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    10 July 2012, Volume 33 Issue 07
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    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.33 No.7(2012)
    2012, 33(07):  0-0. 
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    Letter
    High Sensitive Interface Fluorescent Sensing for DNA Based on Energy Transfermation Between Graphene and QDs Self-assembly Multilayers
    LI Cong-Cong, SUN Xiang-Ying, YANG Chuan-Xiao
    2012, 33(07):  1367-1369.  doi:10.3969/j.issn.0251-0790.2012.07.001
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    Fluorescent self-assembly multilayers(SAMs) Quartz/PDDA/PSS/PDDA/CdTe/ssDNA, with ssDNA fixed onto the outermost layer were designed. The SAMs were fabricated onto the quartz surface using CdTe quantum dots(QDs) as a fluorescence probe, which can effectively sense biomolecules by fluorescence resonance energy transfer(FRET) from QDs to graphene oxide(GO). GO can quench fluorescence of SAMs. When tDNA was added, upon the strong interaction between ssDNA and tDNA, tDNA was accumulated on the surface of SAMs in place of GO. The distance between the SAMs and GO increased, which significantly hindered the FRET between CdTe and GO. Thus, the fluorescence of CdTe increased with tDNA adding. The constructed ssDNA SAMs could be sensing for tDNA at the solid-liquid interface with extremely high sensitivity. A good linear relationship between the relative fluorescence intensity F/F0 and concentration of tDNA is obtained in the range from 7.00?10-13 to 2.13?10-11 mol/L, the detection limit is 7.26?10-14 mol/L.

    Preface
    Reversible Oxygenation Properties of 2,3-Diaminopropanoic Acid Cobalt Complex
    ZHANG Xin-Cun, YUE Fan, HUANG Yan, FU Pei, CHENG Xiang, WANG Ji-De
    2012, 33(07):  1370-1375.  doi:10.3969/j.issn.0251-0790.2012.07.002
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    Oxygenation property and reversibility of 2,3-diminopropanoic acid were continuously determined by means of UV-Vis spectrophotometry under alternating O2 or N2 atmospheres and oxygen electrode. The results show that the reversibility of the complex is excellent in aqueous solution at room temperature. Oxygenation reaction took place at pH=6.5 system and formed a stable species in a pH range of 7.0-10.0 according to pH-A curve. The component of oxygenation species was n(Co)∶n(DAPA)∶n(O2)=1∶2∶1 which was confirmed by equimolar ratio and gas volumetric method. UV-Vis spectra were recorded at 384 nm and room temperature in pH=7.0 aqueous solution. The results show that 5% of its original oxygenation capacity is still remained after DAPA-Co(Ⅱ) continuously undergoes 150 oxygenation-deoxygenation cycles in 85 h.
    Controlled Fabrication of Mn0.6Zn0.4Fe2O4 Magnetic Submicrospheres and Their Magnetic Properties
    WANG Yi-Long, ZHANG Huan, ZHAO Su-Ling
    2012, 33(07):  1376-1382.  doi:10.3969/j.issn.0251-0790.2012.07.003
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    Monodispersed manganese-zinc ferrite(Mn0.6Zn0.4Fe2O4) submicrospheres were synthesized by a simple solvothermal method. The influences of reaction parameters on the structure, morphology, diameter and magnetic properties of the Mn0.6Zn0.4Fe2O4 submicrospheres were investigated. The results showed that metal ions were first hydrolyzed to form ferric hydroxide, manganic hydroxide and zinc hydroxide, which then dehydrated to form Mn0.6Zn0.4Fe2O4 nanoparticles. These Mn0.6Zn0.4Fe2O4 nanoparticles first agglomerated to produce homogeneous submicrospheres with loose structure, and finally evolved into compact monodispersed submicrospheres through Ostwald ripening. Increasing the amount of ethylene glycol or polyethylene glycol or decreasing pH value, the diameter of the submicrospheres could be controlled in a range of 150-500 nm, while the size of nanoparticle which composed the submicrospheres decreased, consequently, saturation magnetization increased, remanence and coercivity decreased.
    Preparation and Properties of High-quality CdSeS Alloyed Quantum Dots in Liquid Paraffin
    ZHANG De-Long, LI Wan-Wan, WANG Xie-Bing, SUN Kang
    2012, 33(07):  1383-1388.  doi:10.3969/j.issn.0251-0790.2012.07.004
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    A phosphine-free route was successfully developed to prepare highly-quality cadmium selenium sulfide(CdSeS) alloyed quantum dots(QDs) using paraffin liquid as the reaction solvent and oleic acid as the ligand. The effects of the reaction temperature, growth time, and the molar ratio of S to Se on the properties of the CdSeS QDs were investigated. The as-prepared alloyed CdSeS QDs with zinc-blend crystalline structure possess a broad emission spectral ranging from 370 nm to 595 nm(from near-ultraviolet to salmon pink) and high photoluminescence quantum yield(PLQY) up to 65%. Moreover, the as-prepared alloyed CdSeS QDs with a gradient "CdS-rich core/CdSe-rich surface" structure also demonstrate good optical stabilities against the temperature change and photobleaching, which suggests their promising application on photoelectric devices and biological fluorescent labeling.
    Preparation and Characterization of BaTiO3-NixZn1-xFe2O4 Core-shell Particles by Homogeneous Coprecipitation
    YU Mei, HU Jing-Zhi, LIU Jian-Hua, LI Song-Mei
    2012, 33(07):  1389-1393.  doi:10.3969/j.issn.0251-0790.2012.07.005
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    BaTiO3-NixZn1-xFe2O4 core-shell particles were prepared by plating NixZn1-xFe2O4 magnetic films on BaTiO3 via homogeneous coprecipitation with urea as the precipitator. The phase structure, morphology, particle size, shell thickness, chemical composition and magnetic performance of the core-shell particles were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), energy dispersive X-ray spectroscopy(EDS) and vibrating sample magnetometer(VSM), respectively. The results show that compact and continuous coatings of NixZn1-xFe2O4 are formed on the surface of the BaTiO3. The magnetic performance of BaTiO3-NixZn1-xFe2O4 core-shell particles could be controlled via regulating the molar ratio of NiCl2·6H2O to ZnCl2 added in the experiment. When the molar ratio of NiCl2·6H2O to ZnCl2 is 7∶3, the saturation magnetization(Ms) and the coercivity(Hc) of the as-sample are 26.999 A·m2/kg and 902.787 A/m, respectively.
    Construction of Bio-functional Nanosized Silica Microspheres for Capture and Separation of Glutathione S-Transferase
    ZOU Xue-Yan, CHU Liu-Jie, DONG Shuo, ZHAO Yan-Bao, LI Bin-Jie
    2012, 33(07):  1394-1400.  doi:10.3969/j.issn.0251-0790.2012.07.006
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    Nanosized silica microspheres with sulfydryl group(nSiO2-SH) were synthesized with(3-mercaptopropyl)trimethoxysilane(MPS) via one-step hydrolyzing process, and the effects of volume ratio of water to ethanol, reaction temperature, reaction time and the volume of MPS on the product morphologies were discussed. Additionally, the possible reaction mechanism was also proposed. The prepared nSiO2-SH microspheres reacted further with glutathione through disulfide bond(-S-S-) to produce nSiO2-GSH microspheres. Their morphology, size and ingredient were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared spectrometry(FTIR) and thermogravimetric(TG) analysis. The behavior of capture and separation of glutathione S-transferase(GST) was detected by sodium dodecylsulfate-polyacrylamide gel electrophoresis(SDS-PAGE) method. The results show that GST can be specifically adsorbed on nSiO2-GSH microspheres in the mixed protein solution. Therefore, nSiO2-GSH microspheres have potential applications in the separation, purification and detection of the GST-tagged fusion proteins.
    Analytical Chemistry
    Investigation of MRP1 Molecules on Cell Membrane Based on Single Molecule Atomic Force Microscopy
    WANG Qing, SUN Xiao-Lan, YANG Xiao-Hai, WANG Ke-Min, WU Chun-Ling, CHEN Tong
    2012, 33(07):  1401-1406.  doi:10.3969/j.issn.0251-0790.2012.07.007
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    Multidrug resistance(MDR) is one of the main factors in the failure of chemotherapy against tumors, and multidrug resistance-associated protein 1(MRP1) is closely related to the generation of MDR. In this work, the interaction force between MRP1 and anti-MRP1 was measured via single-molecule force microscopy(SMFM), and the expression differences of MRP1 on human tongue cancer cells before and after treatment with high-dose bleomycin(BLM) were investigated. The results show that the interaction force between MRP1 and anti-MRP1 is about (182±35) pN as the loading rate is 2.5 μm/s. The expression of MRP1 on human tongue cancer cell membrane increased obviously after treatment with high-dose BLM. This work may provide a new method for studying the expression of MRP1 at the living cell level and can be helpful for the study of MDR.
    Synthesis and Application of an Efficient and Sensitive DNA Fluorescent Probe
    WU Tong, PENG Xiao-Jun, HU Ming-Ming, LIU Fei, FAN Jiang-Li
    2012, 33(07):  1407-1412.  doi:10.3969/j.issn.0251-0790.2012.07.008
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    A novel thiazole orange dimmer derivative Bi-TO3 was developed. The interaction of Bi-TO3 with DNA was investigated through the absorption, emission, circular dichroism spectroscopy and live-cell imaging experiments. As a specific probe for DNA, Bi-TO3 itself was almost non-fluorescent(quantum yield<0.001%) in buffer. Upon binding to DNA, the fluorescence of Bi-TO3 increased approximately 950-fold, even without interferences of responding to RNA, BSA, viscosity, etc. Absorption and circular dichroism spectra showed that Bi-TO3 associated with DNA in a minor groove binding mode. The emission detection limit was 13.3 ng/mL, which manifested that Bi-TO3 could detect trace DNA in solution. Moreover, Bi-TO3 could be applied for live-cell fluorescence imaging with relatively low concentrations of 6-12 μmol/L.
    Prediction of Enantiomeric Excess in Asymmetric Reaction
    ZHANG Qing-You, ZHANG Dan-Dan, SUO Jing-Jie, LI Jing-Ya, LONG Hai-Lin, XU Lu
    2012, 33(07):  1413-1419.  doi:10.3969/j.issn.0251-0790.2012.07.009
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    In order to assist enantioselective catalyst screening for asymmetric hydrogen transfer to acetophenone, the model of quantitative structure-activity relationship between the enantiomeric excesses(e.e.) of the products and the structures of the catalysts was constructed. The chiral catalysts can be synthesized by chiral amino alcohol and metal complex precursor, thus, the chiral catalysts were represented by the combination of conformation-independent chirality codes or conformation-dependent chirality codes which were derived from the structures of chiral amino alcohols and indictor variables which were used to distinguish metal complex precursor. The variables selection was performed by genetic algorithm, and then the mathematics model was built by Random Forest to make prediction of e.e. A correlation coefficient of R2=0.769 was obtained for the test set, and the result of out-of-bag(OOB) cross-validation of the whole dataset was R2 =0.785.
    Detection of Hepatitis B Virus DNA Hybridization Based on Dual Gold Nano-probes
    XING Ya-Si, ZOU Neng-Li, MAO Hong-Ju, XU Xia, GE Yu-Qing, JIN Qing-Hui, ZHAO Jian-Long
    2012, 33(07):  1420-1425.  doi:10.3969/j.issn.0251-0790.2012.07.010
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    A novel Hepatitis B virus(HBV) DNA detection method based on dual gold nano-probes and gene chip was developed. Two types of probes including capture probe and reporter probe were designed according to conservative HBV DNA. A pair of complementary gold nanoparticles probes was used to amplify the signal of HBV DNA and visualized by silver staining on gene chip. The optimized detection limit of this method was 10 fmol/L, and the entire test could be completed in 1.5 h. This strategy could be potentially used for HBV DNA detection due to its rapid, high-sensitivity and low-cost properties.
    Covalent Immobilization of Avidin onto Magnetic Nanoparticles and Application in Rapid Determination of Protein A
    SUN Shu-Guo, MA Mei-Hu, QIN Fang, XU Ya-Ru, YU Wen-Zhen, LUO Zhang
    2012, 33(07):  1426-1431.  doi:10.3969/j.issn.0251-0790.2012.07.011
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    Covalent immobilization of avidin onto Fe3O4 magnetic nanoparticales(MNPs) via a facile solvethermal synthetic method was carried out using glutaraldehyde as a crosslinking agent. Immobilization process was monitored and avidin immobilized magnetic nanoparticles(Avi-MNPs) were characterized by TEM, XRD, UV-Vis, FTIR and fluorescence spectroscopy. Evaluation of Avi-MNPs activity and its application for the determination of the concentration of protein A were also performed. TEM images show the average particle diameters of the non-functional MNPs and Avi-MNPs are approximately 30 and 50 nm, respectively, and all the nanoparticles have a uniform distribution. XRD analysis indicates that the characteristic diffraction peaks of MNPs are the same as Fe3O4 and MNPs are high purity. Firstly glutaraldehyde was linked to MNPs and then avidin was immobilized onto the surface of the functional MNPs, which were verified by UV-Vis, FTIR and fluorescence spectroscopy. The activity evaluation of Avi-MNPs shows that the activity is 4.706 U/mg of D-biotin bound/mg Avi-MNPs and lower than 14.1 U/mg D-biotin bound/mg free avidin. The Avi-MNPs were applied to the determination of the concentration of protein A, the results indicated that this method has an advantage of saving time and effort compared to the traditional enzyme-linked immunosorbent assay and can be carried out with a simple UV-Vis spectrophotometer.
    Fluorescence Spectrometry and UV-Vis Absorption Spectra Analysis of Interaction of Core-shell CdTe/CdS QDs with Palmatine Chloride and Its Applications
    YIN Peng-Fei, GONG Hui-Ping, LI Ping-Ping, LIU Zheng-Qing, HE You-Qiu
    2012, 33(07):  1432-1437.  doi:10.3969/j.issn.0251-0790.2012.07.012
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    Core-shell CdTe/CdS quantum dots(QDs) were synthesized using mercaptoacetic acid as stabilizer. A novel method for the determination of palmatine chloride(PC) was developed based on the quenching of the fluorescence of CdTe/CdS QDs at an excitation wavelength of 340 nm. Fluorescence spectrometry and ultraviolet-visible(UV-Vis) absorption spectra were utilized to study the interaction between CdTe/CdS QDs and PC. With the optimum reaction conditions of pH=7.4 Tris-HCl buffer solution, the quenched fluorescence intensity of CdTe/CdS QDs was linearly proportional to the concentration of PC with a correlation coefficient of r=0.997, and the detection limits were in the range of 25-1×104 ng/mL and the detection limit(3σ) for PC was 7.7 ng/mL. This new method can quickly, simply, conveniently and quantitatively detemine PC.
    Effect of CCl4 on Antibiotics Levofloxacin’s Ultrasonic Degradation
    WEI Hong, LI Juan, LI Ke-Bin, SUN Jian-Yu, ZHAO Feng
    2012, 33(07):  1438-1443.  doi:10.3969/j.issn.0251-0790.2012.07.013
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    The ultrasonic degradation of quinolone antibiotics levofloxacin in water with CCl4 enhancement was investigated. The effects of CCl4 dosage, ultrasonic power, pH value and initial concentration of levofloxacin were discussed. The products were examined by HPLC and LC-MS/MS. The results indicated that the ultrasonic degradation of levofloxacin was obviously enhanced by CCl4 addition; the degradation efficiency increased from 1.9% to 69.2% with CCl4 dosage changed from 0 to 0.06%(volume fraction). The enhancement effect was attributed to the increasing ·OH radical concentration and formation of chlorine-containing radicals in the presence of CCl4 during ultrasonic processes. Levofloxacin degradation efficiency by ultrasonic in the presence of CCl4 increased with the increasing of ultrasonic power in 100-200 W. The pH values of solution had prominent effect on levofloxacin degradation, while the initial concentration of levofloxacin had a negative effect. The temperature between 33-49 ℃ was found to be favorable to levofloxacin degradation. Moreover, HPLC analysis showed that two main by-products were simultaneously produced in the course of the ultrasonic degradation of levofloxacin in addition of CCl4, the two products were confirmed by LC-MS/MS analysis.
    Synthetic Reaction Mechanism of Octogen by Chemometrics and Infrared Spectroscopy
    ZHANG Shu-Li, XIONG Xian-Feng, YU Tao, WANG You-Bing, WANG Bo-Zhou, GE Zhong-Xue, ZHAI Gao-Hong, LI Hua
    2012, 33(07):  1444-1449.  doi:10.3969/j.issn.0251-0790.2012.07.014
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    Online IR spectrum was used for monitoring the reaction process of synthesizing octogen(HMX). The concentration profiles and IR spectra of reactants, intermediates and product were determined by analyzing the spectral data using multivariate curve resolution-alternating least squares(MCR-ALS) and heuristic evolving latent projection(HELP), and the reasonable mechanism was deduced. The stable geometry of intermediates was optimized at B3LYP/6-31G* theoretical level. Its vibrational frequencies and IR spectra were obtained on the basis of vibrational analysis. The results showed that the variation of intermediates could be obtained quickly with the aid of chemometric resolution and provided significant guidance to the choice of reaction.
    Characterization of Transformation Pattern of Baicalin Using UV Spectrometric Analysis and Multivariate Curve Resolution
    ZHENG Xin-Tian, QU Hai-Bin
    2012, 33(07):  1450-1455.  doi:10.3969/j.issn.0251-0790.2012.07.015
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    Investigation of the transformation pattern of bacalin contributes to the quality control of scutellaria preparations. In this work, UV spectrometric method was used to record the UV spectra during transformation process of baicalin under different conditions. Multivariate curve resolution was utilized to analysis the spectra for resolving concentration and spectra profiles of the reactant species. The transformation kinetic profile of baicalin was evaluated as consecutive two-step one-order reaction. Transformation products were deduced by high performance liquid chromatography-tandem multistage mass spectrometric and time-of-flight mass spectrometric analysis of samples collected at different times during reaction process. The transformation products of baicalin included isomerides of baicalin, baicalein and dimmer of baicalein. The possible transformation pathway of baicalin was also inferred.
    Organic Chemistry
    Synthesis of Poly(ethylene glycol)-poly(L-lysine) Diblock Copolymer Incorporating Tetra-(p-sulfoazophenyl-4-aminosulfonyl)phthalocyanine Chloride Aluminum(Ⅲ) Polyion Nanoparticles and Its in vitro Photodynamic Therapy Efficacy
    MA Dong-Dong, LIN Ping-Ping, CHEN Li-Li, WANG Yu-Hua, HE Dan-Dan, CHEN Wan-Ling, ZHANG Tian-Tian, CHEN Kui-Zhi, PENG Yi-Ru
    2012, 33(07):  1456-1461.  doi:10.3969/j.issn.0251-0790.2012.07.016
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    A novel tetra-(p-sulfoazophenyl-4-aminosulfonyl)phthalocyanine aluminum(Ⅲ) chloride(S-AlPc) was synthesized and characterized by elemental analysis, IR, 1H NMR and ESI-MS. Polyion nanoparticles(S-AlPc/PbP) loaded with S-AlPc were formed through electrostatic self-assemble by negatively charged sulfonate groups with positively charged PLL of the poly(ethylene glycol)-poly(L-lysine) amphiphilic diblock copolymer(PEG-b-PLL). The diameter of S-AlPc/PbP was about 10-20 nm. The photophysical properties of S-AlPc/PbP and S-AlPc were compared by UV-Vis, steady-state and time-resolved fluorescence spectroscopy. The time-depended uptake amounts of S-AlPc and S-AlPc/PbP in the human umbilical cord blood endothelial cells(HUVEC) were studied. The uptake amounts of S-AlPc/PbP by HUVEC reached maximum about one hour earlier than that of the S-AlPc. The phototoxicity of S-AlPc and S-AlPc/PbP was evaluated by MTT method. The inhibition rate of S-AlPc/PbP was also significantly increased. These results obviously indicated that S-AlPc/PbP is a potential 3rd generation photosensitizer for photodynamic therapy.
    Synthesis and Characterization of 4,4'-Di(p-aminophenylethynyl)-6,6'-bis[N,N-bis(ethoxycarbonylmethyl)amino methyl]-2,2'-bipyridine
    CAO Xi-Jie, XIE Wen-Bing, PAN Li-Hua, CHANG Yu, CUI Shan-Zi, ZHANG Hong-Jie, DANG Dan-Dan
    2012, 33(07):  1462-1465.  doi:10.3969/j.issn.0251-0790.2012.07.017
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    In order to obtain a new solid phase time-resolved fluorescence immunoassay chelate, a new intermediate compound 4,4'-(p-aminophenylethynyl)-6,6'-bis[N,N-bis(ethoxycarbonylmethyl)amino methyl]-2,2'-bipyridine was prepared from 4,4'-dinitro-2,2'-bipyridine-6,6'-dimethyl bis(trifluoroacetate) by hydrolyzation, bromination, esterification and substitution. The structure of the compound was charactered by DSC, IR, 1H NMR and HRMS. The compound was hydrolyzed in the solution of europium ion, forming a rare earth fluorescence chelate. The fluorescence spectrum of the chelate excited by an light source has peaks peculiar to the europium ion.
    Selective Synthesis of Bromo-substituted Naphthalene Dianhydride Derivatives
    ZHANG Ping-Zhu, WEI Chao, DUAN Xiao-Xu, ZHANG Xiao-Yuan, WANG Ke-Rang, CHEN Hua, LI Xiao-Liu
    2012, 33(07):  1466-1470.  doi:10.3969/j.issn.0251-0790.2012.07.018
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    In recent years, core-substituted 1,4,5,8-naphthalene diimides (cNDIs) have been widely used in numerous research fields, such as materials and supramolecular chemistry. As the important precursors for the synthesis of cNDIs, 2-bromo and 2,6-dibromo-1,4,5,8-naphthalene dianhydride derivatives are difficult to separate from each other, but their mixture is easily obtained according to the most synthesis conditions which have been reported. In order to develop an efficient, practical method to obtain 2-bromo and 2,6-dibromo-1,4,5,8-naphthalene dianhydride derivatives respectively, the reaction were performed with NaBr and oleum as the bromide reagents under atmospheric pressure, and the effects of reaction time, temperature, SO3 content in oleum and NaBr quantity were investigated. 2-Bromo and 2,6-dibromo-1,4,5,8-naphthalene dianhydride derivatives were selectively synthesized. Their structures and yields were characterized by derivatization of them for their napnthalimide compounds.
    Synthesis and Characterization of a Series of Olefinated Aromatic Heterocyclic Compounds
    ZHANG Bian-Xiang, YANG Qi, HE Xiao-Xia, CHAO Jian-Bin, CHANG Jiao, WU Qun
    2012, 33(07):  1471-1475.  doi:10.3969/j.issn.0251-0790.2012.07.019
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    Heteroaromatic compounds are among the most important heterocyclic compounds. Olefinated aromatic heterocyclic compounds are important intermediates used not only as building blocks in the synthesis of natural products but also as key structural units of compounds with interesting biological activity. In this study, a series of olefinated aromatic heterocyclic compounds were prepared by palladium-catalyzed olefination via cross dehydrogenative coupling of C—H bonds. The effects of various conditions[5%(molar fraction) Pd(OAc)2, 60 ℃, 24 h] on the reaction were investigated by HPLC analysis. Their structures were determined by UV spectra, proton magnetic resonance and single crystal X-ray diffraction. The reaction was highly region- and stereoselective, giving trans-olefins predominantly by solvent controlled(AcOH/Ac2O), and its reaction mechanism was discussed.
    Optimization of Synthetic Method of Marinopyrrole A Derivatives
    PAN Li-Li, CHENG Chun-Wei, SONG Hao
    2012, 33(07):  1476-1480.  doi:10.3969/j.issn.0251-0790.2012.07.020
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    Marinopyrrole A, containing a novel structure with high halogenated bipyrrole, was found to exhibite antibacterrial activity against Methicillin-resistant staphylococcus aureus(MRSA), and against the human cancer cell(HCT-116). Owing to its low potency and high toxicity in vivo, the synthesis of Marinopyrrole A derivatives has become a new hot spot in natural products research.6-Flourobenzene of Marinopyrrole A was obtained by protection, addition step-by-step, oxidation, deprotection of the Ts group, chlorinated and deprotection of methyl group reactions from the starting material dialdehyde compound 1, and finally the yield was 13% after 9-step reactions. The structures of the compounds were confirmed by IR, 1H NMR, 13C NMR and HRMS. Especially, the cyclic ether intermediate 3, necessary in original way, was no longer formed using the addition step-by-step and oxidation, and the total yield was improved. The examination approach provides a new synthetic way for the series Marinopyrrole A derivatives.
    Synthesis and Bioactivity of N-(2-Alkoxy-2-substituted phenyl-ethyl)phenyl Amide
    YAO Hong-Wei, CUI Can, LI Yong-Qiang, WANG Li-Zhong, LI Zheng-Ming, ZHAO Wei-Guang
    2012, 33(07):  1481-1485.  doi:10.3969/j.issn.0251-0790.2012.07.021
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    Mandipropanid is the first mandelamlamide fungicide on the market. A series of novel N-(2-alkoxy-2-substituted phenyl-ethyl) phenyl amide(8) was designed according to exchange the position of NH and C=O from mandipropamid. The target compounds were synthesized from benzene acetic acid and acetophenone(3) by bromination, amination and so on. Their structures were characterized by 1H NMR, elemental analysis or high resolution mass spectra(HRMS). The results of the preliminary biological activity tests show that some of them like compound 8k exhibit good anti-fungal activities against Pseudoperonospora cubenis at 100 μg/mL. The study also finds that these compounds have a certain control on the effect of Tetranychus cinnabarinus.
    Synthesis of 18F-c(RGDfK) as Integrin αvβ3 Targeted PET Tracer via Click Chemsitry with Cu(Ⅰ) Catalyst Systems
    SHI Ling-Li, LI Jian-Bo, WANG Cheng, JIA Li-Na, WANG Yong-Xian, ZHANG Lan
    2012, 33(07):  1486-1489.  doi:10.3969/j.issn.0251-0790.2012.07.022
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    As one of the most important types of Click chemistry, copper-catalyzed 1,3-dipolar cycloaddition reaction has attracted great attention. In this study, 2-[18F]fluoroethyl azide([18F]FEA) was synthesized by nucleophilic substitution of 18F-. Then, [18F]fluoroethyl-1H-1,2,3-triazole-4-c(RGDfK)[18F-c(RGDfK)] was radio-synthesized as integrin αvβ3 targeted PET tracer fast and efficiently via Click reaction of [18F]FEA with propioloyl c(RGDfK). Three catalyst systems of click reaction were investigated: CuSO4/NaVc, CuI(s) and CuI/NH4OH, the last two have been used in peptide-click-labeling for the first time. While CuSO4/NaVc catalysing the Click reaction, the total radio-chemistry yield of 18F-c(RGDfK) was 62% and the synthesis time was about 60 min(decay-corrected). Click chemistry has demonstrated to be an extraordinarily efficient and convenient method for the preparation of 18F labeled peptides.
    Complex Pd(Ⅱ) with Vinylphosphine and Its Application in Sonograshira Cross Coupling Reaction
    FU Yu-Hong
    2012, 33(07):  1490-1492.  doi:10.3969/j.issn.0251-0790.2012.07.023
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    During the past years, the interest in complexes of transition metals with organophosphorus ligands has been growing considerably in the light of their versatile applications in coordination chemistry and homogenerous catalysis. The palladium system has good prospects in the catalytic application. Particularly for a lack of selectivity under classic conditions or for base sensitivity of the functional groups, transition metal catalysis under mild and neutral conditions offers a promising and superior alternative. A (1,2-diaryl)vinylphosphine ligand has one aryl group at the α-position and one aryl group at the β-position, respectively. The ligand more steric hindrance and electron-richness around the phosphorus atom was synthesized. Complex of palladium-(1,2-diaryl)vinylphosphine as a catalyst shows highly catalytic activity in Sonograshira cross coupling reaction.
    Biological Chemistry
    Effect of Phosphorylation on the Production of 7900 and 9300 Fragments of D1 Protein
    CHEN Liang-Bing, DU Li-Bo, TIAN Qiu, JIA Hong-Ying, GAO Yan-Li, LIU Yang
    2012, 33(07):  1493-1497.  doi:10.3969/j.issn.0251-0790.2012.07.024
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    So far it is unclear whether the phosphorylation protects D1 protein by decreasing the production of 7900 and 9300 fragments of this protein, and reactive oxygen species affect the production of these two fragments in phosphorylation condition. In this study, 7900 and 9300 fragments of D1 protein were detected in non-phosphorylated and phosphorylated photosystem Ⅱ(PSⅡ) membranes using Western blotting technique. It was found that reactive oxygen species including superoxide anion, hydrogen peroxide and hydroxyl radical were involved in the production of 7900 and 9300 fragments of D1 protein in both the non-phosphorylated and phosphorylated forms. And it was also found that phosphorylation could partially inhibit the production of 7900 and 9300 fragments of D1 protein, which played a protective role in D1 protein.
    Expression of Aspergillus aculeatus β-Glucosidase Ⅰ Gene in Pichia pastoris and Its Application on the Synthsis of Alkyl Glucoside
    WEI Bin-Ru, LIU Duan-Yu, HAN Shuang-Yan, LIN Ying, ZHENG Sui-Ping
    2012, 33(07):  1498-1504.  doi:10.3969/j.issn.0251-0790.2012.07.025
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    β-Glucosidases, as a specific group of glycosyl hydrolase could catalyze the hydrolysis of β-1,4-glycosidic bond presented in short-chain oligosaccharides(containing 2-6 monosaccharides), are widely used in the degradation of cellulose, the improvement of food flavor and so on. The gene of Aspergillus aculeatus NO. F-50 β-glucosidase Ⅰ was cloned and integrated into Pichia pastoris GS115, in which β-glucosidase Ⅰ can be expressed and secreted in an active form. The recombinant β-glucosidase Ⅰ had an optimum pH of 5.0 and an optimum temperature of 65 ℃ using 4-nitrophenyl-β-D-glucopyranoside(pNPG) as substrate. The highest hydrolytic activity and protein expression level at 50 ℃ in the culture supernatant of recombinant strain were up to 33.8 U/mL and 0.388 mg/mL, respectively. The recombinant β-glucosidase Ⅰ was found to be able to catalyze the synthesis of alkyl glucoside through reverse-hydrolysis or trans-glycosylation reaction. Some major influential factors in water/organic two-phase system such as pH value, water content, overall concentration of glucose and enzyme concentration were optimized. The yield of butyl glucoside, hexyl glucoside, octyl glucoside and decyl glucoside was 51.4%, 28.8%, 6.9% and 3.0%, respectivly.
    Physical Chemistry
    Ab initio Investigation on Unhydrated Ion-associated Species Between Na+, Li+, Mg2+ and SO42- Ions
    WAN Su-Qin, ZHANG Yi, ZHANG Hao, SUN Chia-Chung
    2012, 33(07):  1505-1510.  doi:10.3969/j.issn.0251-0790.2012.07.026
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    The structures of ion-associated species between Na+, Li+, Mg2+ and SO42- ions were optimized via ab initio calculations. And the influences of the cations to the ν1-SO42- frequencies were also investigated. For the ion-associated structures, when there are fewer cations, the repulsion between cations will decrease and thus the bidentate associated structures are easy to form, in which there is shorter distance between metal ion and SO42-. Contrarily, comparing with the increase of the number of cations in the ion clusters, especially for more Mg2+ ions which have more positive charge, the repulsions between metal ions would make the clusters instable and more monodentate structures are formed, in which the distances between metal and SO42- ions are longer. The metal ions could influence the ν1-SO42- frequencies via two ways. The first one is polarization of the cation, which leads the ν1-SO42- frequency red-shift, while another one is M-O bonding action, which lead the opposite blue-shift. When the number of metal ions ≤2, the first one is dominated. The first metal ion can lead the ν1-SO42- frequency red-shift, while more metal ions from different directions would decrease the red-shift. When the number of metal ions >2, the M-O bonding action is the main interaction manner. The increase of the monodentate associated structures in the quadruple or quintuple ion clusters, which can lead the more blue-shift than those of the bidentate ones, will make the ν1-SO42- frequency more blue-shift than those in the triple ion clusters.
    Preparation and Photocatalytic Properties of Magnetically Separable Photocatalyst Nanospheres with Egg-like Structure
    XU Shi-Hong, ZHAO Song-Jian, TAN Dong-Dong, SHI Peng-Hui, BI De-Fu
    2012, 33(07):  1511-1516.  doi:10.3969/j.issn.0251-0790.2012.07.027
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    A novel magnetically separable photocatalyst nanosphere TiO2@SiO2@NiFe2O4(TSN) with egg-like structure was prepared by reverse micelles method and electrostatic self-assembly method. The photocatalyst shows high photocatalytic activity for the degradation of methyl orange in water. The magnetic property measurements indicate that the photocatalyst possesses a superparamagnetic nature, which can be separated and recycled conveniently through an external magnetic field. X-ray diffractometer(XRD) and transmission electron microscope(TEM) were used to characterize the structure of the TSN photocatalyst nanosphere. The results indicate that nickel ferrite core nanoparticles are completely encapsulated into silica nanospheres as carrier, and titania nanoparticles are assembled onto the surface of SN nanospheres, forming a TiO2 shell for photocatalysis. The SiO2 layer between the NiFe2O4 core and the TiO2 shell effectively prevents the injection of charges from TiO2 particles to NiFe2O4, which gives rise to an increase in photocatalytic activity.
    Sum Frequency Generation Vibrational Spectroscopy Study of Fe3O4 Nanoparticles Modified by Oleic Acid Molecules
    HUANG Zhi, GUO Yuan
    2012, 33(07):  1517-1522.  doi:10.3969/j.issn.0251-0790.2012.07.028
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    The sum frequency generation vibrational spectroscopy(SFG-VS), an interface selective and chemical specific nonlinear optical technology, was used to study the Fe3O4 nanoparticles modified by oleic acid molecules. The SFG spectra of two different experimental configurations(configuration 1: the incident angle of visible laser beam is 63?; configuration 2: the incident angle of visible laser is 45?) and three polarization combinations(ssp, ppp and sps) were investigated. The coherent features of SFG spectra in different experimental configurations were analyzed and the vibrational modes of the spectral peaks were assigned according to the polarization selection rules.
    Volumetric Properties of Binary Systems of n-Butanol or n-Pentanol+JP-10
    XIAO Juan, GUO Yong-Sheng, YANG Yu-Zhong, GONG Xian-Jie, FANG Wen-Jun, LIN Rui-Sen
    2012, 33(07):  1523-1527.  doi:10.3969/j.issn.0251-0790.2012.07.029
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    The kinematic viscosities and densities of the binary mixtures of n-butanol/n-pentanol+JP-10(exo-tricycle[5.2.1.02.6]decane, C10H16) were determined at 298.15 K via Ubbelohde viscometer and Anton PaarDMA55 vibrating-tube digital densimeter. Thermodynamic functions of activation of the binary systems were calculated according to the absolute rate theory approach of Eyring, which indicate ΔH0≠ plays a major role. Excess molar volumes, excess partial molar volumes, apparent molar volumes and partial molar volumes were calculated based on the densities data. The results indicate that VmE of the binary systems are positive.
    Microwave-assisted Preparation and Microwave Enhanced Photodegradation Dyes of the Three-dimensional Spherical ZnO Nanoclusters
    LI Li, LI En-Shuai, GAO Yu, ZHAO Yue-Hong, ZHUO Na, LU Lu
    2012, 33(07):  1528-1533.  doi:10.3969/j.issn.0251-0790.2012.07.030
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    The spherical ZnO nanoclusters with high photocatalytic activity were prepared through microwave-assisted method. The samples were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), scanning electron microscope(SEM), and nitrogen adsorption/desorption determination. The results indicate that the produced ZnO has wurtzite crystal structure, and the ZnO synthesized through microwave-assisted shows spherical nanoclusters, and its diameter is at about 3-4 μm. The inside and outside of the nanoclusters are different and the epidermis is formed by closely and neatly packed uniform ZnO nano-rods, the kernel has a lots of layered frame consisted by nano ZnO particals. The material is mesoporous and has larger surface area. Photocatalytic properties of the as-synthesized ZnO were tested by the UV irradiation and the microwave enhanced photodegradation of Rhodamine B(RhB). The results show that spherical ZnO nanoclusters synthesized by microwave-assisted exhibit higher photocatalytic activities than that of the sample no microwave irradiation in the prepared process and P25 in microwave situation. In addition, the spherical ZnO nanoclusters can degrade many kinds of dye, the degradation rates of dyes, except for methyl orange, are over 90% within 40 min.
    Effect of Heat-treated Temperature on the Carbon-supported Cobalt Pyridine Electrocatalysts for Oxygen Reduction
    XU Li, LIN Rui, DING Lei, DAI Xian-Feng, QIAO Jin-Li
    2012, 33(07):  1534-1539.  doi:10.3969/j.issn.0251-0790.2012.07.031
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    CoPy/C catalysts for the oxygen reduction reaction(ORR) were prepared with 40/60(mass ratio)(15%Co25%Py/C) using cobalt sulfate hepathydrate(CoSO4·7H2O) and pyridine(Py) as the Co and N precursors supported on Vulcan XC-72R followed by heat treatment in an inert atmosphere at different temperatures ranging from 600 ℃ to 900 ℃. The catalysts were characterized by TEM, XRD and SEM-EDS anlaysis. Their ORR activities as the function of heat treatment temperatures for catalyst synthesis were evaluated by cyclic voltammograms(CVs) and rotating disk electrode(RDE) measurements. The results show that high temperature treatment can greatly improve the ORR activity of CoPy/C catalyst, for which the catalyst synthesized at 800 ℃ exhibits the best ORR activity. The nanoparticles of the catalyst as-prepared, with a diameter of 17 nm, uniformly dispersed on Vulcan carbon(Vulcan XC-72R). XRD and EDS anlaysis indicate that the structure of CoPy/C is destroyed after high temperature pyrolysis, and changed as the different valence cobalt oxide and cobalt sulfide, which are with N and S as the active sites for ORR. In 3.0 mol/L KOH, 15%Co25%Py/C(in O2) can produce the obvious ORR current, giving the onset potential at 0.026 V(vs. SCE) with a half-wave potential of -0.069 V. RDE results further reveal that 15%Co25%Py/C catalysts in 3.0 mol/L KOH solution catalyze the ORR via four-electron pathway, through which the molecular oxygen is directly reduced to H2O.
    Synthesis and Supercapacitance Performance of PANI/MCFs Materials
    WU Juan, WU Xue-Yan, WEI Xiao, WANG Kai-Xue, CHEN Jie-Sheng
    2012, 33(07):  1540-1544.  doi:10.3969/j.issn.0251-0790.2012.07.032
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    A composite material was prepared through the electrochemical polymerization of aniline in the pores or on the surface of mesoporous carbon nanofibers by an electrochemical polymerization method. The surface morphology and structure of the composite material were characterized by scanning electron microscope(SEM) and transmission electron microscope(TEM). The supercapacitance performance of the composite material was investigated by cyclic voltammetry(CV), galvanostatic charge-discharge and Nyquist impedance test with a three-electrode system in 1 mol/L H2SO4 solution. The specific capacitance of the composite material is as high as 391 F/g at a current density of 0.5 A/g in the potential range of -0.2-0.8 V. The cycling stability is much better than that of pure polyaniline.
    Theoretical Studies on Carrier Transport Properties of Oligofluorenythiophene Compounds
    ZHANG Bing, GENG Yun, TANG Xiao-Dan, DUAN Yu-Ai, WU Yong, SU Zhong-Min
    2012, 33(07):  1545-1551.  doi:10.3969/j.issn.0251-0790.2012.07.033
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    Oligothiophene derivatives, as typical carrier transport materials, have received considerable attention. The influence of the thiophene chain length, variation of the substituents and the incorporation of fluoro were investigated by combining density functional theory(DFT) with Marcus theory, focusing on geometries and electronic structures, intramolecular reorganization energy, intermolecular transfer integral and hopping rate. The results show that the electronic hopping rate increases with the increasing of thiophene chain length in the order of compound 1b to 1d. Among compounds 1d, 2a and 2b, compound 1d has the best carrier transport properties due to its better face-to-face π-stacked structure. Compared compound 2b with compound 3, the incorporation of fluoro may be beneficial to the improvement of the stability and transport ability.
    Preparation and Energy Stored Photocatalytic Properties of WO3/TiO2 Composite Fibers
    LI Yue-Jun, CAO Tie-Ping, SHAO Chang-Lu, WANG Chang-Hua
    2012, 33(07):  1552-1558.  doi:10.3969/j.issn.0251-0790.2012.07.034
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    Heterostructured WO3/TiO2 composite fibers were prepared via electrospinning fabrication of anatase fibers by adopting n-butyl titanate as precursors and hydrothermal growth of WO3 nanostructures on anatase fibers substrate. The morphology and structure of WO3/TiO2 composite fibers were characte-rized by X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), transmission electron microscopy(TEM) and high resolution transmission electron microscopy(HRTEM) techniques. The results showed that flower-like WO3 microsphere could evenly grow on the TiO2 fibers surface and thus heterostructured WO3/TiO2 composite fibers were successfully obtained. By employing Rhodamine B degradation as the model reaction, the WO3/TiO2 heterostructures showed enhanced photocatalytic efficiency compared with the bare TiO2 fibers under UV light irradiation. The enhanced photocatalytic efficiency could be ascribed to the promoted electron-hole pairs separation induced by the heterojunction and thus enhanced quantum efficiency. Degradation experiment displays that Rhodamine B can be degraded in darkness by the WO3/TiO2 composite fibers photocatalyst with energy storage degradation activity.
    Preparation and Catalytic Properties of Fe-Ti-MCM-41
    YANG Mu, WANG Xiao-Na, XU Jin-Wu, WANG Ge
    2012, 33(07):  1559-1564.  doi:10.3969/j.issn.0251-0790.2012.07.035
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    Fe incorporated Ti-MCM-41 catalysts were prepared by incipient wetness impregnation method. The samples were characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), high resolution transmission electron microscopy(HRTEM), nitrogen adsorption-desorption isotherms and inductively coupled plasma atomic emission spectrometry(ICP). The effects of doping amounts of Fe and calcination temperature on the catalytic performance of the catalyst were investigated. Catalytic activity tests were conducted in the epoxidation of cis-cyclooctene with aqueous H2O2 as an oxidant. It is found that incorporation of low amount of ferric into the mesoporous material favors to obtain Fe-Ti-MCM-41 catalyst with high catalytic activity. The enhanced catalytic activity may be attributed to that the majority of Fe3+ are highly dispersed by single molecule, which brings up efficient excitation of Ti active sites. More loading amount of Fe3+ leaded to the cluster, so the conversion and selectivity of cyclooctene epoxide decreased.
    Polyacrylamide Gel Synthesis and Visible-light Photocatalytic Activity of TbFeO3 Nanoparticles
    LIN Guan-Jun, YANG Hua, XIAN Tao
    2012, 33(07):  1565-1571.  doi:10.3969/j.issn.0251-0790.2012.07.036
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    A polyacrylamide gel method was used to prepare TbFeO3 nanoparticles, and the influences of diffe-rent chelating agents on the phase purity, particle size and morphology were investigated. X-ray diffraction(XRD) results indicate that single-phase TbFeO3 particles can be prepared at a calcination temperature of 650 ℃ using tartaric acid, citric acid or ethylenediamine-tetraacetic acid(EDTA) as the chelating agent, but the average grain size has a dependence on the choice of the chelating agent. The use of acetic acid or oxalic acid as the chelating agent is difficult to achieve the synthesis of single-phase TbFeO3 samples. Scanning electron microscope(SEM) observations reveal that the particles prepared using tartaric acid as the chelating agent are regularly spherical in shape and highly uniform in size with a small average diameter of ca. 50 nm; the particles prepared using citric acid as the chelating agent mainly exhibit sphere-like shape and have a relatively broad size distribution with an average size of ca. 100 nm; and the particles prepared using the chelating agent EDTA are ellipsoid-like in shaped with adhesive behavior to some extent, but have a uniform size distribution with an average size of ca. 110 nm. The BET specific surface areas of the three samples are 15.4, 8.3 and 6.8 m2/g, respectively. Ultraviolet-visible diffuse reflectance absorption spectra indicate that the TbFeO3 nanoparticles have a bandgap energy of 1.95-1.98 eV. The photocatalytic activity of the TbFeO3 particles has been investigated by the degradation of various organic dyes including methyl orange(MO), rhodamine B(RhB), methylene blue(MB), acid fuchsine(AF), and congo red(CR). It is demonstrated that the products exhibit a pronounced photocatalytic activity under visible-light irradiation. The highest photocatalytic efficiency is observed for the tartaric acid-derived sample.
    Synthesis and Sustained Release Property of Fe3O4@(TF-LDHs) Nanocomposites
    ZHAO Man, XU Jie, HOU Wan-Guo
    2012, 33(07):  1572-1578.  doi:10.3969/j.issn.0251-0790.2012.07.037
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    A series of nonocomposite Fe3O4@(TF-LDHs) possessing a core/shell structure with a tegafur(TF) intercalated Zn-Al layered double hydroxides(LDHs) shell coated onto the surface of magnetic Fe3O4 core was assembled via one step coprecipitation method. The chemical composition, crystal structure, magnetic property, arrangements of TF within interlayer and drug release behavior of the magnetic nanocomposite were investigated systematically by XRD, FTIR, TEM, VSM, ICP and UV-Vis techniques. The results show that Fe3O4@(TF-LDHs) have a paramagnetism and the saturation magnetization were enhanced with increasing the magnetic substrates content. Tegafur molecules were arranged as a bilayer with the long axis slightly tilted to the LDHs layers. The release kinetics of TF from Fe3O4@(TF-LDHs) nonocomposite was investigated in pH=7.2 and pH=4.8 buffer solutions, and it was found that the release process might fit the pseudo-second-order release kinetics and the diffusion of tegafur through the LDHs particle played an important role in controlling the drug release rate. The in vitro drug release rate from the nanocomposite was remarkably lower than that from the corresponding physical mixture, which showed that the Fe3O4@(drug-LDHs) nanocomposites could be considered as a potential magnetic targeting drug delivery-controlled-release system.
    Polymer Chemistry
    Synthesis and Coating Properties of Biomembrane Mimetic Copolymers
    YANG Shan, WANG Yan-Bing, ZONG Ming-Ming, GONG Ming, MA Jia-Ni, GONG Yong-Kuan
    2012, 33(07):  1579-1585.  doi:10.3969/j.issn.0251-0790.2012.07.038
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    2-Methacryloyloxyethyl phosphorylcholine(MPC), a hydrophilic monomer mimicking the cell outer membrane structure, was copolymerized with hydrophobic monomer stearyl methacrylate(SMA), lauryl methacrylate(LMA) and n-butyl methacrylate(BMA), respectively, by monomer-starved polymerization technique. By changing the molar ratio of the monomers in feed, a series of amphiphilic biomembrane mimetic copolymers bearing different hydrophobic alkyl chain groups was synthesized. The 1H NMR and elemental analysis results showed that the compositions of the amphiphilic random bipolymers were similar to the ratios in feed. The DSC results suggested that the glass transition temperature of these copolymers were low. The surface tension measurement indicated that the copolymer coatings rarely dissolved in water. The dynamic contact angles(DCA) of the copolymer coatings in water suggested a changeable surface structure of the coating. When exposed in air, the hydrophobic alkyl chains of the coating oriented onto the surface; while in aqueous conditions, the hydrophilic phosphorylcholine groups migrated and oriented onto the interface to form the cell outer membrane mimetic structure. This study provides theoretical support for improving the biocompatibility of biomaterials simply by immersing in or spraying with the solutions of the cell membrane mimetic amphiphilic copolymers.
    In vitro Studies of Chitosan-based Multifunctional Drug Delivery Nanosystem
    CHEN Rou, YANG Jin-Rong, YANG Xiao-Ying, WANG Yu-Mei, LI Rong-Shan, WANG Rui-Ling, WANG Yin-Song
    2012, 33(07):  1586-1590.  doi:10.3969/j.issn.0251-0790.2012.07.039
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    The preparation method of a chitosan-based multifunctional nano-drug carrier system and its drug release properties were reported. Methotrexate conjugated chitosan(MTX-CS) was synthesized and characterized, and the substitution degree of MTX was 6.3%. MTX-CS had amphiphilic property, thus could form self-assembled nanoparticles in aqueous medium. The mean diameter of MTX-CS nanoparticles was (269.5±18.3) nm, and the zeta potential was (25.7±0.9) mV. MTX-CS nanoparticles could effectively load antitumor drugcombretastatin A-4(CA-4); CA-4 loading content and entrapment efficiency were 15.7% and 62.8%, respectively, when the feed mass ratio of drug and carrier was 1∶4. The in vitro release experiment shows that CA-4 rapidly releases from MTX-CS nanoparticles, but MTX release rate obviously slows, which is favorable for the combination tumor therapy.
    Synthesis of Fluorinated Polyimide with High Thermal Stability and Its Application for Thermo-optic Switch
    JIN Lin, LIU Yu, CAO Zi-Jian, MENG Jie, JIANG Zhen-Hua, ZHANG Da-Ming
    2012, 33(07):  1591-1594.  doi:10.3969/j.issn.0251-0790.2012.07.040
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    A novel material fluorinated hyper branched polyimide(FHBPI) was synthesized for using in thermo-optic waveguide switch applications. This material has high thermal stability. Differential scanning calorimeter(DSC) and thermo-gravimetric analysis(TGA) were taken to evaluate the glass transition temperature(Tg) and the thermal decomposition temperature(Td,5%). The results indicate that Tg and Td,5% are 189 and 596 ℃, respectively. The film quality of FHBPI is excellent. The atomic force microscopy(AFM) exhibits the surface roughness of FHBPI film, which is 0.54 nm. FHBPI has a high optical transparency in the infrared communication region. The thermo-optic switch device was designed, fabricated and tested by FHBPI. The rise time and fall time of the switch are 267.9 and 254.1 μs, respectively.
    Influence of Alkyl Side Chains on the Packing Behavior of Main Chain of N-Alkylated Poly(p-phenylene terephthamide)
    KONG Lei, ZHAO Ying, SHI Hai-Feng, WANG Du-Jin, XU Duan-Fu
    2012, 33(07):  1595-1599.  doi:10.3969/j.issn.0251-0790.2012.07.041
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    A series of comblike N-alkylated poly(p-phenylene terephthamide) comb-like polymers(denoted as PPTACns, n=8, 10, 12, 14, 16, 18, number of carbon atoms in alkyl side group) with rigid main chain was prepared using N-alkylated method. The methods of DSC, XRD and FTIR were utilized to investigate the packing behavior of the rigid main chain, conformation of the comblike polymer and thermal behavior, and the correlation between these properties with the alkyl side chain length. The results of XRD and DSC indicate that the alkyl side chains crystallize when the carbon number of the side chain reaches 14. The XRD results indicate that PPTACns have layered structure and their layer spacing depends on the carbon number of the side chain. The FTIR results indicate that the conformation of the PPTACns molecular chain is affected by the variation of the crystalline state of the alkyl side chain. For PPTACns with crystallized alkyl side chain, the conformation of the molecular chain undergoes an obvious change as the side chain is melt. The peak position of νC=O and γC-H bands in PPTACns with molten alkyl side chain are similar to that of PPTACns with non-crystallizable alkyl side chain.
    Preparation and Dielectric Properties of a-MWNTs/ Poly(metal phthalocyanine)imide Copolymers
    ZHANG Li-Mei, WANG Qi-Tong, YANG Xu, JIANG Zhen-Hua, ZHANG Yun-He
    2012, 33(07):  1600-1604.  doi:10.3969/j.issn.0251-0790.2012.07.042
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    Poly(metal phthalocyanine)imide copolymers [P(MPc)I] were prepared with tetra-phthalocyanine teraamines(4NH2-MPc), 4,4'-diamino diphenyl ether(4,4'-ODA), and 4,4'-oxydiphthalic anhydride(ODPA). The dielectric constants of the polymer are higher than traonditional polyimide(PI). Carbon nanotubes/poly(copper phthalocyanine)imide [a-MWNTs/P(CuPc)I] composites with different contents of carbon nanotubes were prepared using solution method. Carbon nanotubes show good dispersion in P(CuPc)I matrix. The composite containing 20% carbon nanotubes have high dielectric constant of ca. 200 and low dielectric loss of ca. 2.25(at 1 kHz) which show good dielectric properties.
    Preparation and Characterization of a Novel Polyimide-urethane Reverse Osmosis Composite Membrane Material
    LIU Li-Fen, XU De-Zhi, MAO Pei-Qing, ZHANG Lin, GAO Cong-Jie
    2012, 33(07):  1605-1612.  doi:10.3969/j.issn.0251-0790.2012.07.043
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    The common aromatic polyamide composite reverse osmosis(RO) membrane is easy to be oxidated. N,N'-dimethyl-m-phenylenediamine(DMMPD) as a key functional monomer could be reacted with 5-choroformyloxyisophthaloyl chloride(CFIC) to prepare a chlorine resistance polyimide-urethane RO membrane material by interfacial polymerization technology. In this study, the membrane formation conditions such as solvent of aqueous phase, composition and concentration of amine in aqueous phase, and contact time of two phases were optimized. The results show that the NaCl rejection rate of DMMPD-CFIC membrane prepared from only DMMPD is not ideal, but the combination of DMMPD and 4-methyl-m-phenylenediamine(MMPD) at a mass ratio of 1∶2 to prepare the MMPD/DMMPD-CFIC membrane can obviously improve the NaCl rejection of the resulting membrane, and the chlorine resistance performance of membrane just has slight change. Furthermore, the surface chemical structure of membrane active layer was analyzed by combination of attenuated total reflectance infrared(ATR-FTIR) and X-ray photoelectronic spectroscopy(XPS), and the surface morphology of membrane was observed via scanning electronic microscopy(SEM) and atomic force microscope(AFM).
    Synthesis, Structure and Thermal Properties of Poly(vinyl alcohol)-g-isocyanate-fatty Alcohol Comb Copolymers
    SHI Hai-Feng, LI Jian-Hua, YIN Yi-Ping, ZHANG Xing-Xiang, WANG Du-Jin
    2012, 33(07):  1613-1618.  doi:10.3969/j.issn.0251-0790.2012.07.044
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    Using the bridging role of tolylene diisocyanate(TDI), poly(vinyl alcohol)-g-tolylene diisocyanate-fatty alcohol copolymers were synthesized with the fatty alcohols as the thermal storage units along the PVA backbone via the "grafting to" method. The thermal storage behavior, thermal stability and crystalline structure of PVA-g-TDI-C(n) copolymers were detailed investigated by Fourier transform infrared spectroscopy(FTIR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA), X-ray diffraction(XRD). The results show that PVA-g-TDI-C(n) copolymers exhibit the better thermal storage ability, and the value of enthalpy increases with the side-chain length and the grafting ratio. Compared with the pure fatty alcohols, the grafted ones show the decreased thermal storage efficiency due to the confined mobility of longer methylene groups. Besides the confined mobility of methylene groups, the effect of PVA backbones and the bridging units of TDI also contribute to the decrement of thermal storage ability of PVA-g-TDI-C(n) copolymers. Additionally, PVA-g-TDI-C(n) copolymers exhibit the higher thermal stability than that of pure n-fatty alcohol, and the thermal degradation temperature is located at 324-330 ℃, proving that it can be used as the solid-solid phase change materials in the aspects of buildings, fiber and textiles, thermal fluids, etc. So, the packing manner and thermal behavior of PVA-g-TDI-C(n) copolymers were further discussed and analyzed from the viewpoints of microstructural mobility.
    Fabrication of Electrospun Porous SnO2 Nanofibers as Anodes Materials for Lithium-ion Batteries
    HUANG Hui-Min, ZHANG Su-Qiang, WANG Wei, WANG Ce, YU Jie
    2012, 33(07):  1619-1623.  doi:10.3969/j.issn.0251-0790.2012.07.045
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    SnO2 porous nanofibers were prepared by electrospinning and calcination treatment. Investigations of SEM and XRD indicate that the SnO2 porous nanofibers consist of many SnO2 nanoparticles about 30 nm. The first reversible capacity of the SnO2 porous nanofibers is 717 mA穐/g, and 320 mA穐/g is remained after 20 cylces. Such SnO2 porous nanofibers could be a promising anode material in lithium ion batteries.
    Micellization of PAA-F108-PAA Block Copolymer Using NMR Spectroscopy
    MENG Ling-Min, HUANG Qing-Rong, DENG Jing, WU Yi-Jie, SHI Tong-Fei
    2012, 33(07):  1624-1630.  doi:10.3969/j.issn.0251-0790.2012.07.046
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    Poly(acrylic acid)-F108-Poly(acrylic acid) copolymer(PAA-F108-PAA) was synthesized by atom transfer radical polymerization(ATRP), followed by the hydrolysis of tert-butyl groups from the tert-butyl acrylate. The effects of temperature, acrylic acid neutralization degree and salt concentration on the micellization behavior of PAA-F108-PAA block copolymer were investigated by 1H NMR spectroscopy combined with nuclear Overhauser effect spectroscopy(2D NOE). The neutralization degree of carboxyl acid groups(α) had little influence on the critical micellization temperature(CMT) of PAA-F108-PAA. When α=0.14, the PAA-F108-PAA copolymer was in a collapsed state at low temperature, at high temperature the poly(propylene oxide) block(PPO) was dehydrated and associated into a hydrophobic micellar core, while PEO entangled with PAA and formed the micellar shell; when α=0.80, PAA-F108-PAA copolymer was in a stretched state at low temperature, while at high temperature the micellar core was still composed of the hydrophobic PPO, with PEO and PAA separating from each other and forming the micellar shell. Salt species and concentration had great influence on the CMT of PAA-F108-PAA copolymer, which The CMT of PAA-F108-PAA copolymer decreased significantly by increasing KCl concentration to 1 mol/L. KCl showed a dehydration effect for both PPO and PEO block. In contrast, 1 mol/L KI increased the CMT of PAA-F108-PAA to a slightly higher value, suggesting that KI weakened the interaction between PPO and water but enhanced the interaction between PEO and water.
    Site-Controlled Synthesis and the Optimum Reaction Conditions of Diethoxy Phosphoryl Chitooligosaccharides
    MA Li, LI Ke-Rang, LI Li-Min, LIU Pu
    2012, 33(07):  1631-1634.  doi:10.3969/j.issn.0251-0790.2012.07.047
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    Using low molecular weight chitooligosaccharide and dialkyl phosphite as raw materials, the site-controlled diethoxy phosphoryl chitooligosaccharides were synthesized through varying the amount of triethlamine. Then, N-diethoxy phosphoryl chitooligosaccharide and N,O,O-diethoxy phosphoryl chitooligosaccharide were obtained. The optimal synthetic conditions were studied by the single factor variable method. And the optimum reaction conditions of N-diethoxy phosphoryl chitooligosaccharide were as follows: 2 g COS, nCOS∶nTEA=1∶6, nCOS∶nDEPH=1∶3, 2 h for the time of dropwise for the solution of DEPH in CCl4, 2 h for the time at the low temperature. The maximum phosphorus content achieves 1.50% under the optimum conditions. The optimum reaction conditions of N,O,O-diethoxy phosphoryl chitooligosaccharide were as follows: 2 g COS, nCOS∶nTEA=1∶6, nCOS∶nDEPH=1∶5, 2 h for the time of dropwise for the solution of DEPH in CCl4, 4 h for the time at the low temperature, 8 h for the reaction time at the room temperature. The maximum phosphorus content achieves 3.42% under the optimum conditions. Moreover, a possible reaction mechanism was proposed to explain the formation of diethoxy phosphoryl chitooligosaccharides.
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