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    24 August 1993, Volume 14 Issue 8
    Articles
    Studies on Synthesis of Ferric Saponite and Ferric-Nickel Saponite and Cross-linking with Hydroxyl Aluminium
    SUN Tie, JIANG Da-Zhen, LIU Zi-Yang, MIN En-Ze, FU Hong-Gang
    1993, 14(8):  1035-1038. 
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    Ferric saponite and ferric-nickel saponite are synthesized by the hydrothermal method.Their cross-linking products are prepared with hydroxyl aleuminium oligomer.By the characterization with XRD, DTA, IR, TPR, Mossbauer spectra and chemical analysis, it is proved that iron exists in the framework of the synthesized clay.The position of cross-linking maybe locates on the tetrahedral iron with the formation of Alp-O-Fe bond.
    Preparation of Ultrafiltration γ-Alumina Membrane with Preferential Orientation Structure by SOL-GEL Process
    PENG Ding-Kun, XIA Chang-Rong, MENG Guang-Yao, LI Fan-Qing, LU Bin, SHI Lei
    1993, 14(8):  1039-1042. 
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    γ-alumina porous membranes without pinholes or cracks were prepared by sol-gel process.The boehmite sol obtained from hydrolysis of aluminum tri-sec-butoxide was applied to porous α-alumina support by a dipping procedure.The effect of sol properties such as viscosity and concentration on the membrane performance was investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction and nitrogen ad-sorption-desorption(BET).It was found that the resulted γ-alumina membrane with nanoscale pore size and a narrow pore size distribution exhibited a preferential orientation structure in which the (110) crystal face of γ-alumina membrane paralleled to the support surface.
    NMR Studies on the Conformation of Oxygen-Nitrogen Donor Macro- cycle Containing N-Carboxylmethyl and Its Complexes in Solution
    YAO Tian-Ming, SUN Hong-Zhe, LI Cun, YOU Xiao-Zeng
    1993, 14(8):  1043-1047. 
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    The 1HNMRspectra of 1, 12-diaza-3, 4-: 9, 10-dibenzo-5, 8-dioxacy-clopentadencane-N, N'-diacetic acid (sodium salt) and its complexes in solution are reported.Two sets of three split peaks have been observed in the low temperature NMRspectra of the macrocycle, which is related to the nonequivalence of 1- and 2- protons on the conformation of the macrocyclic ligand.The 1HNMRspectra of the nickel complex is very similar to those of the zinc complex.This can be interpreted as a low-spin, square plannar molecular structure of the nickel complex.For all of the zinc, nickel and cobalt complexes, the ether oxygen atoms in the macrocyclic ligand do not coordinate to the central metal ion.
    Synthesis and Characterization of Hydrotalcite-Containing Rare Earth
    LI Lian-Sheng, HUI Jian-Bin, LIU Xin-Sheng, LIU Xiao-Xun, ZHANG Yan-Qiu, XU Ru-Ren
    1993, 14(8):  1048-1050. 
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    Anovel hydrotalcite containing rare earth lanthanum was synthesized hydrothermally and characterized by means of XRD, FTIR, XPSand ionic exchanging reaction at room temperature.The results show that rare earth lanthanum has incorparated into the layer lattice of the product.The catalytic activity of the product was characterized by an esterification reaction.
    Synthesis and Structure of Dinitrato Bis(octylcaprolactam) Uranyl ( Ⅱ ) Complex
    CAO Zheng-Bai, WANG Han-Zhang, ZHU Li-Min, GU Jian-Sheng, LU Zhen-Rong, YU Kai-Bei
    1993, 14(8):  1051-1054. 
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    The complex (这里有图片19930805-1051-1.gif) was prepared in organic solvent.The crystal belongs to space group P1 of triclinic system.The cell parameters are a=0.8986(2) nm, b=0.9750(2) nm, c=2.3687(4) nm, α=82.70(1), β=81.29(2).γ=61.67(1)°, V=1.8020(6) nm3, Z=2, Dc=1.56 g/cm3, R=0.036.The result shows that the central uranyl ion is coordinated by six oxygen atoms, two of them are from the carbonyl groups of two octyl-caprolactam molecules, and the other four are from two nitrate groups.In the crystal cell, a dimer was formed, owing to the attraction of four long carbon chains in the two complex molecules.
    Studies on the Thermodynamics of Axial Coordination Reaction of Porphinatoiron( Ⅲ )
    ZHU Zhi-ANG, RUAN Wen-Juan, JIANG Dong-Qing, CHEN Rong-Ti
    1993, 14(8):  1055-1057. 
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    Athermodynamic study is reported for the axial coordination of meso-tetrame-sitylporphinatoiron (Ⅲ) chloride (Fe(Ⅲ)TMPCl) with imidazole (Im), 2-methylimidazole (Melm), clotrimazole (CMZ ), 2-ethyl-4-methylimidazole (EMIm ) and 4'-imidazol-1-yl-ace-tophenone(ImAPh) in dichloromethane (这里有图片19930806-1055-1.gif) (1)The equilibrium constant (β) and stoichiometric number(n) of reaction (1) were measured by spectrophotometer technique.
    Normal Projection Target Factor Analysis and Its Application to Spectrophotometric Analysis ——Study for Simultaneous Determination of Rare Earth Elements Multicomponent Mixture
    DONG Ke-Ling, WANG Hong-Yan, WANG Duo-Xi
    1993, 14(8):  1058-1062. 
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    Singular value decomposition (SVD) method has been used to decompose the data matrix of absorption value.The difficulty of matrix loss rank has been well resolved, and so the precision of the calculated result of concentration has been increased apparently.The more the components in the system, the more similar the absorption spectra of complexes, the more remarkable the increasing degree.It has been proved that normal projection matrix can be applied to realization of target transformation.Now target test criterion, similar coefficient (Qta), has been used so that the calculated results were improved.By using this method, three-component synthetic samples of rare earth elements such as La,Sm and Tm have been determined and calculated.The results are satisfactory.
    Studies on the Electronic Cloud Symmetry of Triphenyl methane Dye and Enhancement of Sensitizing Effect on Color Reaction
    ZHANG Gui-Zhu, GAO Zhi, HE Xi-Wen, LAI Cheng-Ming, YUAN Man-Xue, SHI Hui-ming
    1993, 14(8):  1063-1067. 
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    The color reactions of several triphenylmethane dyes were studied by spectropho-tometry, infrared spectrum, quantum chemistry and solution state.The optimum enhancement of sensitivity on color reaction is in relation to the symmetry of electronic cloud for triphenylmethane dye.The basic principle and experimental method of electronic cloud symmetry of the reagents in surfactant micella are used to analyze polycomponent complex.The property of reagents in micella can be deduced and the main reason of sensitization can be predicted.
    Twisted Intramolecular Charge Transfer of DMABA in β-Cyclodextrin and Cetyltrimethylammonium Bromide Mixed Media
    JIANG Yun-Bao, HU Jing-Song
    1993, 14(8):  1068-1069. 
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    Twisted intramolecular charge transfer ( TICT ) of p-N, N-dimethy-laminobenzaldehyde (DMABA) in β-cyclodextrin (β-CD) and cetyltrimethylammonium bromide (CTMAB) mixed media is monitored by its typical dual fluorescence.The ratio of the intensity of TICTfluorescence band (a band) to that of normal band (b band) decreases with introducing CTMABat CTMABconcentration lower than β-CDin the solution, with the concomitant red shift of a band and the decrease of total fluorescence intensity,and the trends are opposite when CTMABconcentration is higher than β-CDconcentration.It is concluded that CTMABand /β-CDform a 1:1 inclusion complex and a premicellar aggregate of CTMABis present in CTMAB-β-CDmixed system at the concentration of CTMABhigher than that of β-CD,whose formation would be induced by β-CD.
    Studies on Simultaneous Determination of Inorganic Anions Inorganic Cations and Organic Acids by Single- Column Anion Chromatography
    YU Hong, FENG Shi-De, LIU Qing-Lin
    1993, 14(8):  1070-1072. 
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    The method of simultaneous determination of inorganic anions, inorganic cations and organic acids by single-column anion chromatography was described.An anion-exchange column was employed for separation with conductivity detection.EDTAwas used as eluent.The eluent pHshould be controlled in the range of 5.5-7.5.Linear plots of logarithm of the adjusted retention time of the ions vs.the logarithm of the concentration of the eluent were obtained.The detection limits, variation coefficient and calibration curve for those substances were obtained at eluent concentration of 0.5 mmol/Land pH=7.0.The method was applied to analyzing chloride.calcium and oxalic acid in Ringer's injection with satisfactory results.
    Studies on Application of Ion Associate to Amperometric Biosensors for Glucose Based on Paste Modified by FeCp2
    SUN Chang-Qing, SONG Wen-Be, GAO Qian, DU Wen-Yuan, XU Hong-Ding
    1993, 14(8):  1073-1075. 
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    This paper describes the design and testing of amperometric glucose biosensor in whichelectrical communication between the flavin redox centers of glucose oxidase and a conventionalcarbon paste electrode containing (C6H5).1B · N+(CH3)1 has been achieved by using electron-transfer relay system based on ferrocene (FeCp2).Characteristics of the biosensor has been shown by cyclic voltammetry and stationary potential measurements.The biosensor responds rapidly to glucose, with steady-state current responsed achieved in less than 50 s.The response to glucose under N2 saturation showed apparent Michcells-Menten constant, KMapp, 21 mmol/L.The biosensor can be operated in a potential range where the oxidation of common interfering species, such as Vc and uric acid does not occur.Life of the biosensor is 50 days and plasma glucose assays were correlated with spectropllotometric determinations(Y=10.04 + 0.886X, r=0.99, n=9).
    The Study on ο-Phenanthroline-H2O2-Sn(Ⅳ) Chemiluminescence System
    LI Huan, YU Zhen-An
    1993, 14(8):  1076-1078. 
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    In this paper a new sensitive and selective analytical method for determination of trace amounts of Sn( Ⅳ ) is proposed.The method was on the basis of chemiluminescence of o-phenan-throline-H2O2-Sn( Ⅳ ) system.Reversed flow injection technique was used.The linear range of the working curves is 2.0× 10-9-7.0×10-7 g/mLand the detection limit is 0.16 ng/mL Sn ( Ⅳ ).The method was applied to the determination of Sn (Ⅳ) in synthetic water and plating waste with satisfactory results.
    Catalytic Reduction of Some Nitrogenous Functional Group Compounds with Borohydride Exchange Resin
    QIN Cai-Qin, CHEN Jia-Wei
    1993, 14(8):  1079-1082. 
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    Borohydride exchange resin (BER) was synthesized by a commercial macroporous strong basic anion exchange resin.Some nitrogenous functional groups, such as nitro, cyano and diazo compounds were reduced by using this polymeric reducing agent under the catalysis of some metal compounds, such as CuCl2, CoCl2 and NiCl2, respectively.The effects of the reaction temperature and solvents, etc.on reducing reaction were also investigated.The reducing reaction mechanism was proposed.It is found that BER-CuCl2/EtOHsystem was effective for reducing nitro, cyano and diazo compounds.
    Studies on Catalysis of μ-Oxo-bisporphinatomanganese ( Ⅲ ) for Cyclohexane Monooxygenation
    GUO Can-Cheng, LIU Lian-Ying
    1993, 14(8):  1083-1086. 
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    This paper first reported the catalysis for cyclohexane monooxygenation with PhIOat room temperature and in air atmosphere by μ-oxo-bisporphinatomanganese ( Ⅲ ) compounds.Compared with other metalloporphyrins reported so far, μ-oxo-bisporphinatomanganese ( Ⅲ) showed the better catalytic properties on cyclohexane hydroxylation.The kinetic researches found that there existed Hammett relationship between the substituents on porphyrin rings and the rate constants of the reactions catalyzed by μ-oxo-bisporphinatomanganese (Ⅲ).
    Syntheses of Organoarsino-Containing Ferrocenyl Amine Derivatives
    DU Hong-Guang, SHI Shu-Jian
    1993, 14(8):  1087-1091. 
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    N,N-dimethylaminomethylferrocene ( Ⅰ ) was lithiated to the monolithio compound, which was then reacted with an equimolar diphenylchloroarsine (DPCA) to form 2-(dtpheny-larsino) dimethylaminomethylferrocene ( Ⅱ ) and a small amount of 2, 5-di (diphenylarsino) dimethylamino-methylferrocene ( Ⅲ ) as the by-product.When Iwas lithiated in the presence of N,N,N',N' -tetramethyl ethylene diamine (TMEDA) and then condensed with 2 mol of DPCA, 2,1' -di(diphenylarsino)dimethylaminomethylferrocene (Ⅳ) was obtained.When the products were allowed to react with an excess of methyl iodide, different methiodides were formed under different conditions.At 40℃ and a reaction time of 10 min, Ⅱ yielded a monomethiodide Ⅴ, which on hydrolysis with aqueous alkali yielded 2-(diphenylarsino)ferrocenylmethanol ( Ⅵ ).This shows that Ⅴ is a quaternary ammonium salt instead of an arsonium one, otherwise it would yield Ⅰ as the hydrolyzed product.When the reaction time was prolonged to 9 h, Ⅰ gave a dimethiodide Ⅶ, which should be a quaternary ammonium-arsonium compound.When IVwas allowed to react with an excess of methyl iodide at 80℃ for 11 h, a trimethiodide of quaternary ammonium-diarsonium compound Ⅷ was produced.The structures of the products were confirmed by elemental analysis, IRand 1HNMRspectra.The MSof Ⅱ and Ⅲ are also given.
    The Kinetic Studies of Hydrolysis of 2-, 3- and 4- Bromomethyl Pyridines
    YE De-Yong, YANG Chu-Yao
    1993, 14(8):  1092-1095. 
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    The rates of hydrolysis of 2-, 3- and 4-bromomethyl pyridines to the corresponding hydroxymethyl pyridines at 60℃ and ion strength μ=0.15 over the pHrange from 0.9 to 9.9 in buffer solutions were measured by means of HPLC.Through the mathematical treatment, the first-order and the second-order reaction-rate constants for bromomethyl pyridines and the first-order reaction-rate constants of bromomethyl pyridines conjugated acids were obtained.The mechanisms of the hydrolysis were proposed to be unimolecular nucleophilic substitution(SN1) and bimolecular nucleophilic substitution (SN2).
    Studies on the New Method for Syntheses of 1H-Indazoles (Ⅰ)
    ZHONG Zhen-Qi, XU Tong-Sheng, CHEN Xiao-Nai, QIU Yu-Zhu, HU Hong-Wen
    1993, 14(8):  1096-1099. 
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    In this paper, we put forward a new and convenient method for the synthesis of 1H-indazoles.In the presence of PPA, the cyclization of a series of 2,6-dialkoxyl (or hydroxy)ace-tophenone hydrazones(2a-f) gave 3-methyl-4-alkoxyl (or hydroxy)-1H-indazoles (3a-f).This new method offers several advantages: easy access of the reagents, reasonable yield and short reaction time.We also studied its applied range.The application of this method to 2-methoxy-4,6-dimethylacetophenone hydrazone (2g) gave 3, 4,6-trimethyl-1H-indazole (3g).But the application of it to salicyaldehyde, o-methoxybenzaldehyde, 2,4-dihydroxybenzaldehyde or o-hydroxy-acetophenone, 2-hydroxy-3, 5-dimethylacetophenone hydrazones (2h-l) could not bring about ring closure, resulted in the formation of the corresponding azines (3h-l) in excellent yields.
    The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(Ⅷ) ——Studies on the Synthesis of Aliphatic α-Oxo Ketene Cyclic Dithioacetals with Potassium tert-Butoxide as Base
    LIU Qun, ZHU Zai-Ming, YANG Zhi-Yun, XU Bai-Ling, ZHAO Hong-Wu
    1993, 14(8):  1100-1102. 
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    Ten title compounds were synthesized starting from aliphatic ketones with potassium tert-butoxide as the base.The yields are strongly dependent on the concentration of the base and solvents used.Lower concentration is favorable to raising the yields.When the concentration of the base was 0.4 mol/L, the best yield was obtained.The solvent mixed with benzene and DMFfavored the increase of the yields of products with cyclic ketones as the substrates.For the IRspectra, the carbonyl absorptions of compounds 1 are normally lower than 1647 cm-1.This might result from the strong conjugation in compound 1.Among the products, 1d-1j are new compounds.
    Studies on the Surface-Enhanced Raman Spectra of meso-Tetrakis (4-N-methoxycarbonyl methyl pyridyl)porphyrin and Its Nickel Complexes
    HE Ji-Ping, ZHOU Xiang, WU Xuan-Jie, CHEN Zhang-Ping
    1993, 14(8):  1103-1106. 
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    The surface-enhanced Raman spectra (SERS) and resonance Raman spectra (RRS) of Ni( Ⅱ)TrNEAMsPyP(4) were measured and compared with the Raman spectra of Ni( Ⅱ )TMPyP (4).Band assignments are made by analogy to those for Ni( Ⅱ )TMPyP.pH-dependent spectra of Ni( Ⅱ )TrNEAMsPyP(4) and H2TrNEAMsPyP(4)+ are presented.It has been found that the neutral aqueous solution of Ni complexes contains 4-coordinate Ni( Ⅱ )TrNEAMsPyP(4) and 6-coordinate Ni( Ⅱ )TrNEAMsPyP(4)(H2O)2. In acid solution, we assign the structure as the diaquo complexes or cat ionic complexes Ni( Ⅱ )TrNEAMsPyP(4)+ and show the transition from diaquo to hydroxy monomer/μ-Odimer complexes in the slightly alkaline solution.At pH 14.0 a second equilibrium process was observed, leading to dihydroxy complex.
    General Osmotic Coefficient
    ZHANG Suo-Jiang, HAN Shi-Jun
    1993, 14(8):  1107-1110. 
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    In this paper a new concept, known as general osmotic coefficient ( Φs), is proposed in terms of Bjerrum osmotic coefficient (Φ ), and its definition formula is given.In fact, general osmotic coefficient is an extension of Bjerrum osmotic coefficient.According to the new concept the mutually related formula between general osmotic coefficient and electrolyte activity coefficient, which has just the same form as that in the single solvent electrolyte system, is conducted.Thus the mutual calculation of the thermodynamic properties between solute (electrolyte) and solvent can be easily carried out and the non-ideal degree of the mixed solvent can be measured by it.So general osmotic coefficent has a theoretical and practical signification.
    The Diffusion Coefficient and Solubility of Tellurium in Mercury
    ZHANG Chang-Geng, XU Yi-Xin, Mu Lan
    1993, 14(8):  1111-1114. 
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    The cathodic stripping chronoamperometry is used for the determination of the diffusion coefficient and solubility of tellurium in mercury.The hanging mercury drop electrode is used as the working electrode.The pre-electrolysis is perfomed in a solution of 1 mol/L NH3-NH4Cl + 1.00×10-3 mol/L TeO32- at -0.90 V.As a result, tellurium( Ⅳ ) is reduced to elemental tellurium which then is reduced to Te2- on cathodic stripping in another cell.The cathodic stripping determination is perfomed in 0.1 mol/L NaOHat -1.40 Vby chronoamperometry.According to the following equation the diffusion coefficient Dand solubility Sof tellurium in mercury is calculated:D=r02/(πt0), S=[4nF(πD)3/2t0]-1 (ΔIt/Δt-1/2).The experimental results show that telluriun exists as the monoatomic state in mercury.
    Quantum Chemical Studies on Microstructure and Reaction Characteristics of Poly(ether ether ketone)
    NIU Li, GUO Chun-Xiao, HUANG Dong-Lu, JIANG Da-Zhen, WANG Cai-Xia, ZHANG Wan-Jin
    1993, 14(8):  1115-1117. 
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    We use AM1 programs to optimize the structure of repeat unit of poly (ether ether ke-tone) and to derive complete microconformation of PEEKmolecule chain from it.Using information of bond order, net charge and frontier orbitals that are made out from quantum chemical calculation based on optimized structure of repeat unit, we studied a few characteristics of sulphona-tion reaction and pyrolysis reaction theoretically.
    Studies on the Mechanism of p-Se Electrodeposition and Its Conversion to n-CdSe
    LIU Dong, WU Hui-Huang, ZHANG Ying-Zhou, ZHOU Shao-Min
    1993, 14(8):  1118-1121. 
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    The electrochemical formation of Se semiconductor thin-film on Ti substrate and its conversion to CdSe were studied by linear potential sweep photovoltammetry etc.The results show that p-Se thin film can be obtained by electrodepositing in H2SeO3 solution and the film can further transformed into n-CdSe in acidic CdSO4 solution cathodically.The kinetics of Se elec-trodeposition was analyzed and the possible mechanism of conversion to n-CdSe was proposed.The principle was suggested to be used for preparation of p-n semiconductor heterojunction.
    Quenching of CH(A,B) Radicals by Alkane and Amine Molecules
    CHEN Cong-Xiang, RAN Qin, YU Shu-Qin, MA Xing-Xiao
    1993, 14(8):  1122-1126. 
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    The measurements of quenching rate constants of CH(A,B) radicals by (CH3)2NH, (C2H5)2NH, (C2H5)3N, n-C5H12, n-C6H14 and n-C7H16 are presented by using laser photolysis of CHBr3 at 266 nm and time-resolved fluorescence quenching technique.It is found that the quenching rate constants for both Aand Bstates increase almost linearly with increasing C-Hnumber contained in the alkane molecule.But for larger alkane molecules, it appears that the quenching rate increase is smaller than that for small alkane molecules.The formation cross sections of complexes between electronically excited CHand amine and alkane molecules were calculated by using collision complex model.It is found that the dependence of the formation cross section of complex on the number of C-Hbonds in the alkane molecules is in good agreement with that of the measured quenching cross section.This implies that the attractive forces between CH (Aand B) and alkane molecules are probably important in collisional quenching processes of CH (Aand B) by alkane molecules.The similar conclusion could be drawn for quenching of CH(Aand B) by amine molecules.
    An Investigation of the Photochemical Reactions ( Ⅱ ) ——The Photochemical Reactions of Sulfur Dioxide and i-Pentane
    DU Yao-Guo, ZHANG Ying, XU Zi-Li, GUO Hai-Chen
    1993, 14(8):  1127-1130. 
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    The photochemical reactions of sulfur dioxide and i-pentane in the presence or absence of oxygen systems were studied.Aerosol and a series of products such as alcohols, aldehydes, ketones, acids, esters, hydrocarbons and organic sulfur compounds were identified by GC/MS.According to the characters of such compounds and the free radical theory, the mechanism of these photo-chemical reactions were suggested.These results are very important in the studies of chemistry of air pollution.
    Reactions of C60 with Multichloroethanes in Gas Phase
    LIU Zi-Yang, GUO Xing-Hua, SONG Feng-Rui, LIU Shu-Ying
    1993, 14(8):  1131-1134. 
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    In the ion source of mass spectrometer, the reactions between C60 with the main fragments of 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane and 1,1,2,2-tetra-chloroethane were performed and the corresponding adduct ions were formed by using a chemical inization mathod.C60 is very active to many organic ions in the gas phase.The odd electron fragments were more reactive with C60 than the even electron ions, this shows the radical capture property of C60.
    Catalytic Behaviour of Pillared Materials in the Disproportionation Reaction of β-MN
    SHEN Jian-Ping, JIANG Ting-Sun, MA Jun, JIANG Da-Zhen, MIN En-Ze
    1993, 14(8):  1135-1139. 
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    The catalytic reactions of β-methylnaphthalene(β-MN) were carried out over the prepared pillared materials with different pillar height, pillar density and content in the layer and pillar.The results show that β-MNis mainly converted to a-MNby isomerization over the samples.The activity and selectivity of isomerization and disproportionation have good relation to acid amount, weak acid amount and Lacid amount, respectively.Low pillar height and high pillar density are in favour of the formation of 2,6-DMN.
    Studies on Sensitization of PMACME LB Film to n-Si(100)
    JIANG Lei, WANG De-Jun, GAO Mang-Lai, ZHAO Ying-Ying, LI Tie-Jin
    1993, 14(8):  1140-1142. 
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    Based on the synthesis of mono-[6-(4,1' -azonaphthalene)-oxy] hexyl ester of ploy-maleic (PMACME), the PMACME LBfilm was deposited on CaF2 and n-Si(100) substrates.The properties and structure of the film were characterized by UV-Vis and IRtechniques.The experiment of surface photovoltage spectrum (SPS) indicates that there is a great sensitization of the films to the n-Si(100).The interfacial charge transfer process was also discussed primitively.
    Variational Transition State Theory Studies on the Systems OCS,CO2 and CS2
    YANG Yu-Wei, JU Guan-Zhi
    1993, 14(8):  1143-1145. 
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    In this paper, the variational transition state theory is first used to study the kinetics of exoergic reactions O+CS→CO+S, O+CO→CO+Oand S + CS→S+CSon the potential energy surface without any saddle point.The features in the kinetic bottleneck regions of these reactions are measured.The reaction rate constants are calculated, and those for the reaction O + CSare compared with the results obtained by the classical trajectory method and the experiment values.Our results are consistant with them.
    Aggregations of C60 Cations and Anions Induced by Laser
    HUANG Rong-Bin, HUANG Feng, LIN Feng-Chen, LIU Zhao-Yang, ZHENG Lan-Sun, LIU Zhao-Xiang, HOU Hui-Qi, QIN Qi-Zhong
    1993, 14(8):  1146-1147. 
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    The pure buckerminsterfullerene sample was ablated by pulsed laser beam in high vacuum.The recorded mass spectra of positive and negative ions both show that the fullerene can aggregate to form even larger cluster ions.The magic numbers are 118, 168, 224, 278 and 332 for the cations and 118, 176, 228 and 282 for the anions.
    The Magnetic Field Effect on Electrolysis of NaCl Solution
    SHENHe-Bai, Hiroi Masao
    1993, 14(8):  1148-1150. 
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    The magnetic field effect on anodic processes and chlorine evolution efficiency in electrolysis of NaCl solution of different pHvalues was studied by the measurements of cyclic voltam-mograms (CV) and determination of chlorine evolution efficiency.This effect can be explained by the electrolyte agitation caused by the magnetohydrodynamic (MHD) effect.
    TPR Studies of Pd/HM Catalyst for Isomerization of Light Normal Paraffins
    SU Yun-Lai, HU Jia-Fen, LI Quan-Zhi
    1993, 14(8):  1151-1153. 
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    TPRwas applied to study the reduction behavior of the catalyst of Pd/HMfor the iso-merization of light normal paraffins.The results show that palladium can be completely reduced with 10%H2-Ar steam at about 200℃.The TPRspectrum consists of three reduced peaks at 27℃, 80℃ and 125℃ respectively.They corresponded to the reduction of Pd2+ ions occupying different sites in channels of HMand the Pd2+ ions are reduced by one step which is as follows: Pd2+ + 2e=Pd.The distribution of palladium on H-mordenite is about 10% on external surface, 65% in main channel of 12-membered ring and 25% in the channel of distorted 8-mem-bered ring.
    Studies on the Preparation, Structure and Reaction Performances of Supported MoO3/Al2O3 Ultrafine Catalysts
    ZHANG Chi-Ming, CHEN Song-Ying, PENG Sao-Yi, HAO Jian-Gang
    1993, 14(8):  1154-1156. 
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    In this paper, the supported MoO3/Al2O3 ultrafine catalysts have been synthesized with the supercritical drying method.The n-heptane reforming reaction has been used as a model reaction, the different qualities between the ultrafine and the conventional catalysts have been discussed, the ultrafine MoO3/Al2O3 catalysts have more stability than the conventional catalysts, this is because there are much more strong reactions between the active component and support as well as less volatility of active component.The ultrafine catalysts have less cracking conversion and selectivity, this is because there are weak acid centers on the Al2O3 surface.
    H2/D2 Isotope Effects in Syngas Conversion Reactions over Vanadium-promoted Rhodium Catalyst
    WANG Hai-You, LIU Jin-Po, FU Jin-Kun, TSAI Khi-Rui
    1993, 14(8):  1157-1158. 
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    H2/D2 isotope effects in syngas conversion reactions over V-promoted rhodium catalyst were investigated by performing CO+H2 and CO+D2 reaction alternatively.Noticeable deuterium inverse isotope effects on hydrocarbons (including CH4, C2, C3, and C4) formation and on oxygenatesGncluding CH3OH,CH3CH2OH,CH3CHO) formation were simultaneously observed.
    Liquid Crystalline Properties of Novel Polyazomethineethers with Mesogens Containing Biphenyl Core and Pendant Group
    ZHANG Qi-Zhen, LI Xiao-Fang, XUE Qing-Bin
    1993, 14(8):  1159-1162. 
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    The liquid crystalline properties of novel main chain polyazomethineethers series(SBn, n=3-8.10) were characterized by polarized microscopy with a hot stage, DSCand X-ray diffractions.The disclination and band texture were observed for seven polymers.Their melting points are affected by number of methylene group in the flexible units and show an odd-even effect in zigzag manner.
    Studies on the Characteristics of Inverse Microemulsion Copolymerization of (2-Methacryloyloxyethyl )trimethyl Ammonium Chloride and Acrylamide
    HA Run-Hua, HOU Si-Jian
    1993, 14(8):  1163-1166. 
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    In this paper, selecting (SPAN80 + OP10) complex and K2S2O8-Na2SO3 redox system as the emulsifier and initiator, respectively, the inverse microemulsion copolymerization of (2-methacryloyloxyethyDtrimethyl ammonium chloride and acrylamide was developed.The effects of monomer's ratio, electrolyte concentration and oil/water ratio on the molecular weight and cationic strength of copolymer were studied.
    Interpenetrating Polymer Networks with Introduced Hydrogen Bonding ( Ⅴ ) ——The Effecct of Composition on Phase Structure and the Properties
    XIAO Hong, JIANG Ming, YU Tong-Yin
    1993, 14(8):  1167-1171. 
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    IPN's of polybutyl acrylate (PBA) and PS(OH), a copolymer of styrene and HFMS (a hydroxyl-containing monomer) were prepared by a sequential process, DSCand TEMshow that all the IPN' s display two-phase structure even when the hydroxyl content in PS (OH) reached 30 mol%.The compositions of the two phases were calculated from the Tg values based on the “copolymerization equation”.It is found that there is no composition change of the two phases when the content oi PS(OH) in the IPN' s is less than 50%.Apparent Tg increase of the PBA-rich phase is found when the hydroxyl content in PS (OH) is as high as 30 mol% and PS (OH) becomes the major component in the IPN' s(>60%).This indicates that PS(OH) can be partially solubilized in the PBA-rich phase only when there are enough hydrogen bonds existing.The relative modulus of the IPN' s as a function of the total composition shows that in the composition range of PS(OH) about 30%-50% there is a drastic change of the modulus accompanying the variation of the phase structure.The modulus data are in good agreement with the Budi-ansky equation rather than the Kerner equation implying some extent of phase continuity.
    A Polymer Lewis Acid Catalyst——Cation Exchange Resin SnCl4 Complex
    LIU Fu-An, TIAN Ming-Yuan, LI YAO-Xian, HUANG Hua-Min
    1993, 14(8):  1172-1175. 
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    Amacroporous cation exchange resin-supported SnCl4 was synthesized in CS2 to form a stable complex of containing 8.4% of Sn.The SnCl4 complexed in the ion exchange resin is resistant to water and air.The polymer Lewis acid complex catalyst can be used to catalyze many organic reactions with high yield, such as esterification, acetalization and ketal formation.The catalyst is also effective for Friedel-Crafts alkylation reaction.The title catalyst can be reused at least 10 times.
    The Effect of Hard Segment Content of CAMDA-Extended Polyurethane-Urea on Morphology and Properties
    GAO Yun, LI Mai-Jin, WANG De-Ning, HU Chun-Pu, YING Sheng-Kang
    1993, 14(8):  1176-1181. 
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    Anew aromatic diamine (CAMDA) as chain extender for RIMpolyurethane-urea (PUU) was synthesized.Structure of CAMDAwas confirmed by IR, 1HNMRspectra and MSanalysis.CAMDAis a viscous liquid chain extender with proper reactivity which can not only be used for RIMoperation but also for casting elastomer.The ultimate physical properties of CAM-DA-extended RIMPUUis close to that of DETDAextended one.Aseries of CAMDA-extended PUUsamples with hard segment content of 10%-45% were prepared for studying morphology by DSC, SEM, the corresponding mechanical properties were measured.The results showed that the hard segment rich domain changed from loosen parallel streaks, interlacing streaks to spherulitic superstructures with increasing the hard segment content, the strength of PUUincreased with this trend of morphology change.
    Preparation and Characterization of Functional Ultrathin Ordered Molecular Deposition Film
    GAO Mang-Lai, KONG Xiang-Xing, ZHANG Xi, SHEN Jia-Cong
    1993, 14(8):  1182-1183. 
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    The fabrication and structure characterization of a new kind of self-assemble film, molecular deposition (MD) film, were reported.According to the salt-forming reaction of organic or inorganic anionic and cationic compounds, an ordered layer structure ultrathin film was formed by alternative deposition of anionic polyelectrolyte (or bipolar) and cationic polyelectrolyte (or bipolar).MDis a novel technique for fabrication of organic ultrathin film, and also is a self-assemble ultrathin ordered film.