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    10 October 2007, Volume 28 Issue 10
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    目次
    高等学校化学学报2007年第28卷第10期目次
    2007, 28(10):  0.  doi:
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    其他
    2005~2006年ISI-JCR中国科技期刊(化学类)在学科中的总被引频次排名
    2007, 28(10):  0.  doi:
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    目次
    下期目次预览
    2007, 28(10):  0.  doi:
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    其他
    2005~2006年ISI-JCR中国科技期刊(化学类)在学科中的影响因子排名
    2007, 28(10):  0.  doi:
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    研究论文
    Preparation, Structure and Properties of La2Ni1-yCoyO4+δ Layered Compounds
    HUANG Duan-Ping, XU Qing*, ZHANG Feng, CHEN Wen, LIU Han-Xing
    2007, 28(10):  1807-1811.  doi:
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    La2Ni1-yCoyO4+δ(y=0—0.2) fine powders were synthesized by a polyaminocarboxylate complex method, and the structure and mixed conducting properties of the resulting ceramics were investigated. X-ray diffraction Rietveld refinement results indicate that La2Ni1-yCoyO4+δ compositions have an orthorhombic structure with Fmmm space group. The substitution of partial La3+ with Co at the B-site caused an increase in the length of Ni/Co—O1 bond in the ab plane and La/Sr—O2 bond along c axis. Moreover, it was detected that the oxygen nonstoichiometry(δ) became larger with increasing Co content. The cobalt substitution resulted in a shift of the temperature for the electrical conductivity maximum to higher temperature direction and a decline of electrical conductivity together with a modification of oxygen ionic conducting properties. The effect of cobalt substitution on the mixed conducting properties of La2NiO4+δ ceramic can be interpreted with respect to the variation in crystal structure parameters.
    Self-assembly and Photoluminescence of a Unique ZnO Nanostructure
    ZHOU Ze-Guang1, CHAI Chun-Fang2, MI Yan1, TAN Xue-Cai1, WU Jian1, HUANG Zai-Yin1,2*, YUAN Ai-Qun1
    2007, 28(10):  1812-1816.  doi:
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    A unique ZnO nanostructures were synthesized with hydrothermal method. The composition, morphology and size of the sample was determined with XRD, EDX and FE-SEM. Photoluminescence(PL) properties were studied by room-temperature PL spectra, temperature-dependent shifts and its Gaussian-fitted spectra. The results of XRD, EDX and FE-SEM analysis show that the products are the hexagonal wurtzite ZnO nanostructures, with a length of ~10 μm and diameter of ~2 μm; UV, violet and green peaks, which exhibit blue-, S-shaped (red-blue-red) and redshift, respectively, and the decrease of intensity, with the temperature increasing from 8 K to 300 K, are observed in the PL spectra. The original and different temperature dependence of the UV, violet and green peaks is discussed.
    Hydrothermal in stiu Synthesis, Crystal Structure and Fluorescence Property of Two Cadmiun Coordination Polymers
    ZHANG Dao-Jun, GUO Ye, SHI Jing, SONG Tian-You, WANG Li, WANG Ying, FAN Yong*, XU Jia-Ning*
    2007, 28(10):  1817-1820.  doi:
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    Two cadmiun coordination polymers Cd(AmTAZ)Cl(1) and [Cd(AmTAZ)(BDC)(H2O)2]·1.25H2O(2)(AmTAZH=3-amino-1,2,4-triazole, H2BDC=benzene-1, 4-dicarboxylic acid) were synthesized under hydrothermal in stiu conditions and characterized by IR, TG-DTA, CHN elemental analysis and single crystal X-ray diffraction analysis. The fluorescent properties of compounds 1 and 2 are also discussed. Compound 1 crystallizes in the triclinic space group P2(1)2(1)2(1) with a=0.6452(3) nm, b=0.7848(5) nm, c =1.0449(6) nm, V=0.5291(5) nm3, Z=4, R1=0.0226, wR2=0.0377, GOF=1.087. Compound 2 crystallizes in the orthorhombic space group Pmc2(1) with a=0.7100 nm, b=0.9920 nm, c=1.2561 nm, V=0.8847 nm3, Z=8, R1=0.0934, wR2=0.2456, GOF=1.031.
    Synthesis of Pt4(OCOCH3)4(OCOCH=CH2)4 and Its Assembly and Grafting on n-Si(111) Crystalline Surface
    XU Qing-Hong*, WEI Ya-Bo, ZHAO Yu-Xue
    2007, 28(10):  1821-1825.  doi:
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    A platinum complex, Pt4(OCOCH3)4(OCOCH=CH2)4, was synthesized by the reaction of Pt4(OCOCH3)8 with acrylic acid in dichloromethane as solvent, four equatorial acetate ligands in Pt4(OCOCH3)8 were selectively replaced by acrylates. At the same time, n-Si(111) crystalline was modified by this complex and many island-like particles were formed on the silicon wafer. Characterizations of XPS as well as SEM and FTIR spectrum reveal that the platinum clusters close to the wafer covalently connected to silicon in Si—C bonds and the assembly is stable at a high temperture and in some acidic solutions.
    Hydrothermal Synthesis and Characterization of a New Indium Phosphite [In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O) with Intersectin
    LIU Cheng-Zhan1,2, ZHU Guang-Shan1, JIN Zhao1, XUE Ming1, SUN Fu-Xing1, FANG Qiang-Rong1, QIU Shi-Lun1*
    2007, 28(10):  1826-1829.  doi:
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    A new three-dimensional indium phosphite, [In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O), was synthesized under hydrothermal conditions in the system containing HF using ethylenediamine as the template and characterized by IR spectroscopy, TG, ICP and C, H, N elemental analysis. The result of single-crystal X-ray diffraction analysis reveals that the title compound crystallized in trigonal system, space group P3 with unit cell parameters a=1.37883(7) nm, c=0.93450(9) nm, V=1.53862(2) nm3, Z=2, Dc=2.489 Mg/m3, R1[I>2σ(I)]=0.0526, wR2[I>2σ(I)]=0.1328, GOF=1.082. Its structure is built up from shared vertex linking InO6, InO5(H2O) octahedral and HPO3 pseudo-pyramidal units by O atoms, forming intersecting twelve-membered ring channels along a and b axes directions. Guest water and diprontonated ethylenediamine molecules exist in the channels.
    研究快报
    Enhancing the Visible-light Photocatalytic Activity of BiFeO3 by Heating in Molten Salt
    SUN Shang-Mei1,2, PANG Guang-Sheng1*, LI Chun-Guang1, HUANG Yu-Liang1, FENG Shou-Hua1
    2007, 28(10):  1830-1832.  doi:
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    The visible-light photocatalytic activity of BiFeO3 can be enhanced by treating in LiNO3 molten salt. BiFeO3 is prepared by pyrolysis of tartaric acid complex. The as-prepared BiFeO3 is mixed with LiNO3 salt by ball milling for 4 h with the molar ratio 12∶1 of LiNO3 to BiFeO3. The mixture was heated at 270 ℃ for 12 h, and LiNO3 was removed from the product by washing with distilled water. The visible light photocatalytic activity is evaluated by measuring the decoloratation of Congo red aqueous solution. After heating in LiNO3 molten salt, the decoloratation of Congo red aqueous solutions increased significantly from 31.6% to 95.4%. The enhancement of the photocatalytic activity is attributed to surface modification of BiFeO3 by treating in LiNO3 molten Salt.
    研究简报
    Effects of the Dimerization of [Ru(Phen)2dppz]2+ on the Calf Thymus Binding Properties
    NIE Jing, HAN Mei-Jiao, WANG Ke-Zhi*
    2007, 28(10):  1833-1835.  doi:
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    The dimerization of a well-known DNA light-switch [Ru(phen)2dppz]2+(phen=1,10-phenanthroline, dppz=dipyrido[3,2-a:2',3'-c]phenazine), and its effect on calf thymus binding properties were studied by UV-Vis and emission spectroscopy in Tris-HCl buffered 50 mmol/L NaCl(pH=7.1). The results show that the complex has a strong tendency to dimerize with a dimerization constant of (1.8±0.3)×106 L/mol at the same order of magnitude as the DNA binding constant of (6.0±1.2)×106 L/mol for the Ru(Ⅱ) complex dimer, but one order of magnitude less than (4.9±1.5)×107 L/mol for the Ru(Ⅱ) complex monomer. This study has provided insight into a fundamental but important issue that should be taken into account for the DNA binding studies.
    Synthesis and Structure of Binuclear Cage-like Rare Earth Complex [Eu2(TCM)2(DMSO)6]·2DMSO
    CAI Zheng-Hong1*, TANG Jing1, TANG Yu2, TAN Min-Yu2, YU Kai-Bei3
    2007, 28(10):  1836-1838.  doi:
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    A new binuclear cage-like complex, [Eu2(TCM)2(DMSO)6]·2DMSO, was synthesized via the reaction of H3TCM(H3TCM={2,4,6-tris[(2-carboxyphenoxy)methyl]-1,3,5-trimethylbenzene}) and Eu3+. Single crystal X-ray diffraction study reveals a centro symmetric binuclear neutral entity, space group P21/c with a=1.5188(2) nm, b=1.7135(3) nm, c=1.7578(2) nm, β=95.34(2)°, V=4.5549(9) nm3, Z=4. In the complex, Eu3+ metal centers are bridged together by mono- and bidentate carboxylate groups from two ligands. The most interesting fact is that the size of solvent molecules has a great influence on the binuclear cage-like complex in the shape of binuclear cage, the coordination mode of carboxylate group and the coordination number of Eu3+.
    Improvement on the Electrochemical Properties of Cathode Material LiNi1/3Co1/3Mn1/3O2 by Ti-F Co-substitution
    DING Yan-Huai1,2, ZHANG Ping1,2*, JIANG Yong1,2, YIN Jiu-Ren1,2, LU Qi-Bin3, GAO De-Shu3
    2007, 28(10):  1839-1841.  doi:
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    Layered LiNi1/3Co1/3Mn1/3O2 as the cathode materials for lithium ion batteries was synthesized with the co-precipitated metal carbonate as the precursor. The effects of Ti-F co-substitution on the structure and electrochemical properties of LiNi1/3Co1/3Mn1/3O2 were studied by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), electrochemical impedance spectroscopy(EIS) and galvanostatic charge-discharge experiments. Ti-F co-substitution leads to the change in the content of transition metal ions with a low valence, thereby induces an expansion in lattice volume. Furthermore, the increase of charge-transfer resistances during the cycling was suppressed by Ti-F co-substitution. The initial discharge capacity of substituted sample is 165.23 mA·h/g and the capacity retention rate is 94.9% up to 20 cycles.
    研究论文
    Microwave Plasma Torch Double Detector System and It's Response Characteristics for Gas Chromatography
    SHI Yu-Hua*, WU Li-Hang, LI Hong-Mei, YU Ai-Min, ZHANG Han-Qi, JIN Qin-Han
    2007, 28(10):  1842-1845.  doi:
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    A double detector system in which MPT is used as the atomic emission spectrometry detector and ionization detector simultaneously for gas chromatography is developed firstly. Argon is used as the plasma gas and oxygen as the sheath gas. The relative response coefficient and the detection limit of different organic compounds are determined. The atomic emission signal and ionic signal is firstly obtained at the same time.
    Development of a Quantitative Method for Analyzing Gas-phase Free Radicals in Mainstream Cigarette Smoke
    ZHOU Jun1,3, WU Ke2, SUN Yue3, CONG Jian-Bo2, WANG Chang-Zhen2, CHANG Xiang3, XIAN Hong2, ZHU Yong-Fa1*
    2007, 28(10):  1846-1851.  doi:
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    An improved method was developed for the determination of the gas-phase free radicals in mainstream cigarette smoke. A trap device for the gas-phase free radicals was developed, which could be easily attached to and removed from a commercial linear smoking machine. N-t-Butyl-α-phenylnitrone(PBN) was used to trap the gas-phase free radicals and the formed adduct was detected with EPR technique. The adduct was immediately frozen in liquid nitrogen for degassing and stabilization of the adduct. 2,2,6,6-Tetramethyl-piperidinyl-l-oxy(TEMPO) and strong pitch was used as calibration samples to quantitatively analyze the gas-phase free radicals. The sampling, conditioning and selection of cigarettes in the test were accordant with ISO 4387. It was proved that the established method was highly sensitive, reproducible, practicable and accurate for the detection of the gas-phase free radicals in routine tests.
    Single Molecule Fluorescence Imaging of Thrombin Aptamer Folding

    MA Xin-Yong, WANG Jun, CHEN Bo, FANG Xiao-Hong*

    2007, 28(10):  1852-1856.  doi:
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    The folding of the thrombin DNA aptamer was studied with single molecule fluorescence imaging. The aptamer was singly labeled with TMR and immobilized on the glass surface. In the presence of K+ , the folding of the aptamer resulted in the formation of G-quartets, thus brought TMR close to the guanosines. This led to the fluorescence decrease of TMR through the electron transfer between the dye and guanosines. From the fluorescence intensity of individual TMR, the distribution of aptamer molecules between the folded and random coil conformations was monitored at different concentrations of K+. The results show a new approach for the investigation of aptamer conformational change by electron transfer induced fluorescence quenching, which is complementary to the commonly used fluorescence resonance energy transfer in single molecule study.
    Bioeffects of Silica-coated Nanoparticles on COS-7 Cells
    LIU Fang, HE Xiao-Xiao, WANG Ke-Min*, GE Jia, TAN Wei-Hong
    2007, 28(10):  1857-1862.  doi:
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    In this paper, the cell livability, cell cycle and cell growth curve were analyzed to evaluate the bioeffects of silica-coated nanoparticles on COS-7 cell line. The results indicate that the cytotoxicity of FSiNPs on COS-7 cells was concentration dependent. No measurable cytotoxic effects of FSiNPs were observed on the cell livability, cell cycle and cell growth if the nanoparticles concentration below 0.2 μg/μL. But the cytoto-xic of FSiNPs on COS-7 cells would increase with the increasing of nanoparticles concentration. Meanwhile, the cellular uptake of FSiNPs at low concentration by COS-7 cells was also examined by employing the fluorescence dye RuBpy doped as a signal for tracking the silica coated nanoparticles. It was found that cells can uptake FSiNPs at random by cell membranous' endocytosis when they co-cultured together, and then they excluded parts of FSiNPs to cell culture medium, also parts of FSiNPs can be distributed to the next generation cells. Moreover, the content of FSiNPs in cells are less and less following the manifold of new cytoplasm and cells reproduction, while cells still remained a good shape and growth state after the uptake of nanoparticels. These results provide safely standards for the research, analysis and application of FSiNPs in cell biology. Also, it was a foundation of the research of bionano-device based on the novel nanoparticles.
    Optimization Method for Blending Traditional Chinese Medicine Herbs to Ensuring the Content Stability of Multiple Indicative Constituents
    YANG Hui-Hua1,2, WANG Yong1,3, ZHANG Hong-Yang1,3, LIANG Qiong-Lin1, WANG Yi-Ming1, LUO Guo-An1*
    2007, 28(10):  1863-1868.  doi:
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    A novel approach to ensure the stability of multiple indicative constituents in Traditional Chinese Medicine(TCM) was put forward, which firstly assays the content of multiple indicative constituents in diffe-rent batches of raw herbs, and then utilizes the linear and nonlinear optimization theories and methods to get an appropriate proportions for each herb, and finally blends each batch of herbs with this proportion so as to get rid of the fluctuation of the content in different batches of raw herbs. The key of the approach was credited to the optimization problem presented, which consists of 7 objective functions and several agile constrains. To demonstrate the approach's feasibility and validity, a series of experiments were carried out, in which 10 batches of different Radix isatidis were used as raw materials, and the goal was set to ensure the stability of 5 HPLC peak-areas in chromatograms, and the result shows that the maximum relative error of the peak-areas was 6.3%, compared with five standard peak-areas.
    Electrochemiluminescence Performances of Compositing Films of Polyluminol with Metal Ions and Its Analytical Application
    SONG Ling, ZHENG Xing-Wang*, LI Gui-Xin
    2007, 28(10):  1869-1874.  doi:
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    In this paper, it was found that the compositing films made from polyluminol and some metal ions(such as Ni2+, Fe2+ and Co2+ ) can be easily generated on the surface of the graphite electrode by electropolymerization of luminol and these metal ions in the acidic medium. Compared to other resulting films, the compositing films made from polyluminol and Ni2+ presented the better electrochemiluminescence(ECL) analytical performance for urea based on its sensing effect for weak ECL signal of electro-oxidation polyluminol. On the basis of these results, a novel ECL method for the determination of urea in urine samples was developed, and a new method to improve the ECL analytical performances of polyluminol by compositing metal ions was also proposed. Under the optimum experimental conditions, the ECL response was linearly to the concentration of urea within the range of 2.0×10-9—1.0×10-7 g/mL with a detecting limit of 1.7×10-10 g/mL.
    研究快报
    Fast Determination of Protein Diffusion Coefficient by Taylor Dispersion Analysis and Capillary Electrophoresis System
    ZUO Min1,2, CHEN Yi1*
    2007, 28(10):  1875-1877.  doi:
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    A method for the fast and accurate measurement of diffusion coefficient of minute proteins was developed. A protein sample plug was introduced into the capillary and forced to flow through a capillary coated dynamically by poly(diallyldimethylammonium chloride). Its concentration profile was then monitored by the UV absorption detector mounted on Beckman MDQ capillary electrophoresis system. Accurate diffusion coefficient was obtained. The key conditions for the accurate measurement include: (1) systematic peak should be developed in a laminar flow; (2) radius diffusion is negligible compared with the longitudinal diffusion; (3) the capillary is well thermostated and (4) the solute should not be overloaded. In common case, the deviation of the measurement was kept within 4%.
    研究简报
    Preparation of Molecularly Imprinted Monolith for Trimethoprim Molecule and Its Chromatographic Property
    LIU Xiang-Jun, LIU Ji-Zhong, ZHAO Rui*, LIU Guo-Quan, CHEN Yi
    2007, 28(10):  1878-1880.  doi:
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    A monolithic molecularly imprinted polymer(monolithic MIP) for trimethoprim(TMP) was prepared by in situ polymerization method as the HPLC stationary phase. Methacrylic acid(MAA) and ethylene glycol dimethacrylate(EDMA) were used as functional monomer and cross-linker, respectively. The obtained MIP monoliths were characterized by high performance liquid chromatography and scanning electron microscope. The SEM analysis result clearly shows that many macropores and flow-through pores were embedded in the network skeleton of the TMP-imprinted monolith, which allowed the mobile phase to flow through the monolithic MIPs with a very low flow resistance. When the flow rate was high to 9.0 mL/min, the backpressure was only 11.1 MPa. Moreover, the imprinting factor was up to 10.3, which demonstrates that the obtained monolithic MIP showed a strong affinity and selectivity to the template molecule.
    研究论文
    Synthesis of Quino[1,2-c][1,3]benzoxazin-6-ones by [4+2] Reaction of [1,3]Benzoxazin-2-onium Ions with Olefins
    WANG Jun-Pu, ZHANG Wei*, HUANG Li-Min
    2007, 28(10):  1881-1884.  doi:
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    The N-acyliminium cations are powerful intermediates in the construction of nitrogen-containing heterocycles. They are much more reactive than iminium cations in both intramolecular cyclizations and intermolecular cycloadditions. In this paper, a new and efficient route for the synthesis of quino[1,2-c][1,3]benzoxazin-6-ones (3a—3h) and quino[1,2-c][1,3]naphthoxazin-6-ones (3i—3j) was developed via Diels-Alder reaction of N-acyliminium cations with olefins (2a—2d) in moderate and good yields at an ambient temperature. The N-acyliminium cations, N-phenyl[1,3]benzoxazin-2-onium ion and N-phenyl[1,3]naphthoxazin-2-onium ion, are easily prepared by BF3·OEt2 catalyzed dehydroxylation of 4-hydroxy-3-phenyl[1,3]benzoxazin-2-ones (1a—1c) and 4-hydroxy-3-phenyl[1,3]naphthoxazin-2-one(1d).
    Identification of P-gp Substrates Using a Random Forest Method Based on Chemistry Development Kit Descriptors
    MA Guang-Li1, ZHAO Xiao-Ping2, CHENG Yi-Yu1*
    2007, 28(10):  1885-1888.  doi:
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    A model to identify P-glycoprotein(P-gp) substrate was constructed with a random forest method based on open source software CDK(Chemistry Development Kit) descriptors and a training data set which contained 170 compounds(96 P-gp substrates). The study on the relationship between CDK descriptors and P-gp substrates indicates that sum of the atomic polarizabilities and charged partial surface area play important roles in identifying P-gp substrates. An external test data set containing 42 compounds(24 P-gp substrates) was employed. The correct classification rate on the training set is 99.42% and the correct classification rates for P-gp substrates, non-substrates and the total compounds on the test set are 87.50%, 83.33% and 85.71%, respectively. Leave-One-Out cross-validation correct classification rate(212 compounds) was 77.4%.
    Synthesis of Benzoimidazo[1,2-c]quinazoline Derivatives Promoted by Low-valent Titanium
    SHI Da-Qing1,2*, LI Zheng-Yi2, DOU Guo-Lan2, SHI Chun-Ling2, WANG Xiang-Shan2, JI Shun-Jun1
    2007, 28(10):  1889-1892.  doi:
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    Quinazoline is an important heterocyclic compound which has potential biological and pharmaceutical activities. It was reported that benzimidazo[1,2-c]quinazoline derivatives have a high anticancer activity. In this paper, a series of benzimidazo[1,2-c]quinazoline derivatives such as benzimidazo[1,2-c]quinazoline, 5,6-dihydrobenzimidazo[1,2-c]quinazoline and benzimidazo[1,2-c]quinazolin-5-one were synthesized via the reaction of 2-(o-nitrophenyl)benzimidazoles with triethyl orthoformate or acetone or triphosgene promoted by the low-valent titanium reagent(TiCl4-Zn system). The products were characterized via IR, 1H NMR, MS and elemental analysis. The structure of compound 4c was confirmed by X-ray single crystal diffraction. A possible reaction mechanism was put forward in this paper. This new method possesses the advantages of easily accessible starting materials, convenient manipulation and high yields.
    Purification, Sequencing and Biological Activity of Polypeptide from Velvet Antler
    YAN Ming-Ming1, QU Xiao-Bo1, WANG Xu1, LIU Ning2, LIU Zhi-Qiang2, ZHAO Da-Qing1*, LIU Shu-Ying2
    2007, 28(10):  1893-1896.  doi:
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    The velvet antler polypeptide CNT14 was extracted and purified by gel filtration, ion exchange chromatography and RP C18, which showed a single peak in HPLC chromatography and a single band in SDS-PAGE. The molecular weight measured by MALDI/TOF/MS spectrum was 1479.9028. The polypeptide consisted mostly of Glu, Leu, Val, Pro. The amino acid sequence of the polypeptide was detected with ESI-MS/MS, and the sequence was E-P-T-V-L-D-E-V-C-L-A-H-G-P. The experiments of biological activity of polypeptide CNT14 in vivo were carried out, and the results show that CNT14 has stimulant effects on the growth of rat HT22 cells. Then we produced the polypeptide CNT14 according the amino acid sequence by solid phase synthesis, confirmed the sequence of the polypeptide to be consistent with the amino acid sequence of polypeptide CNT14 which was separated from the velvet antler.
    Hydrophobic Channel Framework Constructed by Second-sphere Coordination
    YUAN Lei, GUO Fang, ZHANG Shuang, HU Zhi-Quan, XIA Fang, GUO Wen-Sheng*
    2007, 28(10):  1897-1901.  doi:
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    Protonated N,N,N',N'-tetrabenzyl-ethylenediamine(L) can form second-sphere complexes with [MCl4]2-(M=Mn, Co, Cu). In these crystals, thick 1D ribbons and 2D layer frameworks are constructed through N—H…Cl interactions. The orientations of benzyl groups of compound L in the ribbon or layer are horizontal and perpendicular, respectively, through C—H…Cl interactions, so that the ribbon and layer with alternately convex-concave site arrangement are formed. The caves between layers are formed by C—H…H—C interaction of convex-concave sites on the layers, thus constructing a 3D hydrophobic channel framework, and alcohol molecules are accommodated in the channel. However, due to the absence of C—H…Br interactions between benzyls and [CuBr4]2- in L·2H+·[CuBr4]2-, the orientation of benzyls of compound L adopts the same direction as a molecular long axis , thus, the 2D layer framework formed by compound L with [CuBr4]2- is planar, and the 3D hydrophobic channel framework and the inclusion of alcohol molecules are not observed.
    Synthesis and Fungicidal Activities of a Novel Series of 4-[3-(Pyrid-4-yl)-3-substituted phenyl acryloyl]morpholine
    MU Chang-Wei1, YUAN Hui-Zhu2, LI Nan1, FU Bin1, XIAO Yu-Mei1, MA Yong-Qiang1, QI Shu-Hua2, QIN Zhao-Hai1*
    2007, 28(10):  1902-1906.  doi:
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    In searching for novel and high active fungicides with pyridyl moiety, with Dimethomorph as a model compound and isonicotinic acid as the main starting material, twenty-seven title compounds were designed and synthesized through chlorination, Friedel-Crafts acylation, Wittig-Horner reaction and other steps. All the target structures were confirmed via 1H NMR and elementary analysis. In the preliminary fungicidal evaluation, all the compounds exhibit a significant inhibiting activity against Rhizoctonia solani Kuhn and Phytophthora drechsler Tucker. Among them, the EC50 values of compounds 4-20, 4-21 and 4-22 to Rhizoctonia solani Kuhn were 28.94, 5.27 and 0.87 μg/mL, respectively, compared to 1.54 μg/mL of Carbendazim and 60.95 μg/mL of Dimethomorph; and to Phytophthora drechsler Tucker were 0.33, 0.27 and 0.09 μg/mL, respectively, compared to 20.39 μg/mL of Chlorothalonil and 0.24 μg/mL of Dimethomorph. The results suggest that they might be valuable in the control of plant diseases.
    Roles of Wilm's Tumor Suppressor(WT1) in the Regulation of Human Inducible Nitric Oxide Synthase(hiNOS)
    SONG De-Gui1, ZOU Fang2, WU Kai-Lang2, LIU Yan2, ZHU Ying2, WU Jian-Guo1,2*
    2007, 28(10):  1907-1910.  doi:
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    The Wilm's tumor suppressor gene is one of the important tumor suppressor factors correlated with liver tissue functional abnormalities. The human inducible nitric oxide synthase(hiNOS) has important biological functions via catalyzing the production of nitric oxide(NO), which is a signal modulator involved in various immune response, chronic inflammations, as well as carcinogenesis. The roles of Wilm's tumor suppressor(WT1) in the regulation of hiNOS was reported in this paper. We inserted hiNOS promoter to pGL3-basic vector carrying luciferase gene and got the plasmid p8.3iNOS, which was used as a report system for the study of the relationship between WT1 and the hiNOS promoter activity. The results from the luciferase assay demonstrate that WT1 could suppress the transcription of hiNOS gene in two hepatoma derivative cells lines, HepG2 and Hep3B. Moreover, the alternative splicesomes of WT1 had different effects on the inhibition of hiNOS expression among which the alternative splicing form WT1(-/-) had the strongest inhibitory effect on hiNOS in a dose-dependent manner. Western blot assay reveals that over-expressed WT1(-/-) down-regulated the expression of hiNOS protein in HepG2 cell. These results suggest that WT1 could control the expression of hiNOS in transcriptional level.
    研究简报
    Synthesis and Characterization of C-Methylsubstituted 1-Ferroceneacyloxysilatranes and Crystal Structure of FcCOOSi(OCHCH3CH2)(OCH2CH2)2N
    CHANG Wei-Xing, YE Zhi-Hai, CHEN Li, PENG Bin, XIE Qing-Lan, SUN Li-Juan*
    2007, 28(10):  1911-1913.  doi:
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    As silatranes and its related compounds have specific structures and have been demonstrated to show a significent biological activity, eleven new C-methylsubstituted 1-ferroceneacyloxysilatranes were synthesized via the reaction of ferrocenecarboxylic acids and C-methysubstituted 1-ethoxysilatrans. They were characterized by means of IR, 1H NMR and elemental analysis. X-ray structure determination of compound 1 indicates the presence of N→Si bond with a bond length of 0.2113(4) nm. It belongs to monoclinic system, space group P2(1)/c with a=1.4050(16) nm, b=1.2758(14) nm, c=1.1196(12) nm, α=90°, β=108.598(18)°, γ=90°, Z=4.
    Effect of Specific Hydrogen Bond on Activity and Thermostability of Hyperthermophilic Esterase APE1547
    BI Yun-Feng1, XIE Gui-Qiu1,2, GAO Ren-Jun1, LU Jing3, CAO Shu-Gui1*
    2007, 28(10):  1914-1916.  doi:
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    Thermophilic esterase APE1547 from Aeropyrum pernix K1 contained a β-propeller with seven blades. There are three hydrogen bonding interactions(Thr127-Gly154,Leu182- Arg145-Glu122) between blades 3 and 4 in the β-propeller domain of the APE1547. To examine the role of these hydrogen bonds, we eliminated these three hydrogen bonds between blades 3 and 4, by site-directed mutagenesis. The analysis results of kinetics, thermostability and differential scanning calorimetry(DSC) of the mutants show that Kcat/Km value of each mutation increased, and stability decreased dramatically than wild-type protein. These results strongly suggest that the three specific hydrogen bonds played an important role on maintaining the stability and activity of the esterase APE1547.
    Synthesis and Reversible Recognition for Organic Ammoniums of a Molecular Receptor Based on Calixarene
    TU Chun-Lai, ZHENG Chao, CHEN Yan, SHU Mou-Hai*
    2007, 28(10):  1917-1919.  doi:
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    Calixarenes often serve as molecular host in supramolecular chemistry, however, they show a conformation flexibility due to the inversion of the aromatic rings. It is important to control the structure flexibility of calixarenes. In this work, a C3v-symmetrical molecular receptor calixTPA was synthesized and characterized via 1H NMR, 13C NMR, ESI-MS, and X-ray structural analysis. Molecular recognitions of calixTPA for small organic ammoniums were investigated with 1H NMR, and the inclusions of the straight chain ammoniums were reversiblly controlled by the acidity of the solution. The results indicate that the introduction of a tripodal N4-crypto cap is beneficial to rigidify the structure in a cone conformation, the hydrophobic cavity is an efficient receptor for organic guests, and the reversible recognition of straight chain ammoniums can be potentially applied in separation of organic amines.
    研究论文
    Optical Oxygen Sensing Properties of Mesoporous SBA-15 with a Covalently Grafted Ruthenium(Ⅱ) Complex
    ZHANG Hao-Ran1, LI Bin2*, LEI Bing-Fu2, LI Wen-Lian2
    2007, 28(10):  1920-1924.  doi:
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    Novel oxygen sensing materials consisted of [Ru(Phen)3]2+ portion covalently grafted to the functionalized mesoporous SBA-15 backbones are prepared by co-condensation of tetraethoxysilane(TEOS) and the functionalized Ru(Ⅱ) complex [Ru(Phen)2Phen—Si]2+ in the presence of Pluronic P123 surfactant as a template. The obtained oxygen sensing materials are characterized by Fourier transform infrared(FTIR) and luminescence intensity quenching Stern-Volmer curves. The Demas and Lehrer models are used to fit the obtained nonlinear Stern-Volmer curves. The functionalized mesoporous sensing materials appear to be highly sensitive to the O2 concentration in N2. The results show that the covalently-grafted sample shows reversible signals and higher photochemical stability since these Ru(Ⅱ) molecules are strongly covalently-grafted to the Si—O network via the CH2—Si bonds.
    Effect of Dendronization on the Luminescence Behavior of Fluorene-based Polymers
    WU Yi-Shi1,2, LI Jing3, AI Xi-Cheng2, FU Ya-Qin3, ZHOU Jian-Jun3, LI Lin3, BO Zhi-Shan3*, ZHANG Jian-Ping2*
    2007, 28(10):  1925-1928.  doi:
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    Steady-state absorption and fluorescence together with picosecond time-resolved photoluminescence(PL) spectroscopies were used to investigate the effect of dendronization on the luminescence character of fluorene-based polymers. For dilute tetrahydrofuran solution at 1×10-5 mol/L, non-dendronized 9,9-dioctyl-polyfluorene(PF), the first-generation dendronized PF(PFg1), the second-generation dendronized PF(PFg2) and third-generation dendronized PF(PFg3) show identical spectra in their steady-sate absorption and fluorescence measurement, indicating that the conjugated core is not affected by dendronization. However, highly-packing PF chains appear to form aggregate in film form. Further picosecond PL studies on dendronized PFs show that the fluorene-based emission in dilute solution follows a single exponential decay, whereas those in thin film decayed in a multi-phase manner and the lifetime prolongs with the generation of dendronization. These observations are discussed in terms of dispersive transport happening between adjacent chains in film. The dispersive relaxation can be controlled by site isolation of bulky dendrons. Our results prove that dendronization is highly effective in controlling the inter-chain interactions of fluorene-based polymers.
    Synthesis, Characterization and Catalytic Properties of Three-dimensional Wormhole-like Mesoporous Ag2O/Ce0.6Zr0.35Y0.05O2 Nanoparticles in Methane Oxidation
    ZHANG Yu-Juan, WANG Guo-Zhi, ZHANG Lei, DAI Hong-Xing*, HE Hong, ZI Xue-Hong
    2007, 28(10):  1929-1934.  doi:
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    Highly-specific-surface-area wormhole-like mesoporous Ce0.6Zr0.35Y0.05O2(CZY) solid solution nanoparticles with a cubic crystal structure were synthesized by using a modified co-precipitation strategy with hexadecyltrimethyl ammonium bromide as the template, and the CZY-loaded 0.2%—2.0% Ag2O catalysts were prepared with the incipient wetness impregnation method. The physicochemical properties of these materials were characterized with XRD, HRSEM, HRTEM/SAED, H2-TPR and XPS techniques. We also examined the catalytic performance of the Ag2O/CZY catalysts for the total oxidation of methane. It is found that among the x% Ag2O/CZY(x=0.2—2.0) catalysts, the one at x=2.0 showed the best catalytic activity: under the conditions of n(CH4)/n(O2)=1:4, space velocity=50000 h-1 and reaction temperature=600 ℃, methane could be oxidized completely to carbon dioxide and water, furthermore over this catalyst the hysteresis pheno-menon of methane conversion versus temperature during the processes of temperature rise and drop was basically eliminated. On the basis of the above results, we concluded that the good catalytic performance of Ag2O/CZY is associated with the formation of three-dimensional wormhole-like mesoporous structure, larger specific surface area, stronger oxygen storage and release ability, and the stabilization of active phase Ag2O by CZY.
    Selective Electrochemical Reduction of Nitrobenzene in Ionic Liquid EMimBF4
    CHEN Song1,2, MA Chun-An1*, CHU You-Qun1, MAO Xin-Biao1
    2007, 28(10):  1935-1939.  doi:
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    The electroreduction of nitrobenzene in room temperature ionic liquidEMimBF4 on Pt electrode was investigated. The experimental results from cyclic voltammetry and constant-potential electrolysis show that the mechanism of the reaction was two molecules and three steps electrochemical process with eight-electrons transferred: anion radical arose in the first step; two-electrons were transferred in the second step and accompanied with coupling reaction of radicals and protonation and dehydrate, the main product was azoxybenzene; two-electrons were transferred in the third step, and azobenzene was achieved. The stronge interaction between EMimBF4 and nitrobenzene, and its intermediates yielded in the process of electroreduction caused the selective reaction. By controlling the reduction potential, the electroreduction of nitrobenzene to azoxybenzene and azobenzene had a high selectivity and high conversion. The concentrations of nitrobenzene and water in EMimBF4 have great effect on the electrochemical behavior. With the increasing of nitrobenzene concentration, the electroreduction peak potential of cyclic voltammogram around -1.47 V was shifted to negative value, and the current density was increased, as well as the water had reversed effect on the electroreduction peak potential, and increased current density.
    Chemical Model of Crystal Defect of Acceptor-doped BaPbO3
    LU Yu-Dong1,2, WANG Xin1*, ZHUANG Zhi-Qiang1, LIU Bao-Ling1
    2007, 28(10):  1940-1943.  doi:
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    Since the behavior of undoped BaPbO3 indicates that it already has an excess of acceptor impurities, acceptor-doped BaPbO3 merely represents an extension of that behavior. The behavior of undoped and acceptor-doped BaPbO3 can be divided into three regions: highly oxygen-activity region, the midrange of oxygen-activity, and lower oxygen-activity region. On the basis of the measurement of the equilibrium electrical conductivity with a four-probe dc technique as a function of oxygen pressure(10-12—105 Pa), the concentration of holes, electrons, oxygen vacancies, lead vacancies, and acceptor impurities were determined. And a defect model for acceptor-doped BaPbO3, which emphasized the role of holes, electrons, oxygen vacancies, lead vacancies, and acceptor impurities, was presented.
    Construction of Ultralong Nanowires of a Perylene Bisimide Dye in Acetic Acid
    CAO Ya-Feng, XIE Bo-Yu, SUN Jing-Zhi*
    2007, 28(10):  1944-1947.  doi:
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    A perylene bisimide bearing amide groups was synthesized. In acetic acid, the UV-Vis spectra of the compound displayed a characteristic band at 647 nm, indicating that the molecules aggregated to form “black phase”, in which the perylene chromophores packed in an in-phase mode. The band shifted to 571 nm as ethanol was used as solvent, indicating the formation of “red phase”, in which the chromophores packed in an interdigital mode. SEM and TEM images demonstrat that the morphology of black phase was characterized by nanowires in length of hundreds micrometers and diameter of 100—200 nm; while the morphology of red phase was predominated by shuttle-like microstructures. The black solid changed into red solid in acetic acid aqueous solution with volume fraction of 40%, both the UV-Vis and FTIR spectra monitored the transition from black to red phase, and SEM images demonstrate the decomposition of long nanowires and the formation of short shuttle-like microstructures at such a concentration.
    Surface Morphology and Electrocatalytic Property of Pt /Thioglycolic Acid/GC Electrodes
    YU Zhi-Hui1, XIE Jia1, XIA Ding-Guo1*, YU Chun-Yang1,2
    2007, 28(10):  1948-1951.  doi:
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    The Pt/thioglycolic acid/GC composite electrode was prepared by self-assembling Pt nanoparticles on GC modified with thioglycolic acid. The composite electrode was characterized by SEM and cyclic voltograme method. The results show that the compact absorbing layer was formed because of thioglycolic characteristic absorb on the surface of GC electrode. The composite electrode, which had been self-assembled for 19 h, in the 2.5 mmol/L H2PtCl6 and 1.0 mmol/L PVP mixture solution, gave a good electrocatalytic oxidation of methanol in acidic system.
    Investigation of Electron Transfer Reaction Between Ferri/Ferrocyanide and TCNQ on Polarized Water/1,2-Dichloroethane Interface by Scanning Electrochemical Microscopy
    HUANG Feng, ZHANG Zhi-Xin, FENG Guo-Dong, YU Ai-Min, ZHANG Zhi-Quan*
    2007, 28(10):  1952-1956.  doi:
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    A liquid/liquid interface supported on a metallic electrode was used to study the electron transfer(ET) reactions by scanning electrochemical microscopy(SECM). The system is composed of an aqueous droplet adhered on a platinum disc electrode and immersed into an organic electrolyte solution containing 7,7,8,8-tetracyanoquinodimenthane(TCNQ). The droplet with a redox couple of K3Fe(CN)6 and K4Fe(CN)6 was employed, both were used as a reference electrode on the platinum disc, and as an electron donor/acceptor at the polarized liquid/liquid interface. With the present experimental approach, the liquid/liquid interface can be polarized externally. The apparent heterogeneous rate constants for the ET reactions were extracted by fitting the experimental approach curves obtained from SECM experiments to the theoretical values. These rate constants obey the Butler-Volume formula in some ranges, and they are found to be potential dependent. This method enables a fast and convenient method to measure ET and ion transfer(IT) reactions kinetic parameter.
    Theoretical Study on Structures and Stability of Ion NC2S+
    YU Guang-Tao, LI Fei, YU Jian-Kang, Huang Xu-Ri*, SUN Chia-Chung
    2007, 28(10):  1957-1961.  doi:
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    The structures, energetics, spectroscopies, and stabilities of the singlet NC2S+ system were explored with density functional theory and ab initio method. At the B3LYP/6-311G(d) level, eight isomers were located, which are connected with 15 interconversion transition states. At the CCSD(T)/6-311+G(2df)//QCISD/6-311G(d)+ZPVE level, the lowest-lying isomer is linear NCCS+ 1(0.0 kJ/mol)with 1Σ state followed by linear CNCS+ 2(54.8 kJ/mol). Two low-lying isomers 1, 2 and another high-lying species CCNS+ 3(323.8 kJ/mol) with a linear structure possess considerable kinetic stability. All the three isomers should be experimentally or astrophysically observable. The bonding natures of isomers 1, 2 and 3 were also analyzed.
    Theoretical Study on Red and Blue Shifting Hydrogen Bonding Between Pyridine and HCl, CHCl3
    WANG Su-Wen1, LI An-Yong1*, TAN Hong-Wei2
    2007, 28(10):  1962-1967.  doi:
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    Ab initio quantum mechanics method(MP2) is employed to investigate intermolecular interactions in the complexes of C5H5N…HCl(1), C5H5N…HCCl3(2) and C5H5N HCCl3(3) at the 6-31G(d,p), 6-311+G(d,p), aug-cc-pVDZ basis sets. For compounds 1 and 2, Cl—H…N(C—H…N) red shifting H-bond is formed with Cl—H(C—H) bond elongation and a concomitant red shift of the corresponding IR stretching frequency. However, for compound 3, C—H…π blue shifting H-bond is formed with C—H bond contraction and concomitant blue shift of the corresponding IR stretching frequency. It is indicated that both Cl—H and C—H stretch increases in intensity and broadens in the spectral band on formation of compounds. It is concluded that a negative permanent dipole moment derivative of the proton donor is not a necessary condition for the formation of the blue shifting hydrogen bond. The NBO analysis shows that the X—H bond length in X—H…Y is controlled by a balance of three main factors. X—H bond lengthening due to n(Y)→σ*(X—H) hyperconjugative interaction is balanced by X—H bond shortening due to increase of s-character and polarization of the X—H bond and redistribution of electron density in proton donor. In compounds 1 and 2, hyperconjugative interaction dominates which results in red shifting H-bonds. In compound 3, the condition is reverse which results in blue shifting H-bonds.
    Stability and Aromaticity of B6X-(X=N, P, As, Sb, Bi) Clusters
    XIONG Jie-Ming1, GONG Liang-Fa1*, LI Qian-Shu2
    2007, 28(10):  1968-1971.  doi:
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    The geometries and chemical bonding of B6X- (X=N, P, As, Sb, Bi) clusters have been investigated using ab initio and density functional theory computations with MP2, B3LYP and B3PW91 methods. Analytical gradients with the polarized split-valence basis sets (6-311+G*) were used for B, N, P, and As. The relativistic effective core potential with the LANL2DZ basis set was chosen for Sb and Bi. It is seems that the very reasonable looking pyramidal minimum structure (C2v symmetry) is the most stable. The analyses of molecular orbital, natural bond orbital, and nucleus-independent chemical shift for these quasi-pyramidal B6X- systems revealed a double-aromatic character(π and σ), which had been reported to play an important role in the chemical bonding, structure, and stability of the pure boron clusters.
    CAS Calculations on the Ground and Low-lying Excited States of Ethylthio Radical, Cation and Anion
    LI Bu-Tong1, WEI Zi-Zhang1, PAN Qing-Jiang2, ZHANG Hong-Xing1*, SUN Chia-Chung1
    2007, 28(10):  1972-1974.  doi:
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    The quantum calculations at CASPT2/CASSCF level were performed for the low-lying excited states of the ethylthio radical, cation and anion. In Cs point group geometry, total twelve electronic states were optimized at CASSCF level and the frequencies analyses were performed for these three molecules. The single point energy corrections were carried out at CASPT2 level. The adiabatic ionization energies and the electron affinity energies were obtained through the comparison between the energies of the ground state of the radical and those of the corresponding ions were made. All results obtained are consistent with the available data from the literatures.
    研究快报
    Reaction Path Dynamics and Theoretical Rate Constants Calculation for CHnF4-n+O3→HOOO+CHn-1F4-n(n=2,3) Reactions
    YANG Jing1,3, ZHANG Shao-Wen1, LI Qian-Shu1,2*
    2007, 28(10):  1975-1977.  doi:
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    The hydrogen abstraction reactions by ozone from fluoromethanes(CH3F, CH2F2) are the most suitable processes for modeling and testing methodologies that could be applied to larger molecules or to the complete reaction kinetic schemes for the degradation of HFCs. We presented a theoretical study of the hydrogen abstraction reactions from CH3F and CH2F2 by ozone molecule. The geometries, harmonic vibrational frequencies of all stationary points were calculated at MPW1K level of the theory. The energies of all the stationary points were refined by using higher-level(denoted as HL) energy calculations. The minimum energy paths(MEPs) were obtained by the MPW1K/6-31+G(d,p) level. Energetic information of the points along the MEPs is further refined by HL method. The rate constants were evaluated on the basis of the MEPs from the HL level of theory in the temperature range of 200—2500 K with the conventional transition state theory(TST), the canonical variational transition state theory(CVT) and the microcanonical variational transition state theory(μVT) based on the ab initio calculations. A general agreement was found among the TST, CVT, and μVT theories. The fitted three-parameter Arrhenius expressions of the calculated forward CVT/SCT, and μVT/Eckart rate constants of the ozonolysis of fluoromethane are kCVT/SCT(T)=2.76×10-34T5.81 e(-13975/T) and kμVT/Eckart(T)=1.15×10-34T5.97 e(-14530.7/T), respectively. The fitted three-parameter Arrhenius expressions of the calculated forward CVT/SCT, and μVT/Eckart rate constants of the ozonolysis of difluoromethane are kCVT/SCT(T)=2.29×10-36T6.42 e(-15451.6/T) and kμVT/Eckart(T)=1.31×10-36T6.45 e(-15465.8/T), respectively.
    研究简报
    Preparation and Luminescence Characterizations of BaAl2S4:Eu2+ Nanoparticles
    SHEN Lian-Chun, YU Lian-Xiang, ZHU Wan-Chun, TIAN Yu-Mei*
    2007, 28(10):  1978-1980.  doi:
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    BaAl2S4:Eu2+ nanoparticles with a size distribution of 50—150 nm were prepared by the sol-gel method. The particles were near spherical and had an intensive green emission when they were excited at 254 nm, after calcining at 1000 ℃ in a mixture of H2S(volume fraction 10%)+N2(volume fraction 90%) for 1.5 h. X-ray diffraction patterns indicate that BaAl2S4:Eu2+ has a cubic structure. The emission and excitation spectra show that emission was from the 4f65d→4f7 transition of the activated Eu2+. The highest photoluminescence(PL) luminance is 420 cd/m2. This study indicate that the BaAl2S4:Eu2+ could be used as photoluminescent nanocomposite materials.
    Theoretical Study on the Partial Potential Energy Surface and Resonance State for HO+CH4→H2O+CH3 System
    LU Xi1, WANG Hua-Yang2, CAI Zheng-Ting1*, FENG Da-Cheng1
    2007, 28(10):  1981-1983.  doi:
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    Reaction resonance or Feshbach resonance in polyatomic reaction is one of the most fascinating phenomena in chemical reaction dynamics. The HO+CH4→H2O+CH3 reaction is one of the pivotal polyato-mic reactions concerned with both the experimental and theoretical scientists. Reaction probabilities and other dynamic properties of this system were calculated with quantum scattering theory method, but a simple QH(v)+HO(j)→Q+H2O(m,n) reaction model was used, in which only three degrees of freedom and the rotating of OH were considered while making CH3 as a pseudo atom. In this paper, by an ab initio method, partial potential energy surface(PPES) was constructed and all the 15 internal degrees-freedom were given. Feshbach resonance mechanism of this reaction can be obtained by the dynamic Eyring Lake on the PPES and the lifetime of the reactive resonance-state can be estimated using the gap of the vibrational energy levels of transient collision complex in the critical transition-state region. Above interesting dynamic properties would not be given by simple pseudo atomic reaction model.
    Synthesis, Physical Properties and Biocompatibility of Poly[di(ethyl glycinato)phosphazene]
    WANG Hong-Xia, GAO Chang-You*
    2007, 28(10):  1984-1989.  doi:
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    Polyphosphazene substituted by amino acid ester in side chains is a kind of attractive biomaterial because it is readily biodegradable and nontoxic. In this work, poly[di(ethyl glycinato)phosphazene](PEGP) was synthesized and its physical and biological properties were assessed. The intermediate polydichlorophosphazene was obtained via a ring-opening polymerization of hexachlorocyclotriphosphazene, which resulted in the final PEGP with a nucleophilic substitution with glycino ethyl ester. Characterizations by infrared spectroscopy(IR), nuclear magnetic resonance(NMR) and elemental analysis confirmed the molecular structure of the resulted polymer. Vapor-pressure osmometer(VPO) and differential scanning calorimetry(DSC) were used to measure the number average molecular weight as 12959, and glass transitation temperature to be -21.5 ℃, respectively. In vitro culture of HepG2 cell line and human fibroblasts was performed on the PEGP membranes to assess the PEGP cytocompatibility. Both HepG2 cells and fibroblasts could normally spread on the PEGP membrane with nondetectable cytotoxicity. The fibroblasts cultured on the PEGP membrane had a comparable proliferation rate with that cultured on tissue culture dish, while the HepG2 cells cultured on the PEGP membrane had a significantly faster proliferation rate than that cultured on tissue culture dish. Therefore, PEGP has a great potential to be used in the fields of tissue engineering and regenerative medicine.

    研究论文
    Preparation and Chracaterization of Novel Graft Copolymers of LLDPE
    XIN Zhi-Rong1,2, ZHAO Yu-Xia2, HOU Wan-Guo1, YIN Li-Gang3, QIU Zhao-Ming2, LIU Xiao-Li2, LIU Chan2, YIN Jing-Hua3*
    2007, 28(10):  1990-1994.  doi:
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    A series of novel fluorine surfactants, a, b, c, d , e and their acrylates, A, B, C, D and E, were synthesized via poly(ethylene oxide)(PEG)(200, 600,1000, 2000, 5000) and perfluorooctane poly(ethylene oxide) ether as the main starting materials. Their chemical structures were characterized by means of FTIR and 1H NMR. The surface activity and surface tension(γ) of surfactants a, b, c, d and e were evaluated by maximum bubble pressure method. Surfactants A, B,C, D and E were adopted as the grafting monomers of linear low density polyethere(LLDPE), and grafting reaction was carried out by melt reactive extrusion procedure. Their surface properties were characterized with measuring contact angle and XPS. It was found that the hydrophilic property of the graft copolymers was better than the palin LLDPE. Thermal properties of graft copolymers were studied by DSC. It was found that their crystalline temperatures of graft copolymers were faster than that of the plain LLDPE.

    Synthesis and Characterization of Novel Amphiphilic Chitosan Derivatives and Its Solubilizing Abilities for Water-insoluble Drugs
    HUO Mei-Rong, ZHOU Jian-Ping*, ZHANG Yong, LÜ Lin
    2007, 28(10):  1995-1999.  doi:
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    Novel chitosan derivative with long alky groups as the hydrophobic moieties and carboxymethyl groups as the hydrophilic moieties was synthesized. The chemical structure of N-octyl-O,N-carboxymethyl chitosan(OCC) was characterized via FTIR, 1H NMR and elemental analysis. The physical properties were analyzed with wide angle X-ray diffraction(WAXD) and differential scanning calorimetry(DSC). The solubilities in some solvents were investigated and solubilization abilities of OCC for water-insoluble drugs were evaluated. The results show that the degree of substitution of carboxymethyl groups and octyl groups are determined to be 115.9% and 58.0%, respectively. OCC are insoluble in organic solvents while show a much better solubility in water and formed opalescence solutions, which increased the solubility of paclitaxel up to 500 folds in water. The drug loading and drug encapsulation efficiency of OCC are 34.6% and 89.9%, respectively. It was concluded that the present OCC could be potentially useful as the novel delivery carrier materials for insoluble drugs.
    Encapsulation and Release of the Micelles-enhanced PE Capsules Filled with Rhodamine B
    LI Xiao-Dong1,2*, SHEN Jia-Cong2
    2007, 28(10):  2000-2005.  doi:
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    The encapsulation of “micelles-enhanced” polyelectrolyte capsules to Rhodamine B, a positively charged small molecule, and in vitro release behavior of Rhodamine B containing capsules, were studied. Studies on the encapsulation kinetics and loading amount of capsules to water-soluble Rhodamine B suggest that water-soluble substances can be efficiently entraped into this type of “micelles-enhanced” polyelectrolyte capsules. In vitro release tests suggest that there were difference in release behavior between Rhodamine B-containing capsules that performed in release media with various pH values. However, for these release profiles, a similar trend was displayed, and the whole release curves have several periods with different Rhodamine B release rates, which include a burst release, a lag period, a rapid release phase and a sustained release stage. The burst release in the first stage was significant, which should be ameliorated in the following study. Simultaneously, ion strength seemed to have no significant effect on the release behavior of Rhodamine B-loaded capsules.
    Non-isothermal Crystallization Behavior of PLLA-PEG Copolymer
    REN Jie*, GUI Bao-Zhu, REN Tian-Bin, YANG Jun, GU Ming-Hao
    2007, 28(10):  2006-2009.  doi:
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    Poly(L-lactic acid)-poly(ethylene glycol) was copolymerized with direct melt copolymerization, and its crystallization was studied via WAXD and DSC. Via using Avrami equation modified by Jeziorny, the crystallization kinetics under a non-isothermal condition was analyzed. The crystallization of PLLA was obvious, while the PEG's could not observed. But the flexibility of PEG promoted PLLA's crystallization. And the crystalline temperature, velocity and crystallinity of PLLA-PEG increased with the increase of molecular weight of PEG and the feed weight ratio.
    Gelatinization Behavior Dihydrazide Derivatives
    XIN Hong, WANG Hai-Tao, BAI Bing-Lian, ZHANG Qi-Xian, LI Min*
    2007, 28(10):  2010-2013.  doi:
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    It was found that compound N,N-(5-alkoxyl-1,3-dicarboxylic benzene)-N',N'-di(4-methylbenzoyl) dihydrazide(An) could form thermoreversible gels in appropriate organic solvents, such as benzene, toluene, nitrobenzene, chloroform etc. whose concentrations were well below 1%(mass fraction). SEM observations and X-ray diffraction results indicate that the molecules self-assembled into the fibrous aggregates and kept a layer conformation in their gel states. FTIR and 1H NMR studies confirm that the hydrogen bonding played a key role in the formation of these supra-structures and was considered as the driving force. And it was also found that the length of lateraly substituted alkoxy chain in the compounds could affect their gels formation ability and transition temperature, while their gel morphologies and structures weren't affected by the length of lateraly substituted alkoxy chain.
    Effect of Monolayer Graphite Phase in Carbon Fiber on the Mechanical Property
    GAO Yu1, HUANG Ke-Ke1 , HUA Zhong2, GAO Zhong-Min1* , LI Xiang-Shan3
    2007, 28(10):  2014-2017.  doi:
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    According to the character of the X-ray diffraction patterns of different phases in PAN carbon fiber, it can be affirmed that there still exist plentiful monolayer graphite with six-membered ring, besides multilayer graphite. We also found two kinds of quantative methods for analyzing crystaline phase with defaults, which can be used to study the effect of monolayer graphite in carbon fiber upon its mechanical property.
    研究快报
    Molecular Weight and Molecular Weight Distribution Control of Ring-opening Metathesis Polymerization of Norbornene
    DU Chuang1, WANG Chun-Yu2, ZHANG Guo1, TANG Jun2*
    2007, 28(10):  2018-2020.  doi:
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    Ring-opening metathesis polymerization of norbornene catalyzed by Grubbs catalyst [(PCy3)2·(Cl)2Ru=CHPh] was carried out. The results of 1H NMR demonstrated that the polymerization of the norbornene monomer proceeded by the ROMP mechanism. The molecular weight and molecular weight distribution of this reaction can be controlled by changing the stirring time of catalyst, choosing different solvents and the adding of PPh3 during the polymerization. The results show that stirring the catalyst for 15 min, using more polar solvent and adding 2 equiv of PPh3 can optimize the conditions of this reaction. The polydispersity indices(PDIs) of the poly(norbornene) were nearly monodisperse(PDIs about 1.18).
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