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Table of Content

    10 June 2013, Volume 34 Issue 6
    Content
    Cover and Content of Chemical Journal of Chinese Universities Vol.34 No.6(2013)
    2013, 34(6):  0-0. 
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    Article: Inorganic Chemistry
    Synthesis and Characterization of Mesoporous Silica Vesicles Using Cationic-anionic Binary Surfactant as Template
    MU Ming-Wei, PENG Ce, WANG Song, JIN Chun-Yang, CAO Xian-Ying, CAI Qiang
    2013, 34(6):  1309-1312.  doi:10.7503/cjcu20130106
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    Mesoporous silica vesicles were synthesized using cationic surfactant hexadecyl trimethyl ammonium bromide(CTAB) and anionic surfactants sodium dodecyl sulfonate(SDS) in molar ratios of 1.0-2.3 as templates, tetraethyl orthosilicate(TEOS) as silica source at 68℃ in ammonia solution medium. The samples were characterized by scanning electron microscopy(SEM), small angle X-ray diffraction(SXRD), transmission electron microscopy(TEM), thermo gravimetric analysis(TGA) and nitrogen adsorption-desorption isotherms measurments. The results indicate that the samples are the continue aggregates of mesoporous silica vesicles with diameters of ca. 50 nm. The Brunauer-Emmett-Teller(BET) surface area and nonlocal density functional theory(NLDFT) pore diameter of the samples are 826 m2/g and 4.0 nm, respectively. The formation mechanism of the vesicles was also discussed.

    Synthesis, Characterization and Luminescence of a Chiral MOF Based on Camphor Derivative
    CAI Kun, ZHANG Ling-Na, HAN Li-Qin, QU Feng-Yu
    2013, 34(6):  1313-1317.  doi:10.7503/cjcu20130069
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    A chiral camphor derivative, D-4-(3-carboxy-2,2,3-trimethylcyclopentanecarboxamido)benzoic acid (D-H2ctba) was designed and synthesized by simple organic reaction. Then, a self-assembly reaction occurred between D-H2 ctba and cadmium(Ⅱ) nitrate, [Cd3(ctba)3·H2O]n(1) was obtained and characte-rized by single-crystal X-ray diffraction(XRD), powder X-ray diffraction(PXRD), elemental analysis, thermogravimetric analysis(TGA) and circular dichroism(CD) measurement. Single-crystal structure analysis of compound 1 reveals that it crystallizes in the chiral orthorhombic space group P21212 and shows a 3D chiral structure. Compound 1 exhibits a kind of metal-carboxylate cluster which contents six octahedral Cd(II) centers and twelve carboxyl groups. Meanwhile the metal-carboxylate clusters are joined together by carboxyl to form infinite(—Cd—O—C—) rods, and these rods consist the rod-shaped secondary building units(SBUs). The rod-shaped SBUs are stacked in parallel and connected by the ctba ligand to give 3D framework. Additionally, the luminescent spectrum of compound 1 shows a strong fluorescence at room temperature.

    Assembly of Rare-earth Complex [Eu(Bipy)2]Cl3 and [Tb(Bipy)2]Cl3 on Surface Modified Exfoliated LDHs and Photoluminescent Properties of the Assemblies
    ZHAO Xiu-Qiao, WANG Hui, DONG Li-Jun, XU Qing-Hong
    2013, 34(6):  1318-1326.  doi:10.7503/cjcu20121156
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    [Eu(Bipy)2]Cl3 and [Tb(Bipy)2]Cl3 are assembled on surface of exfoliated Mg2Al-NO3-LDH modified with N——acetamide by covalent bonding and photophysical properties of the assembly were studied. Emission spectra show that the fluorescence intensities of the rare earth complexes are increased on the surface of exfoliated Mg2Al-NO3-LDH greatly. The fluorescence intensities of EM-Mg2Al-NO3-LDH/[Eu(Bipy)2]3+ and EM-Mg2Al-NO3-LDH/[Tb(Bipy)2]3+ are 43.5 and 53.7 times of the pure compelex. XPS and UV-Vis studies show that the increase is illuminated from the interactions between the host and guests, and the affections from host’s structure to the luminance of guests were studied carefully.

    Rapid Fabrication of Hydrogel Microfluidic Chip and Its Application for Cell Metabolites Detection
    HUO Dan-Qun, FANG Ke-Jing, HOU Chang-Jun, YANG Mei, FA Huan-Bao, HUANG Cheng-Hong, LUO Xiao-Gang
    2013, 34(6):  1327-1332.  doi:10.7503/cjcu20130237
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    Taking advantage of the ultraviolet polymerization characteristic of poly(ethylene glycol) diacrylate(PEGDA) hydrogel material, a double-layer hydrogel microfluidic chip was fabricated rapidly by photopolymerization method. Moreover, feasibility of the chip culture for tumor cell metabolism detection was validated. The hydrogel material with better biocompatibility and handleability compared to traditional microfluidic chip material could be directly processed to obtain desirable micro-structure. The experimental results showed that the proposed method could achieve the fabrication of double-layer cell culture and detection chip with short time treatment. Cells could be well captured and cultured in the hydrogel microfluidic chip with excellent activity. Chip integrated with porphyrin colorimetric sensor array system could effectively distinguish different types of tumor cell by metabolism characteristics detection. The hydrogel microfluidic chip has the potential of practicable application once large-scale preparation is accomplished.

    Immunoanalysis of E. coli O157: H7 Based on Au Nanoparticles Labelling Antibody Using SPR Biosensor
    LIU Xia, LI Rong-Zhuo, LI Lei, LI Wen-Jin, ZHOU Chun-Jiao
    2013, 34(6):  1333-1338.  doi:10.7503/cjcu20130132
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    The anti-E. coli O157: H7 polyclonal antibodies(PAb) were labelled with Au nanoparticles(AuNPs), which was used as secondary antibodies. The PAb, which was used as primary antibodies, was immobilized on the sensor surface with amino coupling method. The E. coli O157: H7 was detected using direct assay and enhancing sandwich assay based on the two channels surface plasmon resonance(SPR) biosensor. The result indicated a good linear relationship between the SPR signal and logarithmic value of E. coli O157: H7 concentration ranging from 103 cfu/mL to 109 cfu/mL, with the limit of detection(LOD) of 103 cfu/mL for the direct assay. For AuNPs enhancing sandwich assay, the linear range and the limit of detection were determined to be 10-1010 cfu/mL and 10 cfu/mL, respectively. The sensitivity is 100 times higher than that of direct detection. By introducing AuNPs-PAb compound, a wider detection range and lower detection limit could be obtained. This method is rapid, and has good selectivity and reproducibility.

    Analytical Chemistry
    Sensing Mechanism and Application for Recognition of Ethanol by Calixarene Supramolecules Based on Hydrogen Bonds Interaction
    ZHOU Ting, CAO Zhong, DAI Yun-Lin, CAO Ting-Ting, HE Jing-Lin, XU Lei-Tao, LONG Shu
    2013, 34(6):  1339-1346.  doi:10.7503/cjcu20130110
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    Four calixarenederivatives were employed as adsorptive coating materials of quartz crystal microbalance(QCM) for the detection of ethanol gas in environmental atmosphere, indicating that C-ethylcalix[4]pirogallarene(3) was the most effectively active material to ethanol. The single crystal of complex C-ethylcalix[4]pirogallarene·2CH3CH2OH(5) was prepared and subjected to X-ray diffraction analysis, showing that the recognition mechanism was based on the formation of C-H…π, O-H…π and O-H…O hydrogen bonds interaction between the supramolecular host calixarene 3 and the guest ethanol molecule. When the coating mass of calixarene 3 was 24.70 μg, the coated QCM sensor possessed the highest sensitivity, which was 10.53 Hz/(mg·L-1). The kinetics processes for adsorption and desorption of ethanol on calixarene 3 have been examined, and the initial speeds of the adsorption and desorption processes for ethanol gas on cali-xarene 3 were obtained as -0.04600 Hz/s and 0.03896 Hz/s, respectively. With rapid test time, good selectivity, reversibility, reproducibility and stability, the calixarene 3 coated QCM sensor could be used for the detection of ethanol samples with a recovery of 94.8%-105.2%, which was in well consistent with those obtained by gas chromatography, showing its potential application on the determination of ethanol gas in living environment.

    Preparation and Application of Barium Fluoride Particles as Stationary Phase for TLC-FTIR Analysis
    LIU Wei, WU Hai-Jun, WANG Xiu-Peng, ZHU Qing, KANG Ting-Guo, HE An-Qi, WENG Shi-Fu, YANG Zhan-Lan, XIA Jin-Ming, XU Yi-Zhuang, WU Jin-Guang
    2013, 34(6):  1347-1352.  doi:10.7503/cjcu20120976
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    In this study, we modified the preparation of barium fluoride fine particles by a reaction between sodium fluoride and barium chloride. However, the experimental result turned out that the yield of BaF2 is rather low. By inductive coupled plasma(ICP) and X-ray diffraction(XRD) analysis, we found barium fluorochloride was produced with barium fluoride in the reaction. During the washing of precipitates, barium fluorochloride was dissolved in water with low concentration of Cl- and F-, leading to the lost of barium ions and low yield of BaF2. To solve the problem, aqueous solution of NaF was used to wash the product of the reaction between barium chloride and sodium fluoride. Both XRD and ICP results confirmed that barium fluorochloride converted into barium fluoride. Hence, the yield of barium fluoride increases significantly. The average diameter of the BaF2 particles is around 100 nm by SEM and nanometer particle size analyzer. We used settlement volatilization method to prepare TLC plate without using polymeric adhesive. TLC experiments prove that the TLC plate using BaF2 fine particles as stationary phase can separate the mixture of Rhodamine B and Malachite green. FTIR analysis confirms that the FTIR spectra of the separated Rhodamine B and Malachite green spots are in good agreement with the FTIR spectra of pure Rhodamine B and Malachite green.

    Preparation and Adsorption Properties of Novel Magnetic Tetrabromobisphenol A Molecularly Imprinted Composite Material Based on Graphene Oxide Surface
    RAO Wei, CAI Rong, CHEN Xing, LIU Yu-Nan, CHEN Hong-Jun, ZHANG Zhao-Hui, NIE Li-Hua
    2013, 34(6):  1353-1359.  doi:10.7503/cjcu20120960
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    A novel magnetic molecularly imprinted polymer(Fe3O4@GO@MIP) based on magnetic graphene coated with silicon dioxide layer was synthesized using heated polymerization technique. The MIP was characterized by transmission electron microscopy(TEM), scanning electron microscopy(SEM), Fourier transform infrared spectroscopy(FTIR), thermogravimetric analysis(TGA) and vibrating sample magnetometer(VSM). The results showed that a thermal stability magnetic imprinted layer with the thickness of 55-65 nm was coated steadily on the graphene oxide surface. Adsorption performance of the Fe3O4@GO@MIP was investigated combined with magnetic solid phase extraction(M-SPE) and high-performance liquid chromatography(HPLC) technology, and the results indicated the Fe3O4@GO@MIP possessed higher selectivity towards tetrabromobisphenol A with the maximum adsorption capacity of 16.33 mg/g. The magnetic molecularly imprinted composite material was applied to separation and enrichment of tetrabromobisphenol A in environmental water samples combined with HPLC technology.

    Interaction of Herring Sperm DNA with Lomefloxacin Hydrochloride-Cu(Ⅱ) Based on Changes in the Fluorescence Intensity of GSH-CdTe/CdS Quantum Dots
    SHEN Yi-Zhong, LIU Shao-Pu, YIN Peng-Fei, HE You-Qiu
    2013, 34(6):  1360-1367.  doi:10.7503/cjcu20120913
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    Glutathione(GSH)-capped CdTe/CdS quantum dots(GSH-CdTe/CdS QDs) were synthesized in aqueous solution. The particle sizes and morphological characteristics of GSH-CdTe/CdS QDs were investigated by transmission electron microscopy(TEM). The results exhibits that the particle size of as-prepared QDs has a narrow size distribution and good dispersivity. In Tris-HCl buffer medium(pH=7.6), lomefloxacin hydrochloride-Cu(Ⅱ) coordination compound(LMFH-Cu2+) was adsorbed to the surfaces of GSH-CdTe/CdS QDs through electrostatic attraction and formed ground state complex, which resulted in the quenching of the fluorescence of GSH-CdTe/CdS QDs. Adding herring sperm DNA(hsDNA) to GSH-CdTe/CdS QDs-LMFH-Cu(Ⅱ) system led to the fluorescence intensity of GSH-CdTe/CdS QDs recover, which can be explained by that the addition of hsDNA to the system induced LMFH-Cu(Ⅱ) to dissociate from the surface of GSH-CdTe/CdS QDs and embed into its double helix structure. According to the fluorescence quenching and restoration for GSH-CdTe/CdS QDs, fluorescence reversible control of GSH-CdTe/CdS QDs was realized. Compared with the interaction between GSH-CdTe/CdS QDs and LMFH, the interaction of GSH-CdTe/CdS QDs-LMFH-Cu(Ⅱ)-hsDNA was studied by fluorescence(FL), resonance Rayleigh scattering(RRS) and ultraviolet-visible absorption(UV-Vis) spectra. Meanwhile, the interaction mechanism was discussed and corresponding model of interaction was built.

    Synthesis of Azosalicylic Aldehyde of Benzoyl Hydrazone Based Sensor and It’s Colorimetric Sensing Properties for Cyanide Anions in Aqueous Solutions
    HU Jing-Han, YAN Nong-Ping, CHEN Juan-Juan, LI Jian-Bin
    2013, 34(6):  1368-1373.  doi:10.7503/cjcu20120875
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    A colorimetric anions sensor bearing phenol -OH and -NH groups was synthesized. The binding properties of the receptor with anions such as F-, Cl-, Br-, I-, CH3COO-, H2PO4-, HSO4-, ClO4-, CN-, SCN-, SO2-4 and NO-3 were examined by UV-Vis and 1H NMR spectra. Upon the addition of CN-anions, the sensor displayed apparent color changes from colorless to yellow while other anions did not cause obvious color changes. The UV-Vis spectroscopic titration experiments and MS data indicated the formation of 1: 1 addition compound between CN- and the sensor. The results showed that the sensor in DMSO/H2O(volume ratio 5: 5) solution indicated colorimetric single selectivity for CN- which could be observed by naked eyes due to the nucleophilic addition reaction of cyanide.

    Chemical Constituent Changes of Wu-tou-tang in Compatibility Process with Fritillariae cirrhosae and Fritillariae thunbergii
    QI Yao, LI Shi-Zhe, ZHU Hong-Bin, SONG Feng-Rui, LIN Na, LIU Zhi-Qiang
    2013, 34(6):  1374-1378.  doi:10.7503/cjcu20120824
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    Wu-tou-tang was chosen to investigate the chemical constituent changes of Aconitum-Fritillariae combination taboo in prescription. The ultra performance liquid chromatography coupled with mass spectrometry(UPLC-MS) and tandem mass spectrometry methods were used to evaluate the chemical composition of Wu-tou-tang and its co-decoction with Fritillariae cirrhosae and Fritillariae thunbergiiin with a mass ratio of 1: 1. The total ion chromatograms(TIC) of the co-decoctions were processed by Mzmine 2, and then the dataset was analyzed by partial least squares discriminant analysis(PLS-DA). Significant differences between the group of Wu-tou-tang and Wu-tou-tang combined with Fritillariae cirrhosae and Fritillariae thunbergii in PLS-DA model were observed. Seven of the eight potential chemical markers in Wu-tou-tang and Fritillariae cirrhosae compa-tibility process were identified, the relative content of neoline, fuziline and benzoylmesaconine increased and talatizidine, 10-OH benzoylmesaconine, 10-OH benzoylaconine and benzoyldeoxyaconine decreased. Chuanfumine, songorine, talatizidine, neoline, fuziline, benzoylmesaconine and 10-OH benzoylmesaconine were found as potential chemical markers in Wu-tou-tang and Fritillariae thunbergii compatibility process, respectively. The result shows that relative content of all potential chemical markers in Wu-tou-tang and Fritillariae thunbergii co-decoction was less than that in Wu-tou-tang.

    Detection of a Novel Metabolite of Urea in Soil by Extractive Electrospray Ionization Mass Spectrometry
    PAN Su-Su, ZHAO Na, OUYANG Yong-Zhong, HUANG Ke-Ke, DING Jian-Hua, CHEN Huan-Wen, YUAN Long, WANG Xing-Xiang
    2013, 34(6):  1379-1384.  doi:10.7503/cjcu20120814
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    As an important nitrogen(N) source for the growth of many organisms, urea is intensively used as a nitrogen fertilizer. A better understanding of urea metabolism is required. Using extractive electrospray ionization tandem mass spectrometry(EESI-MSn), a new urea metabolite(3,3-diamino-3-hydroxypropanoic acid) was detected in soil extracts from the rhizosphere of Pinus massoniana. A 3,3-diamino-3-hydroxypropanoic acid standard was synthesized from urea, sodium acetate and lithium tert-butoxide. The protonated molecular ion and the sodium adduct were observed in the mass spectrum. With tandem mass spectrometry, the two signals from the synthetic sample were quickly identified and verified the protonated molecular ion from the soil extracts. It can be inferred that 3,3-diamino-3-hydroxypropanoic acid is a metabolite from urea in soil, and this study provides clues for future research of nitrogen transformation processes in urea fertilized soils. EESI-MS is a promising tool for the rapid and accurate identification of trace levels of short-lived metabolites.

    Preparation and Quality of SERS Test Strips
    ZHANG Wen-Yi, XIAO Xin-Ze, LIU Xue-Qing, ZHANG Ran, XU Ying
    2013, 34(6):  1385-1388.  doi:10.7503/cjcu20120811
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    Based on connatural hierarchical micro/nanostructures of filter paper, convenient and efficient surface-enhanced Raman scattering(SERS) test strips were prepared by coating a silver layer on paper through simple physical vapor deposition(PVD). The limit of detection(LOD) over the SERS test strip is 10-10 mol/L with the Rhodamine 6G as probe molecule. Placing the test strips in airtight N2 atmosphere could remain the activity for a long time.

    Effect of Morphology and Channel Structure of Chemosensor on Its Detection Ability for Hg2+
    ZHANG Na, LI Gang, CHENG Zhu-Hong
    2013, 34(6):  1389-1393.  doi:10.7503/cjcu20120769
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    Three Hg2+ chemosensors were prepared by immobilizing a Rhodamine B(RhB) derivative on hexagonal mesoporous silica(HMS) via 3-aminopropyl-triethoxysilane(APTES), 3-(triethoxysilyl)propylisocyanate(Tri) and gold nanoparticles, respectively. The prepared chemosensors were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), N2 physical adsorption-desorption and Fourier transform infrared spectroscopy(FTIR). Further fluorescence spectra of chemosensors in sensing Hg2+ was detected. The results show that the immobilization process of Rhodamine B(RhB) is very successful and all of the chemosensors have Hg2+ detection ability. Moreover, the morphology and channel structure of the chemosensors have effects on the detection ability, that is, RhB-Au-HMS with intact morphology and wormlike channel structure has the most powerful detection ability and RhB-APTES-HMS with the collapsed channel structure has the weakest detection ability.

    Synthesis and Antibacterial Structure-activity Relationship of Novel 1,2,3-Triazoles
    PENG Chun-Yong, LU Jun-Rui, XIN Chun-Wei, LI Jian-Fa, JI Dan, BAO Xiu-Rong
    2013, 34(6):  1394-1402.  doi:10.7503/cjcu20121063
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    According to active groups combination principle, seventeen compounds 1-(4-substituted phenyl)-5-substituted phenylbutyronitrile-4-substituted 1,2,3-triazoles(7a-7c, 13a-13d) and 1-(4-substituted phenyl)-5-substituted benzylamino-4-substituted 1,2,3-triazoles(5a-5c, 10a-10c and 14a-14d) were designed and synthesized through diazotization, cyclization and condensation reactions from 4-substituted aniline, while compounds 5a-5c, 7b, 7c, 10a, 10c, 13b-13d and 14b-14d have never been reported. Their structures were confirmed by IR, 1H NMR and 13C NMR. The preliminary bioassay showed that all target compounds possessed efficient antibacterial activities, especially, they all exhibited better activities against Escheri-chia coli than fluconazole, while against Staphylococcus aureus, compounds 7a and 10c were more effective than fluconazole, and compounds 13a and 13c were as good as triclosan against Monilia albican.

    Organic Chemistry
    Synthesis and Properties of a Novel Organic Non-linear Optical Chromophore Containing Bifuran Conjugating Bridge
    REN Li-Ke, TANG Xian-Zhong, TANG Xiang, WANG Yang, YOU Ying-Cai, JIA Kun-Peng
    2013, 34(6):  1403-1407.  doi:10.7503/cjcu20121023
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    It has been demonstrated that organic second-order nonlinear chromophore, with hetero-aromatic ring as the conjugating bridge, has large hyperpolarizability. In this work, with the aim of studying the hyperpolarizability influenced by the length of conjugating bridge, a novel organic non-linear optics(NLO) chromophore MF3C containing bifuran conjugating bridge, tricyanofuran as electron acceptor and dimethylamine as donor was synthesized through Wittig reactions and Vilsmeier reactions. The new chromophore was characte-rized by FTIR, 1H NMR and elemental analysis. Thermogravimetric analysis(TGA) test revealed that the decomposition temperature(Td) of the molecular was up to 228℃. Solvatochloroform method was used to calculate the hyperpolarizability(μgβ). We got the μgβ value of MF3C led to 5.9×10-44 esu at 1064 nm. With good thermal stability and large hyperpolarizability simultaneously, the chromophore shows great potential applications in electro-optic devices.

    Synthesis and Anticancer Activity Evaluation of Derivatives of Emodin
    LIU Cheng, ZHENG Yan-Yan, HONG Fang, HU Jian-Da, ZHAO Wen-Na, YUAN Yao-Feng, SHAO Jing-Wei, WANG Wen-Feng
    2013, 34(6):  1408-1415.  doi:10.7503/cjcu20120982
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    In order to improve the anticancer activity of emodin, seven emodin derivatives containing nitrogen heterocycle and three emodin derivatives containing quaternary ammonium salt were designed and synthesized by suitable modification at C6 position of emodin, their structures were characterized by IR, 1H NMR and MS and their activities against leukemia cell line Molt-4 and lymphoma cell line CA46 in vitro were tested by MTT method. Thereinto, compounds 8, 9a+9b, 20a, 20b and 20c show higher anticancer activities than emodin, which indicates that benzimidazole and quaternary ammonium salt are good pharmacophores for the anticancer activity of emodin. We propose to introduce many such pharmacophores into emodin to improve the anticancer activity of emodin in further.

    Design, Synthesis and Herbicidal Activity of Novel Sulfonylureas Containing Monosubstituted Pyrimidine Moiety
    PAN Li, LIU Zhuo, CHEN You-Wei, LI Yong-Hong, LI Zheng-Ming
    2013, 34(6):  1416-1422.  doi:10.7503/cjcu20120972s
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    Sulfonylureas, a unique group of herbicides, were extensively applied to controlling a range of weeds in a variety of crops and vegetables. In order to find efficient sulfonylurea herbicides, the title compounds were designed by introducing monosubstituted pyrimidinamines into some well-known sulfonylurea skeletons. A series of sulfonylurea compounds were synthesized and characterized by 1H NMR and HRMS. Herbicidal activities and IC50 values of the title compounds were determined by Pot plant test and Petri dish test against Brassica napus, Amaranthus retroflexus, Echinochloa crusgalli and Digitaria adscendens. Some compounds exhibited herbicidal activities. Compounds 7b and 7d possessed significant inhibition effects against Brassica napus and Amaranthus retroflexus. Further structural modification of novel sulfonylureas containing monosubstituted pyrimidine moiety will be required for improving efficacy against weeds in our lab.

    Iodine-catalyzed Electrophilic Cyclization of 2-Alkynylanilines with Diselenides
    TAO Li-Ming, LIU Wen-Qi, ZHOU Yun, LI Ai-Tao, LIU Hui
    2013, 34(6):  1423-1427.  doi:10.7503/cjcu20120971
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    Indoles, particularly 3-selenenylindoles, are important compounds found in a wide range of biologically active compounds and natural products, as well as are useful building blocks in organic synthesis. For the reasons, a new and efficient method for the selective synthesis of 3-selenenylindoles was developed by electrophilic iodocyclization of 2-alkynylanilines with diselenides. In the presence of I2 and toluene, a variety of 2-alkynylanilines selectively underwent the electrophilic cyclization with diselenides leading to the corresponding 3-selenenylindoles in moderate to excellent yields. Importantly, these reactions were conducted under metal-free conditions, and will open a new door to functionalized indoles synthesis.

    Physical Chemistry
    Thermokinetic Study of Formation Reaction of N,N,O,O-Tetradentate Ligand-palladium(Ⅱ) Complex and Its Catalytic Performance in Suzuki Reaction
    SHEN Li-Qun, HUANG Su-Yu, LEI Fu-Hou, HUANG Zai-Yin
    2013, 34(6):  1428-1433.  doi:10.7503/cjcu20130031
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    A new N-O ligand 1-(6-chloro-pyridin-2-yl)-5-hydroxy-1H-pyrazole-3-carboxylic acid methyl ester was prepared and structurally analyzed. The solid lattice of the compound at 296 K reveals one dimensional chain structure connected by intermolecular hydrogen bonds [C3—H3…O2, 0.2535(17) nm] and halogen bonds [C1—Cl1…O1, 0.3161(18) nm, Cl atom as Lewis acid and oxygen atom as Lewis base] interactions. The ligand adds to palladium(Ⅱ) to give high yield of air-stable complex 1 that was fully characterized by infrared(IR) spectroscopy, nuclear magnetic resonance(NMR) spectroscopy and high resolution mass spectrum(HRMS). The dynamic thermochemistry for the formation of complex 1 in liquid-phase was explored by a microcalorimeter. Thermodynamic parameters(the activation enthalpy, the activation entropy and the activation free energy), kinetics parameters(the apparent activation energy, the pre-exponential constant and the reaction order) and rate constants of the coordination reaction were procured. Complex 1 was used as catalyst for the Suzuki cross-coupling between different aryl bromides and phenylboronic acid in water/ethanol with KOH as base under microwave irradiation and afforded the corresponding cross-coupled biaryls in 80.7%-95.9% yields. Furthermore, the reactions of aryl chlorides and phenylboronic acid were also successfully achieved in comparable yields.

    Dilational Rheology Properties of Branch-performed Particle Gel by Relaxation Measurements
    TANG Li, LUO Lan, FANG Hong-Bo, ZONG Hua, ZHANG Lei, ZHANG Lu, ZHAO Sui
    2013, 34(6):  1434-1440.  doi:10.7503/cjcu20121153
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    The interfacial dilational rheological properties of a novel polyacrylamide derivative, branch-preformed particle gel(PPG), were studied by interfacial tension relaxation measurements. The effects of electrolytes and conventional polyacrylamide on dilational rheological properties of PPG were studied. The dilational elasticity and viscosity components of different systems were calculated by Fourier transform and displayed as Cole-Cole curves. The results show that interfacial elasticity and viscosity components of PPG solutions both increase due to the formation of interfacial net structure with the increasing bulk concentration. Electrolyte will neutralize the excess charge of PPG, thus decreases dilational elasticity and viscosity. When mixed with liner polyacrylamide, the more complex structure is formed, but the overall viscoelasticity of the system is still determined by PPG.

    Adsorption Properties of Comb-shaped Copolymer of Polycarboxylic Acid Superplasticizer on the Interface of Fipronil Particles
    MA Chao, XU Yan, GUO Xin-Yu, LUO Xiang-Ren, WU Xue-Min
    2013, 34(6):  1441-1449.  doi:10.7503/cjcu20121138
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    The main methods in performing the study of the adsorption properties of hyperdispersant on fipronil interface were UV-Vis, FTIR, XPS and SEM. The kinetics and the thermodynamics of TERSPERSE®2700 adsorption on fipronil were studied, and the results suggested that the adsorption of TERSPERSE®2700 on the interface of fipronil particles was correspond with Langmuir equilibrium. The low activation energy of 29.28 kJ/mol suggested that it was a physical adsorption process. The free energy of the adsorption at all temperatures were negative indicating a spontaneous process. The peak intensity of F1s, N1s and Cl2p of the interface of fipronil particle decreased obviously. The adsorption layer thickness of TERSPERSE®2700 on the fipronil interface was measured through the XPS spectrum and the results showed that the adsorption layer thicknesses of TERSPERSE®2700 was about 1 nm. The results of the present study suggested there were hydrogen bonds between fipronil molecules and it was also the main force combining fipronil particles and the dispersant. The results of SEM showed that the fipronil particles became rougher and their dispersion was in good order after adsorption. This study provided a theoretical foundation for development of stable fipronil suspension concentrate and the spectroscopy quantitative analysis of it.

    Dynamic Study of the Isotopic Effect on Ca+CD3I→CaI+CD3 Reaction Used Quasi-classical Trajectory Method
    ZHANG Zhi-Hong, LEI Peng
    2013, 34(6):  1450-1453.  doi:10.7503/cjcu20121116
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    The dynamics of Ca+CD3I→CaI+CD3reaction was studied by means of quasi-classical trajectory calculations based on a constructed extended Lond-Eyring-Polanyi-Sato(LEPS) potential energy surface. Calculated results show that due to the deuterium isotopic effect, the vibrational population of the product CaI moves to lower population, and the cross-section changes slightly in the areas of the low collision energies and high collision energies, corresponding to the non-deuterium case. Meanwhile, the mass combination factor increment causes the value of product rotation decrease and the alignment of product rotational increase. The product angle distribution is not effected significantly by the isotopic effect.

    Dissipative Particle Dynamics Simulation Study on the Micellization and Gelation Behavior of PEO-PPO-PEO Solution
    XIE Yu, LÜ Zhong-Yuan, SUN Zhao-Yan, AN Li-Jia
    2013, 34(6):  1454-1459.  doi:10.7503/cjcu20121054
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    Dissipative particle dynamics(DPD) simulation was used to study the micellization and gelation behavior of triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)(PEO-PPO-PEO) in solution. The critical micellization concentration and the critical gelation concentration were obtained for the system at 298 K. The shape of the micelles was spherical as the concentration was below 40%(mass fraction), in accordance with experimental results. Furthermore, the effect of the length of PEO block on micelle shape and gelation behavior was studied. For block copolymer with short length of PEO block, the prolate ellipsoid micelles formed more easily. Moreover, the critical gelation concentration decreased with increa-sing the length of PEO block.

    Preparation and Properties of Highly Monodisperse Spherical Poly(vinylsilsesquioxane) Nanoparticles
    CHEN Lian-Xi, LI Jie, LI Xi, ZHAI Peng-Cheng, ZHANG Jiang-Tao, ZHANG Zhong-Ming
    2013, 34(6):  1460-1465.  doi:10.7503/cjcu20121002
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    In aqueous solution, highly monodisperse spherical poly(vinylsilsesquioxane)(PVSQ) particles with various sizes have been prepared successfully in the presence of surfactant sodium dodecyl benzene sulfo-nate(SDBS) using vinyl triethoxysilane(VTES) as precursor and ammonia hydroxide as catalyst by sol-gel method. The research results show that the amounts of catalyst(NH3·H2O) and surfactant(SDBS) have great effects on size and size distribution of PVSQ. However, the amount of precursor(VTES) has unobvious effect on size and size distribution of PVSQ. The shape, size and size distribution, structure, surface property and thermal behavior of the resulting products were analyzed and characterized by field emission scanning electron microscope(FESEM), Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and thermal gravimetric analysis(TGA), respectively.

    Fabrication of Multifunctional Polymer Nano-membrane via Biomimicing of Petals Surface
    LIU Qing, LIU Na, FENG Lin, WEI Yen
    2013, 34(6):  1466-1469.  doi:10.7503/cjcu20120959
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    Red rose petals were used as templates for their surface multiple properties of super-hydrophobic, high adhesion and structure color. Multifunctional polymer films were obtained via biomimetic synthesis with nanoimprint pattern transfer method. Artificial films with special petal color were fabricated by dying films and explored the relationship between chemical color and structure color.

    Performances of Dye-sensitized Solar Cell Based on ZnO Photoanode Sensitized with Cadmium Complexes Cd(phen)2(NO3)(NO2)
    ZHANG Ling-Yun, YANG Yu-Lin, FAN Rui-Qing, ZHANG Yan-Jiao, WANG Ping, LI Liang
    2013, 34(6):  1470-1474.  doi:10.7503/cjcu20120949
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    The ZnO photoanode was co-sensitized with cadmium complexe Cd(phen)2(NO3)(NO2) absorbed in the ultraviolet light region and dye N719. The performances of co-sensitized dye-sensitized solar cell(DSSC) and the properties of cadmium complexe were investigated by the cyclic voltammetry measurement, UV-Visible absorption spectroscopy, fluorescence spectrum, electrochemical impedance spectroscopy and photocurrent-photovoltage curve. The results show that cadmium complexe is suitable for sensitization of ZnO photoanode, and the complexe can be reduced by the electrolyte. The light absorption of DSSC is enhanced and the current density is improved 63% by co-sensitization. The decreased resistance of interface of DSSC is in favor of the electron transport. The conversion efficiency of DSSC based on ZnO photoanode is improved 37% by co-sensitization.

    Stabilization of Oil/Water Emulsions by Microfibrillized Bacterial Cellulose
    JIA Yuan-Yuan, WAN Tong, HUO Ming-Ming, YAN Meng-Meng, JIA Shi-Ru, CHEN Han, ZHOU Yu-Lai
    2013, 34(6):  1475-1482.  doi:10.7503/cjcu20120935
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    Pickering emulsions(O/W)were stabilized by bacterial cellulose(BC) nanofibers which had been disintegrated by two methods, ultrasonication and high pressure homogenization, corresponding to USBC and HGBC. Influences of fiber content, pH, and disintegration method on the stability of emulsions were investigated. Emulsions prepared with higher loading of BC had better stability; and the BC suspensions with higher pH values gave higher emulsion stability index(ESI), and the ESI reached the highest at pH=12. Since fibers disintegrated from high pressure homogenization were shorter than those from ultrasonication, emulsifying effect of HGBC was better than that of USBC. Nanofibers distributed on the surface of emulsified drops, forming a network, were visualized by SEM. The three-phase contact angle of BC nanofibers on the interface of water and liquid paraffin is calculated to be 73.1°, implying both hydrophilic and lipophilic nature, which renders BC adequate to stabilize O/W emulsions. As a biological origin nanofiber, BC has the potential to substitute conventional surfactants, especially in food, pharmaceutical and biodegradable products.

    Impact of Core on Structures and Properties of Tetrathiafulvalene Terminated Star-shaped Molecules
    WEN Zhi, KAN Yu-He, YAN Wen-Yan, DING Yan-Yan, WANG Xin-Long
    2013, 34(6):  1483-1489.  doi:10.7503/cjcu20120911
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    The geometries, electronic absorption spectra and charge transfer properties of five novel star-shaped compounds with different core(electron-rich core: nitrogen, triazatruxene and triindole; electron-deficient core: 1,3,5-triazine and triquinoxaline), styrene as bridge and tetrathiafulvalene(TTF) as a terminal group, were studied with density functional theory(DFT) method. The results show that LUMO levels and energy gaps can be adjusted effectively via altering the cores. The time-dependent DFT calculation indicates that there are two absorption bands in 300-450 nm. The results of the transition density matrix and charge difference density reveal that high energy excitation mainly arises from charge transfer from TTF donor moiety to core and bridge moiety. The low-lying excitations in electron-deficient core compounds are predominantly TTF donor-bridge and core charge transfer transition from two intra-branch. This differs from electron-rich compounds, whose low-energy transitions are assigned to prominently intra-branch localized excitation from TTF moiety. The reorganization calculations show that the hole and electronic reorganization energy are nearly equal except NST, and CST shows the lowest reorganization energy.

    Theoretical Study on the Carrier Transport Properties of Indolo[3,2-b]carbazole Derivatives
    WANG Guang-Yu, DUAN Yu-Ai, GENG Yun, ZHANG Bing, TANG Xiao-Dan, WU Shui-Xing, HAO Li-Zhu, SU Zhong-Min
    2013, 34(6):  1490-1496.  doi:10.7503/cjcu20120887
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    The influence of introduction of chlorine and long alkyl side chains on the hole transport properties of indolo[3,2-b]carbazole derivatives was investigated by combining density functional theory(DFT) with Marcus theory in hopping regime. The results show that the introduction of chlorine atoms induces more delocalized HOMO of 2,8-dichloro-indolo[3,2-b]carbazole(2) and 2,8-dichloro-5,11-dihexyl-indole[3,2-b]carbazole(3) than indolo[3,2-b]carbazole(1), while the LUMO is just the opposite. Besides, both the HOMO/LUMO energy levels and the reorganization energies of compounds 2 and 3 are lower than those of compound 1, and the former is ascribed to chlorine exerting conjugate effect to HOMO but electron-withdrawing effect to LUMO. With the introduction of both chlorine and long alkyl side chains on indolo[3,2-b]carbazole derivatives, compound 3 has higher mobility, which is the result of denser intermolecular packing of dimer A in compound 3 than compounds 1 and 2, thus larger electronic coupling and higher the mobility are measured for compound 3. The results obtained from the band model are consistent with those calculated by hopping regime. Finally, our calculation clarify again in theory that rational chemical modification can improve the carrier transport property of indolo[3,2-b]carbazole derivatives.

    Influence of Solvent Effect on Interaction Between Chiral Imidazole Derivates Enantiomer and Stationary Phase
    HU Gui-Xiang, LUO Cheng-Cai, YIN Kai-Liang, ZOU Jian-Wei, YU Qing-Sen
    2013, 34(6):  1497-1504.  doi:10.7503/cjcu20120858
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    The interaction between the enantiomers of two chiral imidazole derivates and polysaccharide-based chiral stationary phase cellulose tris(4-methylbenzoate)(Chiralcel OJ) was studied via molecular simulation. The result shows that the solvent effect has significant influence on the interaction. In the solvent A with strong polarity, the complexes between R-enantiomer of the compounds and the stationary phase are more stable than those of S-enantiomer, which leads to S-enantiomer eluting firstly and R-enantiomer following. The result is accordant with the separation experiment reported in the reference. Under the condition of solvent B with weak polarity, the binding energies are similar between R and S enantiomers of the two compounds and the stationary phase, which can not make R and S enantiomers separated effectively. The analysis on the simulation result demonstrates that the enantiomers and the stationary phase repulse each other under long-distance effect. In the strong polar solvent, the long-distance electrostatic interaction is weakened, which is beneficial to distinguish the difference of the steric interaction between the enantiomers and the stationary phase and further separate the enantiomers. The analysis of energy shows that the intermolecular van der Waals energy, especially dispersion energy determines whether the enantiomers separated effectively or not on the stationary phase.

    Effects of Laser Irradiation on the Ferrocene-doped Single-wall Carbon Nanotubes
    ZHANG Jing, YAO Ming-Guang, LIU Ran, CUI Wen, LU Shuang-Chen, LIU Bing-Bing
    2013, 34(6):  1505-1509.  doi:10.7503/cjcu20120823
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    Utilizing single-wall carbon nanotubes and ferrocene as raw materials, we synthesized ferrocene-doped carbon nanotubes with a high filling rate through gas phase diffusion method. The obtained materials were confirmed by Raman and infrared spectra. By adjusting laser power on irradiation of samples, obvious changes in the Raman spectra were found, depending on the laser power. The results show that when the laser power is up to 20 mW with the irradiation time of 10 s, some stable new peaks in the Raman spectrum pappeare. In comparative analysis, it was noted that ferrocene formed the iron carbide after laser irradiation and then part of the carbon source transformed into carbon nanotubes and formed double-wall carbon nanotubes. It indicated that the iron carbide was the intermediate products during the conversion of pyrolysis of ferrocene to the inner layer, which was of crucial importance in the comprehension of preparation of double-wall carbon nanotubes by ferrocene-doped carbon nanotubes.

    Preparation of Metalloporphyrin with Disulfide Bond and Electrocatalytic Reduction of Oxygen
    HUANG Xiu-You, HU Bing-Cheng, XU Shi-Chao
    2013, 34(6):  1510-1515.  doi:10.7503/cjcu20120803
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    A novel amino acid derivatised mesoporphyrin Co(Ⅱ)-[2,7,12,18-tetramethyl-3,8-diethyl-13,17-(propionylaminoethyl-dithio-ethyaminoformylethyl)-29, 34-bis-(methoxy-formyl)]-prophyrin[Co(Ⅱ)MPDTEP, Ⅴ] was prepared from hemin by a six-steps reaction including deferrization, esterification, cataly-tic hydrogenation, hydrolyzation, condensation and complexation. The target products were characterized. The effects of the reaction time and temperature on the yields of the product [2,7,12,18-tetramethyl-3,8-diethyl-13,17-(propionylaminoethyl-dithio-ethyaminoformylethyl)-29,34-bis-(methoxy-formyl)]-prophyrin(MPDTEP, Ⅳ) were investigated. A gold electrode modified by Co(Ⅱ)MPDTEP was prepared by self-assembly of disulfide on gold. The properties of the modified electrode were investigated by FTIR as well as electrochemical methods. This modified electrode was successfully used for the electrocatalytic reduction of oxygen.

    Polymer Chemistry
    Effect of Stirring on Layer-by-layer Assembly Films in Different Stages
    FU Yu, LIU Xia, XU Jing, ZHANG Ji-Dong, JIAO Yong-Hua
    2013, 34(6):  1516-1520.  doi:10.7503/cjcu20130108
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    We explored the effect of flow field under stirring on layer-by-layer(LbL) assembly films in different stages. The agitation was respectively introduced in the deposition and rinsing stages, then we designed an orthogonal experiment in which the deposition stage and rinsing stage were set as the two elements and agitation and still standing were set as the two standards. Afterwards, UV-Vis spectroscopy was used to track the assembly process, atomic force mircroscope(AFM) was used to observe the surface roughness of the film, and X-ray reflection(XRR) was used to estimate the thickness and surface roughness of the film. The results show that flow field could accelerate the contact between the polymer and the substrate to promote the assembly speed in deposition stage, while flow field produced more strong flushing action to smooth the film surface in rinsing stage. This study has indicated the important role that the rinsing stage plays in the LbL assembly and provides new strategy to rapidly fabricate thin films and to adjust film structures.

    Gel Structure of the 17R4/F127 Mixed Solutions
    XIE Yu, LV Zhong-Yuan, SUN Zhao-Yan, AN Li-Jia, LI Xiu-Hong, WU Zhong-Hua
    2013, 34(6):  1521-1526.  doi:10.7503/cjcu20130040
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    Rheology and small angle X-ray scattering(SAXS) were used to study the effect of the content of 17R4(PO14EO24PO14) and temperature on the gel structure of the 17R4/F127(EO99PO65EO99) mixed solutions. It was indicated that the structures of sol, soft gel and hard gel were corresponding to disorder phase, disorder/cubic coexisted phase and cubic phase. With increasing temperature, hard sphere radius and aggregation number of micelle decreased. For pure 17R4, it is difficult to form micelles. However, when the temperature was increased, 17R4 chains took part in the formation of micelles and therefore the number of micelles increased, which made the number of F127 chains in one micelle decrease. Thus, the number of PEO blocks of F127 in coronal part decreased and then the coronal part became softer. As a result, a fcc-bcc transition occurred in the system with 17R4/F127 molar ratio of 2.

    Preparation of the Zwitteronic Hydrogel Layer by UV-initiated Surface Grafting and Its Antibacterial Adhesion Performance
    LIU Yun-Hong, LI Guang-Ji, LUO Xi-Wen, PENG Xin-Yan, WANG Li-Ying
    2013, 34(6):  1527-1535.  doi:10.7503/cjcu20130010
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    To construct a zwitterionic polymer hydrogel layer on the surfaces of various substrates, a poly-merizable and crosslinkable organic/inorganic hybrid material or an organosilicon/SiO2 hybrid sol was employed as a transition layer between the substrate and the zwitterionic monomer layer. The reactions involving double bonds in the zwitterionic monomer solution and the sol were initiated by UV irradiation to produce the zwitterionic polymer layer and the hybrid layer that plays an assistive bonding role, thus constructing the zwitterionic hydrogel layer on the substrate surface. The surfaces of the zwitterionic hydrogel layer and the hybrid layer were characterized by attenuated total reflectance Fourier transform infrared(ATR FTIR) spectroscopy, atomic force microscope(AFM) and contact angle measurement. Based on these analyses, the anti-bacterial adhesion performances of the glass surface modified with zwitterionic gel layer and the untreated glass surface as a control sample were investigated and analyzed by the bacterial adhesion experiment using S. aerues and E. coli as a test strain, respectively. The results indicate that it is effective to introduce the linear siloxane chains [(Si-(CH2)2-O-] to the organosilicon/SiO2 hybrid transition layer for increasing its adhesion to the substrate surface and improving its flexibility. The zwitterionic hydrogel layer can be simply and firmly grafted onto the substrate surface through the UV-initiated reactions of double bonds in the zwitterionic monomer solution and the sol. Compared to the corresponding control sample, the glass surface modified with the zwitterionic hydrogel can exhibit an obvious antibacterial adhesion performance.

    RAFT Dispersion Polymerization of Styrene in Supercritical CO2
    LIU Xiao-Wei, LI Hui, ZHAO Zhen, MIAO Xia-Ran, HAN Zhe-Wen
    2013, 34(6):  1536-1541.  doi:10.7503/cjcu20130006
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    A block copolymer polydimethyllsiloxane-b-polystyrene(PDMS-b-PS) was prepared by reversible addition fragmentation chain transfer(RAFT) polymerization of styrene in supercritical CO2(scCO2), using polydimethylsiloxane terminated by trithiocarbonate(PDMS-TTC) as a macromolecular chain transfer agent. The polymerization reaction kinetics, composition, molecular weight and morphology of the product were investigated by FTIR, 1H NMR, GPC and SEM. Since PDMS chain segments could be dissolved in scCO2 while PS segments were insoluble, the polymerization was a RAFT dispersion polymerization using the block copolymer itself as a dispersion stabilizer, and the resultant products were spherical particles with more uniform particle size, which was proved by SEM characterization.

    Preparation of Polymer Microtubes via RAFT Polymerization of N,N'-Methylene Bisacrylamide Gel Fibers
    LI Qi, TANG Li-Ming, LIANG Yong
    2013, 34(6):  1542-1546.  doi:10.7503/cjcu20121163
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    Polymer microtubes were fabricated by copolymerizing N,N'-methylene bisacrylamide(MBA) organogel fibers and triethylene glycol diacrylate(TEGDA) via reversible addition-fragmentation chain transfer(RAFT) polymerization. The tubular structure and compositions of the polymer microtubes were demonstrated by scanning electron microscopy(SEM), transmission electron microscopy(TEM), Fourier transform infrared(FTIR) spectrometer and elemental analysis. In presence of TEGDA, the yield of the polymer microtubes was enhanced significantly and the resulting tubes had self-supporting ability. The in-situ observation of the polymer microtubes by environmental scanning electron microscopy(ESEM) indicated the swelling property of the tubes in solvent. The mechanical properties of the gels were measured by a rheometer. The results show that the storage modulus(G') and loss modulus(G") of the polymer gel are much higher than those of the MBA organogel.

    Microwave-Assisted Synthesis of Novel Polybenzimidazole Resin and Performance of Its Proton Exchange Membranes
    XU Yan-Yan, YU Shu-Ping, HAN Ke-Fei, YU Jing-Hua, ZHU Hong, WANG Zhong-Ming
    2013, 34(6):  1547-1554.  doi:10.7503/cjcu20121158
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    A series of novel aliphatic polybenzimidazole(PBI) copolymers was synthesized from 3,3'-diaminobenzidine, adipic acid and 2,6-pyridinedicarboxylic acid by adjusting the molar ratio of adipic acid and 2,6-pyridinedicarboxylic acid via solution condensation reaction in poly(phosphoric acid) with microwave synthetic method which is timesaving relative to conventional ways. The casting PBI membranes made from the copolymers were characterized mainly by Fourier transform infrared spectrometer(FTIR), thermogravimetric analyzer(TGA), water uptaking, swelling ratio, proton conductivity, tensile strength as well as Fenton test. Among the membranes, the PBI-C2 membrane made from the resin by polymerization using adipic acid and 2,6-pyridinedicarboxylic acid in a molar ratio of 3: 2, showed good proton conductivity as high as 30 mS/cm at 160℃ after doped with H3PO4. The tensile strength(77.54 MPa) and elongation at break(39.25%) were measured at room temperature. By dynamic mechanical thermal analysis(DMTA), the parameters including the maximum storage modulus(9.0623 MPa), the maximum loss modulus(8.36 MPa) and glass transition temperature(360℃) were obtained. The Fenton test indicates that PBI-C2 membrane has good anti-oxidative stability. The results suggest that the PBI-C2 membranes show a promising application in high temperature proton exchange membrane fuel cell.

    Synthesis, Characterization and Properties of a Novel Unsaturated Polyphosphoester
    WANG Dan, BAI Yin-Juan, HE Gui-Qiang, ZHANG Yu-Cheng, GONG Yong-Kuan, ZHANG Shi-Ping
    2013, 34(6):  1555-1559.  doi:10.7503/cjcu20121131
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    A new biodegradable and biocompatible unsaturated polyphosphoester bearing quaternary ammo-nium pendent groups was synthesized and characterized by 1H NMR, FTIR, gel permeation chromatography (GPC) and elemental analysis. Physical properties of the synthesized polymers were also characterized by means of thermal analysis, in vitro degradation and swelling behavior. The experimental evidence demonstrated that the introduction of quaternary ammonium pendent groups reduced the melting point and the decomposition temperature of polyphosphoester. The experiments of in vitro degradation and swelling behavior revealed that the more polyphosphoester in the polymer tablets, the faster degradation rates and the higher swelling ratio.

    Preparation of Water Soluble Conjugate Polyelectrolyte and Application in Organic Electrochromic Devices
    HU Jian-Hua, YIN Bin-Bin, BAO Xiang-Jun, ZHONG Yi-Ping, LIU Ping, DENG Wen-Ji
    2013, 34(6):  1560-1564.  doi:10.7503/cjcu20120930
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    The water-soluble polythiophene electroyte, poly[3-(1'-propyloxy-3'-acid sulfonate) thiophene](PTH-n3-SO3H), was prepared. Its application as electroyte in organic electrochromic devices was investigated. 5,5"'-diformyl-2,2': 5',2": 5",2"'-tetrathiophene(4T-2CHO) and 5,5"'-dicyane-2,2': 5',2": 5",2"'-tetrathiophene(4T-2CN) films showed reversible, clear color changes in PTH-n3-SO3H aqueous solution. When the voltage were applied between the ITO working electrode and the platinum wire counter electrode, the 4T-2CHO film showed reversible, clear color changes from yellow to blue-green, while the 4T-2CN film showed reversible, clear color changes from light yellow to blue. The results also indicate that PTH-n3-SO3H can be used as electroyte in organic electrochromic devices.