Table of Content

10 August 2010, Volume 31 Issue 8

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Contents

Cover and Content of Chemical Journal of Chinese Universities Vol.31 No.8(2010)

2010, 31(8):  0. 

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Letter

Selective Adsorption of Organic Light Emitting Molecule on PANI Microstructure

TIAN Lu, BU Feng-Quan, HUANG Chun-Yu, Lü Nan*

2010, 31(8):  1485-1487. 

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We developed a method for patterning organic light emitting molecules with polyaniline(PANI) \{microstructure\} as a template. Its microstructure was characterized with atomic force microscopy(AFM). PANI microstructure was treated with O₂ plasma at low power and short time to get the hydroxyl groups on the silicon substrate, meanwhile, which can minimize the impact on PANI structure. We modified the \{structure\} with fluoro\|silane reagent through self\|assembly to make substrate bearing different surface energies on \{different\} areas. Finally, we deposited dyes on substrate by evaporation. The results show that the dyes on the \{fluoro\|silane\} monolayer can move toward the PANI structure during storage duration and form the structure of organic light emitting molecules.



Articles

In-situ Synthesis and Properties of Hydroxyapatite-SOD Nanocomposite

WU Li-Yan, WANG Yue-Yi, YANG Dong-Sheng, MENG Qing-Fan, TENG Li-Rong, ...

2010, 31(8):  1488-1490. 

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Hydroxyapatite(HAP)-superoxide dismutase(SOD) nanocomposites(HAP-SOD) were in-situ synthesized using calcium acetate and ammonium dihydrogen phosphate as initial materials and characterized through X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR) and scanning electronic microscopy(SEM). Besides, SOD activity was detected and the release behavior was inspected. The results show that the particle size of HAP-SOD nanocomposite was under 100 nm, and the relative activity of SOD in the composites was up to 84.7%. The cumulative release rate of the complex was up to 81.2% in 24 h.

Synthesis and SERS Properties of Flowerlike Ag Micro-nano Structures

ZHANG Bo, ZHAO Ai-Wu*, WANG Da-Peng , GUO Hong-Yan, LI Da, LI Ming

2010, 31(8):  1491-1495. 

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Novel nanoplate-composed flowerlike Ag micro-nano structures were fabricated by a simple aqueous solution route. The products were characterized by X-ray diffraction(XRD), scanning electronic microscopy(SEM), transmission electron microscopy(TEM), high resolution transmission electron microscopy(HRTEM), and selected area electrical diffraction(SAED). The effect of pH on the morphology of the products was investigated and the mechanisms of the formation of the flowerlike Ag micro-nano structures were discussed preliminarily. The products were composed of a great deal of interlaced nanoplates, experiments indicated that these micro-nano structures have very strong SERS activity as SERS substrates.

Synthesis and Crystal Structure of Nickle 3,5-Pyridinedicarboxylates

JIN Qiang, ZHAO Jiao, SHI Xin*

2010, 31(8):  1496-1501. 

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Three new nickle 3,5-pyridinedicarboxylates coordination polymers, [Ni(3,5-Pydc)(H₂O)₄·H₂O]_n(1), [Ni₂(3,5-Pydc)₂(H₂O)₈·(H₂O)₂]_n(2) and [Ni(3,5-Pydc)(H₂O)₂]_n(3) were synthesized by hydrothermal method and characterized by single-crystal X-ray diffraction, FTIR and TGA. X-ray crystallography reveals that both complexes 1 and 2 are 1D zigzag chains, while complex 3 is a 2D layered network. In complex 1, 3,5-Pydc ligand links two different Ni(Ⅱ) into 1D zigzag chain. There are two independent 1D zigzag chains with same coordination mode in complex 2 and each zigzag chain is formed by 3,5-Pydc ligand connecting with Ni(Ⅱ). Complex 3 is a 2D network constructed by twenty-membered rings comprising three Ni(Ⅱ) and three 3,5-Pydc ligands. Furthermore, three compounds form 3D supramolecular frameworks through O—H…O hydrogen bonds among chains or layers. The guest water molecules are defined in supramolecular frameworks of complexes 1 and 2.

Gold Nanoparticles Prepared by Aqueous Synthesis and Its Fluorescence Properties

Lü Bing-Feng, LI Guo-Ping*, LUO Yun-Jun

2010, 31(8):  1502-1505. 

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Au nanoparticles encapsulated by PAMAM dendrimers were prepared using PAMAM dendrimers as template and ethanol as reducing agent in water medium, respectively, which have good water-solubility and well-stability in water phase for more than 1 year. Au nanoparticles with controlled size in a range of 1—4 nm were obtained by changing the molar ratio of Au³⁺ to PAMAM dendrimers. The results show that there was a strong resonance Rayleigh scattering peak at 385 nm and a fluorescence peak at 402 nm. The photoluminescence quantum yield of the prepared Au nanoparticles was more than 10% at room temperature, which is about 2 orders of magnitude higher than that of Au nanoparticles prepared by other methods, so it have potential application prospect in fingerprint recognition, photocatalysis and so on.



Online Base Barrage Focusing and Capillary Electrophoresis of Aromatic Amines

WANG Xiao-Yu, CHEN Yi*

2010, 31(8):  1506-1509. 

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A base barrage focusing approach online-coupled to capillary electrophoresis(CE) was developed and used for the analysis trace aromatic amines. To realize online focusing, a plug of 200 mmol/L NaOH was introduced in front of a sample zone just before electrophoresis. This method is facile and can be conducted on any CE system. After some optimization of the base barrage length and concentration, the method could be applied to the assay of m-phenylenediamine, o-phenylenediamine and melamine, with limits of detection down to 0.10 μmol/L m-phenylenediamine, 0.05 μmol/L o-phenylenediamine and 0.05 μmol/L melamine respectively, producing about 100-fold increase of sensitivity compared with the common method. Linear relationship was found between the peak area and sample concentration over two grades of magnitude, with linear correlation coefficients better than 0.999. As a validation, the method has also been applied to the analysis of a commercial hair dye, with the recovery between 94% and 97%.

Characterization of Adsorption Behavior of Exogenous Thorium on Soil

GUO Peng-Ran, JIA Xiao-Yu, MU De-Hai, QIU Rong-Liang, CHEN Hang-Ting*

2010, 31(8):  1510-1516. 

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The risk and degree of harm of exogenous thorium to soil environment are depended on the adsorption behavior of thorium on soil. The adsorption of exogenous thorium on soil samples, collected from rare earth industrial park in Baotou, China, and mineral components(kaolin, montmorillonite, CaCO3, hydrous iron and manganese oxides, humic acid) were investigated by the static adsorption manner, and the adsorption behaviors were characterized by SEM, EDS, XRD and FTIR. The results show that the strong adsorption ability of exogenous thorium(10-4 mol/L) on soil samples was observed by high adsorption ratio of over 97%, however, the adsorption rate of soil mineral components to exogenous thorium(1 g/L) is in the range of 28%—46%. According to the results of SEM and EDS, exogenous thorium is adsorbed onto soil through working with soil mineral components, and likely formed the stable calcic thorium carbonate and thorium phosphate; and based on the results of FTIR, exogenous thorium is adsorbed onto soil by reacting with active adsorption sites of soil mineral components, which is the physical adsorption and chemical adsorption processes; and the results of XRD show that soil mineral components are not almost changed before and after adsorption of thorium on soil, but crystal phase states changes of soil minerals occurred. Owing to the different adsorption manners of soil mimeral components, the adsorbed thorium exists in soil as different fractions.

Solvent Induced Phase Transition Extraction Method for High Performance Liquid Chromatography-Mass Spectrometry Analysis of Plasma Samples of Pretreatment

ZHANG Ming-Shan, LIU Guo-Zhu, LI Sheng-Jun, CHEN Bo*, YAO Shou-Zhuo

2010, 31(8):  1517-1521. 

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Hydrophobic solvent such as chloroform can be used as modifier to induce phase separation of the acetonitrile aqueous mixture. Capitalizing on this phase transition phenomenon, a novel approach, named solvent induced phase transition extraction(SIPTE), was proposed to extract drug in plasma. SIPTE is superior to conventional liquid-liquid extraction(LLE) as the recovered acetonitrile solution can be directly injected into the RP-LC system, which greatly simplifies the sample preparation procedure. Furthermore, the proposed SIPTE is excellent due to the function of automatically preconcentrating the sample. Nitrendipine was used as the test drug to design and validate the SIPTE method. Nitrendipine was separated on a RP-C₁₈ column, using acetonitrile/water containing 20 mmol/L of ammonium formate(70∶30, volume ratio) as the mobile phase. Nimodipine was selected as the internal standard for the quantification purpose. The obtained good linear, accuracy and precision results prove that the SIPTE method is sensitive and accurate enough to be used for pharmacokinetic study.

Interpretation of Mass Spectral Characteristic Fragmentation Mechanisms of Indole Alkaloids Through Determining the Initial Ionization Site

LUO Xiao, OUYANG Yong-Zhong, LIANG Yi-Zeng*, WANG Qin

2010, 31(8):  1522-1528. 

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Determination of initial ionization site is the most important step in the EI mass spectral interpretation. In this article, a new method for determining the initial ionization site by calculated spin density of molecular radical cation, the changes of charges and the variations of the molecular structures from neutral to ca-tionic form was presented. The characteristic fragmentation mechanisms for the derivatives of indole alkaloids were investigated through determining the initial ionization site. The results predicted by this method can be comparable, even superior to those based on ionization energy method. It will play an important role in predicting the main primary α-cleavage fragmentation not only for indole alkaloids and other compounds which containing N atom, but also for small molecules and gas-phase peptide radical cations.

Interaction Between Berberine and Human Gamma Globulin in Membrane Mimetic Environments

LI Ying*, WANG Chao, HU Zhi-De

2010, 31(8):  1529-1534. 

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The interaction between berberine and human gamma globulin(HGG) in AOT/ isoctant/water reverse micellar was studied by fluorescence quenching technique, UV absorption spectroscopy, circular dischroism(CD) spectroscopy and dynamic light scattering(DLS) technique. The interaction of HGG with berberine at 289, 296, 303 and 310 K in water-surfactant molar ratio(ω0=25) reverse micellar was characterized by one binding site with the affinity constant K at 4.50×104, 4.18×104, 4.13×104 and 3.76×104 L/mol, respectively. The affinities in reverse micellar were much higher than that in buffer solution. The CD spectra results proved that the protein secondary structure changed in the reverse micellar in the absence and presence of berberine compared with the free form of HGG in buffer. The binding process was exothermic and spontaneous, as indicated by the thermodynamic analyses. The results show that hydrophobic and electrostatic interaction play the main roles in the binding of berberine to HGG. Furthermore, the DLS data suggested that HGG may locate inside of the reverse micellar and berberine could interact with them.

Proteomic Analysis of Olfactory Memory Related Proteins in Mice

ZHENG Jun-Fang, HUA Lin, ZHANG Qiu-Xia, LI De-Long, HE Jun-Qi*

2010, 31(8):  1535-1540. 

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To investigate olfactory memory related proteins, olfactory bulb proteins from C57BL/6J mice after olfactory discrimination task were extracted and subjected to 2D gel electrophoresis. Protein quantification was performed and the differentially expressed spots were identified using mass spectrometry and Swiss-Prot database searching with MASCOT software. Olfactory bulb proteins from C57BL/6J mice after olfactory discrimination task were significantly different. Expression levels of 2 spots upregulated significantly; expression levels of 3 spots downregulated significantly. Functions of these identified proteins were involved in neurogenesis, signal transduction, cytoskeleton and nucleotide acid metabolism. These proteins improved insights into the olfactory memory mechanism and provided new targets for the study and treatment of cognitive diseases.

Synthesis and Anti-cancer Activity of Nitric Oxide Donor-based Matrine Derivatives

HE Li-Qin, GU Hong-Xia, YIN Deng-Ke, ZHANG Yi-Hua*, WANG Xiao-Shan

2010, 31(8):  1541-1547. 

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Matrine, one of the major active alkaloids isolated from the Sophora alopecuroides L which is a useful Chinese herbal drug, possesses antipyretic, anti-inflammatory, analgesic, and notable antiviral activities, and has been used for the treatment of lipopolysaccharide-induced liver injury. Recently, it was reported that matrine could inhibit the growth of tumor cells. Nitric oxide(NO), a free radical molecule, is involved in numerous physiological and pathological processes. High levels of NO usually are toxic to tumor cells. It was therefore of interest to determine whether the hybrid of matrine and NO donor furoxan would provide a hitherto unknown class of matrine derivatives that possess potent anticancer activity. Herein furoxan-based matrine compounds 11a—11m were designed and synthesized, and their structures were confirmed by MS, IR, ¹H NMR spectra and elemental analysis. All target compounds exhibited expectedly much more stronger anti human hepatocellular carcinoma cells(HepG2 cells) activity than that of parent compound matrine in vivo. Furthermore, compounds 11a—11c, 11h and 11i had stronger cytotoxic activities than that of control 5-fluorouracil. The concept of designing NO donor-based matrine derivatives that possess potent anticancer activity warrants further investigation.

Synthesis of Thermoregulated Noyori Ligand and Its Application in Asymmetric Transfer Hydrogenation of Acetophenone

MING Yan-Hua, FAN Ai-Li, JIN Zi-Lin, JIANG Jing-Yang*

2010, 31(8):  1548-1553. 

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A novel poly(ethylene glycol) chain modified thermoregulated Noyori ligand was designed and synthesized. Its Ru complex was used as a catalyst in the asymmetric transfer hydrogenation of acetophenone in aqueous/cyclohexane biphasic system with sodium formate as hydrogen source. The effects of reaction temperature, reaction time, the amounts of sodium formate, molar ratio of acetophenone to catalyst and the volume of organic solvent on the enantioselective catalytic hydrogenation of acetophenone were investigated. The results reveal that the catalyst containing aqueous phase possesses cloud point and the complex catalyst is effective and highly enantioselective for the asymmetric transfer hydrogenation of acetophenone. With a n(HCO₂Na)∶n(acetophenone)∶n(catalyst)=300∶100∶1 in a n(cyclohexane)∶n(water)=1∶1 reaction medium, the reaction runs at 30 ℃ for 6 h to give the results that the conversion of acetophenone is 99.7% and the e.e. value of the product α-phenylethanol is 93.9%. The aqueous phase containing catalyst can be easily separated from the organic phase and reused for consecutive reaction directly. During recycling, the catalyst activity decreases obviously each time whereas the enantioselectivity of the product is unchanged.

Synthesis, Electrochemistry and Optical Limiting Properties of Spirobifluorene-fulleropyrrolidine Derivatives

LI Cai-Hua, HUO Zhi-Ming, ZENG He-Ping*

2010, 31(8):  1554-1559. 

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Three novel fullerene(C₆₀/C₇₀) derivatives containing spirobifluorene, named 2-(9,9′-spirobi[fluorene]-2-yl)-1-methylfullero[C₇₀]pyrrolidine(6), 2-(9,9′-spirobi[fluorene]-2-yl)-1-methylfullero[C₆₀]pyrrolidine(7) and 2′-(1-methyl- fullero[C₆₀]pyrrolidin-2-yl)-9,9′-spirobi[fluorene]-2-carbaldehyde(8), respectively, were synthesized and their structures were confirmed by IR, ¹H NMR, ¹³C NMR, MALDI-TOF. Their electrochemical properties were studied by cyclic voltammetry. The results show that reduction peaks of C₇₀ derivative 6 shift to more negative than that of C₆₀ derivative 7 about 0.1, 0.12 and 0.01 V, respectively. Their optical limiting properties were investigated by nanosecond and femtosecond laser system. Comparative study on their optical limiting properties indicated that they showed different optical-limiting mechanisms for nanosecond and femtosecond laser. The optical limiting thresholds of 13.7, 15.3 and 23.3 J/cm² in nanosecond timescale were determined for compounds 6—8. The results show that they are effective optical limiters for laser protection.

Resolution of N-Acetyl-D,L-3-methoxy-alanine by Immobilized Cells with Aminoacylase

XIONG Ji-Bin, LIU Jun-Zhong, LIU Qian, JIAO Qing-Cai*

2010, 31(8):  1560-1563. 

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As a pharmaceutical intermediate, L-serine plays an important role in organic synthesis and peptide synthesis. Also N-acetyl-D,L-3-methoxy-alanine is an intermediate in synthesis of L-serine from methyl α-bromo-β-methoxypropionate. In this thesis, a new method of resolution of N-acetyl-D,L-3-methoxy-alanine by immobilized cells with aminoacylase was studied. Several factors of this enzymatic reaction were investigated. The optimal temperature and pH are 50 ℃ and 7.0. In 10 mL reaction solution, the optimal concentration of N-acetyl-D,L-3-methoxy-alanine is 500 mmol/L and the amount of immobilized cells is 1 g. 10^-4 mol/L of Co²⁺ and Mg²⁺ are benefit to aminoacylase, while Cu²⁺ and Zn²⁺ show clearly inhibitory effect. Under the optimal conditions, molar conversion rate of N-acetyl-L-3-methoxy-alanine is 96%.

Synthesis of Cinchonine Quaternary Ammonium Salts and the Catalysis of Asymmetric Alkylation

LI Zhi, LIAN Ming-Ming, MENG Qing-Wei*

2010, 31(8):  1564-1569. 

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Eleven catalysts bearing a free hydroxyl group were prepared by direct N-alkylation with corresponding substituted benzyl bromides under a reflux condition in good yields(57%—88%). Other 4 catalysts with the chiral secondary alcohol protected by allyl, benzyl, propynyl and benzoyl were synthesized via two steps. The ether group at the phase-transfer catalysts could be approached before or after the N-benzylation reaction. In contrast, the hydroxyl group was changed to benzoic acid ester when the quaternary ammonium salt had been prepared. Fifteen phase-transfer catalysts were gotten, and 5 catalysts of them had never been reported. Then, various catalysts were screened for alkylating reactivity of glycine imine ester. Cinchonine derived catalysts Cn-9 proved to be highly reactive in 93% yield with 91% e.e. value.

Synthesis of 1,5-Diaryl-3-(2-hydroxyl-4,6-dimethoxylphenyl)-2-pyrazolines as Fluorescent Sensors for Cu²⁺

XU Zhu-Xiong, WU Jing, SHEN Jian, WANG Bing-Xiang*

2010, 31(8):  1570-1573. 

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The design and synthesis of chemosensors for Cu²⁺ constitute a very active area of research as a result of the demand for more sensitive and selective chemosensors for in vitro and in vivo purposes. The synthetic Cu²⁺ selective fluoroionophores so far reported suffer from low sensitivity and, in general, higher concentrations of interfering metal ions disturb the selectivity towards Cu²⁺. Four 1,5-diaryl-3-(2-hydroxyl-4,6-dimethoxylphenyl)-2-pyrazoline(4a—4d) were synthesized and fluorescent sensors for Cu²⁺ ion were investigated. The structures of all the products were determined by IR, ¹H NMR, MS and elemental analysis. Their UV and fluorescence spectra were measured. The influences of eight metal ions such as Cu²⁺, Zn²⁺, Co²⁺, Ni²⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺ on their fluorescence properties were studied. Spectroscopic studies revealed that the compounds 4a—4d had rather strong affinity toward Cu²⁺. The specificity of the probes 4a—4d toward Cu²⁺ were determined. Nearly no fluorescence intensity changes were observed in emission spectra with Zn²⁺, Co²⁺, Ni²⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺. However, under identical conditions, the results show fluorescence quenching with Cu²⁺. So we have developed four new fluorescent sensor 4a—4d. They show high sensitivity and selectivity toward Cu²⁺ in DMSO.

Synthesis of Some Novel Substituted Benzamides, Their Inhibition of AHAS and Herbicidal Activity

LI Wen-Ming, WANG Jian-Guo*, LI Yong-Hong, WANG Su-Hua, LI Zheng-Ming*

2010, 31(8):  1574-1578. 

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Based on the strategy of bio-rational design of AHAS inhibitors, 8 novel N-(phenylsulfonamidophenyl)benzamide and 7 novel N-{[N-(phenylsulfonyl)phenylsulfonamido] phenyl}benzamide derivatives were designed and synthesized by starting materials 4-fluoro-3-nitroaniline and 2-amino-5-nitrobenzonitrile, and their structures were confirmed by IR, MS, ¹H NMR and elemental analysis. The preliminary bioassay indicated that some compounds exhibited bioactivity either in vitro or in vivo. Compounds 4c, 4d and 7c show inhibition to Arabidopsis thaliana AHAS of 66%, 76% and 68% at 100 μg/mL. Compound 4a, 4c, 7a and 7b show inhibition on the growth of rape root of 76%, 70%, 89% and 82% at 100 μg/mL. The present results provide helpful guidance to further design more potential AHAS inhibitors.

Immobilization of Laccase on Epoxy Group-functionalized Periodic Mesoporous Organosilicas

LAN Jia-Ning, NA Wei, WEI Qi*, Li Qun-Yan, WANG Wei, NIE Zuo-Ren

2010, 31(8):  1579-1584. 

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Epoxy group-functionalized periodic mesoporous organosilicas(FPMOs) was synthesized by the co-condensation of 1,2-bis(triethoxysilyl)ethane(BTESE) and 3-glycidoxypropyltrimethoxylsilane(GPTMS) in the presence of triblock copolymer poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)(P123) under acidic conditions and utilized as a support for laccase immobilization. The effect of epoxy group-functionalization on the immobilization of laccase and the stability of immobilized laccase were investigated in detail. The level of functionalization, the pore structure and the laccase immobilization were detected by means of solid-state NMR, N2 adsorption and UV-Vis, respectively. It is revealed that epoxy groups are successfully attached covalently to the pore wall of PMOs and the functionalized materials retain a desirable pore structure. Laccase immobilized on functionalized FPMOs exhibits a higher activity and stability than that adsorbed on pure PMOs.

Synthesis, Characterization and Electrochemical Properties of a New Asymmetrical Nickel Phthalocyanine

GAO Jun-Shan, SHI Tie-Zheng, ZHAO Qing-Huan, DU Xi-Guang*, ZHANG Hai-Qian*

2010, 31(8):  1585-1589. 

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A new asymmetrical nickel phthalocyanine(NiPc2 for short) was synthesized by increasing the temperature of the classical synthetic method, and its structure was characterized by MS, IR and UV-Vis-NIR spectroscopy. Meanwhile, a hypothetical mechanism was suggested and the electrochemical properties was studied by cyclic voltammetry. NiPc2 has strong absorption in near infrared region and prone to be J-aggregates because of the red-shift of the Q band. The NiPc2 has potential application on organic function devices.

Synthesis, Characterization and Antibacterial Activities of N-[(1-Aryl-3-phenyl-pyrazol-4-yl)methylene]-2-hydroxybenzohydrazide Derivatives

ZOU Min, LU Jun-Rui*, XIN Chun-Wei, LU Bo-Wei, ZHU Shan-Shan, LIU Qian, ...

2010, 31(8):  1590-1595. 

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A series of novel N-[(1-aryl-3-phenyl-pyrazol-4-yl)methylene]-2-hydroxybenzohydrazide derivatives were designed and synthesized by combining o-hydroxyl phenyl and phenyl pyrazole with hydrazone bond, according to the superposition principle of biological activities. Six compounds are all novel. Substituted aniline was diazotized and subsequently reduced to give substituted phenylhydrazine, acetophenone arylhydrazone were obtained by the condensation of acetophenone with substituted phenylhydrazine. 1-Aryl-3-phenyl-4-formylpyrazoles were obtained with N,N-dimethylformamide and phosphorus oxychloride, which was reacted with salicylic hydrazide to get the title compounds. The structures of all title compounds were confirmed by ¹H NMR, IR and elemental analysis. The reaction mechanism of acquiring 3a—3f show that catalytic reaction activity is enhanced by electron-donating groups of the first phenyl ring, but reduced by electron-withdrawing groups of the first phenyl rings. The result of preliminary bioassay show that the inhibitory rate against Monilia albican and Escherichia coli of the title compounds can be high to 100% at 0.01% mass fraction, inhibitory rate against Staphlococcus aureus is over 70%. They will be a series of potential antibacterial compounds against fungi and gram-negative bacteria. The analysis of structure-activity relationship show that the antibacterial activities of title compounds are enhanced by the halogen groups of the phenyl ring, but reduced by electron-donating and electron-withdrawing groups of the phenyl ring, such as NO₂ and CH₃.

Effects of Chemical Composition and Nano-structures on the Wetting Behaviour of Lotus Leaves

WANG Jing-Ming*, WANG Ke, ZHENG Yong-Mei, JIANG Lei*

2010, 31(8):  1596-1599. 

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Anneal, chemical extraction, stripping were used to change the chemical composition and microstructure on the surface of the lotus leaf. The morphology and chemical composition of samples were characterized by environmental scanning electron microscope(ESEM) and total reflection infrared spectroscopy(ATR). Besides, atomic force microscope(AFM) was further used to avoid other external factors affecting the real morphology of samples. The sample wettability was characterized by the apparent contact angle. The results show that surface hydrophobicity is mainly caused by the wax on lotus leaf surface. The micro-scaled structure enhances its hydrophobicity, and the nano-scaled structure take important role in low tilt angle.

Ab-initio Investigation on Ion-associated Species and Association Process in NaClO₄ Solution

ZHANG Hao, YU Jian-Kang*, SUN Chia-Chung

2010, 31(8):  1600-1604. 

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The associated species and process in the NaClO₄ solution were investigated at the HF/6-31+G* level. The ClO₄^- ions binding with hydrated Na⁺ ions can form solvent-shared ion pairing, contact ion pairing and multiple(including triple) ion clusters. When there are abundant water molecules, the regular octahedral hexacoordinated structure of Na⁺ ion can be kept while the irregular penta- and tetra-coordinated structures will form with lacking water. The ν₁-ClO₄^- frequencies in the species above are 4.7, 8.5 and 14—17 cm^-1 larger than the reference value in hydrated ClO₄^-, which is corresponding with the results in experiment after multiplied by a scale factor. The associated process in the NaClO₄ solution can be expressed as “free hydrated ion→solvent-shared ion pairing→mono-dentate contact ion pairing→cation-anion-cation triple ion cluster→catenulate multiple ion cluster→reticular multiple ion cluster→amorphous crystal”. The process is not analogous with those in the Mg(NO₃)₂, Mg(ClO₄)₂ and NaNO₃ systems but the MgSO₄ system.

Thermodynamic Equilibrium Analysis of Transformation and Removal of Lead During Sludge Incineration

LIU Jing-Yong, SUN Shui-Yu*

2010, 31(8):  1605-1613. 

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The thermodynamic equilibrium model were applied to predict the transformation of lead during the sludge incineration and the adsorption effects of Pb by four sorbents(Al₂O₃, SiO₂, TiO₂ and CaO) were simulated with the minimized Gibbs free energy approach. The interaction between Pb and sulfur, chlorine, together with the reaction between sorbents and Pb caused by sulfur and chlorine were considered in this procedure. The result showed that the transformation of Pb was affected greatly by sulfur, chlorine and minerals. At low temperature the lead existed in the form of PbSO₄(solid) under the presence of sulfur, while it changed into PbO(gas) at high temperature.The Pb was volatized because chlorine was easy to combine with Pb forming the metal chloride with low boiling point, and the increase of chlorine could speed up the volatilization of Pb. The four sorbents mentioned above were able to remove Pb in some degree. Al₂O₃ could capture Pb in a wide range of temperature, while CaO was not so good. Because sulfur and chlorine had stronger reaction with Pb, they restrained the reaction between sorbents and Pb, during which effective temperature area was narrowed, adsorption rate was reduced, and even Pb removal ability was lost. The effect of chlorine appeared much more than that of sulfur.

Preparation and Fluorescent Sensing Applications of HPS-PVA Composite Films

XIA Hui-Yun, HE Gang, GAO Li-Ning, PENG Jun-Xia, FANG Yu*

2010, 31(8):  1614-1619. 

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A novel fluorescent film was fabricated by doping the aggregates of hexaphenylsilole(HPS) into a polyvinyl alcohol(PVA) film. It has been demonstrated that the composite film exhibited the typical three-dimensional network structure and the fluorescence emission of the film is stable, presumably the network structure of the substrate film is favorable for the stabilization of the fluorescence emission of the hybrid film through preventing the further aggregation of silole aggregates. Sensing experiments show that the photoluminescence emission of the hybrid film is highly sensitive to the presence of volatile organic compounds(VOCs), especially benzene-like organic gases. Furthermore, the sensitivity of composite film depends on the volatility of the VOCs and surface structure of the composite film. Fluorescence lifetime measurements and the light-emitting mechanism of HPS aggregates suggest that quenching mechanism should be dissolution quenching. It is also revealed that the response of the films to VOCs in gas phase is fully reversible.

Studies on Atomic Asymmetry of 2D Molecule

ZHANG Qing-You, ZHOU Yan-Mei, LONG Hai-Lin, HAO Jun-Feng, LIU Xiu-Hua, XU Lu

2010, 31(8):  1620-1625. 

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The methods of weighed atomic sums were suggested on the basis of binary code of molecular periphery for the descriptions of atomic asymmetric environments. The weighed atomic sum of an atom is a measure of the asymmetry of the atomic environment as obtained by circulating around the molecule going in opposing directions, and so the weighed atomic sum of an atom in a molecule and that of corresponding atom in the opposite enantiomer are of the same magnitude but of the opposite sign. Weighed atomic sums were available in not only chiral molecule, but also achiral molecule. Compared with atomic sums approached by Randic′, weighed atomic sums are more distinctive and better than atomic sum to represent atomic asymmetry.

Molecular Dynamics Simulation for the β-Sheet Aggregation of Peptides

Lü Ming, ZHAO Xi, SHEN Xing-Gui, GAO Xue-Feng*

2010, 31(8):  1626-1629. 

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The aggregations and thermodynamics stability of a nine peptide forming amyloidal fibril were studied using molecular dynamics simulation methods under acidic and alkaline condition, respectively. The results show that the peptide can form parallel β-sheet under alkaline condition, whereas forms anti-parallel β-sheet under acidic condition, and thermodynamics stability of the anti-parallel β-sheet is more stable than that of parallel β-sheet. The above observations are consistent with the experimental results. In addition, in the two β-sheet forms, the peptide chain both extends along direction of the corresponding sheet and forms left-helix, but the angle between adjacent peptide chains are different: the angel in parallel β-sheet form is less than that in anti-parallel β-sheet form. Therefore, it is concluded that parallel β-sheet is form easily aggregation, comparing with the anti-parallel β-sheet. The conclusion can explain why the diameter of amyloidal fibril under alkaline condition is larger than that under acidic condition in experiment.

Calculation of Complexes of the Recombinant Kringle 1 Domain of Human Plasminogen and Its Ligands by ABEEMσπ/MM Method

ZHANG Wen-Long, CHEN Shu-Ling, YANG Zhong-Zhi*

2010, 31(8):  1630-1635. 

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The semi-flexible docking studies were performed in order to understand the interaction between the recombinant Kringle 1 domain of human plasminogen and five ligands[ε-aminocaproic acid(EACA), trans-4-(aminomethyl) cyclohexane-1-carboxylic acid(AMCHA), L-lysine(Lys), 7-aminoheptanoic acid(7-AHA) and benzylamine] by means of ABEEMσπ/MM. The results show that the simulated structure is very close to the crystal structure. The calculated binding energies of the five complexes are in the order of AMCHA>EACA>7-AHA>Lys>Benzylamine, which is in agreement with the value of the equilibrium association constant(K_a) from experiment.

Molecular Modeling Studies on the Selectivity of 4-Benzylpiperidine Antagonists for hCCR3

LI Jin-Lian, WANG Jian-Ping, HU Dong-Hua, SHAO Chen, SU Zhong-Min*

2010, 31(8):  1636-1642. 

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The “antagonist-bound” three-dimensional models of the hCCR3 and hCCR1 receptors were constructed by homology modeling, using the X-ray structure of bovine rhodopsin as the template, and refined with molecular modeling and molecular dynamics(MM/MD) methods. We also carried out an automated docking of several 1,4-disubstituted piperidine antagonists into the hCCR3 and hCCR1 model. The binding hypothesis and the reliability of the hCCR3 model were confirmed by the reasonable correlation between the estimated binding free energy and the experimental -lgIC₅₀ values(r²=0.94). The docking results reveal that the face-to-face van der Waals interaction between piperidine ring and Tyr255 plays an important role on the selectivity of 4-phenzylpiperidine antagonists to hCCR3. Simultaneously, the more hydrophobic of the EL2 in hCCR3 is favorable for the selectivity of 4-phenzylpiperidine antagonists.

Synthesis and Catalytic Properties of Ordered Mesoporous Phenol-Formaldehyde Resins as Solid Acid Catalysts

MOU Li*, QU Xue-Jian, WANG Chun-Yan

2010, 31(8):  1643-1646. 

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A novel ordered mesoporous solid acid catalyst(FDU-16-SO3H) was prepared by sulfonation of mesoporous polymers(FDU-16). The sample was carefully investigated by XRD, N2 adsorption, TEM and IR. Characterization results suggested that the mesostructure of the sample was retained during the sulfonation. Catalytic esterification and acylation over FDU-16-SO3H show high catalytic activities, which is attributed the strong acidity, mesoporous structure and hydrophobic framework. Excellent catalytic properties ensure such mesoporous solid acid great potential application in industry.

Antireflection and Photovoltaic Properties of Microstructures Design on the Single Crystalline Silicon Surface

CHENG Ke, WANG Shu-Jie, FU Dong-Wei, DING Wan-Yong, ZOU Bing-Suo, DU Zu-Liang*

2010, 31(8):  1647-1650. 

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Two different microstructures were constructed on the single crystalline silicon surface which was used as antireflection coatings. The reflection spectra show that these period microstructures have an antireflection effect in some regions of the spectrum. The surface photovoltaic spectra show a corresponding photovoltaic enhancement in these spectrum regions. The antireflection mechanism was also discussed. This antireflection coating technique can be used to product and design the single crystalline silicon solar cells for high photoelectric conversion efficiency.

Relationship Between Electric Conductivity and Ion Structure of Sodium Aluminate Solution

LI Xiao-Bin, WANG Dan-Qin, LIANG Shuang, LIU Gui-Hua*, PENG Zhi-Hong, ...

2010, 31(8):  1651-1655. 

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A better understanding of the relationship between transference number of aluminate anions(t) and the structure of sodium aluminate solutions is of great significance for strengthening and optimizing the alumina production technologies. Combining with the characterization of FTIR analyses of the solution, the intrinsic relationship between the electric conductivity and the structure of sodium aluminate solutions was investigated by measuring the electric conductivity of the solution and calculating t in the solution of different alkali concentration and molar ratio of Na₂O to Al₂O₃. The results show that in the solution of low concentration of c(Na₂O)<175 g/L, the aluminate anions dominantly exist in the form of Al(OH)₄^- and t is approximately 0.6; that in the solution of medium concentration of c(Na₂O) from 175 g/L to 330 g/L, the aluminate anions mainly exist in the form of Al(OH)₄^- and [Al₂(OH)₈(H₂O)₂]^2-, in which t is approximately 0.2; and that in the solution of high concentration of c(Na₂O)>330 g/L, aluminate anions exist dominantly in the form of Al₂O(OH)₆^2- and [Al₂(OH)₈(H₂O)₂]^2- with a little Al(OH)₄^-, where t is almost zero. This illustrates that the electric conduction ability of the aluminate anion in the sodium aluminate solution is closely related to its structure.

Aggregation-Induced Emission Enhancement Properties of Phosphaphenanthrene-containing Styrene Derivant and Its Application of Detection to Transition Metal Ions

SHEN Jin-Bo, TONG Bin, SHI Jian-Bing, SUN Shu, FENG Xiao, ZHI Jun-Ge, ...

2010, 31(8):  1656-1660. 

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Fluorescence of the organic light-emitting compounds are often quenched when the luminophors are fabricated into solid thin films, which have greatly limited their scope of practical applications. So, it is important to design and synthesize the novel organic luminophors with excellent light emission property in solid state. Phosphaphenanthrene-containing styrene derivant(MED) was synthesized by means of two-step esterification from 2-(6-oxide-6H-dibenz(c,e)<1,2>oxaphos-phorin-6-yl)dihydroxyphenylenes(ODOPB), 4-(pentyloxy)benzoic acid and 4-ethylenebenzoic acid, respectively. And then the compound was characterized by ¹H NMR, FTIR, mass spectra, UV-Vis and PL. When MED aggregates to a certain degree in mixture of water and acetonitrile, the fluorescence strength of MED proportionably increases, which shows obvious aggregation-induced emission enhancement(AIEE) property because the aggregation state of MED restricts the intramlecular rotation of phosphaphenanthrene group based on π-π stacking and polarity interaction between the molecules. Pt²⁺, Ru³⁺, Fe²⁺ and Fe³⁺ ions(1×10^-4 mol/L) can efficiently quench the emission intensity of MED(1×10^-5 mol/L) and higher than those by Pb²⁺, Zn²⁺, Cd²⁺, In²⁺, Co²⁺, Cu²⁺, Ni²⁺ and Ag⁺ ions. The quenching efficiency of Pt²⁺ and Ru³⁺ are the same when they are added into the mixture of water-acetonitrile(90/10, volume ratio) during or after the aggregation state formation of MED. Fe³⁺ shows the highest quenching efficiency to the PL of MAD during aggregation. If being added into the aggregated systems, Fe³⁺ has the same quenching ability to MED. Fe²⁺ only shows its quenching effect on MED during aggregation. This novel phenomenon may enable the molecule to find applications to discriminating chemosensors to detect the transition metal ions.

Fabrication of a Silver Nanoparticle/polydopamine Modified Glassy Carbon Electrode and Its Electrocatalytic Reduction for p-Nitrophenol

SU Bi-Quan, ZHANG Yu-Zhen, DU Yong-Ling, WANG Chun-Ming*

2010, 31(8):  1661-1664. 

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A glassy carbon electrode modified with silver particles under polydopamine film was prepared successfully by means of electropolymerization and pulsed electrodeposition. A detailed analysis of the scanning electron microscope images reveals that silver deposit, obtained under pulsed electrodeposition conditions, appears as homogeneously compact and the crystallites are well dispersed on the overoxidized polydopamine substrate than that observed on the unmodified glassy carbon surfaces. The resulting silver nanoparticle/polydopamine modified glassy carbon electrode(Ag/PDA/GC) was electrochemically characterized through the reduction of p-nitrophenol(pNP). The potential needed for the reduction of the compound on the Ag/PDA/GC electrode is significantly less negative than that observed on the unmodified glassy carbon electrode substrates. A linear relationship between pNP concentration and current response was obtained in the range of 4×10^-5—3×10^-4 mol/L. The Ag/PDA/GC would be used in the practical application for detecting toxic nitrophenols.

Photoelectric Properties and Thermal Stability of PEDOT Nanoparticles Based on Reversed Micelle Method

ZHENG Hua-Jing*, JIANG Ya-Dong, XU Jian-Hua, YANG Ya-Jie

2010, 31(8):  1665-1670. 

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In recent years, conducting polymer nanostructure has been attracted more attentions due to their excellent optic, electric and gas sensitivity performances. Based on a new type of conducting polymer poly(3,4-ethylenedioxythiophene)(PEDOT), small-sized PEDOT nanoparticles were prepared by reversed micelle method and characterized by UV-Vis spectroscopy, scanning electron microscopy(SEM) and XRD. The optical and electrical properties and the thermal stability of PEDOT nanoparticles were investigated. The results show that the amount of oxidizer, ultrasonic treatment, polymerizing temperature and doping degree have different influence on morphology, electrical ability and gas sensitivity of PEDOT nanoparticles. The Bragg peaks of the nanoparticles at 6.7°, 12.7°, 25° were observed by XRD and this well orientation of molecular chain was due to the effective doping of p-toluenesulfonate, which also resulted in an enhancement of thermal stability of nanoparticles than conventional PEDOT.

Rheological Behavior of Isotactic Polypropylene(iPP) Melts in Supercooling State

LIU Yu-Hai, LI Hui-Zhen, LIU Xi, HU Li-Ping, YANG Zhan-Lan, XU Yi-Zhuang, ...

2010, 31(8):  1671-1675. 

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Decreasing the processing temperature can prevent thermal degradation of polymeric material and reduce energy consumption in the manufacturing process. In this paper, capillary rheometer was used to investigate the rheological behavior of isotactic polypropylene(iPP) in supercooling states. Experimental results demonstrate that the iPP melt in supercooling state have an induction period. After the induction period, the iPP melt undergoes gelation that is manifested by rapid increasing of the shear viscosity and leads to solidification and crystallization of iPP. During the induction period, the rheological behavior of iPP melt in supercooling states are similar to the conventional iPP melt whose temperature is above the melting temperature of iPP. The length of the induction period depends on the temperature of the melt. At 160 ℃, the length of the induction period is long enough so that it is possible to produce iPP fibers by spinning supercooling melt. In the suitable process conditions, the mechanical performance, FTIR spectra and XRD patterns of the iPP fibers produced from supercooling iPP melt are similar to those of the iPP fibers prepared from high temperature iPP melt. Thus, this work suggests that it is possible to develop an energy-saving technique to manufacturing of iPP fibers.

Synthesis and Self-assembly Behavior of a Novel Amphiphilic Block Glycopolymer

CHEN Li-Qiong, ZHANG Li-Ming*, CHEN Jian-Jun, YANG Jian, LI Rong-Xian

2010, 31(8):  1676-1681. 

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A novel amphiphilic block polymers based on peracetylated maltoheptaose and poly(2-ethyl-2-oxazoline)(AcMH-b-PEtOz) was synthesized by endcapping reaction. Their structures were confirmed by the combined analyses from hydrogen nuclear magnetic resonance(¹H NMR), gel permeation chromatograph(GPC) and Fourier transform infrared spectrometry(FTIR). Their micellar formation and characteristics in an aqueous phase were investigated by means of ¹H NMR, fluorescence spectrum, transmission electron microscopy(TEM), dynamic light scattering(DLS) and UV-Visible spectrum. It was found that the obtained block polymers could self-assemble into nanosize spherical micelles with a core-shell structure in aqueous solution triggered by its amphiphilic character without any organic solvent and exhibited thermal sensitivity. The critical micelle concentration(cmc) of the micelles ranged from 4 to 7 mg/L with mean diameters in the range of 83—115 nm and lower critical solution temperatures(LCST) in the range of 49—64 ℃. The cmc, size and thermal sensitivity of the self-assembled micelles could be tailored by changing the PEtOz content of the resultant block polymer.

Preparation and Characterization of PLGA Nanospheres Surface Modified with Biotinylated Chitosan

CHEN Hong-Li*, TANG Hong-Bo, YANG Wen-Zhi, CHEN Han, WANG Yin-Song, MEI Lin, ...

2010, 31(8):  1682-1687. 

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Biotinylated chitosan(Bio-CS conjugates or Bio-CS) were synthesized and characterized. The degree of substitution(DS), as defined as the number of biotin per 100 anhydroglucose units of CS, was determined by ¹H NMR and ICP. Poly(lactic-co-glycolic acid)(PLGA) nanospheres were prepared by a solvent evaporation technique(W₁/O/W₂). The surface of PLGA nanosphere was modified with Bio-CS by covalent binding. PLGA nanospheres were almost spherical in shape under the scanning electron microscopy(SEM) observation, and their mean diameter determined by the laser light scattering technique was (248.4±21.0) nm. Bio-CS modified PLGA nanospheres were also spherical in shape; their mean diameter and Zeta potential value were (268.3±23.4) nm and -(21.21±2.13) mV, respectively. The surface chemistry of nanospheres was quantitatively studied by X-ray photoelectron spectroscopy(XPS). The results show the N region corresponding to the primary amide of CS and the S region corresponding to the biotin, indicating that PLGA nanospheres were successfully surface-modified with Bio-CS. The content of biotin on the surface of Bio-CS modified PLGA nanospheres with DS of biotin of 31% was determined using a commercially available Quant*TagTM Biotin Kit and its value was (1.36±0.34) mol/100 mg.



Preparations of Nano/Micro Structured Polyaniline Membranes for pH Sensing

SONG Ji-Xia, HAN Dong-Xue*, LI Fei, NIU Li

2010, 31(8):  1688-1692. 

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Effect of acidity on the growth of polyaniline nanostructures was investigated in various acidic media, such as 0.1 mol/L H₂SO₄, phosphate buffer solutions(PBS) at pH=4 and pH=7, and 0.1 mol/L ammonium hydroxide. PANI nanostructures, such as nanocactus, micromats, microflakes, microroses and interconnected three-dimensional networks, microdendrimers, microbranches, etc., were synthesized using ammonium persulfate as oxidant under frozen condition in solution and on dipped substrates, respectively. A possible mechanism for forming those PANI nanostructures, ascribed to pH effect and the crystalline anisotropy of ice to direct growth, was proposed. In addition, induction of dipped substrates and diffusion-limited growth play key roles in forming dendritic morphology on them. Moreover, pH responses of those four nanostructured PANI membranes in-situ deposited on glass substrates were further examined in the range of pH=3—9, which resulted in a high sensitivity.