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10 November 2006, Volume 27 Issue 11

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高等学校化学学报2006年第27卷第11期目次

2006, 27(11):  0.  doi:

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研究论文

Synthesis, Structure and Magnetic Property of a Novel U(Ⅳ) Coordination Compound: UNa₂(pdc)₃·6H₂O

JIANG Yu-Sheng, BI Ming-Hui, LI Guo-Dong, CHEN Jie-Sheng


2006, 27(11):  2005-2008.  doi:

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Uranium is the most extensively studied element in actinide chemistry. In the past few years, many uranyl coordination compounds had been synthesized, whereas the report on the U(Ⅳ) cooridination compounds is much less. Here we reported the synthesis, crystal structure and magneticproperty of a novel U(Ⅳ) coordination compound UNa₂(pdc)_3^·6H₂O(H₂pdc=pyridine-2,6-dicarboxylic acid). The title compound crystallized in the monoclinic space group P2₁/n, with unit cell parameters a=1.0205(2) nm, b=2.2221(4) nm, c=1.2537(3) nm, β=94.98(3)°, V=2.8323(10) nm³, Z=4. The centered uranium atom is bonded to three pdc ligands via three nitrogen atoms and six oxygen atoms in a tricapped trigonal prismatic coordination. The temperature dependence of magnetic susceptibility reciprocal curve shows that the title compound has a paramagnetic behavior which obey to Curie-Weiss equation above 50 K(C=1.01 cm³·K·mol^-1, θ＝-63.21 K).

Synthesis and Temperature Sensitized Photoluminescence Property of Eu(Ⅲ)-Tb(Ⅲ)-Gd(Ⅲ) Hexafluoroacetylacetone Ternary Complex with Triphenylphosphine Oxide

ZHANG Yan¹, ZHAO Yu¹, LI Ye-Gen¹, SHENG Xia¹, HU Quan², QIAN Guo-Dong¹

2006, 27(11):  2009-2012.  doi:

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Ternary lanthanide hexafluoroacetylacetonate complex with triphenylphoshine oxide, Eu_0.4Tb_0.4Gd_0.2(HFA)₃(TPPO)₂(HFA=hexafluoroacetylacetonate, TPPO=triphenylphoshine oxide), was synthesized and identified by elemental analysis and FTIR. The photoluminescence(PL) spectra were measured and the characteristic transitions of Eu³⁺ and Tb³⁺ were observed. Temperature dependent PL properties of the ternary complex were also studied as well as the influences of Tb³⁺ and Gd³⁺ ions on PL properties of Eu³⁺ ions. As a result, the phonon assisted energy transfer from Tb³⁺ ions to Eu³⁺ ions, which enhanced the characteristic fluorescence intensity of Eu³⁺ ions at room temperature, was observed, and the sample exhibits different luminescent colors at different temperatures. The decay curves from the ⁵D₀ level of europium ions were measured at various temperatures and the lifetimes were obtained from fitting the data. It is seen that the lifetime decreases with increase in temperature. The complex is promising for being used as temperature detector and thermal-sensitive probe.

Research on Grafting Chiral Compound (+)-Dibenzoyl-L-Tartaric Acid to the Surface of SBA-15 Molecular Sieve


CAO Xi-Chuan^1,3, ZHANG Zhuo-Qi², Ketan Patel³, Michael W. Anderson³


2006, 27(11):  2013-2016.  doi:

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A sample of SBA-15 mesoporous silicate was synthesized and characterized by XRD and N₂ adsorption. It is confirmed from N₂ adsorption and ¹³C, ²⁹Si NMR techniques that the surface of SBA-15 was chemically modified with 3-aminopropyltrimethoxylsilane. According to integration of the curve of the ²⁹Si MAS(Magic Angle Spinning) NMR calculation it can be interpreted that about a quarter of the silonol(Si—OH) surface of the mesoporous material was modified. Under gentle conditions the optically active compound, (+)-dibenzol-tartaric anhydride, can be easily absorbed onto the surface of modified SBA-15 material. FTIR spectrum confirms that this absorption procedure results in covalently tethering to the silonol surface rather than just physical absorption. Subsequently, pore size distribution experiments reveal that the state of aminopropyl group absorbed onto the surface is in head to head position with a pore size of 4.00 nm. Whereas, when the (+)-dibenzoyl-tartaric acid was attached to the modified SBA-15 surface, it is orientated in a layered format over the SBA-15-(CH₂)₃NH₂ surface, resulting in a pore diameter of 3.50 nm.

Performances of Layered LiNi_0.5Co_0.5O₂ Prepared by Microwave\|solid Phase Compound Heat Method


YANG Shu-Ting^1,2, YUE Hong-Yun^1,2, YIN Yan-Hong^1,2, YANG Jin-Xin^1,2, YANG Wei-Guang^1,2, WANG Hui^1,2

2006, 27(11):  2017-2021.  doi:

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Layered cathode materials for lithium ion batteries, LiNi_0.5Co_0.5O₂, was prepared by microwave-solid phase compound heat method using polyacrylamide(PAM) as template. The effects of calcination temperature and time on the electrochemical performance, crystal structure and morphology of the materials were studied by using cyclic voltammetry, XRD, SEM techniques and charge-discharge test. The results show that the discharge capacity reaches 154 mA·h/g for the material(with pure layer structure) calcined at 750 ℃ for 4 h. And it was still above 148 mA·h/g after ten cycles. At the same time, morphology of the material synthesized under the same conditions was sphere-like, which contributed to increasing the density of electrode.

Synthesis and Characterization of High-pressure Metamorphic SiO₂ Minerals

SUN Jing-Shu¹, LIU Xiao-Mei¹, XU Da-Peng¹, SU Wen-Hui^1,2,3, ZHANG Guo-Qiang¹, WANG De-Yong¹, WANG De¹

2006, 27(11):  2022-2025.  doi:

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We suggest a new laboratory method for synthesizing coesite in the earth's crust by considering the similarity characteristics of local collisions and shearing strength between the earth's plates and high energy mechanical ball milling(MBM), combining the high-energy MBM and high static pressure and high temperature technique, and using mixtures of α-quartz and graphite as the initial material. The nanometer amorphous mixture of α-quartz and graphite was prepared by high-energy MBM. The lowest pressure and temperature for synthesizing coesite are 3.7 GPa, 970 K. The Raman spectrum of synthetic coesite possessed ten peaks located at 120, 152, 179, 206, 270, 329, 357, 428, 467 and 521 cm^-1. The obtained spectrum is coesite Raman spectrum with the most peaks among published results. The author attempts to look for useful information about the mineral circumstance of coesite in the Earth'surface and the mechanism of the ultrahigh-pressure metamorphism.

Preparation and Characterization of Mesoporous Y₂O₃ and Nd₂O₃ Films

WANG Tong-Wen¹, LIU Ling¹, LIU Wei-Ping², MA Zi-He¹, Yang Zhi¹, DUAN Ai-Hong¹, RUAN Qiong¹


2006, 27(11):  2026-2029.  doi:

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With poly(ethylene-co-butylene)-block-poly(ethylene oxide) block copolymer(PHB-PEO) as the template, mesostructured Y₂O₃ and Nd₂O₃ thin films were successfully synthesized through the well-documented evaporation-induced self-assembly approach. The obtained samples calcined at different temperatures were characterized in detail by using small- and wide-angle X-ray diffraction and transmission electron microscopy(TEM). The results show that our presented Y₂O₃ and Nd₂O₃ thin filmspossessed an Im3m body-centered-cubic(BCC) array of distorted spherical pores with an average p
ore diameter of about 11.5 and 12.5 nm, respectively. Furthermore, the partial crystalline pore walls can stabilize at 450 ℃. The investigation also indicated that a rapid self-assembly process is necessary to generate the mesoporous Y₂O₃ and Nd₂O₃ thin films. It can be achieved by the utilization of PHB-PEO template and the fast dip-coating process of evaporation-induced self-assembly.

Preparation and Electrical Properties of Composite Cathode Material La_1-xSr_xCuO_3-δ-SDC for IT-SOFCs

ZHENG Min-Zhang¹, LIU Xiao-Mei¹, ZHU Cheng-Jun¹, XU Dan¹, SUN Jing-Shu¹, SU Wen-Hui^1,2


2006, 27(11):  2030-2033.  doi:

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The cathode material La_1-xSr_xCuO_3-δ(x=0.15, 0.2, 0.3, 0.4) was synthesized by a sol-gel method. X-ray diffraction reveals that it is a single phase of perovskite. The investigation of the electrical properties suggest that La_0.7Sr_0.3CuO_3-δ has the highest electrical conductivity. La_0.7Sr_0.3CuO_3-δ powder was mixed with different amount of SDC(Sm_0.15Ce_0.85O_1.925) powder(5%—30%, mass fraction) as composite cathodes. Electrochemical properties of the composite cathodes were researched further. The investigation suggests the addition of appropriate amount SDC to La_0.7Sr_0.3CuO_3-δ can improve the electrochemical properties, and a better cathodic performance can be obtained. Using La_0.7Sr_0.3CuO_3-δ-SDC composite materials as a cathode based on SDC electrolyte higher current density and power density can be obtained at intermediate temperatures.

Synthesis, Crystal Structure and Characterization of Carboxylic Derivatives of Sulfonylcalix[4]arene


GUO Qian-Ling¹, QU Yi-Xin¹, MA Shu-Lan², ZHU Wen-Xiang²

2006, 27(11):  2034-2038.  doi:

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The lower-rim partially substituted sulfonylcalix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,26,27-tris[(ethoxycarbonyl)methoxy]-2,8,14,20-tetrasulfonylcalix[4] arene(L1) and 5,11,17,23-tetra-tert-butyl-25,26,27-tris(oxyacetic acid)-2,8,14,20-tetrasulfonyl calix[4]arene(L2), and the complexes of L2 were synthesized and characterized. The crystal structure of L1 was determined by X-ray diffraction. The results show that the composition of it is C₅₂H₆₅KO₁₈S₄·0.5H₂O. It belongs to triclinic crystal system, P1 space group, with a=1.2607(6) nm, b=1.5820(8) nm, c=1.648 0(8) nm, α=83.720(8)°, β=69.327(8)°, γ=79.342(9)°, Z=2, V=3.019(3) nm³, D_c=1.270 g·cm^-3, F(000)=121.8, μ=0.293 mm^-1, R₁=0.0937, wR₂=0.2580. The calix[4]arene adopts a partial cone conformation.

研究简报

Synthesis and Crystal Structure of a Three-dimensional Supramolecular Network [Cu₂(ETU)₆]SO₄ Based on Hydrogen Bonds

ZHANG Jing, ZHU Qin-Lei, HUANG Ru-Dan, FU Yin-Xia, HU Chang-Wen

2006, 27(11):  2039-2041.  doi:

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A novel coordination polymers [Cu₂(ETU)₆]SO₄(1)(ETU=ethylidene thiourea) was synthesized under solvothermal conditions. The crystal structure of the polymer was determined by X-ray diffraction: trigonal, space group R3c(No. 161), a=1.27509(8) nm, b=1.27509(8) nm, c=3.5747(7) nm, γ=120°, Z＝6, CCDC Number: 605501. In the structure of the polymer, each metal ion Cu(Ⅰ) coordinates to three S atoms attached to the ring of ETU forming two triangular pinwheel-shape monovalent cations [Cu(ETU)₃]⁺, in one of which the counter-ion SO^2-₄ is located. The ions with contrary charge, [Cu(ETU)₃]⁺ and SO^2-₄, are held together via the N—H…O hydrogen-bonded interactions resulting in a three-dimensional supramolecular network.

Preparation of Ag/SBA-15 Nanocomposite and Its Bactericidal Activity

CAI Xiao-Hui^1,2, ZHU Guang-Shan², GAO Bo³, ZHANG Wei-Wei², ZHANG Da-Liang², WEI Yu-Hong², QIU Shi-Lun², WANG Ce¹


2006, 27(11):  2042-2044.  doi:

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Silver nanoparticles were prepared in the channels of mesoporous silica SBA-15 through silver mirror reaction. The results of X-ray diffraction(XRD) and transmission electron microscopy(TEM) reveal that Ag nanoparticles with uniform size about 2—3 nm were dispersed inside the channels of mesoporous SBA-15. UV-Vis absorption spectra indicate the quantum size effect of the Ag nanoparticles. Bacteriological tests were performed in Luria-Bertani(LB) medium on solid agar plates and in liquid systems supplemented with different concentrations of Ag/SBA-15. This nanocomposite was shown to be an effective bactericide against Staphylococcus.

Hydrothermal Synthesis and Crystal Structure of a Novel Threedimensional Silver Coordination Polymer [Ag₃(IN)₂(CF₃COO)]

TIAN Ge, YUAN Hong-Ming, CHEN Yan, LI Guang-Hua, FENG Shou-Hua

2006, 27(11):  2045-2047.  doi:

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A three-dimensional silver coordination polymer, [Ag₃(IN)₂(CF₃COO)](IN=Isonicotinic acid), was synthesized under mild hydrothermal conditions and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P-1, with unit cell parameters a=0.91848(5) nm, b=1.01392(6) nm, c=1.06705(6) nm, Z=2, R₁=0.0365, wR₂=0.0955. The Ag centers are bridged by the IN and CF₃CO₂ ligands to form three-dimensional structure. There are strong Ag-Ag bond interaction in the framework.

研究论文

Determination of Wear Metals in Aviation Lubricating Oil by Using a Simultaneous MPT Spectrometer with an Automatic Reflux Extraction System

WANG Shu-Hua, FENG Guo-Dong, ZOU Xiang-Yu, JIANG Jie, HUAN Yan-Fu, DOU Wen-Chao, JIN Qin-Han

2006, 27(11):  2048-2051.  doi:

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A novel, simple and economic sample pretreatment system based on reflux extraction was developed for the determination of wear metals in the used aviation lubricating oil by using a simultaneous microwave plasma torch atom
ic emission spectrometer(MPT-AES). The operating parameters for both sample pretreatment and analysis were studied and optimized. The detection limits are 0.084, 0.043, 0.022, 0.052, 0.064 μg/g for Zn, Cd, Cu, Fe and Pb, respectively. The relative standard deviations are less than 5%(n=5), and the recovery ratios of these elements are in the range of 94.5%—107.4%. The new system was successfully applied to the analysis of the lubricating oil samples.

AMWFA Method Applied to Comparative Analysis of Two-dimensional Data with Overlapped Peaks

YI Lun-Zhao, LIANG Yi-Zeng, ZENG Zhong-Da, YUAN Da-Lin, WANG Ping

2006, 27(11):  2052-2055.  doi:

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In "OMICS" researches, comparison study of components present in different complex systems is very difficult because of the existence of many overlapped peaks. Herein, a new method, named alternative moving window factor analysis(AMWFA), was proposed, which is the combination and development of multicomponent spectral correlative chromatography(MSCC) and subwindow factor analysis(SFA). The method could be utilized to determine the number of common components of different samples and resolve overlapped peaks using the common selective information hiding in two data matrixes. The advantages of AMWFA are its extensive adaptability to the systems with no or only weak selective information, self-verified to the resolution results, no experienced user request. In this paper, the powerful ability of the proposed method has been proved by the group of simulated GC-MS data.

Differential Chronopotentiometric Stripping Method for the Determination of Purines and DNA Concentration Using an Electrochemically Pretreated Glassy Carbon Electrode

JIA Wen-Li, LI Tian-Hua, ZHANG Jing-Jing, WANG Huai-Sheng


2006, 27(11):  2056-2060.  doi:

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The differential chronopotentiometric stripping method wasused for the sensitive and selective determination of DNA and purines bases or the nucleosides concentrations in 0.1 mol/L phosphate buffer solution with pH=4.0 by using an electrochemically pretreated glassy carbon electrode. The results indicate that the electrochemically modified GCE could accumulate purines and ssDNA by effective adsorption and produce sensitive differential stripping peaks. The stripping peak heights(dt/dE) were linear with the concentrations of purine bases and denatured DNA in the suitable range. Some useful information related to DNA damage could be also acquired.

Studies on Ginsenoside Rb₁ and Rd Binding to Cytochrome c by Electrospray Ionization Mass Spectrometry

ZHANG Hua-Rong, ZHANG Han-Qi, WANG Yu-Tang, LI Dan, DING Lan

2006, 27(11):  2061-2065.  doi:

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Electrospray ionization mass spectrometry was applied to investigating the noncovalent interaction between ginsenosides and cytochrome c. Several noncovalent complexes with different stoichiometric relationships were observed from the mass spectra. The competition experiment was performed to validate the results. The dissociation constants of the complexes obtained by different systems are consistent with each other.

Studies on Paeoniflorin by Electrospray Ionization Tandem Mass Spectrometry

DONG Hong-Juan^1,2, LIU Zhi-Qiang¹, SONG Feng-Rui¹, YU Zhan¹, LI Hui-Lin¹, LIU Shu-Ying¹

2006, 27(11):  2066-2069.  doi:

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Paeoniflorin was studied by using Electrospray Ionization Tandem Mass Spectrometry(ESI-MSⁿ) both in positive and negative modes. Through the experimental method of hydrogen and deuterium exchange, the collision-induced dissociation fragmentation pathways were described and it proved that the precursor ion of paeoniflorin was clines to loss one molecule benzoic acid in both positive and negative MS² spectra, furthermore, the loss of glucose residue was observed in positive ion mode, while, only one formaldehyde molecule loss from C-6 of glucose was observed in negative ion mode. The established method could be used for the sensitive and rapid identification of monoterpene glycoside in Paeonia albiflora.

研究简报

Determination of Eugenol in Several Chinese Herbal Medicines by Capillary Electrophoresis with High Frequency Conductivity Method

LIN Wei-Feng¹, WU Xiao-Lin², CHEN Zuan-Guang³, LI Quan-Wen³, CAI Pei-Xiang¹, MO Jin-Yuan¹

2006, 27(11):  2070-2072.  doi:

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A method based on capillary electrophoresis with a high frequency conductivity method was developed for the determination of eugenol in several Chinese herbal medicines from different producing areas. In this study, some key factors for separation and detection were studied and the best analysis conditions were obtained. In the buffer system of 2.0 mmol/L triethylamine +0.74 mol/L methanol at separation potential of 18.0 kV, the optimal separation and detection wasobtained. Under the chosen conditions, eugenol was eluted within 7 min. The linear range of eugenol was 2.0—540 μg/mL, the limit of detection was 0.6 μg/mL, and the recovery ranged from 93.3% to 106%.

Chromatographic Characteristics of Valinomycin Used in Capillary Gas Chromatography as a New Stationary Phase

AI Ping, LIU Kai-Hua, ZI Min, QI Su-Hua, YUAN Li-Ming

2006, 27(11):  2073-2075.  doi:

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Fused-silica capillary column containing valinomycin and OV-1701(mass ratio 15∶85) as a new stationary phase component was prepared. The column was thermal stable below 176 ℃, the average value of McReynold constants was 157, and its column efficiency was 2083 plate/m when the retention factor was 2.20. Some aromatic positional isomers and chiral compounds, such as cresol, xylene, nitrotoluene, D,L-valine, D,L-leucine, (±)isopinocampheol, (±)roseoxide, (±)dihydrocaruvyl acetate were separated. It showed excellent selectivity toward aromatic positional isomers and chiral compounds.

Studies on the Cellular Uptake of SiNPs with Different Surface Charges

XING Xin-Li^1,2,3, HE Xiao-Xiao^1,2,3,4, WANG Ke-Min^1,2,3,4, PENG Jiao-Feng^1,2,3, TAN Wei-Hong^1,2,3

2006, 27(11):  2076-2078.  doi:

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The uptake of silica nanoparticles(SiNPs) with positive surface charge and negative surface charge by HepG cells, MCF-7 cells and L-02 cells were investigated by using the RITC doped in SiNPs as a synchronous fluorescent signal indicator. The experimental results show that the uptake of SiNPs by the three kinds of cells were all a concentration-, charge-, time-, and serum-dependent endocytic process. To the same kind of SiNPs, the uptake by the three kinds of cells all enhanced with increasing of the SiNPs concentration and incubation timeand gradually reached saturation. However, the effect of serum was different to the uptake of SiNPs with different surface charge. The results display that serum existed in culture medium decreased the cellular uptake of NSiNPs. Whilethe serum existed in culture medium would not affect the cellular uptake of PSiNPs. These results provide a theoretical foundation for the further modification of SiNPs, which could improve the stability of SiNPs in the medium and made it be well applied to biomedicine.

研究论文

Synthesis of Isophthalic Aldehyde Bis-arylthiosemicarbazone and Their Anion Recognition Properties

ZHANG You-Ming, REN Hai-Xian, WEI Tai-Bao


2006, 27(11):  2079-2083.  doi:

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Five new isophthalic aldehyde bis-arylthiosemicarbazone receptors were designed and synthesized. The binding properties of the receptors with anions such as F^-, Cl^-, Br^-, I^-, CH₃COO^-, HSO^-₄ , H₂PO^-₄ and NO^-₃ in DMSO were investigated byUV-Vis and ¹H NMR spectroscopy. A clear color change was observed from colorless to deep yellow upon addition of F^- and CH₃COO^- to the solution of the five receptors in DMSO. The results show that the five receptors had a better selectivity of F^- and CH₃COO^-, but had no evident binding with Cl^-, Br^-, I^-, HSO^-₄, H₂PO^-₄ and NO^-₃. It was regular that the five receptors had different binding abilities with F^- and CH₃COO^-. The UV-Vis data indicate that a 1∶1 stoichiometry complex was formed between the receptors and the two anions. ¹H NMR titrations and solvation effect confirmed hydrogen bonding interaction between the receptors and anions.

Property Analysis of Taxol-binding Site in β-Tubulin

LI Yao-Wu, ZHOU You-Jun, ZHU Ju, ZHENG Can-Hui, ZHANG Min, SHENG Chun-Quan, CHEN Jun, L<SPAN lang=EN-US style=

2006, 27(11):  2084-2087.  doi:

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Multi-copy simultaneous search(MCSS) was used to analyze the maps of four kinds functional groups(the hydrophobic, hydrophilic, positive charge and negative charge functionalities) in the taxol-binding site of the β-tubulin. Based on the result, the hydrophobic groups were distributed above Phe270, and thenamong Asp26, Glu27, Val23 and Pro358. While the hydrophilic functionalities scattered around the hydroxyl of Glu22, Asp224 and Asp26 and beneath the guanidyls of Arg276 and Arg282. The positive charge functionalities were around the carboxyl of Asp224, Asp26 and Glu22, and the hydroxyl of Gln278. The negative charge ones were beneath the guanidyl of Arg276 and Arg282, and between the sidechains of His22 and Leu228.

Preparation of Organicinorganic Nanoparticles Composite and Their Laccase Immobilization

HUANG Jun, WANG Jun-Tao, LI Bin, XIAO Hai-Yan, LIU Cheng, DING Li-Yun, JIANG De-Sheng

2006, 27(11):  2088-2091.  doi:

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CoTAPc-Fe₃O₄ nanoparticle composites were prepared by organic-inorganic nanoparticles complex technology and characterized by IR, XRD, EDS, field emission gun scanning electron microscopy and magnetometer. It is proved that the CoTAPc could disperse randomly onto the surface of Fe₃O₄ nanoparticles. The nanoparticles composites had the shape of spheres with the mean diameter about 70 nm. They had the coercive force of 316.4 A/m and were approximately superparamagnetic. The laccase was immobilized on the surface of the composite by crosslinking method. The optimal temperature and pH forthe laccase immobilization were 45 ℃ and pH 3.0, respectively. The immobilized laccase had better thermal, storage and operation stabilities than free laccase. This work provide a good basis for developing the fiber optic biosensor with excellent properties.

Synthesis and Biological Activities of 2-oxo-2-[1-(3-pyridylmethylamino)-1'-aryl]methyl-4-aryl-5,5-dimethyl-1,3,2-dioxaphosphinane

SUN Feng-Mei, SHI De-Qing, TIAN Man-Man, TAN Xiao-Song

2006, 27(11):  2092-2096.  doi:

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Nine novel title compounds were synthesized by the addition reactions of imines and cyclic phosphites, their structures were characterized by ¹H NMR, ³¹P NMR, MS, elemental analysis and X-ray diffraction analysis. Preliminary bioassays indicate that all thecompounds have good herbicidal activities and fungicidal activities to some extent.

Synthesis and Thermal Rearrangement of 1,2-Di(p-tolyl)-1,2-dimethyldisilanylene Bridged Bis(cyclopentadienyl)tetracarbonyldiiron

SUN Huai-Lin, ZHANG Hui-Li, MA Yu-Xi


2006, 27(11):  2097-2100.  doi:

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Cl₂MeSiSiMeCl₂(1) reacted with C₅H₅Li and subsequently with p-tolylmagnesium bromide to afford C₅H₅(p-Tol)MeSiSiMe(p-Tol)C₅H₅(2). The latter further reacted with Fe(CO)₅ gave the title complex [η⁵, η⁵-C₅H₄(p-Tol)MeSiSiMe(p-Tol)C₅H₄]Fe₂(CO)₂(μ-CO)₂(3). Meanwhile, two mono-silicon bridged by-products [η⁵, η⁵-(p-Tol)₂MeSiSiMe(C₅H₄)₂]Fe₂(CO)₂(μ-CO)₂(4) and [η⁵, η⁵-(p-Tol)Me₂SiSiMe(C₅H₄)₂]Fe₂(CO)₂(μ-CO)₂(5) were also obtained. Product 3 contains predominantly the cis isomer(3a), which was isolated inpure form by simple recrystallization. Compound 3a underwent the metathesis rearrangement reaction between Si—Si and Fe—Fe bonds under thermal conditions giving complex [η⁵-(p-Tol)MeSiC₅H₄Fe(CO)₂]₂(6). This product was a mixture of cis and trans isomers with a molar ratio about 4:3, demonstrating that the reaction does not involve a concerted process. The molecular structure of compound 4 was determined by X-ray diffraction method.

Synthesis and Anti-tumor Activities of a Series of Novel Tricycle Diterpenes

XIONG Yi¹, WANG Kui-Wu¹, PAN Yuan-Jiang¹, SUN Hong-Xiang²

2006, 27(11):  2101-2105.  doi:

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The tri-ring diterpenes with trans-configuration showed the antitumor potency from many previous inverstigations, but the research for the tri-ring diterpene with cis-configuration has not been regarded so far. During our chemical studies on the bioactive compounds from the plants, a novel tri-ring diterpene (+)-7-deoxynimbidiol which attracts our intensive interest for its good anti-tumor activity was isolated from Celastrus hypoleucus. cis-(±)-7-Deoxynimbidiol(compound 4), the diastereoisomer of (+)-7-deoxynimbidiol, was total synthesized via eight-step reactions with geranic acid as the starting material, and modified by etherification of the phenolic hydroxyl with the substituted benzyl bromide. Eight novel tri-ring diterpenes(compounds 5a—5h) were obtained. The anti-tumor activities of all the new compounds were evaluated. Compound 5d was found to have potency against the cultured human-tumor cell line MCF7(IC₅₀=7.49 μg/mL). The fluorine atom on the benzyl group was speculated to enhancethe anti-tumor activities.

Detection of Potato Spindle Tuber Viroid Using RNA Hybridized Chips

GU Yu^1,3, DU Zhi-You², LANG Qiu-Lei², CHEN Ji-Shuang², HE Nong-Yue³

2006, 27(11):  2106-2109.  doi:

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Potato diseases caused by potato spindle tuber viroid(PSTVd) bring about substantial losses in agricultural production. So developing a high throughput, rapid, sensitive and specific detection method is necessary. This article reports a new method to detect plant viroid——RNA glass slide hybridization. This method combines dot blot hybridization technique with cDNA microarray technique. We could spot a number of RNA samples extracted from new leaves of potatoes onto a silanated glass slide directly and then perform the hybridization on the slide with Cy5-labeled probe of PSTVd prepared by PCR. Analyzing the results of hybridization, we could ascertain which sample is infected by PSTVd. The factors affecting the results were optimized and used to test six potato samples with PSTVd-specific probes. The developed method was used to detect two samples which infected by PSTVd. These results were in good accordance with those from the RT-PCR approach and the samples are proved to be PSTVd by cloning and sequencing. So it is an accurate and reliable method for detecting plant viroid and the first report for the diagnosis of PSTVd using dot blot hybridization and RNA glass side hybridization with fluorescently labeled probe.

Preparation and Property Studies on Modified Hyaluronic Acid as Novel Glutathione Peroxidase(GPX) Mimic

CHEN Jia¹, ZHANG Bo-Xun¹, AN Yang², HONG Shui-Sheng¹, JIANG Guang-Zhi¹, FENG De-Ri¹, FANG Xiang-Yang², LIU Lan-Ying¹


2006, 27(11):  2110-2113.  doi:

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On the basis of the framework of hyaluronic acid(HA), two novel modified hyaluronic acid compounds, named as SeHA and TeHA, were synthesized to be functioned as mimics of glutathione peroxidase(GPX) by using the method of chemical modification. The structures of the two mimics were characterized by means of IR and NMR with the conclusion that the target —SeH and —TeH were located at —CH₂OH of the N-acetyl-D-glucosamine. After the new compound was prepared and purified, DTNB method was used to determine the selenium content in SeHA to be 1.2%. The GPX activities of the mimics with H₂O₂, tert-butyl hydroperoxide(t-BuOOH) and cumenyl hydroperoxide(CuOOH) as the substrates were measured, the result of which illustrates that CuOOH is the optimal substance of the mimics. In the steady-state kinetic studies, a ping-pong mechanism was observed from the data of the double reciprocal plots. All the results show that the mimics behaved similar to the native GPX. BHT and iodoacetate were applied to investigate the catalyzing mechanism of the mimic respectively. It is shown that the catalyzed mechanism is free radical and the mimic cannot be inhibited by iodoacetate.

研究快报

Synthesis of 4-Methoxybenzaldehyde Oxime in a Microfluidic Chip

MU Jin-Xia, YIN Xue-Feng, WANG Yan-Guang

2006, 27(11):  2114-2116.  doi:

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In this paper the design and development of a novel experiment system and method for organic synthesis in a microfluidic were described chip. The phase-transfer reaction for the synthesis of 4-methoxy-benzaldehyde oxime from 4-methoxybenzaldehyde and hydroxylammonium chloride was carried out in glass microfluidic chips by using a negative pressure system to control the transformation reactants through the microchannels at a constant flow rate. The effect of reaction time on the yield was determined and compared with the standard batch system. The demonstrated advantages of organic synthesis in microfluidic chip included faster reaction rate, less consumption of reactants and labor contaminant, which proved microfluidic chip to be a powerful tool for synthetic applications.

研究简报

Monitoring of Solid-phase Synthesis of 7-Fluoro-2H-1,4-benzoxazine-3(4H)-ones via FTIR Spectroscopy

HUANG Ming-Zhi^1,2, CHEN Wei-Min¹, HUANG Ke-Long³, HUANG Lu², YANG Guang-Fu¹

2006, 27(11):  2117-2119.  doi:

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The solid-phase synthesis of 7-fluoro-1,4-2H-benzoxazine 3(4H)-ones on Wang resin via esterification, etherification, reduction, cyclization and cleavage reactions was studied, and the reaction conditions were optimized after analyzing the reaction kinetics according to the IR spectrum.

A New Triterpene from Akebia Quinata Stem

LIU Gui-Yan¹, MA Shuang-Cheng², ZHENG Jian², YU Zhen-Xi², LIN Rui-Chao²

2006, 27(11):  2120-2122.  doi:

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To study the chemical constituents, the ethanol extract of dried stem of Akebia quinata(Thunb.) Decne. was seperated by dichloromethane, n-butanol in sequence. The n-butanol extract was further isolated by D101 macroporous resin and silica gel column chromatography. A new triterpene with two known triterpenes were isolated, their structures were identified as 3α,24-dihydroxy-30-norolean-12,20(29)-dien-28-oic acid (Ⅰ), 3α,24,29-trihydroxyolean-12-en-28-oic acid (Ⅱ), 2α,3β,23-trihydroxyolean-12-en-28-oic acid (Ⅲ). The new compound Ⅱ was nominated as quinatic stem acid. The structures were identified and elucidated by physicochemical properties and spectral analysis.

研究论文

In situ Electrochemical FTIR Spectroscopy of Adsorption and Oxidation Process of Methanol on PtRu/C Electrocatalyst

WANG Qi^1,2, SUN Gong-Quan¹, YAN Shi-You¹, WANG Guo-Xiong¹, XIN Qin¹, CHEN Qing-Song³, LI Jun-Tao³, JIANG Yan-Xia³, SUN Shi-Gang³

2006, 27(11):  2123-2127.  doi:

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A modified polyol process was used to prepare Pt/C, PtRu/C and Ru/C electrocatalysts. Calculated from XRD patterns, the mean particle size of PtRu/C electrocatalyst was 2.2 nm and the percentage of Ru alloyed was 71%, respectively. Adsorption and electrooxidation progress of methanol on PtRu/C electrocatalyst was investigated by in situ FTIRS, combined with electrochemical experiments. It is revealed that the activity of PtRu/C electrocatalyst for methanol oxidation was much higher than that of Pt/C. Addition of Ru in PtRu/C electrocatalyst changed the characteristic of methanol adsorption, and Ru—OH species could oxidize linear bonded CO(CO_L) at a lower potential, thus inhibited the catalyst poisoning. In addition, from FTIRs results, CO_L was evidently identified to the main poisonous species and the major product was CO₂. Methyl formate was also identified. Based on these results, the mechanism of methanol oxidation was discussed.

Electrochemical Temporo-organization in Pt-electrode BZ Reaction System Constrained by Temperature Controlling of Heat Compensation Type——From Limit Cycle Oscillation to Intermittent Torus-like Electrochemical Oscillation

ZHONG Dong-Hui, FAN Yu-Yu, LUO Jiu-Li

2006, 27(11):  2128-2131.  doi:

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Under the lab-condition of temperature controlled by heat compensation, the fictitious isothermal electrochemical oscillation in type of limit cycle will degenerate owing to the undulation of temperature in the range allowed by controlled accuracy. In this paper we show that the Pt-electrode BZ reaction system under the lab-condition of temperature controlled can be reduced to a three-variables dynamic system with two slow varying parameters. Furthermore, by a linearized stability analysis for the quasi-steady states of this kind of electrode reaction system on the slow-manifold, it turns out that in every undulating period of the temperature the corresponding quasi-steady state shuttle back and forth between both the oscillation regime and the non-oscillation regime a long with the slow variation of the temperature of the thermostat. As a result, a kind of intermittent torus-like oscillation will appear in this system. The argument formed in this paper was verified by computerized simulation.

Surface-enhanced Raman Spectroscopic Activity on Bare Nickel Electrode Roughened by Electrochemical Method

GU Wei¹, CUI Yan¹, LIU Guo-Kun², GU Ren-Ao¹, REN Bin², TIAN Zhong-Qun²

2006, 27(11):  2132-2135.  doi:

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Surface-enhanced Raman scattering(SERS) active Nickel electrode was roughened by electrochemical potential step technique combined with cyclic voltammetry(CV) in 0.5 mol/L NaClO₄ solution. It could be seen from the SEM images that uniform and nanometer level Ni particles which might induce an optimal SERS activity were produced on the Ni surface. Meanwhile, the studies of potential-dependent SERS of pyridine revealed that pyridine was interacted with Ni surface via N atom vertically because of the observation of in-plane vibration mode and Ni—N stretching vibration. Furthermore, the roughness factor of the Ni electrode was measured by comparing the differential capacitance of roughened surface with mechanical polished smooth surface, and thus the surface-enhancement factor(SEF) of the roughened Ni electrode was calculated in the range of about four orders, and it was one to two orders larger than that reported by the previous surface pretreatments.

Electrochemical Properties of Boron-doped Polycrystalline Diamond Films

LI Chun-Yan¹, PAN Kai², LU Xian-Yi¹, LI Ming-Ji¹, LIU Zhao-Yue², BAI Yu-Bai², LI Bo¹, JIN Zeng-Sun¹

2006, 27(11):  2136-2139.  doi:

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Boron-doped diamond films were deposited by EACVD(Electron Assisted Chemical Vapor Deposition) method in this paper. SEM, Raman spectroscopy and Hall effect measurements were employed to analyze the morphology, the growth mechanism, the carrier concentration and the electrical conductivity of the samples. The results show that the samples are high-quality polycrystalline diamond films composed of micrometer-sized grains. The carrier concentration and the resistivity of the samples are 4.88×10²⁰ cm^-3 and 0.03 Ω·cm, respectively. These diamond films were used as the electrochemical electrodes, and cyclic voltammetry was used to measure the current-voltage curves of the diamond electrodes in KCl solution, K₄Fe(CN)₆ solution, and CySH solution, respectively. The results show that these diamond film electrodes have a wide electrochemical window of about 3.7 V and a low background current close to zero in the aqua solution, and they have a high sensitivity and good stability in the biopreparates detection experiment, which makes boron-doped diamond film being an excellent material of electrochemical electrode.

Surface Enhanced Raman Spectroscopic Detection of Heavy Metal Ions

YUAN Ya-Xian, MA Jun-Yin, WANG Mei, YAO Jian-Lin, GU Ren-Ao

2006, 27(11):  2140-2143.  doi:

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The mercaptobenzoic acid (MBA) was served as the self-assemble modified and Raman-labeled molecules for the modification on a smooth gold surface and gold nanoparticles by self assemble monolayer method. By the interaction between heavy metal ions and the carboxyl groups from MBA attached to the gold surface and gold nanoparticles, the sandwich structure of "modified gold ubstrate/heavy metal ion/modified gold nanoparticles" was built for detection. The observation of nanoparticles in SEM images and the detection of surface enhanced Raman spectroscopy(SERS) of MBA in the sandwich structure indicated the existence of heavy metal ions in the solution. By using the strong chelation of EDTA with metal ions, the sandwich structure was immersed into EDTA solution to remove the heavy metal ions and the nanoparticles to obtain a fresh MBA modified gold substrate for the cyclic detection.

Electrooxidation of 3-Picoline in Acetone/Water Mixed Solvents

XU Yu-Ling, CAO Xue-Jing, ZHANG Heng-Bin, ZHANG Yu-Min, LI Ke-Chang

2006, 27(11):  2144-2147.  doi:

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In an electrolytic cell with proton exchange membrane as the diaphragm, it was found from the electrooxidation of 3-picoline at a PbO₂ electrode in acetone/water mixed solvents that the current density at the same anode potential not only increases remarkably, but also the selectivity and the current efficiency of electrooxidation from 3\|picoline to nicotinic acid increase obviously compared with the pure water as the solvent. Electrooxidation conditions of 3-picoline in acetone/water mixed solvents was studied, and the selectivity and the current efficiency under various conditions were compared.

Effects of Property of Primary Droplet on Micro-droplet Formation

LIANG Li-Hua¹, JIANG Ying-Lü¹, WANG Jia^1,2


2006, 27(11):  2148-2151.  doi:

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Micro-droplet formation was reported recently that a large amount of tiny water droplets formed around a primary droplet on a corrodible mental surface under suitably higher relative humidity, which may have a close relationship to the atmospheric corrosion initiation. The effect of the property of the primary droplet on the micro-droplet formation and the forming approach of the micro-droplets was investigated by using microscope observation and electrochemical techniques. The results show that no micro-droplets could be observed for the acidic primary droplet with pH value lower than 1, and the higher the pH value of the main droplet, the faster the micro-droplets formed, confirming the characteristic of the micro-droplets area with a higher pH value, higher potential and intensive oxygen reduction. In addition, phenolphthalein test and surface tension test proved that the micro-droplets could come from the adsorption and condensation of the water vapor around the primary droplet through the gas phase, instead of through surface spread from the primary droplet. It is under work whether the water vapor for the micro-droplets formation comes form the primary droplet or from humid air directly.

Chemiluminescence Oscillation in the Belousov-Zhabotinsky(B-Z) Reaction Catalyzed by Ru(bpy)²⁺₃ Complex

HAN He-You^1,2, HE Zhi-Ke², ZENG Yun-E²

2006, 27(11):  2152-2155.  doi:

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A new chemiluminescence oscillation in the Belousov-Zhabotinsky(B-Z) reaction(reduction of bromate by malonic acid) catalyzed by Ru(bpy)²⁺₃ is reported. The effects of concentrations of Ru(bpy)²⁺₃, KBrO₃, malonic acid and H₂SO₄ on chemiluminescence oscillation reaction were studied. The possible mechanism of chemiluminescence oscillation was also discussed. The chemiluminescence oscillation, which is due to the reduction of Ru(bpy)³⁺₃ by some strongly reducing radical with formation of the emitting excited state of Ru(bpy)²⁺₃, shows a very peculiar time behavior.

Quantum Chemical Investigation for Electronic Structure and Spectrum of F-substituted Alq₃ Derivatives: An Approach to Blue Luminescence of Alq₃ Derivatives

LIU Xiao-Dong^1,2, REN Ai-Min¹, FENG Ji-Kang^1,2, YANG Li¹, XU Hai^2,3, SHI Min-Min⁴, SUN Chia-Chung¹

2006, 27(11):  2156-2159.  doi:

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The ground state and electronic spectra in F-substituted Alq₃ derivatives [q=8-hydroxyquinoline], an important electroluminescent material, are studied by using density functional theory(DFT) B3LYP/6-31G in programme Gaussian 03. The effect of substituted position in Alq₃ on their energies, HOMO-LUMO gap and the electronic spectrum are discussed. It is found that F-substitutions in Alq₃ resulted in the decrease of both HOMO and LUMO energies, and the degree of such decrease in energy of HOMO and LUMO levels is dependent on the F-substituted position. Significantly, the HOMO-LUMO bandgap of 6-FAlq₃ is found to be increased, as a result, its absorption and emission spectra are greatly blue-shifted. The results obtained from the theoretical investigation was in agreement with the experimental ones, providing an approach to obtain the important blue luminescence Alq₃ derivatives.

Relaxation Modulus of PTFE Studied by Fractional Maxwell Model


CHEN Yan¹, CHEN Hong-Shan^1,2, KANG Yong-Gang¹

2006, 27(11):  2160-2163.  doi:

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The stress relaxation modulus of PTFE(polytetrafluorethylene) was studied by using fractional Maxwell model. The asymptotic solutions of fractional Maxwell model were assumed to be the starting point to decide the parameters(β, α, τ, E), but the relaxation time τ fitted by experimental data is in contradiction with the conditions of the asymptotic solutions. The principles for choosing the parameters were discussed. The relaxation exponent β and α (the order of the fractional derivatives) can be decided according to the relaxation behavior of the initial and terminal time respectively. Choosing the relaxation time τ properly, the modulus E can be determined by using the experimental data of the initial time. By optimiz
ing the parameters τ and α, the fractional Maxwell model can describe viscoelastic relaxation process very well. The relative error of the relaxation modulus of PTFE fitted by fractional Maxwell model is 0.64%.

TD-DFT Studies on Electronic Structures and Spectrum Properties for Tectorigenin and Tectoridin

WU Yin^1,2, WANG Jin-Feng², TENG Yun-Lei², MENG Xiang-Ying^1,2, BAO Yong-Li^1,2, BO Hua-Ben², LI Yu-Xin¹

2006, 27(11):  2164-2167.  doi:

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Tectorigenin and tectoridin were optimized by using ab initio HF and DFT B3LYP method, and the characteristics of the frontier molecular orbitals and the distribution of energy levels were analyzed. Time Depended Density Function Theory(TD-DFT) B3LYP and semi-empirical ZINDO method were employed to claculated electronic structure and spectrum properties of tectorigenin and tectoridin. It was found that the main absorption spectra originate from the π→π^* electronic transition among the molecules orbitals. The change on the molecular structure can affect the distribution of the frontier molecular orbitals of the titled compounds and change absorption spectra property, and make UV spectra red shift to withdrawing electronic group. The TD-DFT and ZINDO methods can be employed for the calculation of spectra properties of the compounds.

A Theoretical Study of Excited States of HO₂ Radical

LI Bu-Tong¹, WEI Zi-Zhang¹, PAN Qing-Jiang², ZHANG Hong-Xing¹, SUN Chia-Chung¹

2006, 27(11):  2168-2170.  doi:

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CASSCF and CASPT2 calculations on the HO₂ radical were performed in atom natural orbital basis sets(ANO-L and ANO-L⁺). The geometries for three electronic states are optimized at CASSCF level and the energies of these electronic states were located adiabatically at CASSCF, SS-CASPT2 and MS-CASPT2 level. The first excited energy were simulated as 0.779 eV vertically and 0.921 eV adiabatically. These data are consistent with those of the experimental values 0.74—0.88 eV, compared to the vertical energy of 1.12 eV from literature. Three Rydberg states and eleven valence excited states are located vertically in CASSCF, SS-CASPT2 and MS-CASPT2 levels. The lowest four low-lying electronic states are 1²A', 2²A' and 3²A' in the order of energy which disagreed with the former confirmed order X²A', A²A" and B²A'. Through discussing the discrepancies in detail the important significance of the dispersion orbital for the title molecule are confirmed.

Theoretical Study on the COCl₂…NH₃ and COCl₂…H₂S Complexes

WU Gong-Bing, YU Jian-Kang, WU Di, SUN Chia-Chung

2006, 27(11):  2171-2174.  doi:

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By means of ab initio calculations of MP2/aug-cc-pvtz method, the optimized geometries and frequencies of the COCl₂…NH₃ and COCl₂…H₂S complexes are obtained. The basis set superposition error(BSSE) was also considered according to the counterpoise(CP) method proposed by Boys and Bernardi. Four stationary structures of COCl₂…NH₃ and two stationary structures of COCl₂…H₂S were found. The found stationary structures can be divided into two types. In complexes Ⅰ, Ⅱ, Ⅴ the monomer lies with N(S)…C contact. In complexes Ⅲ, Ⅳ, Ⅵ the monomer lies with almost linear N(S)…Cl—C contact. The interaction energies of the first type are larger than the second type, so it's more stationary. Complex Ⅰ is the most stationary one in all of the six complexes.

Density Functional Theory Study on the Reactions of Pyrazole Derivatives with CH₃I

SHEN Fu-Gang, DUAN Wen-Yong, SUN Hong-Wei, CHEN Lan, CHEN Pei-Quan, LAI Cheng-Ming, LI Zheng-Ming

2006, 27(11):  2175-2178.  doi:

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Density functional(B3LYP) calculations, using the 6-31G* and LANL2DZdp ECP Polarization basis sets, were employed to study the reaction pathway involving 3-methylthio-4-cyano-pyrazole and iodomethane. According to the structure of pyrazole derivatives, two possible reaction pathways were examined. Pathway Ⅰ proceeded associated with the dehydrogenation of the reactants and the attack of CH₃I on both nitrogen atoms of pyrazole. Pathway Ⅱ was as follows: first, due to the hydrogen transfer of the reactants, two isomers are formed; then CH₃I attacks on nitrogen atom of the isomers to form intermediates; finally the intermediates dehydroiodinate to form two products. The results from the calculation suggest that pathway Ⅱ is the dominant reaction channel.

研究快报

Preparation of PANI Nanodots Array and the Coulomb Staircase Phenomena

WENG Shao-Huang, ZHOU Jian-Zhang, WEN Li, QI Li, CAI Cheng-Dong, YAO Guang-Hua, LIN Zhong-Hua

2006, 27(11):  2179-2181.  doi:

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PANI nanodots array was fabricated in AAO template with potentiostatic method in a short time. The topographic image of PANI nanodots array was characterized by scanning electron microscopy(SEM) and atomic force microscopy(AFM). The I-V characteristics of conducting PANI nanodots array was measured with conducting atomic force microscope(C-AFM) in atmosphere at room temperature. Coulomb staircase phenomena was observed in the I-V curves.

研究简报

Physical and Chemical Properties of Hydrophobic Imidazolium Ionic Liquid Mixtures

MA Liang-Liang, LIU Yi-Feng, YUAN Jun, WU Yi-Hua


2006, 27(11):  2182-2184.  doi:

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RTIL consisting of 1-methyl-3-butyl-imidazolium(BMIm) cation and bis(trifluoromethane sulfone) imide(TFSI) anion was mixed with 1-methyl-3-n-butyl-imidazolium hexafluorophosphate(BMImPF₆) at different ratios. Their room temperature conductivity, MS, LV were measured and the effect on association phenomenon by mixing is analyzed.The results demonstrate that the mixtures of ionic liquids can reduce the association degree of single ionic liquid with the better effect of properties, which mesans that the properties of the mixtures are not the average of single RTIL, but have a synergism effect.

Unusual Molecular Charge Property of Amphoteric Quinolones in Physiological Environment

SUN Jin, FAN Xiao-Wen, ZHANG Tian-Hong, HE Zhong-Gui

2006, 27(11):  2185-2187.  doi:

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In this paper the effect of the unusual molecular charge property of amphoteric quinolones, including grepafloxacin and olamufloxacin, on the binding to the negatively charged lipid membrane under the physiological conditions was investigated. The subtle pH variation around 7.4 can significantly change the molecular charge property of the two amphoteric quinolones, which results in a significant change of the electrostatic forces. The liposome/water system was undertaken to measure the drug-phospholipid membrane interactions. In the liquid-crystal liposome, the binding to membrane of the two quinolones was increased in the negatively charged liposome while decreased in the neutral liposome, with pH from 7.4 to 6.8. Similarly, the same tendency occurred in the gelstate liposome, that the binding to membrane increased in the negatively charged liposome from 7.4 to 6.8, mimicking drug transfer process from extracellular into intracellular fluid. In conclusion, the molecular electrical charge for amphoteric quinolones was very sensitive to pH variation around physiological pH, which may play an important role in the in vivo drug pharmacokinetics.

研究论文

Copolymerization of Acrylic Acid with Styrene in Supercritical Carbon Dioxide

CAO Xian-Fu^1,2, CHEN De-Hong^1,2, ZHANG Liang-Liang^1,2, XU Kai¹, CHEN Ming-Cai¹

2006, 27(11):  2188-2192.  doi:

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A series of hydrophobically associating polymers were synthesized in suppercritical carbon dioxide by copolymerization acrylic acid with different amounts of styrene at 65℃. The effects of the pressure of CO₂ and the concentrations of styrene were observed. The structure and compositions of the copolymer were determined by IR, UV and ¹H NMR spectra. The products were perfect white solid powder. Different pressures and contents of styrene led to different morphology of the products and yields. The conversion of each comonomer was above 90% when the mass fration of styrene in the comonomers was below 5% at 15—19 MPa and 65 ℃. The viscosities of aqueous solution of the copolymers showed an obvious dependence on pH and shearing time, which suggests that the copolymers can hydrophobically associate in aquatic solution.

Crystallization Behavior of Poly(L-lactide)-poly(ethylene glycol) Diblock Copolymers

WU Tong, HE Yong, WEI Jia, FAN Zhong-Yong, LI Su-Ming


2006, 27(11):  2193-2197.  doi:

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Poly(L-lactide)-poly(ethylene glycol)(PLLA-PEG) diblock copolymers were characterized by ¹H NMR, SEC, XRD and DSC. Depending on the composition, one or two melting peaks were detected although both components were intrinsically semi-crystalline. A copolymer with equivalent block lengths was selected for melt crystallization studies by DSC and POM. The experimental data were calculated with Avrami equation. On the other hand, the crystallization characteristics of PLLA-PEG were analyzed by using Lauritzen-Hoffmann theory. The nucleation constant K_g(POM) was found to be 5.23×10⁵ K₂ in the temperature range from 343 to 367 K. Both values of K_g and fold surface free energy σ_e of the copolymer are higher than those of the PLLA homopolymer, which suggests that the crystallization behavior of PLLA is affected by the presence of PEG block, nucleation being more difficult in the case of the copolymers.

Investigation on Isothermal and Non-isothermal Cryst allization Kinetics of Poly(ε-caprolactone)

MENG Yan-Feng^1,2,3, WEN Hui-Ying¹, LI Hong-Fei¹, TANG Yu-Jing¹, MEN Yong-Feng¹, JIANG Shi-Chun¹, AN Li-Jia¹


2006, 27(11):  2198-2203.  doi:

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The crystallization kinetics and the development of lamellar structure during the isothermal crystallization of poly(ε-caprolactone)(PCL) were investigated by means of differential scanning calorimetry(DSC) and real-time synchrotron small angle X-ray scattering(SR-SAXS) techniques, respectively. The Avrami analysis was performed to obtain the kinetics parameters. The value of Avrami index, n, is about 3, demonstrating a three-dimensional spherulitic growth on heterogeneous nuclei in the process of isothermal crystallization. The activation energy and the surface free energy of chain folding for isothermal crystallization were determined according to the Arrhenius equation and Hoffman-Lauritzen theory, respectively. In the process of nonisothermal crystallization of PCL, the value of Avrami index, n, is about 4, which demo
nstrates a three-dimensional spherulitic growth on homogeneous nuclei. In addition, lamellar parameters were obtained from the analysis of SR-SAXS data. The results indicate that long period and the thickness of amorphous layer firstdecrease and then keep constant with the increase of the crystallization time. At the same time, the long period increases with increasing the crystallization temperature, which is the same as the thickness of amorphous and crystalline layers.

Adjustment of Responsive Temperature and Loading Behavior of Temperature-sensitive Core-shell Micelles Prepared via in-situ Polymerization

REN Xian-Wen, JIANG Ming

2006, 27(11):  2204-2208.  doi:

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In-situ polymerization, which had been developed in our group, was employed to prepare thermo\|sensitive poly(D,L-lactic acid)/poly(N-isopropyl acrylamide-co-acrylamide)(PLA/PNIPAM-co-AM)core-shell micelles. The resultant micelles N₁₀₀, N₉₀ and N₈₀ were obtained in which the mass fractions of hydrophilic AM units in the feeds were 0, 10% and 20%, respectively. SEM, TEM and AFM were used to observe the morphologies of the micelles and the results confirmed the core-shell structure. The nanoparticles show a significant size change with the variation of temperature. The diameter of N₁₀₀ decreases from 207.3 nm to 140.1 nm when temperature increases from 27 ℃ to 41 ℃. The responsive temperatures of N₁₀₀, N₉₀ and N₈₀ were found to be 33, 41 and 56 ℃, respectively, which means that the responsive temperature of the micelles can be adjusted by changing the shell compositions. In addition, the dye-loading behavior of the nanoparticles was also studied.

Stability of a PPV Oligomer with Central Biphenyl Bridge and Peripheral Carbazole Substituents

SONG Xue-Liang, JIN Jia-Ke, DONG Hao-Yu, TANG Ben-Zhong, SUN Jing-Zhi


2006, 27(11):  2209-2212.  doi:

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An oligo(phenylene vinylene) with central biphenyl bridge and peripheral carbazole founctionalities was synthesized. The structure and purity were characterized by using ¹H NMR, MS and elementary analysis techniques. Thermal analysis data indicated that the obtained compound possessed both high chemical and morphological stability. The glass transition temperature was 142.05 ℃; the mass-loss temperature started at 306 ℃. The observed absorption features and X-ray diffraction patterns suggested an amorphous state of the spin-coating films, and the annealing treatment at 80 ℃ for 4 h did not change the amorphous property. The results above showed that the molecular design of introducing a central biphenyl bridge and bonding peripheral bulky carbazole functionalities can not only effectively decrease the aggregation of chromophores but also keep the stability of biphenyl bridged DSB derivatives.

In situ Polymerization of Ammonium Ion Monomers Intercalated in the Montmorillonite Template

FENG Li¹, YANG Mu², WANG Ge²


2006, 27(11):  2213-2216.  doi:

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The protonated forms of four ammonium salts(dimethyl diallyl ammonium chloride, DMDAAC; trimethylallyl ammonium chloride, TMAAC; acryloxyethyl trimethylammonium chloride, DAC; 2-methyl acryloxyethyltrimethylammonium chloride, DMC) were introduced into the interlayer region of montmorillonite template through ion-exchange reaction. X-ray diffractometry and FTIR spectra displayed that all the four monomers were intercalated into the layer region
successfully, but only two monomers undertook in situ polymerization. The different reaction activities of the four monomers were attributed to the different
space arrangement and steric hindrance of the monomers in the interlayer of montmonrillonite template.

Synthesis and Characterization of Soluble Poly[3-(ferrocenyl-ethyl formate)triethoxy]thiophene

ZHANG Qi-Xian, YANG Gui-Fu, SHAN Chang-Sheng, WANG Xiao-Dan, NIU Li


2006, 27(11):  2217-2220.  doi:

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Poly[3-(ferrocenyl-ethyl formate)triethoxy]thiophene was prepared by chemical polymerization with iron(Ⅲ) chloride as an oxidant. The resulting polymer is soluble in ordinary solvents, such as chloroform, tetrahydrofuran, acetone, xylene, etc.. The polymer structure was further confirmed by NMR and IR. The optical and electrochemical properties were examined by UV-Vis and PL spectroscopies and cyclic voltammetry. It exhibits a maximum of absorption at 553 nm and a maximum emission at 654 nm in chloroform solution, the doped polymers show two broad absorption peaks at 502 and 860 nm, which are characteristic of the presence of bipolarons. In addition, cyclic voltammetric measurements reveal that the ferrocene substituents remain a high redox activity and stability. Moreover, this resulting polythiophene derivative containing tetraethoxy units show a great selectivity and sensitivity towards sodium cation.

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2006年度国家自然科学基金化学科学部资助项目一览表

2006, 27(11):  2221-2242.  doi:

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