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Table of Content

    10 February 2008, Volume 29 Issue 2
    目次
    高等学校化学学报2008年第29卷第2期目次
    2008, 29(2):  0.  doi:
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    下期目次预览

    2008, 29(2):  0.  doi:
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    综合评述
    Preparation and Incorporation of Luminescent Nanocrystals into Polymer Composites
    ZHANG Hao, YANG Bai*
    2008, 29(2):  217-229.  doi:
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    Due to quantum confinement effect, inorganic nanocrystals(NCs) show unique size-dependent optical, electronic, and magnetic properties. However, NCs are usually in the form of colloidal solution or solid powder. For practical applications, moreover, it is required to incorporate these unstable NCs into inert matrix, such as polymer. In this context, polymer has a good compatibility with many materials, and can be easily molded to various shapes. Besides, some polymers inherently have stimulus-responsive properties, which are potentially used to tailor NC properties. Consequently, incorporation of NCs into polymers will bring many advantages, including the improvement of NC stability, combination of multiple functionalities in one system, and even modulation of NC properties in polymer matrix. In this review article, the methods of fabricating NC-polymer composites are systematically summarized with the aim to achieve new generation of composite materials.
    研究论文
    High-quality CdTe Quantum Dots Synthesized in Liquid Paraffin Wax
    XING Bin, LI Wan-Wan, DOU Hong-Jing, SUN Kang*
    2008, 29(2):  230-234.  doi:
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    A novel route was developed to synthesize high quality oil soluble CdTe quantum dots. Liquid pa-raffin wax system was used to replace tri-n-octylphosphine oxide(TOPO) as the solvent for the synthesis of highly luminescent CdTe QDs at relatively low temperatures(200—260 ℃). Compared with TOPO, liquid paraffin is cheaper, more friendly to environmentally, and more stable in the air. The effects of the reaction temperature, growth time, precursor concentration, and the quantities of the ligands on the properties of the CdTe QDs were investigated in this paper. This new route reduces the raw material cost and enables us to obtain CdTe QDs with a broad emission spectral ranging from 570 to 720 nm at relatively low temperatures. The as-prepared CdTe QDs also possess a high PLQY(up to 65%) and good thermal stability.
    Biomimetic Synthesis of Calcium Carbonate Controlled by Anionic Amino Acid Surfactant
    LI Li-Ying, ZHANG Gan, SUN Ping-Chuan, CHEN Tie-Hong*
    2008, 29(2):  235-239.  doi:
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    N-Lauroylsarcosine sodium(Sar-Na) was used to control calcium carbonate crystalization in ethanol or ethanol/water solution at ambient temperature. By means of SEM, XRD and IR, the morphology and structure of the samples were characterized. It is revealed that with increasing the reaction time, the morphology of the CaCO3 particles generally varies from aragonite polyhedron to amorphous calcium carbonate spheres in pure ethanol and in the ethanol/water solution, with increasing the amount of N-lauroylsarcosine sodium, the morphology of the CaCO3 particles varies from flower-like to spheres. Pure vaterite crystals with a spheres shape were obtained at n(Ca2+)∶n(Sar)=1∶2. At a fixed n(Ca2+)∶n(Sar)=1∶1, with increasing the volume fractions of distilled water, the morphology of the CaCO3 particles varies from flower-like to spheres.
    Hydrothermal Synthesis of Bismuth Sulfide Nanotubes and Its Formation Mechanism
    ZHU Gang-Qiang*, LIU Peng, ZHOU Jian-Ping, BIAN Xiao-Bing, WANG Xiao-Bo, LI Jiao
    2008, 29(2):  240-243.  doi:
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    Large-scale high-quality Bi2S3 nanotubes were successfully prepared by a facile hydrothermal reaction between Bi(NO3)3 and Na2S at a low reaction temperature. The morphology and structure of as-prepared samples were investigated by X-ray Diffraction(XRD), Scanning Electron Microscopy(SEM), Transmission Electron Microscopy(TEM), Selective-area Electron Diffraction(SAED) and High-resolution Transmission Electron Microscopy(HRTEM). The characterization results show that the nanotubes are well-crystallized orthorhombic Bi2S3 nanotubes with out diameter 100—500 nm, inner diameter 50—200 nm and lengths between 1 to 5 μm respectively. The growth mechanism of Bi2S3 nanotubes was proposed on the basis the results of experiment. The effects of reaction temperature and different mineralizers were also investigated.
    Directly Solvothermal Synthesis of Copper Phthalocyanine Crystals
    XIA Dao-Cheng1, YU Shu-Kun2, MA Chun-Yu1, CHENG Chuan-Hui1,2, GUO Zhen-Qiang2, JI Dong-Mei2, FAN Zhao-Qi1,2, DU Xi-Guang4, WANG Xu3, DU Guo-Tong1,2*
    2008, 29(2):  244-246.  doi:
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    A novel method for directly synthesizing β-form crystals of copper phthalocyanine(CuPc) was pre-sented in this article. With quinoline as a solvent, crystals were grown after cooling the reaction mixture to room temperature in an autoclave which contains 1,3-diiminoisoindoline, NH4MoO4 and Cu(AcO)2·2H2O in quinoline solvent. These high quality crystals were suitable for characterization measurements. Needle-like single crystals of CuPc with a size up to 10.5 mm in length were obtained. The influences of different temperatures and times on the crystal yields were also discussed. The optimum reaction condition of the crystal growth was as follows: reaction temperature was 270 ℃, the reaction time was 8 h, and the reaction solvent volume was 10 mL, and the highest crystal yield was 51.3%. This method is called solvothermal synthesis method. Moreover, this method may be easily applied in the crystal growth for other organic functional raw materials, and acts as an important part both in scientific experiments and industrial productions.
    Luminescence Characteristics and Two-way Energy Transfer of Ce and Dy in Cd0.5Zn0.5B4O7
    CHANG Shu-Lan*, ZHU Tian-Qi
    2008, 29(2):  247-250.  doi:
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    A series of blue-white dual emission luminescent materials, Cd0.5Zn0.5B4O7∶Ce/Dy, were prepared via the high temperature solid state method for the first time. Investigating results of XRD show that Cd0.41Zn0.5B4O7∶Ce0.04/Dy0.02 belongs to orthorhombic crystal system with Pbca space group and lattice para-meters of a=1.3885 nm, b=0.8020 nm, c=0.8670 nm. There are two kinds of luminescence center, Ce3+ and Dy3+, in Cd0.5Zn0.5B4O7∶Ce/Dy system. Excited by 254—350 nm UV, the emission is mainly due to 4F9/26H15/2 and 4F9/26H13/2 of Dy3+, while excited by 355—390 nm UV, the emission is mainly due to 5d→4f of Ce3+. Excited by 340 nm UV, the intensity of the phosphor co-doped Ce/Dy is 31 times of the same concentration of Dy single-doped. Ce3+ is a high efficient sensitization agent of Dy3+. However, when excited by 355—390 nm UV, Dy3+ is the sensitization agent of Ce3+. A kind of singular two-way transfer of energy phenomenon, Ce3+→Dy3+ and Dy3+→Ce3+, exists in the system.
    研究快报
    Hydrothermal Synthesis of Polymer/BaZrO3 Hybrid Hollow Nanospheres
    DONG Zheng-Hong, ZHAO Yong-Nan*, YU Jian-Guo, ZHOU Pei, SU Hao, PANG Sha
    2008, 29(2):  251-253.  doi:
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    Hybrid polymer/BaZrO3 hollow nanospheres were successfully synthesized via a simple polymer assisted hydrothermal route. Polymer additives play a key role on the formation of hollow nanospheres. The samples prepared in the absence of polymers are microcubes. The basicity also plays an important role on the formation of hollow nanospheres. In low [OH-] concentration medium, the products are microcubes. Hollow spheres formed when the [OH-] is larger than 4 mol/L. Pure hollow spheres could be formed with the [OH-] over 8 mol/L. IR and TG data indicate the hybrid feature of the products. The polymer content(mass fraction) declined from 33% to 6% by adjusting the basicity from 8 to 16 mol/L. The diameters of nanos-pheres are tunable in the range of 300—100 nm via increasing the basicity.
    研究论文
    Glyoxal Induced Apoptosis Studied by Near-infrared Surface-enhanced Raman Scattering
    TANG Hong-Wu1*, SMITH D. A.2
    2008, 29(2):  254-257.  doi:
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    We report on the capabilities of near-infrared surface-enhanced Raman scattering(SERS) by introducing 60 nm gold nanoparticles into live human osteosarcoma cells to obtain detailed chemical information with a high spatial resolution from these cells. A comparative study between viable and glyoxal induced apoptotic cells indicates that most of the gold nanoparticles enter the living cell reside in the cytoplasm and around the nucleus, whereas apoptotic cell shows relatively uniform distribution of gold nanoparticles and interestingly, DNA fragments can be easily found throughout the cell including the cell surface. The ability to acquire very sensitive SERS inside single cells indicates the potential of this technique as a useful tool in biomedicine.
    Spectroscopic Studies on the Interaction of Cu2+ with Myoglobin
    MA Jing1, ZHENG Xue-Fang1,2*, TANG Qian1,2, YANG Yan-Jie1,2, SUN Xia1, GAO Da-Bin2
    2008, 29(2):  258-263.  doi:
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    The interaction of Cu2+ with Myoglobin(Mb) was investigated by UV-Vis absorption spectra, fluorescence spectra, synchronous fluorescence spectra and circular dichroism(CD) spectra. It is shown that Cu2+ enhanced the intensity of UV absorption peak of Mb, accompanied with blue shift. The fluorescence spectrum shows that Mb fluorescence at 323 nm was quenched regularly with the addition of Cu2+. The quenching belongs to the static fluorescence quenching. The binding constants and the numbers of the binding sites at different temperatures were calculated. The thermodynamic parameters were calculated(ΔH=-11.60 kJ/mol, ΔS=33.77 J·mol-1·K-1) according to van′t Hoff equation, which indicate that the static interaction played major roles in the binding process. The binding distance r between Cu2+ and Mb was obtained(2.56 nm) on the basis of Förster theory of non-radiation energy transfer. The effect of Cu2+ on the conformation of Mb was further analyzed by synchronous fluorescence spectra and circular dichroism. The results indicate that Cu2+ had a strong impact on Mb conformation with the change of the microcircumstance of aromatic amino residues and decreases of α-helical content of the protein.
    Patterned SERS Active Substrate Fabricated by Dewetting of Silver Nanoparticles Solution
    SONG Wei, ZHU Di-Fu, LI Zhi-Shi, LIU Hui-Hui, YANG Bai, ZHAO Bing*
    2008, 29(2):  264-267.  doi:
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    We present a simple and controlled method for direct fabrication of ordered 2D arrays of Surface-enhance Raman scattering(SERS) rings and disks substrate. Silver rings and disks are fabricated on patterned self-assembled monolayers on Au substrate by dewetting the solution of CTAB-coated silver nanoparticles in CHCl3. It is found that two different silver patterns assemblies are formed when the concentration of the silver nanoparticles in CHCl3 solution changes. We characterized the formation and structure of these two different silver patterns assemblies using contact mode atomic force microscopy. Surface enhanced Raman mapping of 4-MPY SAM on this novel SERS active substrate are also investigated.
    Preparation and Chromatographic Behavior of Novel Tetrazole Bonded Stationary Phase for Ion-exchange Chromatography of Proteins
    LEI Gen-Hu1, XIONG Xiao-Hu1, HUO Yan-Min1, WEI Yin-Mao1,2*, ZHENG Xiao-Hui2
    2008, 29(2):  268-272.  doi:
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    A novel tetrazole bonded ion-exchange stationary phase was presented. Tetrazole-functionalized stationary phase was prepared by treatment of silica gel with γ-glycidoxypropyltriethoxysilane, then 3-hydroxypropionitrile, followed by the Zn(Ⅱ)-catalyzed(3+2) azide-nitrile cycloaddition, which is an element of “click chemistry”. The resulting column(4.6 mm×50 mm i.d.) exhibited an excellent separation ability for proteins with high protein mass recoveries of more than 93%, and displayed a property of weak cation ion-exchange chromatography, but the changes in the retentions of protein with pH variation were diffe-rent from those obtained on the carboxylic acid bonded ion-exchanger, for which the reason was preliminarily explained.
    Electrochemical Study of the Inhibitory Effect of Sinapic Acid and Its Derivatives on Tyrosinase Reactivity
    ZHANG Dong-Mei1, ZHOU Nan-Di1, ZHOU Hui1, CHEN Ting2, LI Gen-Xi1*
    2008, 29(2):  273-276.  doi:
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    On the basis of the electrocatalytic response of tyrosinase to catechol, an enzyme electrode, which was prepared by immobilizing tyrosinase in silica sol-gel, was employed to investigate the inhibitory effect of sinapic acid and its derivatives, the components in the chinese traditional medicine, Semen sinapis. This electrode exhibited a fast and steady state response to catechol, with a linear range from 1.0×10-7 to 6.0×10-5 mol/L and a sensitivity of 60.93 nA·L/μmol. The kinetic process of the chronoamperometric response to catechol, performed in the absence and in the presence of sinapine, sinapic acid and sinapic-acid methyl ester, was analyzed. Sinapic acid was known to show the highest inhibition ability, followed by sinapic-acid methyl ester and sinapine. Further studies reaveal that the inhibition mechanism of sinapine corresponds to the noncompetitive one, while those of sinapic acid and sinapic-acid methylester can be modeled as the mixed one. Using the Lineweaver-Burk linearization and a secondary one, the inhibition parameters (inhibition constant and coefficient of 50% inhibition) were calculated.
    Surface-modification of CdTe Nano-particles by Pepsin and Its Analytical Application
    CHEN Li-Hua1,2*, QIN Shi-Dong1, LI Zhao-Yang3
    2008, 29(2):  277-282.  doi:
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    CdTe semiconductor nano-particles were synthesized with mercaptoethylic acid as the stabilizer as well as surface-modification reagent. The average size of CdTe nano-particles estimated from TEM graph was ca. 3 nm. The CdTe nano-particles exhibited a strong ultraviolet absorption at 320 nm and fluorescence emission at 524.8 nm, respectively. When surface-modification of CdTe nano-particles were replaced with pepsin, ultraviolet absorption peak kept the same, absorption intensity at 320 nm increased. It can be observed that the fluorescence emission intensity decreased as well as the fluorescence peak shifted to 467.2 nm. Temperature, ion strength and pH value influenced the surface-modification of CdTe nano-particles. Under the optimal conditions, a mass concentration of pepsin in the range of 4—40 mg/L shows a linear relationship with the fluorescence intensity decreasing value of CdTe nano-particles, with a detection limit 3σ of 0.28 mg/L(n=10). The proposed method was applied to detection of the concentration of pepsin in human gastric juice.
    Characterization of On-column Conductivity Detection by Electrical
    Coupling in Chip Electrophoresis
    WU Zhi-Yong*, FANG Fang
    2008, 29(2):  283-287.  doi:
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    Electrical coupling is usually considered as a side effect in the development of an electrochemical detection system for capillary electrophoresis. However, this effect can also be used for some electrochemical detection purposes. In this paper, an on-column dc contact conductivity detection using the coupling effect was presented, and the principle was elucidated. The characters of the method were demonstrated by chips of glass and polymer substrate with double-T detection cell. During the electrophoresis process, the electric field with a high strength was coupled to the sensing electrodes through the two detection channels, generating a potential difference that can be detected by the two electrodes in the outlet reservoirs. When a solute band passes a detection cell that was defined as a section of the separation channel, the potential drop will change and is proportional to the resistance of the solute in the cell. The level of coupled potential depends on solute conductivity, length of cell and electrical field strength, while the ratio of the potential over baseline depends only on the physical characters(conductivity or resistance) of the solution in the cell. The analysis results also show that this method responded not only to the charged species, but also to uncharged species. Electrical field strength above 450 V/cm could be applied with an homemade high input resistance signal transformer. Fast, reprodu-cible and sensitive detection was demonstrated for the separation of K+ and Na+ with a detection limit down to 5 μmol/L in 1 mmol/L Tris-HCl buffer and linear range over two orders of magnitude (10 μmol/L—2 mmol/L). This detection method can be used as a universal detector for capillary or chip electrophoresis system.
    Effect of Selective Extraction on the Non-residual Fractions, Structures and Adsorption Characteristics of Clay Mineral in the Surficial Sediments
    WANG Xiao-Li2, LI Yu1,2*, WANG Yi-Zhe3, DONG De-Ming2, LI Xu-Qian2
    2008, 29(2):  288-293.  doi:
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    The selective extraction and separation of Mn oxides, Fe/Mn oxides and organic materials were performed via NH2OH·HCl, (NH4)2C2O4 and H2O2, and the surface area, infrared spectra, scanning electron micrographs and X-ray powder diffraction patterns of the sediments before and after extraction treatments were also investigated. The results indicate that the surface and particulate characteristics of the sediments after each extraction significantly changed, and the BET specific surface area increased, dispersing degree of the sediment particles enhanced, as well as the crystal structure was more distinct. But XRD and FTIR spectra changed slightly after each extraction due to the identified peaks were mainly contributed by minerals in the sediments. The adsorption capacities of the sediments after extraction decreased along with the dispersing degree increase of the sediment particles, the coarse of sediment surfaces was weakened, implying that the surface characteristics of the sediments also contributed to the adsorption of heavy metals to the sediments. And the negative correlation between the BET specific surface areas and the adsorption capacities of the sediments suggests that the adsorption contributions from the sediment components were significantly greater than those from surface and pore structure of the sediments.
    Liquid Transfer Characteristics in Complex Electroosmotic Pump System
    ZHANG Wei-Bing1,2,4*, YOU Hui-Yan2,3, ZHANG Li-Hua2, ZHANG Yu-Kui2
    2008, 29(2):  294-297.  doi:
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    On the basis of the discussion for middle pressure-producing principle, the transfer characteristics for liquid in a new type of complex parallel, or series electroosmotic pump system was investigated. In a multi-series electroosmotic pump, the pressure of a pump can be elevated by increasing the progression of an electroosmotic pump or applied voltage. But it has disadvantage because of its limit in liquid transfer. In a multi parallel connection electroosmotic pump, the flux of a pump can also be elevated by increasing the progression of an electroosmotic pump or applied voltage. The system can be used in a wide range due to the fold of liquid flux. But it has disadvantage in controlling the operation condition because of its smaller linear range caused by Joule heat.
    研究快报
    Photolithographic Patterning of Hydrogels and Their Applications
    LIU Xin1,2, SHEN Zheng1,2, WU Da-Peng1,2, WANG Qi3, QIN Jian-Hua1* , LIN Bing-Cheng1*
    2008, 29(2):  298-300.  doi:
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    Hydrogel micropatterns of poly(ethylene glycol) and polyacrylamide were prepared with a facile photolithographic method. Monomer solutions containing photoinitiator were directly polymerized by UV illumination through a transparency photomask, forming 2-dimensional gel patterns on silanized glass surfaces. The chemically patterned surfaces thus prepared could be used as the template for patterning mammalian cells and formation of structured droplets.
    研究论文
    Hydrosilylation of Aldehydes Catalyed Selectively by μ-Hydroxo Organotin Dimer
    ZHANG Zheng-Hua, XU Wei-Jian, XIONG Yuan-Qin, AN De-Lie, PENG Zhi-Hong*
    2008, 29(2):  301-304.  doi:
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    A kind of μ-hydroxo organotin dimmer [Bu2Sn(OH)(OTf)(H2O)]2(1) was prepared from Bu2SnO and CF3SO3H(TfOH), and the hydrosilylation of aldehydes catalyzed by compound 1 were studied. The conditions of hydrosilylation catalyzed by compound 1 were discussed. Compound 1 can catalyze hydrosilylation of aromatic aldehydes as well as aliphatic aldehydes without byproducts such as ether or alkyl forming. Compared with conventional Lewis acid catalysts, μ-hydroxo organotin dimer as an efficient catalyst has some merit as follow: the catalyst can be synthesized in a simple way; due to its stability in water and air, the catalyst can be saved and used conveniently; the catalyst concentration is very low and high chemoselectivity is readily attained. The hydrosilylation of aldehydes can be catalyzed exclusively but the other carbonyl compounds and some reductive groups in one molecular or in one reaction system couldn′t be catalyzed.
    Oxepine and Bibenzyl Compounds from Bulbophyllum kwangtungense
    WU Bin1, CHEN Jian-Bo2, HE Shan1, PAN Yuan-Jiang1*
    2008, 29(2):  305-308.  doi:
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    Phytohemical investigation of the EtOAc extract of leaves and stems of Bulbophyllum kwangtungense Schlecht., belonging to the orchid family was carried out. Two new stilbenods were isolated by repeat column chromatography and characterized: one is bibenzyl compound, 5-(2,3-dimethoxyphenethyl)-6-methylbenzo[d][1,3]dioxole(1), and the other dibenz[b,f]oxepine, 10,11-dihydro-2,7-dimethoxy-3,4-methylene-dioxy dibenzo[b,f]oxepine(2). Their structures were established on the basis of analyses of spectroscopic evidence, particularly by two-dimensional NMR spectroscopic analysis. Bibenzyl compound with a methyl group in the benzene ring is rarely found from natural sources. Natural oxepines are very rare, and most of them were reported to have good anti-tumor activities. In addition, anti-tumor activities of the new compounds were also evaluated. Among the compounds isolated, compound 2 showed anti-tumor activities with IC50 value of 47.2 μg/mL in vitro against cultures of Hela cells.
    Solvent-free Synthesis of 4,6,10,12,16,18,22,24-Octa-hydroxy-2,8,14,20-tetra{(tri-(3-phenyl-2,4,8,10-tetraoxaspiro[5.5]undecyl))-(4-(2-(4,6,10,12,16,18,22,24-octa-hydroxy)Calixresorcinarenyl)phenyl)}calixresorcinarene Spiro macromolecul
    WEI Rong-Bao*, LIANG Ya
    2008, 29(2):  309-313.  doi:
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    The terephthalaldehydes mono-acetal was prepared by the reaction of terephthalaldehyde and ma-lononitrile. The 2-(4-dicyano-vinyl-phenyl)-9-(4-formylphenyl)-2,4,8,10-tetraxaspiro[5.5]undecanes(3) were given through terephthalaldehydes mono-acetal reacting with pentaerythritol and then the hydrolysis occurred in the presence of InBr3. The calixresorcinarenes 6 was prepared by using terephthalaldehydes mono-acetal and resorcinol as the material. Through compound 6 reacting with compound 3, calixresorcinarene macromolecular dendrimer of 4,6,10,12,16,18,22,24-octahydroxy-2,8,14,20-tetra{(tri(3-phenyl-2,4,8,10-tetraoxaspiro[5.5]undecyl))-(4-(2-(4,6,10,12,16,18,22,24-octahydroxy)calixresorcinarenyl)phenyl)} calixresorcinarene(9) was produced. The product was characterized by IR, 1H NMR, 13C NMR, MS and elemental analysis. The effect factors on the reactions were discussed.
    Chemical Synthesis, Characterization and Biological Properties of a Novel Cyclic ADP-Ribose Analogue
    WANG Pei, ZHANG Yan, YANG Zhen-Jun, ZHANG Liang-Ren*, ZHANG Li-He
    2008, 29(2):  314-318.  doi:
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    For the investigation of the structure-activity relationship of the analogues of cyclic ADP-ribose (cADPR), a novel cyclic IDP-ribose analogue, cIDPRN, in which the northern ribose was replaced by N-carbobenzyloxy-alkylimine bridge was designed and synthesized. The enzymatic stability of cIDPRN was evaluated by the incubation with Jurkat T-lymphocytes for 0, 2 and 18 h. The result analyzed by capillary electrophoresis indicated that cIDPRN antagonized the hydrolysis, whereas cADPR was easily hydrolyzed. The Ca2+ signal release behavior was investigated in intact Jurkat T-lymphocytes by spectrofluorometer. It showed that cIDPRN induced calcium release either in extracellular Ca2+-containing or Ca2+-free condition. The result indicated that cIDPRN was a mild membrane-permeant agonist of cADPR/RyR signaling system. This study provided further information for understanding the effect of structure of northern ribose moiety of cIDPR on the calcium motivation activity.
    Synthesis and Biological Activity of New Trisubstituted Pyrimidine Phenylsulfonylurea Derivatives
    GUO Wan-Cheng, TAN Hai-Zhong, LIU Xing-Hai, LI Yong-Hong, WANG Su-Hua, LI Zheng-Ming*
    2008, 29(2):  319-323.  doi:
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    In order to develop new herbicidal active compounds and research the structure-activity relationship, twenty-two new sulfonylurea derivatives with trisubstituting group in the pyrimidine ring were designed and synthesized. Their structures were confirmed by 1H NMR, MS and elemental analysis. Preliminary herbicidal activity of these new sulfonylurea compounds was determined by pot bioassay experiments at dosage of 1.5 kg/ha. The results show that these trisubstituted pyrimidine phenylsulfonylurea derivatives display weak heribicidal activity and the addition of 5-substituting group of the pyrimidine ring affected the herbicidal activity slightly.
    Synthesis, Crystal Structure and Quantum Chemistry Studies of 3,4',5-Trimethoxystilbene
    HAO Jin-Ku1,2*, SHEN Yong-Li2, BAI Dong-Hua1, ZHUGE Shang-Qi1, CAO Ying-Yu1, YANG En-Cui1
    2008, 29(2):  324-327.  doi:
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    3,4',5-Trimethoxystilbene was synthesized via Wittig-Horner reaction with different solvents. It belongs to triclinic system with crystal space group P1. Hydrogen bond interaction existed between different structure units in a crystal cell. There were two different conformations in the crystal structure unit. The results, obtained by quantum chemistry method with DFT/B3LYP/6-31G, 6-311G(5D, 7F) sets, show that the total energy of the two separated conformations was higher than that of the two conformations in one structure unit, ΔEBSSE=5.51 kJ/mol. Otherwise the optimization of all the molecular shows that when the crystal formed, the plan-structure of different conformations was twisted, which indicate that there was a π-π effect between the two conformations.
    Kinetic Resolution of Racemic Propranolol by Bulk Liquid Membrane
    HU Wei-Guo, JIAO Fei-Peng, HUANG Ke-Long*, WANG Wei-Ling
    2008, 29(2):  328-331.  doi:
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    Bulk liquid membrane(BLM) was developed for the resolution of racemic propranolol(PPL), via the formation of complex between (S,S)-di-n-dodecyl tartrate(DDT) and boric acid, the complex was used as chiral the carrier which was preliminarily characterized by calorimetry. The influences of the molar concentration ratio of PPL to DDT and pH in aqueous phase on the resolution performance were investigated. The optimal resolution conditions were obtained. The resolution process was also analyzed by means of kinetics. At last, the primary research law of BLM resolution was obtained. The law shows that the kinetic resolution is demonstrated to be a process of kinetic resolution. Using the higher DDT concentration will be in favor of increasing the flux of enantiomer and enantioselectivity of resolution. pH of aqueous phase has an important influence on BLM resolution. The resolution process was controlled by extraction reaction. The transport of enantiomer across membrane can be described by two consecutive irreversible pseudo first order reactions.
    Synthesis, Characterization and Properties of Novel Polyfluorene Copolymers with Good Visible Spectral Coverage
    WU Jiang-Yong, HUO Er-Fu, WU Zhi-Bing, LI Ying, XIE Ming-Gui, JIANG Qing*
    2008, 29(2):  332-335.  doi:
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    Conjugated polymers are increasingly concernful as the emerging semiconductors due to their low cost, ease of processing, flexibility and excellent optic-electro properties. In this paper, two novel polymeric photovoltaic materials on the basis of fluorene having fluoren-9-one and fluoren-9-units in the main chain were synthesized. The polymers were characterized via FTIR and NMR. The polymers possess a satisfactory thermal stability and machinability with thermal decomposition temperature(Td) of 461.2 and 448.1 ℃ and glass-transition temperature(Tg) of 122.4 and 146.6 ℃, respectively. The materials perform a good absorption around about 300—700 nm covering a large part of the visible spectrum. Their effective reversibilities of redox reaction were determined, and the polymers exhibited a correspondingly low bandgap of 1.94 and 1.86 eV detected by cyclic voltammetry(CV). Therefore, these polymers will be potential light-absorbing and electro-transport materials applied in organic photovoltaic devices.
    Experimental Study on the Metastable Phase Equilibria of the Quaternary System Na2CO3-Na2SO4-Na2B4O7-H2O at 273 K
    ZHENG Zhi-Yuan1, ZENG Ying1*, CHEN Jun2, LIN Xiao-Feng1
    2008, 29(2):  336-340.  doi:
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    The solubilities and densities of equilibrium solutions in the quaternary system Na2CO3-Na2SO4-Na2B4O7-H2O were studied at 273 K by isothermal evaporation method. On the basis of the solubility data, the phase diagram of the system was plotted. The phase diagram consists of two invariant point, five univariant curves and four crystallization fields, which correspond to the salt Na2CO3·10H2O, Na2SO4·10H2O, Na2B4O7·10H2O and 2Na2SO4·Na2CO3. In this system, the double-salt(2Na2SO4·Na2CO3) was formed, and this double-salt also exists in the other quaternary or higher-component systems which contain the Na2CO3-Na2SO4-H2O ternary system. The crystallization forms of sodium carbonate and sodium sulfate are Na2CO3·10H2O and Na2SO4·10H2O, respectively. The inextenso molecular fomula of sodium borate is Na2B4O5·(OH)4·8H2O. Na2CO3 has salt-out effect to Na2B4O7 in the solution.
    Synthesis, Characterization and Catalytic Performance of Ni-V-O Catalysts
    XU Ai-Ju1,2, LIN Qin1, ZHAORIGETU Bao2*, JIA Mei-Lin2
    2008, 29(2):  341-345.  doi:
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    Catalysts Ni3V2O8, Ni2V2O7, NiV2O6 were prepared and characterized by X-ray diffraction(XRD), BET, H2-TPR, XPS and conductivity measurement. Their catalytic performance for the oxidative dehydrogenation of propane to propene was investigated. The results show that the selectivities to propene were 69.13%, 70.21% and 64.41% over p-type semiconductor Ni3V2O8, Ni2V2O7 and n-type NiV2O6 catalysts with 10% propane conversion, respectively. These results suggest that p-type semiconductor catalysts have a better catalytic performance than n-type ones, that C3H6 selectivity has a good correlation with the electrical conductivity and that selectivity depends on the existence of Ni3V2O8 or Ni2V2O7 phase. XPS results illustrate that high catalytic performance on p-type semiconductor Ni3V2O8 and Ni2V2O7 was related to the abundant oxygen species O- and V4+ existing over these catalysts.
    Investigation of Inhomogeneous Dye-adsorption in Porous TiO2 Films by Intensity Modulated Photocurrent Spectroscopy
    LIU Wei-Qing1, DAI Song-Yuan1*, HU Lin-Hua1, DAI Jun1, FANG Xia-Qin1, XU Wei-Wei2
    2008, 29(2):  346-349.  doi:
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    The phenomena of inhomogeneous dye-adsorption in porous TiO2 film was likely to exist in dye sensitized solar cells(DSC). Dye-adsorption behavior in two kinds of TiO2 films with different microstructure and different adsorbing time was investigated by the Intensity Modulate Photocurrent Spectroscopy(IMPS). The influence of inhomogeneous dye-adsorption for IMPS response and the photovoltaic of DSC was discussed. The result shows that IMPS is a useful tool to detect inhomogeneous dye-adsorption occurred in some TiO2 films. The phenomena of inhomogeneous dye-adsorption had notable influence on the photovoltaic of DSC.
    Coulomb Staircase Phenomena and Electrochemical Impedance Spectroscopy Study of Monolayer Protected Gold Clusters Self-assembled on Gold Electrode
    WEN Li2, LIN Zhong-Hua1, WENG Shao-Huang2, ZHOU Jian-Zhang1*
    2008, 29(2):  350-355.  doi:
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    Quantized capacitance charging was observed for octanethiolate self-assembled monolayer protected gold clusters(C8AuMPC) self-assembled on a gold electrode surface. The result from differential pulse voltammetry(DPV) shows that four pairs of well-defined quantized capacitance charging peaks appeared within the potential range from -0.8 V to +0.8 V. Electrochemical impedance spectra(EIS) of the monolayer protected clusters(MPC) modified electrode show that the electrode interfaces with adsorbed MPC consisted of two components, namely, the electrode-MPC interface and the MPC-solution interface. The interfacial capacitances of the electrode-MPC interface(CDL1) and the MPC-solution interface(CDL2) almost had no change near the potential of zero charge(ca.-0.2 V), then CDL1 and CDL2 both changed along with increasing or decreasing the electrode potentials. Quantized capacitance charging of MPC was further theoretically analyzed by using the theory of Coulomb blockade in normal metal two tunnel junctions, confirming that EIS method was an effective method for studying quantized capacitance charging of MPC. In addition, the effect of the electroactive species-ferrocene on quantized capacitance charging of C8AuMPC was studied. The results show that the electroactive species in the solution almost made no contribution to the electron transfer of the MPC-solution interface, which mostly occurred between the nanoparticles.
    Hydrogen Generation from the Hydrolysis of Al-Sn Alloys
    FAN Mei-Qiang1,2, LIU Ying-Ya1,2, YANG Li-Ni1,2, CAO Chao-Xia1,2, SUN Li-Xian1*, XU Fen1*
    2008, 29(2):  356-359.  doi:
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    In this paper the Al-Sn materials were firstly prepared by the mechanical alloying. The results of the hydrogen-produced curves and X-ray diffraction patterns show that the additives(Zn or hydride) and the prolonged milling time favor to make the composition blend uniformly. The milled materials have good hydrolysis properties in water at room temperature, especially that the Al-10%Sn-5%Zn-5%MgH2(mass fraction) material milled for 10 h produced 785 mL/g with the hydrogen generation rate of 78.5 mL H2/(min·g).
    Liquid-solid Phase Equilibrium for the Quinary System Na+, Mg2+//Cl-, SO42-, NO3-, H2O Saturated with NaCl at 298.16 K
    HUANG Xue-Li*, MA Feng-Yun, SUN Hong-Mei
    2008, 29(2):  360-364.  doi:
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    Solubilities in the system Na+, Mg2+//Cl-, SO42-, NO3-, H2O saturated with NaCl were investi-gated by isothermal method at 298.16 K. According to the experimental data, the solvent-free, NaCl-free and water projection phase diagrams of this system were plotted. In this system, eight crystallization fields with two saturated salts were observed: MgSO4·Na2SO4·4H2O+NaCl, NaNO3+NaCl, NaNO3·Na2SO4·2H2O+NaCl, MgCl2·6H2O+NaCl, Na2SO4+NaCl, Mg(NO3)2·6H2O+NaCl, NaCl+MgSO4·7H2O and MgSO4 ·(1—6)H2O+NaCl. The respective crystallization areas are being separated from each other by thirteen univariant curves with three saturated salts which intersect in six invariant points corresponding to NaCl+Na2SO4+Na2SO4·MgSO4·4H2O+Na2SO4·NaNO3·2H2O, NaCl+NaNO3+Na2SO4·MgSO4·4H2O+Na2SO4·NaNO3·2H2O, NaCl+NaNO3+Na2SO4·MgSO4·4H2O+MgSO4·7H2O, NaCl+NaNO3+Mg(NO3)2·6H2O+MgSO4·7H2O, MgSO4·(1—6)H2O+Mg(NO3)2·6H2O+MgSO4·7H2O+NaCl, MgSO4·(1—6)H2O+NaCl +MgCl2·6H2O+Mg(NO3)2·6H2O. Application of these phase diagrams were discussed for industry.
    Theoretical Study of Potential Energy Surface for the Reaction H+HCNO
    WANG Song1, YU Jian-Kang1,2*, DING Da-Jun2, SUN Chia-Chung1
    2008, 29(2):  365-368.  doi:
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    A mechanistic study of the reaction H+HCNO, in which the products Pi with i=1,2,3,4 are involved, is carried out with CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPVE to determine a set of reasonable pathways. It is shown, from the potential energy surface, that the P1(HCN+OH) is the major product channel, with a minor contribution of both P2(CO+NH2) and P3(CH2O+N), whereas the P4(CH2+NO) is less favorable. The present work can provide some useful information for the experimental studies.

    Investigation of Spectrum Shift of nπ* Transition for Acetone Molecule by Averaged Solvent Electrostatic Potential/Molecular Dynamics Method
    DU Tao1, ZHU Quan2, SHAN Min-Hua1*, LI Xiang-Yuan2*
    2008, 29(2):  369-373.  doi:
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    Instead of continuous medium theory, quantum mechanics/molecular dynamics method was adopted to deal with the electrostatic effect on the spectrum of the solute molecule by considering the concrete structure of solvent molecules. By constructing the external electric field felt with solute molecule and introducing the molecular polarizability of the solvent molecule, the mutual polarization between the solute and the solvent was taken into account and reasonable charge distributions of the solute and the solvent molecule were obtained. With a detailed deduction, we found that the spring energy of the permanent dipole of the solvent molecule was ignored unreasonably in the expressions of the solvation energy for equilibrium and nonequilibrium states. Including the energy contribution of this part, the new expression for the solvation energy and formulas for the spectral shifts of light absorption and emission were established. With the modified averaged solvent electrostatic potential/molecular dynamics program, the calculated spectral shift of the nπ* transition of acetone molecule in water is very close to the experimental value and the rationality of our new formula is testified.
    Quantitative Structure Property Relationship Study on pKa of Nonmetal Hydrides
    ZHANG Yun-Tao*, LI Li
    2008, 29(2):  374-379.  doi:
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    Tomasi′s Polarized Continuum Model(PCM) and ab initio method were applied to calculate quantum chemical parameters for HmA in water. Seven quantum chemical parameters, which were correlated with electronic density of the center atom A, were used to derive two equations of QSPR for the pKa of HmA by multiple linear regression(MLR) and stepwise regression(SR) respectively, and the correlated coefficient R and standard derivation s of the MLR and SR equations are 0.9984, 0.9947 and 1.7349, 2.3618, respectively. By the leave-one-out method prediction, the R and s of MLR and SR equation are 0.9689, 0.9895 and 7.5985, 3.3118, respectively. The results show that the SR equation, which is composed of three parameters, is the best in prediction, and the three parameters, NC(Net Charge), TP(Total Population) and ELUMO are the key factors affecting the acid intensity of HmA. The physical meaning and the influence of the three parameters on pKa of HmA were investigated. The study indicates that NC, TP and ELUMO are the main factors which affect the electronic density of center atom A; ELUMO and TP are the decisive factors affecting the change of acid intensity of HmA in the same group and period respectively.
    Theoretical Studies on Structures and Spectrocopic Properties for Iridium(Ⅲ) Complexes Based on Ligands Quinoline Derivatives and Acetylacetonate
    LI Xiao-Na1,2, FENG Ji-Kang1,2*, REN Ai-Min1
    2008, 29(2):  380-384.  doi:
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    Theoretical studies of electronic structures and photochemical properties were performed via DFT/B3LYP method on three Ir(Ⅲ) complexes, each of which contains two quinoline derivatives and a single acetylacetonate. Our calculation results indicate that the substitution of biphenyl and naphthalene instead of benzene can decrease PI and increase EA values, especially for complex 3, which can be used as the electron-transport materials and hole-transport materials. At the same time, this substitution can decrease the energy gap between HOMO and LUMO which leads to the red-shift of absorption spectra. The T1 state transitions are mainly HOMO→LUMO, and the process of phosphorescence emission of T1→S0 is the mixture of MLCT and LLCT.
    Theoretical Investigation on Rearrangement Mechanism of 2-(2-Methylallyl)-3-(3-methylbuta-1,2-dienyl) Cyclohex-2-enone
    ZHU Yuan-Qiang1, GUO Yong1, XIE Dai-Qian2*
    2008, 29(2):  385-388.  doi:
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    The sequential rearrangement mechanism from the 2-(2-methylallyl)-3-(3-methylbuta-1,2-dienyl)cyclohex-2-enone to form eight-ring membered compounds was studied at the B3LYP/6-31G(d,p) level. Two pathways were considered. The first pathway includes five processes while the second pathway undergoes only two processes. Both the two pathways have the same rate determining step of the [1,5]-hydrogen migration. In addition, the effect of toluene solvent was assessed by the polarizable continuum model. The calculation results indicate that the second pathway is favorable both in the gas phase and in toluene solvent.
    Theoretical Study of Excited States Properties of Phenyl Modified [Au(PH3)]+
    JIAO Yu-Qiu1, PAN Qing-Jiang1,2, ZHANG Hong-Xing1*
    2008, 29(2):  389-395.  doi:
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    The structures in ground and lowest-energy triplet excited states for [Au(PH3)]C6H5(a), 1,4-bi(AuPH3)-C6H4(b) and 1,3,5-ter(AuPH3)-C6H3(c) were optimized by the MP2 and CIS methods, respectively. It was shown that the introduction of [Au(PH3)]+ decreases the electron density around phenyl ring, which weakens the C—C bonding in the ring. The lowest-energy phosphorescences of a—c were predicted at 442.7, 461.3 and 428.9 nm by the CIS method, respectively. Comparison with that of benzene shows that the phosphorescent emissions of a—c exhibit the π*→π transition involved in the phenyl ring, accompanied by Au(6p)→Ph and Au(6p)→Au(5d) charge transfer transitions.
    研究快报
    Performance of Some Density Functional Methods in the Prediction of the Adiabatic Electron Affinities
    DING Xiu-Li, WU Jian-Ming*, XU Xin
    2008, 29(2):  396-398.  doi:
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    In this paper, we examined the performance of 12 density functionals(B3LYP, X3LYP, O3LYP, PBE0, B3PW91, BLYP, OLYP, OPBE, PBE, BPW91,VSXC and TPSS), combined with two basis sets[DZP++ and 6-311+G(3df,2p)] in the prediction of the adiabatic electron affinities against a set of 91 well-established experimental values. We have reached a conclusion that all these modern functionals are ge-nerally good, giving a mean absolute deviation(MAD) less than 0.24 eV. B3LYP and X3LYP are among the most reliable methods for this test set. When the DZP++ basis set is adopted, X3LYP is the best with a MAD of 0.14 eV, while B3LYP leads to a MAD of 0.16 eV. When the basis set is extended to 6-311+G(3df,2p), B3LYP improves its MAD to 0.13 eV, while the MAD of X3LYP remains to be 0.14 eV. Most hybrid functionals outperform the corresponding GGA functinals, with the exception of PBE0. The meta-GGA functionals(VSXC and TPSS) are not necessarily better than the GGA functionals. Our calculations also reveal that there are flaws associated with the OPTX exchange functional in the calculations of EA.
    研究论文
    Preparation of Carboxyl Monodispersed Colour Microspheres
    LI Qian, CHEN Xin-Fu, ZHANG Zheng-Pu*
    2008, 29(2):  399-403.  doi:
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    Monodispersed polystyrene microspheres with three distinct dyes and carboxyl group in the size range of 400—800 nm were prepared with seed polymerization and swelling, which affords a new method to combine the dyes with the microspheres. Monodispersed polystyrene seed was produced via emulsifier-free emulsion polymerization. It was swollen first by di-n-butyl phthalate(DBP), then by the mixture of styrene(St)-acrylic acid(AA)-divinylbenzene(DVB)-dyes including an oil-soluble initiator. The final microspheres were obtained via the polymerization of monomer mixture in the swollen seed microspheres at 70 ℃. The average size, size distribution and surface morphology of the final beads were characterized via SEM. The effects of the quantity of DBP, monomer and monomer proportion on the size distribution and surface morphology were discussed.
    Preparation of SiO2/Graft Copolymer Hybrid Nanopartciles by RAFT Copolymerization
    LIU Chun-Hua1,2, PAN Cai-Yuan1*
    2008, 29(2):  404-408.  doi:
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    By condensation reaction of the hydroxyl groups on the silica nanoparticle surface with coupling agent KH-560, epoxy groups were covalently attached to silica nanoparticles. The reversible addition-fragmentation chain transfer(RAFT) agent, dithiobenzoate, was anchored on the surface of the silica nanoparticles by the reaction of carboxylic acid in the RAFT agent, carboxypropyl dithiobenzoate with the epoxy group. The resultant RAFT agent was used in the surface RAFT copolymerization of styrene(St) and maleic anhydride(MAh) at room temperature, and SiO2/poly(St-alt-MAh) hybrid materials were obtained. Since MAh is highly reactive, poly(ethylene oxide) methyl ether(MPEO) was grafted onto the copolymers on the surface of particles via reaction of hydroxyl group in MPEO with MAh, forming SiO2/P[St-alt-(MAh-g-PEO)] composite particles. The composition, structure and morphology of the composite particles were confirmed via FTIR, TGA and TEM. This provides a new approach to graft biocompatible and hydrophilic PEO onto silica particles.
    Preparation of Temperature- and pH-Sensitive PVME/CMCS Hydrogels via Electron Beam Irradiation Cross-linking and Their Properties
    YU Yang1, YIN Jing-Bo1*, LUO Kun1, XIE Yong-Tao1, YAN Shi-Feng1, MA Jia2, CHEN Xue-Si2*
    2008, 29(2):  409-414.  doi:
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    Hydrogels based on poly(vinyl methyl ether) (PVME) and carboxymethylchitosan (CMCS) were prepared with electron beam irradiation(EB) cross-linking at room temperature. The effects of temperature, pH, CMCS content on the swelling properties of PVME/CMCS hydrogels were studied. The release behavior of a drug was tentatively investigated as well. The results show that the gel fraction of PVME/CMCS blend gels increases rapidly and then levels off above the radiation dose of 40 kGy, and it decreases with the increase of CMCS content in PVME/CMCS system. The hydrogels are thermo- and pH-sensitive, and show a fast swelling reversibility. At pH<3.0 and pH>5.0, the hydrogels have a higher swelling ratio; however, the swelling ratio is relatively lower in the pH range of 3.0—5.0 due to the electrostatic force. Increasing CMCS content and decreasing irradiation dose can improve the drug loading. The release of 5-fluorouracil can be governed by regulating the CMCS content and irradiation dose.
    Preparation of PANI/TiO2 Composite Nanofiber Materials by Interfacial Polymerization
    TONG Yong-Chun1,2, HU Chang-Lin1, WANG Qing-Yun1, BAI Jie1, LEI Zi-Qiang1, SU Bi-Tao1*
    2008, 29(2):  415-418.  doi:
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    PANI/TiO2 composite nanofibers were successfully synthesized by interfacial polymerization(IP). TEM, FTIR, XRD and TG were used to characterize the composite materials with regard to their morphologies, structures and thermal stability. The effects of the monomer concentration and the active treatment of TiO2 on the morphologies of the composite materials were investigated. The results show that TiO2 nanoparticles were inserted into the nanofibers and are more homogeneously dispersed in the PANI nanofibers and the stability of PANI was improved. For the interfacial self-assemble polymerization, its conditions are mild without employing/removing template approach and the product is easy to be handled and the yield is high.
    Synthesis of Amphiphilic Chitosan Derivatives and Their Self-aggregation Phenomenon
    WANG Zheng*, TU Chun-Ling
    2008, 29(2):  419-424.  doi:
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    A series of chitosan derivatives were synthesized via mPEG as hydrophilic group, sebacic acid as hydrophobic groups. Chitosan derivatives were characterized by FTIR, 1H NMR and XRD. The degree of substitution(DS) was calculated by elemental analysis(EA). Chitosan derivatives were dissolved in double-distilled water to form micelles. The morphology of polymer micelles was measured by transmission electron microscopy(TEM), and the size and distribution of polymer micelles was determined by dynamic light scattering(DLS). The critical aggregation concentration(CAC) was detected by a fluorescence technique using pyrene as a probe. It was found that the CAC was decreased by increasing the DS of acyl group, meanwhile, the size of polymer micelles was decreased.
    Preparation and Characterization of a Kind of New Radiopaque Sugar-containing Terpolymers
    WANG Xiang, GENG Xue, YE Lin, ZHANG Ai-Ying, FENG Zeng-Guo*
    2008, 29(2):  425-429.  doi:
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    A kind of new radiopaque sugar-containing terpolymers of poly[2-(2-triiodobenzoyl)oxoethyl me-thacrylate-co-2-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyloxy) ethyl methacrylate-co-methyl methacrylate] were synthesized via the radical terpolymerization in bulk. A study was carried out towards the effect of changing the monomer feed ratio and the content of the chain transfer agent on the molecular weight and mole-cular weight distribution of the terpolymers. Their detail chemical composition and structure were characterized via FTIR, 1H NMR and GPC analyses. The feed ratio change shows a little effect on the terpolymer molecular weight, while the decrease of the content of the chain transfer agent obviously increases its molecular weight. The molecular weight distribution is in a range of 2 to 3, in agreement with the radical polymerization principle. The resulting terpolymers indeed possessed the radiopacity altered with the sample thickness.
    研究快报
    Synthesis of Branched Polyethylene from Ethylene via in situ Copolymeri-zation Catalyzed by β-Diketonate Zirconium/AlEt2Cl/MAO
    HU Wen-Yan1, YANG Min1, ZHAO Xin2, LIU Bin-Yuan1, HAO Xiao-Yu1, YAN Wei-Dong1*
    2008, 29(2):  430-432.  doi:
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    A novel catalytic system to prepare branched polyethylene with single catalyst activated by two different co-catalysts is reported in this paper via the tandem catalysis, with ethylene as single monomer. Such catalytic system is composed of β-diketonate zirconium complexes, i.e.(acac)2ZrCl2(Ⅰ) and (dbm)2ZrCl2(Ⅱ) as catalyst precursors, diethylaluminium chloride(AlEt2Cl) as a co-catalyst for ethylene oligomerization and methylaluminoxane(MAO) as another one for the in situ copolymerization with ethylene. The oligomers obtained were mainly α-olefins, and the contents of them in weight were 76.84% for Ⅰ and 65.99% for Ⅱ, while the part being able to be copolymerized was 62.12% and 55.32% for Ⅰ and Ⅱ, respectively. The branched polyethylene via in situ copolymerization of ethylene was prepared by the tandem catalytic system Ⅰ/AlEt2Cl/MAO or Ⅱ/AlEt2Cl/MAO. 13C NMR spectrum reveals that the resultant copolymer was branched polyethylene with total branches of 2.1/1000C, including ethyl group of 1.2/1000C, butyl group of 0.8/1000C and longer branches of 0.1/1000C. With increasing the molar ratio of AlEt2Cl to MAO, the melting temperature of the polymer obtained decreased from 133.7 to 116.7 ℃ for Ⅰ/AlEt2Cl/MAO and from 131.7 to 118.8 ℃ for Ⅱ/AlEt2Cl/MAO as well as the change of crystallinity. The catalytic activities for catalyst Ⅰ/AlEt2Cl/MAO and Ⅱ/AlEt2Cl/MAO were from 2.48×104 to 0.10×104 g PE/(mol Zr·h) and from 1.00×104 to 0.32×104 g PE/(mol Zr·h), respectively. The results indicate that the branched polyethylene can be obtained by such a catalytic system.
    Preparation of Functionalized PLA with Pendant Carboxyl and Its Blood Compatibility and Cell Adhesion
    WANG Wei1, JIA Xiao-Hua1, LIU Yuan1, WANG Liang1, YUAN Zhi1*, TANG Shi-Ming2, LIU Min2, TANG Hua2
    2008, 29(2):  433-435.  doi:
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    Biodegradable α-hydroxyl polyesters, such as poly(lactic acid)(PLA) and poly(lactic-co-glycolic acid)(PLGA) were investigated as scaffolds for tissue engineering. However, polymeric materials on the basis of lactide are limited in blood vessel engineering due to their poor hydrophilicity and low affinity for the cells. In this study, the functional polylactide with pendant carboxyl(PLMACA) was synthesized, which was expected to improve the blood compatibility and cell adhesion of polyester based on PLA. The structure and composition of PLMACA were confirmed via 1H NMR spectrum and the compatibilities for blood and cell were stu-died. The results show that the PLMACA is hopeful to be used as blood vessel substitute with good HUVEC adhesion and anti-platelet adhesion.
    Synthesis and Structure Characterization of a Novel Electroactive Polyamide via Oxidative Coupling Polymerization
    CUI Li-Li, CHAO Dan-Ming, MAO Hui, ZHANG Wan-Jin*
    2008, 29(2):  436-438.  doi:
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    By oxidative coupling polymerization a novel electroactive polyamide, with fixed conjugated length of oligoaniline(amine-capped aniline pentamer) in the main chain, was successfully synthesized. The structure of the electroactive polyamide was confirmed via FTIR and NMR. The UV-Vis spectra were used to monitor the chemical oxidation process of the reduced polyamide. Moreove, its electrochemical behavior was investigated by cyclic voltammetry(CV) measurement. It was found that the obtained electroactive polyamide with amine-capped aniline pentamer segments had a quasi-reversible electrochemical property in the cyclic voltammetry, which was the same as polyaniline. Its electrical conductivity is about 1.24×10-6 S/cm at room temperature upon preliminarily protonic-doped experiment.