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Table of Content

    24 December 1990, Volume 11 Issue 12
    Articles
    Crystal Structure of Tri(8-quinolinol) Yttrium-Tri(8-quinolinol) Nickel Perchlorate [YQ(HQ)2][NiQ3](ClO4)
    Zhang Ming-jie, Huang Chun-hui, Xu Guang-xian
    1990, 11(12):  1313-1316. 
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    Yttrium 8-quinolinol and nickel 8-quinolinol ionic adduct[YQ(HQ)2][NiQ3](ClO4) was synthesized. The X-ray diffraction cryxtal structure of it showed that the crystal is monoclinic, space group P21/c with a=16.972(4)Å, b=14.128(3)Å, c = 22.615(4)Å,β=103. 16(2)°, V = 5280.14 Å3,F(000) = 2264, Z=4. [YQ(HQ)2]2+ cation and [NiQ3]- anion were of six-coordinated octahedral geometry. Its IRspectra was recorded.
    Isomorphous Substitution of Metallic Elements for Zeolite Y in Aqueous Solution
    Tang Yi, Xu Jin-suo, Gao Zi
    1990, 11(12):  1317-1321. 
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    The substitution of Ti, Fe and Zr into zeolite Yin aqueous solution of(NH4)2TiF6, (NH4)3ZrF7 and (NH4)3FeF6 is investigated systematically. It is found that Al in the framework was replaced by the metallic elements and the extent of substitution depends on the M/Al ratio of the solution. The maximum allowable M/Al ratio of the aqueous solution is related with the radius of Matom and the stability constant of the MFam- complex. The substituted, zeolite samples with crystallinity > 80% were characterized with XRD, IR, DTA and TPR. The incorporation of Ti, Fe and Zr into the zeolite leads to an increase in unit cell parameter, a lowering of thermal stability and a red shift of the asymmetric stretch frequency. The extent of these changes is correlated with the ionic radius of the metallic element and the degree of substitution. Results of various characterization methods show that the heteroatoms are substituted readily into the zeolite framework using this preparation method.
    A Kinetic Study on Dismutation of Superoxide Ion by Macrocyclic Dioxotetramine-Copper(Ⅱ) Complex by Using Pulse Radiolysis
    Shen Meng-chang, Luo Qin-hui, Zhu Shou-rong, Tu Qing-yun, Dai An-bang, Liu An-dong, Gu Hong-chun, Li Feng-mei, Di Shao-jie
    1990, 11(12):  1322-1326. 
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    We studied the reaction kinetics of dismutation for superoxide ion by copper ( Ⅱ ) complex of macrocyclic dioxotetramine ligand 12-(4'-nitro)-benzyl-1,4,7,10-tetraazacyclotridecane-11, 13-dionato copper( Ⅱ )by using pulse radiolysis. The rate constants of dismutation kcat were obtained to be 1. 78×106 mol-1·L-s-1(at pH 7.0) and 1.06×106 mol-1·L·s-1(at pH 7.8). The reaction mechanism is similar to that catalyzed by superoxide dismutase.
    Stereoselectivity in Tris(phenanthroline) Chromium (Ⅲ) Binding to DNA
    Zhao Gang, Tang Wen-xia, Dai An-bang
    1990, 11(12):  1327-1330. 
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    Binding of rac, △, -[Cr(phen)3]3+to calf thymus DNAwas studied by equilibrium dialysis and circular dichroism. △ isomer selectivity in binding to a right-handed duplex of DNAwas found.
    Luminescence Centers in BaFCl:Ce3+ and BaFCl : Gd3+ Crystals
    Su Mian-zeng, Liao Chun-sheng
    1990, 11(12):  1331-1334. 
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    Rare earth ions RE3+ doped in BaFCl should randomly replace the sites of barium ion Ba2+ and form defects REBa·. Their extra one positive charge may be compensated by different negatively charged defects, possiblly introduced in the crystals during various preparation conditions. In these cases the charge compensation defects would influence the local environment of the doped rare earth ions, modifying their site symmetry, and therefore different types of luminescence centers should be formed. The authors have investigated the luminescence centers in Ce3+ and Gd3+ ions doped BaFCl crystsls by fluorescence spectroscopy for samples, synthesized or post-treated under various chemical conditions. There might exist two types of luminescence centers. One is related to the associates of RE3+with F'1, the other to the associates of RE3+ with O'F.
    Studies on the M(Ⅲ)X(V)O4-Type Microporous Crystals——The Syntheses and Structures of Microporous Gallophosphates
    Xu Ru-ren, Feng Shou-hua
    1990, 11(12):  1335-1339. 
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    Anew family of microporous gallophosphates (namely GaPO4-Ca, n= 1~12) was crystallized in (0.5~3)R.Ga2O3.(1~1.5)P2O5.(25~100)H2O systems hydrothermally at 150~200℃ by using various amines and quarternary ammoniums as the templates(R) and characterized by means of chemical composition analysis, XRD, DTA-TG and NMR techniques. Their absorption properties were investigated by the measurements of water adsorption isotherms and adsorption capacities of "plug gauge" molecules with known diameters, as a result, the pore sizes of GaPO4-Ca change from 3 to 6 Å. Three members of microporous gallophosphates were structurally determined by means of single crystal X-ray diffraction,these include GaPO4-C3,-C4,-C7. Some characteristics related to the structures such as coordination state of Ga, framework window and role of the template in the framework were discussed in more detail.
    Investigation on Pulse Polarography(Ⅳ)——Theory and Verification for Reversible Wave of Differential Pulse Polarography Influenced by Adsorption
    Zhang Jian-rong, Zhang Zu-xun
    1990, 11(12):  1340-1344. 
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    An equation and its current-potential charaters of differential pulse polarography for reversible waves influenced simultaneously by, the adsorption of both reactant and product are presented and discussed in this paper. The results obtained are the same as those calculated by numerical solution. Teste are carried out to verify the equation by using three systems. The curves described by the theory are in good agreement with the experimental results.
    Expert System for Structural Interpretation of IR Spectra
    Chen Ling-ran, Zhang Mao-sen
    1990, 11(12):  1345-1348. 
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    A new expert system has been developed which can be used to aid' chemists in structural interpretation of infrared spectra. The system consists of five essential components: knowledge-base, inference engine, database, knowledge-acquisition module and explanatory interface. The system is implemented in Turbo PROLOG artificial intelligence language. This system has the following advantages compared with other spectral interpretation, systems: the system has a greatly friendly user interface, two kinds of methods for managing knowledge-base, several useful explanatory facilities, such as WHY explanation, HOWexplanation etc. ; it can run on the IBM PC/XT and its compatible microcomputers. The system's another important feature is that it can simulate the reasoning an experienced chemist employs in interpreting spectra as well as deducing complete molecular strucures. So the system can also be used as a helpful learning tool for training chemistry students in IRspectrum interpretation and organic structure elucidation.
    Biosensors Based on the Tissue of Plant as Catalytic Material for Amino Acid
    Qi De-yao, Zhuang Yun-long, Chi Qi-jin
    1990, 11(12):  1349-1352. 
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    Two new tissue electrodes are described in this paper. It is shown that a portion of intact tissue from apple or cactus can be coupled with potentiometric ammonia gas sensing electrode to prepare sensors for some amino acids with good response properties. Their optimum operational conditions and properties with respect to buffer sort, pHof the bulk solution, selectivity, linearity, stability, sensitivity and response time are studied and discussed. At the same time, the dynamic parameters, namely Km and Vm, of L-glutamine deaminase and L-asparagine deaminase have been obtained by means of these tissue electrodes.
    A Study on Fundamental Properties of Microwave Plasma Torch Source
    Jin Qin-han, Wang Fen-di, Gary M. Hieftje
    1990, 11(12):  1353-1356. 
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    The emission profile of microwave plasma torch (MPT) discharge was studied with computed tomography. It was shown that the source was in good symmetry and there was a central channel which is beneficial to the introduction of samples. The optimum analytical zone is in the region from 5 to 10 mm above the top of the torch. The laser Thomson scattering and Rayleigh scattering were used to study the electron temperatures, electron number densities and gas temperatures of ArMPT and HeMPT discharges. The electron temperature of the MPT was shown to be very high and the gas temperature was relative low and, therefore, it was a non-thermal emission source. There existed an over-population of high-energy electrons and the excitation power of the source was very high.
    Chemometrics Research on Basic Algorithms and Applications
    Yu Ru-qin
    1990, 11(12):  1357-1361. 
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    Some aspects of the fundamental problems of chemometrics have been reviewed based on the research work undertaken in the author's laboratory. The topics touched upon include analytical information theory, experimental design and optimization, sampling, analytical detection theory, calibration, signal processing, chemical pattern recognition, and digital simulation.
    Studies on the Polys,accharides of the Pollen of Typha Angustifolia L.
    Miao Ping, Lin Yao, Jin Sheng
    1990, 11(12):  1362-1366. 
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    Three polysaccharides TAA, TAB, TAC have been isolated, purified from the pollen of Ty-pha angustifolia L. by hot water extraction, alcohol precipitation, sevage method, Gel filtration (Sephadex G50), ion-exchange chromatography on DEAE Sephadex A25 and DEAE-cellulose.The structure determination was carried out by paper chromatography of the hydrolysis products, GLCanalysis of the alditol acetates, methylation analysis, 1H NMRand 13C NMR spectra. TAAis mainly composed of a-L-arabinofuranose, β-D-galactose and a-D-galacturonic acid. TACcontains the backbone mainly composed of (1→5)-linked-.L-arabinosyl residue.
    A New Route for the Synthesis of Ferrocenyl a-Diketones
    Shi Shu-jian, An Rong, Yuan Han-cheng
    1990, 11(12):  1367-1371. 
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    Anew route for the synthesis of ferrocenyl a-diketones has been developed. The method consists of reacting formylferrocene with propanedithiol-1, 3 to form ferrocenyl dithiane, which is lithiated with BuLi to yield lithiodithiane of ferrocene, and this intermediate is then treated with esters. The addition products of ferrocenyl dithiane are finally hydrolyzed in the presence of HgCl2-CdCO3 to give the subject prodcuts. All the synthesized ferrocenyl dithiane and a-diketoncs, except Ia and Ic, are new compounds with their structures comfirmed by elemental analysis, 1R and 1H NMR. The yields of the synthesis are moderately good. Only in two cases the yields are low, the reasons for which are proposed. It is also distinct from that reported in the previous literatures in two respects : there is no 2 : 1 addition product formed in the synthesis, and all the ferrocenyl acyl dithiancs arc very easily hydrolysable with HgCl2-CdCO3. These unexpected results are tentatively explained. Abrief discussion for the IR and 1H NMRof the products is given.
    A Research in the Asymmetric Reactions of Some Thiophosphoryldichlorides
    Chen Ru-yu, Liu Li-jian
    1990, 11(12):  1372-1375. 
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    The asymmetric condensation reactions of some thiophosphoryldichlorides 1 with(+)-1R, 3S-1,2,2-trimethyl-1, 3-diamino-cyclopentane 2 have been investigated, and an excellent optically inductive effect of chiral reagent 2 appeared. Most products from the reactions were composed of two unequal amounts of diastereoisomers in which the chiral phosphorus atom formed in the reaction procedure had two opposite configurations of 3Rand 3S. The influences by the substituents of 1, temperature, solvents and time of the reactions have also been discussed.
    Studies on Glycosides (Ⅸ)——An Alternate Method for Highly Stereoselective Synthesis of1-Thioglycosides
    Li Zhan-jiang, Liu Ping-li, Qiu Dong-xu, Cai Meng-shen, Huang Li-ru, Qiao Liang
    1990, 11(12):  1376-1380. 
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    Anew method for the synthesis of 1-thio-glycosides using 1-O-trifluoroacetyl-2,3,4,6-te-tra-O-benzyl-a-D-gluco- or manna-pyranose with R'SHin the presence of Lewis acid is reported. The reaction conditions were very mild. 1-thio-a-D-glycosides 3a-e and 6a-c were obtained in high yields and a high stereoselectivity. Their structures were proved by IR,1H NMR, 13C NMR and elementary analysis.
    An ESR Study of the Organozirconium (Ⅲ) Complexes
    Wang Ji-tao, Bai Ling-jun, Zhang Yun-wen, Li Jiang-sheng
    1990, 11(12):  1381-1385. 
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    Thermo-stable paramagnetic organozirconium (Ⅲ) complexes are formed when thermolysis or photolysis of Cp2ZrHCl,(Cp2ZrCl)2 or Cp2ZrH(μ-H)(Cp=η5-C5H5) are carried out in the presence of nitrogen or phosphorus ligands. ESRspectra of these complexes are monitored and ESR parameters of 17 complexes are given.
    A New Steroidal Saponin from Smilax Menispermoides
    Ju Yong, Jia Zhong-jian
    1990, 11(12):  1386-1387. 
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    Anew steroidal saponin, m. p. 310℃, [a]20D= -90.0℃, was isolated from 70% alcoholic crude saponin extract of the rhizome of Smilax menispermoides D. C. by silica gel column chromatogra-phy and further purified by Sephadex LH-20. Its structure was determined as : (25D) spirost-5-en-3β, 17α,27-triol-3-O-[β-L-rhamnopyranosyl (1-2)] [a-L-rhamnopyranosyl (1-4)]-α-D-glucopyra-noside by means of IR, MS, 13C NMR, DEPTand chemical methods.
    A Versatile Synthesis of5-Monosubstituted Isopropylidene Malonates
    Huang Xian, Wu Jin-long
    1990, 11(12):  1388-1390. 
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    Alkylidene isopropylidene malonates prepared in situ from Meldrum's acid and carbonyl compounds in benzene were reduced directly to give monosubstituted isopropylidene malonates by sodium borohydride in the presence of phase transfer catalyst.
    Acidic and Catalytic Properties of SAPO-11 Molecular Sieve
    Yan Ai-zhen, Liu Yang, Yu Zhen-chen, Xu Qin-hua
    1990, 11(12):  1391-1395. 
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    The acidic properties of SAPO-11 molecular sieve were studied by IRand TPD methods. The catalytic properties of n-heptane cracking and ethanol dehydration on SAPO-11, HZSM-5 and SAPO-5 were performed. The results indicated that both Bronsted and Lewis acid sites are present in the sample of SAPO-11. From the spectra of NH3-TPD on SAPO-11 the amount and strength of acid sites were measured and NH3 desorption activation energy was calculated, showing that it has medium acidic strength.
    The Conductive Characteristics of Perovskite Oxide Electrodes Duringthe Polarization Process
    Zhou Yun-hong, Luo Pei-fang, Wu Zhi-yuan, Zha Quan-xing(Cha Chuansin)
    1990, 11(12):  1396-1399. 
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    The polarization of perovskite oxides and their electrocatalytic activity for the oxygen reduction are investigated. It is found that the electrode resistance increases significantly when the reduction of the oxides electrode takes place during the cathodic polarization process with a corresponding drop of eletrocatalytic activity. Whereas the electrode resistance decreases when the reduced oxides are reoxi-dized during the anodic polarization process. The electrode conductivity is reversibly changed. The influence of the electric conduction of perovskite and the effect of the resistance change of the electrode on the performance of the electrode are discussed.
    Preface
    Studies on the Reaction of Photolysis of O-Acyl-a-Oximinoketones by the Method of Monte Carlo Simulation
    Tong Wei-da, Yang Yu-liang, Sun Meng, Yu Tong-yin
    1990, 11(12):  1400-1404. 
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    Photoreactions were studied by means of Monte Carlo simulation for the first time. The experimental results of photolysis of five O-acyl-a-oximinoketones were compared with the results of Monte Carlo simulation and kinetic method. The conclusion shows that if the first order approximation of absorbed light, which makes the simultaneous differential equations solvable, is used in the kinetic method, the theoretical reaults deviate from the experimental results in the later period of the reaction. However, the Monte Carlo simulation could get rid of this approximation and agreed with the experiments very well.
    Studies on Lattice Parameter,Molar Volume and Excess Molar Volume of Pb-Based a-Phase Solid Solution in Pb-Sn-Cd Ternary System
    Liu Heng-li, Long Xiang, Gao Zhong-min, Zhao Mu-yu
    1990, 11(12):  1405-1409. 
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    The lattice parameters a and the molar volumes Vm of Pb-based a-phase solid solution in the Pb-Sn-Cd ternary system were determined by means of X-ray diffraction. The lattice parameters a vary linearly with the molar fractions, the lattice distortion is mainly affected by the size effect of components. The molar volumes show a positive deviation from the behavior of the ideal solution, and the contribution of the solute Cd to excess molar volumes VE is much larger than that of the solute Sn. According to Vegard's law-or sub-regular solution model, the relationship between a or Vm and the compositions of alloy is obtained by the mathematic regressive method, the prediction precisions of both the formulae are within the limits of experiment error.
    Articles
    Investigation of Extraction Process by Titration Calorimetry(Ⅰ)——Formation of Reversed Micelle in Organic Phase and Its Effect on Extraction Process
    Shen Xing-hai, Gao Hong-cheng
    1990, 11(12):  1410-1414. 
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    The formation of reversed micelle in extractants-organic phase was studied by titration calorimetry. Critical micellar concentration (CMC), aggregation number(n), formation constant (K) and thermodynamic function of the micellar formation △G, △H, △S were determined for system: D2EHPA(Na)-sec-octyl alcohol-kerosine and trialkylmethyl ammonium chloride-sec-octyl alcohol-kerosine. According to the above mentioned results, the effect of formation of micelle on the extraction coefficient and mechanism is discussed.
    Preface
    A Hybrid Approach to the Solution of Coupled Channel Equations for Inelastic Scattering
    Xie Dai-qian, Tang Au-chin
    1990, 11(12):  1415-1418. 
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    Ahybrid approach for solving the coupled channel equations in atom-molecule scattering theory is presented. This method combines the LOG-derivative(LOGD) integrator of Johnson at strong interaction region with a new potential-following method in which the reference potential has the form V=-A2/16 + Be(-AR) at the weak interaction region. The method has been tested on the rigid rotor problem of Lester-Bernstein.
    Articles
    The Surface Photovoltage and Gas Sensitive Properties of 7,7,8,8-Tetracyanoquinodimethane
    Jiang Lei, Wang De-jun, Liu Wang, Chai Xiang-dong, Li Tie-jin
    1990, 11(12):  1419-1422. 
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    In this paper, the surface photovoltage technique (SPV) was applied to the study of the pho-tovoltic and gas sensitive properties of 7,7,8,8-tetracyanoquinodimethane polycrystal. It was found that SPVshowed two peaks at 390 nm(P1) and 480 nm(P2) in the ultraviolet-visible region, and they are opposite in phase. The results of gaseous adsorption reveals that P1 shows a characteristics of acceptor, while P2 shows that of donor. During the adsorption, the donor gas interacts with conjugate H* orbital, while the acceptor gas with C≡Nradical.
    Studies on Optical Properties of Polymer as Solid Matrix for Laser Dye
    Zhang Xue-xin, Hong Huai-mao, Li Zhuo-mei
    1990, 11(12):  1423-1426. 
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    One noteworthy attraction of the use of a solid matrix such as a polymer for dye laser is that it obviates many of the common problems associated with flowing dye systems. In this paper, the optical properties of a modified copolymer of MMA-MA as the main matrix doped with dye Rh6Ghas been studied, e. g. the absorption spectrum of Rh6Gin the materials, fluorescence properties of Rh6G in the materials, and laser conversion efficiency of Rh6Gin the material. It has found the maximal laser conversoin of Rh6G in the material is 20%, as high as the level which Rh6G can attain when it is dissolved in ethyl alcohol. The optical homogeneity of the material also has been studied.
    Preface
    Curing Theory for Poly condensation Reaction of Aa1,Aa2-Bb1Ba2 Type
    Li Ze-sheng, Ba Xia-wu, Sun Jia-zhong, Tang Au-chin
    1990, 11(12):  1427-1430. 
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    The curing theory for polycondensation reaction of Aa1,Aa2-Bb1Ba2 type is investigated in detail to give sol fraction for post-gel and gelation condition explicitly. Furthermore, a recursion formula for evaluating the polymer moments is obtained. This formula is suitable for both pre-gel and post-gel.
    Studies on the Capacity of Separation of Neutral Amino Acids with Ligand Exchange Resins
    Wang Shou-ting, Wang Bu-sen, He Bing-lin
    1990, 11(12):  1431-1434. 
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    Four neutral amino acids (Gly, Ala, Val and Leu) were separated with ligand exchange resins. The separation capacity of the ligand exchange resins was compared with that of common ion exchange resins. The effects of eluent, column temperature were tested, and the structure of the resins, functional groups,and the effect of ions in ligand centre on the separation were studied.
    Studies on Pervaporation Separation of Ethanol/Water Mixture with Membranes of Polypropylene Sulfonate Salts
    Xu Yin-bin, Lin Shao-kun, Lin Shang-an
    1990, 11(12):  1435-1438. 
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    Sulfonated polypropylene membranes loaded with different kinds of counter-ions were prepared by heterogenous chlorosulfonation reaction of polypropylene membrane followed by hydrolysis and ion-exchange reaction. The membranes were used for selective separation of ethanol/water mixture by pervaporation. The effects of counter-ion species, ion-exchange capacity, solution composition, thickness of membrane and temperature on the separation behavior of the membrane were investigated. Micro-structure and morphology of the membrane were examined by X-ray and SEM.
    Effect of the Micro-Surroundings of Propagating Radical in Bulk Polymerization
    Shen Jia-cong, Wang Guo-bin, Yang Mei-lin, Zheng Ying-guang
    1990, 11(12):  1439-1443. 
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    The present paper deals with the heterogeneity of the activity and physical micro-state of propagating radical in bulk polymerization of methyl methacrylate and styrene by ESRtechnique and pulsed gradient-field NMR spin echo technique. Some discussion and equations formulaing the effect of the heterogeneity are given.