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    10 April 2009, Volume 30 Issue 4
    高等学校化学学报2009年第30卷第4期目次
    2009, 30(4):  0.  doi:
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    目次
    下期目次预览
    2009, 30(4):  0.  doi:
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    Magnetic Behavior at Low Temperature of LaMn1-xMgxO3
    LIANG Hong-Wei, CHEN Yan, ZHANG Xiao-Xia, ZHANG Shi-Jing, ZHANG Gang-Hua, YUAN Hong-Ming, FENG Shou-Hua
    2009, 30(4):  643-646.  doi:
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    The substitution of Mn with Mg in LaMnO3 strongly affects the magnetic properties at low temperature and the crystal structure of the LaMn1-xMgxO3 system. Sample displays weak ferromagnetic at low tempe-rature when x≤0.08, and the spin-glass state was observed at low temperature when x≥0.18; the existance of nonferromagnetic Mg2+ ions in perovskite B site is an important factor for magnetic behavior at low temperature of LaMn1-xMgxO3 samples. Magnetic ordered temperature and spin frozen temperature monotonously decrease with the increase of Mg-substitution.

    Effect of Atmosphere on the Growth of MnCr2O4 Spinel Nanowires
    LUO Li-Jie, TONG Zhang-Fa, MO Li-Bin, LIANG Zhong-Yuan, CHEN Yong-Jun*
    2009, 30(4):  647-650.  doi:
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    MnCr2O4 spinel single-crystalline nanowires were synthesized by heating commercial stainless steel foil under a reducing atmosphere. The hydrogen content in the atmosphere has important influence on the yield and morphology of the grown nanowires. It was found that the reducing atmosphere plays a key role in the nanowire growth. In the reducing atmosphere, the Mn and Cr elements in the stainless steel could be selectively oxidized because of their higher affinity for oxygen than the Fe and Ni elements. The Fe and Ni elements in the stainless steel, however, acted as the catalyst for the vapor-liquid-solid(VLS) growth of the MnCr2O4 nanowires.

    Synthesis and Application of New Color Reagent Meso-tetra-(4-hydroxy-3-ethoxyphenyl) Porphyrin
    XIA Ai-Qing, YU Shuang-Jiang, GAO Yan-Song, PIAO Zhong-Shu, SHI Tong-Shun*
    2009, 30(4):  651-654.  doi:
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    A new color reagent, tetra(4-hydroxy-3-ethoxyphenal) porphyrin, was synthesized and characterized by elemental analyses, MS, UV-Vis spectrum, Infrared spectrum, and 1H NMR spectrum. In a pH=11 solution with NaOH and Na[B4O5(OH)4]·8H2O, the complex of this color reagent with Pb was formed. The apparent molar absorptance of the complex was 2.08×105 L/(mol·cm)(λ=473 nm ). Beer′s low was obeyed for Pb in the range of 0—12 μg/25 mL. The reagent was applied to the determination of Pb in the certified reference material(GBW07601) successfully.

    Syntheses, Structures and Theoretical Calculations of Three Novel Cu(Ⅱ) Complexes
    HUANG Rong-Yi, CHEN Hong, YAN Juan, ZHU Kun, LIU Guang-Xiang*, REN Xiao-Ming
    2009, 30(4):  655-660.  doi:
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    Three novel coordination complexes, [Cu(mbix)2(H2O)]·2NO3·CH3OH(2), [Cu(mbix)(N3)(OAc)]·CH3OH(3) and [Cu(mbix)2]·(SiF6)·2(CH3OH)(4), with a novel flexible ligand 1,3-bis(imidazol-1-ylmethyl)benzene(mbix, 1) with Cu salts, were prepared and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complex 2 exhibit a two-dimensional two-fold interpenetrating network; complex 3 process a hinge-chain structure with dinuclear Cu(Ⅱ) clusters as secondary building units which are bridged through azide anion, while complex 4 features a one-dimensional infinite chain structure. The results show that the counteranions play important roles in the assembly of the complexes. Moreover, theoretical calculations were carried about the conformation of the ligand in three complexes.

    Identified of Urinary Modified Nucleosides of Lymph Cancer Patients by HPLC/ESI-Q-TOF MS
    LI Hua-Yu, LIU Hong-Min*, BU Shan-Shan, LI Juan, HAN Dong, WU Guang-Yin, WANG Shao-Min, ZHANG Ming-Zhi
    2009, 30(4):  661-669.  doi:
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    As modified nucleosides reflect altered tRNA turnover which is impaired in the body of cancer patients, they have been evaluated as potential tumor markers. High performance liquid chromatography(HPLC) was combined with full-scan mass spectrometry, MS/MS analysis and accurate mass measurements in order to identify modified nucleosides which purified from urine. Potential urinary nucleosides were assessed by their evident UV absorbance in the HPLC chromatogram and then further examined by the mass spectrometric techniques. In this manner the information of 9 nucleosides were reproduced with the standard compounds and 17 modified nucleosides without commercial standards were identified in the urine samples from lymph cancer patients including 6 novel urinary modified nucleosides: N3-methyladenosine, N7-methyladenine, 5′-dehydro-2′-deoxyinosine, N3-methylguanine, O6-methylguanosine and N7-methyl-N1-ethylguanosine. This new method is rapid and specific to identify the complex biological samples without control compounds.

    Total Cholesterol Biosensor Based on Direct Electrochemistry of Proteins
    WAN Li, ZHAO Chang-Zhi*, XU Hua-Jun, WANG Qin, JIAO Kui
    2009, 30(4):  670-674.  doi:
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    A highly selective cholesterol biosensor based on the direct electron transfer of hemoglobin-encapsulated chitosan-modified glassy carbon electrode was developed for the determination of total cholesterol in human serum samples. The enzyme electrode was prepared by immobilization of hemoglobin, cholesterol oxidase and cholesterol esterase in chitosan matrix. The H2O2 produced from the catalytic oxidation of cholesterol by cholesterol oxidase was reduced electrocatalytically by immobilized hemoglobin and used for the achievement of sensitive amperometric response to cholesterol. The linear response of cholesterol concentrations was from 10.0 to 110 mg/dL with the correlation of 0.9965, and the detection limit of cholesterol was estimated to be 5.0 mg/dL at a signal/noise ratio of 3. The cholesterol biosensor can efficiently exclude the interference of commonly coexisted ascorbic acid and uric acid. The relative standard deviation was under 6.2%(n=7) for the determination of real samples. The biosensor is satisfactory to the determination of human serum samples in comparison with the GPO-PAP method.

    Determination of Free Aliphatic Amines in Environmental Water by EASC Derivatization and Identification with LC-APCI-MS
    ZHAO Huai-Xin, SUN Xue-Jun, SUN Zhi-Wei, YAN Tao, ZHANG Zai-Qing, LIU Qin-Ze, SUO You-Rui, LI Yu-Lin, YOU Jin-Mao*
    2009, 30(4):  675-681.  doi:
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    On a reversed-phase Hypersil BDS C18(4.6 mm×200 mm, 10 μm i.d.) column, 12 aliphatic amines were derivatized using 10-ethyl-9-oxo-9,10-dihydroacridine-2-sulfonyl chloride(EASC) as a new pre-column derivatization reagent. The complete baseline resolution was obtained in conjunction with a gradient elution with acetonitrile/H2O as mobile phase within 20 min. The optimum excitation and emission wavelengths were at λex/λem=270 nm/430 nm. Comparing with the widely used Dansyl-Cl, EASC has stronger photoluminescence characteristics(ultraviolet and fluorescence): UVEASC/UVDansyl-Cl=3.2(UV: ultraviolet absorption intensity); I(EASC)/I(Dansyl-Cl)=30.0∶1—105.4∶1(I: relative fluorescence intensity); fluorescence quantum yield: Φf(EASC)/Φf(Dansyl-Cl)=43.0∶1. Fast and accurate quantitative analysis of aliphatic amines with fluorescence and corresponding post-column ion trap mass spectrometry(LC-APCI-MS) were obtained. EASC-amines exhibited stronger mass spectrometric sensitivity relative to that of dansyl-amine derivatives: MSEASC/MSDansyl-Cl=1.6∶1—6.2∶1 times(MS: relative intensity of ion current). The established method for the determination of aliphatic amines in environmental water samples exhibited good reproducibility and recovery. Excellent linear responses were observed with the correlation coefficients >0.9995. The detection limits(at signal-to-noise of 3∶1) were at levels of 4.0—12.7 fmol.

    Expression and Activity Experiment of Anti-tumor Bispecific Immunological Directing Agent CAtin
    LI Xiao, JIN Ning-Yi*, LI Chang, TIAN Ming-Yao, CHEN Lu, JIA Peng, LIU Li-Ming, LIU Yan, GAO Peng
    2009, 30(4):  682-686.  doi:
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    Combining the bioinformatics methods and the analysis of the nucleotide sequences of anti-carcinoembryonic antigen(CEA) single chain Fv fragment(scFv), the anti-CEA disulfide stabilized single chain fragments(scdsFv) was chemical synthesized after molecular designing and codon optimizing. Apoptin gene was linked downstream to anti-CAE scdsFv via soft linker peptide and cloned into the prokaryotic expression vector pET28a. Then the recombinant plasmid was transferred into Escherichia coli strain BL21. After induce expression by isopropyl β-D-1-thiogalactopyranoside(IPTG), the protein expression was analyzed by SDS-PAGE and Western-Blot. The results show that target protein CAtin is well expressed and the maximal production is 44.1 mg/L. Human hepatoma carcinoma cell(HCC) was used to detecting antibody affinity, cellular binding activity and cellular killing activity after the purification and renaturation of the CAtin by washing and glutathione methods. The results indicate that CAtin can bind and suppress the cells effectively. The work presents here suggest that CAtin is an anti-tumor bispecific immunological directing agent which has both specific recognition activity and specific killing activity.

    NMR Investigation of Synthetical Compound S-A
    WANG Jun-Mei, OUYANG Jie, XU Mei-Feng, DENG Zhi-Wei*, MA Feng-Nian, ZHANG Cong
    2009, 30(4):  687-690.  doi:
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    In this work, the behavior of synthetical compound S-A dissolved in CDCl3 was investigated with NMR techniques. It was confirmed that there was a hydrogen-bounding process in this solution, and which would affect the performance of NMR experiments and spectra results, obviously. Considering this phenomena, the sample system or testing condition was adjusted with either introducing an extra agent, or changing the testing temperature. As the result, the NMR spectra with fair quality were obtained, and finally NMR structu-ral confirmation was achieved for this compound.

    Studies on Chitosan Coated on Silica for Imprinting Bovine Hemoglobin
    LIU Qiu-Ye, HE Xi-Wen*, LI Wen-You, CHEN Lang-Xing, ZHANG Yu-Kui*
    2009, 30(4):  691-696.  doi:
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    The silica modified with chitosan was synthesized as a carrier material. The glutaraldehyde was coupled with amido group of chitosan, and template protein-bovine hemoglobin was immobilized by aldehyde group. Then, the carrier was coated by sol-gel, after template protein was removed; molecularly imprinted polymer was prepared for selectively recognizing bovine hemoglobin(BHb). The results of IR and scanning electron microscope(SEM) demonstrated the formation of a grafting polymer layer on the modified silica gel surface. Selectivity adsorption experiments under equilibrium adsorption show that the imprinted polymers have good adsorption capacity and specific recognition for BHb in aqueous solution, and imprinted polymer hold good recognition capability for BHb when completive substances are present. The MIP synthesis strategy is promising for separating and purifying specific protein compositions in bio-samples. It may have good prospect for riching target protein, which is required to further study.

    Analysis of Tobacco by Near-infrared Spectroscopy and Support Vector Machine
    ZHANG Yong, CONG Qian, XIE Yun-Fei, ZHAO Bing*
    2009, 30(4):  697-700.  doi:
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    In this study, in order to establish analysis models of near-infrared spectroscopy(NIR) of tobacco, 120 samples of tobacco from different cultivation area were surveyed by near-infrared(NIR) spectroscopy. As the new pattern recognition, support vector machine(SVM) can avoid over-fitting problem and owns the superior generalization ability and prediction accuracy, were applied in this study. The quantitative and qualitative analysis models of tobacco samples were studied separately in this experiment using radial basis function(RBF) SVM. For reducing dimension and moving noise, the spectrum variables were highly effectively compressed using the wavelet transformation(WT) technology and the haar wavelet was selected to decompose the spectroscopy signals. Simultaneously, the parameters of the models were also discussed in detail. The best experimental results were obtained using the RBF SVM regression with kernel parameter σ=1.0, 1.2, 1.4, 0\^6, separately corresponds to total-sugar, reducing sugar, nicotine, total-nitrogen, and RBF SVM classifier with kernel parameter σ=1.6. Meanwhile, the values of appraisal index, namely coefficient of determination(R2), root mean squared error of prediction(RMSEP) and mean relative error(RME), indicate its excellent generalization for quantitative and qualitative analysis results and high prediction accuracy. The overall results show that NIR spectroscopy combined with SVM can be efficiently utilized for rapid and accurate analysis of chemical compositions in tobacco and discrimination of tobacco of different origins. On the other hand, the research can show that SVM is effective modeling tools to NIR spectroscopy and can provide technical support for quantitative and quantitative analysis of other NIR applications.

    New Magnetic Beads-based Enzyme Linked Aptamer Colorimetric Assay for Trace Amount Protein Detection
    SHEN Rui, TANG Ji-Jun, ZHANG Zhao-Yang, GUO Lei, XIE Jian-Wei*
    2009, 30(4):  701-705.  doi:
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    Choosing nucleic acid aptamers as a high efficient and special recognition/sensing element, we developed a novel colorimetric assay based on magnetically separation and special capture to achieve the goal of capturing/tracing target protein. Two different aptamers simply biotinylated, which bound the thrombin in different sites with high affinity, were chosen to develop a sandwich assay. The protein was captured by aptamer-functionalized magnetic beads and detected after the addition of the second biotinylated aptamer and of streptavidin labeled with an enzyme, and the detection of the product generated by enzymatic reaction was achieved by colorimetric assay. This magnetic beads based enzyme linked aptamer assay was capable of capturing thrombin with high specificity, didn′t be affected by other interfering proteins in complex matrix such as human serum albumin and bovine hemoglobin. The detection of thrombin in serum could be carried out with naked eyes, without the need of expensive analytical instruments and more assay time. A linear range from 10 to 80 nmol/L is obtained with a detection limit of 10 nmol/L for thrombin.

    De Novo Sequence of Novel Protein Based on Chemically-assisted Method Using 4-Sulfophenyl Isothiocyanate Derivatization by Mass Spectrometry
    ZHOU Xin-Wen, YAN Qin, ZHOU Pei, YANG Peng-Yuan*
    2009, 30(4):  706-711.  doi:
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    Eight tryptic peptides of a novel ginsenoside Rb1 hydrolase(β-glucosidase) purified from Paecilomyces bainier were identified with chemically assisted de novo sequencing followed 4-sulfophenyl isothiocyanate(SPITC) derivatization by MALDI-TOF-TOF mass spectrometry. Some relatively complete sequences were obtained from sulfonated peptides with very low signal/noise ratio. A pair of peptides were identified with non-oxidation and oxidation at methionine, respectively. The results indicated that the sulfonated peptide by SPITC significantly enhanced MALDI-TOF-PSD fragmentation signals and produced a spectrum containing only y+ ions. This method facilitated de novo sequencing and spectrum interpretation. By comparing the eight identified peptide sequences with the NCBI database, this purified β-glucosidase proves to be a novel protein that has not yet been reported. Two relatively conserved peptides are remarkable contribution to further research.

    Syntheses and Herbicidal Activities of Novel 1,2,4-Triazolinone Derivatives
    LAN Feng, XU Jun-Ying, LI Yong-Hong, WANG Su-Hua, LI Zheng-Ming*
    2009, 30(4):  712-715.  doi:
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    Triazolinone herbicides which is environment-benign have a broaden application perspective. Several triazolinone compounds such as amicarbazone, sulfentrazone, azafenidin and carfentrazone-ethyl have been developed as herbicides. In order to search for novel 1,2,4-triazolinone derivatives with high herbicidal activities, 2-(2,4,5-trichlorophenyl)-4-(2-substituted-benzyl)-5-methyl-2H-1,2,4-triazol-3(4H)-ones and 2,4-disubstitued-1,2,4-triazol-3(2H)-ones were designed and synthesized. Their structures were identified by 1H NMR, MS and elemental analysis. The results of preliminary biological activity tests show that some compounds display excellent herbicidal activity and some display good activity of promoting cucumber cotyledon root-formation at 1.5 kg/ha.

    Synthesis, Characterization and Enzyme Activity Assays of Peptides Nitriles as Inhibitors of Cathepsin K
    LI Hong-Wei, LIU Xin-Chen, YANG Jin-Gang, JIANG Kun, FANG Xue-Xun, WU Yu-Qing*
    2009, 30(4):  716-719.  doi:
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    Cathepsins are a family of cystein proteases that is specifically expressed in the osteoclasts. They are responsible for terminal protein degradation in acidic environment, and therefore are involved in many serious human diseases, such as osteoporosis, osteoarthritis, and bone cancer and so on. Of all the 11 human cystein cathepsins, Cathepsin K is the predominant one as it is an important drug target and has gained special attention recently. According to the structural characteristics of the active site in cathepsin K, we designed and synthesized a series of dipeptide nitriles as inhibitors of cathepsins and have gained a potent and high selective inhibitor of it, b(Ki=15.9 nmol/L) and f(Ki=19.1 nmol/L). Inhibition activity was tested by measuring the hydrolysis of initially quenched fluorogenic peptide substrates. Studies on structure-activity relationship reveal large differences of 100-fold in activity suppression as a result of difference in NH linker between P3 aryl and P2 leucinamide moieties and P3 moieties. Our results also suggest that less amide bonds may be good for the selectivity of peptide nitriles to cathepsins.

    Inclusion Interaction of Pyrimorph with β-Cyclodextrin
    XIAO Yu-Mei, WANG Jian, LIU Ji-Ping, WANG Ming-An, YUAN Hui-Zhu, QIN Zhao-Hai*
    2009, 30(4):  720-723.  doi:
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    The inclusion complexation behavior of pyrimorph with β-CD was investigated quantitatively by UV measurement. The results show that they can form 1∶1 inclusion complex and the formation constant reduce with elevation of the temperature, indicating that inclusion reaction is exothermic. Thermodynamic parameters of inclusion reaction(ΔH, ΔS, ΔG) were all negative, which suggested that interaction process between β-CD and pyrimorph was spontaneous driven by enthalpy changes of complexation. Phase-solubility experiments demonstrated that the water-solubility of pyrimorph was greatly enhanced in the presence of β-CD. The results were favored to develop water-based pesticide formulation. In addition, the bioassay testified that inclusion interaction had no obvious effect on fungicidal activity of Pyrimorph. The structure of the inclusion complex was characterized with IR and 2D ROESY spectrum. The results present that the benzyl rings of pyrimorph enter into the cavity of β-CD through the narrow rim and the tertiary butyl is closely to the wider rim, but the other residues of the molecule are not included.

    Synthesis and Azo-quinoid Tautomerizm of Azocalixarene
    FAN Ping*, JIN Zhe, PAN Yi, LIU Guang-Jin
    2009, 30(4):  724-727.  doi:
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    The introduction of chromophoric azo group into calixarene was of great value for the development of functional calixarenes, and the azo-coupled calixarene usually showed large UV-Vis band shifts when base was added. Eight azocalixarene compounds were synthesized by diazo-coupling reaction. These compounds were characterized by IR, 1H NMR, ESI-MS and elemental analysis. The effect of varying pH values upon the absorption ability of both 5,11,17,23-tetra[(2-benzothiazole)azo]-25,26,27,28-tetrahydroxycalixarene and 5,17-di[(1-naphthyl)azo]-25,26,27,28-tetrahydroxycalixarene was tested to study the azo-quinoid tautomerizm phenomena. Observed result exhibit that with the increasing of pH, the proportion of quinoid tautomer in azo-quinoid tautomerizm equilibrium is rised. Unexpectedly an conjugated system may be formed in the condition of pH=-1 for 5,17-di[(1-naphthyl)-azo]-25,26,27,28-tetrahydroxycalixarene, of which the UV absorption spectra show substantial bathochromic shifts(Δλ=477—545 nm).

    Synthesis and Biological Activities of Some Novel N-Aryl Sulfonyl Trytophanates and N-Aryl Sulfonyl Glutamates
    LI Wen-Ming, TAN Hai-Zhong, WANG Jian-Guo*, LI Yong-Hong, LI Zheng-Ming*
    2009, 30(4):  728-730.  doi:
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    Based on the crystal structure of acetohydroxyacid synthase(AHAS) in complex with sulfonylurea herbicides, molecular docking was performed to virtual screen MDL/ACD-3D database to obtain some meaningful chemical structures with low binding energy and high scores using molecular docking. We had synthesized 22 new compounds of the N-aryl sulfonyl trytophanates and N-aryl sulfonyl glutamates which had potential biological activities, their structure were confirmed by 1H NMR, MS, IR and elemental analysis. The in vitro and in vivo biological activities of all the title compounds were tested. Preliminary bioassay results in vitro indicated that the two types of compounds had week inhibition to AHAS. The bioassay results in vivo indicate that compounds 4d, 4g and 4k had certain herbicidal activity. Their inhibition rate on the growth of rape root was 70.8%, 52.4% and 50.2% at 100 μg/mL, respectively.

    Superhydrophobic TiO2 Nanofabric Mesh Fabricated by Electrospinning
    WANG Li-Fang, ZHAO Yong, JIANG Lei*, WANG Fo-Song
    2009, 30(4):  731-734.  doi:
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    A TiO2 mesh with superhydrophobic property is facile fabricated through electrospinning process followed by calcinations with silicon oil. The PVP/titania mesh interweaved by nanofibers, which is of rough surface structures, is firstly prepared by electrospinning. Then the silicon oil is dropped on the titania mesh. After this mesh is calcinated, it turns to TiO2 and silican composite with micro/nanoscale roughness. This composite mesh exhibits superhydrophobic property with high water contact angle and low sliding angle, which is attributed to the combination of low surface free energy and high surface roughness. This study provides a simple and effective method for generating non-wetting materials and may blazes interesting insights to design novel materials including non-loss liquid transport, self-cleaning surface and many other applications.

    Molecular Dynamics Simulation of the Inclusion Complex of β-Cyclodextrin with CTAB at Air/Water Interface
    PANG Jin-Yu, XU Gui-Ying*, BAI Yan, ZHAO Tao-Tao
    2009, 30(4):  735-740.  doi:
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    Molecular dynamics simulation was used to study the inclusion complex of β-cyclodextrin(β-CD) with CTAB at air/water interface. Two systems were chosen: the molar concentration ratio of β-CD and CTAB was 1∶1 and 2∶1, respectively. We investigated the energy of the systems, radial distribution function and mean square displacement in this paper. As a result, it was suggested that CTAB molecules and β-CD molecules form inclusion complexes at air/water interface in which the guest is included within the β-CD cavity and they are easily to form 1∶1 inclusion complexes.

    Preparation of SWNTs/Pt Composites Using SWNTs as Reducing Agent and Their Catalytic Properties
    CAO You-Ming, WANG Zhi-Yong, NIU Fang, SONG Wei-Guo, SHI Zu-Jin*, GU Zhen-Nan
    2009, 30(4):  741-745.  doi:
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    SWNTs/Pt composites for catalysis were prepared through redox reaction between SWNTs and K2PtCl6. Characterization of the composites by TEM, XPS and TG techniques revealed that large quantities of Pt particles with diameters of ~1.5 nm distribute evenly on the SWNTs. The influences of concentration of K2PtCl6 solution and solvents of SWNTs on the quantity and size of Pt particles were investigated. SWNTs/Pt composites containing 24.76%(mass fraction) Pt were obtained using high purity SWNTs and K2PtCl6 solution of 10 mmol/L. The SWNTs/Pt composites exhibit high catalytic activity for hydrogenation of cyclohexene. The conversion rate from cyclohexene to cyclohexane is up to 100% at room temperature.

    Effects of Plasma Introduction Mode on Ni/γ-Al2O3 Catalysts for CH4 Reforming with CO2
    GUO Fang, CHU Wei*, SHI Xin-Yu, ZHANG Xu
    2009, 30(4):  746-751.  doi:
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    For CH4 reforming with CO2 reaction, the effect of the plasma introduction mode in catalyst preparation processing on the catalytic performance of nickel-based catalysts was investigated. The catalysts were characterized by H2-TPR, BET, CO2-TPD, XRD, CO2-TPSR, TGA and XPS analyses. The catalyst treated by N2 plasma before reduction showed higher activity at low temperature than conventional calcination catalyst. The catalyst prepared by this way exhibited an improved dispersion of nickel and an increased amount of absorbed CO2. Furthermore, the formation of coke was inhibited and only one carbonaceous species presented on the used catalyst. Owing to the plasma treatment, the nitrate decomposition and catalyst reducibility were remarkably promoted, and a higher specific surface area was obtained.

    Effect of Heated-treating Temperature on the Electrocatalysis of Oxygen Reduction for Carbon Black-supported CoTMPP/BP2000
    WANG Ai-Qin, REN Qi-Zhi*, LIU Shuang-Yan, MA Xiao-Xia, XIE Xian-Yu
    2009, 30(4):  752-756.  doi:
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    Carbon black-supported cobalt tetramethoxyphenylporphyrin CoTMPP/BP2000 was prepared as cathode electrocatalyst for the oxygen reduction in proton exchange membrane fuel cell(PEMFC).The effect of various heated-treating temperature from 200 ℃ to 900 ℃ on the electrocatalytic activities for oxygen reduction of CoTMPP/BP2000 were investigated by cyclic voltammogram(CV) and Koutecky-Levich plot.Results show that the heat-treatment can enhance the catalytric activity and stability of the catalyst, 900 ℃ is found to be the most suitable temperature.The influence of heate-treating temperature of CoTMPP/BP2000 was analyzed by UV-Vis, TEM, IR, TG and XPS methods. Results reveal that heated-treatment can change the central structure of catalyst, the porphyrin ring and Co—N4 band of the catalyst can not exited with and after 400 ℃ heat-treatment.The most stable Co—Nx—C structure was formed with 900 ℃ heat-treatment, this new active site can efficiently improve the catalytic ability of oxygen reduction of CoTMPP/BP2000.

    Photoconversion of Phenol in Ice with the Presence of Nitrate
    KANG Chun-Li*, TANG Xiao-Jian, GUO Ping, GAO Hong-Jie, PENG Fei, LIU Xing-Juan
    2009, 30(4):  757-761. 
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    The photolysis of nitrate ion(NO3-) is widely studied in water. The formation of mutagens by photochemical reaction of aromatic compounds in aqueous solution was also observed and attributed to a photochemical nitration. While NO3- is one of the dominating anions found in ice samples in both polar regions, the photolysis of NO3- in ice is still an unknown field. Hence, the aim of this paper is to determine the kinetics and pathways of phenol photoconversion induced by NO-3 in ice. Using 125 W high-pressure mercury lamp as light source, under the condition of low temperature(-14—-12 ℃), the ice photoconversion reaction of phenol was studied when NO3- existed in ice. Each factor on phenol photoconversion in ice and phenol photoconversion dynamics were inspected. The results showed that initial concentration of phenol, initial concentration of NO3-, pH value and light strength all had greater influence on phenol photoconversion in ice. The photoconversion rate of phenol increases rapidly with the increasing of the initial concentration of NO3- and light intensity, and decreases with the increasing of the initial concentration of phenol. Under the strong acid or alkali were decreased the photoconversion rate of phenol. The photoconversion of phenol follows first-order kinetics equation. The photoproducts of phenol photolysis in ice were analyzed by GC-MS and LC-MS and on this basis the photoconversion mechanism of phenol was proposed.

    Studies on Deterioration Process of Organic Coatings Using EIS and SKP
    ZHANG Wei, WANG Jia*, ZHAO Zeng-Yuan, JIANG Jing
    2009, 30(4):  762-766. 
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    Deterioration process of the organic coatings on carbon steel substrate during exposure to 3.5% NaCl solution was investigated using the electrochemical impedance spectroscopy(EIS) and scanning Kelvin probe(SKP). According to the EIS and SKP responses, the entire deterioration process can be divided into three main stages shown as follows. Stage Ⅰ was the water penetration into coatings. In this stage the EIS plots showed single semi-circel with the impedence of the coatings drops gradually and the Volta potential obtained by SKP keeps decreasing but the potential distribution remaines flat. Stage Ⅱ was the corrosion initiation under coatings. In this stage the EIS plots changed from a single loop to double capacitive loops with the resistance of the coatings decreased sharply, at the same time the surface Volta potential difference of the metal surface increased rapidly. Stage Ⅲ was the corrosion development and extension.The Nyquist plots of the electrochemical impedence showed a capacitive loop in the HF and a oblique line in the LF, with the potential difference remained in the high level. It was confirmed that the novel combination of EIS and SKP can complement and perfect each other to get more exact and credible details in studying the deterioration process of the organic coatings.

    FTIR Spectroscopic Studies of PEO-based Polymer Electrolyte with Ionic Liquid
    JIN Lan-Ying, JIANG Yan-Xia*, LIAO Hong-Gang, ZENG Dong-Mei, SUN Shi-Gang
    2009, 30(4):  767-771. 
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    Polymer electrolytes based on poly(ethylene oxide)(PEO) was prepared using LiTFSI as lithium salt and doping with 1-butyl-3-methylimidazolium hexaflurophosphate(BMIMPF6) by solution casting method. The addition of BMIMPF6 resulted in an increase of the ionic conductivity. When the amount of the ionic liquid is 40%, the ionic conductivity could reach 1.80×10-4 S/cm at 40 ℃. The samples were explored by emission FTIR spectroscopy at elevated temperatures, which illustrated the dependence of crystalline PEO phase on temperature. Based on results of SEM, XRD, transmission FTIR and emission FTIR, the effect of ionic liquid on the ionic conductivity was analyzed. It was revealed that the ionic liquid decreased cystallinity of the polymer, and resulted in the increase of ionic conductivity. The study has demonstrated that the FTIR spectroscopy is an important method for investigations of lithium batteries.

    Influence of Water Addition on the Electrochemical Behavior of Polypyrrole Synthesized in Organic Solution
    WANG Yuan, MU Dao-Bin, ZHANG Cun-Zhong*, WU Feng, AN Xiao-Ke
    2009, 30(4):  772-776. 
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    Using potential step method, polypyrrole films were synthesized directly on the surface of Pt micro-disk electrode in 0.1 mol/L pyrrole-0.1 mol/L LiClO4-PC solution containing different proportion of water(0, 2%, 4%, 6%, 8%, in volume fraction). The electrochemical properties of polypyrrole film electrodes were characterized with the methods of cyclic voltammetry(CV) and chronoamperometry, the morphologies of films were observed by scanning electron microscope(SEM) as well. It is shown that the addition of 6% water is the one which is favorable to PPy electro-deposition and its characteristics. Besides more compact surface, polypyrrole film synthesized in this condition exhibits better redox reversibility and higher capacity.

    Action of Molecular Kinetic Energy on a Gas-solid Chromatography
    ZHANG Da-Li, KE Jia-Jun, LU Li-Zhu
    2009, 30(4):  777-780. 
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    The migration velocity, the migratory activation energy and the action of molecular motion on migration were researched for five alkanes in the gas-solid chromatography of N2/GDX-101 system. Maxwell distribution of energy which originally shows the molecule fraction of molecular translation energy exceeding E, was used for expressing the time fraction of the translation energy exceeding E. The kinetic energy of rotation and vibration was expressed by the times of kT/2 in the light of the principle of equiparation of energy, to modify the ideal equation. The migratory activation energy(E) which is calculated with the rate equation, could well explain the migration velocity. The kinetic energy of rotation and vibration observably influences E. These properties were also authenticated with the estimate of statistical thermodynamics. The calculation showed that E was obviously smaller than the desorption enthalpy(ΔHDesorption). The solute migration might not reach the state of desorption. The solute driven by mobile phase should mainly slip under the state of adsorption.

    Molecular Docking Studies on the Metallonucleases and Polyamides with Double-strand DNA Molecules
    ZHU Yan-Yan, SU Yan-Wei, QI Yao, TAN Hong-Wei, WANG Yan*, CHEN Guang-Ju*
    2009, 30(4):  781-785. 
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    The studies on molecular docking of metallonucleases and polyamides with DNA were investigated via AutoDock program. Our studies demonstrate that the results of docking metal nucleases and poly-amides with double-strand DNA are consistent with those of the experiments. The characteristics of the optimal conformations for the two copper nucleases with DNA are that the two copper nucleases are docked into the minor groove of DNA. With the increase of the charges at copper center, the biggest docked energies for the two copper nucleases increase gradually. For BPA ligand, the nuclease with the different charges on copper center is docked into the different sites in the minor groove. However, for IDB ligand, the nuclease is docked into the similar site in the minor groove even if the charges on the copper center are changed from 0.5 e to 2.0 e. The feature of the optimal conformations of the flexible molecule-polyamide with double-strand DNA is that the polyamides are also docked into the minor groove of DNA, which agrees with the experimental estimation.

    Whether the Coordination Number Influence Dependence of Static First Hyperpolarizability on the Atomic Number of Alkali Metal
    XU Gong-Liang, LI Zhi-Ru, WU Di, CHEN Wei, YU Guang-Tao, WANG Qin
    2009, 30(4):  786-788. 
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    Using the MP2 method, the optimized structures of the one-coordination M—X(X=NH3, NCH, HF) and two-coordination M—(FH)2(M=Li, Na, K) with all real frequencies were calculated. Further, their static first hyperpolarizabilities(β0) were studied by QCISD/6-311++G(3df, 3pd) level. The dependence of β0 on the atomic number of alkali metal(M) is not monotonic in these one-coordination electrides. However, the dependence of β0 value on the atomic number of alkali metal was observed in the two-coordination electrides M—(FH)2(M=Li, Na, K), the dependence is accorded with that of reported four coordination related systems. These results show that the dependence of β0 value on the atomic number of alkali metal is related to coordination number.

    Synchronization in Unidirectional Coupled Hindmarsh-Rose System
    LI Ji, LI Qian-Shu
    2009, 30(4):  789-791. 
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    The dynamic behavior of two unidirectional coupled Hindmarsh-Rose neurons under different initial conditions were numerically studied. The results show that coupling strength has important influence on synchronization between the two neurons. When control parameters are different, that is, the drive system and the response system are both chaotic and the drive system is periodic oscillating while the response system is chaotic, under these two cases, the firings of the drive system and the response system both can transition from asynchrony to phase synchronization, and then to almost complete synchronization with the increase of coupling strength.

    Effect of Cu2+ on the Optical Properties of Poly(3-hexylthiophene) in Different Phases
    ZHU Jun, PENG Rui-Xiang, WANG Ming-Tai
    2009, 30(4):  792-795. 
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    The interactions between Cu2+ and poly(3-hexylthiophene)(P3HT) in three different phases(dilute solution, dispersive solution and film), were investigated with UV-Vis absorption spectroscopy and photoluminescence spectroscopy. Our results indicate that the phase state of P3HT has a remarkable influence on the interactions. In the dilute THF solution, there is almost no chemical interaction between Cu2+ and P3HT due to the high degrees of solvation of both them, while in the dispersive solution, the Cu2+ partially enters into the dispersive particles and leads to weak oxidative doping of P3HT. In P3HT films, the presence of Cu2+ makes the conjugation length of P3HT become shorter and causes a blue-shift in the absorption spectroscopy.

    Synthesis of Chitosan-stabilized Nanoscale Zero-valent Iron for Removal of Hexavalent Chromium from Surface Water
    GENG Bing, LI Tie-Long, JIN Zhao-Hui*, QI Xin-Hua
    2009, 30(4):  796-799. 
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    The use of nanoscale zero-valent iron is a promising technology for in situ environment remediation. However, due to the extremely high reactivity, nanoscale zero-valent iron tends to agglomerate or is easily oxidized by air resulting in the reduction of their chemical reactivity. We present here a simple method for the synthesis of nanoscale zero-valent iron(mean particle size 82.4 nm) on the basis of chitosan as a stabilizer. This chitosan-stabilized nanoscale zero-valent iron show no changes in reduction activity on storage at room temperature in air for 2 months. The TGA curve demonstrated that after modification by chitosan nanoscale zero-valent iron had a good thermal stability below 340 ℃. The synthesized chitosan-stabilized nanoscale zero-valent iron was powerful in reducing Cr(Ⅵ) and batch experiments indicated that after exposure to air atmosphere over a 60 d period the chitosan nanoscale zero-valent iron still exhibit high reducing capacity. Due to the presence of the —NH2 and —OH groups chitosan has a better ability to chelate Fe(Ⅲ) and can inhibit the formation of Fe(Ⅲ)-Cr(Ⅲ) precipitation which increases the rates of iron corrosion and reduction of Cr(Ⅵ). Due to the good stability against oxidation in air the chitosan-stabilized nanoscale zero-valent iron have the potential to become an effective agent for in situ environment remediation.

    Synthesis and Properties of Aminoalkyl Substituted Red-emitting Triphenylamine-based Polymers
    SHI Wei, ZENG Wen-Jin, WANG Lei, ZHANG Yong, YANG Wei, CAO Yong
    2009, 30(4):  800-805. 
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    A series of amino-alkyl substituted, triphenylamin and fluorene-based red-emitting polymers with different feed ratios of 4,7-di-2-thienyl-2,1,3-benzothiadiazole(DBT) component were synthesized by Suzuki coupling reaction. The chemical structures of these polymers were confirmed and the optoelectronic properties of them were investigated. PLEDs using these polymers as emitting-layer with high work function metal, Al, as cathode exhibited fairly good devices′ performance. The device with structure of ITO/PVK/PFT-DBT-5/Al show emission peak at 647 nm, and the maximum external quantum efficiency reached 1.24%.

    Synthesis of Liquid Crystalline Poly(9-substituted fluorenylidene-phenylene) and Influence of the Catalysts on the Stereoregularity, Mesophase and Optical Properties
    WEN Gang, ZHENG Shi-Jun*, DANG Dong-Feng, ZHAO Kun, CAO Shao-Kui, ......
    2009, 30(4):  806-812. 
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    Poly(9-substituted fluorenylidene-phenylene)s were synthesized with Suzuki cross-coupling reaction using different Pd catalyst in order to develop new organic materials used in organic light-emitting field-effect transistors. The polymers were soluble in common organic solvents. The studies of DSC, X-ray diffraction and polarizing optical microscope(POM) show that the polymers are enantiotropic liquid crystal and form Nematic phase. It is found that the polymers prepared with different Pd catalysts have the similar molecular weights. The kind of catalysts has a great impact on the stereoregularity of the polymer main chain, mesophase as well as optical properties of the polymers. The polymer prepared by Pd(PPh3)4 has higher stereoregularity, wider mesophase ranges, higher fluorescence qutum yield and better optical properties.

    Studies on Regioselective Catalyzed Modification of Poly(methylhydrosiloxane) Using Quaternized Poly(amidoamine) Dendrimer-Encapsulated RuRh Bimetallic Nanoparticles
    PENG Xiao-Hong*, PAN Qin-Min*, Garry L. Rempel, PENG Xiao-Chun
    2009, 30(4):  813-817. 
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    Partially quaternized fifth-generation poly(amidoamine) dendrimer-encapsulated RuRh bimetallic nanoparticles(DENs) were prepared via co-complexation method. The formation of DENs, the particle size and distribution of RuRh bimetallic nanoparticles were investigated by UV-Vis absorption spectroscopy, laser scattering analysis, and TEM. The results of FTIR and NMR spectroanalyses show that a high efficiency of regioselective hydrosilation modification of poly(methylhydrosiloxane) is achieved with the RuRh bimetallic DENs catalysts.

    Interaction Between Phenol and Poly(4-vinylpyridine) Using Solid State NMR Method
    ZHANG Jing, CHEN Ying-Chao, ZHANG Sai-Hui, SUN Ping-Chuan,YUAN Zhi*
    2009, 30(4):  818-820. 
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    The interaction between phenol and poly(4-vinylpyprine) was investigated by means of the technique of dipolar filtered fast magic angle spinning(DF-MAS) combined with deuterium dilution 1H NMR. Experiment results reveal that strong hydrogen bond exist between phenol and poly(4-vinlypyridine), which is in good agreement with the data obtained from liquid state 1H NMR. Moreover, the difference in signals of water in MAS NMR disclosed that water was replaced by phenol in the binding with P4VP, and the interaction site between P4VP and phenol was on the H atoms which were near the N atom. Thus, this protocol was proved to be a powerful method for studying adsorption mechanism between insoluble adsorbents and target molecule in situ, which may facilitate the designing for new materials for adsorption and separation.

    Effect of Heat Treatment on Surface Properties of Superhydrophobic PMMA-PFAEA Film
    WEI Hai-Yang, HE Wen-Xiao1, SU Xiao-Li, LI Xin-Xin*, HAN Zhe-Wen
    2009, 30(4):  821-824. 
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    The superhydrophobic films of perfluoroalkyl ethyl acrylate(FAEA) and methyl methacrylate(MMA) copolymers were prepared with one-step casting technique with 1,1,2-trifluoro-trichloro-ethane(F113) as solvent. It was found the contact angle(CA) decreased while sliding angle(SA) changed a lot as the heat treatment continued. Although these original films had large CA and small SA, while annealed for 3 h to 6 h, the films showed large SA hysteresis. However, if continued annealing for a longer time to 32 h, the SA reversed to very small again. The unique changes of hydrophobic properties of these films were due to the changes in surface roughness, which was shown by SEM.

    Biocompatibility and Biodistribution of a Novel Cationic Polymer——Hyperbranched Poly(sulfone-amine) as an Intracellular Delivery System
    CHEN Su-Yun, SUN Guo-Ming, JIANG Lei, LI Nan, LI Pei-Yong*, ZHU Xin-Yuan*
    2009, 30(4):  825-829. 
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    Hyperbranched poly(sulfone-amine)(PSA) is a novel class of hyperbranched macromolecule. In order to assess its feasibility of using PSA as a drug delivery system, we synthesized PSA-FITC by conjugating a fluorescent diagnostic agent fluorescein isothiocyanate(FITC) to the terminal amino groups of PSA covalently. As measured by UV-Vis spectrophotometer at 488 nm, the resulting conjugate contained 19 molecules of FITC per unit of PSA, or 0.08 molecules of FITC per repeat unit of PSA. Cellular internalization ratio of PSA were studied by flow cytometry(FACS) and demonstrated that the cellular uptake was time dependent. The in vitro biocompatibility was examined by MTT method against 3T3 cell line and showed no notable effect on bioactivity of the cells. FITC labeled PSA was injected i.v. into normal nude mice. The optical imaging of dissected major organs/tissues revealed that preferential accumulation in specific organs was not observed at 24 h postinjection. The results suggest that PSA has characteristics of good biocompatibility, high efficiency of cellular uptake and modifiable surface function groups as well, which can serve as excellent platforms for a variety of therapeutic and imaging agents. It can be taken as an attractive drug/gene carrier system for intracellular delivery.

    Synthesis and Characterization of Fast pH-Responsive Silk Sericin/Poly(methacrylic acid) Interpenetrating Polymer Network Hydrogel
    WU Wen, WANG Dong-Sheng, WANG Li-Qun*
    2009, 30(4):  830-834. 
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    Interpenetrating polymer networks(IPN) composed with poly(methacrylic acid)(PMAA) and silk sericin(SS) were prepared by the simultaneous-IPN method. The swelling behavior of the resultant IPN hydrogels was studied at various pH values. The results show that the swelling ratios of the IPNs depend significantly on pH of the aqueous solutions. In pH=9.2, the IPNs have a higher swelling ratio due to the repulsion between —COO- groups derived from —COOH of the polymer chains and the osmosis. However, the swelling ratios diminish with the decrease of pH values. All IPN hydrogels show a fast deswelling rate and reversible swelling-shrinking property.

    Determination of the Degree of Substitution at Secondary Hydroxyls of Hydroxypropyl Guar Gum by Periodate Oxidation
    YE Ying-Qing, DING Bin, WANG Ke, HE Jian-Ping, CUI Jun-Jie, JIANG Bo*
    2009, 30(4):  835-840. 
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    Perioate oxidation of vicinal hydroxyls is a highly selective reaction which leads to the cleavage of the C—C bond and formation of dialdehyde groups. The reactions of periodate with guar gum(GG) and hydroxypropyl guar gum(HPG) were investigated at pH=4.3 and 25 ℃ and the oxidized products were characterized with IR and NMR. The results show that aldehyde groups in oxidized GG and HPG are in the form of hemiacetal structures like other polysaccharides such as starch and cellulose. The oxidation degree and the content of vicinal hydroxyls in GG and HPG were determined by the consumption of periodate(Pt) and the degree of substitution at the secondary hydroxyls(DSS—OH)of HPG was calculated by probability analysis. The results of HPGs with different molar substitution of 0.04, 0.14, 0.36, 0.51, 0.78, 1.05 and 1.53 are 0.02, 0.09, 0.18, 0.30, 0.46, 0.59 and 1.03 respectively, which are in good agreement with the values found in the literature by other methods. Other polysaccharides, such as methyl cellulose also gave good results on the values of by the method of periodate oxidation.

    Synthesis and Thermal Properties of Crosslinkable Alternating Poly(aryl ether ketone)s Containing Pendant Phenylethynyl Groups
    LI Wan-Wan, TANG Hao-Yu, CHEN Xiao-Fang, FAN Xing-He, SHEN Zhi-Hao, ZHOU Qi-Fen
    2009, 30(4):  841-844. 
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    A series of crosslinkable alternating poly(aryl ether ketone)s containing pendant phenylethynyl groups were synthesized via aromatic nucleophilic substitution reaction. The resultant polymers show good solubility in ordinary organic solvents. The polymers not only underwent thermal crosslink reaction at elevated temperature but also exhibited good thermal stability during thermal cure process. The glass transition temperature of the cured polymers was improved. Furthermore, polymers with different average number molecular weight showed similar glass transition temperature and decomposition temperature.