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    24 October 1996, Volume 17 Issue 10
    Articles
    Synthesis of Fast Ionic Conductor by Microwave Method
    FENG Shou-Hua, PANG Guang-Sheng, XU Ru-Ren
    1996, 17(10):  1495-1499. 
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    A series of potassium vanadium phosphates K3Sb3P2O14,K2SbPO6,KSbP2O8,KSb2PO8,K5Sb5P2O2Oand Li2+2xZn1-xGeO4(0.36<x<0.85) were synthesized for the first time by microwave radiation,All microwave reactions are usually completed within60~120 minutes at a microwave frequency of 2450 MHz and power of 50~650 W.The XRDpatterns and SEMphotographs indicate that the grains of samples prepared by microwave heating are small and uniform.Compared with the conventional synthetic method,the microwave dielectric heating effect not only leads to the dramatically rapid rate of solid state reaction,but also allows some control of materials'properties and reaction selectivity.The results of preliminary study on the mechanism of microwave radiation synthesis show that the heating media can stimulate the absorption of micro-wave radiation by the reactants,and then the ionic diffusion rate on the interface of reactant and product increased.The formation of crystallites of fast ionic conductor and the crystal growth were also induced by microwave dielectric loss heating.
    Synthesis and Characterization of Layered Double Hydroxides Pillared with Peroxoheteropolyanions
    HUA Rui-Nian, SHAN Qiu-Jie, GONG Jian, Qu Lun-Yu
    1996, 17(10):  1500-1503. 
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    Pillared layered double hydroxides(LDH),Zn2Al(OH)6-SiW11(TiO2)O39 and Zn2Al(OH)6-SiW9(TiO2)3O37 were synthesized by direct ion-exchange reaction in aqueous solution,and characterized by elementary analysis,XRD,IR and XPS spectra.The interlayer spaces of the pillared products increase from 0.92 nm to 1.47 nm with the peroxoheteropolyanions displacing the NO3- ions in the gallery.The results from IR,XPS and chemical analysis show that the structures of peroxoheteropolyanions are well remained.
    The Photophysical and Photochemical Properties of Water-soluble Metalloporphyrins in Aqueous Solution
    LIU Zhi-Xian, MU Lin-Jing, SHI Shuang-Qun, ZHOU Yong-Qia, SHEN Pan-Wen
    1996, 17(10):  1504-1508. 
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    Several photophysical(spectra,oscillator strength,lifetimes,and quantum yields for fluorescence),excited state redox properties and photo-stability of five water-soluble metalloporphyrins(ZnTMAPP,ZnTMPyP,MgTMPyP,ZnTBPyP,and ZnTTPS4 where TMAPP=tetrakis-(trimethylaminophenyl) porphyrin,TMPyP=tetrakis(N-methylpyridyl) porphyrin,TBPyP=tetrakis(N-benzylpyridyl) porphyrin,and TTPS4=tetrakis(3-sulphpotolyl)porphyrin) were investigated.It was found that MgTMPyPis a good photosensitizer compared with others.
    Studies on Structure and Fluorescence Spectra of High-pressure-treated EuI2
    WANG Lin-Tong, WANG Shi-Hua, ZHAO Xin-Hua, SUN Ji-Rong
    1996, 17(10):  1509-1512. 
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    The structure and fluorescence properties of high-pressure-reated EuI2 were studied.The structural change of EuI2 from monoclinic to orthorhombic and the increase of both structural symmetry and coordination number of Eu2+ were observed respectively.It was found that high-pressure treatment could split the energy levels of 4f65d and made the central energy levels lower so as to induce the red shift of emission spectra.Moreover,a new emission peak (449 nm) is assigned and a new phase(EuI2-Ⅴ) is reported.
    Microwave Synthesis of Luminescent Materials of Rare-earth Phosphates
    XU Wen-Guo, TIAN Yi-Guang, LIU Miao, LIU Hai-Tang, FANG Guang-Hua, PANG Wen-Qin
    1996, 17(10):  1513-1515. 
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    In this paper,we report a new route to syntheses of a series of pure luminescent materials of rare earth phosphates with crystalline phase,microcrystalline glass and glass using microwave method under the condition of appearance microwave power at 20%~70% level(100% power is equal to 650 W of microwave energy, adjusting at 10 level) and reaction time at 7~10 min.The molar ratio of Re2O3 and P2O5 plays an important role for the formation of the luminescent materials of crystalline phase,micro-crystalline glass and glass.The crystal structures were characterized by X-ray diffraction.The infrared spectra of these luminescent materials formed under microwave condition showed that the NO3,NH4+ and H2O species in the starting mixture were completely removed,giving pure luminescent materials for crystalline phase,micro-crystalline glass and glass.The luminescent properties were investigated by fluorescence emission and excitation spectra.The experiment results show that the Vion in the substrate is sensitive to Eu3+,Dy3+,Sm3+,Tb3+ increasing the luminescent intensity,for example,the emission intensity of the sample Y0.95(V0.03, P0.97)O4:Eu0.05 is 80 times more than that of the sample without Vion.
    Studies on Synthesis and Characterization of the Ternary Complexes of Europium(Ⅲ)-β-diketonate-4,4'-bipyridine-N,N'-dioxide
    LIN Hui-Wen, ZHU Wen-Xiang
    1996, 17(10):  1516-1518. 
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    A new ligand 4,4'-bipyridine-N,N'-dioxide and two europium (Ⅲ) ternary complexes of β-diketonate and 4,4'-bipyridine-N,N'-dioxide were first prepared[the β-diketonates are thenoyltrifluoracetonate(TTA-) and dibenzoylmethanate(DBM-)].Their compositions were determined as formulae of Eu(TTA)3·0.5L and Eu(DBM)3·0.5L(L=4, 4'-bipyN2O2) by elementary analysis,Their properties were studied with IRabsorption and fluorescence spectroscopies.Their possible structures are also proposed.
    Investigation of the Microwave Radiation Syntyhesis and Ionic Conductivity of SrCeO3
    XU Xiu-Ting, CUI De-Liang, FENG Shou-Hua, XU Ru-Ren
    1996, 17(10):  1519-1521. 
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    Single phase SrCeO3 was prepared by microwave radiation synthesis method,and the effect of microwave power and reaction time on the products was investigated.The sample was characterized by XRD,complex impedance and TG-DTA techniques,and its ionic conductivity was measured under certain humidity.The activation energy for ionic conduction of SrCeO3 is 74.65 kJ/mol.
    Spline Wavelets Analysis of Step Voltammetry Signals
    ZOU Xiao-Yong, MO Jin-Yuan
    1996, 17(10):  1522-1527. 
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    For the first time,this paper presents spline wavelets application to step voltammetry signals,The method has advantages as follows:taking short time to deal with all data,having no necessary to find the relations with variables in any other systems,handling the target functions and initial conditions directly from sample data and obtaining few data necessarily.Some reasonable noises are added to the theoretical data,Signal-to-noise ratio varies from 0.1 to 100.The result is satisfactory and exciting even if the S/Nratio decreases to 0.15.Experimental data from a low concentration of Ti(Ⅳ)-H2C2O4 and W (Ⅳ)+Mo(Ⅳ)-HAPP-KClO3 system are utilized to demonstrate the application of wavelet analysis.The agreement between the theoretical and experimental results is excellent.
    A PVC Membrane Electrode Sensing Phosphate Ion Based on Binuclear Organotin
    LIU Dong, CHEN Wen-Can, HE De-Liang, SHEN Guo-Li, Yu Ru-Qin
    1996, 17(10):  1528-1531. 
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    Remarkable progress has been achieved in the development of electrodes sensing various anions since the introduction of quaternary ammonium salts as carriers.Question remains,however,as to the preparation of electrodes sensing the phosphate ion.In this report,bis(tribenzyltin) oxide is tested as a carrier for phosphate ions.Liquid membrane containing this carrier,o-nitrophenyl octyl ether as plasticizer,and poly(vinyl chloride)(PVC) as membrane matrix showed Nernstian response for hydrogen phosphate in the 5×10-6 mol/Lto 10-1 mol/Lactivity range with a slope of-30.1 mV/dec.in pH=7.2±0.02 solutions.The electrode displayed selectivity patterns sequence:HPO42-~I->Br->NO3->Cl->Ac->SO42-,which is not in accordance with the selectivity sequence pattern obtained from classical anion exchangers.Also included here is the comparison of potentiometric response characteristics between the binuclear and mononuclear organotin compounds,An enhanced response towards from binuclear compound based electrode was observed,showing that binuclear organometallic compounds may become a new promising class of carrier for anions.
    Studies on Nickel Phthalocyanine-Surfactant Film Modified Electrode and Its Catalytic Properties
    LIU Ting, HU Nai-Fei, ZENG Yong-Huai
    1996, 17(10):  1532-1536. 
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    Nickel phthalocyanine(NiPc)-didodecyldimethylammonium bromide(DDAB) surfactant film electrode could be prepared by casting the mixture of NiPc with DDABchloroform solution on the surface of pyrolytic graphite electrode and then leaving the chloroform evaporated.Cyclic voltammetric experiments showed that,in KBr solution,the film electrode have two pairs of well-defined and stable reduction and oxidation peaks,For the first pair of peaks,Epc1=-0.64 Vand Epa1=-0.60 V(vs.SCE),while for the second pair,Epc1 =-0.84 V,and Epa1=-0.80 V,respectively,This paper studied the electrochemistry of the second pair emphatically.The electrochemical parameters,such as electron diffusion coefficient,De,and apparent heterogeneous electrode reaction rate constant,k0',were estimated.The NiPc-DDAB film electrode could be used to catalyze electrochemical reduction of various halogenated acetic acids.The NiPc-DDAB films were also characterized by various techniques of surface analysis.
    The Compression and Reconstruction of IR Spectra by Wavelet Transform
    WANG Hong, SI Sheng-Zhu, XIONG Jian-Hui, ZHANG Mao-Sen
    1996, 17(10):  1537-1540. 
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    An introduction of wavelet transform and multiresolution analysis is presented.The IRspectra of polyethylene are compressed and reconstructed successfully by Daubechies'compactly supported orthogonal wavelet bases and Mallat's algorithm.The IRspectra can be reconstructed satisfactorily even though the original data are compressed 5 times,and the mean variance is 0.260.This makes the storage,index and processing of IRspectra more conveninet.
    Polarographic Catalytic Determination of Glycyrrhizic Acid in the Presence of KIO3
    GUO Wei, ZHAO Min-Ren, SONG Jun-Feng, LIU Yun
    1996, 17(10):  1541-1543. 
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    A polarographic catalytic wave of glycyrrhizic acid(GA) in the presence of KIO3 was observed.Based on the catalytic wave,a new method for the determination of GAwas developed.In0.1 mol/L NaAc-HAc-2×10-3 mol/L KIO3 buffer solution(pH=4.60±0.05),the first derivative peak height of the catalytic wave of GAis proportional to its concentration in the range from 2.0×10-7 to 2.4×10-5 mol/L,The sensitivity of the proposed method is about 20 times higher than that without KIO3.100-fold glucose,200-fold glycine,20-fold cysteine do not interfere in the determination of 4×10-6 mol/L GA,The proposed method was applied to the determination of GAin pharmaceutical Potenlin injection.
    Studies on the Determination of Trace Iridium in Fossil of Dinosaurian Eggs with Catalytic LTLS
    YAN Hong-Tao, YANG Sheng-Ke
    1996, 17(10):  1544-1546. 
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    A new method for the determination of trace iridium in fossil of dinosaurian eggs with catalytic laser thermal lensing spectrometry is presented in this paper.The method is based on the kinetic reaction in which trace iridium catalyzes the decomposition of hydrogen peroxide in basic condition and on the determination of the magneson Ⅱfading speed.The detection limit is 5.2×10-12 g/mLfor iridium.The linear range of the calibration curve is 0.2~35 ng/mLof iridium and correlation coeffcient is 0.9974.The method has been applied to the determination of the trace iridium in fossil of dinosaurian eggs in Nanyang region,China.
    Catalytic Kinetics of Tetraiodofluorescein,Rose Bengel and 3,5-Diiodo-L-tyrosine
    BAI Ya-Li, GUO Wei, SONG Jun-Feng
    1996, 17(10):  1547-1549. 
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    The kinetic behaviour of tetraiodofluorescein(TIF), rose bengel(RB) and 3,5-diiodo-L-tyrosine(3,5-DIT) to catalyze Sandell-Kolthoff reaction was studied.The results showed that the order of catalytic abilities of organic iodine-containing compounds mentioned above is 3,5-DIT>RB≈TIF.A new method for detecting the compounds by kinetic-oscillopolarography was described.16~8μg/mLof 3,5-DIT,5~50 μg/mLof RBand 1~50μg/mL of TIF can be determined by using initial velocity method at room temperature.
    2D NMR Studies of Chinese Rape Pollen Dodecapeptide
    SONG Yan-Ling, GAO Xin-Feng, WAN Kai-Ke, SUN Hong-Yin, JIN Sheng
    1996, 17(10):  1550-1554. 
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    The dodecapeptide(RPP) is an active peptide,which we extracted from chinese rape pollen.The dodecapeptide enhances the activity of TNFon murine tumor cells and also shows immunopromotive activities.The possible conformation of the RPP,which has been previously studied by circular dichroism,has been studied by one and two dimensional NMR spectroscopy.All resonance assignments were made by use of two dimensional correlation spectroscopy.The problem of sequential resonance assignments was solved by using two dimensional NOE spectroscopy.The dihedral angles of the amide planes of the RPP,were calculated from the measured coupling constants using Karplus equation.The temperature coefficient and NOEin different solvents together suggest that RPP exists mainly as random coil in aqueous solution and some sections in the RPPexist as γ-turn.
    Studies on the β-Galactosidase from Gram──Gatalytic Reaction Kinetics of ONPG Hydrolysis and the Chemical Modification of Activity Sites
    LI Xu-Yuan, ZHAO Ke-Hao, MEN Yan-Fa, MA Jian-Tai
    1996, 17(10):  1555-1559. 
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    The catalytic properties of β-galactosidaseⅠand Ⅱpurified from gram germination seeds as ONPGhydrolysis catalysts were investigated.According to the Michaelis Menten mechanism of enzyme catalytic reaction,the kinetic parameters KM,rm and Ea of catalytic hydrolysis reaction of ONPG were measured.By using of various chemical dressing reagents for enzyme,we studied the function groups of β-galactosidaseⅠ.The relationship between the function groups and catalytic activity of enzyme revealed that hydrosulphonyl and tryptophan existed in β-galactosidase Ⅰand they were the composition groups in the active site of β-galactosidaseⅠfor the catalytic hydrolysis reaction of ONPG.
    Studies on the Activities and Synthesis of N-Substituted Pyrimidinyl or Triazinyl-3-carbamoyl-4-hydroxy-2H-1,2-benzothiazine-1,1-dioxides
    ZHAO Guo-Feng, ZOU Xiao-Mao, YANG Hua-Zheng
    1996, 17(10):  1560-1564. 
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    In this paper new 3-carboxamides of 4-hydroxy-2H-1,2-benzothiazine-1,1-dioxides were synthesized by aminolysis of 4-hydroxy-2-hydro(methyl)-2H-1,2-benzothiazine-3-carboxylic acid ethyl ester-1,1-dioxides with substituted aminopyrimidines or aminotriazines.Their structures were characterized by 1H NMR,IR,MSand elementary analysis.The biological tests indicated that the majority of these compounds showed herbicidal activity and some showed better plant-grownth regulating activity and antiinfammatory activity.
    Studies on the Synthesis and Biological Activity of the Derivatives of 4-Hydroxyl-3-acyl (alkoxylcarbonyl)-2H-1,2-benzothiazine-1,1-dioxides
    ZHAO Guo-Feng, YANG Hua-Zheng, WANG Ling-Xiu
    1996, 17(10):  1565-1569. 
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    In this paper 20 new derivatives were synthesized by the reaction of 4-hydroxyl-3-acyl(alkoxylcarbonyl)-2H-1,2-benzothiazine-1,1-dioxides(Ⅱa-c) with aryl isocyanates,phenyl hydrazine,methyl chloroformate and ethylene glycol,and the reaction of compounds Ⅱa-c with aryl isocyanates was studied under the different molar ratios of strong base NaH.Their structures were characterized by 1H NMR,IRand elementary analysis.The biological tests indicated that the majority showed good herbicidal activity and plant-growth regulating activity.
    Addition Recation of Buckminsterfullerent with Amines and Electrospray Ionization Mass Spectrometry Determination of Reaction Products
    WEI Xian-Wen, WU Ming-Fei, ZHANG Cheng, QI Ling, XU Zheng, CAO Ya-Cheng, ZHOU Ke-Yu
    1996, 17(10):  1570-1573. 
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    The addition reactions of C60 with trimethylenediamine and 3-dimethyl-aminopropylamine were reported.The reaction products were determined directly by ESI-MSwithout pre-ionization.The reaction product precipitated from toluene,which prevented from polyaminates and led the mono-diamine adduct as a main product.Addition to main product there are some C60On(NH2CH)2CH2CH2NR2)m(R=H,CH3) when the reaction runs at open air.The mono-diamine adduct may be gotten with control reaction condition.
    Studies on the Reactions of Polyphenylmethyl-and Polybenzylmethyl-Siloxanes with Fluorinated Acyl Peroxide
    GONG Yue-Fa, LUO Gui-Xian, ZHAO Cheng-Xue
    1996, 17(10):  1574-1577. 
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    Polyphenylmethyl and polybenzylmethyl siloxanes were prepared individually by the condensation of phenylmethyldiethoxysilane or benzylmethyldiethoxysilane,and their reactions with fluorinated acyl peroxide(FAP),carried out under mild conditions,were investigated by the titration,IR,1H NMRand 19F NMRspectrometry.It was found that no detectable fluorinated carboxylic acid was formed during the reactions,and the predominantly formed product was the polysiloxane fluoroalkylated in benzene ring.The utilization ratio of fluoroalkyl group in FAPwas obviously dependent upon the molar ratios of the reactants and the solvent used,and it was observed that over one fluoroalkyl group in FAPcould be introduced into the benzene ring of polyphenylsiloxane.In addition,the surface tension of the polyphenylsiloxanes was markedly reduced by the introduction of fluoroalkyl group at low fluoroalkylation ratios.Based on the experimental observations,we can consider that the FAPwas valuable reagents for introducing fluoroalkyl group into polyphenylsilioxanes conveniently,and the reactions,initiated by the thermal decomposition of FAP,possibly underwent via the fluoroalkyl radical attack on the benzene ring.
    Studies on Design and Synthesis of New Triazole Compounds Containing 2H-Pyrazole
    SHI Yan-Nian, YANG Yang, FANG Jian-Xin, LU Wen-Shuo
    1996, 17(10):  1578-1582. 
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    Ten new derivatives of new triazole compounds which contain the ring of 2H-pyrazole were designed and synthesized.The structures of new compounds were confirmed by 1H NMR,IR,MS and elemental analysis.The way and mechanism of the reaction ofα,β-unsaturated ketone and phenylhydrazine were also discussed.The results of bioassay indicate that each compounds has some biological activities.
    Studies on Organo-Silicon Compounds with Biological Activity(ⅩⅢ)──Synthesis or 1-(O,O-dialkyl-phosphorodithioate)methy 1-2,8,9-trioxa-5-aza-1-silatricyclo[3,3,3,01, 5]undecanes
    LIAO Ren-An, CHEN Xiao
    1996, 17(10):  1583-1585. 
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    Nine 1-(O,O-diakyl-phosphorodithioate) methy1-2,8,9-trioxa-5-aza-1-silatricyclo[3,3,3,01,5]undecanes(1-9) were synthesized.Their structures were established by elemental analysis,IR,1H NMRand MS.Their bioassay has been done.
    Studies on the Synthesis of Methy-1-5-O-benzoy-1-2,3-dideoxy-3-nitro-D-pentafuranoside
    SHI Da-Qing, ZHOU Long-Hu, GAO Yuan, DAI Gui-Yuan
    1996, 17(10):  1586-1588. 
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    The synthesis of methy1-5-O-benzoy1-2,3-dideoxy-3-nitro-α-and β-D-pentafuranoside 1a and 1b from D-(+)-xylose is described.The four isomers,the intermediates for synthesis of 1a and 1b,methy1-5-O-benzoy1-3-deoxy-3-nitro-D-ribo and D-xylo,α,β-pentofuranoside 7a,7b,7c and 7d were separated and identified.The isomerization of C-3 nitro group of compounds 6,7 were studied.
    Dynamic Behavior of Trimolecular Reaction in One Dimension Medium
    WAN Rong, HU Hong, LI Ru-Sheng
    1996, 17(10):  1589-1593. 
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    It is well known that the dynamic behavior of chemical reactions in fractional or low dimension medium is greatly different from that ruled by the classical chemical dynamics.In this paper,the anomalous dynamic behavior of trimolecular reaction Xin one dimension medium is studied.Anew theoretical method is developed,by which an analytical solution to the dynamic behavior of this reaction under different initial conditions is obtained.In addition,this new method is verified by the results based on some numerical simulations.
    Quantum chemical Study on Mo2C8 Cluster
    FENG Ji-Kang, GE Mao-Fa, HUANG Xu-Ri, YANG Cheng, SUN Chia-Chung
    1996, 17(10):  1594-1597. 
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    There is considerable interest in metal-carbon clusters because of the possible applications of metal-carbon cluster to catalytic and new electronic materials,pollution control,chemical tracers,superconductive materials and in site-specific protein chemistry.In recent years,studies have especially focused on transition-metal carbon clusters.In this paper,quantum chemical ab initio method is used to study the geometric and electronic structures of the Mo2C8 cluster.In trying to determine likely candidates for the structure of ground state of Mo2C8,a number of possible isomeric structures were investigated.The most stable structure is found to possess C2h symmetry,where two Mo atoms connect directly each other and each Mo atom connects to four carbon atoms,Mo atom is enclosed by Catoms,so as the spatial effect and bond forming property are concerned,the reactions of Mo2C8- with NH3,H2O are difficult.In fact,experiment had observed Mo2C8- ion are indeed completely unreactive with NH3 and H2O.Furthermore,our calculated EAof this isomer is 3.6 eV,which is just the upper limit of the experimental value(the experimental value of EA(Mo2C8) is between 2.7±0.2 eVand 3.3±0.3 eV),and this structure can also explain other existing experimental results perfectly.
    Langevin Mode Study of Solvent Viscidity Influence on the Properties of 18-Crown-6
    YANG Jie, TANG Zuo-Hua, WU De-Yin, LI Ze-Rong, TIAN An-Min, YAN Guo-Sen
    1996, 17(10):  1598-1602. 
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    Both conformers(Ci,D3d) of 18-crown-6 have been studied by Langevin mode method under four viscidities of solvent:0.0,3.0×10-4,6.0×10-4 Pa·s(about the viscidity of methol at room temperature),9.0×10-4 Pa·s(about the viscidity of water at room temperature).For viscidity of 9.0×10-4 Pa·s,both Oseen method and Rotne-Prage method were used in the calculation.The results showed that the viscidities of solvent greatly influenced on the properties of 18-crown-6,especially the distribution of the vibrational frequency and the librational angle of the bond vector.The effects of nondiagonal elements of the frictional matrix must be considered by using Oseen or Rotne-Prage method when the viscidity of solvent is large.At the same time,the results also show that Langevin mode method is a very effectivce model for interpreting molecular motion in solution.
    The Effect of Organic acids on the Cloud Points of Triton X-100
    SHEN Ming, GUO Rong, LIU Zheng-Ming, LIU Tian-Qing
    1996, 17(10):  1603-1607. 
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    The effect of organic acids on the cloud points of Triton X-100 was related to the hydrophilicity and space structure of organic acids and solubilization position in the micell.The addition of straight chain monoacids made the cloud point of Triton X-100 system decrease.The longer the chain length of straight chain monoacids is,the stronger the effect on the cloud points is.The effect of the straight chain diacids on the decreasing of the Triton X-100 cloud points is weaker than that of the straight chain monoacid.And it made the cloud points of Triton X-100 system increase if the carbon number of acid nc<6,and decrease if nc≥6.The addition of acids with branch chain and acids substitute made the cloud points of Triton X-100 system decrease within a lesser range,because of their steric hindrance effect.
    Thermodynamic Study of Coordination of Meso-substituted Iron(Ⅲ)Tetraporphyrin with Substituted Imidazoles
    CHEN Hong-Wei, ZHU Zhi-Ang, RUAN Wen-Juan, CHEN Zheng-Hua, ZHANG Zhi-Hui, CHEN Rong-Ti
    1996, 17(10):  1608-1612. 
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    The thermodynamics of axial coordination reaction of Fe(Ⅲ)T(m-X)PPCl(X=—CH3,—H,—OCH3,—Cl,—NO2)with ligands of the substituted imidazole(L=Im(imidazole),2-Melm(2-methylimidazole),GMZ(clotrimidazole),at different temperature in DMSOhave been studied.
    Synthesis and Properties of N-Benzylindotricarbocyanine Dyes
    CHEN Xin, YAO Zu-Guang
    1996, 17(10):  1613-1616. 
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    Five N-benzylindotricarbocyanine dyes were synthesized,all of which are new compounds and have not been reported yet.Their structures were confimed by IR,1H NMRspectroscopy and elementary analysis.Electronic absorption spectra,fluorescence emissin spectra,photostabilities and solubilities were also studied.It was found that the λmax of dye solutions and dye films were all within 780~830 nm;the solubilites of dyes in 1,2-dichloroethane were better than those in ethanol;introducing benzyl group on nitrogen atom improved the photostabilities greatly(compared to HITCI)
    Catalytic Behavior for Oxidative Dehydrogenation of Ethane over Doped MTiO3 Catalysts
    CHEN Tong, LI Wen-Zhao, YU Chun-Ying, JI Ya-Ying, YU Zuo-Long
    1996, 17(10):  1617-1621. 
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    The catalytic behavior of the various doped-MTiO3(M=Ca,Sr) catalysts for the oxidative dehydrogenation of ethane(ODHE) was examined in the temperature range of 700 ~850℃.All of the catalysts have certainly shown a catalytic activity for ODHE.When Li+substituted Ti4+ in CaTiO3,a much better improvement in the C2H4 selectivity was observed.Selectivity 71.7% for C2H4,and conversion 87.8% for C2H6 could be obtained over the catalyst,CaTi0.9Li0.1O3-δ at 850℃.The substitution of Sr for Ca in Ca1-xSrxTi0.9Li0.1O3-δ could give a high selecitivity(≥90%) for C2H4 in a very widely temperature range(700~850℃).The effect of Li+ doping was explained by the increment of oxygen vacancy and the formation of non-fully reduced oxygen species.The non-fully reduced oxygen species are suggested as the active sites responsible for ethylene selecivity,and the reaction between reactants and catalyst is inhibited by CO2.
    Influence of Hindered Molecular Structure on Luminesence Behavior of 2,4,6-Triphenyl Pyrylium Salt
    CHEN Yi, WU Shi-Kang
    1996, 17(10):  1622-1625. 
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    The photophysical properties of 2,4,6-triphenyl pyrylium salts(compounds 1 and 2) were investigated.It was found that the intramolecular charge transfer in excited state of compound 2,in which the rotation of 4-phenyl is hindered,is stronger than that of compound 1,in which the rotation of 4-phenyl is free.The quantum yields of compound 1 increased with increasing viscosity of solvents,while the quantum yields of compound 2 decreased under the same condition.It was also shown that the hindered rotation of 4-phenyl in the molecule of 2,4,6-triphenyl pyrylium salt is unfavorable to its fluorescence emission.
    A Study of XPS and Mossbauer Spectra for EuMO3
    LI Li-Ping, WEI Quan, KANG Zhi-Jian, YANG Xu-Wei, SU Wen-Hui
    1996, 17(10):  1626-1629. 
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    XPS,IR,and 151Mossbauer spectra were measured for EuMO3.The relations of lattice parameters,ionic radii,core level binding energy of Eu4d and isomer shift(IS) were disscussed.It is found that the binding energies of Eu4d and ISare all related to the changes of Mions.The relationship between binding energy and IS is linear.
    Thermosensitive Hydrogel from N-Isopropylmethacrylamide
    CAO Wei-Xiao, CHEN Si-Wen, WANG Chang-Hua
    1996, 17(10):  1630-1633. 
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    N-Isopropylmethacrylamide(NIPM) was prepared from methacrylonitrile and isopropanol,The polymeization of NIPM in different solvents using ammonium persulfate-N,N,N',N'-tetramethylethylene diamine as the initiator and N,N'-methylene-bisacrylamide as crosslinking agent has been studied.The results show that the hydrogels from NLPM-MBAor NIPM-MBA-ionic monomers possesses thermosensitive properties.The swelling ratios of hydrogels at different temperatures were determined
    Characteristic of Polystyrene with C60 in the Side Group
    WANG Chang-Chun, SHU Chang, FU Shou-Kuan
    1996, 17(10):  1634-1637. 
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    Various methods,such as UV,FTIR,DSC,TG & TAand GPC,were employed to characterize polymeric C60 derivatives.The UV spectra of polymeric C60 derivatives were obviously different from C60 or PS,the similar results were also obtained from FTIR.For all the polymeric C60 derivatives,only a single galss transition temperature was observed in each case,and the values for the glass transition temperatures were found to increase with increasing amount of C60 in the derivatives.All experimental results proved that C60 was covalently linked with the side group of polystyrene through three-step reactions,i.e.,chloromethylation,azidization,cycloaddition.GPCand UVresults also showed that fullerene C60 was mainly monosubstituted.The contents of C60 in the polymeric derivatives were estimated by the TG method.
    Studies on the Copolymerization of Chloromethylthiirane with Epichlorohydrin by Rare Earth Coordination Catalysts
    SUN Wei-Lin, SHEN Zhi-Quan, LI Wei-Shi, ZHANG Yi-Feng
    1996, 17(10):  1638-1643. 
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    The copolymerization of chloromethylthiirane(CMT) with epichlorohydrin(ECH) was investigated by using rare earth coordination catalysts for the first time.It has been discovered that rare earth coordination catalysts,especially Nd (acac)3-Al(i-Bu)3 and Nd(naph)3-Al(i-Bu)3 are highly active catalysts for the copolymerization giving rather high molecular weight([η]=0.16 dL/g) alternate-rich copolymer in fairly high yield(~60%),and the catalytic efficiency of Nd(acac)3-Al(i-Bu)3 reached 10000 g copolymer/mol Nd.The characteristics of the copolymerization of CMTand ECHwith Na(acac)3-Al(i-Bu)3 had been studied in detail.The reactivity ratio of CMT(1) and ECH(2) was obtained to be 0.22(r1) and 0.097(r2) from the sulfur contents of the copolymers determined by oxygen combustion method.The structure and the molecular weight of copolymer were characterized by IR,13C NMR,GPC and VPO.
    Studies on the Two Class Glass Transition and the Typical VTF Behaviour of an Amorphous Comb Polymer Electrolyte
    DING Li-Ming, SHI Jing, MA De-Zhu, DONG Shao-Jun
    1996, 17(10):  1644-1648. 
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    A comb polymer(CP350) with oligo-oxyethylene side chains of the type-(CH2 CH2O)7CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly(ethylene glycol) methyl ether.The polymer can dissolve LiNO3 salt to form homogeneous amorphous polymer electrolyte.This electrolyte system was first found to have two class glass transitions,and the two Tgs were observed to increase with increasing salt content.The ionic conduction was measured by using the complex impedance method,and conductivities were investigated as functions of temperature and salt concentration.At 25℃,the ionic conductivity maximum of this system can get to 3.72×10-5S/cm at the [Li]/[EO] ratio of 0.057.The appearance of the conductivity maximum has been interpreted as being due to the effect of Tg and the so called physical crosslinks.The temperature dependence of the ionic conductivity displaying non-Arrhenius behaviour can be analyzed using the Vogel-Tammann-Fulcher equation and interpreted on the basis of the configurational entropy model.
    Studies on the Polymer Moments of A2+Aα Type Condensation Involving Initiation Step
    HUANG Xu-Ri, XIAO Xing-Cai, LI Ze-Sheng, SUN Chia-Chung, TANG Au-Chin
    1996, 17(10):  1649-1652. 
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    By means of the probability analysis method,the polymer moments of A2+Aα type condensation involving initiation step are studied.The 0-th,1-th and 2-th polymer moments and the recursion formula which can be used to calculate the polymer moments are presented.Furthermore,the behaviour of the polymer moments near the gel point is discussed and a general scaling law is obtained.
    Solvent Effects on Sol-Gel Transition for Polyelectrolyte Solutions
    ZHENG Hong-He, ZHANG Qing-Zhi, WANG Jian-Ji, WANG Zheng-Yu, Mikio Konno, Shozaburo Saito
    1996, 17(10):  1653-1656. 
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    The coorperation of solute and solvent is taken as gelation condition.The three dimensional percolation of blobs is taken as gelation model.Phase transition of polyelectrolyte solution is then considered as the process of the formation and the percolation of blobs.Together with the gelation of alginate solutions induced by different divalent cations(Cu2+,Ca2+,Mn2+,Co2+),the nature of sol-gel transition has been suggested.Critical exponent of relative viscosity near the gelation point was obtained to be in the range of 0.90~1.14,which is in good agreement with the values predicted by percolation based on various models.Effect of the formation of bolbs on the gel point is discussed.In addition that,the correct range of f in the power-law relation of relative viscosity near gelation point,ηrel∝fe-f)-k,has been defined.
    Toughened Poly(butylene terephthalate) by Epoxided Ethylene-Propylene-Diene-Rubber
    WANG Xue-Hui, ZHANG Hui-Xuan, WANG Xin-Hua, WANG Zhi-Gang, JIANG Jun-Guang, JIANG Bing-Zheng
    1996, 17(10):  1657-1659. 
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    Blends of poly(butylene terephthalate)(PBT) and epoxided ethylene-propylenediene terpolymer(EEPDM) were prepared.Their mechanical properties and morphology were studied by Izod impact test machine and scanning electronic microscope respectively.It was found that the notched Izod impact strength of blend PBT/EEPDMwas as about 23 times as that of pure PBTand about 10 times as that of blend PBT/EPDMat room temperature.The dispersed rubber particles were much smaller and the phase boundary was more blurred in blend PBT/EEPDMthan in blend PBT/EPDM.The toughness of blend PBT/EEPDMwas much more better than that of blend PBTand PBT/EPDM,which was in good agreement with the difference between their morphologies.