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    24 October 1995, Volume 16 Issue 10
    Articles
    Studies on the Polymerization Between High Polymeric Silicate Anions and Mono-Aluminate Anions and the Hydrothermal Crystallization Behaviour
    LI Shou-Gui, MAO Ya-Chun, XU RU-Ren, TANG Ao-Qing
    1995, 16(10):  1491-1494. 
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    The polymeric state of silicate anions and aluminate anions were studied by means of 27AlNMR, UV-Vis spectra and silicate molybate method. It was found that the state of reaction products is affected by the polymeric state of silicate anions. The reaction between mono-aluminate anions and polymeric silicate anions(polymeric degree> 40)results in the formation of a gel,but during the reaction of mono-aluminate anions with mono- or di-silicate anions a precipitate was formed. The hydrothermal crystallization behaviour was also studied under the same conditions. Zeolites A, X, Yand P were crystallized in the area of precipitate, mixture, gel and sol respectively.
    Preparation and Characterization of Nanocrystalline ZnFe2O4Particles and EPR Study on Their Properties
    LI Xin-Yong, FENG Liang-Bo, LU Gong-Xuan, LI Shu-Ben
    1995, 16(10):  1495-1499. 
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    Nanocrystalline ZnFe2O4particles of several nanometers in size have been prepared by an improved coprecipitation method. Their particle structure, morphology and EPRproperties were examined by XRD, TEM and EPR, respectively. It was found that ZnFe2O4nanocrystalline could be produced at rather low temperature and was small. The EPR properties of the ZnFe2O4nano powders were presented and discussed in terms of the observed temperature effect.
    Studies on Stability of Ternary Mixed-ligand Complexes of M (Ⅱ)(ATP)2-and Nucleic Acid Bases (Adenine and Cytosine)
    LE Xue-Yi, WU Fu-Hai, SONG Fen-Yun, JI Liang-Nian
    1995, 16(10):  1500-1503. 
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    The stability constants of binary complexes ML2+(M2+=Cu2+, Co2+, Ni2+,Zn2+, Cd2+; L=Adenine, Cytosine) and their ternary complexes with ATP (Adenosine 5'-triphosphate) were determined by potentiometric pHtitration in aqueous solution (T=25℃,I=0.1mol/L NaClO4), the stability of ternary complexes in relation to the stability of their binary parent complexes was characterized by the equilibrium constants △lgKm(△lgKM=lgKM(ATP)LM(ATP)-lgKMLM) corresponding to the equilibrium M(ATP)2-+ML2+=M (ATP)L2-+M2+. The results obtained show that the △lgKmfor L=Adenine and cytosine is larger than that of the corresponding complexes of imidazole or ammonia due to the intramolecular ligand-ligand stacking interaction and hydrogen bond of the ternary complexes.
    Studies on Coordination Behavior Between PrCl3·H2O and 18C6 in C2H5OH and Syntheses and Characterization of Coordination Compounds
    XUE Gang-Lin, REN De-Hou, HU Shao-Ming, FAN Shao-Ying, YANG Yi-Xin, LI Qian-Ding
    1995, 16(10):  1504-1507. 
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    The solubilities of ternary system, PrCl3·3H2O-18C6-C2H5OH, at 25℃ were investigated by a semimicro method for the study of phase equilibrium and the refractive indexes of saturated solutions were determined. Three kinds of stoichiometrical coordination compounds can be formed in the system, their chemical compositions are 2PrCl3·18C6·6H2O·C2H5OH, 4PrCl3·3(18C6)·12H2O and PrCl3·18C6·3H2O. The three kinds of coordination compounds were prepared on the basis of the result of phase equilibrium, and characterized by IR spectra, conductivity measurements, TG, DTG and DSC.
    The Electronic Spectra and Its Theoretical Analysis of [Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2(OBz-=Benzoate)
    ZHANG Hua, ZHU Xiao-Lei, FU De-Gang, HONG Hui-Xiao, WANG Guo-Xiong
    1995, 16(10):  1508-1511. 
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    The UV-Vis spectra for trinucleariron complex of [Fe3O(OBz)6(CH3OH)3](NO3)·(CH3OH)3(OBZ-=benzoate)were studied. The d-d transitions were assigned and the ligand field parameters(10Dq, B, C)were calculated according to ligand field theory(Tanabe-Sugano Diagram) in terms of Ohsymmetry and reasonably good fits were obtained between the calculated and observed frequencies. CNDO/2 method was used to calculate the ligand field parameter(10Dq) of the simplest octahedron model[FeO6]9-of [Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2. From the 10Dq(R) and 10Dq(Q/R5)curves, it is found that this simplest model is suitable to the illustration of the ideal situation of ligand field theory.
    Room-Temperature Fluorescence of C60-Glycine Ester Derivatives in Solution
    ZHOU De-Jian, GAN Liang-Bing, TAN Hai-Song, LUO Chu-Ping, YAO Guang-Qing, HUANG Chun-Hui
    1995, 16(10):  1512-1513. 
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    Two new C60-glycine ester derivatives C60(EtOOCCHNHCHCOOEt)(A) and C60(PbCH2OOCCHNHCHCOOCH2Ph)(B) were synthesized and purified. Their room temperature photoluminescence was measured for the first time from their CHCl3solutions.It was first observed for fullerenes that their fluorescence could be quenched by concentration. The fluorescence lifetime was determined to be 1.5±0.3 ns for sA and 1.6±0.3 ns for B, respectively, using the frequency-domain method.
    Determination of Polyhydroxy Antibiotics by Capillary Electrophoresis with Amperometric Detection at a Copper Electrode
    FANG Yu-Zhi, FANG Xiao-Ming, YE Jian-Nong
    1995, 16(10):  1514-1518. 
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    Capillary electrophoresis(CE) was employed to separate polyhydroxy antibiotics in alkaline solution, combined with electrochemical detection at copper electrode. The electrode used was a 350 μm diameter Cu disk operated in a wall-jet configuration. Asample mixture containing 7 different polyhydroxy antibibeics was separated within 30min. The linearity varied over a 2-3 order of magnitude and the detection limits were 0.5 μmol/L.The reproducibility for the peak current and the migration time of 50 μ mol/Ldoublemycin injected every hour in a period of 8h, was 7.6% and 2.2% RSD, respectively, and the recovery of the determination of the real sample was 99.6%.
    Three-dimensional fluorescence Spectrometry and Its Application to Simultaneous Determination of Polyaronatic Hydrocarbons by Detecting Total Fluorescence Intensity
    YAN Yuan, WANG Le-Tian, LIN Zhu-Guang, XU Jin-Gou, CHEN Guo-Zhen
    1995, 16(10):  1519-1522. 
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    Three-dimensional fluorescence spectrometry for simultaneous determination of polyaromatic hydrocarbons, naphthalene, pyrene and perylene,by measuring total fluorescence intensity was proved. The results show that the method could be used not only to simultanously determine above-mentioned polyaromatic hydrocarbons, but also to improve,the signal to noise ratio by 22, 33 and 26 folds, respectively. Meantime, the effect of the integration region had been studied.
    Studies on Structure-Property Relationship Between Color Reagents and Contrast of Their Color Reactions with Cerium by Topological Indices
    LI Hua, XU Lu, SU Qiang
    1995, 16(10):  1523-1526. 
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    In this paper, three topological indices Am1, Am2 and Am3 have been applied to multivariate analysis in structure property relationship studies. The topological indices of fourtythree asymmetrical phosphono bisazo derivatives of chromotropic acid have been calculated. The structure-property relationship between color reagents and contrast of color reactions with cerium has been studied by Am indices and structure selective factors. Good results have been obtained.
    Investigation on the Triangular-Wave Current Excitation Oscillographic Chronopotentiometry
    QI Hong, ZHU Jun-Jie, GAO Hong
    1995, 16(10):  1527-1531. 
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    The theory of the triangular-wave current excitation oscillographic chronopotentiometry has been derived by the use of Fourier transformation technique and response function additivity principle. The effect of current amplitude i0, frequency f and depolarizer's Cto E-t curve were discussed. The modified E-t equation was also obtained when the effect of double electrode layer differential capacity be considered.
    Equations for Differential Oscillographic Voltammetric Curves
    BI Shu-Ping, GAO Hoog
    1995, 16(10):  1532-1534. 
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    Equations describing various differential oscillographic voltammetric curves i'f,i″f(single cell)and(Δif)',(Δif)"(double cells)were developed in this paper. Some valuable conclusions were obtained:(1)curves of the type(Δif)',(Δif)"=f(E) having the same shapes as those of i'f,i"f=f(E), are more sensitive than the latter ones;(2)the peak-peak values can be enhanced by adjusting suitable electric parameters i0 and f, which is beneficial to the observation of oscillogram changes at the end-point in titrations.
    A New Analytical Method Based on Reaction Heat-Induced Laser Beam Deflection
    ZHU Xiao-Yun, YAN Hong-Tao
    1995, 16(10):  1535-1538. 
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    A new analytical method based on chemical reaction heat-induced laser beam deflection is presented in this paper. The basic theory of the method is discussed. Dependence of the signal of laser beam deflection on the determination concentration and the effect factors have been investigated. The method is applied to the determination of following reactions: neutralization, oxidation-reduction, complexing, precipitation and domperidone in motilium tablet with satisfactory results. It is shown that the method can be used widely to the studies on analytical chemistry, solution chemistry, biological chemistry, and thermodynamics.
    Peroxidase Immobilized in Regenerated silk Fibroin Membrane and Its Application to the Sensor in Organic System
    QIAN Jiang-Hong, LIU Yong-Cheng, LIU Hai-Ying, YU Tong-Yin, DENG Jia-Qi
    1995, 16(10):  1539-1540. 
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    Peroxidase is successfully imobilized in regenerated silk fibroin membrane. The immobilized enzyme is constructed to the H2O2sensor and is used in the iso-propanol-water system. Moreover, its parameters are checked.
    SERRS of Novel Copper and Nickel Porphyrins and Effect of DNA
    ZHOU Guan-Ming, SHENG Rong-Sheng, Xiong Ya, XU Zhi-San, WANG Xiao-Hua, ZENG Yun-E
    1995, 16(10):  1541-1543. 
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    The SERRS spectra of Copper and Nickel complexes of meso-tetrakis(4-N-ethoxycarbonyl methyl pyridyl) porphyrins on Ag sols and the effect of calf thymus double strand DNAhave been investigated. The SERRS hands assignments are given.
    IPSO Nitration and Bromination of the Multi-substituted Benzene
    YU Zhong-Heng, ZHANG WEN-Chun, JIANG Ming-Qian, DAI Cui-Chen
    1995, 16(10):  1544-1549. 
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    In order to study substituent effects on the substitution reactions of 10 multi-sub-stituted benzene, (这里有图片199510-1549-1.gif)the relative yields of the products from their nitration and bromination in different solventsare investigated.The esteric group(X=-CH2OAc) of compound 2(R1=t-Bu and R2=-Me)vields 60%-60% ipso-product 2b(X=NO2,R1=t-Bu and R2=Me) for the nitration in a solution of 65% nitric acid and Ac2O, and 84% ipso-roduct 3b(X=Br, R1=-t-Bu and R2=Me)for the bromination in a solution of 65% nitric acid,NaBr and EtOH. Under the same conditions.the esteric group(X=CH2ONO2) of the compound 4(R1=t-Bu and R2=Me)gives 30% 2band 95% 3brespectively. An interesting bromination of compound 3(R1=t-Bu,R2=Me and X=CH2Br)in a solution of 65% nitric acid and EtOH yields 95% ipso-product 3b. Firstiy, this bromination proceeds practically through a intermediate 4 which resulted from the replacement of Br-by NO3- and then the esteric group(X=CH2ONO2)of intermediate 4 is substituted by Br2resulting from the oxidation of Br-by nitric acid. No matter what the alkyl groups,R1 and R2, are, no ipso-product was found from the nitration of thecompounds,where X=-CH2Cl and-CH2Br in acetic anhydride,which means that the esteric groups,-CH2OAc and-CH2ONO2,and only them are ipso-directors in the case of thepresented compounds, The esteric groups would seem to make it possible for the reactions toproceed through the six-membered cyclic transition states such as:  Steric effect of the alkyl groups helps the esteric group to yield ipso-product.the group,X=-CH2OAc, of compounds 8(R1=R2=Me) gives only 5% ipso-product for the nitration.
    Studies on Synthesis and Property of Monoaza Crown Ethers(Ⅱ)──Synthesis of Amphiphiles and Self-assembly of the Amphiphiles in Aqueous Dispersion
    WU Lin, QIAN Xiang-ping, TAI Zi-Hou, BIAN Qing, ZHANG Jin-Qi, ZHU Chun-Sheng
    1995, 16(10):  1550-1554. 
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    Anew series of amphiphilic monoaza crown ethers which contain aliphatic amido group were synthesized by the reaction of alkyloyl halide or acidic anhydride with N-(3′-aminophenyl)-azacrown. Transmission electron microscopy shows that these amphphiles can form the vesicles with diameters of 30-150 nm and their widths are 5-25 nm when dispersed in water. UV-Vis spectroscopy and differential scanning calorimetry were applied to examine the aggregate state and phase transition behavior of aqueous dipersions of these amphiphiles.
    Synthesis of α-Oxo-α-(1H-1,2,4-triazo-1-yl) Ketene N,S-Acetals and Their Biological Activities
    LI Zheng-Ming, HUANG Zhen-Nian
    1995, 16(10):  1555-1558. 
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    The reaction of α-(1H-1,2,4-Triazol-1-yl) substituted acetophenone with isothiocyanate in the presence of a base and subsequent alkylation afforded twenty-six new α-ox-oketene N,S-acetals containing 1H-1,2,4-Triazole. Their structures were confirmed by IR,1HNMR, elementary analysis. The preliminary biological test showed that some componds obtained have plant-regulatory activities.
    Studies on Heterocrown Ether(Ⅺ)──The Syntheses or o-Benzene Diselenium Type of Selenacrown Compounds
    LI Wei-Ping, WU Jun, LIU Xiu-Fang, XU Han-Sheng
    1995, 16(10):  1559-1562. 
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    The key to the syntheses of selenacrown ethers is the syntheses of selenium-con-taining intermediates, This paper described an improved method to prepare poly(o-diselenobenzene), and poly(o-diselenobenzene) was used as the intermediate for the syntheses of o-benzene diselenium type of selenacrown ether compounds: under an alkaline condition,poly(o-diselenobenzene) was reduced by potassium borohydride into o-benzenediselenolateanion, which condensed with dihalides, and seven selenacrown compounds were obtained.Besides[1+1] products,[2+2] products were also isolated. All the selenacrown compounds were identified by elemental analysis, MS,1HNMR and IR, and their syntheti methods and spectral characteristics were discussed.
    Reactions of N-Phosphoryl Serine and Threonine and Their Esters Catalyzed by Imidazole
    YAN Qing-Jin, YIN Ying-Wu, WANG Qian, MAO Qing-Qun, ZHAO Yu-Fen
    1995, 16(10):  1563-1566. 
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    N-phosphoryl amino acids could be catalyzed by imidazole to result in solvolysis such as ester exchanges on phosphorus, esterification, formation of peptides and N→Omigration of the phosphoryl group. For serine and threonine, a phosphaoxazole product was also detected. Only N-phosphoryl serine and threonine methyl esters were catalyzed by imidazole, Anew type of pentacoordinate phosphorus intermediate was proposed.
    A Convenient and Efficient Method of Tosylation of β-Cyclodextrin in Tetrahydrofuran-Water
    LIU Yu, ZHANG Yi-Min, SUN Shi-Xin, CHEN Rong-Ti
    1995, 16(10):  1567-1568. 
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    6-o-tosyl-β-cyclodextrin(6-OTs-β-CD)was prepared by the reaction of β-CD with p-toluenesulfonyl chloride in the presence of potassium hydroxide using tetrahydrofuran-water(1:1)as the solvent.Potassium hydroxide(0.4 g) and β-cyclodextrin (10g)dissloved in water(100mL)-tetrahydrofuran (70mL) were placed in a flask(250 mL) and the mixture was stirred about 15 min under a nitrogen gas at the room temperature. To the mixture was added dropwise p-toluenesulfonyl chloride(1.68g) in THF (30mL) for 1.5h, and the solution was stirred continuously for 3 h.Then the solution was poured into acetone(40 mL).After having been placed for enough time in the icebox, the solid was filtered, washed with water, dried, and washed with ether thoroughly, and then recrystallized twice from water to give pure product 4.5g(37.6%).The compound has been characterized by means of elemental analysis, UVF-Vis, IRand 1HNMR spectra. The results indicated that higher yield of 6-OTs-β-CD was obtained and the use of toxic pyridine was circumvented.
    Design and Synthesis of Deltorphin Ⅰ, Ⅱ Analogues
    HU Xiao-Yu, WANG Rui, JIA Qing, JI Hong
    1995, 16(10):  1569-1571. 
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    Endogenous opioid deltorphinⅠ(DELⅠ),Ⅱ(DELⅠ)and their five analogues ([L-Ala2]DEL Ⅰ,[L-Ala2]DEL Ⅱ,[Val4,Asp5]DELⅠ,[Val4,Asp6]DELⅠ,[Gly4,Asp7]DELⅠ)were designed on a rational basis and were synthesized by solid phase peptide synthesis method.The synthesis was performed manually on BHAresin prepared by ourselves,DCC was used as coupling reagent and TFAas deboc reagent. Peptide-resin was cleavaged by HF, the crude peptides were obtained after lyophylization. The crude peptides were desalted on a sephadex Glo column, then the pure peptides were obtained by partitional chromatography on a sephadex G25 column. The purities of all synthetic peptides were greater than 95%, which were acquired by reversed HPLC analysis. The data we got from FABMS,AAA and sequence analysis were in agreement with the caculated values.
    Studies on the Reaction and Mechanism of Tetrachloromethane with Magnesium──A Novel Method for the Generation of Dichlorocarbene
    LIN Hai-Xia, XU Liang-Heng, HUANG Nai-Ju
    1995, 16(10):  1572-1574. 
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    The reaction of tetrachloromethane with magnesium under general Grignard reaction condition was studied. It is found for the first time to produce dichlorocarbene which is trapped with different olefins to prepare gem-dichlorocyclopropane derivatives in good yields, The reaction having the advantages of easy work-up,mild reaction condition and high yield is a convenient method for the generation of dichlorocarbene. Apossible mechanism (single electron transfer,SET)was proposed. The solvent effects on the reaction were studied.
    The Structure of a New Flavonol Glycoside from Epimedium koreanum Nakai
    LI Wen-Kui, XIAO Pei-Gen, LIAO Mao-Chuan, ZHANG Ru-Yi
    1995, 16(10):  1575-1576. 
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    A new flavonol glycoside(1) was isolated from Epimedium koreanum Nakai.Its structure was elucidated as 5,7-dihydroxyl-4'-methoxyl-8-(γ-methoxyl-γ, γ-dimethyl)-propyl-flavonol-7-O-β-D-glucopyranoside and named as caohuoside D.
    Studies on N-Aryl-isopropyl-carbamoyl Methyl Phosphonamidate
    CHEN Ru-Yu, LI Hui-Ying, REN Kang-Tai
    1995, 16(10):  1577-1579. 
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    Eight of the title compounds, N-aryl-isopropyl-carbamoyl methyl phosphonamidate(Ⅰ)(i-prNHC(O)P(O)(OMe)NHAr, Ar=substituted phenyl, substituted pyridyl),were synthesized by reacting the phosphonyl chloride with arylamine under a mild condition in order to study the method of the synthesis of this kind of compounds and look for efficient antiviral drugs and pesticides. The preliminary bioassay showed that the title compounds had little bioactivity. The structure of the compounds had been studied and 1HNMR showed that there were two kinds of inter-molecular hydrogen bondings in the compounds.
    A Study of UV-Vis Spectra of Substituted Cyclopentadienyl Chromium, Molybdenum and Tungsten Carbonyls
    LI Song-Lan, LI Gui-Ping, LIAO Dai-Zheng, WU Lin, ZHU Jiang-Zhen, SONG Li-Cheng
    1995, 16(10):  1580-1582. 
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    The UV-Vis spectra of the substituted cyclopentadienyl chromium, molybdenum and tungsten carbonyls have been measured in five solvents, The concentration effects of the CT(CO-M) bands, n-π*bands have been studied and the phenomena mentioned above were interpreted by the Franck-Condon principles. The CTbands undergo a gradual red shift as the concentration of the solution increases and the nonlinear relation between the λmax of the CT band and Cwas simulated by a computer.
    Quantum Chemical Studies on the Structures and Spectra for the Addition Product C2H5C60H
    TENG Qi-Wen, FENG Ji-Kang, WU Shi, SUN Chia-Chong
    1995, 16(10):  1583-1586. 
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    The INDO series of methods have been used to study the structures for two kinds of isomers, which are 1,2-addition and 1,4-addition of the product C2H5C60H. It is indicated that 1,2-C2H5C60H has the Cs symmetry, but 1,4-C2H5C60H has no symmetries, furthermore the total energy of 1,2-C2H5C60H isomer is lower than that of 1,4-C2H5C60H. The electronic spectra for both the isomers have been calculated based on the optimized geometries and the reason for the red-shift of the spectra has been discussed. Meanwhile the NMR spectra of both the isomers have been explored.
    Theoretical Studies on Bent Bond, Strain and Bonding Behavior of Strained Organic Molecules
    ZHAO Cun-Yuan, QIU Wen-Yuan, XU Xian-Fang, ZHANG Chang-Yan, FANG Wei-Hai, YOU Xiao-Zeng
    1995, 16(10):  1587-1591. 
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    The calculation formulae of the bent bond and strain characteristics in any strained organic molecules are proposed. The relationship among structure, strain, stability and reactivity on 38 typical hydrocarbons-cyclic, bicyclic hydrocarbons, propellanes, polyhedranes and some unsaturated hydrocarbons has been revealed:(a)the C-C bond of strained organic molecules with three-or four-membered rings are much greater than those with five-or six-membered rings,(b) the bond length of bent bonds in strained organic molecules is less than that of acyclic hydrocarbons. The bond length increases with the increase of ring size and the decrease of bent angles. The bond length of C-C bonds in polyhedroang increases with the increase of the size of polyhedral framework;(c) the real bond angles (defined as equation 7 in the paper) have a tendency towards tetrahedral angle 109.5°,whatever the bent angle(0-32°) and bond angles(60-140°)are greater or small. The real bond angles of high strained organic molecules are much more greatly deviated from the tetrahedral angle 109.5°than those of less strained or strainless molecules. However, the real bond angles H-C-Hor H-C-C of three-membered rings have a tendency towards the angle 120°rather than 109.5°, It can be concluded that the deviaton(△β) of bent bond angles from the tetrahedral angles 109.5°can be used to evaluate the molecular strain and stability.
    Studies on the Quantitative Structure-Activity Relationship of 1-Cyclopropyl-5,7,8-substituted-6-fluoro-1,4-dihydro-4-oxo-3-quinoline Acid by Comparative Molecular Field Analysis
    ZHU Long-Guan, YU Qing-Sen, CHEN Kai-Xian, LIN Rui-Sen, CAI Guo-Qiang
    1995, 16(10):  1592-1596. 
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    In this paper, we studied the quantitative structure-activity relationship(QSAR)of 1-cyclopropyl-5,7,8-substitute-6-fluoro-1,4-dihydrogen-4-oxo-3-quinoline acid with CoMFA(Comparative Molecular Field Analysis)of 3D-QSAR. The probe and a 20 nm separation between the lattice points is the best CoMFA model which has a very good prediction. We designed some new compounds and calculated their activities from CoMFA coefficient plots. The activity of restraining the Gram-positive organism of some compounds is higher than that of synthesized compounds.
    Studies on the Interaction Parameters of the Excess Gibbs Free Energy Between Solutes in Quanternary Mixture
    BAI Tong-Chun, ZHANG Xin-Kuan, LU Yan, LU Jin-Suo
    1995, 16(10):  1597-1601. 
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    The retention values of eight organic solutes(i)(benzene,tetrachloromethane,chloroform,dichloromethane,ethyl acetate,tetrahydrofuran,acetone and methyl ethyl ketone)in stationary solution of urea(j)+sodium perchlorate (k)+formamide (s) at 298.15 Khave been measured by a gas-liquid chromatographic method(GLC).The McMillan-Mayer's solution theory,in which all the thermodynamic excess properties of multi-component solution can be expressed by a virial expansion,was used to relate the excess Gibbs free energy of the system to a series of pairs,triplet and higher order interaction parameters. An equation for expressing the relationship between the interaction parameters and the specific retention volume(Vg)of GLCwas obtained,that RTln [Vg(s+j)/Vg(s+j+k)]=2vgikmk+3v2gikkmk+6vgijkmjmkwhere Vg(s+j)and Vg(s+j+k)are the specific retention volumes of organic solutes (i) in multi-component stationary solution of s+j and s+j+k respectively.gik is the pair interaction parameters between i and k, gikkand gijkare the triplet interaction parameters of i-k-k and i-j-k.The values of gk,gijkikkj,mkand Vgdata to the equation given above. Some information about the solute(i)-solute(k) interaction in formamide and the effect of urea on gik have been discussed,For all solutes of i,gik>0,that means the interaction of i and k makes a positive contribution to GiEIn the presence of urea,the gikvalues become more positive than those in the absence of urea,which enhance the salting-out effect on the noneiectrolyte solutes.For the values of triplet interaction parameters,gijk<0,and the contribution of gikkto GiEcan be neglected.
    Electron Structure and Absorption Spectrum of Ion Cluster CoF64-in Crystal of LiF and MgF2by Ab Initio
    SHI Shou-Heng
    1995, 16(10):  1602-1604. 
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    Absorption spectrum of ion cluster CoF64-in crystal LiF and MgF2 was calculated by using ab initio calculation method.The calculated results coincided with experimental data, and show that it is workable to take CoF64-in Madelung field of ion crystals of LiF and MgF2as theoretical model to calculate its absorption spectrum, An indistinction in absorption spectrum term classified in literature was clarified.
    The Effect of Mixed Micelle of Surfactant on the Alkaline Hydrolysis of Esters
    ZENG Xian-Cheng, LI Qi-Lin, CHEN Min-zhu, WANG Qian, QIN Zi-Ming, Zou Ping, LI Gan-Zuo, HUANG Qi-Zhong
    1995, 16(10):  1605-1609. 
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    The alkaline hydrolyses of aromatic and normal aliphatic acid esters have been studied at 25℃ in mixed micelles of surfactants(SDS-Brij 35,DTAB-Brij 35, TTABBrij 35, CTAB-Brij 35, CTAB-Triton X-100, SDS-Triton X-100)with spectrophotometry and the method of thermokinetics in this paper. The critical micellar concentrations of the corresponding systems have been measured with spectrophotometry. k1min micellar psuedophase has been calculated.The ratios of k1mto k1wfor all mixed micellar systems investigated are less than 1.The alkaline hydrolyses of the esters are inhibited by them. The inhibtion of the mixed micellar systems is stronger than that of corresponding single micellar systems because micropolarity of compact Stern layer of mixed micelles is lower.
    Photoelectrochemical Invetigations on Size-quantized Particulate CdS Film Electrodes
    WANG Bao-Hui, WANG De-Jun, CUI Yi, LI Tie-Jin
    1995, 16(10):  1610-1613. 
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    Particuiate CdS film electrodes were fabricated on ITO by a novel electrochemical method.The photoelectrochemical behavior was investigated by surface photovoltaic spectroscopy and photo-electrochemical technique. The results show that these electrodes exhibitobvious size quantization effects and high photoelectric response.The propertis can be explained by a unique mode of the generation of photovoltage.
    Studies on the 13CNMR Chemical Shift Differences Between Diastereomers
    YOU Tian-Pa, YAO Li-Hong, QIAO Xiao-Xin, ZHU Zhou-Yuan, GUO He-Min, LU Fei
    1995, 16(10):  1614-1617. 
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    Eight pairs of diastereomeric amides have been prepared,and their 13C NMR chemical shift data and the corresponding shift differences between each pair of diastereomers were reported.Acorrelation model was proposed on the basis of the preferred conformation with the observed 13C NMR chemical shift nonequivalences of these amides.
    The Interaction Between C14BE and NaCMC(Ⅰ) ──The Effect of NaCMC on the Surface Activity of C14BE
    LI Gan-Zuo, SUI Wei-Ping, XU Gui-Ying, ZHENG Li-Qiang
    1995, 16(10):  1618-1621. 
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    The interaction between C14BE and NaCMC has been studied by using the surface tension method.In the neutral water solution, the effect of NaCMC on the surface activity of C14BE is weak, but with the addition of NaCl, two transition points appeared on the surface tension-concentration curve.This indicated that a water soluble C14BE/NaCMC complex was formed by hydrophobic effect. In the solution of pH=2,the existence of two transition points also indicated the formation of C14BE/NaCMC complex because of hydrogen-binding.It is the advantage for zwitterionic surfactant that the effect of electrolyte on it is weaker compared with that of its ionic surfactant.
    Studies on Molecular Assembly of the Lipid Bearing Barbituric Acid and Tetraaminopyrimidine
    WANG Zhi-Qiang, WANG Li-Yan, ZHANG Xi, SHEN Jia-Cong
    1995, 16(10):  1622-1623. 
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    Based on the complementary structure of the lipid bearing barbituric acid and 2,4,5,6-tetraaminopyrimidine, regular and laminar.molecular aggregates were formed simultaneously in water,and their structures were confirmed by use of SEM and X-ray diffraction. There is a thermal phase transition corresponding to about △H=12.2kJ/mol in their DSCcurves,which disappears in the cooling and the following heating and cooling runs. Combined the data of IRspectra,this transition is due to the hydrogen-bond in the aggregate,and thus the results obtained support the concept of hydrogen-bond-directed formation of molecular aggregate.By use of these types of heading compounds as anchor molecules,a new kind of funciton supermolecular materials is greatly anticipated.
    Preparation of Molybdenum Sulphide Nanotubes from Direct Laser Ablation
    ZHANG Qiang, HUANG Rong-Bin, LIU Zhao-Yang, ZHENG Lan-Sun
    1995, 16(10):  1624-1625. 
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    Molybdenum sulphide nanotubes with various structural configurations were prepared from direct laser ablation of MoS2sample at high vacuum.MoS2nano-particles were found on the tip of the tubes,and they might act as homogenous deposition centers for the nanotubes formation.
    High Resolution EELS and Ab-Initio Calculation for CoO(100)Surface
    SHI Shou-Heng
    1995, 16(10):  1626-1628. 
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    The d-d transition of Co2+on the CoO(100) surface and its EELS were indentified by using ab initio calculation.In addition to the previously documented EELS of CoO(100)surface,two new states at energy of 0.45 eV and 0.7-0.8 eV were found.
    Studies on Water-Soluble Metalloporphyrins as Tumor Targeting Magnetic Resonance Imaging Contrast Agents
    LUO Yi, MEI Er-Wen, ZHUO Ren-Xi
    1995, 16(10):  1629-1632. 
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    The development of nuclear magnetic resonance imaging technique has provided a noninvasive method for in vivo research in biological systems.Compounds which affect the relaxation time could provide additional contrast for NMR images and are potentially useful in a clinical setting.Synthesis of targeting MRI contrast agents for specific tissue and organs is the most attractive field in the recent MRI studies.In this work,four water-soluble metalloporphyrins,Cu(Ⅱ)-TSPP,Mn(Ⅱ)-TSPP.Cu(Ⅱ)-TMAP,Mn(Ⅲ)-TMAP Were synthesized and their structures were confirmed by UV,IR,1HNMR and elemental analysis.Targeting to S180tumor cells of these water-soluble porphyrins was studied in vitro by microscope fluorescence-Hadamard transform three-dimensional image analysis.The spin-lattice relaxivity(R1)of Mn(Ⅱ)-porphyrin chelate is 1.5-2 times larger than that of Gd-DTPA.
    Synthesis of Crosslinked Polyphosphates and Drug Release
    LUO Yi, ZHUO Ren-xi, FAN Chang-Lie
    1995, 16(10):  1633-1636. 
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    Ring-opening polymerizations of 2-hydro-2-oxo-3,2-dioxa-phospholan and/or 2-hydro-2-oxo-1,3,2-dioxaphosphorinane were studied using(i-Bu3)Al as initiator. After chlorination and hydrolysis, crosslinked polymers were obtained.The in vitro release of 5-fluorouracil from its single-matrix pellets,double-layered pellets and sandwich pellet with the crosslinked polyphosphates as drug carriers were carried out in phosphate buffer solution(pH7.4)at 37℃. Sustained release from the sandwich pellet was more controlled than that from the single-matrix pellets and double-layered pellets.
    Studies on Polyepichlorohydrin-Based Polyurethane/ Poly(MMA-co-St)IPNs
    CHEN Bao-Quan, HAN Xiao-Zu, GUO Feng-Chun
    1995, 16(10):  1637-1640. 
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    Interpenetrating polymer networks of polyepichlorohydrin-based polyurethane/ploy(MMA-co-St)have been prepared with simultaneous method by changing the weight fraction of MMA(WMMA)in copolymer of MMA with styrene. The IPNs have been studiedby DSC,TEM and dynamic mechanical spectroscopy(DMS).The results show that the IP-Ns have only one Tgwhen WMMAis greater than 0.6 But when WMMAis less than0.4, theIPNs have two Tgs, and phase separation is observed on TEM. The phenomenon is ex-plained according to the solubility parameters(δ)and the fraction of hydrogen bond(δh) of P(MMA-co-St).The study reveals that there is a close correlation among the δ,domain sizeand mechanical properties of PU(PECH)/P(MMA-co-St)IPN.
    Graft Polymerization of Acrylamide onto Carbon Black Surface
    WU Bi-Yao, LIU An-Hua, ZHOU Xing-Ping, JIANG Zi-Duo
    1995, 16(10):  1641-1644. 
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    Using a redox initiating system,which consists of ceric ions and hydroxymethylgroups on carbon black surface, free radical graft polymerization of acrylamide onto carbonblack surface was investigated.It was found that the polymerization was influenced by theconeentrations of acrylamide,nitric acid and ceric ions.The measurements of zeta electricpotential, FTIR and TEM observations showed the presence of graft polymer on the modi-fied carbon black particles,but the zeta electric potential of the particles was not changed.The surface modified carbon black particles possessed excellent dispersion stability in water.
    Synthesis,Structure and Conductivity Characteristics of Segmented Copolymer Electrolyte with Sulfonate
    MA Jian-Ming, LUO Xiao-Lie, WANG Xiao-Yan, LIU Wan-Yu, MA De-Zhu
    1995, 16(10):  1645-1649. 
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    The transesterification and polycondensition of hydroxy terminated polyethylene oxide and ethylene glycol with dimethyl terephthalate and sodium dimethyl isophthalate sulfonate lead to the formation of ethylene oxide-(ethylene terephthalate-CO-sodium ethylene isophthalate sulfonate)segmented copolymer(EOTM-SO3Na).This segmented copolymer is a new single cationic conductor.The chain and aggregate structure of EOTM-SO3Na segmented copolymers were characterized by 1HNMR, WAXD and DSCmethods. The ion mobility measured by polar inversion method was approach to 1. The room temperature conductivity of EOTM-SO3Na cationic conductor can get 2.3× 10-6S·cm-1. The temperature dependence of the cationic conductivity for EOTM-SO3Na system can be described by VTF equatlon.
    Studies on FTIR On-Line Following of Reaction Injection Molding of Poly(urethane urea)s
    LUO Ning, PAN Zhao-Qi, WANG De-Ning, YING Sheng-Kang
    1995, 16(10):  1650-1652. 
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    On-line following of reaction injection molding(RIM)of poly(urethane urea) s,which finished within several seconds, has been carried out by a 5SX FTIR. A mini-RIM machine and a single reflector for infrared sampling which were made in our laboratory were used successfully in the experiments. There is a very strong tendency of phase separation during RIMpolymerization of poly(urethane urea)s.Although there was not a marked effect of dibutyltin dilaurate concentration on overall rate of polymerization, the effect was intense on phase separation and hydrogen bonding of RIMpoly(urethane urea)s.
    Studies on the Reactivity Ratios of Styrene and Butyl Acrylate
    WU Ping-Ping, WU Yu-Fang, YANG Quan-Xing, HAN Zhe-Wen, ZHU Qing-Ren
    1995, 16(10):  1653-1655. 
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    In this study, copolymerizations of styrene(St,M1) and butyl acrylate(BA,M2)were carried Out at 60,80, 100, 120 and 140℃ at two sensitive feed compositions. Compositions of copolymers were analyzed by 1HNMR, Reactivity ratios were calculated by Errorin-Variable method to be r1=0.688.r2=0.157; r1=0.378,r2=0.174;r1=0.772,r2=0. 201; r1=0.810,r2=0.216 and r1=0.851,r2=0.241 at various polymerization temperatures above. The differences of activation energies between homo-polymerization and copoly merization were obtained to be E11-E12=2.97KJ/mol,E22-E21=6.13KJ/mol, The chain length distribution at 60℃ and Q, e values of BA at 60℃ were also calculated.