Table of Content

10 December 2006, Volume 27 Issue 12

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高等学校化学学报第27卷(1~12期)学科分类目次

2006, 27(12):  0.  doi:

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目次

高等学校化学学报2006年第27卷第12期目次

2006, 27(12):  0.  doi:

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研究论文

Intercalation Assembly and Luminescent Properties of a Novel Luminescent Supramolecular Composite Material, Eu(Ⅲ) Complex with Tetrapodal LigandMontmorillonite

JIANG Wei^1,2, TANG Yu¹, LIU Wei-Sheng¹, TAN Min-Yu¹

2006, 27(12):  2243-2247.  doi:

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Eu(Ⅲ) complex with tetrapodal ligand, [EuL(NO₃)]²⁺[L=1,1,1',1'-tetra(2-pyridinecarboxylester)-di(trimethylpropane)] was intercalated into the interlayer space of montmorillonite(MT) by ion exchanging, and a novel luminescent supramolecular composite material [EuL(NO₃)]²⁺-MT was obtained. Its composition and structure were characterized by elemental analysis, XRD and FTIR spectra. The luminescent property of the material was also studied. The results show that the intercalation composite material has a regular layered structure and good luminescent property. Under ultraviolet light the material could emit the characteristic red luminescence emission of Eu³⁺ strongly. The relative luminescence intensity, the monochromaticity and the luminescence lifetime of the Eu(Ⅲ) complex in the composite material are much better than those of the complex dissolved in ethanol solution. It is also found that the luminescent property and the stability of [EuL(NO₃)]²⁺ in the composite material are distinctly improved after it is intercalated into the MT. We deduce that the supramolecular interaction between the host layer and the guest complex ion and the rigid layered structure of the material may be the main reasons of this result.

Synthesis and Photoelectric Property of Four New D-A Compounds

YANG Sen-Gen, LIU Jian-Yong, WU Zhen-Yi, FAN Su-Hua, ZHAN Meng-Xiong

2006, 27(12):  2248-2251.  doi:

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In the present work, four new D-A compounds, H₂P_o-C₇₀, H₂P_p-C₇₀, ZnP_o-C₇₀ and ZnP_p-C₇₀ were prepared by 1,3 dipolar cycloaddition reaction of C₇₀. The new D-A compounds were characterized by UV-Vis, FTIR, ESI-MS, as well as elemental analysis. The results show that four novel types of covalently linked porphyrin-fullerene dyads were formed. The photovoltaic effect(PVE) of the new D-A compounds on GaAs electrode in electrochemical photovoltaic cell were measured. The results show that the values of ΔV and ΔI for H₂P-C₇₀/GaAs and ZnP-C₇₀/GaAs electrode are much greater than those for pure GaAs electrode. So that the photoelectric properties for the new D-A compounds are excellent. In addition, the photoelectric property of a H₂P-C₇₀/GaAs and ZnP-C₇₀/GaAs electrode is related to the thinkness of the sample film and the media.


Synthesis and Properties of Nanosized Tin-zinc Composite Oxides as Lithium Storage Materials

YUAN Zheng-Yong^1,2,3, YUAN Liang-Jie¹, SUN Ju-Tang¹

2006, 27(12):  2252-2255.  doi:

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The precursor was prepared with liquid precipitation method. A series of tin-zinc composite oxides with different components and structures were synthesized as the anode materials for lithium ion batteries when the precursor was pyrolyzed at different temperatures. The products were characterized by XRD, TEM and electrochemical measurements. The reversible capacity of amorphous ZnSnO₃ is 844 mA·h/g in the first cycle and the charge capacity is 695 mA·h/g in the 10th cycle. The reversible capacity of ZnO·SnO₂ is 845 mA·h/g in the first cycle and the charge capacity is 508 mA·h/g in the 10th cycle. The reversible capacity of SnO₂·Zn2SnO₄ is 758 mA·h/g in the first cycle and the charge capacity is 455 mA·h/g in the 10th cycle. The results show that amorphous ZnSnO₃ exhibits the best electrochemical property among all of the tin-zinc composite oxides. With the formation of crystallites in the samples, the electrochemical property of tin-zinc composite oxides decreases.

Crystal Structure and Fluorescence Property of Lanthanide Coordination Polymer {[Eu(2,5-PDA)(OAc)(H₂O)]·1.5H₂O}_n

LIU Chong-Bo¹, XIANG Li², LI Xin-Xin³, WEN Hui-Liang⁴

2006, 27(12):  2256-2259.  doi:

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The europium coordination polymer [Eu(PDA)(OAc)(H₂O)]_n·1.5H₂O(PDA=2,5-pyridinedicarboxylate, OAc=acetate) was synthesized by hydrothermal method, and characterized by single crystal X-ray diffraction and elemental analysis. The crystallographic data show that the complex crystallizes in a monoclinic system, space group P2₁/n, cell parameters a=0.935 01(15) nm, b=0.834 77(13) nm, c=1.677 9(3) nm, β=106.18°, V=1.257 8(3) nm³, Z=4, the final indentical factors [I>2σ(I)]: R₁=0.024 3, wR₂=0.060 5. One carboxyl group of PDA ligand and OAc ligand links two europium(Ⅲ) ions of two asymmetric units to form a dinuclear unit, while PDA ligands join dinuclear units from two directions, which are 88° and 56° dihedral angles with acetate ligands, respectively. Along the α-axis, a three-dimensional structure constructed by coordinated bonds is thus formed by PDA and OAc ligands, in which uncoordinated water molecules exist in the crystal via hydrogen bonds with coordinated water molecules. The photoluminescence property of the title compound was also investigated. The intensity ratio I(⁵D₀→⁷F₂/⁵D₀→⁷F₁) is ca. 1.44, which indicates that the Eu(Ⅲ) ion in the title compound is not located at the center of inversion.

研究简报

Synthesis and Crystal Structure of a Chainlike Coordination Polymer [Cu(en)₂]₂[Cu(en)₂α-As^Ⅲ₈V^Ⅳ₁₄O₄₂(HPO₄)]·8H₂O

LI Ya-Feng, ZHANG Li-Mei, LIU Chun-Lei, ZHANG Fan, ZOU Jin, SUN Jin-Xu, BAI Yuan, SUN Yan-Qun, TIAN Yong

2006, 27(12):  2260-2262.  doi:

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A novel coordination polymer, [Cu(en)₂]₂[Cu(en)₂α-As^Ⅲ₈V^Ⅳ₁₄O₄₂(HPO₄)]·8H₂O, was hydrothermally synthesized and structurally determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system, space group P2(1)/c, a=1.501 0(2) nm, b=1.860 9(3) nm, c=2.646 7(4) nm, β=102.169(5)°, V=7.227(2) nm³, Z=4, D_c=2.551 Mg/m³, F(000)=5 364. The structural refinement indicated that the tilted compound was a chainlike coordination polymer based on cluster [α-As₈V₁₄O₄₂·(HPO₄)]^6- as the building blocks. Two of the three Cu(en)₂ groups acted as the balance cation and the other one connected the anion cage [α-As₈V₁₄O₄₂(HPO₄)]^6- to form the 1D chain.

Synthesis and Crystal Structure of Azaanalog of Copper Phthalocyanine

JIANG Wen-Hai¹, WANG Xu², MA Chun-Yu³, YU Shu-Kun¹, YE Kai-Qi², CHANG Yu-Chun^1,3, DU Guo-Tong^1,3


2006, 27(12):  2263-2265.  doi:

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The azaanalog of copper phthalocyanine(aza-CuPc) complex C₂₄H₈CuN₁₆ was prepared by the so-lid phase synthesis technology and its single crystals was characterized by high power X-ray from the synchrotron radiation. The crystal belongs to monoclinic system, space group P2₁/n with a=1.612 3(3) nm, b=0.529 40(11) nm, c=1.906 4(4) nm, β=105.25(3)°, V=1.569 9(5) nm, Z=2, M_r=584.00, D_c=1.235 g/cm³, F(000)=586, the final R=0.063 1 and wR=0.153 9 for 757 observed reflections with I>2σ(I), GOF=1.340.

研究论文

Detection of Thrombin with a Novel Nano-biosensor Based on Aptamer Fluorescence

TU Yong-Hua¹, CHENG Gui-Fang¹, LIN Li¹, ZHENG Jing¹, WU Zi-Rong², HE Ping-Gang¹, FANG Yu-Zhi¹

2006, 27(12):  2266-2270.  doi:

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Thrombin is an important enzyme in physiology. It palys an important role in some physiological and pathological process, such as blood solidification, wound cicatrization and inflammation. Therefore, thrombin detection is very important in medicine. A novel nano-biosensor based on aptamer was designed and thrombin detection with sandwich-type based on magnetic separation was proposed. The equation of calibration plot is I=09758×1011c-668 in the concentration range of 2.24×10^-11—4.03×10^-9 mol/L and the detective limit is 1×10^-11 mol/L of thrombin. The relative standard deviation(n=10) was 2.56%. The fluorescence intensity obtained was very stable, even no attenuation observed after 24 h. The experiments results demonstrate that the proposed method possesses the feasibility, high specificity and sensitivity. It is also hopeful to be applied to the field of biomedicine.

Investigation of Thermodynamic Mechanism for Extraction of Active Constituents in Lycoris radiata and Rhizma Polygoni Cuspidati Using Microwave-assisted Extraction

FAN Hua-Jun^1,2, LIN Guang-Xin¹, XIAO Xiao-Hua¹, LI Gong-Ke¹

2006, 27(12):  2271-2276.  doi:

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The extraction mechanism of lycorine, lycoramine, galanthamine and resveratrol, emodin in two dissimilar plants namely Lycoris radiata and Rhizma Polygoni Cuspidati was investigated by using the closed microwave-assisted extraction(MAE), respectively. Solvent reflux extraction(SRE) was also performed for comparison study. A simple model was applied to calculate partition coefficients K, ΔH⁰, ΔS⁰ and ΔG⁰ of the constituents determined for MAE and SRE, and their thermodynamic behavior, chemical structures and polarities were further discussed. With the observation of scan electron microscopy, the cell microstructures of Lycoris radiata Herbert and Rhizma Polygoni Cuspidati were changed in MAE process. The results show that MAE and SRE were endothermic and entropy increase processes, the effects of microwave on cell led thermodynamic functions to greater change, MAE with the higher yields was more spontaneous than SRE.

Codes of DNA Primary Sequences and the Similarity Calculation

ZHANG Bao-Hua, WANG Hai-Shui, XU Lu

2006, 27(12):  2277-2280.  doi:

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The first exon of DNA primary sequence such as β-globin gene was translated into “structure graph” based on the rules suggested in this paper. Then the invariants, such as molecular connectivity indices, were extracted from those graphic representations of DNA primary sequences, and used to calculate the similarities among the ten species. From these similarities/dissimilarities the homologies can be revealed that they are in agreement]with the phylogenetic tree satisfactorily.


Resonance Rayleigh Scattering Method for Determination of Some Anionic Surfactants with Chlorpromazine Hydrochloride as Probe

YANG Qing-Ling^1,2, LIU Zhong-Fang¹, LU Qun-Min¹, LIU Shao-Pu¹

2006, 27(12):  2281-2284.  doi:

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In HAc-NaAc buffer medium with pH 3.0—5.0, Chlorpromazine can react with some anionic surfactants(AS) such as sodium dodecylbenzene sulfonate(SDBS), sodium dodecyl sulfate(SDS) and sodium lauryl sulfonate(SLS). As the result, the Resonance Rayleigh scattering(RRS) was enhanced greatly, and a new RRS spectrum appeared. The maximum RRS wavelengths of three anionic surfactants were located at 277, 369 and 277 nm, respectively. The method has a high sensitivity, the detection limits for three anionic surfactants are 0.018 μg/mL for SDBS, 0.046 μg/mL for SDS and 0.200 μg/mL for SLS. There is a linear relationship between the RRS intensity and the drug mass concentration in the range of 0.09—10.0 μg/mL for SDBS, 0.15—15.0 μg/mL for SDS and 0.67—12.5 μg/mL for SLS, respectively. In this work, the spectral characteristics of RRS, the optimum conditions of the reaction and the properties of analytical chemistry were investigated. A sensitive, simple and new method for the determination of anionic surfactants based on RRS was developed.

Selective Extraction and Separation of Non-residual Components in the Surficial Sediments(Surface Coatings) and Adsorption Characteristics of Cu and Zn

LI Yu^1,2, WANG Xiao-Li², ZHANG Zheng², GUO Shu-Hai³

2006, 27(12):  2285-2290.  doi:

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The selective separation of non-residual components of surficial sediments(surface coatings) was performed via chemical extraction techniques and then Cu and Zn adsorption to the non-residual components and residual component of surficial sediments(surface coatings) were investigated. The results indicate that 0.1 mol/L NH₂OH·HCl+0.1 mol/L HNO₃, (NH₄)₂C₂O₄-H₂C₂O₄ buffer solution and 30% H₂O₂ could remove Mn oxides, Fe/Mn oxides and organic materials from the non-residual components of surficial sediments(surface coatings) with the efficiency ranging from 63.15% to 97.59%, and the effects of extraction on non-target components were negligible. Cu adsorption to the surficial sediments(surface coatings) and the individual component of surficial sediments(surface coatings) were much greater than those of Zn, and the adsorption capability of surficial sediments was much smaller than that of surface coatings. Furthermore, Cu and Zn adsorption to the non-residual components of surficial sediments(surface coatings) were much greater than those to residual component, and that the greatest contribution to metals adsorption on a molar basis was from Mn oxides in the non-residual component. Metals adsorption capacities of Mn oxides exceeded those of organic materials by two orders of magnitude, and the estimated contribution of the residual component to metals adsorption was insignificant. These results imply that the role of surface coatings in transformation and cycling of heavy metals in aquatic environments was more important than that of surficial sediments, and the relative importance for controlling heavy metals in aquatic environments was attributed to metal(Fe and Mn) oxides.

研究简报

Establishment and Application of On-line Parallel-trap SFE-HPLC System

ZHANG Jie¹, LIANG Zhen¹, ZHANG Li-Hua¹, ZHANG Wei-Bing¹, HUO Yu-Shu², ZHANG Yu-Kui¹

2006, 27(12):  2291-2293.  doi:

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A novel on-line parallel-trap supercritical fluid extraction(SFE)-high performance liquid chromatography(HPLC) system was established. The interfere consisted of automated ten-port valve and parallel traps were used to carry out continuous and alternate trapping and transferring of the sample extracted with supercritical carbon dioxide, and HPLC was used to analyze the transferred sample. The novel on-line system was used to monitor the extraction process of fruiting bodies of Ganoderma lucidum. The extracts of six consecutive cycles were analyzed and the optimum extraction time was determined, which accorded with the result obtained with off-line extraction. Using this system, the whole process can be monitored and the optimum extraction time can be determined with single run. In addition, it has many other advantages, such as low sample loading, high sensitivity and accuracy, short analysis time, avoiding sample pollution and easily operation etc. The system shows a great potential in the extraction and analysis of the complicated samples including traditional Chinese medicine and environmental samples etc.

Voltammetric Behavior of Dopamine at dsDNA-modified Ni²⁺/poly(o-aminophenol) Carbon Paste Electrode

YANG Tao^1,2, JIAO Kui¹, YANG Jie¹, ZHAO Chang-Zhi¹, QU Wen-Ying¹

2006, 27(12):  2294-2296.  doi:

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The Ni²⁺/poly(o-aminophenol) electropolymerization was carried out by a continuous cyclic voltammetric scanning at a carbon paste electrode in a mixture of 0.02 mol/L o-aminophenol, 0.3 mol/L NiSO₄ and 0.6 mol/L HClO₄. dsDNA was linked to the conducting polymer via three-dimensional structure of polymer film and electrostatic attraction between the negatively charged phosphate backbone of DNA and Ni²⁺ ion. The results were testified by the electrochemical methods by using Co(phen)²⁺₃ as an electrochemical indicator. The currents of redox peaks of Co(phen)²⁺₃ increased after immobilizing dsDNA. The conditions for the preparation of Ni²⁺/P-OAP/CPE and DNA immobilization were optimized. The voltammetric behavior of dopamine was investigated at the modified electrode. It was found that the modified electrode exhibited a highly electrocatalytic activity toward dopamine oxidation. Differential pulse voltammetry was used for determination of dopamine in pH 5.1 phosphate buffer solution. A linear response of the peak current versus the concentration was found in the range from 5.0×10^-6 to 2.0×10^-4 mol/L with 1.0×10^-2 mol/L AA(ascorbic acid) coexisting. The presence of a high concentration of AA did not interfere with the determination. The proposed method exhibits a good recovery and reproducibility.

Labeling Analysis of Neuropeptides with 7-Methoxycoumarin-3-carboxylic Acid N-Succinimidyl Ester

LI Jun¹, LIU Xiang-Jun¹, ZHAO Rui¹, XIONG Shao-Xiang¹, MA Hui-Min¹, L<SPAN lang=EN-US style=

2006, 27(12):  2297-2299.  doi:

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Labeling analysis of three neuropeptides(Met-enkephalin, Leu-enkephalin, and neurotensin) with 7-methoxycoumarin-3-carboxylic acid N-succinimidyl ester(MCSE) was investigated. The experimental conditions for labeling reaction and HPLC analysis of the neuropeptide derivatives were optimized. It was found that the labeling reatction could be achieved at 37 ℃ for one hour in H₃BO₃-NaCl-Na₂B₄O₇ buffer(pH=83) with a labeling ratio of about 80%. The derivative mixture from the three peptides can be separated in a 40 min linear gradient from 60% to 20% of solvent A(100 mmol/L sodium acetate, pH=50) and from 40% to 80% of solvent B[60%(volume fraction) acetonitrile in water]. The resulting labeled products were also confirmed by MALDI-TOF-MS analysis. Compared with the native neuropeptides, the resulting labeled products have a longer absorption and fluorescence wavelengths, which is beneficial to the effective elimination of background fluorescence interference from biological matrix.

研究论文

Synthesis of 4,4-Diethylthio/benzylthio-but-3-en-2-one and Application as Odorless Thiol Equivalents in Thioacetalization

YU Hai-Feng^1,2, WANG Yan-Ru³, OUYANG Yan¹, WANG Yan¹, LIU Qun¹

2006, 27(12):  2300-2303.  doi:

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4,4-Diethylthio/benzylthio-but-3-en-2-ones 2 were prepared in excellent yields by the acid-catalyzed deacetylation of 3-(diethylthio/benzylthio)methylene-pentane-2,4-diones(1). With ketene diethylthio/benzylthioacetals(2) as the odorless thiol equivalents, in the presence of acetyl chloride, a series of diethylthio-/dibenzylthioacetals were prepared via the reaction of compound 2 with aldehydes/ketones in methanol under mild conditions.

Synthesis of a Kind of New Bivalent Ionic Liquids and Preliminary Study on Relationship Between Structure and Properties

ZHANG Qing-Shan, ZHAO Jun-Bo, GUO Bing-Nan, WU Feng

2006, 27(12):  2304-2307.  doi:

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As a new novel media for chemical reaction, room temperature ionic liquids(RTILs) are recognized and accepted, because of many novel properties which are shown on RTILs. Research on the multivalent ionic liquids has been less reported, so we designed and synthesized four kinds of new bivalent ionic liquids. The ionization between two molecular N-heterocyclic compound and one molecular 1,4-dibromobutane gave four kinds of bivalent ionic liquids, three of which were prepared by the treatment of 1,4-dibromobutane with morpholine, piperidine, and pyridine respectively, and the fourth one was synthesized firstly by the formation of N-methylmorpholinium cation using N-methyl morpholine and 1,4-dibromobutane following its future quaternary ammoniumization with pyridine. The melting points of dipiperidinium based salt are above 100 ℃, and the melting points of the rest are below 100 ℃. We calculated some properties of the bivalent ionic liquids, and hope that this will help the deep research on the relationship between structure and property of RTILs.

Design, Synthesis and Optical Properties of a New Type of Chiral Molecular Square with Double Helical Structure

AN De-Lie, ZHANG Ying-Jun, CHEN Qiang, ZHANG Zhi-Yang, YAN Hong, MENG Gui-Ying, CHEN Yan-Gui, ZHAO Wen-Ying, YU Zheng-Ying

2006, 27(12):  2308-2313.  doi:

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(R)- and (S)-2,2'-diethynyl-1,1'-binaphthyl with highly stable chiral configurations were used as the structural templates and linking bridges, and a new type of chiral molecular square with helical structure (R,R,R,R)-1 and (S,S,S,S)-1 were synthesized in enantiopure form via four steps including the introduction of protecting-group, intermolecular coupling reaction, removal of protecting group, and intermolecular cross-coupling cyclyzation. Compound 1 was characterized by MS, IR, ¹H and ¹³C NMR as well as elemental analysis. The specific rotations([α]²⁵_D) of the two isomers in CH₂Cl₂ are +887.3° and -889.7°, respectively, and their circular dichroism(CD) spectra represented exactly the mirror images of each other. These results reflected unambiguously enantiomeric relationship between the two isomers.

Catalytic Oxidation of Alkylbenzenes with Molecular Oxygen in Ionic Liquids

LIU Yao-Hua^1,2, CUI Peng¹, SUN Jing¹, YANG Fan¹, TANG Jie¹

2006, 27(12):  2314-2318.  doi:

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Using ionic liquid [Hex-mim]BF₄, [Bmim]BF₄, [Bmim]PF₆, and [Omim]BF₄ as the solvent, respectively, the oxidation of alkylbenzenes by molecular oxygen was investigated under atmospheric pressure with Co(Ⅱ), Mn(Ⅱ), or Ni(Ⅱ)/NHPI (or AIBN) as the catalysts. The [Hex-mim]BF₄/Co²⁺(or Mn²⁺)/NHPI system was demonstrated efficient for the oxidation of alkylbenzene. Under the optimized condition, ethylbenzene, n-propylbenzene, and n-butylbenzene were oxidized to the corresponding aromatic ketone with yields up to 90%, 94%, and 93%, respectively, toluene and p-substituted toluene were oridized to benzoic acid and the corresponding p-substituted benzoic acid with yields of 32%—47%. The ionic liquid and metal catalyst could be reused by removing water from them under a reduced pressure.

Stereoselective Synthesis and Study on the Stereochemistry of trans-2-Substituted-thiosemicarbazido-4-aryl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanes

FENG De-Xin, CHEN Ru-Yu, HUANG You

2006, 27(12):  2319-2323.  doi:

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1,3,2-Dioxaphosphorinane derivatives are an important class of organophosphorus heterocycles, which continue to attract considerable interest due to their unique stereochemical features and diverse potential biological importance. It has been found that the stereochemistry is important for the bioactivities of 1,3,2-dioxaphosphorinane compounds. Therefore, there is still a need for the development of a more simple and convenient method for the stereoselective synthesis of 1,3,2-dioxaphosphorinane derivatives. In this article, novel trans-2-substituted-thiosemicarbazido-4-aryl-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanes 5a—5j were synthesized via a series of reactions such as aldol-Cannizzaro, cyclization and addition and their structures are characterized by elemental analysis, ¹H NMR, ¹³C NMR and ³¹P NMR. Their epimers at the phosphorus atom were found by the isomerization in DMSO-d₆. This study gave a good explanation for the correlation between the configurational assignments and the chemical shifts of C4—H and ³¹P NMR.

Syntheses of (15R,16R,19R,20S,34S) and (15S,16S,19S,20R,34S) Aza-solamin

WANG Meng, SHEN Jing-Kang

2006, 27(12):  2324-2328.  doi:

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A convergent synthesis of two possible diastereomers of aza-solamin(threo-trans-erythro)(2a and 2b), which possessed pyrrolidine ring in place of THF ring of solamin, was accomplished. The key building block 5a and 9a were originated from chrial starting material. The stereochemistry of pyrrolidine core unit was determined by ¹H NMR spectroscopic analysis. The preliminary results of in vitro test against A-549 and HCT-116 cell lines show that both compounds have almost the same activity.


¹H Nuclear Magnetic Resonance Applied to Hepatic Fibrosis of Rat Liver Tissues

DENG Hui-Wen¹, FAN Ming-Xia², LI Jian-Qi¹, YU Yi-Hua¹

2006, 27(12):  2329-2333.  doi:

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The metabolite profiles from rat hepatic fibrosis were investigated by using high-resolution magic-angle spinning ¹H nuclear magnetic resonance(HR-MAS NMR) and principal component analysis(PCA) on the intact tissue. The metabolite characters of hepatic fibrosis were directly observed on ¹H NMR spectra by the elevated level of lipids, depleted levels of glucose, glycogen, taurine and inositol, and the decreased levels of choline(Cho) and glycerophosphocholine(GPC) compared with that of phosphocholine(PC). There was a dramatic tendency observed for the level of lipids from the normal to the aggravated stages of hepatic fibrosis, which ascended greatly at first and descended a little bit at the last stage. However, no evident changes of other metabolites in different hepatic fibrosis stages were observed. The results of PCA manifested that hepatic fibrosis tissue samples were separated well from those of the control and no obvious diversities were observed among the samples at different hepatic fibrosis stages.


研究简报

Acylation of α-Acetyl Ketendithioacetals with Acyl Chloride

YIN Yan-Bing^1,2, WANG Yan¹, ZHAO Yu-Long¹, TAN Jing¹, LIU Qun¹

2006, 27(12):  2334-2336.  doi:

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As a kind of versatile synthons, α-oxoketene dithioacetals have found their wide utilizations in organic synthesis. Owing to the interaction between two electron donating groups(RS) and an electron withdrawing group in the α position, the α-carbon atom of α-EWG ketene S,S-acetals shows a high nucleophilicity. In this paper, the reactions of α-acetyl cyclic ketendithioacetals with a series of acyl chlorides were performed and a new route to the C—C bond formation reaction at the α-carbon atom of α-oxoketene dithioacetals was described. By the above reactions, α-acetyl-α-acyl ketendithioacetals were prepared with good to high yields(55%—82%) via the acylation of α-acetyl cyclic ketendithioacetals at the α-carbon atom of α-acetyl ketendithioacetals mediated by titanium tetrachloride in dry dichloromethane at reflux temperature. The mechanism of the acylation between compound 1 and acyl chloride was proposed, which belongs to nucleophilic addition-elimination reaction.


Synthesis and Charaterization of Ru Complex with Terpyridine on Quartz Substrates Surface

ZHAO Jian-Ying^1,2, MA Li¹, JIN Ri-Zhe¹, GAO Lian-Xun¹

2006, 27(12):  2337-2339.  doi:

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The 6-carboxaldehyde-2, 2'∶6',2"-terpyridine was synthesized and assembled on the aminosilanization quartz substrate by the Schiff base interfacial group. Then the substrate was reacted with ruthenium and 6-bromo-2,2'-bipyridine to form a new Schiff base type Ru complexes. The process of the complexes assembled was characterized by UV-Vis absorption spectra and XPS. The film exhibited photoluminescence arising from π*-t_2g ligand-to-metal transition of Ru complex. From the fluorescent spectra, we observed the behavior of Ru(Ⅱ) complexes is greatly affected by the schiff base ligand. The novel Schiff base ligand Ru(Ⅱ) complexes exhibited strong and pure luminescent intensity. It was different from the other type ruthenium complexes. The result shows that there are many ralations between the structure and the properties of the complex.

研究论文

Microwave Assisted Synthesis of Emission-tunable ZnS∶Cu Nanocrystals

JIAN Wen-Ping, ZHANG Da-Wei, WANG Ling-Ling, ZHUANG Jia-Qi, YANG Wen-Sheng, BAI Yu-Bai

2006, 27(12):  2340-2343.  doi:

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Copper doped ZnS(ZnS∶Cu) nanocrystals were synthesized by using MPA(3-mercaptopropionic acid) as the stabilizer under microwave irradiation. XRD, UV-Vis and photoluminescence measurements were employed to study the crystal structure and optical properties of the ZnS∶Cu nanocrystals respectively. It was found that by varying the microwave irradiation conditions, the size of nanocrystal could be changed and the luminescence could be tuned continuously within the range from 460 to 572 nm. The photoluminescence properties of ZnS∶Cu were clarified by considering the quantum size effect.

Torus-like Chemical Oscillation Induced by Heat Conduction-diffusion Coupling Between Chemical Reaction System Characteristic of Multi-steady States Transitions and Related Environment

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

2006, 27(12):  2344-2348.  doi:

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With Schlögl model as the chemical reaction system characteristic of multi-steady states transition, new dynamic behavior induced by both the diffusion and the heat conduction between this kind of dynamic system and its coupled environment was studied systematically in which the torus-like chemical oscillation along with slow variable is of special importance. Furthermore, a linearized stability analysis for the quasi-steady state is also established. By means of it, the dynamic mechanism dominating the transition from the limit cycle to the torus-like oscillation becomes clear. It is a new kind of chemical oscillation, different from the discontinuous limit cycle oscillation originating from the small parasitic parameters.

Isobaric Vapor-liquid Equilibria of Binary System of Maleic Anhydride and Dimethyl Phthalate at 4.00, 8.00 and 12.00 kPa

XU Wei, ZHU Rong-Jiao, LIU Zhi-Hua, TIAN Yi-Ling, LI Dan

2006, 27(12):  2349-2352.  doi:

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Isobaric vapor-liquid equilibrium(VLE) data for the binary system of maleic anhydride(MAN)+dimethyl phthalate(DMP) at 4.00, 8.00 and 12.00 kPa were determined by using the ebulliometric method. Also, saturated vapor pressures of pure DMP were measured and Antoine constants were obtained. The parameters of the NRTL model for the binary system were obtained by calculating the equilibrium compositions of the liquid and vapor phase with the experimental equilibrium temperatures, pressures and feed compositions. Moreover, VLE data for the binary system were predicted by use of the UNIFAC model. The predicted results were compared with those from the ebulliometric method, and showed a good agreement.

Synthesis of MCM-41-HY Composite Molecular Sieves and Their Application to Deep Hydrodesulfurization

REN Jing¹, WANG An-Jie^1,2, LI Xiang^1,2, CAO Guang-Wei¹, LU Mo-Hong¹, HU Yong-Kang^1,2

2006, 27(12):  2353-2356.  doi:

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MCM-41-HY composite molecular sieves were synthesized hydrothermally, and characterized by means of XRD, N₂ adsorption and SEM. A comparison was made between the mechanical mixture of MCM-41 and HY, and the synthesized MCM-41-HY composite molecular sieves as the hydrodesulfurization(HDS) catalyst support. Both exhibit excellent activities in the HDS hydrodesulfurization of dibenzothiophene, but, the composite shows a much lower hydrocracking activity than the mechanical mixture. It is proposed that the lower hydrocracking activity of MCM-41-HY composite molecular sieves may be attributed to the bimodal structure in which HY zeolite is wrapped by the mesoporous MCM-41.

DFT Studies on Dehydrogenation Mechanism of Methane Activated by Gas-phase Niobium Cations

LI Jian-Hui, XIA Wen-Sheng, WAN Hui-Lin

2006, 27(12):  2357-2361.  doi:

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Density functional calculations were employed to investigate the quintet, triplet and singlet energies of methane direct- or inserted- dehydrogenation by gas-phase Nb⁺ as well as the influence of spin-inversion on the reaction mechanism. The results indicate that the inserted-dehydrogenation mechanism is more favorable than the direct-dehydrogenation. The minimum energy reaction path is thought to be related to the spin flip from 2S+1＝5 to 3, which decreases the activation barrier of methane-dehydrogenation significantly. The formed intermediate HNbCH⁺₃ is transformed into(H₂)NbCH⁺₂ via a four-centered transition state, and the final product is the triplet NbCH⁺₂+H₂. The rate determined step of reaction is the dehydrogenation of (H₂)NbCH⁺₂. In addition, the reactivities of gas-phase group V cations(V⁺, Nb⁺ and Ta⁺) towards the dehydrogenation of methane were also discussed.

Dielectric Spectroscopy of Nonconductive Microspheres Suspensions——Investigation of Relaxation Mechanism and Analysis of Interfacial Information

LI Jiao-Yang, ZHAO Kong-Shuang

2006, 27(12):  2362-2365.  doi:

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Dielectric measurement was carried out on the polystyrene(PSt) suspensions in electrolyte aqueous solution with different concentration. A couple of dielectric relaxations were found in frequency range from 40 Hz to 110 MHz. On the basis of dielectric model, theoretical analysis for the mechanism of the two relaxations show that low(kilohertz) and high-frequency(megahertz) relaxation were respectively attributed to the diffusion of counter ions in electrical double layer and to the accumulation of space charges on phase interface. Phase parameters and electric information of the microsphere interior were estimated from the relaxation parameters by using Hanai's equation, and reasonable explication was suggested. The validity of the model and method used in this work have been examined by theoretical calculation.

Conversion of Hydrocarbons over Nano-HZSM-5 Catalysts

ZHANG Pei-Qing¹, GUO Hong-Chen², ZHU Hong-Jie¹, WANG Xiang-Sheng², JIANG Xue-Mei¹, WANG Ping¹

2006, 27(12):  2366-2371.  doi:

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The nanoscale HZSM-5(20—50nm) catalyst was prepared, and characterized by XRF, TEM, NH₃-TPD and so on. The performance of the nanoscale HZSM-5 catalysts for conversion of n-octane, the mixture of n-octane and benzene was evaluated. The transformation behavior of both single and mixing hydrocarbons as the model reactants over the nanoscale HZSM-5 catalyst was investigated, the influences of the reaction conditions on product distribution were investigated, and reaction mechanism was also studied. The results indicate that the nanoscale HZSM-5 catalyst exhibits a higher ability to convert hydrocarbons, and the hydrocarbons were converted mainly into aromatics and iso-paraffins which have a high octane value by isomerization, aromatization, alkylation reactions and so on, as a result, the total amount of the iso-paraffins(C₄—C₆)and aromatics in products was above 90%(mass fraction). The aromatization from single hydrocarbons mainly produced benzene via dehydrocyclization process, whereas the aromatization from the mixing hydrocarbons formed alkyl-aromatics mostly by alkylation of benzene and small molecule hydrocarbons. The formation of benzene and C⁺₉ could be restrained by regulating the reaction conditions. The analysis of the products shows that the cracking, aromatization and isomerization reaction of hydrocarbons such as octane and benzene-n-octane over the nanoscale HZSM-5 catalyst followed the carbonium ion mechanism.


Density Functional Theoretical Study on the Potential Energy Surface of the Propene Hydrogenation Catalyzed by Metal Ir₄ Cluster

GENG Cai-Yun¹, LI Ji-Lai¹, SUN Guang-Ling², HUANG Xu-Ri¹, SUN Chia-Chung¹

2006, 27(12):  2372-2375.  doi:

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Using density functional theory(DFT), the reaction mechanism of propene hydrogenation catalyzed by metal Ir₄ cluster were explored in detail theoretically. At B3LYP level, the geometries of stationary points(reactions, intermediates, transition states and product) were optimized and the ground state potential energy surface was ploted. The calculated results suggest that for the propene hydrogenation catalyzed by metal Ir₄ cluster, the reaction may follow three reaction channels, which is c, d and e. In the major reaction channel c, the H-atom at Ir₁ site first transforms to intermediate 1 after surmounting TSR-1, followed by the addition of H-atom to the side C of propene, leading to forming intermediate isomer 3. After that, the H-atom at Ir₂ site can add to the middle C, passing through transition state TS3—5, intermediate 5 and transition state TS5-P respectively. Channel c is the most feasible reaction channel on the PES on both kinetic and thermodynamic considerations. As the highest transition states in channel d and e are a little higher than that of in channel c, they are less competitive and belong to minor channels.

Vapour Phase ortho-Selective Alkylation of Phenol with Methanol over Cobalt Chromite Catalyst

WANG Yan-Li^1,2, LIU Gang¹, JIA Ming-Jun¹, ZHU Xiao-Mei¹, ZOU Xiu-Jing¹, ZHANG Wen-Xiang¹, JIANG Da-Zhen¹

2006, 27(12):  2376-2380.  doi:

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The vapour phase ortho-selective alkylation of phenol with methanol was investigated over spinel-type cobalt chromite catalyst with K as the supported catalyst. The result shows that the relatively high reaction temperature is benefit to the improvement of the catalytic activities and the selectivity of 2,6-xylenol. With the decrease of weight hourly space velocity(WHSV), both the phenol conversion and the selectivity of 2,6-xylenol increase, while the selectivity of o-cresol decreases gradually, suggesting that 2,6-xylenol is the consecutive product obtained from the alkylation of o-cresol. Introducing a small amount of K species could result in the decrease of the phenol conversion and the selectivity to 2,6-xylenol, but considerable increase of the selectivity to o-cresol. The main reason should be due to the decrease of the relatively strong acidic sites on the K supported catalysts.


Investigation on Second-order Nonlinear Optical Property of Amino Acid Bridged Chiral Porphyrin Dimmer

YING Xiao¹, ZHANG Xin-Wei¹, LIAO Shi-Jun², LIU Hai-Yang², CHANG Chi-Kwong³

2006, 27(12):  2381-2385.  doi:

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Geometries of amino acid bridged bis-porphyrin 1,2,3,4 and their zinc(Ⅱ) complexes were optimized at semiempirical PM3 quantum chemistry level. Static second-order NLO coefficients of these bis-porphyrins were then calculated by TDHF/PM3 method. The calculation results show that all L-type amino acid bridged bis-porphyrins exhibit right-handed helix structures. Within the electric-dipole approximation, second-order NLO coefficients β of these bis-porphyrins change little with the varying of amino acid side chains. However, the second-order NLO chiral components β_xyz of amino acid bridged bis-porphyrins are significantly different. The chiral component β_xyz and the helix structure parameter r²ζ/L⁴ matches β_xyz∝r²ζ/L⁴, indicating the second-order chiral NLO response of helix chiral bis-porphyrins could be well described by one-electron helical model theory. The analysis of β components indicates that these amino acid bridged bis-porphyrins are multipolar molecules with ‖β_J=3‖/‖β_J=1‖≈11—17. In comparison to free-base helix bis-porphyrin, the insertion of Zn(Ⅱ) ion favors the accretion of the second-order NLO dipolar component and chiral component β_xyz of molecules.

Theoretical Study on Anchimeric Assistance on the Second Electrophilic Region of Carcinogenic β-Methylnitrosopiperazine

ZHAO Li-Jiao, ZHONG Ru-Gang, DAI Qian-Huan

2006, 27(12):  2386-2389.  doi:

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The anchimeric assistant mechanism of the second electrophilic region on β-methylnitrosopiperazine was studied by using ab initio and density functional theory(DFT) method with the 6-311G(d) basis set. The results show that the anchimeric assistance of N' atom on the piperazine ring or the oxygen atom on the N'-substituted group enhances the reactivity of β-methylnitrosopiperazine metabolites, which can be used to explain the phenomenon that the carcinogenicity of methyl substituted N-nitrosopiperazines is much more potent than that of their parent compounds. This research provids a theoretical evidence for the formation of the second electrophilic region on the γ-positions of N-nitrosopiperazines in their carcinogenic metabolism.


A Theoretical Study on the Potential Energy Surface of the Reaction ^·C₃H₅+NO


ZHANG Hao, SUN Yan-Bo, LI Ze-Sheng, SUN Chia-Chung

2006, 27(12):  2390-2393.  doi:

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In this article, the singlet potential energy surface of the reaction ^·C₃H₅+NO was studied at CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p) levels. The most favorable pathway leading to the product P1(CH₃CHO+HCN) is as follows: R(CH₃CHC^·H+NO)→m1(trans-CH₃CHCHNO)→m2(cis-CH₃CHCHNO)→m8(CCNO four-member ring)→P1(CH₃CHO+HCN). In the title reaction, other products P2(CH₃CHO+HNC), P3(H₂CO+CH₃CN) and P4(CH₃CCH+HNO) have also lower energies than the reactant, but the pathways leading to these products are all unfeasible in dynamics so that they are minor product channels. The comparison with the analogous C₂H₃+NO reaction was discussed. The two systems were analogous in the channels leading to the most favorable products P1 except that the former is feasible in kinetics and the latter is opposite.


Preparation of High Alloying Pt-Ru/CMK-3 Catalysts at Room Temperature and Electrocatalytic Oxidation of Methanol

WU Wei¹, CAO Jie-Ming¹, CHEN Yu², LIU Jin-Song¹, CAO Yu-Lin¹, FANG Bao-Qing¹, HE Jian-Ping¹, TANG Ya-Wen², YANG Chun², LU Tian-Hong²


2006, 27(12):  2394-2397.  doi:

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High-alloying Pt-Ru solid solution was prepared by complexing reaction and uniformly dispersed on rigid ordered mesoporous carbon CMK-3 to form the two-element composite catalysts. XRD patterns show that Pt atoms with fcc structure were almost replaced by Ru atoms with hcp structure. XRD and TEM measurements indicate that the average diameter is 2.7 nm with a uniform size. The electrocatalytic activity of Pt-Ru/CMK-3 for the ethanol oxidation was studied and compared with that of Pt-Ru/XC-72 of E-TEK congeneric catalyst. The results show that the catalyst of Pt-Ru/CMK-3 possesses a bigger electrocatalytic activity area, the electrocatalytic activity for the oxidation of methanol and the ability of resisting CO poison exceed the same kind catalysts because of the appropriate extent of alloying and average particle diameter.

DFT Studies on the Second-order Nonlinear Optical Properties of [M₆O_m(C₂₅N₄H₁₈)_n]^2-(M=W, Mo; n=1, 2; m=1

SHI Shao-Qing, YANG Guo-Chun, DOU Zhuo, SU Zhong-Min

2006, 27(12):  2398-2401.  doi:

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The geometries of Lindqvist polyoxometalates bonded with terpyridine ligands(systems 1—4) were optimized by using DFT. The optimized main bond lengths are found to be in good agreement with experimental values. On the basis of the stable structures, the second-order nonlinear optical properties were calculated by using DFT/LB94 under the zero field condition. The β_vec values of systems 1 and 2 are 154.4×10^-30 and 124.8×10^-30 esu, respectively. These results indicate that systems 1 and 2 have larger nonlinear optical properties. The β_vec value for systems containing Mo atom is larger than that of systems containing W atom. With increasing of the number of the segment, the β_vec value increases remarkably. The β_vec of the system 1 is larger than that of system 2. The β_vec of system 3 is larger than system 4. Moreover, the β₃ and β₄ are larger than β₁ and β₂, respectively. But, there is not the obvious multiple relationships between the β_vec value and the number of the segment.


研究简报

Electrochemical Properties of Natural Graphite Anodes in Room Temperature Ionic Liquid Electrolyte

ZHENG Hong-He¹, QU Qun-Ting¹, ZHOU Ke-Lei¹, WANG Jian-Ji¹, Abe Tekeshi², Ogumi Zempachi²

2006, 27(12):  2402-2404.  doi:

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Electrochemical properties of a natural graphite anode in ionic liquid and organic electrolytes was comparatively investigated. The results reveal that the organic cation reversibly inserted into and deinserted from graphene interlayer. The addition of chloroethylenene carbonate(Cl-EC) resulted in significant electrochemical enhancement. The mechanisms responsible for the electrochemical enhancement were discussed through ac impedance, SEM, and FTIR measurements.

Controlled-hydrolysis of [PtCl₆]^2- Studiedwith 1st Derivative Spectra

YU Ying-Tao^1,2, WANG Jing¹, YANG Hai-Jun², XU Bo-Qing²

2006, 27(12):  2405-2407.  doi:

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The aquochloro ligand exchange between [PtCl₆]^2- and H₂O is an important factor to regulate the facet growth in shape-controlled synthesis of Pt nanocrystals because the electric charge and coordination structure of Pt precursor strongly influences its adsorption and reduction on Pt nanocrystal surface. In this contribution, the exposure to violet light(415 nm) is found to efficiently weaken the characteristic LMCT absorption and increase the conductance of 1.5×10^-4 mol/L K₂PtCl₆ aqueous solution that is fairly stable in dark aging. And, the variations of both the LMCT adsorption and the conductance are closely related with the exposure time. The 1st derivative spectra of ultraviolet absorption shows that the characteristic LMCT absorption shifts toward shorter wavelength along with the exposure which is mainly attributed to the aquochloro ligand exchange of [PtCl₆]^2-.

Effect of Iodine-doping on Photocatalytic Activity of TiO₂ Photocatalyst

WEN Chen, SUN Liu, ZHANG Ji-Mei, DENG Hua, WANG Peng

2006, 27(12):  2408-2410.  doi:

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Iodine doped nanocrystalline TiO₂ photocatalyst was prepared by sol-gel method. The results show that crystallinity of anatase was improved upon iodine doping, and iodine not only suppressed phase transition anatase to rutile, but also exhibited an absorption in the wave length range of 400—550 nm. The photocatalytic activity of I-doped TiO₂ photocatalysts(500 ℃) exceeded that of pure TiO₂ photocatalyst prepared by the same method when the molar ratio of HIO₃ to Ti was kept in the range of 0.05—0.20.


Construction and Photoelectrocatalytic Properties of TiO₂ Nanotubes Arrays on Titanium Substrates


LIU Ping¹, LI Xin-Yong¹, WANG Yu-Xin¹, JU Xiao-Dong¹, CHEN Guo-Hua²

2006, 27(12):  2411-2413.  doi:

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In this paper, vertically aligned nanotubes arrays of titanium oxide were fabricated on the surface of titanium substrate by direct anode oxidation with HF being the supporting electrolyte. Under the condition of applying the same bias on the electrodes, a higher anodic photocurrent of the TiO₂ nanotubes electrode was obtained than that of TiO₂ film electrode, which is due to the larger specific surface area, novel microstructure and higher efficient surface-interface electron migration of nanotube electrode. The degradation of a textile azo dye, Acid Orange 7(AO7), in aqueous solution with TiO₂ nanotubes electrode was carried out using photoelectrocatalytic(PEC) process, comparing with electrochemical process(EP) and photocatalytic(PC). A significant photo-electrochemical synergetic effect was observed. The reason is attributed to the surface state characteristics and higher separation efficiency of photo-generated charge carrier of nanotube system.

Attenuated-total-reflection Surface-enhanced Infrared Absorption Spectroscopy on Cadmium Electrode

LI Qiao-Xia¹, YAN Yan-Gang¹, XU Qun-Jie², CAI Wen-Bin^1,2

2006, 27(12):  2414-2416.  doi:

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Surface-enhanced IR absorption spectroscopy in attenuated-total reflection(ATR-SEIRAS) configuration was extended for the first time to a cadmium electrode with the adsorption of pyridine as the model system. The SEIRAS active Cd film electrode was prepared by electrodeposition of Cd mulitlayers onto a underlying Au nanofilm on Si in 0.01 mol/L CdSO₄ +0.1 mol/L KClO₄. The morphology of the as-prepared Cd film exhibits an island structure. In the potential range of -1.2 to -0.8 V(vs. SCE), only in-plane vibrations belonging to the A₁ symmetry were detected whereas those to the B₁ symmetry virtually were not, suggesting that pyridine coordinates vertically or at a little angle to the Cd electrode surface via its nitrogen end without edge-tilted rotation of its ring plane. The Py adsorption configuration is closed to that found on a Au electrode, but different from that on a Ni or Pt electrode, which may be assigned to different structures of valence electron shells for the substrate metals.

研究论文

Structure and Characteristics of Polyampholyte Super-absorbent Nanocomposite

XU Kun^1,2, CHEN Qiang^1,2, XIANG Sheng^1,2, YUE Yu-Mei^1,2, ZHANG Wen-De¹, WANG Pi-Xin¹

2006, 27(12):  2417-2421.  doi:

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A novel polyampholyte super-absorbent nanocomposite with acrylate sodium, acryloyxyethyl trimethyl ammonium chloride(DAC) and montmorillonite(MMT) was synthesized by in situ solution polymerization in aqueous solution. The morphology structures of composites were investigated by XRD and TEM. The results show that a series of intercalated polymer-MMT super absorbent nanocomposite were produced. Due to the introduction of MMT, the swell ratio of nanocomposite was up to 2 380 g/g and the gel antipressure intensity was enhanced by 180%. In the same time, the investigation indicates that the formation of intercalated nanocomposite was promoted by the addition of DAC owing to the strong interaction between DAC and the platelets of MMT. On the other hand, the sensitivity of ampholyte composite to pH could be observed when the polyampholyte super-absorbent nanocomposites were soaked into NaCl solution with a mass fraction 09% at different pH values.

Effect of Crosslinker Content on the Properties of the Micelles Prepared via in situ Polymerization and Preparation of Hollow Spheres

REN Xian-Wen, JIANG Ming

2006, 27(12):  2422-2425.  doi:

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Tunable temperature-responsive poly(D,L-lactide acid)/poly(N-isopropyl acrylamide-co-acrylamide) (PLA/PNIPAM-co-AM) core-shell nanoparticles were prepared by in situ polymerization. It was found that the content of cross-linker has a great effect on the properties of the micelles, i.e., the higher the cross-linker content is, the thicker the shell is. The hydrodynamic diameter of the nanoparticles increases from 170.2 nm to 886.5 nm at 25 ℃ when the crosslinker molar fraction increases from 5% to 15%. The corresponding hollow sphere could be obtained by the removal of the PLA core via biodegradation. FTIR was used to monitor the biodegradation and showed that the biodegradation is the reverse reaction of the step growth polymerization. The hollow structure was observed with AFM. The results of DLS also show that the hollow spheres possess the similar size dependent on the temperature as the parent core-shell nanoparticles do.

Equilibrium Statistical Characteristics of Hyperbranched Reaction System of AB_g Type

SONG Jian-Min^1,2, WANG Hai-Jun^1,3

2006, 27(12):  2426-2429.  doi:

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The equilibrium statistical characteristics of hyperbranched reaction system of AB_g type is studied from two viewpoints by using the principle of statistical mechanics. The equilibrium free energy and a relationship between the conversion and some thermodynamic quantities are obtained. Furthermore, two new methods that can be used to evaluate the number fraction distribution of hyperbranched polymers are reported. As an application, it is found that the effect of polymerization is significant on the equation of state proposed by the improved lattice-fluid theory.

Crystallization Kinetics and Morphology of High Impact Polypropylene

LIU Xiu-Xia^1,2, CHEN Yong¹, CHEN Ye¹, ZHANG Wan-Xi², CHEN Wei³, YANG De-Cai¹

2006, 27(12):  2430-2434.  doi:

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Crystallization kinetics and morphology of high impact polypropylene(HIPP) and polypropylene homopolymer(iPP) were studied comparatively by differential scanning calorimetry(DSC), polarized optical microscopy(PLM) and field-emission scanning electron microscopy(FESEM) techniques. The crystallization and melting temperatures of HIPP are lower than those of iPP. The results of isothermal crystallization kinetics study indicates that the crystallization half-time(t_1/2) of HIPP is longer, while its activation energy(ΔE) and chain folding surface free energy(σ_e) are higher, compared with those of iPP. These results show the partial compatibility between the copolymeric components and the matrix of HIPP, which hinders the crystallization of the matrix. The PLM and FESEM images of HIPP reveal that there are uniformly dispersed rubbery particles(ca. 1—2 μm in diameter) with a core-shell structure in the matrix of HIPP. The uniform dispersion, strong interfacial adhesion and core-shell morphology of the rubbery phase in HIPP matrix are the key factors for the superior toughness-rigidity balance of this material.

Synthesis of Eight-arm Polystyrene by Atom Transfer Radical Polymerization

YU Xi-Fei^1,2, ZHANG Guo¹, SHI Tong-Fei², AN Li-Jia²

2006, 27(12):  2435-2437.  doi:

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A new initiator for atom transfer radical polymerization(ATRP), (Cl₂HCCOOCH₂)₄C(TDCAP) was designed and successfully synthesized. The initiator was used to initiate the polymerization of styrene via ATRP to method yield an eight-arm polystyrene with functional end-group chlorides. The different polymers could be prepared via ATRP of different monomers at 130 ℃ using TDCAP/CuCl/bPy as the initiating system. The initiator and eight-armed polymer were characterized by means of ¹H NMR, FTIR and GPC.

研究简报

Synthess of Electroactive Poly(aryl ether ketone) via Oxidative Coupling Polymerization Method

MA Xiao-Bo, CHAO Dan-Ming, CUI Li-Li, ZHANG Wan-Jin

2006, 27(12):  2438-2440.  doi:

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A novel electroactive poly(aryl ether ketone), with fixed conjugated length of oligoaniline(phenyl-capped aniline tetramer) in the main chain, was successfully synthesized via oxidative coupling polymerization method. The structure of poly(aryl ether ketone) was systematically studied by Fourier-transform infrared(FTIR) spectra, ¹H NMR, and X-ray powder diffraction(XRD). And its electrochemical behavior was studied by cyclic voltammetry(CV) measurement. It was found that the obtained poly(aryl ether ketone) bearing phenyl-capped aniline tetramer　segments had a reversible electrochemical property in the cyclic voltammetry, which was the same as that of polyaniline. Moreover, the thermal properties of poly(aryl ether ketone) were evaluated by thermogravimetric analysis(TGA).