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Table of Content

    10 June 2007, Volume 28 Issue 6
    目次
    高等学校化学学报2007年第28卷第6期目次
    2007, 28(6):  0.  doi:
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    下期目次预览
    2007, 28(6):  0.  doi:
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    研究论文
    Investigation of Triboluminescence of Sm(TTA)3phen and the Relationship Between Triboluminescence Phenomena of Rare Earth Complexes and Properties of Ligands
    DENG Rui-Ping1,2, YU Jiang-Bo1, ZHANG Hong-Jie1*, LI Zhe-Feng1,2, ZHOU Liang1,2, PENG Ze-Ping1,2, GUO Zhi-Yong1,2
    2007, 28(6):  1005-1008.  doi:
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    The triboluminescence(TL) of Sm(TTA)3phen was firstly investigated, and its TL spectrum showed the characteristic transitions of the Sm3+ ion. The relationship between the TL phenomena of the rare earth complexes and the properties of the ligands was also discussed. It is suggested that the ligands with a strong electron donor-acceptor system would benefit the TL of the rare earth complexes, and the ligand molecules should be rigid enough for the growth of the rare earth complex crystals.
    Synthesis, Crystal Structure and Thermal Stability of Coordination Polymer [Co2(HO-BDC)2(bpe)2(H2O)2]n·n(py)·nH2O with Nanoscale C
    ZHUO Xin1,2, PAN Zhao-Rui2, WANG Zuo-Wei2, LI Yi-Zhi2, ZHENG He-Gen2*
    2007, 28(6):  1009-1013.  doi:
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    A novel coordination ploymer [Co2(HO-BDC)2(bpe)2(H2O)2]n·n(py)·nH2O[where HO-H2BDC is 5-hydroxyisophthalic acid and bpe is 1,2-bis(4-pyridyl)ethane, py is pyridine] with nanoscale channels was synthesized and characterized via elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to triclinic crystal system, space group P1, with a=1.0245(3) nm, b=1.1467(3) nm, c=1.2430(4) nm, α=68.915(5)°, β=67.163(4)°, γ=71.373(4)°, V=1.2279(6) nm3, Z=1, Mr=979.70, Dc=1.325 Mg/m3, F(000)=506, μ=0.740 mm-1, the final R1=0.0515 and wR2=0.1058 for 3625 observed reflections with I>2σ(I). The coordination polymer has a 2D rectangular grid framework parallel to the ac plane with a dimension of 1.025 nm×0.1354 nm via strong hydrogen-bonding interactions. TGA curves of the coordination polymer show three main weight losses in the range of 110—150 ℃, 200—300 ℃ and 320—450 ℃ corresponding to the removal of non-coordinatated water molecules, non-coordinatated py molecules and the water and bpe molecules attached to metal, respectively, and the final residue is identified to be Co2O3.
    Hydrothermal Synthesis and Structure Characterization of a 2D Coordination Polymer [Cu(ox)(4,4'-bpy)]n
    REN Hong1, XU Jia-Ning2, YU Lian-Xiang2, YE Jun-Wei3, BI Ming-Hui1, ZHANG Ping2*, SONG Tian-You1*
    2007, 28(6):  1014-1017.  doi:
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    A new polymer [Cu(ox)(4,4'-bpy)]n(1)(ox=C2O42-, 4,4'-bpy=4,4'-bipyridine) was hydrothermally synthesized and characterized via elemental analyses, IR spectrum and single crystal X-ray diffraction. The polymer crystallizes in a monoclinic system, space group Cm, a=1.1921(7) nm, b=1.153(7) nm, c=0.5155(4) nm, β=113.38(3)°, V=0.6291(7) nm3, Z=2. Cu atom in the title compound is in an octahedral geometry with four O atoms from two bis-chelating oxalate ligands in equatorial plane and two N atoms from the 4,4'-bpy ligands in the axial position. The crystal structure possesses infinite {Cu(ox)}n chains connected with each other by the bridging 4,4'-bpy ligands in a perpendicular manner, leading to a 2D layered network with rectangular grids. The layers stacking in a staggered fashion are further assembled by C4,4'-bpy—H…Oox hydrogen bonds and lead to a 3D supramolecular architecture.
    研究快报
    Hydrothermal Synthesis and Structure Characterization of a Novel [CuI(dpq)2]+ Complex Cations Modified Arsenic-Vanadium Polyoxometalate [Cu(dpq)2]4[As8V14O
    DONG Bao-Xia, ZHANG Peng-Peng, PENG Jun*
    2007, 28(6):  1018-1020.  doi:
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    A novel inorganic-organic hybrid compound [Cu(dpq)2]4[As8V14O42(H2O)]·2H2O(dpq=dipyrido[3,2-d:2',3'-f]quinoxaline) was synthesized under the hydrothermal condition and its structure was characterized via single-crystal X-ray diffraction, elemental analysis, IR and XPS spectra. The title compound crystallizes in a monoclinic crystal system, space group P21/c with crystal parameters a=1.8973(3) nm, b=2.5816(2) nm, c=2.8941(2) nm, β=106.61(2)°, V=13.5846(12) nm3, Z=4, R1=0.0674, wR2=0.1750. It possesses a spherical [As8V14O42(H2O)]4- cluster anion, four [CuI(dpq)2]+ counter cations and two lattice water molecules. The cationic complexes form ca. 0.8 nm×0.8 nm stellate channels along the c axis through strong π…π stacking interactions due to the multiple aryls in the dpq ligands. The polyoxoanions are embedded in the channels through extensive C—H…O short contact interactions.
    研究简报
    Synthesis of Lead Iodide Nanorods by Inverse Microemulsion Method
    ZHU Qi-An*, ZHANG Qi, LIU Gui-Song, WANG Xian-You, SUN Xu-Feng, CHEN Wan-Ping
    2007, 28(6):  1021-1023.  doi:
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    Lead iodide nanorods with a length of 500—3200 nm and a diameter of 35—130 nm were synthesized in an inverse microemulsion system consisting of water, Triton X-100, cyclohexane and n-hexanol. The prepared products were characterized via TEM and XRD. The results show that ω0(the molar ratio of water to surfactant), the concentration of reactants, reaction temperature and aging time all can affect the morphology and size of the lead iodide nanorods prepared. The as-prepared nanorods belong to hexagonal system.
    Synthesis and Characterization of A Novel Red Phosphor MY2S4∶Er3+(M=Sr2+, Ba2+)
    LIAN Shi-Xun*, TIAN Ke-Ming, YIN Du-Lin, ZHU Ai-Ling, LIU Li-Min
    2007, 28(6):  1024-1026.  doi:
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    Carbonate coprecipitate precursors were prepared by mixed nitrate solutions containing M2+(M2+=Sr2+, Ba2+), Y3+ and Er3+ as the cation sources and (NH4)2CO3 as the precipitator. MY2S4∶Er3+ phosphors were synthesized by calcining the carbonate precursors with CS2 as the sulfurization reagent at 1050 ℃ for 4 h. XRD patterns show that the synthesized SrY2S4 and BaY2S4 crystalline powders possess the orthorhombic [CaFe2O4]-type structure. Photoluminescent measurements indicate that there were mainly red emitting(4F9/24I15/2) and green emitting(2H11/24I15/2 and 4S3/24I15/2) of Er3+ in the SrY2S4 while there was only red emitting(4F9/24I15/2) in BaY2S4∶Er3+. BaY2S4∶Er3+ is considered as a novel red phosphor candidate with a high monochromaticity.
    研究论文
    Applying Novel Three Dimensional Holographic Vector of Atomic Interaction Field to QSAR Studies for Several Classical Drug Systems
    ZHOU Peng1, MEI Hu1, TIAN Fei-Fei1, LI Zhi-Liang1,2*
    2007, 28(6):  1027-1030.  doi:
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    In order to classify the atoms in organic compounds in terms of their families in periodic table of elements and hybridization status, a novel three dimensional holographic vector of atomic interaction field (3D-HoVAIF) is derived from molecular steric structures based on drug-receptor nonbonding interactions. Applying 3D-HoVAIF to QSAR studies on a series of classical drug systems, it is confirmed that 3D-HoVAIF is able to efficiently extract molecular sterical potential information, thus well related with the bioactivities.
    Rapid Detection of K-ras Oncogene Point Mutation by Real-time Fluorescence Allele-specific Amplification
    ZHU De-Bin, XING Da*, LI Xian, ZHANG Lan
    2007, 28(6):  1031-1034.  doi:
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    Mutation analysis is of great importance in molecular genetics. However, conventional electrophoresis-based methods have many shortcomings, such as time-consuming, multi-step, and using radioactive isotopes or other hazardous materials. In this work, a one-step real-time fluorescence allele specific amplification(ASA) method was developed for rapid detection of K-ras oncogene point mutation at codon 12. Thirty-one colon cancer samples were analyzed by the assay. Genome DNA was amplified by a pair of mutant specific primers, only the mutant sample could be amplified, producing double-stranded DNA product, which can be detected by the fluorescence of SYBR Green Ⅰ, a double-stranded DNA-selective fluorescent dye. The results show that the sensitivity of the assay was 1/1000 of mutant/wild-type DNAs. The positive rate for K-ras oncogene point mutation was 48.4%. The real-time fluorescence ASA method is rapid, simple, sensitive, safe, high throughput, and low cost. It can be used for screening a large amount of clinical samples.
    High-throughput SNP Genotyping Method with PCR on Magnetic Nanoparticles
    LIU Hong-Na1, LI Song1,2*, WANG Zhi-Fei2, HE Nong-Yue2, HE Quan-Guo1*
    2007, 28(6):  1035-1038.  doi:
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    Single nucleotide polymorphisms(SNPs) assay is important for elucidating the genetics of indivi-dual differences in drug response and disease susceptibility. This report described a novel high-throughput SNP genotyping method using magnetic nanoparticles as PCR primers carriers. PCR products were directly amplified on MNPs and interrogated by hybridization with a pair of dual-color fluorescence(Cy3, Cy5) probes to determine SNP, and then genotype of each sample can be simultaneously identified by scanning the microarray printed with the denatured fluorescent probes on an unmodified glass slide. As the results, the homozygous wild type, homozygous mutant type and heterozygote type yield strongly green, red and yellow fluorescent signals, respectively. The methylenetetrahydrofolate reductase(MTHFR) gene C677T polymorphism of nine di-fferent samples was detected and their fluorescent signals of the nine samples were quantified. The fluorescent ratios(match probe signal to mismatch probe signal) of homozygous samples were over 9.0, whereas heterozygous samples had ratios near 1.0. The genotyping results were additionally validated by sequencing. Without any purification and concentration of PCR products, the approach reported here should be a simple, sensitive, high-throughput and high accurate genotyping method.
    Analysis of Alkyl Benzenes in Printing Ink on Food Packaging Materials and Its Migration by Gas Chromatography-Mass Spectrometry
    MENG Zhe1,2, LIAO Xun2, SUN Dan-Dan3, LIAO Yi-Ping2, LIU Hu-Wei2*
    2007, 28(6):  1039-1042.  doi:
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    Gas chromatography-mass spectrometry was used to analyze alkyl benzenes in the printing ink on the food packing materials. Quantification was carried out via a selected ion monitoring(SIM) mode, and naphthalene was used as an internal standard. The migration of alkyl benzenes from paper and plastic packaging materials into food was also tentatively studied. The results indicate that the risks of food contamination are associated with the migration of harmful components from printing ink on packaging materials into the food.
    Theoretical Prediction of Direct Chemiluminescence Behavior of Biologically Active Compounds in Liquid Phase
    GUO Li-Li, XU Chun-Li, LI Bao-Xin*, LÜ<
    2007, 28(6):  1043-1048.  doi:
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    Based on the quantitative structure-property relationship studies, molecular topology indices were used to describe the structure of some classical active compounds, which could react with common oxidants in a liquid phase to produce chemiluminescence emission, and some inactive compounds. The discriminant function was suggested with cosine coefficient as a descriptor. Finally, the discriminant function was applied to predicting the direct chemiluminescence behavior of 101 compounds with a success of 95.05%. The present work would give new idea to quickly develop suitable direct chemiluminescent analytical method in rather simple way.
    Kinetic Model of Microwave-assisted Extraction of the Effective Constituents from Lycoris radiata and Rhizma Polygoni Cuspidati
    FAN Hua-Jun1,2, XIAO Xiao-Hua1, LI Gong-Ke1*
    2007, 28(6):  1049-1054.  doi:
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    A mathematical model of microwave-assisted extraction (MAE) kinetics based on Fick's second diffusion law was established for Chinese traditional medicine. The model proposed has been verified via using experimental data from MAE of Lycoris radiata and Rhizma Polygoni Cuspidati at different levels of temperature, extraction time and granularity. The simulated results show that the values calculated by the model were consistent with the experimental data. The diffusion coefficients of the effective constituents in Lycoris radiata and Rhizma Polygoni Cuspidati were calculated according to the kinetic modeling method and compared reasonably with those obtained with SRE method, and intensifying factor was introduced as a parameter to estimate the microwave effects on the extraction process of the constituents with MAE and the interaction difference between the different matrices of Chinese traditional medicine was revealed successfully.
    Design of a Direct-heating Fast Temperature Programming Device for Fast Gas Chromatography
    XU Feng, GUAN Wen-Na, LIAN Mei, XU Yuan, GUAN Ya-Feng*
    2007, 28(6):  1055-1058.  doi:
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    A direct-heating fast temperature programming device for fast gas chromatography was designed and evaluated. A metal capillary column was used both as a separation column and as a heating element. Pulsed current heating strategy was used to heat the column, and at the same time, gave the time lag for self-equilibrium of the metal tubing during a temperature programming. A fast PID control was used to facilitate the fast pulse heating. The correlation coefficients of temperature programming curves were more than 0.9996 between 40—150 ℃, with tunable heating rates varying from 1 to 5 ℃/s. The power consumption of the device was 74 W max, and was less than 50 W on average. The separation time was within 34 s for n-alkanes(nC8nC17), with relative standard deviations of the retention times between 0.22% and 0.55%. The cool down time plus the equilibration time is less than 30 s. The device is suitable for the analysis of semi-and volatile organic compounds in portable GC.
    Studies on Preparation and Performance of GSH Molecularly Imprinted Polymers
    LI Qiong1,2, DU Yan-Li1, YANG Ke-Ke1, LI Fang1*
    2007, 28(6):  1059-1063.  doi:
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    GSH molecularly imprinted polymers were synthesized with UV spot high pressure mercury lamp. This realized the preparation of MIPs in which the template molecules were unstable by means of reducing the time of polymerization from 48 to 2 h at a low temperature. A series of binding experiments in static state was done and the binding performances of MIPs with different molar ratios of templates to monomers was observed by using fluorescence measurement. The character trials which involved the determination of the binding isothermal, the analysis of Scatchard plot and the TLC separation tests were carried out on the MIPs in which the molar ratio of templates to monomers was 1∶8. In these experiments, the MIPs showed comparatively excellent characters. For example, the binding amounts reached 45.4 mg/g and the particularity factors 4.98 were achieved in binding experiments. From Scatchard analysis, it can be known that there were two sorts of binding sites of which the saturated binding amounts were 20.2 and 64.5 mg/g and the equilibrium dissociation constants were 0.435 and 1.48 mmol/L, respectively. The MIPs represented the best separation ability in TLC tests that was attested by the most separation factors of Gly or Glu to GSH on the TLC of MIP, NMIP and silica gel.
    Spectroscopic Characterization of An Antimicrobial Peptide(RTCⅠ) from Skin of Rana temporaria chensinensis, David
    ZHOU Jie, MENG Qing-Fan, TIAN Xiao-Le, CHENG Ying-Kun, JIANG Fu-Jia, LI Qing-Shan, TENG Li-Rong*
    2007, 28(6):  1064-1068.  doi:
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    An anion antimicrobial peptide(RTCⅠ) was purified from skin of Rana temporaria chensinensis, David, which has an antimicrobial activity against many strains of clinical multi-drug resistant bacteria. When excited at 276.5 and 356.5 nm, it exhibited a single emission band(λmax=448 nm). IR spectroscopy, Raman spectroscopy, fluorescence spectroscopy and amino acid composition analysis were used to study the structure basis of the characters observed in fluorescence spectra. Tyr, Asn(Asp) and Glu(Gln) are the mainly amino acid composition of RTCⅠ, it is suspected that the specific fluorescence spectra and electronic absorbance spectra are related to the strong hydrogen bond of Tyr phenolic hydroxyl groups and the side chains of Asn. The peculiar fluorescence will provide the possibility for further studies of the antibacterial mechanism on molecular level.
    研究快报
    Fabrication of Novel Microdisk Sensor and Its Application to Monitoring Nitric Oxide Release from Single Cell
    DU Fu-Ying, HUANG Wei-Hua*, WU Wen-Zhan, WANG Zong-Li, CHENG Jie-Ke*
    2007, 28(6):  1069-1071.  doi:
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    A novel nitrogen oxide(NO) sensor fabricated by modifying the only planar surface of a carbon fiber microdisk electrode(CFMDE) with single-walled carbon nanotubes(SWNTs) and Nafion membrane was reported for the first time. The modification of SWNTs dramatically improves the sensitivity of CFMDEs and the detection limit of NO was 4.3 nmol/L. The sensor was successfully applied to the measurement of NO released from single isolated human umbilical vein endothelial cells.
    研究论文
    Synthesis, Characterization and Binding of Tea Polyphenol-Manganese and Apoptosis Rate of Induced Tumor Cells
    HUANG He-Ning1,3, LI An-Zhang1, WENG Lu-Na1, LIN Qing-Mei2, HUANG He-Qing1,2*, ZHENG Zhong-Hui1, LI Qi-Fu1, CAI Zong-Wei4
    2007, 28(6):  1072-1076.  doi:
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    Both tea polyphenol-manganese(TP-Mn) and germanium(TP-Ge) were synthesized with organic synthesis approaches. The characterizations of TP-Mn were clearly revealed via infrared spectrometry and HPLC-ESI-Q-TOF mass spectrometry, respectively. Both HPLC and ICP-MS methods were employed to study the capacities for bovine serum albumen(BSA) binding to TP-Mn, indicating these capacities feasibility. Apoptosis rates in Hela ovarian induced with TP and TP-Mn were studied by a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenly tetrazolium bromide(MTT) method. The experimental results show that both TP and TP-Mn can induced the cancer cell apoptosis, but the apoptosis rate with TP-Mn showed two times higher than that with TP. As compared experiments, the same apoptosis rates, going with up to approximately 86%, in Raji human B lymphoma induced with both TP and TP-Mn were observed directly. Human serum albumen might be employed to be a pharmacy carrier for transferring TP-Mn and TP-Ge in vivo.
    Synthesis and Bioactivities of α-Phenyloxyl-(2-subsitituted-oxy)-benzyl Acetate
    YANG Er-Bing, LI Yong-Hong, LIU Xiu-Feng, LI Zheng-Ming*
    2007, 28(6):  1077-1079.  doi:
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    For the purpose of finding compounds which have the herbicidal activity, eight new compounds were synthesized by esterification of 2-substituted-oxy-benzyl alcohol and 2-(o-substituted phenyl) acetic acid. Their structures were confirmed by elemental analysis and 1H NMR. Their herbicidal activities were tested and compound 6 shows some herbicidal activity.
    Synthesis, Crystal Structure Characterization and Biological Activity of 2-[3-Phenoxymethyl-4-phenyl-[1,2,4]triazole-5-thio]acetanilide
    WEI Tai-Bao, TANG Jing, LIN Qi, LIU Hong, ZHANG You-Ming*
    2007, 28(6):  1080-1083.  doi:
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    A series of triazole deviratives were synthesized from phenoloxyacetyl hydrazide under the condition of microwave irradiation, and the crystal structure of compound 5f was characterized by X-ray diffraction analysis. The supramolecular with tri-dimensional netlike structure is formed by intermolecular hydrogen bonding and van der Waals forces. It is found that the deviratives can remarkably enhance the root elongation.
    Synthesis of Cyclic Carbonates Catalyzed by Zinc Maleate Under Supercritical Carbon Dioxide Conditions
    QI Chao-Rong, JIANG Huan-Feng*, LIU Hai-Ling, YANG Shao-Rong, ZOU Bo
    2007, 28(6):  1084-1087.  doi:
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    Under supercritical carbon dioxide conditions, the reaction of carbon dioxide and epoxides occurred with zinc maleate as the catalyst. Zinc maleate as a sole catalyst showed a low catalytic activity. The coexistence of organic bases, such as DBU, triethylamine(Et3N), imidazole, pyridin-4-ylamine, DMAP or pyridine, could promote this reaction, and the yields of the product were increased obviously. The activity order of organic bases as a function of cocatalyst was DBU>Et3N>imidazole>4-aminopyridine>DMAP>pyridine. Propylene carbonate could be obtained in 83.4% yield at 110 ℃ under 8 MPa of carbon dioxide pressure for 48 h in the presence of the binary catalyst system of zinc maleate and DBU. A verity of epoxides could also be transformed to the corresponding cyclic carbonates with a high yield in the presence of the binary catalyst system.
    Separation, Purification and Structure Characterization of Polysaccharide from Roots of Cudrania tricuspidata(Carr.) Bur.
    SHI Lei1,2, CHEN Kao-Shan1, DONG Qun2, FANG Ji-Nian2, DING Kan2*
    2007, 28(6):  1088-1091.  doi:
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    A water-soluble polysaccharide(CPS-0) was obtained from the root of Cudrania tricuspidata(Carr.) Bur., by hot water extraction(70 ℃), deproteination with enzymolysis and Sevag method, precipitation with ethanol, and fractionation through DEAE-Sephadex A-50 chromatography. The purity of CPS-0 was determined via HPLC and the structure was characterized with monosaccharide composition analysis, methylation analysis, GC, GC-MS, NMR spectra(1H NMR, 13C NMR, HMQC), UV, IR, and elemental analysis. The CPS-0 was found to contain glucose residue solely, with an average repeating unit of decasaccharide, ha-ving a backbone consisting of 1,4-linked α-D-glucopyranosyl residues, to which the side chain consisting of terminal and 1,4-linked α-D-glucopyranosyl residues was attached at position 6 of the branching residues.
    Preparation and in vitro Experimental Study of Methotrexate-Lactosyl-Chitosan Conjugate
    WANG Yin-Song1*, HAN Yue-Lian2, LI Ying-Xia3, WANG Yu-Mei1, LI Rong-Shan1
    2007, 28(6):  1092-1097.  doi:
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    N-Lactosyl-chitosan(LCH) with different degrees of substitution(DS) of lactosyl group was synthesized and characterized with Fourier transform infrared(FTIR) and proton nuclear magnetic resonance(1H NMR). The result of radioactive experiment in vitro shows that LCH was a specific ligand for asialoglycoprotein receptor(ASGPR) when the DS of lactosyl group ranged from 15.5% to 38.9%, which indicates LCH could be used as a novel kind of hepatic targeting carrier. Methotrexate-lactosyl-chitosan(MTX-LCH) was prepared via the following synthetic route: MTX was firstly coupled with chitosan, and then reacted with lactobionic acid to produce MTX-LCH. The DS of MTX moiety of MTX-LCH was determined via ultraviolet(UV) spectroscopy to be 5.6%, and the DS of lactosyl group to be 33.8%. MTX-LCH was water-soluble in the pH range of 1—14. The dynamic dialysis study shows that MTX-LCH was stable, and the release of MTX was very slow. These results provided a reference for the further study of liver-targeting polymeric prodrugs.
    研究快报
    Synthesis and Characterization of Chitosan Nanoparticles Modified by Glycyrrhetinic Acid as a Liver Targeting Drug Carrier
    ZHA Rui-Tao1,2, HE Xiao-Ting1, DU Tian1, YUAN Zhi1*
    2007, 28(6):  1098-1100.  doi:
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    Chitosan derivative with glycyrrhetinic acid(GA), which was accumulated specifically in liver, was synthesized. By ion-crosslinking of TPP in GA-CTS solution, GA-CTS-TPP complex nanoparticles were obtained. The physicochemical properties of these nanoparticles were investigated by using TEM and DLS. The experiment in vitro BSA entrapped was studied. GA-CTS-TPP nanoparticles are well dispersed and stable in aqueous solution in 14 months.
    研究简报
    Simple Synthesis of Idebenone
    YANG Chao-Wen, LEI Ze, FU Zheng-Qi, MU Xiao-Yun, YAN Yun-Nan, ZHU Hong-You*
    2007, 28(6):  1101-1103.  doi:
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    Idebenone is a synthetic analog of coenzyme Q10. It has clinical applications in many central ner-vous system degenerative diseases associated with oxidative stress, such as Parkinson's and Alzheimer's diseases, and especially in the therapy of Friedreich's ataxia. According to the established method of synthesizing the quinone using 3,4-cyclopendadiene as auxiliary reagent by Hamamura, the target compound with a good productivity was obtained firstly by using the alkylation reaction of quinone as the key step and coenzyme Q0 and 1,10-decanediol as the first materials of main body and side chain, respectively, the reactions proceed smoothly under mild conditions to give the expected proucts in good yields. Contrast to the original method, this method is more simple,efficient and practical.
    Determination of Basicity of Lewis Basic Extractant Mixture
    SHAN Xin-Chang, QIN Wei*, DAI You-Yuan
    2007, 28(6):  1104-1106.  doi:
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    The extraction method based on the reversible chemical complexation is highly effective and selective for separating polar organic solutes from dilute solutions, and the basicity of the extractant is one of the most important parameters affecting the extraction equilibrium. In this paper, the determination of basicity of Lewis basic extractant and its mixture solvent was first proposed on the basis of extraction behavior of HCl and the appropriate stoichiometric ratio of solute to extractant. The basicities of two Lewis basic chemicals, n-octy-lamine and di-n-butylamine, and some basicity of typical Lewis basic extractant mixture, trioctylamine(TOA)/1-octanol and trialkylphosphine oxide(TRPO)/kerosene, were measured at 25 ℃ by using this me-thod. The results show that this method was more accurate and simple, the basicity of Lewis basic chemicals was in agreement with the values reported in the literature, and the basicity of the mixture solvent depended on the extractant type and concentration.
    研究论文
    CAS Calculations for the Ground- and Excited-state Properties of HSO Radical
    LI Bu-Tong1, WEI Zi-Zhang1, PAN Qing-Jiang2, ZHANG Hong-Xing1*, SUN Chia-Chung1
    2007, 28(6):  1107-1109.  doi:
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    We optimized the structures of ground state and three low-lying excited states for HSO radical using the CASSCF method with ANO-L basis sets. Their single-point energy calculations were performed at the CASPT2 level including more electronic dynamic correlation effects. The results of frequency calculations show that these structures are minimum points on the potential energy surface. The variations of geometry parameters between the ground and excited states were rationalized by the analysis of their electronic structures. The calculated results fall well within the range of reported values.

    Structures and NLO Properties of Molecular Clusters with Alkali Metal Atom
    SUN Xiao-Ying, LI Zhi-Ru*, WU Di, SUN Chia-Chung, TANG Au-Chin
    2007, 28(6):  1110-1112.  doi:
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    By using ab initio calculation, three structures with all real frequencies were obtained for the Li(HF)n(n=1—4) clusters. The dipole moments(μ), polarizabilities(α0) and the first hyperpolarizabilities(β0) of Li(HF)n(n=2—4) were investigated at MP2/6-311++G(3df,3pd) level. The large first hyperpolarizabilities(β0)(53710×10-33—113270×10-33 esu) were found. It is revealed that the contributions of Li polarized to α0 and β0 values are dominantive.
    Theorelical Study of Crystal Structures and Intermolecular Interactions in Isomorphous Adducts [2-ClPyH]2+[MCl42-](M=Co, Cu, Ni)
    BAI Juan, WANG Guo, ZHANG Li, WANG Chao, HUANG Yuan-He, FANG De-Cai, LI Qi*
    2007, 28(6):  1113-1116.  doi:
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    Three complexes [2-ClPyH]2CoCl4(1), [2-ClPyH]2NiCl4(2) and [2-ClPyH]2CuCl4(3) were prepared, and their crystal structures were determined with X-ray crystallography. In each of the structures, the [2-ClPyH]+ cation is almost in the same plane while the [MCl4]2- anion is a slightly distorted tetrahedron. The X-ray crystallography analysis indicates that ultimate structures include the hydrogen bonds N—H…Cl and C—H…Cl, intermolecular Cl…Cl interactions as well as π-π stacking interactions. The title compounds were investigated theoretically via crystal orbital method based on density functional theory, as self-existent anions and a structure units respectively. The hydrogen bonding determines the directions of one-dimensional infinite columns and Cl…Cl interactions plays a crucial role in the final structure.
    Photoelectrochemical Studies of P3CT Modified CdSe Nanorod Composite Film Electrode
    HAO Yan-Zhong1,2*, YIN Zhi-Gang2
    2007, 28(6):  1117-1121.  doi:
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    CdSe nanorods(zinc blende and wulitize) were prepared via hydrothermal method. The CdSe nanorod was formed with a diameter about 100 nm and a length about 300 nm. The photoelectrochemical pro-perties of the CdSe nanorods/P3CT composite film electrode were investigated. The results show that the maximum value of photocurrent appeared at an electrode potential of -0.6 V. The maximum IPCE(13.5%) of the modified film electrode was lower than that of 17.7% CdSe nanorord film electrode. The p-n heterojunction was existed in the CdSe/P3CT composite film electrode.Because of the existence of p-n heterojunction, under certain condition the IPCE of P3CT modified CdSe nanorod was larger than that of CdSe film electrode in the whole long wavelength region(>410 nm).
    Thin Film LiCoO2 Cathode Prepared by Using Ink-jet Printing Technique and Its Electrochemical Properties
    ZHAO Yao-Min1,2, XU Juan2, LIU Ling2, YANG Jie2, JIANG Zhi-Yu2*
    2007, 28(6):  1122-1125.  doi:
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    Thin film LiCoO2 electrodes were successfully prepared with a novel facile and low-cost computer ink-jet printing technique. For preparing the stable colloid “ink”, wet ball-milling was employed to stabilize the nano LiCoO2 particles and conducting agent acetylene black(AB) while two kinds of polymeric hyper dispersants CH10B and CH12B were used, respectively. Nano LiCoO2 particles were synthesized through the self-assembly method using triblock copolymer P123 as a template. The morphology, crystal structure and electrochemical performance of jet printing LiCoO2 thin film electrodes were investigated in detail via SEM, XRD, cyclic voltammograms(CV) and galvanostatic charge-discharge measurements. It was determined that the average thickness of the as-printed thin-film LiCoO2 electrode was about 1.27 m. The CV curves show that the heat treatment was benefit for improving the electrochemical properties of electrode. After a slight annealing process at 450 ℃ for 30 min, the thin film electrode presented a good reversible CV behavior. In the cycling process with constant charge-discharge current 20 A/cm2 within the potential range of 3.0—4.2 V(vs. Li+/Li), the initial discharge capacity of thin film LiCoO2 electrode was 81 mA·h/g, and after 50 cycles it remained 87%. After 10 cycles the charge-discharge efficiency reached near 100%.
    Theoretical Studies on Third-order Nonlinear Optical Property of (ZnS)6—12 Clusters
    ZHANG Xin, HUANG Ting-Ting, TAN Kai, LIN Meng-Hai*, ZHANG Qian-Er
    2007, 28(6):  1126-1130.  doi:
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    The third-order nonlinear optical(NLO) properties of (ZnS)6—12 were investigated under the time dependent density functional theory(TDDFT) at B3LYP/ Lanl2DZ+6-31G* level. The static third-order susceptibilities χ(3) and dynamic behavior of third-order polarizabilities γ in 0—2.5 eV were calculated by using the sum over states(SOS) method. The results show that the χ(3) of (ZnS)6—12 clusters are better than that of the other semiconducting clusters. (ZnS)7 and (ZnS)11, respectively, had a remarkable γ value of -2.38×10-33 and 1.26×10-33 esu at 1.6 and 2.0 eV. The (ZnS)6—12 clusters can produce an obvious phenomenon of the third-order polarizabilities when they are excited in a large γ value area.
    Effect of Structure-Activity Relationship on Electrochemical Degradation of Substituted Aniline
    LIU Xiao-Bo, HUANG Wei-Min , REN Xiu-Bin, DONG Yan-Jie, XU Hong, LIN Hai-Bo*
    2007, 28(6):  1131-1134.  doi:
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    The electrochemical oxidation degradation process of substituted aniline with electron-donating group(—CH3) and electron-withdrawing groups(NO2, Cl-) was studied on PbO2/Ti electrode by using sulfate as the support electrolyte. The results show that the oxidation degradation routes of substituted aniline were all started from hydroxyl radical attacking to form anilinophenol compound, then the anilinophenol compound changed into quinone intermediate on the electrode surface by the losing electron. The electrocatalysis degradation rate of substituted aniline with electron-doning groups was higher than the one with electron-withdrawing groups, because of the higher electron cloud density of benzene ring, it is convenient for hydroxyl attacking. On the contrary, it was difficult for hydroxyl attacking because electron-withdrawing groups could make the electron cloud density of benzene ring lower. The chemistry reaction activity is not consistent with electrochemistry reaction activity for the reason of cathode deoxidization reaction. When the hydroxyl radical attacks the chloroaniline, —Cl leaves and Cl- enters the electrolyte, at the same time, it is oxidized into available chlorine and the degradation rate increased. Although the nitro group is a strong electron-withdrawing group, it can be changed into p-phenylenediamine, then the benzene ring activity was stimulated, finally its degradation rate is much higher.
    Investigation of Electro-oxidation Activity of Pt-CNTs/GC Electrodes
    ZHONG Qi-Ling1*, ZHANG Bing1, RAO Gui-Shi1, DING Yue-Min1, WANG Guo-Fu1, JIANG Yu-Xiong1, REN Bin2, TIAN Zhong-Qun2
    2007, 28(6):  1135-1138.  doi:
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    The morphology and the structure character of the Pt-CNTs/GC electrode were characterized via Transmission Electron Microscopy(TEM) and the selected area electron diffraction. The electro-oxidation behavior of CO and methanol on Pt-CNTs/GC electrode were studied with cyclic voltammograms or Chronoamperometry. Three oxidation peaks were observed for CO observed on Pt-CNTs/GC electrode. Methanol were found to be dissociated spontaneously on the electrode to produce a strong adsorbed intermediate CO. Among the three oxidation peaks, peakⅠ is due to the briged CO adsorbing. But peaks Ⅱ and Ⅲ were assigned to split of the linear CO which is adsorbed on the Pt-CNTs nanocluster with different particle sizes and Pt film. The oxidation current of methanol on Pt-CNTs/GC electrode was always not increasing with the increasing of the amount of Pt loading. The result indicates that there is an optimal Pt loading for methanol oxidation. It is necessary to select the catalyst with proper pt loading when the anode of direct-methanol fuel cell was prepared.
    Calorimetric Studies on Cooperative Relaxation Near Tg for a Series of Glycerol Aqueous Solutions with High Concentrations
    GAO Cai1*, WANG Tie-Jun1, ZHOU Guo-Yan2, HUA Ze-Zhao2
    2007, 28(6):  1139-1142.  doi:
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    In order to examine the validity of entropically based nonlinear Adam-Gibbs equation(AGF) on the describing of cooperative relaxation of H-bond molecular liquid, differential scanning calorimetry(DSC) was employed to obtain the specific heat capacities of glycerol aqueous solutions in the temperature range of 118—218 K. Curve fitting technology was used to obtain the AGF model parameters. The results indicate that AGF formula can be used to predict the relaxation time below (Tg+20 K). The temperature-invariant activation energies(Δμ') and the sizes of cooperatively rearranging region(z*) were analyzed via AGF model and Johari's method. Physically reasonable z* can only be obtained when larger values of configuration numbers(W*) were chosen. The values of Δμ' decreased with increasing water content in the glass. The length scales of the cooperative rearranging region(ξCRR) were also estimated from the temperature fluctuation theory proposed by Donth. It was found that the ξCRR decreased from 3.01 to 2.06 nm when the fraction of glycerol decreased from 1 to 0.6 in the solutions. The values of z* obtained by using Johari's methods is 3.47 for glycerol, which is significantly less than the number of molecules estimated by Donth' method(583) in the CRR.
    Influence of Molecular Structure of Precursors on Microstructure and Gas Separation Performance of Carbon Membranes Derived from Poly(furfuryl alcohol)
    WANG Xiu-Yue, WANG Tong-Hua*, SONG Cheng-Wen, QU Xin-Chun
    2007, 28(6):  1143-1146.  doi:
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    Poly(furfuryl alcohol)(PFA) synthesized over different catalysts(oxalic acid and iodine) was used to prepare tubular C/CMS composite membranes. TG, FTIR and XRD were employed to characterize microstructure change of carbon membranes during the pyrolysis. Gas separation performance of the carbon membranes was also investigated by molecular probe with pure gases. The results show that the original chemical structure of the two PFA are transformed to turbostratic carbon structure from cross-linking polymeric structure by a series of reactions such as cyclization and aromatization during the pyrolysis. Although they followed similar pyrolysis behavior, the chemical reaction during the pyrolysis and the resultant microstructure of carbon membranes are different. In addition, d(002) and La of the carbon membranes polymerized over oxalic acid are smaller while Lc is larger than those polymerized over iodine. This indicates that the microstucture of carbon membranes polymerized over oxalic acid are more ordered and less defected than those polymerized over iodine. Carbon membranes polymerized over oxalic acid show a higher permselectivity and lower permeability.
    Application of Microcalorimetric Technique to the Synthesis of NH2-SBA-15
    YANG Xu-Wei*, ZHANG Xiao-Feng, KAN Qiu-Bin, FU Wei, Huang Jia-Hui, WU Tong-Hao
    2007, 28(6):  1147-1150.  doi:
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    A series of NH2-SBA-15 were prepared via a aminopropyl-triethoxysilane to react with SBA-15 and characterized with N2-BET, XRD, elementary analysis and FTIR and flavanone was synthesize via condensation between 2'-hydroxyphenyl methyl ketone and benzaldehyde catalyzed by the catalyst NH2-SBA-15. The microcalorimetric technique was used to study quantitatively the surface base sites of NH2-SBA-15 with intensity, number and distribution. It was shown that the reaction condition(550,6,1.5) was the most compatible for synthesis of NH2-SBA-15.
    Studies on Interaction of Interface Between Porpyrin and TiO2
    LI Zi-Heng1,2*, ZHOU Xiang-Dong1, WANG De-Jun3, ZOU Xu2, WANG Ying-Nan2, ZOU Guang-Tian2
    2007, 28(6):  1151-1154.  doi:
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    The absorption, photoluminescence and photovoltaic characteristics of porphyrin/TiO2 system were studied with absorption spectra, photoluminescence spectra and transient photovoltage technology, respectively, and the interaction of interface between porphyrin and TiO2 was also studied. The results obtained indicate that the interaction was different before and after Ho atom joined in porphyrin ring, the size of TiO2 also affected the interaction. When porphyrin was affected by TiO2 with 10 nm in diameter, its energy level was degenerated and band edge of porphyrin was red shifted, while it was affected by TiO2 with 56 nm and its energy level had little change. It indicates that the delocalizing interaction existed between the big pi bond of porphyrin and surface of TiO2 with 10 nm in diameter. The delocalizing interaction was also demonstrated via fluorescence spectra and transient photovoltage curves. Results are significant for the effective photo-electric conversion and study on the transfer of photogenerated carriers.
    Preparation, Structural Characterization and Catalyst Activity of CuO-MnO2/Al2O3 Catalysts
    LI Xin*, BIAN Jiang, ZHU Xue-Duo, QIANG Liang-Sheng
    2007, 28(6):  1155-1159.  doi:
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    Al2O3 supported CuO-MnO2 catalysts were prepared via immersion method, and their structures were characterized with SEM and XPS techniques. The effect of the preparation methods and conditions on the catalytic activities were studied and the best reaction conditions was obtained. The results show that the catalysts of CuO-MnO2/Al2O3 have very high catalytic activity, when the immersion time is 5 h, the molar ratio of Cu(NO3)2 to Mn(NO3)2 is 3∶1, and the catalyst was dried at 70 ℃ for 2 h and roasted at 200 ℃ for 3 h.
    Theoretical Investigation of Interaction Between Unclassical Trinuclear Antitumor Platinum Complex and DNA Duplex
    HAO Lan, ZHANG Yong, TAN Hong-Wei, CHEN Guang-Ju*
    2007, 28(6):  1160-1164.  doi:
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    BBR3464([{trans-PtCl(NH3)2}2-μ-{trans-Pt(NH3)2(NH2(CH2)6NH2)2}]4+) is currently in phase Ⅱ clinical trials. It is of considerable interest to understand the patterns of DNA damage. Detailed stu-dies about the geometrical and electrical configurations of the adduct of the trinuclear platinum compound and the 12-mer duplex 5'-d(ATATG*TACATAT)2-3' was made with the molecular mechanics, molecular dyna-mics and quantum chemistry methods. The investigating results show that the coordinate bonds between platinum atoms of the trinuclear platinum complex and two N7's of guanines four base apart on opposite DNA strands are the most important interaction and hydrogen bond interactions are critical factors influencing on the configuration of the adduct. The strong H8-H1' intraresiding electrostatic interaction for purine residues(G5, G17, A3, A7, A9, and A13) is consistent with a syn-conformation of the nucleoside unit, suggesting a delocalized structure and extensive conformational changes in solution. Since DNA is the major pharmacological target of platinum drugs, the unique structural characteristic may be related to the increased cytotoxicity and antitumor activity of BBR3464 as compared to cis-platin(cis-DDP).
    Chemical Etching Properties of Micro-structure in Glasses Modified by Femtosecond Laser Pulses
    JIANG Lu-Jie, DAI Neng-Li*, WANG Ying, ZHANG Ji-Huang, LU Pei-Xiang
    2007, 28(6):  1165-1168.  doi:
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    The chemical etching properties of micro-structure in three typical glasses modified with femtose-cond laser were studied. The micro-structure changes before and after etching were observed. The depen-dences of etching rate on the pulse energy and etching duration were revealed. The mechanisms of glass modifying-chemical etching were discussed. The results show that the femtosecond laser modified tellurite and lead silicate glass have no chemical selective etching, but the selective etching rate of silica glass is higher than 40. The character of chemical selective etching of femtosecond laser modified glass largely depends on the matrix local structures, the glass with a lager molecule volume has no properties of chemical selective etching, such as tellurite and lead silicate glass.
    Effect of Co Doping on the Cartalytic Performace of Molybdenum Carbide for Thiophene Hydrodesulfurization
    JIN Guang-Zhou1*, Fan Xiu-Ju1, SUN Gui-Da1, GAO Jun-Bin1 , ZHU Jian-Hua2
    2007, 28(6):  1169-1174.  doi:
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    Molybdenum carbide and cobalt molybdenum carbide catalysts, prepared by temperature-programmed reaction(TPR) with CH4/H2 gas mixture to carburize molybdenum trioxide and cobalt molybdenum oxide, were characterized via XRD, BET, SEM and XPS techniques. The effect of cobalt doping on the catalytic performance of molybdenum carbide for thiophene hydrodesulfurization(HDS) was studied. The results indicate that the cobalt molybdenum oxide is the compound oxide of MoO3 and CoMoO4, which produces a intergrowth and coexisting product of Co and Mo2C in the TPR carburization. Co dispersed uniformly in the component of Mo2C in the form of fine metallic particles. Co doping could decrease the carburizing temperature and particle size in the preparation process, increase the BET specific surface area and raise the content of Mo2+ on the surface of molybdenum carbide catalyst. The thiophene HDS activity of Mo2C was obviously improved in the presence of Co doped by co-precipitation method with Mo, and the maximum synergistic interaction between Co and Mo appears at the Co/Mo molar ratio of 0.2.
    研究简报
    Study on Three Kinds of Self-assembled Multilayer Films Prepared from Bipolar Hemicyanine Derivatives and H3PMo12O40
    WANG Yi-Bing1, XIA Ji-Ya1, GAO Li-Hua1,2, WANG Ke-Zhi1*
    2007, 28(6):  1175-1177.  doi:
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    Three kinds of new electrostatic self-assembled multilayer films were prepared with alternating adsorption of H3PMo12O40 and hemicyanine derivatives, and characterized with UV-visible absorption spectroscopy and cyclic voltammetry. The results show that these films are vertically uniform and electrochemically active with surface-controlled behavior, and the charge transfer may occur between H3PMo12O40 and hemicyanine derivatives in the films. The electron transfer rates of the three films are derived to be 0.0027, 0.0019 and 0.00066 s-1, respectively, which decrease with increasing the thickness of the hemicyanine layers in the films.
    Low-temperature Catalytic Combustion of Methane over Modified MnOx-CeO2 Mixed Oxide Catalysts
    SHI Li-Min1, CHU Wei1*, ZHENG Li-Na2, CHEN Mu-Hua1, QU Fen-Fen1, LUO Shi-Zhong1
    2007, 28(6):  1178-1180.  doi:
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    MnOx-CeO2 mixed oxide catalysts for methane combustion were prepared with co-precipitation me-thod. With the same content of Mn, the modified catalysts were gained via adding KMnO4. These catalysts were characterized with XRD, LRS, XPS and TPR techniques, respectively. It was found that the solid solution structures of the catalysts were reserved, while the low-temperature activities were promoted remarkably duo to more Mn4+ species and easier reductions through properly changing the adding amounts of Mn(NO3)2 and KMnO4. With a molar ratio of 1∶4, the MnOx-CeO2 catalyst exhibited the highest activity, over which methane conversion reached 90% at a temperature as low as 390 ℃, and a better stability.
    研究论文
    Preliminary Exploration of the Artificial Preparation, Structures and Properties of Regenerated Silk Fibers
    LIN Jiang-Bin, YAO Jin-Rong, ZHOU Li, CHEN Xin, SHAO Zheng-Zhong*
    2007, 28(6):  1181-1185.  doi:
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    Regenerated silk fibroin fibers with remarkable mechanical properties were successfully prepared via wet spinning technique, based on the high concentration and high molecular weight silk fibroin aqueous solution as spinning dope. With the observation of SEM, it could be found that the cellular structure may exist in the core of as-spun fibers. The regenerated silk fibers exhibited a smooth surface and dense structure after the post-drawn process. The NMR and Raman spectra results reveal that the β-sheet content increased with the increase of drawn ratios. It was also found that the steam-annealing can further improve the orientation of the macromolecular chains in the fibers. After the post treatment(both post-drawn and steam annealing), the breaking strength and the elongation at break can reach 0.5 GPa and 22%, separately, which is close or even better than that of natural silk(cocoon) fibers.
    Ring-opening Polymerization of ε-Caprolactone Catalyzed by Rare Earth Trifluoromethanesulfonate [Ln(OTf)3] Catalysts
    ZHU Wei-Pu, TONG Xiao-Wei, SHEN Zhi-Quan*
    2007, 28(6):  1186-1188.  doi:
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    The ring-opening polymerization of ε-caprolactone(CL) catalyzed by rare earth trifluoromethanesulfonate [Ln(OTf)3](Ln= Nd, Er, La) catalysts was reported. The influences of rare earth element, catalyst concentration, polymerization time and temperature on the monomer conversion and polymer molecule weight were investigated. These catalysts exhibit a high catalytic activity with single active center. The polymerization may proceed via active chain end cationic machanism.
    Preparation of Self-dispersible Hairy Polymer Particles Based on Ring-opening Polymerization of D,L-Lactide
    WANG Fang, WANG Chang-Chun*
    2007, 28(6):  1189-1193.  doi:
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    A new type of polymeric particles with hydrophobic hairs of PLA was prepared via initiating ring-opening polymerization(ROP) of D,L-lactide from the polymeric core particles of polystyrene and poly(2-hydroxyethyl methacrylate)[poly(St-co-HEMA)]. Successful grafting and well-dispersible properties of the hairy particles were approved via thermogravimetric analysis(TGA), scanning electron microscopy(SEM) and Fourier transform infrared analysis(FTIR). The experimental results indicate that this grafting procedure is effective and controllable for the preparation of novel hydrophobic hairy particles. The presence of hairy shell on core particles resulted in dramatic improvement of its dispersibility in organic solvent.
    研究简报
    Preparation of High-lightfastness/Chemical Resistance Core-shell-type Fluorescent Nanospheres
    HU Zhen-Kun, ZHANG Qing*, XUE Min-Zhao, SHENG Qiao-Rong, LIU Yan-Gang
    2007, 28(6):  1194-1196.  doi:
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    A class of core-shell-type fluorescent nanospheres with a particle diameter less than 40 nm, which emit orange, yellow, green and cyan light, respectively, were prepared. In fabricating strategy, the water-insoluble, photo-thermostable fluorescent dye molecules are molecularly dispersed and embedded in the nanoscale crosslinked polymeric matrix via a modified miniemulsion polymerization process, and then the biocompatible shells are achieved by a seeded polymerization technique. These obtained nanospheres are uniform in size, highly photostable, of high chemical resistance and high fluorescence quantum-yield.
    Synthesis of Cyclo-PMMA via Click Chemistry Combined with ATRP
    LI Juan1, DUAN Ming2*, FANG Shen-Wen2, ZHANG Lie-Hui2
    2007, 28(6):  1197-1199.  doi:
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    An efficient route to macrocyclic polymers via “click” cyclization was presented. The α-bromine and ω-alkyne PMMA were prepared using the standard ATRP technique, initiated with propargyl 2-bromoisobutyrate, Cu(Ⅰ)Br and N,N,N',N",N"'-pentamethyldiethylenetriamine (PMDETA). Azidation of the terminal bromine was followed in DMF with sodium azide, and α-azide, ω-alkyne PMMA precursor was obtained. Then the “click” cylcization of precursor between terminal azide and alkyne was carried out under the catalysis of CuBr/PMDETA, during the course of the reaction, a pseudo-high dilution technique was utilized to ensure the favored intramolecular cylcization. The nearly complete cylcization has been confirmed by a combination of IR, 1H NMR and GPC analysis, and cyclo- PMMA with an Mn of 15000, PDI of 1.38 was obtained.
    Ultrafine Polystyrene Nanofibers Prepared by Electrospinning
    HUANG Hui-Min, LI Zhen-Yu, YANG Fan, WANG Wei, WANG Ce*
    2007, 28(6):  1200-1202.  doi:
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    Ultrafine polystyrene(PS) nanofibers were prepared via the simple electrospinning technique. Uniform and smooth PS nanofibers were obtained with adding the organic salt BTEAC into the PS solutions and adjusting the concentration of PS solutions. Without the addition of BTEAC, PS fibers with few beads could be achieved with a PS mass fraction of 20%, and the average diameter of the fibers was 280 nm. The addition of the organic salt BTEAC could lower the critical concentration for the fiber formation and reduce the amount of beads on the fibers. Unltrafine PS fibers without any beads were obtained with a PS mass fraction of 10% and an ionic salt mass fraction of 0.5%. The average diameter of the fiber was successfully reduced to 100 nm. The influence of the salt concentration on the morphology and diameter of the PS fibers was also investigated. The viscosity and surface tension changes were measured with changing the concentration of BTEAC. The results show that the changes were so small that these factors could be ignored. It was suggested that variations of the fiber diameter should be mainly resulted from the changes of conductivity and conformation of the polymer chain as the concentration of BTEAC is varied.