Table of Content

24 May 2003, Volume 24 Issue 5

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Articles

Structure Variation and Phase Relationship of the Hexagonal Perovskite System La₂Ca₂MnO₇-Sm₂Ca₂MnO₇

BIE Li-Jian, LI Guo-Bao, LIAO Fu-Hui, LIN Jian-Hua

2003, 24(5):  753-756. 

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La_2-xSm_xCa₂MnO₇samples were prepared from citric acid sol-gel precursor by using solid state reaction. The cell parameters of the sample were refined by using Rietveld method, which evidence the presence of single-phase regions(x≤0. 8 and x≥1. 0) and two-phase region 0.8<x<1. 0. The structure variation of the system can be understood by considering the ionic size of rare earth cation.

Studies on the Isothermal Solubility for Quinary System K₂²⁺,Mg²⁺//Cl₂^2-,SO₄^2--CO(NH₂)₂-H₂O and Its Boundary System MgSO₄-MgCl₂-CO(NH₂)₂-H₂O at 25℃

ZHANG Feng-Xing, WEI Xiao-Lan, LI Jun

2003, 24(5):  757-760. 

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The isothermal solubility for quinary system K₂²⁺,Mg²⁺//Cl₂^2-,SO₄^2--CO(NH₂)₂-H₂Oand its boundary system MgSO₄-MgCl₂-CO(NH₂)₂-H₂O at 25 ℃ have been determined. The solubility diagrams of the system have been drawn. The results showed that the presence of urea in the system is in favor of the process of the reaction K₂Cl²⁺MgSO₄→K₂SO⁴⁺MgCl₂.

Synthesis of Various Stoichiometry Nano-powder of VO₂

HE Shan, LIN Chen, LEI De-Ming, ZHENG Chen-Mou

2003, 24(5):  761-764. 

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The violet polycrystalline (NH₄)₅[(VO)₆(CO₂)₄(OH)₉]·10H₂O(Ⅰ) was synthesized by using V₂O₅, HCl, N₂H₄·2HCl and NH₄HCO₃as the starting materials. The yield was 80%-95%. The TG/DTG and DTA of Iwere studied in a flow of N₂. The effects of partial pressure of oxygen(po₂) in N₂-air flow and temperature of reaction on VO₂stoichiometry were investigated in the pyrolysis of Ⅰ in a silica tube. The results show that x value of VO_xis proportional to po₂at pyrolysis temperature of 500 ℃ At po₂= 30.3 Pa and in the temperature range from 450 to 520 ℃ the products are oxygen-deficient VO₂, and when the temperature is lower than 450℃ or higher than 520℃ the products are oxygen-rich VO₂In this paper, various stoichiometry VO₂powders from VO_1.927to VO_2.080were successfully synthesized by pyrolysizing the precursor. XRD patterns of VO₂show that none of the impurity peaks was observed. The SEM micrograph of sample indicates that as-prepared VO₂is spherical particles with mean size 20 nm and is homogeneous in distribution. Further experiments testify that the composition of nano-powders is homogeneous.

Spectroscopic and Theoretical Studies on Nickel (Ⅱ) Complex of Maleinitriledithiolate and 4,4'-Dimethyl-2,2'-bipyridine

PENG Zheng-He, CAI Ping, FANG Chen-Jie, GUO Wen-Yong, DENG Ke-Jian, ZHOU Yun-Hong

2003, 24(5):  765-771. 

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The electronic spectra in several solvents, complete IR spectra in powder state and quantum chemical theoretical studies of the title complex Ni(mnt)(dmbpy) were reported in this paper. Geometry optimization calculations by PM3 method show that the complex is of a planar structure with the symmetry C_2vand the spin triplet as the ground state. The CIcalculations by ZINDO/S method proved that the bands (450-550 nm) in the visible region in the observed spectra belong to the charge transfer from the ligand dmbpy to another ligand mnt^2-(LL'CT) essentially. Anew method for analyzing vibrational spectra of complicated molecule is established by PM3 calculations. The essential of this method is to give main fixed points and pivotal vibrational units in assignment for each normal mode. Anew vibration type describing heaving along the specified direction was defined by the symbol η(X).

Hydrothermal Synthesis and Characterizaton of [CH₃NH₃][NH₃(CH₂)₆NH₃]H₃[P₂Mo₂W₁₆O₆₂]·H₂O

LIU Zong-Rui, WANG Li, CHEN Bao-Guo, XU Lin, WANG En-Bo, XING Yan, JIA Heng-Qing, LIN Yong-Hua

2003, 24(5):  772-775. 

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Anovel heteropoly tungstomolybdophosphate,[CH₃NH₃][NH₃(CH₂)₆NH₃]H₃[P₂Mo₂W₁₆O₆₂]·H₂O has been synthesized and characterized by elemental analysis, IR, TGA-DSC and single-crystal X-ray structure analysis. Crystal data; monoclinic, space group P2₁/m, a=1.2596(3) nm, b=1.8715(4) nm, c=l. 9816(4) nm, a=γ=90°, β=90. 16(3)° V=4. 671(2) nm³, Z=2, M_r= 4358. 66, D_c= 3. 100 g·cm^-3, μ=19. 978 mm^-1, F(000)=3792, R=0. 0835, R_w= 0. 2026. The structure analysis shows that a kind of micropore with size of 0. 7364 nm×0. 8354 nm was formed in the crystal structure.

Synthesis and Characteristic of a 3-D Inorganic-organic Hybrid Framework Microporous Material Cd(HBTC)(EG)·8(H₂O)

FANG Qian-Rong, ZHU Guang-Shan, SHI Xin, XIN Ming-Hong, WU Gang, TIAN Ge, YE Ling, WANG Chun-Lei, ZHANG Zhen-Dong, QIU Shi-Lun

2003, 24(5):  776-778. 

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The title compound Cd(HBTC)(EG)·8(H₂O) was synthesized under mild conditions and its crystal structure was determined by means of single crystal X-ray diffraction. The crystal structure was solved by direct method and refined by full-matrix least-square method. The compound crystallizes in the monoclinic system and belongs to space group P2₁/n with a=0. 7311(15) nm, b=1. 8306(4) nm, c=0.9500(19) nm, β= 109. 69(3)% V=1. 1970(4) nm³, Z=4, D_c= 4. 832 g/cm³, M_r= 526. 72, μ= 2. 981 mm^-1, F(000)=1716, GOF=1. 146, R=0. 0958, R_w= 0. 2762. Its structure revealed that coordination of HBTC ligands with Cd ions forms a 2-D network along be plane, while 4,4'-bpy as pillars uphold the 2-D network to lead to a 3-D framework along a axis.

Hydrothermal Synthesis and Crystal Structure of a Novel Hexacapped Keggin-type Molybdovanadoarsenate (H₃O)₃[AsMo₁₂O₄₀(VO)₆]·6H₂O

HAO Na, LI Yang-Guang, SHEN En-Hong, WANG En-Bo, LU Ying, DUAN Ying-Bo

2003, 24(5):  779-781. 

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Anovel molybdovanadoarsenate(H₃O)₃[AsMo₁₂O₄o(VO)₆] · 6H₂O has been hydrothermally synthesized and structurally characterized by elemental analyses, cerimetric titration, EPR, and single crystal X-ray diffraction. The compound crystallizes in the triclinic system, space group PI with a=1. 2629(3) nm, b=1. 2635(3) nm, c=l. 7672(4) nm, a=91. 01(3)°, β=89. 98(3)°, 7=90. 00(3)°, V=2. 8198(10) nm³, Z=2, R₁= 0. 0955, wR₂=0. 1788. The polyoxoanion exhibits a hexacapped a-Keggin-type structure, in which six (VO₅) square pyramids were distributed on the surface of (AsMo₁₂O₄₀) unit and made the bridge-oxygen (O_b, O_c) atoms of the a-Keggin-type polyoxoanion occupied.

Unusual Afterglow Properties of Tm³⁺Doped Yttrium Oxysulfide

LEI Bing-Fu, LIU Ying-Liang, TANG Gong-Ben, YE Ze-Ren, SHI Chun-Shan

2003, 24(5):  782-784. 

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One bright unusual afterglow has been observed for the first time in the Tm³⁺doped yttrium oxysulfide phosphors synthesized by flux fusion method. When the phosphors are illuminated with UV light (263 nm) or visible light, one bright orange-yellow light can be seen in the darkroom lasting for about one hour. The bright orange-yellow afterglow light is a mixture of six main emissions including 470, 495)516, 545, 588 and 626 nm, which can be attributed to the 4f-4f transition emissions of Tm³⁺in Y₂O₂S. One conclusion can be drawn from the phosphorescence spectra and the afterglow decay curve that the Tm³⁺doped yttrium oxysulfide is a new phosphor with good afterglow properties. The Tm³⁺doped yttrium oxysulfide not only shows afterglow when excited by UV light or visible light, but also create obviously upcon version afterglow emission peak located at 545 nm when it was excited by near infrared light (798 nm). This unusual afterglow phenomenon maybe finds some new application of the long-lasting phosphor and opens a new field of phosphor research.

Hydrothermal Synthesis and Crystal Structure of Compound [Cu₃(μ₁₀-bta)(μ₂-C₂O₄)(H₂O)₂]_n

LI Chuan-Bi, XU Ji-Qing, ZHANG Li-Juan, SUN Ying-Hua, SU Chang, WANG Tie-Gang

2003, 24(5):  785-787. 

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Anovel 3-Dcoordination polymer, [Cu₃(μ₁₀-bta) (μ₂C₂O₄) (H₂O)₂],(bta=benzene-1,2,4,5-tetracarboxylate), was hydrothermally synthesized from CuMoO₄, H₄bta (H₄bta=benzene-1, 2, 4, 5-tetracarboxylic acid), H₂C₂O₄, NaOH and H₂O, and characterized by elemental analysis, IR spectrum and X-ray crystallography. The crystals of the compound belong to orthorhombic space group Pbcn, a=0. 71017(14) nm, 6=1. 2577(3) nm, γ=l. 5972(3) nm, V=l. 4266(5) nm³. Z=4, D_c= 2. 6309g/cm³, μ=4. 525 mm^-1, F(000)=l 108, GOF=1.054, Δρ_max= 1082 e/nm³, Δρ_min= - 608 e/nm³, R=0. 0381, R_W= 0. 1307. The coordination environment of Cu(2)²⁺is a seriously distorted octahedron, while that of Cu(1)²⁺is a highly symmetric octahedron. In the compound, each bta^4-lig-and displays an unprecedented μ₁₀-coordination mode, whereas C₂O₄^2-ligand shows a μ₂coordination form. There are three-dimensional interpenetrated channels in the solid of the compound.

Spectral Retina Technique Used in an IR Oil Content Analyzer

ZHOU Jian-Guang, ZHENG Jian, SONG Qing-Yu, YU Ai-Min, ZHANG Han-Qi, JIN Qin-Han, LI Bao-Hua

2003, 24(5):  789-792. 

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Spectral retina is a quite new technique in spectroscopy. It has been employed for the first time to an IRoil content analyzer. The instrument using this technique has a series of merits: compact, pegged (without moving parts), simple in operation as well as high speed in measurement. In this paper, a Model 450 oil content analyzer based on spectral retina technique is described in details. The results show that the instrument has such excellent analytical performance as a good stability, a high precision (RSD< 1 %), a low detection limits 0.027 mg/L(oil/extractive reagent), a high sensitivity (a faster of 10 improvement compared), and a wide linear ranges (10³).

Preparation and Application of Sol-gel-HBsAb Immunosensor

LIANG Ru-Ping, QIU Jian-Ding, ZOU Xiao-Yong, XU Jian-Jun, CAI Pei-Xiang, MO Jin-Yuan

2003, 24(5):  793-797. 

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Anew type of nonlabbled immunosensor for the determination of hepatitis Bsurface antigen (HBsAg) was made by utilizing Sol-gel techniques to encapsulate hepatitis Bsurface antibody (HBsAb) on tetraethylorthosilicate(TEOS) derived Sol-gel films and then to coat the Sol-gel-HBsAb layer onto the surface of platinum disk electrode. The effective diffusion section area of K₃Fe(CN)₆attained to the platinum electrode has been decreased along with the increase of the singularity reaction immunocompound of HBsAb and HBsAg, the respond current of K₃Fe(CN)₆on the surface of electrode was directly proportional to the effective diffusion section area of K₃Fe(CN)₆attained to the platinum electrode and inversely proportional to the concentration of HBsAg, so HBsAg could be determined indirectly by utilizing K₃Fe(CN)₆as the oxidation-reduction probe. Cyclic voltammetry (CV) was employed to investigate the electrochemical character of the immunosensor in 5 mmol/L K₃Fe(CN)₆-0. 1 mol/L KNO₃-PBSsystem. The linearity of HBsAg in the range of 5-320 μg/Lwith the correlation coefficient of 0. 997 was obtained from differential pulse voltammetry (DPV) by using the three systems. The dependences of the current response on incubation time, sensitivity and reproducibility were studied, and the stability of the sensor was also evaluated. The immunosensor was free from 30 μg/L CEA and 100 μg/L AFP. More than 87. 5% of the results of the human serum samples obtained by this methode were in agreement with those obtained by enzyme-linked assay (ELISA). The immunosensor was found to be stable for about 2 weeks when storing in a dry state at 4 ℃.

Cholesterol Biosensors Based on Cholesterol Oxidase Immobilized in a Silica Sol-gel Matrix on a Prussian Blue Modified Electrode

LI Jian-Ping, PENG Tu-Zhi

2003, 24(5):  798-802. 

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Acholesterol biosensor prepared by immobilization of cholesterol oxidase in a silica sol-gel matrix on the surface of Prussian Blue-modified glass carbon electrode was reported. The properties of the sensor were investigated. It is based on the detection of hydrogen peroxide produced by ChOx at 0. 0-0. 1 V. The measurements conditions were optimized. Cholesterol can be determined in the concentration range of 5 × 10^-7～8 × 10^-5mol/Lby voltammetry or 5 ×10^-6～5 × 10^-4mol/Lby amperometry. The method gives a high sensitivity owing to the electrocatalytic layer of Prussian Blue to the electro-reduction of enzymatic production of hydrogen peroxide. In addition, the effect of easily oxidizable substances presented in samples such as ascorbic acid and uric acid can be minimized.

Application of the Combination of Capillary Electrophoresis with Wavelet Neural Network in the Assisted Clinical Diagnosis of Breast Cancer

XIONG Jian-Hui, ZHENG Yu-Fang, ZHANG Pu-Dun, SHI Xian-Zhe, YANG Jun, ZHANG Yu-Kui, XU Guo-Wang

2003, 24(5):  803-807. 

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Thirteen kinds of normal and modified nucleosides were determined in urine samples from 46 healthy persons and 26 breast cancer patients by capillary electrophoresis. Awavelet neural network model has been used as a powerful pattern recognition tool to distinguish breast cancer patients from healthy persons. The recognition rate for the training set reached to 100% and above 96% of people in the predicting set were correctly classified. Compared with standard backpropagation neural network, wavelet neural network had stronger abilities of information extraction and approximation. The results also demonstrated that the predicting ability of wavelet neural network was higher than those of principal component analysis and linear discriminant analysis. The combination of capillary electrophoresis and wavelet neural network was expected to be an assisted tool for the clinical diagnosis of breast cancer.

High Sensitive Carbon Fiber Nanoelectrodes Modified by Single-walled Carbon Nanotubes

CHEN Rong-Sheng, XIAO Hua, HUANG Wei-Hua, TONG Hua, WANG Zong-Li, CHENG Jie-Ke

2003, 24(5):  808-810. 

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Microelectrode voltammetry has been considered to be a powerful technique for single biological cell analysis and brain research. In this paper, we have developed a simple method to get a high sensitive carbon fiber nanoelectrode(CFNE) modified by single-walled carbon nanotubes(SWNTs) on the basis of our previous work. The electrochemical behavior of SWNTs modified CFNE was characterized by dopamine(DA) by using cyclic voltammetry(CV). Compared with CFNE, SWNT smodified CFNE has almost the same geometric area but greater available internal surface area per external geometric area, which was supported by SEM images. The modified electrode shows a very high sensitivity and favorable electro-catalytic behavior toward dopamine. The peak current increases linearly with the concentration of DA in the range of 1.0×10^-7-1.0× 10^-4mol/L. The CV detection limit(S/N= 3) of DA is 7. 7× 10^-9mol/ L. The modified electrode exhibited almost the same electrochemical behavior after 15 d. It indicates that SWNTs modified CFNE is pretty stable and has a good reproducibility.

Electrocatalitic Behavior of Nitrophenol Isomers at α-Cyclodextrin Incorporated Carbon Nanotubes-coated Electrode

WANG Zong-Hua, LUO Guo-An, XIAO Su-Fang, WANG Ge-Yun

2003, 24(5):  811-813. 

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In this article, based on providing a new interfacial architecture that involves carbon nanotubes (CNT) and a-cyclodextrin(a-CD), we constructed a novel modified electrode by casting a-CDincorporated carbon nanotubes on the graphite surface to form a functional stereoscopic interfacial layer. The modified electrodes first showed a favorable behavior toward the reduction of nitrophenol isomers. The attractiveness of this modified electrode is the capitalization on the best properties of the two components of the system, such as the electronic and catalytic properties of the CNT and the molecular recognition ability of the a-CD. The selective determination of p-nitrophenol could be obtained by the separation of its reductive peak from that of other nitophenol isomers. Adifferent pulse voltammetric technique for measurement of p-nitrophenol over the range of 1 × 10^-6to 3 × 10^-4mol/Lhas been developed. The detection limit was 2×10^-7mol/L.

Studies on Highly Selective Salicylate Electrode Based on New Complexes of Cobalt(Ⅱ) as Neutral Carriers

CHAI Ya-Qin, LIU Yan, YUAN Ruo, XU Wen-Ju, XU Lan

2003, 24(5):  814-816. 

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In this paper, anion-selective electrode based on bis-salicylaidehydc-diaminodipropylamine cobalt (Ⅱ) metallic complex [Co(Ⅱ)-BSADDPA] as the neutral carrier is reported. The sensor exhibits a u-nique selectivity and high sensitivity toward salicylate ion, which displays an anti-Hofmeister selectivity pattern. It gives a linear response in the concentration range 3. 0× 10^-6-1. 0× 10^-1mol/Land a response slope of -66. 8 mV/dec in buffer solutions of pH 4. 0. The response mechanism is discussed in view of the UVspectroscopy technique. The electrode can be applied to medicine analysis and the result is in fair agreement with the result given by precipitation method.

Separation and Structure Determination of a New 19-nor-Spongian Diterpenoid

SU Jing-Yu, LIN Cui-Wu, ZENG Long-Mei, YAN Su-Jun, FENG Xiao-Long, CAI Ji-Wen

2003, 24(5):  817-819. 

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A new 19-nor-spongian diterpene, zimoclactone A(1) together with a known compound, cholest-5,7-dien-3β-ol(2) were isolated from the Spongia zimocca aubspecles irregularia of marine sponge. The structure of compound 1 was determined by spectroscopic methods as well as X-ray diffraction analysis. Compound 1 showed a moderate cytotoxic activity against P388 cell lines.

Synthesis, Crystal Structure and Activity of Sul fated Daidzein

LIU Qian-Guang, ZHANG Zun-Ting, XUE Dong

2003, 24(5):  820-825. 

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The isoflavonc compound-daidzein has the biological activities of resistance to hypoxia andanoxemia. In this paper, the structure of daidzein was modified by sulfonation reaction. Sodium 4', 7-bi-hydroxylisoflavone-sulfonate(1), the water-solubility derivatives of daidzein were synthesized. Compound 1 was identified by the method of IR and MS. Its biological activities of resistance to hypoxia and anoxemia were tested, the result showed that the biological activities of resistance to hypoxia and anoxemia of compound 1 was better than that of daidzein. The crystal of compound 1 crystallizes in a triclinic space group P₁with cell constants, a=0. 6948(14) nm, b=1. 3277(3) nm, c=2. 0401(4) nm, a=105. 16(3), β=90. 75(3)° γ=92. 73(3)% V=1. 8138(6) nm³, Z=2, μ=0. 266 mm^-1, F(000)=908. There arc nine coordinated water molecules and two kinds of sodium 4', 7-bihydroxylisoflavone-sulfonate isomer in the crystal of compound 1, one is sodium 4',7-bihydroxylisoflavone-3'-sulfonate and the other is sodium 4',7-bihydroxylisoflavone-5'-sulfonate. It should also be pointed out that one dimension polymer chains of Na⁺existed in the crystal structure of compound 1, they not only connected the cations and anions together to form 3D-network structure, but also play a very important role in the formation, the stability and the crystallization of compound 1.

Structural Characteristic and MHC Restriction of Polypeptide Sequence

LIN Zhi-Hua, WU Yu-Zhang, WAN Ying, NI Bing

2003, 24(5):  826-830. 

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The goal of this study is to develop an automated computerized method for the identification of helper T-cell epitope. In order to describe the peptide structure, a new set of descriptors called sequence property vector(ξ) was developed from the primary structures of peptides based on the distance between amino acid side chains and on the electric property of each amino acid side chain, and looking on each amino acid side chain as a pseudo atom. Then a quantitative model was proposed for 28 immunogenic pep-tides including 14 A^dand non-A^drestricted peptide sequence, assigned active and inactive peptides, respectively. In order to explain the accuracy of the prediction system, random sampling validation and cross validation were performed. The results showed that the prediction system exhibited a good stability and excellent prediction ability. This method may also be applied in the study to predict the MHC classes Iand Iepitope of human, and it should be useful in immune recognition studies of protein antigens and the design and study of subunit vaccine.

Stereoselective Synthesis of cis- and trans-2,5- Disubstituted Tetrahydrofurans

SHI Hong-Xin, LIU Hua-Zhang, Bloch R, Mandville G., LIN Hui

2003, 24(5):  831-836. 

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Ageneral route to either cis- or trans-2,5-disubstituted tetrahydrofurans was described by using the nucleophilic addition of organolithium derivatives to tricyclic lactones, followed by a highly stereocon-trolled acid-assisted reduction with sodium cyanoborohydride of the hemiketals formed. The stereoselec-tivity observed can be rationalized by the preferential approach of the hydride on the less hindered face of an oxonium ion intermediate. The cis- or trans-2, 5-disubstituted tetrahydrofurans were provided by the hot decomposition and then hydrogenation of tricycle compounds produced.

Synthesis of Nicotinoyl Disubstituted Pseudo-cyclopeptide and Its Coordination Behavior with Cu²⁺

GUO Wei, WANG Jing, HE Jia-Qi, XIA Zhi-Zhong, CHENG Jin-Pei

2003, 24(5):  837-839. 

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A 26-membered nicotinoyl disubstituted cyclopseudopeptide was synthesized through a simple six-step prvcedure(Scheme 1) with cystine dimethyl ester, iminodiacetic acid, and nicotinoyl chloride hy-drochloride as the starting materials. The structure of the key intermediates 4 and 5 was verified by ¹HNMR and FAB-MS, and that of the final product 7 by ¹HNMR, IR, FAB-MS and elemental analysis. Subsequent treatment of 7 with Cu(ClO₄)₂gives a mononuclear cuprate(Ⅱ) complex whose structure was characterized by IR, FAB-MS. The quick formation of the cuprate-cyclopeptide complex demonstrates that the title peptide can serve as a good reception in Cu(Ⅱ) recognition.

Determination of Uniconazole in Soil with an Enantioselective Way

LI Zhao-Yang, ZHANG Zhi-Chao, LIU Yi-Shan, ZHOU Qi-Lin, GAO Ru-Yu, WANG Qin-Sun

2003, 24(5):  840-842. 

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Afast and precise method was developed for the determination of the enantiomers of chiral pes-ticidc-uniconazole in soil. Matrix solid-phase dispersion (MSPD) technology was used to extract uniconazole from soil. MSPDconditions were optimized stepwise. The MSPD extract was directly used for quantitative determination of uniconazole by silica-based high performance liquid chromatography(HPLC) with UVdetection. The recoveries of uniconazole from three types of soils fortified at three levels of 0. 1, 1, 10 μg/g ranged from 75%-97% with RSDs<7%. On this basis, uniconazole was further isolated from the remainder of MSPD extract by silica-based HPLC and then subjected to chiral HPLCto determine its enan-tiomcric ratio. The determined ERs in the soils spiked with racemic uniconazole agreed sufficiently well with those in the standard solutions within the error limit of the method.

Total Synthesis of Natural Macrocyclic Diterpene(±)-Mayol

LI Shu-Hua, PENG Li-Zeng, ZHANG Tao, LI Yu-Lin

2003, 24(5):  843-844. 

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Afacile and efficient total synthesis of (±)-mayol starting from gcraniol has been carried out in 10 steps. The key steps are the alkylation reaction of allylic iodide 3 with phenyl sulfone 4 and the chromium-induced intramolecular macrocyclization of allylic chloride and aldehyde.

Temperature Effect and Enthalpy-entropy Compensation of the Mixed Micellization of C₁₂-s-C₁₂· 2Br and Alcohol in Aqueous Solution

ZHAO Jian-Xi, YOU Yi, ZHU Yong-Ping, YANG Qi-Yu

2003, 24(5):  845-849. 

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The mixed micellization of quaternary ammonium gemini surfactants C₁₂-s-C₁₂·Br (s=2,3, 4,6) and alcohols(n-propanol, n-butanol, H-pentanol and n-hexanol) in aqueous solutions has been investigated at different temperatures by using conductivity measurements. The results show that the critical micelle concentrationdn(In(cmc)) gradually increases with increasing temperature. The thermodynamic parameters calculated by phase separation model indicate that the mixed micellization of C₁₂-s-C₁₂·Br and alcohol is an entropy-driven process. The entropy-driven is enhanced as temperature is going up. All plots of enthalpy-entropy compensation exhibit an excellent linearity. At a fixed temperature,  is decreased and the micelle stability is enhanced with increasing the carbon atom number(n) in the alkyl chain of alcohol molecule. However, these properties have an opposite trend with increasings.

Model Study on the Suspension in Spherical Shell-structure Numerical Simulation for the Influence of Inner Parameters on the Dielectric Spectroscopy

ZHAO Kong-Shuang, HIKIDA Takumi, LI Zi-Jie, LEI Jian-Ping, QIU Le-Le

2003, 24(5):  850-853. 

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Asimulation study of suspension in spherical shell-structure was made on the basis of Hanai theory. An improved and intelligentized program for solving the tedious equations from Hanai theory has been written with C++ language and complex class, and been applied to the numerical calculations of permittivities and conductivities at different frequencies from 10 to 10⁷Hz. The dependence of dielectric spec-troscopy on the inner parameters of the system was obtained by an example actualized in a microcapsule suspension. The results show that the patterns of the spectroscopy can be reflected qualitatively by the electric and structural parameters of the constituted phases of the system.

NMR Study on the Micellar Microstructures of Three Anionic Surfactants with Different Molecular Structures in Aqueous Solution

FANG Xiao-Wen, JIN Zhi-Qiang, MAO Shi-Zhen, WANG Han-Hui, YU Jia-Yong, DU You-Ru

2003, 24(5):  854-857. 

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The comparison of the micellar microstructures among three pure surfactant aqueous solutions with different molecular structures such as sodium alkylsulfates with normal, branched alkyl chains and with the polyethylene oxide chain inserted between the alkyl chain and the sulfatc polar head has been performed by using nuclear magnetic resonance spin-lattice relaxation time(t₁), spin-spin relaxation time(t₂) self-diffusion coefficient and two dimensional nuclear Overhause enhanced spectroscopy techniques. According to the ratios of t₂to t₁, the hydration layers of the micelles were deduced. The t₂/t₁values show that the hydrocarbon chains of surfactant Ⅱ are more compact in the micelles than that of surfactant I . NMR self-diffusion coefficients show that the micelles formed from surfactant Iare larger than those from surfactant Ⅱ . At last, the 2D NOESY technique was applied to confirm the arrangement of the polyethylene oxide chains outside the hydrophobic micelles.

Preparation and Characterization of Anode Catalysts PtRu/C for Direct Methanol Fuel Cells

ZHOU Wei-Jiang, LI Wen-Zhen, ZHOU Zhen-Hua, SONG Shu-Qin, WEI Zhao-Bin, SUN Gong-Quan, Tsiakaras P, XIN Qin

2003, 24(5):  858-862. 

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PtRu/C (20%-10% in mass fraction) catalysts for direct methanol fuel cell(DMFCs) were prepared by three different methods, XRD and TEM were used to characterize the lattice parameter, particle size and distribution of PtRu metal particles. Polarization experiments of single DMFCs were used to investigate the activity of different PtRu/C anode catalysts directly. It is found that the PtRu/C synthesized in a mixture solvent including ethylene glycol, water and isopropanol has a smaller metal particle size and more improved interaction between Pt and Ru. The single DMFC adopting the PtRu/Cas anode catalyst shows a better performance.

A Density Functional Study on the Phase Stability and Phase Transitions at High Pressure for TiC Solid

ZHANG Yong-Fan, LI Jun-Qian, DING Kai-Ning, CHEN Wen-Kai, ZHOU Li-Xin

2003, 24(5):  863-867. 

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Using the density function theory method based on the first principle, the electronic structures of TiCsolid with the NaCl, WC and CsCl phases have been investigated. The calculated results indicate that, at the zero pressure, the order of relative stability for the three phases is NaCl phase>WCphase> CsCl phase, and this order can be explained by comparing the electronic states near the Fermi level. As the pressure increases, the CsCl phase is to be stable and the structural phase transitions from NaCl phase to CsCl phase occurs at about 475. 9 GPa. The transition from CsCl phase to WCphase needs more higher pressure. Furthermore, the pressure-induced influences on the band structures, chemical bonding and charge densities of the three phases are also discussed.

Studies on the Structures and Stabilities of C₅₉H₃N Isomers

LIANG Yun-Xiao, SHANG Zhen-Feng, WANG Gui-Chang, PAN Yin-Ming, ZHAO Xue-Zhuang

2003, 24(5):  868-871. 

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The structures and stabilities of all 1-2, 1-4 and 1-6 hydrogen adducts of C₅₉HN were studied by using semiempirical MNDO, AMIand PM3 methods. In order to verify the reliability of the semiem-pirical methods, some energetically favored isomers of these hydrogen adducts were calculated by using HF/6-31G for single-point energy. The calculation results indicate that in general, 1-2 adducts are more stable than 1-4 adducts and far more stable than 1-6 adducts. However, the most stable isomer is 6,18- or 12,15- isomer which is a 1-4 adduct and the second most stable isomer is a 1-2 adduct, calculated by the three semiempirical methods the energy of the former is lower than that of the latter by 13-15 kJ/mol. The computed nucleus independent chemical shifts(NICS) indicate that the more stable the isomer, the more aromatic the molecule, aromaticity may be the primary factor governing the stabilities of C₅₉H₃N isomers. By replacing one Catom of the fullerene skeleton with an Natom, the regioselectivity of the carbon cage has been changed. According to the result of frequency analysis, we have predicted the IRspectrum of the most stable isomer.

Studies on Microdynamics of the Reaction Between HO₂and Methane with Direct Ab Initio

CUI Cao-Xiang, LU Wen-Cai, LI Ze-Sheng, SUN Jia-Zhong

2003, 24(5):  872-875. 

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The ab initio direct dynamics method at the B3LYP/6-311+G^** level is employed to studythe HO₂ion reaction CH₄+ HO₂- CH₃+ H₂O₂on a wide temperature range 300-2000 K.The barrier heights obtained for the forward CH₄+ HO₂- CH₃+ H₂O₂and reverse reactions CH₃+H₂O₂- CH₄-HO₂are 11. 83 and 102. 90 kJ/mol, respectively. Comparing with one recent experiment. The ratio of k_cvt/sct/k_exptis within the range 1. 08-2. 85. We can expect that the predicted values at the high temperature are reliable.

Theoretical Study of the Structure, Spectra and Nonlinear Second-optical Susceptibility of Ca@C₇₄

CHENG Hong, FENG Ji-Kang, REN Ai-Min, LIU Jian-Jun, ZHANG Gang, SUN Chia-Chong

2003, 24(5):  876-879. 

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The equilibrium geometry of Ca@C₇₄has been studied by density functional theory (DFT) and the BLYP method at 3-21G^*level. The UV-Vis spectrum and the nonlinear second-optical susceptibility of Ca@C₇₄are examined by using semi-empirical ZINDO methods. The results show that C₇₄is stable than Ca@C₇₄, the carbon cage is enlarged, the unlocation scope is extended, the absorptions of Ca@C₇₄shift to the short band, and the nonlinear second-order optical susceptibility of Ca@C₇₄increases greatly compared with that of C₇₄.

Influence of Bombarding Ions Energy on the Content of sp³C-N Bonds in Carbon Nitride Films

LI Jun-Jie, CAO Pei-Jiang, ZHENG Wei-Tao, LU Xian-Yi, BIAN Hai-Jiao, JIN Zeng-Sun

2003, 24(5):  880-883. 

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The chemical bonding states and the structure of CN_xfilms grown on Si(001) substrate by using RFmagnetron sputtering were studied at different substrate bias voltages (V_b) The incident ions energy bombarding the substrate surface could be controlled by the substrate negative bias, which would influence the chemical bonding states of CN_xfilms. The results of Raman, FTIR and XPS showed that the nitrogen atoms were bound to sp, sp²and sp³hybridized carbon atoms. The content of sp³C-N increased firstly with the increase of V_b, reached to the maximum value at V_b=- 50 V, and then decreased continually. This trend indicated the content of sp³C-N bonds in the CN_xfilms were closely related to change of ions energy.

Synthesis and Luminescence Properties of Thionalid-stabilized CdS Nanoparticles

WEI Fang-Di, YU Jun-Sheng

2003, 24(5):  884-887. 

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The thionalid-stabilized CdS nanoparticles (named as CdS/thionalid) have been synthesized in methanol by colloidal solution method. The images of TEM demonstrate that the average size of CdS/ thionalid nanoparticles is about 10 nm. Spectra of absorption and fluorescence show that both the ratio of [S^2-]/[TN] and concentrations of thionalid and cadmium ion have influence on the size and luminescence properties of the nanoparticles. On varying experimental conditions, the maximum emission wavelength of CdS/thionalid nanoparticles has the largest red shift of 100 nm, and quantum confinement effect can be obviously observed. Values of XPS confirm that the core of CdS/thionalid nanoparticles is CdS.

Photoelectrochemical Studies on the Mercurochrome-sensitized TiO₂Nanoporous Electrode

LIU Zhao-Yue, PAN Kai, YANG Min, WANG De-Jun, BAI Yu-Bai

2003, 24(5):  888-891. 

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Mercurochrome was used as a sensitizer to sensitize TiO₂nanoporous electrode. The UV-Vis, photocurrent and photovoltage spectra indicated that the sensitizer could extend efficiently the response of anodic photocurrent to the visible region, and the aggregated dye could extend the sensitized region. The transient photocurrent of the sensitized electrode was measured at different biases and the influence of the bias on the rate of the light-induced electron transfer and recombination was studied too. Illumination from different directions could markedly influence the generation of anodic photocurrent. The mechanism of the generation of the photocurrent and the recombination of the light-induced charge were discussed by combining the electrochemistry, photoelectrochemistry and UV-Vis spectra.

Preparation and Photocatalytic Properties of TiO₂/Carbonized Resin Complex Nanocatalysts

SU Bi-Tao, CHANG Yue, ZHANG Li, CHEN Hui, SU Zhi-Xing

2003, 24(5):  892-894. 

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A TiO₂/carbonized resin (B) complex nanocatalyst has been synthesized by using a simple method by molecule design and characterized with regard to their components, structure, size, and photo-catalytic properties. The results show that the average size of TiO₂/Bcomplex nanoparticles composed of C, H, Oand Ti elements is about 30 nm, The stacking structure of Ti and Oin the complex belongs to TiO₂anatase. Bwith different lengths of conjugated chains, and TiO₂are chemically bound and their absorption is in an whole UV-Vis region. The TiO₂/B complex nanomaterial is strong polar, resulting in efficient separation of photogenerated charges related to efficiency of light conversion and photocatalytic activities closely. The material is ideal and promising for photoelectric conversion and photocatalysis.

Photochemical Reaction Mechanism of 2-Aryltrisilanes

LIU Cheng-You, YAN Xi-Jie, GAO Yu-Xiang, TIAN Gui-Cai

2003, 24(5):  895-899. 

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The photophysical and photochemical properties of 2-aryltrisilanes (1) was investigated via theory and experiment. The intense fluorescene band of compound 1 was assigned to the intramolecular charge-transfer (ICT) in a polar solvent. Whereas silylene extrusion and 1,3-silyl migration were the major pho-toreactions of compound 1 resulted from the solvolytic cleavage of the Si-Si bond. The temperature dependence of the products distribution suggested that both the silylene extrusion and 1,3-silyl migration came from the different excited states. The results of the photochemical reaction of compund 1 using a nonresonant two-photo(NRTP) excitation show that the silylene extrusion occurs via the ¹L_astate.

Immunological Identification with SERS-labeled Immunogold Nanoparticles by Silver Staining

XU Shu-Ping, WANG Lian-Ying, XU Wei-Qing, ZHAO Bing, YUAN Hang, MA Lan, BAI Yu-Bai, FAN Yu-Guo

2003, 24(5):  900-902. 

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Aspectral measurement combined with nanoparticle labeling and SERStechnique is described. The gold nanoparticles not only modified by the mouse monoclonal antibody agaist Hepatitis Bsurface antigen [IgG(H)] but also labeled by the p-mercaptobenzoic acid (MBA) were used as a probe. The immunogold nanoparticles specially react with the antibody against IgG(H)[anti IgG(H)] which was immobilzed on the quartz substrates. The identification between the immunogold colloids and the anti IgG(H) was examined by surface enhanced Raman specta(SERS) of MBA after and before silver staining and confirmed by UV-Vis absorption spectra.

Electrochemical Polymerization of Pyrrol/Thiophene Conducting Copolymer Nanofibrilla Arrays and Characterization

LU Mei, LI Xiao-Hong, GUO Xin-Yong, LI Hu-Lin

2003, 24(5):  903-905. 

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Copolymer nanofibrilla arrays composed of pyrrole and thiophene were prepared by synthesizing the desired polymer within the pores of the porous anodic aluminum oxide (AAO) template membrane. The results of SEMand TEMreveal that the obtained copolymer nanofibrillas have uniform and well-aligned arrays. The results of infrared spectra and cyclic voltammetry indicate that the obtained nanofibrilla arrays are copolymer rather than mixture of polypyrrole and polythiophene. The higher potential favored the incorporation of thiophene units into the copolymer nanofibrillas.

Volumetric Properties of Glycine, L-Alanine and L-Serine in Aqueous Urea Solutions at 298.15 K

SHAO Shuang, FANG Wen-Jun, LIN Xiao-Mei, LIN Rui-Sen

2003, 24(5):  906-908. 

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Densities of glycine, L-alanine, L-serine in various aqueous urea solutions were measured at 298. 15 Kwith an Anton Paar Model 55 densimeter. From these densities, apparent molar volumes and limited partial molar volumes were calculated, transfer volumes from water to aqueous urea solutions and substituent contributions to the transfer volumes have been obtained. Furthermore, the hydration numbers and volumetric interaction coefficients for the three amino acids were evaluated. Solvent and substituent effects are discussed in detail. The results show that all of the transfer volumes are positive, except alanine in rich-water region, and increase with increasing urea concentration; the side-chain contributions to the transfer volumes are highly related to the nature of side-chain groups; the hydration numbers for the three amino acids in solutions decrease with increasing urea concentration.

Studies on Relationship Between Component Distribution of Aryl Cyclic Oligomers and Its Monomer's Structure

GUO Qing-Zhong, CHEN Tian-Lu

2003, 24(5):  909-912. 

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Based upon Jacoson-Stockmayer theory, matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) was used to analyze the component distribution of a series of cyclic aryl oligomers. The relationship between the component distribution of cyclic aryl oligomers and the monomer structure was investigated. The results indicated the distribution of cyclic aryl oligomers could be accorded with J-Stheory well. The effect of the bond angle of bisphenol monomer on the distribution of cyclic ester and phosphonate oligomers showed that the value of γ in J-Stheory decreased with the bond angle increasing from 100° to 120°. On the premise of a constant monomer, the distribution rule of cyclic aryl ether oligomers affected by the structure of another monomer was consistent with cyclic ester and phosphonate oligomers.

Studies on the Relationships Among Sound Absorption Coefficient Temperature and Frequency on Polymer

YU Xiao-Qiang, MENG Yan, LI Hong-Tu, LI Yao-Xian, WANG Jing-Yuan, TANG Xin-Yi, SUN Jia-Zhong

2003, 24(5):  913-915. 

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The loss factor of polymer is an important parameter that characterizes the damping properties. In this article, the physical model on the relationship between the sound absorption coefficient of polymer and the loss factor was established.

Construction of Sulfoammonium Zwitterionic Structure onto Surface of Polyurethane by Hexamethylene Diisocyanate (HDI) Spacer for Improving Blood Compatibility

YUAN Jiang, YUAN You-Ling, SHEN Jian, LIN Si-Cong

2003, 24(5):  916-919. 

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At the molecular level, it is believed that polymers containing zwitterionic structure should be more compatible with blood. The films of polyether-urethane were constructed with sulfoammonium zwitterionic structure by a three-step procedure. In the first step, the film surfaces were treated with hexam-ethylene diisocyanate(HDI) in toluene at 50 'Cin the presence of dibutyltin dilaurate(DBTDL) as a catalyst. The extent of the reaction was measured by ATR-IRspectra. Amaximum number of NCOgroups were obtained in about 90 min reaction. In the second step, the hydroxy groups of N, N-dimethylethylethanolamine (DMEEA) were allowed to react in toluene with surface bound isocyanate groups. In the third step, sulfoammonium zwitterionic structures were constructed onto the surface through the ring-opening reaction between tertiary amine constructed by the second step and 1,3-propane-sultone(PS). The surface was characterized by ATR-IR and XPS, and as anticipated, the sulfoammonium structure was constructed on the PU films. The platelet adhesion test revealed that films attached to sulfoammonium zwitterionic structure showed an excellent anti-platelet adhesion. These good results are due to the interfacial sulfoammonium zwitterionic structure.

Synthesis of 30-100 nm Nanoscale Magnetic Polymer Particles in Inverse Microemulsion

DENG Yong-Hui, WANG Lei, YANG Wu-Li, FU Shou-Kuan, Elaissary Abdelhamid

2003, 24(5):  920-923. 

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Aone-step method for the synthesis of magnetic polymer nanoparticles in the inverse mi-croemulsion was investigated. The concentration of Fe(Ⅰ) was found to have a drastic effect on the stability of the microemulsion. The magnetic properties of the obtained composite latex particles prepared at different [Fe(Ⅱ)]/[Fe(Ⅲ)] were measured by Vibrating Sample Magnetometer (VSM) and found temperature was crucial to form high magnetic power and superparamagnetic magnetite. DLSindicated a relatively uniform particle diameter about 30-100 nm and the particle size was controlled by the type of alkali, the amount of AOTor monomer. The method is simple, easily controlled, and applicable to various hy-drophilic monomers and the prepared magnetic polymer particles are transparent and stable for several months.

Studies on Interaction Between N,N-Dimethyldodecylamine Oxide and Sodium Polystyrenesulfonate via Light Scattering Method

FENG Xian-Hua, LIU Shi-Zhong, SONG Hui-Ting

2003, 24(5):  924-927. 

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The interaction between sodium polystyrenesulfonate(NaPSS) and N,N-dimethyldodecylamine oxide (DDAO) micelles with different concentrations was studied by using turbidimetry, dynamic light scattering, and electrophoretic light scattering. While the interaction was controlled by ionic strength, the micelle concentration shows no effect on the interaction. Dynamic light scattering reveals that the binding of DDAO micelles to NaPSS occurs at a degree of micelle ionization ft prior to critical degree of micelle ionization, β_c, which was obtained from turbidimetric titration. The critical micelle surface charge density at a point where micelles associate with polyelectrolyte has a difference of 15% for calculation using β₁and β_c. Arapid change in the electrophoretic mobility of the system is also observed in the vicinity of ionization degree of micelles corresponding to β₁in the dynamic light scattering.

Preparation and Properties of Chiorosilane-modified Montmorillonites

ZHAO Chun-Gui, YANG Ming-Shu, FENG Meng

2003, 24(5):  928-931. 

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Montmorillonite(MMT) was modified by chlorosilane derivatives (trimethylchlorosilane and tert-butyldimethylchlorosilane) based on the reaction between OHgroup and chlorosilane. FTIR confirmed that chlorosilane derivatives had reacted with the OHgroups of MMT, and the results of wide angle X-ray diffraction (WAXD) indicated that there was an intercalation taking place during the reaction. The CEC of montmorillonites were detected, after the modification by chlorosilane derivatives, CEC values drastically decreased. The dispersibility measurements of montmorillonites were conducted, the results declared that the dispersibility of modified montmorillonites both in H₂Oand toluene were improved due to the decrease of attractions between particles and layers.

Studies on Atactic Poly (methyl-methacrylate) Stereocomplex at Substrate

WANG Ji-Jun, LU Yong-Lai, SHEN De-Yan

2003, 24(5):  932-934. 

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The formation of stereocomplex and aggregates structure of atactic poly(methyl-methacrylate) (a-PMMA) stereocomplex at substrate was studied by using Atomic Force Microscopy and Reflection Absorption Infrared Spectroscopy(AFMand RAS). Comparing AFM images of pure isotactic and syndiotactic PMMA with that of the mixture of isotactic and syndiotactic PMMA in which stereocomplex formed, it is shown that stereocomplex lead to the dendritic aggregates of PMMA on silicon wafer. The dendritic aggregates of a-PMMA indicated that the stereocomplex formed in a-PMMA, which played an important role in the patterning of a-PMMA at substrate. Reflection Absorption Spectroscopy data show that a-PMMA backbone chain preferred to extend at a substrate than in bulk, it favors to form more stereocomplex.

Studies on PVDF Hollow Fiber Affinity Membrane for Separation of γ-Globulin from Human Plasma(Ⅰ) -Preparation of PVDF Hollow Fiber Affinity Membrane and Its Adsorption Properties

YU Ji, CAN Hong-Yu, HE Yi, YUAN Juan, CHEN Huan-Lin

2003, 24(5):  935-939. 

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Poly(vinylidene fluoride) (PVDF) hollow fiber membrane used as the matrix was hydrophile-modified by alkali and hydroxyethyl-cellulose(HEC) treatment in this paper. After being activated and coupled, the PVDF hollow fiber affinity membranes with phenylalanine as the ligand were prepared. XPS analysis was used for measuring the changes of chemical structure on the membrane surface. The results indicated that on the membrane surface oxygen and nitrogen contents increased from 5. 6% to 16. 5% and 0. 6% to 3. 0% respectively, while fluorine content decreased from 38. 3% to 23. 0%. The affinity membrane was used for separating γ-globulin (HGG) from human plasma. The result showed that adsorption capacity of HGGby the affinity membrane was 5. 85 mg/g membrane under the condition of pH=7. 4, I=0. 18(ionic strength), ρ=1. 0 mg/mL(feed liquid) and the purity of HGGextracted from human plasma was up to 83. 9%.

Preparation of Optical Resins Containing Terbium (Ⅲ) Complexes by In-situ Composite Method and Fluorescent Properties

WANG Dong-Mei, LIN Quan, YANG Bai

2003, 24(5):  940-942. 

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Transparent resins containing lanthanide complexes should possess the optical, electrical, magnetic and laser properties of the lanthanide ion, and also should possess the good properties of polymer such as lightness, good processability, dyeability, high transparency and impact resistance. The composite resin containing ten kinds of lanthanide terbium complexes were obtained by in situ composite method, in which the lanthanide complexes were synthesized in the polymerization process. The relationship between the fluorescence property of the composite resin and the kinds of organic ligands, inertia yttrium (Ⅲ), the relatively molar ratio of organic ligands to lanthanide ion in copolymerization system were investigated. The results indicated that the composite resin by in situ method showed stronger emission intensities and longer lifetime than the composite resin by mixing the lanthanide complexes with copolymerization system straight.

Particle Size Effect on the Filming Process of Polystyrene Latex

QU Xiao-Zhong, SHI Yi, CHEN Liu-Sheng, JIN Xi-Gao

2003, 24(5):  943-945. 

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The film formation process of micro-PSparticles (diameter 742 nm) and nano-PSparticles (diameter 29 nm) was studied by means of AFMand DSC. During a step heating process, the particles were annealed for 0. 5 h at each selected temperature. It is found that the deformation and interdiffusion temperatures are ca. 393-403 Kand 413-423 Kfor the micro-PSparticles, 363 Kand 373-383 Kfor the nano-PSparticles respectively. Comparing to the micro-PS particles, the sintering process of nano-PS particles occurs at much lower temperature determined by the confined state of polymer chains with less interactions between segments, leading to a higher conformational energy, and completed in much narrower temperature range driven mainly by the larger total surface energy.

A New Method for Fabrication of Three-dimensional Polymer Micropatterning-Microtransfer Molding

WANG Zhe, XING Ru-Bo, HAN Yan-Chun, LI Bin-Yao

2003, 24(5):  946-948. 

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Microtransfer molding (μTM) is a kind of soft lithography for polymer micropatterning. In μTM, a liquid prepolymer (or concentrated polymer solution) is applied to the patterned surface of an elas-tomeric mold and then brought into the contact with a substrate. After prepolymer is cured thermally or by UVlight, the elastomeric mold is peeled away. Apattern is left on the surface of the substrate. In this study, ～300 nm lines and three-dimensional patterns of PMMA and epoxy on planar and/or non-planar substrates are realized.