and development of anodic Pd catalyst and Pd\|based composite catalysts in DFAFC. The advantages and disadvantages of the Pd catalyst, the mechanisms of the poor electrocataltic stability of the Pd catalyst, the methods and the mechanism of the increase in the electrocataltic stability of the Pd catalyst are reviewed.
    Preface
    Preparation and Optical Properties of One-dimensional Sub-microstructures of Naphthalene-1,4-dicarbonitrile
    2011, 32(7):  1451-1455. 
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    Solid and tubular one-dimensional (1D) submicrometer scaled structures were prepared from naphthalene-1,4-dicarbonitrile (DCN) with a reprecipitation method. The DCN microstructures have good crystallinity, and the growth direction of the solid structures are different from those of the tubular ones. Because of the ordered molecular packing of DCN, the fluorescence emission spectra of the microstructures undergo a red-shift compared with that of DCN solution. The microstructures reveal good optical waveguiding properties, and the optical loss of the materials are reduced by the air medium in the tubular structures.
    Spectral Studies on the Interaction Between VB6 and Various CopC
    SONG Zhen, ZHENG Xiao-Yan, PANG Er-Guo, YANG Bin-Sheng*
    2011, 32(7):  1456-1459. 
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    The interaction between silver ion and apoCopC, CuN-CopC was investigated through different UV and fluorescence spectra in 10 mmol?L-1 Hepes, pH 7.4, at room temperature. Moreover, the supramolecular behavior between apoCopC, CuN-CopC, CopC-AgC , CuN-CopC-AgC and Vitamin B6 was further studied. The results suggested that the silver ion can occupied the Cu+ site in the 1:1 CopC-AgC complex and the binding constant is (1.68±0.33)×104mol?L-1. After binding of metal ions, the number of binding sites between different proteins and Vitamin B6 was reduced.
    Adjustable Dispersive Property of the Nanocomposite of Gold Nanoparticles in Amino-functionalized  Mesoporous Silica Thin Films
    FANG Jing-Yue, QIN Shi-Qiao, ZHANG Xue-Ao*, LI Xin-Hua, WANG Fei, CHANG Sheng-Li
    2011, 32(7):  1460-1465. 
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    The highly ordered amino-functionalized mesoporous silica thin films (MTFs) have been directly synthesized by co-condensation of tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTES) in the presence of P123 (EO20PO70EO20). Using the neutralization-reaction mechanism followed with a reduction procedure of hydrogen-ambience calcinations, the gold nanoparticles have been effectively introduced into the pore channels of amino-functionalized MTFs, and obtained the Au/SiO2 nanocomposite. The nanomaterials were characterized by XRD, TEM, and UV-vis. It was found that removing the surfactant by ethanol extraction can get well-ordered mesoporous structures compared with the calcinations; gold nanoparticles grow in a preferred orientation of (111) planes of the face-centered-cubic structure in the pore channels and crystallized nicely; the absorption spectrum of Au/SiO2 nanocomposite undergoes a red-shift as the reaction time increase. It is a quantum size effect of gold nanoparticles, and shows that the dipping time could regulate the dispersive property of Au/SiO2 nanocomposite.
    Microwave Synthesis and Electron Transfer Properties of a Series of New Porphyrin-anthraquinone Hybrids with Dipeptide Link and Their Metal Complexes
    CHEN Nian-You*, ZHAO Sheng-Fang, DONG Jia-Qing, TIAN You-Ping, LI Zao-Ying
    2011, 32(7):  1466-1471. 
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    This paper reports the microwave synthesis of a novel porphyrin—anthraquinone hybrid with dipeptide link and its metal complexes. The new compounds have been confirmed by 1HNMR,IR,UV-Vis spectra and elementa1 analysis.The intramolecular electron transfer property (IETP)of these compounds was studied,the influence of the structure for IETP was discussed.
    Convenient Preparation and Characterization of Surface Carboxyl-functioned Fe3O4 Magnetic Nanoparticles
    SU Peng-Fei, CHEN Guo*, ZHAO Jun
    2011, 32(7):  1472-1477. 
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    Hydrophilic magnetic nanoparticles have been widely applied in biological sciences. In this work, we propose a convenient method to synthesize surface carboxylic magnetic nanoparticles. Firstly, hydrophobic magnetic nanoparticles coated with oleic acid were prepared from ferric chloride and ferrous chloride by co-precipitation method, with oleic acid as surfactant. Then the C=C bond of oleic acid coated on the surface of particles was oxidized into -COOH by KMnO4 solution in situ, thereby gaining hydrophobic magnetic nanoparticles with monolayer carboxylic groups functioned. The magnetic nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), Zeta potential analyzer and so on. The results showed that magnetic nanoparticles surface was successfully carboxyl-functioned. The average diameter and the saturation magnetization of the nanoparticles were about 9nm and 64.5emu/g, respectively. The remnant magnetization and coercivity of the nanoparticles were nearly to be 0, which demonstrated it was classic superparamagnetic. The carboxyl-functioned magnetic nanoparticles can be dispersed into water to form ferrofluid, which are stable for more than 6 weeks without precipitation in the pH range of 7-10.
    Synthesis of Spherical Mesoporous SBA-15  with Abundant Carboxyl and Drug Release Profile
    NIE Xin, QU Feng-Yu, LI Xiao-Feng, LIN Hui-Ming
    2011, 32(7):  1478-1482. 
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    Mesoporous SBA-15 spheres with abundant carboxyl were synthesized dy a one-step method. The effect of CTES on the morphologies, pore sizes and BET surface areas of mesoporous SBA-15 have been investigated. The samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption/desorption and infrared (IR). The morphologies of as-obtained products are sphere-like shapes. The materials possess highly ordered hexagonal mesoporous structure, and large specific surface area and pore volume, and the pore sizes range from 0.5 to 1 μm. The results show the pore size and the surface area of the materials decrease with the increase of modified dosage, obviously. The assembly and delivery test shows that the material has good assembly and drug delivery profiles. As-synthesized products have potential applications in catalysis, drug delivery and fillings for chromatography analysis.
    Oxygenation Reaction of Histidine Cobalt Complex by Electrospray Tandem Mass Spectrometry
    FU Ji-Hong, LI Jun-Fang, FU Pei, YUE Fan, ZHANG Xu-Long, WANG Ji-De*
    2011, 32(7):  1483-1487. 
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    Histidine-cobalt compex is a known model compound of oxygen carriers. The investigation of its oxygenation is of great significance in revealing the oxygenation mechanism of reversibly absorbing oxygen. In this paper, a new method was proposed to directly investigate the oxygenation reaction of histidine-cobalt compex by electrospray tandem mass spectrometry. The fragment ions of the oxygenated complexes were found from both aqueous samples of histidine-cobalt compex separately adsorbing oxygen at early 10-20 minutes and continuously adsorbing oxygen for 24 hours. The fragment ions of the oxygenated complexes were confirmed by its sub-fragment ion which just lost a neutral fragment of dioxygen by further fragmentating. Based on these results, the structure, mechanism and the form of dioxygen existed in the complex were deduced. The results showed that the absorption process is a dynamic process, and the structure of the complex could be changed from dinuclear superoxo-bridged complex to dinuclear superoxo-hydroxo dibridge complex according to the progress of oxygenation time. ESI-MS method can be an effective technique of researching the oxygenation reaction and characterizing oxygenated complexes
    Methyl Chloroacetate as Extraction Solvent for Coupling Liquid-liquid Semimicroextraction with Micellar Electrokinetic Chromatography for the Separation of Neutral Compounds with Concentration Enhancement
    TANG Jing*, ZHENG Sheng-Biao, ZHU Jin-Kun, WANG Tian-Lin
    2011, 32(7):  1488-1491. 
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    This paper reports the use of methyl chloroacetate (MCA) as an extraction solvent for coupling liquid-liquid semimicroextraction (LLsME) with micellar electrokinetic chromatography (MEKC) through on-capillary decomposition for the separation of neutral compounds with concentration enhancement. Alkylphenones of C8, C10 and C11 were chosen as modeling compounds. Aqueous samples of the ?alkylphenones were extracted by LLsME into methyl chloroacetate. The organic phase was directly subjected to separation by MEKC. The detection limits (S/N≥3) were 50, 50 and 100 μg/L (ppb) for butyrophenone, valerophenone and acetophenone in water, respectively, and the concentration factors of the extraction were in a range of 63 to 151-fold in terms of peak area for the three alkylphenones. The method developed has no requirement on any special experimental apparatuses other than a basic CE setup and is time-saving and easy in operation. Therefore, it would be readily acceptable for routine analysis, especially for environmental samples.
    Fluorescence Spectroscopy Study on the Interaction Between Pd(Ⅱ) and Tryptophan, Tyrosine and Phenylalanine
    XU Qian-Ying, LIU Zhong-Fang, HU Xiao-Li, KONG Ling, LIU Shao-Pu*
    2011, 32(7):  1492-1496. 
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    When Pd(Ⅱ)reacted with tryptophan(Trp), tyrosine(Tyr) and phenylalanine(Phe), the fluorescence of the three aromatic amino acids was all quenched. From the change of absorption spectrum, the effect of the temperature and the quenching constant Ksv, this procedure was judged to be static quenching on account of Pd(Ⅱ)interacting with the above amino acids to form groundstate coordination compounds. We also thought that in present of certain concentration of Cl-, Pd(Ⅱ)coordinated with amino acids respectively by N, N and N, O to form mixed-type ternary complexes Pd(HR)Cl2 (Trp and Phe system) and Pd(H2R)Cl2(Tyr system), the corresponding structures were presumed. This fluorescence system could not only be used in the study on the interaction between Pd(Ⅱ)and above aromatic amino acids, but also be foundation of fluorescence quenching method determining Pd(Ⅱ)using amino acid (especially Trp ) as probe.
    Distribution and Transition of Stable Conformations of Hen Egg White Lysozymes in Their Unfolding Induced by Urea and Guanidine Hydrochloride Solutions
    ZHANG Tan, BIAN Liu-Jiao*
    2011, 32(7):  1497-1505. 
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    The unfolding of egg white lysozymes induced by urea and guanidine hydrochloride was studied by using intrinsic fluorescence emission spectra and phase diagram method of fluorescence. The result showed that in these two unfolding procedures, an egg white lysozyme intermediate separately existed at about 4.0 mol/L of urea or 3.0 mol/L of guanidine hydrochloride in denaturation solution, and both of these two unfolding procedures followed a three-state model. Based on the three-state unfolding, an equation which describes the residual activity ratios of egg white lysozymes under different urea and guanidine hydrochloride concentrations in denaturation solution was presented and through this equation two characteristic unfolding parameters, the thermodynamic equilibrium constant k for the conformational transition of protein molecules from their one conformational states to their another ones and the number m of denaturant molecules associated with one protein molecule during the unfolding of protein molecules, can be simultaneously derived. Through using these two characteristic unfolding parameters, we could further describe the distribution and transition of each conformational state of egg white lysozymes under different urea and guanidine hydrochloride concentrations in denaturation solution.
    Selective Recognition of Fluoride Ion Based on 2,6-Dibenzamide Pyridinium Hydrochloride
    XUE Yun-Rong, ZHANG Li-Feng, DONG Zhi-Yun, GAO Guo-Hua*
    2011, 32(7):  1506-1511. 
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    2, 6-Dibenzamide pyridinium hydrochloride (3) has been synthesized and applied to recognize anions. Fluorescence and UV-Vis spectrum show that receptor 3 can selectively recognize fluoride and form 1:1 complex, along with visible color change and remarkable fluorescence quenching. The molecular structure of receptors and complex with fluoride are simulated by Gaussian03. The receptor 3 combines with F- through hydrogen bond interaction including N-H …F- and (N-H) + …F-.
    Effect of  Tangshen Formula  on Phospholipids Metabolism of OLETF Rats
    ZHU Chao, HUANG Min, LIANG Qiong-Lin, WANG Yi-Ming, HU Ping, LI Ping, ZHANG Hao-Jun, LU Xiao-Guang, LUO Guo-An*
    2011, 32(7):  1512-1518. 
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    As one of the most common endocrine diseases, diabetic mellitus (DM) has a very close relationship with phospholipids metabolism. Tangshen Formula (TSF) is an often-used prescription with good efficacy for treating DM and diabetic nephropathy (DN). The aim of this study is to understand the effect of TSF on phospholipids metabolism of DM. In this paper, Otsuka Long-Evans Tokushima Fatty (OLETF) rats, a model of slowly progressive obese type 2 diabetes, were employed. Phospholipids profiling of rat plasma was established by using normal phase liquid chromatography-time of flight mass spectrometry (NPLC-TOF/MS). Partial least-squares discriminant analysis (PLS-DA) and quantification of 14 compounds were applied to evaluate the effect of TSF on phospholipids metabolism of OLETF rats and to discover potential biomarkers. The results showed plasma phospholipids metabolic disorders occurred in OLETF rats. The good effect of TSF on phospholipids metabolism was compared with the adverse impact of Monopril. TSF is able to significantly improve phospholipids metabolism of OLETF rats, whereas Monopril exacerbated disturbance of phospholipids metabolism. According to quantitative results, a total of 8 phospholipids compounds which have significant concentration variation between control group and model group were considered as potential biomarkers of type II diabetes.
    Crystal Structure and Theoretical Studies of 3,6-Dihydrazino-1,2,4,5-tetrazine
    FENG Jin-Ling, ZHANG Jian-Guo*, WANG Kun, ZHANG Tong-Lai*
    2011, 32(7):  1519-1525. 
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    3,6-dihydrazino-1,2,4,5-tetrazine (DHT) was synthesized and the single crystal was obtained through slow evaporation of saturated dimethyl sulfoxide solution. The molecular structure was determined by X-ray single crystal diffraction. The crystal belongs to the monoclinic system with a P2(1)/c space group, a=4.032(4) ?, b=5.649(6) ?, c=12.074(14) ?. β=99.32°, Z=2, V=271.4(5) ?3. The tetrazine ring and nitrogen atoms of hydrazino-group are almost coplanar with an axial symmetry structure. A three-dimensional herringbone-like pattern was formed with the extensive hydrogen bonds. Combustion heat and explosion point were obtained through the experiment as 1787kJ?mol-1 and 454 K. The electronic structure and natural bond orbital (NBO) were studied using the density functional theory (DFT) method at the B3LYP/6- 311G* level. The standard heat of formation calculated through the atomic energy method is 1075 kJ?mol-1, which approaches with the experiment value. DHT presents a satisfactory detonation performance, with detonation velocity D of 9.27 km?s-1 and detonation pressure P of 36.02 GPa, both of which are higher than those of TNT and HMX counterparts.
    Biotransformation of Aconitum Alkaloids Before and After the Combination of Radix Aconiti Preparata by Rat Intestinal Flora Using Semiquantitative Analysis Method of Electrospray Ionization Mass Spectrometry
    WANG Xi-Ye, PI Zi-Feng, LIU Wen-Long, SONG Feng-Rui, LIU Zhi-Qiang, LIU Shu-Ying*
    2011, 32(7):  1526-1531. 
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    The biotransformation of diester-diterpenoid alkaloids, monoester-diterpenoid alkaloids and lipo-alkaloids in the co-decoctions of Chinese medicine pairs was studied by electrospray ionization tandem mass spectrometry, and semiquantitativ ananlysis method of electrospray ionization tandem mass spectrometry was established for analysis of aconitum alkaloids before and after metabolism. The content changes of aconitum alkaloids with was analyzed under rat intestinal bacteria in the metabolic process of the co-decoctions of Radix Aconiti Preparata with Bulbus Fritillariae Thunbergii, Rhizoma Pinelliae Preparatum and Ampelopsis Japonica. The results showed that Bulbus Fritillariae Thunbergii increased the content of diester-diterpenoid alkaloids in co-decoction, Rhizoma Pinelliae Preparatum reduced the content of diester-diterpenoid alkaloids in co-decoction, and Ampelopsis Japonica almost has no effect on the content of diester-diterpenoid alkaloids in co-decoction, after the combination; The rat intestinal bacteria can more reduce the toxicity of diester-diterpenoid alkaloids and increase the content of lipo-alkaloids. The mechanism of combination and metabolism of traditional Chinese medicine was proved by the analysis of the content changes of aconitum alkaloids in the processes of combination and metabolism of Chinese medicine pairs
    Synthesis and Imaging Study on the FITC Labeled Folic Derivative
    XIE Jiang, ZHU Jian-Hua
    2011, 32(7):  1532-1536. 
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    The aim of this work is to study on the tumor targeting of the FITC labeled folic derivate. N-(2-aminoethyl)-2-(4-aminophenyl)acetamide was synthesized by 2-(4-aminophenyl)acetic acid and coupled with α- and γ-carboxyl of folate, DMAP/EDCI was used as a coupling reagent to synthesize folate-derived FA-EA, FA-EA was labeled with FITC to get the compound FA-EA-(FITC)2. All the intermediates were identified with HPLC、1H NMR and MS. In vivo fluorescent imaging was carried in KB tumor-bearing nude mouse injected with FA-EA-(FITC)2 through tail vein, the distributions of FA-EA-(FITC)2 in major organs and tumor were observed after sacrificing KB tumor-bearing nude mouse which had been photographed in vivo. The results indicated that FA-EA-(FITC)2 accumulated within tumor obviously while it was nearly invisible in major organs, it manifest that FA-EA-(FITC)2 have preferable ability to target tumor. This work can supply evidence for further developing tumor-imaged agent on folate.
    Synthesis,  Structure and Si—Si Bond Stability of η6-[Tris(trimethylsilyl)phenylsilane]tricarbonylmolybdenum Complexes
    LIU Qiu-Hua, SUN Huai-Lin
    2011, 32(7):  1537-1540. 
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    Tris(trimethylsilyl)phenylsilane, (SiMe3)3SiC6H4R (R = H, p-Me and p-MeO), reacted with tripyridine(tircarbonyl)molybdenum in the presence of BF3, giving corresponding ?6-[tris(trimethylsilyl)phenylsilane]tricarbonylmolybdenum complexes, ?6-[(SiMe3)3SiC6H4R]Mo(CO)3. The new complexes were characterized by 1H、13C NMR、IR and elemental analysis. The molecular structure of ?6-[(SiMe3)3SiC6H4R]Mo(CO)3 (R = H) has been determined by the X-ray diffraction method. The Si-Si bonds in the complexes were found to be stable towards the intramolecular transition metal atom.
    Synthesis and Characterization of N,N'-Diethoxycarbonyl-O,O'-alkyl-dithiocarbamates
    YUAN Lu, ZHONG Hong*, LIU Guang-Yi, XIA Liu-Yin, LI Li-Qing
    2011, 32(7):  1541-1544. 
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    The synthesis and research of thiocarbamate which contains two eater group and two acylamide group was reported. The intermediate N-ethoxylcarbonyl isothiocyanate was synthesized from ethyl chloroformate and sodium thiocyanate by nucleophilic substitution reaction and isomerization. Then using this intermediate with diols as raw materials, the target products N,N’-diethoxycarbonyl-O,O’-alkyl-dithionocarbamates were obtained by nucleophilic addition reaction. The compounds were characterized by elemental analysis, infrared spectrum, 1HNMR and 13CNMR. Small scale flotation experiments showed that, when the dosage of target compounds a~c was 6 g/t, the grade of Cu can reached to 6.12%, 6.35% and 5.92% respectively, the recovery of Cu can reached to 75.31%, 76.50% and 76.35% respectively, the dosage of each collector was far lower than butyl xanthate, while the grade and recovery were higher. So this kind of dithionocarbamates is suggested to be applied in the flotation of sulfur copper as a new collector.
    Synthesis and Anti-TMV Activity of Novel Poly-substituted Pyrimidine-5-amino Amide and Aryl(Thio)urea Derivatives
    XU Wei-Pan, ZHANG Da-Qiang, LI Ru-Xing, YANG Xin-Ling, WANG Dao-Quan, YUAN De-Kai*, FAN Zhi-Jin
    2011, 32(7):  1545-1550. 
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    Pyrimidine plays important roles in pesticide innovation research and pyrimidine sub-structure can be easily found in fungicides, herbicides and insecticides or miticides, etc. As this ring can be easily modified, that makes it more reachable to design and synthesis of novel bio-active heterocycle compounds from some pyrimidine structures. Based on our previous studies on pyrimidine and purine, three series of novel poly-substituted pyrimindine 5-amino derivatives (4) were designed and obtained in high yields by using 2-N,N-diethylamino-4-chloro-5-nitropyrimidine (1) as starting material via substitution, reduction and acylation procedures in turn. The priliminary bioassay results indicate that nearly all the target compounds processing good anti-TMV activity, but no herbicidal or fungicidal activities. Among them, compound 4l exhibits the highest inhibition value, which is higher than that of the positive control virazole (ribavirin) at the same concentration.
    Selective Hydrogenation of Cinnamaldehyde over Pt-Co/ZrO2 Catalyst in the Solvent System of Ethanol/Water
    SUN Cui-Zhi, ZHOU Ren-Xian*
    2011, 32(7):  1551-1555. 
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    The selective hydrogenation of cinnamaldehyde (CMA) to the corresponding cinnamyl alcohol (CMO) was investigated over Pt-Co/ZrO2 catalyst in the solvent system of ethanol/water. Pt-0.4wt.%Co/ZrO2 showed the better catalytic activity for selective hydrogenation of CMA and the higher selectivity to the formation of CMO. The texture of ZrO2 support together with the properties of reducers used in the catalyst preparation, played an important role in the selective hydrogenation of CMA over Pt-Co/ZrO2 catalyst. The support with higher BET surface area and larger pore size was favorable for the dispersion of active phases, as well as the adsorption of reactant molecules, leading to higher catalytic activity. A synergy effect between Pt-Co-B was observed when KBH4 was chosen as the reducer. It significantly promoted the catalytic activity of the catalyst and the selectivity of CMA to CMO.
    Interfacial Interactions Among Aromatic Side Chained N-Acyltaurates Studied by Interfacial Tension Relaxation Measurements
    CUI Xiao-Hong, ZHANG Lei, ZHAO Rong-Hua, LUO Lan, ZHANG Lu*, ZHAO Sui, YU Jia-Yong
    2011, 32(7):  1556-1562. 
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    The dilational viscoelastic properties of sodium N-2-(phenoxy)-tetradecanolytaurinate (12+B-T), sodium N-2-(4-ethylphenoxy)- tetradecanolytaurinate (12+2B-T) and sodium N-2-(4-hexylphenoxy)-tetradecanolytaurinate (12+6B-T) at the air/water and oil/water interfaces were investigated by interfacial tension relaxation method. The effect of aromatic side-chain length on interfacial behavior has been expounded. The influences of surfactant structures on the concentration dependences of limiting dilational elasticity, maximum of dilational viscosity and involving characteristic frequency have been obtained. It is found that 12+6B-T can form more elastic adsorption film at low bulk concentration and surface re-arrangement process controls the nature of film due to the existence of stronger interactions among longer length of aromatic side-chains. Diffusion-exchange process becomes to dominate interfacial behavior with the decrease of interactions by the increasing bulk concentration or the insertion of decane molecules.
    Fabrication of Reproducible SERS Substrate at Toluene/Water Interface
    ZHANG Xue-Jiao, MEI Jin-Hua, NI Dan-Dan, GUO Qing-Hua, XU Min-Min, YAO Jian-Lin*, GU Ren-Ao
    2011, 32(7):  1563-1566. 
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    The Au@SiO2 core-shell nanoparticles with a shell thickness of 4 nm were prepared by the hydrolysis of sodium silicate in boiling water. A novel method for the assembly of Au@SiO2 nanoparticles film at a toluene-water interface has been developed to prepare a close-packed monolayer film. The film was transferred onto a Si substrate. As a comparison, Au@SiO2 nanoparticles were chemically attached on to ITO substrate. The surface enhanced Raman scattering (SERS) activities and reproducibility of the above two kinds of film substrate were investigated by using 1,4-dithiophenol (1,4-BDT) as probe. The results revealed that the shell of SiO2 avoided the direct contact between the probe and the substrate. The adsorbed probe molecules can be removed by the immersion of the substrate into NaBH4 solution. The Au@SiO2/ITO substrate exhibited poor reproducibility and the SERS activity decreased with the increase of the washing times, while the compact film on Si substrate fabricated from the water-toluene interface showed the high stability and reproducibility for the SERS effect. The Au@SiO2 film formed on the double phase interface could be used as a reproducible SERS substrate.
    Depletion Potential Between Two Colloid Particles in an Associating Fluid: a Density Functional Theory Study
    GU Fang, WANG Hai-Jun*
    2011, 32(7):  1567-1572. 
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    The depletion potential between two colloid particles immersed in an associating fluid is investigated by the classical density functional theory for depletion potential proposed by Roth, Evans and Dietrich. An attempt is made to obtain the effects of several factors concerning colloid particles and solvent molecules on the depletion potential, which are the bulk density of solvent, size ratio of colloid particle to solvent, functionality of solvent and its associated energy, and the interaction between colloid particle and solvent. With the depletion potential under various conditions being presented, it is shown that the effects of these factors on the depletion potential are significant, and this can provide some useful clues on regulating the interaction between colloid particles in the related experiments.
    Preparation and Gelation Behavior Studies of Two Dimeric Cholesterol Based Low Molecular Mass Gelators Containing Different Stereoisomerisms
    ZHANG He-Lan, YAN Ni, WU Si-Wen, CAI Xiu-Qin, LIU Kai-Qiang, FANG Yu*
    2011, 32(7):  1573-1580. 
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    Two cholesterol-containing low molecular mass gelators (LMMGs) of A(LS)2 type with glycin in the linkers and butene diacid in the A part were prepared. Their gelation abilities were evaluated in 30 commonly found organic solvents. It was found that the change in the stereo-structure of the linker can produce a dramatic effect upon the gelation behaviors of the compounds. Interestingly, MA-C gels CCl4 spontaneously at room temperature, and the gel as formed exhibits good thermal stability and thixotropic property as revealed by rheological studies. More interestingly, MA-C shows phase- selective gelation of CCl4 from its mixture with water. SEM observation demonstrated that the morphologies of the aggregates of the gelators in the gels depend, but not only, on the structures of the gelators. The concentrations of the gelators, and even their interactions with the solvents also showed great effect upon the morphologies. Temperature and concentration dependent 1H NMR measurements revealed that inter-molecular hydrogen bonding and π-π stacking among the molecules of the gelators are important driving forces for the formation of the gels. XRD study revealed that MA-C assembled into a layered structure in its CCl4 gel.
    Density Functional Theory of Second-order Nonlinear Optical Properties of a Series of Organic Dendrimer Molecules with an Imidazole Chromophore
    LIN Bin-Bin*, CHEN Han, QIU Yong-Qing, SU Zhong-Min
    2011, 32(7):  1581-1587. 
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    Density functional theory (DFT) B3LYP/6-31G* method was employed to optimize the structures of a series of organic dendrimer molecules containing a imidazole chromophore.Results show that the molecules possess A-π-D-π-A (A: acceptor, D: donor) structures, and the dipole moment of the ground state, the polarizability, and the second-order NLO coefficient (β) of the molecules increase with increase of the length of conjugate bridge of the branched chain and the conjugation effect of the chromophore.The molecule with smaller energy gap of the frontier molecular orbital shows larger values of βtot. The calculated electronic absorption spectra of the organic dendrimer molecules exhibit the most intensive excitations in the low-lying region 247.79nm-419.87nm,which are arisen from the charge transfers from Homo to Lumo.
    Theoretical Studies on Photodissociation Mechanism of Glycoladehyde
    CI Cheng-Gang, DUAN Xue-Mei, LIU Jing-Yao*, SUN Chia-Chung
    2011, 32(7):  1588-1593. 
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    The electronic structures of the stationary points and dissociation potential energy surfaces (PES) of glycolaldehyde (HOCH2CHO) in the lowest three electronic states (S0, S1 and T1) have been calculated at the CASPT2//CASSCF/6-311+G(2df, 2p) level of theory by using the multi-reference state method. Combining with the surface intersection points, the wavelength-dependent photolysis mechanisms leading to probable photolysis products have been elucidated. It is shown that in the experimental photolysis wavelength range of 240 – 400 nm, the HOCH2CHO molecule mainly occurs the dissociation reactions on the S1 surface or decays to the ground state via the S0 and S1 vibronic interaction, followed by S0 dissociation reactions. The C-C bond fission to yield ground-state products HOCH2 (2A′)+ HCO (2A′) is the dominant pathway, while in the certain wavelength range, the S0 concerted channel to produce CH3OH (A′) + CO (A1), H-elimination of the aldehyde group and OH-elimination channels are also energetically accessible. The present calculated results show good agreement with the experimental observations.
    Effects of Micro- and Nano-structure on the Adhesive Property of Rose Petals
    WANG Ming-Chao, YANG Qing-Lin, WANG Chun, WANG Jing-Ming*, JIANG Lei*
    2011, 32(7):  1594-1597. 
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    Superhydrophobic surface with high adhesive force has attracted great interest in recent years. An intriguing example is the red rose petals, which is famous with its “petal effect” (i.e. the water droplet adhesion effect) and its novel hierarchical micro-/nano- structure. In this article, the surface adhesive effect was characterized by the high-sensitivity microelectromechanical balance system, and the effects of micro- and nanostructure on the adhesive property of rose petals was investigated. The morphology of obverse and reverse surface of fresh and dry rose petals were observed by environmental scanning electron microscope (ESEM), and the wettability was characterized by the apparent contact angle. The experimental results show that surface hydrophobicity can be enhanced by the micro-scaled structure and the high adhesive force is mainly caused by the nano-scaled structure. It is believed that this work will provide us a new avenue to further understand the wettablilty of solid surface, and design novel microfluidic devices in a wide range of applications, such as many localized chemical or biological reactions, traced analysis, and in situ detection.
    Preparation and Stability of Quaternary Ammonium Based Solid Alkaline Electrolyte Membrane for Fuel Cells
    FU Jing, QIAO Jin-Li*, MA Jian-Xin
    2011, 32(7):  1598-1604. 
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    The solid alkaline electrolyte membranes have been succesfully prepared from poly(vinyl alcohol)/poly(acrylamide-co-diallyldimethylammonium chloride) (PVA/PAADDA) by chemical cross-linking. The molecular structure, morphology, thermal stability, alkali resistance durability, dimensional stability and conductivity of the PVA/PAADDA membranes were characterized using fourier transform infrared spectra (FTIR), scanning electron microscope (SEM), thermogravimetric analysis (TGA) and alternating current impedance technique. FTIR results indicated that PAADDA was successfully blended in the polymer matrix. The phase separation of the PVA/PAADDA membrane in 1:1 mass ratio was observed by SEM. From the TGA, the increasing content of PAADDA into polymer matrics has little effect on the thermal stability and, the good thermal stability around 210 oC was obtained . The membranes showed perfect alkali resistance durability even conditioned at elevated temperatures and high concentration of KOH (80 oC, 6 mol?L-1). Meanwhile, the PVA/PAADDA membrane exhibited good dimensional and conductivity stability towarded water at 60 oC after 300 h due to its dense semi-interpenetrating networks in polymer matrics. In addition, the methanol uptake of the PVA/PAADDA membrane showed almost no changes after conditioned at elevated temperatures and, were 5 times lower than that of Nafion115 membrane after conditioned at 90 oC.
    Effect of CeO2 on the Silver Species and Its Catalytic Activity for  CO Oxidation
    QU Zhen-Ping*, ZHANG Xiao-Dong, CHEN Dan, LI Xin-Yong, WEN Meng, WANG Yi, MA Ding, WU Jing-Jing
    2011, 32(7):  1605-1609. 
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    8 wt% Ag/CeO2-SiO2 catalysts for CO oxidation were prepared by an incipient wetness co-impregnation and two-step impregnation methods. XRD, UV-Vis, BET were used for the characterization of the catalysts and the catalytic activity for CO oxidation was studied. The effects of CeO2 on the silver active species for CO oxidation were discussed. It was found that 8 wt% Ag/1 wt%CeO2-SiO2 showed better catalytic activity for CO oxidation, and the activity was further increased after hydrogen treatment. XRD and UV-Vis characterization results showed that CeO2 favored the dispersion of Ag particles on the surface of SiO2, and silver cluster was the main silver species when more CeO2 is supported on the surface of SiO2.
    FTIR and Thermal Αnalysis  of Silver-doped Hybrid Silica Material by Sol-gel Method
    YANG Jing*, HOU Hai-Yun
    2011, 32(7):  1610-1616. 
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    Ag/MTES-SiO2 hybrid material was prepared by sol-gel method, in which AgNO3 was added into methyl-modified silica sol. According to XRD, FTIR spectra and TG-DTG analysis, the thermal stability of Ag/MTES-SiO2 hybrid material was discussed. The activation energies and frequency factors were figured out by using Coast-Redfern intergral method and Αchar differential method. The results show that, metallic nano-silver peaks can be clearly found in the silica materials calcined above 120°C. The metallic silver results from the reduction of AgNO3. The Si?CH3 vibrational bands disappear completely when the calcination temperature is increased to 600 ℃, which mineralized when the calcination temperature is further increased to 750 ℃. The introduction of Ag nanoparticles nearly has no influence on the thermal stability of -CH3 groups. As the calcining temperature is increased, the diffraction peaks of metallic silver in intensity and the tendency of silica particles to form crystals increase. The metallic silver results from the reduction of AgNO3. There are four steps in the thermal decomposition of Ag/MTES-SiO2 materials in N2 atmosphere, with different mechanism functions. The activation energies are 71.92、125.78、235.73 and 417.37 kJ?mol?1, and the frequency factors are 1.18×109、7.14×1010、8.35×1013 and 1.16×1020 s?1 for the four steps, respectively.
    Carbonization Treatment of Diatomite with High Ignition Loss and Reinforcement of Natural Rubber
    XUE Bing, JIANG Yin-Shan, YANG Dian-Fan*, SHI Xiao-Di
    2011, 32(7):  1617-1621. 
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    A carbonized diatomite was prepared by calcining Inner Mongolia diatomite rich in organic matter under reducing atmosphere. The carbonized diatomite was partly substituted for carbon black to reinforce natural rubber (NR). Fourier-transform infrared spectra (FTIR), X-ray diffraction (XRD), thermoanalysis (TG-DTA), scanning electron microscope (SEM), energy-dispersive spectrometer (EDS) and mechanical properties test were employed to character the resultant carbonized diatomite and NR vulcanizates. The results showed that the organic matter in diatomite could be translated into amorphous carbon adsorbed on the surface of diatomite and in the micropore of diatomite after 600oC calcination under reducing atmosphere. Because the carbon in carbonized diatomite could improve the compatibility between diatomite and NR, the introduction of carbonized diatomite into NR matrix could enhance the mechanical properties. When 25wt% carbon black was replaced with carbonized diatomite, the tensile strength and tear strength of NR vulcanizates was significantly improved.
    Preparation and Bioactivities of PLGA/Nano-hydroxyapatite Scaffold Containing Chitosan Microspheres for Controlled Delivery of Mutifuncational Peptide-adrenomedullin
    WANG Lin, LI Chun-Yan, HE Pan, FU Li, ZHOU Yan-Min*, CHEN Xue-Si
    2011, 32(7):  1622-1628. 
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    In the presence of tripolyphosphate ( TPP) ,chitosan microspheres (CMs) loaded with adrenomedullin(ADM) were prepared by an emulsion-ionic cross-linking method .Then, Porous CMs/ nano-hydroxyapatite/ Poly(Lactide-co-Glycolide) composite was developed by thermally induced phase separation. Scanning electron microscope was used to analyze the characterization of the microspheres and scaffold. In vitro the drug release from microspheres and scaffold have been tested, also the hemolytic effect of the scaffold was tested to evaluate the toxicity of the biomaterial. The MG63 cell line and HUVEC cell line were cultured for testing the bioactivity of the scaffold loading ADM. The cell proliferation and differentiation was analyzed by MTT assay and ALP assay The result demonstrated the diameter of the microspere was well-distributed. The nHAC/PLGA/ADM scaffold showed a typical microstructure of polymeric foam prepared by thermally induced phase separation. The pore size ranged from 30μm to 220μm.and and the pores were interconnected.The hemolytic rate of the biomaterial was less than 5% ,which was in line with national standard of medical materials.The nHAC/PLGA/ADM and nHAC/PLGA scaffold could accelerate the proliferation of osteoblast-like cells and vascular endothelial cells, also were the stimuli for the differentiation of osteoblast-like cells.
    Dissolubility of the Cellulose in Urea/Caprolactam/NaOH/Aqueous Solution and the  Performance of Regenerated Cellulose
    ZHAO Di-Shun*, LI He, LIU Meng-Shuai, FU Lin-Lin, ZHANG Juan
    2011, 32(7):  1629-1633. 
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    Dissolution of cellulose in urea/caprolactam/NaOH aqueous and the performance of regenerated cellulose were discussed. The best ratio of urea/caprolactam/NaOH in solution was found by orthogonal design(wt): urea10%, caprolactam4%, NaOH8%. The both original cellulose and regenerated cellulose from urea/caprolactam/NaOH aqueous were characterized by Fourier transform infrared spectroscopy(FT-IR), thermogravimetry (TG) and X-ray diffraction (XRD) measurements. Results show that the novel system is a good direct cellulose solution. The solubility cellulose in urea/caprolactam/NaOH aqueous was better at lower temperature. The crystal of regenerated cellulose has changed and the thermostability of regenerated cellulose slightly decreased.
    Photochemical Behavior of Polystyrene Photonic Crystals Film
    ZHANG Yu-Qi*, HAO Xin, WEI Qing-Bo, YANG Hua, WANG Qiao, SONG Yan-Wei
    2011, 32(7):  1634-1638. 
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    The morphology, optical properties and wettability of polystyrene (PS) photonic crystals (PC) film were studied under UV irradiation. The chemical composition change of the film surface was characterized by FTIR, and the results demonstrated that the hydrophilic carbonyl group formed on the surface of PS microsphere after UV irradiation. Scanning electron microscopic images testified that the PS sphere would contract, deform and melt down companying with longer time of UV irradiation. The in situ reflectance and transmittance spectra indicated that the PS PC film could preserve good optical properties and the wettability turned from hydrophobicity to hydrophilicity under UV light exposure for 20 min. Therefore, the hydrophilic functional polymer PC film with good optical properties can be obtained by controlling the UV irradiation time, which will be of great importance for the application of PC in the special system.
    Synthesis and Characterization of Multi-generations Hyperbranched Waterborne Polyurethane
    SUN Ning*, LIU Yu-Hang, TONG Zhen*
    2011, 32(7):  1639-1644. 
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    A series of different generation hyperbranched waterborne polyurethanes(HPU) was prepared successfully from toluene 2,4-diisocyanate (TDI), dimethylol propionic acid(DMPA) and diethanol amine(DEOA) via monomer coupling reaction. The highest yield of the HPUs was up to 91%. The HPU products(generation from 2 to 5) and the line waterborne polyurethane(LPU), which have a similar chemical component, were characterized by the FT-IR, NMR, thermo gravimetric analyzer(TG) and differential scanning calorimeter(DSC), respectively. The molecular weights of the HPUs were measured by triple-detectors GPC; FT-IR and 13C NMR results proved that the hyperbranched structure was synthesized successfully. TG results showed that different generation HPUs and LPU had a similar initial degradation temperature at about 200℃.But the HPUs and LPU had a different degradation course obviously.; DSC results showed that the Tg of HPUs were higher than LPU apparently, and with the increasing of the generation, the Tg of HPUs rose from 115.2℃ to 150.3℃. Comparing with the different generation HPUs with LPU mixed films, the gloss and hardness improve significantly.
    EQCM Studies of Electropolymerization and Electrochemically Controlled Phenol Separation of Polyaniline Film
    LI Hui, LI Yue, HAO Xiao-Gang*, ZHANG Zhong-Lin, LIU Shi-Bin
    2011, 32(7):  1645-1650. 
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    Electroactive polyaniline (PAN) thin films were synthesized on platinum substrates by electrochemical polymerization, the electrochemical quartz crystal microbalance (EQCM) technique was adopted to investigate the polymerization process of the PAN film and its redox behavior in phenol solution. Combined with cyclic voltammetry (CV), electroactivity and stability of the PAN film cycled between the reduced, leucoemeraldine (L) state and the half-oxidized, emeraldine (E) state or between L and the fully oxidized, pemigraniline (P) state were investigated in 0.5 mol/L H2SO4 solution. In mixed solutions of phenol and H2SO4, chronocoulometry and FT-IR were also used to investigate the electrochemically controlled phenol separation property of PAN film. Experimental results indicate that the abrupt changes of the film mass exist during the redox switching of PAN with the ion ejection/injection, especially with the increase of the films thickness; and PAN films have good electroactivity and stability when films are controlled between L and E during cycling process. Phenol in electrolyte will enter into the film when PAN is controlled as E; while release from the film into electrolyte again when PAN is modulated to L. Phenol enter or release from film can controlled freely by modulating the potential of PAN films, this characteristic can be used to separate the phenol from the solution.
    Effect of Solvent Molecular Size on the Self-assembly of Amphiphilic Triblock Copolymer in a Selective Solvent with a Monte Carlo Simulation
    FAN Juan-Juan, HAN Yuan-Yuan, JIANG Wei*
    2011, 32(7):  1651-1655. 
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    The effect of solvent molecular size on the self-assembly of ABA amphiphilic triblock copolymer in a selective solvent was studied by means of Monte Carlo study. The simulative results showed that the solvent molecular size is one of the key factors that determine the morphologies of the copolymer aggregates. The morphologies formed by ABA amphiphilic triblock copolymers changed from spheres to rod and then to vesicle by increasing the solvent molecular size. By analyzing the variations of the contact number between monomers, it was found that the morphological transition was induced by the decreasing of the solvent solubility when increasing the solvent molecular size. Moreover, the phase diagrams in terms of the core-solvent interaction and the solvent molecular size as well as the corona-solvent interaction and the solvent molecular size were given respectively. The results revealed that increasing solvent molecular size, core-solvent interaction and decreasing corona-solvent interaction had an equivalent effect on the self-assembled structure for the ABA amphiphilic triblock copolymers.
    Synthesis and Electrochemical Behavior of Polyainiline by Composite Emulsifier Microemulision Polymerization
    MA Li*, JIA Chun-Yue, GAN Meng-Yu, HAO Shao-Na, LIU Xing-Min, LI Zhi-Chun
    2011, 32(7):  1656-1660. 
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    The polyaniline(PANI) was prepared by microemulsion polymerization in the presence of composite emulsifier. The effects of the mass ratio of sodium dodecylbenzenesulfonate (SDBS) to Triton X-100(TX-100) and the amout of composite emulsifier(E) and oxidant(APS) on the electrochemical properties(cyclic voltammogram, tafel) of PANI were discussed via cyclic voltammogram (CV) using the carbon paper loaded PANI as working electrode, and the characterization result of the electrochemical properties of the PANI was also proved by the contrast analysis of the conductivity and yield of PANI. The experimental results showed that when the mass ratio of SDBS to TX-100 and E to anilin(An) was 1/2 and 5/3, the molar ratio of APS to An was 1.2, the properties of the PANI were the best; besides, the peak current of CV, the corrosion potential and conductivity of product were higher than PANI synthsized by microemulsion polymerization in the presence of single emulsifier (SDBS or TX-100).