1996 Volume 7 Issue 7

STUDIES ON SYNTHESIS AND PROPERTIES OF NEW TETRATHIFULVALENE DERIVATIVES
Hong Qi LI , Zhong Qi YAO
1996, 7(7): 597-599
[Abstract](144) [FullText HTML] [PDF 170KB](0)
Abstract:
Synthesis of three new tetrathiafulvalene (TTF) derivatives-tetrakis (p-halobenzylthio)-tetrathiafulvalene and their precursors 4, 5-bis (p-halobenzylthio)-1, 3-dithiole-2-thione is reported. The electronic absorption spectra of these TTF derivatives show that the energy differences between their π-orbitals are smaller than that between BEDT-TTF. The surface pressure-area isotherm for tetrakis (p-chlorobenzylthio) tetrathiafulvalene (TCBT-TTF) indicates that the new TTF derivatives may have good film-forming properties and may be used to prepare Langmuir-Blodgett films.
PHASE TRANSFER CATALYZED SYNTHESIS OF DIARYL 2-NITRO-1,4-PHENYLENEDIOXYDIACETATES
Xi Cun WANG , Tai Bao WEI , Ji Chou CHEN
1996, 7(7): 600-602
[Abstract](145) [FullText HTML] [PDF 118KB](0)
Abstract:
A series of new diaryl 2-nitro-1, 4-phenylenedioxydiacetates were synthesized by the reaction of 2-nitro-1, 4-phenylenedioxydiacetyl chloride with various substituted phenols under the condition of liquid-liquid phase transfer catalysis using polyethylene glycol-400 as the catalyst.
BASE-CATALYZED PROTODESILYLATION OF (2H)-PYRI-DAZINON-5-YL SILYLMETHYL SULFIDES
Zheng Jie HE , Zheng Ming LI
1996, 7(7): 603-604
[Abstract](144) [FullText HTML] [PDF 95KB](0)
Abstract:
Protodesilylation of (2H)-pyridazinon-5-yl silylmethyl sulfides 1 proceeds smoothly with cleavage of sp3 hybridized carbon-silicon bond in the presence of catalytic amount of sodium hydroxide at room temperature. The presence of aryl R on silicon atom and (2H)-pyridazinon-5-yl group on sulfur atom plays a critical role in the occurrence of this reaction.
SYNTHESIS AND PROPERTIES OF THERMOTROPIC COPOLY (ESTER IMIDE) S
De Wen DONG
1996, 7(7): 605-608
[Abstract](142) [FullText HTML] [PDF 162KB](0)
Abstract:
A series of copoly (ester imide)s is synthesized by thermal polycondensation of N, N'-hexane-1, 6-diylbis (trimellitimide), p-hydroxybenzoic acid and diphenols with different structures. Their thermotropic liquid crystal properties are studied by DSC measurements and polarizing microscopy. It is found that the steric effect of nonlinear bisphenol modifiers is the most important factor in controlling the liquid crystallinity of the resulting copoly (ester imide)s.
CHEMICAL INCORPORATING PESTICIDES 2.SYNTHESIS OF NEW SUCCINIMIDO ORGANOPHOSPHATES AS POTENTIAL PESTICIDES
Er Le ZANG , He Hui ZHENG , Ping LI
1996, 7(7): 609-610
[Abstract](137) [FullText HTML] [PDF 84KB](0)
Abstract:
A series of succinimido-organophosphate analogues was synthesized with maleic anhydride as starting material via maleimide and its analogues as intermediates and characterized by IR, 1HNMR and elementary analysis.
ENZYMATICALLY SOLVENT-FREE SYNTHESIS OF SUGAR ESTER CONTAINING ω-3 POLYUNSATURATED FATTY ACID
Zu Yi Li , Owen P. Ward
1996, 7(7): 611-614
[Abstract](159) [FullText HTML] [PDF 115KB](0)
Abstract:
A enzymatic synthesis of sugar ester from isopropylidenesugar and ω-3 polyunsaturated fatty acid was studied. Esterification with Lipase N-435 gave the best result.
INTERMOLECULAR PHOSPHORYL GROUP TRANSFER FROM N-(O,O-DIISOPROPYL) PHOSPHORYL ASPARAGINE TO TRYPSIN
Wei Hua ZHOU , Yu Fen ZHAO
1996, 7(7): 615-616
[Abstract](141) [FullText HTML] [PDF 77KB](0)
Abstract:
In Tris-HCl buffer, an intermolecular phosphoryl group transfer from N-(O, O-diisopropyl) phosphoryl asparagine (DIPPAsn) to trypsin was confirmed. The result suggested an novel way to phosphoiylate the protein without kinase participation.
A NEW STYRYL-LACTONE COMPOUND FROMGONIOTHALAMUS LEIOCARPUS
Qing MU , Chao Ming , LI Hong , Jie ZHANG , Yu WU , Han Dong SUN
1996, 7(7): 617-618
[Abstract](149) [FullText HTML] [PDF 70KB](0)
Abstract:
A new styryl-lactone compound, named as leiocarpin A (1), was isolated from Goniothalamus leiocarpus. Its structure and relative configuration were determined by means of spectrum particularly 2D NMR including 1H-1H COSY, 1H-13C HETCOR, COLOC and NOESY techniques.
A NEW NEO-CLERODANE DITERPENE FROM ASTER SOULIEI
Liang Ming WANG , Shou Jun GUO , Zhong Jian JIA , Dong Liang CHENG
1996, 7(7): 619-620
[Abstract](145) [FullText HTML] [PDF 104KB](3)
Abstract:
A new neo-clerodane type diterpenoid, named soulidiol, has been isolated from Aster souliei and its structure was elucidated on basis of spectral and chemical methods to be 18, 19-dihydroxy-5α, 10β-neo-cleroda-3, 13 (14)-dien-16, 15-olide.
A NEW REARRANGED ABIETANE DITERPENOID FROM CARYOPTERIS INCANA (THUNB) MIQ
Jian Jun GAO , Gui Qiu HAN , Jiu Feng YAN , Yan WU
1996, 7(7): 621-622
[Abstract](144) [FullText HTML] [PDF 81KB](0)
Abstract:
A new rearranged abietane diterpenoid, incanone was isolated from the whole plant of Caryopteris incana (Thunb. ) Miq. On the basis of HRMS, EIMS, 1HNMR, 13CNMR, DEPT, 1H-1H COSY, HMQC, HMBC and NOESY, incanone was determined as 11, 12, 14, 16-tetrahydroxyl-17 (15-16) abeo-abieta-8, 11, 13-triene-7-one.
CYCLIC VOLTAMMETRY STUDY ON ANTIMALARIAL MECHANISM OF ARTEMISININ (QINGHAOSU) DERIVATIVES
Hua Liang JIANG , Kai Xian CHEN , Yun TANG , Jian Zhong CHEN , Ying LI , Qing Mi Wang , Quan LI , Ru Yun JI , Qian Kun ZHUANG
1996, 7(7): 623-626
[Abstract](139) [FullText HTML] [PDF 183KB](0)
Abstract:
Cyclic voltammetry method was used to determine the cyclic voltammogram of artemisinin derivatives and reduction potentials (RPs) of these compounds were obtained. Combining the determination results of Zhang and co-workers, QSAR analysis was performed between the activity and reduction potentials (RPs), which illustrated the antimalarial mechanism of artemisinin analogs. The experimental result verified and tested our previous theoretical calculation results.
STUDIES ON THE RELATIONSHIP BETWEEN THE HELICAL STRUCTURE AND OPTICAL ACTIVITIES OF SOME CHIRAL CYCLICESTERS Ⅰ
Bing DENG , Xiu Lin YE , Qi Yi XING
1996, 7(7): 627-630
[Abstract](139) [FullText HTML] [PDF 166KB](0)
Abstract:
A method to analyze the relationship between the helical structure and optical activity was proposed by the study of the conformations and X-ray structures of some cyclic esters possessing a C2-symmetry element which were prepared by esterification of L-(+)-2, 3-O-isopropylidene threitol with dicarboxylic dichlorides.
THEORETICAL STUDIES ON NUCLEOPHILIC VINYLICHALIDE SUBSTITUTION
Lin Jing YANG , Xiao Yuan FU , Shao Wen ZHANG
1996, 7(7): 631-634
[Abstract](147) [FullText HTML] [PDF 199KB](0)
Abstract:
The reactions of vinyl fluoride, chloride, bromide and iodide with CN- and OH- were studied. The trend of reactivity of vinyl halide with these two nucleophile is:fluoroethene - tends to be a multi-step process while the reactions of the other three vinyl halides with CN-. OH- are all single-step processes. The nucleophilicity of CN- is stronger than that of OH-.
TERMINAL-GROUP EFFECT ON COAGGREGATION
Guo Zhen JI , Xi Lin CUI
1996, 7(7): 635-637
[Abstract](146) [FullText HTML] [PDF 133KB](0)
Abstract:
The coaggregating tendencies of dodecane, octadecane, dodecanol, octadecanol, dodecanoic acid, octadecanoic acid, methyl dodecanoate, methyl octadecanoate have been investigated by the fluorescence method, in 40:60 V/V (φ=0.40) DX-H2O system at 25℃. using naphthylene lauryl ether (Np-12) as fluorescence probe. These long chain molecules with different terminal groups have different coaggregating tendencies. The order is alkane >methyl ester of fatty acid >fatty alcohol >fatty acid. The unusual properties of carboxyl as terminal-group have been discussed.
A THEORETICAL STUDY ON THE REACTIONBETWEEN FO AND H2O
Bao Shan WANG , Xiao Ping ZHANG , Jing Zhong GUO , Chuan Pu LIU
1996, 7(7): 638-640
[Abstract](157) [FullText HTML] [PDF 147KB](0)
Abstract:
The thermodynamic and kinetic information concerning reaction of FO with H2O are calculated using the general statistical theory and the transition state theory. The influence of temperature on this system is discussed. The view that FO is inactive to H2O in the atmosphere is confirmed. We also provide a standard program to study elemental reactions.
INCLUSION PROPERTY AND SOLID STATEPHOTOREACTION OF 2-STYRYLBENZOXAZOLE
Ting KANG , Yong Mei WANG , Ji Ben MENG
1996, 7(7): 641-642
[Abstract](154) [FullText HTML] [PDF 86KB](0)
Abstract:
Trans-2-styrylbenzoxazole () was included by host compound 1, 1, 6, 6-tetraphenylhexa-2, 4-diyn-1, 6-diol () and the inclusion ratio was 1:1. Syn-head-to-tail dimer () of was obtained by irradiating the inclusion complex () with 400W High Pressure Mercury Lamp (HPML). The possible mechanism of the reaction was also discussed.
SEMI-EMPIRICAL QUANTUM CHEMISTRY STUDY ON ELECTROCHEMICAL REDUCTION OF DIMETHYLGLYOXIMATONICKEL
Min Bo CHEN , Kui GAO , Ya Min NI
1996, 7(7): 643-646
[Abstract](146) [FullText HTML] [PDF 157KB](0)
Abstract:
The mechanism of the electrochemical reduction of the nickel (Ⅱ) complex with dimethylglyoxime and ammonia is studied by means of INDO, energy localization and electrostatic potential methods.
THE APPLICATION OF THE MPB4 THEORY TO THE INTERFACE BETWEEN TWO IMMISCIBLE ELECTROLYTE SOLUTIONS.PART4.THE DIFFERENTIAL CAPACITANCE OF THE WATER/NITROBENZENE INTERFACE IN THE PRESENCE OF 2:2 ELECTROLYTE
Qi Zhi CUI , Yan Xiu ZHOU , Guo Yi ZHU , Er Kang WANG
1996, 7(7): 647-650
[Abstract](144) [FullText HTML] [PDF 158KB](0)
Abstract:
We have developed a new theoretical model based on the MPB4 theory to calculate the differential capacitance of the interface of 0.05mol/L MgSO4 in water and 0.1mol/L TBATPB in nitrobenzene. Our results coincide with the experimental values very well. It indicates that our model may describe well the structure of ITIES not only in the presence of 1:1 electrolyte but also in the presence of 2:2 electrolyte.
COMPOSITION-THERMODYNAMIC PROPERTY RELATIONSHIPS FOR TERNARY POLAR MIXTURE VIA NEURAL NETWORKS
Yi Lin CAO , Shu Ting YANG , Qing Zhang LU
1996, 7(7): 651-652
[Abstract](143) [FullText HTML] [PDF 98KB](0)
Abstract:
Artificial neural network (ANN) models have been employed to the calculations of densities and excess molar volumes of water+methanol+ethylene glycol ternary system at different temperatures. The results were satisfactory comparing with the experimental values. The method was convenient in operation, rapid in calculation and easy in extending to multicomponent systems.
THE RELATION BETWEEN MOLECULAR MOTION AND ION CONDUCTIVITY ON A NEW COMBLIKE POLYMER
Li QI , Yun Qing LIN , Fo Song WANG
1996, 7(7): 653-656
[Abstract](142) [FullText HTML] [PDF 171KB](0)
Abstract:
A new amorphous comblike polymer (CBP) based on methylvinyl ether/maleic anhydride alternating copolymer backbone and on oligooxyethylene side chain was synthesized. The dynamic mechanical properties of CBP-Li salt complexes showed that there were two glass transitions. There are two peaks in the plot of the ionic conductivity vs. Li salt concentration. The plot of Log σ against 1/(T-To) shows an unusual dual VTF behavior when using side chain glass transition temperature (Tβ) as To.
THE CHIRAL SELECTIVITY IN ACROSS-MEMBRANE TRANSPORT OF 1,2-DIAMINOCYCLOHEXANE PLATINUM (II) COMPLEXES AND THE CONTRIBUTION OF LEAVING GROUPS
Juan ZOU , Xiao Cai YANG , Gang LIU , Rong Chang LI , Kui WANG
1996, 7(7): 657-660
[Abstract](142) [FullText HTML] [PDF 191KB](0)
Abstract:
The uptake kinetics of platinum (Ⅱ) complexes of 1, 2-diaminocyclohexane (dach) isomers (1R, 2R-dach, 1R, 2S-dach, 1S, 2S-dach) with various leaving groups, chloride (Cl), oxalate (OX), squaric acid (SA), and demethylcantharic acid (DA) was studied in the plasma isotonic buffer. The experimental results show that across-membrane transport of all the platinum complexes studied follows a firstorder kinetic process and a passive diffusion mechanism. The uptake rate constants of these platinum (Ⅱ) complexes decrease in the following sequence with the k value (h-1) :Cl >SA >OX >DA. It is noteworthy that the k values of the platinum (Ⅱ) complexes with same leaving group reduce as:1R, 2R-dach >1R, 2S-dach >1S, 2S-dach. Based on these results, it is firstly suggested that the erythrocyte membrane recognizes the chirality of these platinum complexes.
A HREELS STUDY OF THE INTERACTION OF CYCLOHEXANONE AND PHENOL WITH Pt (Ⅲ) SURFACE
Shu Xian ZHUANG , Xu Ming WEI , Ying Sheng WANG , Run Sheng ZHAI
1996, 7(7): 661-662
[Abstract](137) [FullText HTML] [PDF 118KB](0)
Abstract:
The adsorption and decomposition of cyclohexanone and phenol on Pt (Ⅲ) have been investigated by HREELS and TDS. The configuration of both adsorbates and the decomposition mechanisms are also discussed.
SYNERGIC EFFECT OF POLYMER SUPPORTED Pd-Pt BIMETALLIC CATALYSTS ON THE HYDROGENATION OF NITROAROMATICS
Bin YANG , Zheng Kun YU , Yun XU , Shi Jian LIAO , Dao Rong YU
1996, 7(7): 663-664
[Abstract](155) [FullText HTML] [PDF 101KB](0)
Abstract:
Hydrogenation of nitroaromatics has been carried out under mild conditions using poly-N-vinyl-2-pyrrolidone supported Pd-Pt bimetallic catalysts (PdCl2 and H2PtCl6 as catalyst precursors). The catalytic activities of the bimetallic catalysts are significantly higher than those of the monometallic Pd or Pt catalyst especially in the case of the hydrogenation of substituted nitroaromatics due to a remarkable synergic effect. The ratio of Pd to Pt in the catalyst influences the activity of the catalyst.
A THEORETICAL INVESTIGATION ON THE STRUCTURE OF THREE-DIMENSIONAL MESOGEN
Fu Jiang DING , Liang Fu ZHANG
1996, 7(7): 665-668
[Abstract](138) [FullText HTML] [PDF 205KB](0)
Abstract:
In order to investigate the relation between molecular structure and liquid crystal properties, structural studies were carried out on three-dimensional mesogen tetrasubstituted tribenzosilatrane using PM3 semiempirical calculations. The results show that the corresponding terminal cyano group compound (alkyl R2 replaced by CN) has much bigger dipole moment and much better similar to sphere than alkyl compounds. Cyano compound is probably a better candidate for sphere-like mesogen.
CRYSTAL PACKING OF POLY (ETHER KETONE KETONE)
Xue Yan ZhANG , Ye CHEN , Yang Chuan KE , De Cai YANG
1996, 7(7): 669-670
[Abstract](139) [FullText HTML] [PDF 103KB](0)
Abstract:
The crystal structure of poly (ether ketone ketone)(PEKK) is predicted by using Cerius2 software according to the wide angle X-ray diffraction (WAXD) experiment result. The predicted structure has a planar zigzag chain conformation between ether oxygen and ketone carbons in an orthorhombic lattice. Average zigzag angle is 126° and average torsion angle is 30.32°, The WAXD powder pattern calculated from the crystal packing model is in good agreement with the experiment result.
NEW SOLID BASE DERIVED FROM AIPO4-5 SUPPORTED KF
Jian Hua ZHU , Qin Hug XU , Hideshi HATTORI
1996, 7(7): 671-674
[Abstract](134) [FullText HTML] [PDF 172KB](0)
Abstract:
Dispersion of KF on AlPO4-5 molecular sieve created basic sites and caused 1654 cm-1band of bidentate carbonate in CO2 adsorption. After pre-treated above 823K, 5%KF/AlPO4-5 exhibited basic catalytic activity in the isomerization of butenes at 273K, and the activity increased with the pre-treatment temperature up to 923K.
STUDY ON THE BEHAVIOR OF RARE EARTH IONS BY PHOSPHORESCENT PROBE METHOD
Gui Bin MA , Fei GAO , Liang CHEN , Pin YANG
1996, 7(7): 675-678
[Abstract](116) [FullText HTML] [PDF 185KB](0)
Abstract:
Utilizing the effect of dioxygen molecules on the luminophors' phosphorescent life, the first attempt to investigate the interaction between the molecules of rare earth coordination compound and cells was carried out. This work has supplied a new research method for the studies of transmembrane process for rare earth ions.
PREPARATION OF Cr-POLYSTYRENE COMPLEX BY METALVAPOR SYNTHESIS
Shi Hua WU , Chang Ying ZHU , Wei Ping HUANG
1996, 7(7): 679-680
[Abstract](122) [FullText HTML] [PDF 78KB](0)
Abstract:
Chromium atom-hexane solution prepared in a metal atom reactor was transferred into a solution containing polystyrene in diethylene glycol dibutyl ether at -78℃, followed by gently warming the mixture to 0℃ to react for two hours, yielding a brown-green solid product. Ultraviolet-visible and infrared spectra showed that the product was a bi-(η6-arene) chromium complex.
SYNTHESIS AND MAGNETISM OF μ-OXAMIDO COPPER (Ⅱ)-LANTHANIDE (Ⅲ) HETEROBINUCLEAR COMPLEXES
Cui Wei YAN , Yan Tuan LI , Dai Zheng LIAO
1996, 7(7): 681-684
[Abstract](125) [FullText HTML] [PDF 168KB](0)
Abstract:
Four new μ-oxamido heterobinuclear complexes of Cu-Ln (Ln:Y, Pr, Ho, Gd) were synthesized and characterized. The magnetic susceptibility measurements (4~300 K) of the Cu-Gd complex indicate a weak ferromagnetic interaction between the two metal ions, with the exchange integral JCu-Gd=2.03 cm-1.
MAGNETIC INVESTIGATION OF THE NICKEL COMPLEXES OF MULTI-SULFUR 1.2-DITHIOLATES
Tian Ming YAO , Xian Fa SHI , Xiao Zeng YOU
1996, 7(7): 685-686
[Abstract](128) [FullText HTML] [PDF 92KB](0)
Abstract:
The magnetic susceptibility of[Bu4N][Ni (MEDT)2]and[BU4N] [Ni (PHDT) 2] (MEDT:5-methyl-6-hydro-1, 4-dithiin-2, 3-dithiolate, PHDT:5-phenyl-6-hydro-1, 4-dithiin-2, 3-dithiolate) was measured in the temperature range of 75-300K. The magnitude of magnetic moments is consistent with a doublet state arising from Ni (Ⅲ). Antiferromagnetic properties were discussed in consideration of molecular structure.
SILVER SOLS PREPARED BY THE METHODOF PHYSICAL DEVELOPMENT
Yong Jun ZHANG , Wen Fang ZHAO , Bing HUANG , Xin Min REN
1996, 7(7): 687-690
[Abstract](117) [FullText HTML] [PDF 162KB](0)
Abstract:
A new type of silver sol was prepared by a method similar to physical development in photographic science. Silver particles have many crystalline forms with bigger size than that of usual silver sols. Kinetic study indicates that the reaction is an autocatalytic reaction. The result can also explain the particle size effect on the color of silver particles deposited by physical development in photographic science.
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