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Table of Content

    24 January 1994, Volume 15 Issue 1
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    Articles
    Studies on Connectivity Between Bonding Parameter Topological Index and F Center Energy Bands in Alkaline Halides
    CHEN Wei, MA Ru-Zhang, SU Mian-Zeng
    1994, 15(1):  1-4. 
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    It is deduced from the bonding parameter topological index H41 and box-well potential model of Fcenter that a positive correlation must be exist ed between H41 and Fenergy bands E(F).This theoretical deduction is confirmed by the calculation results.Agood linear dependence of E(F) on H41 reveals that bonding parameter topological index can be really used to correlate the properties of inorganic compounds.
    The Synthesis and Characteristics of Missile Type Porphyrin with Radio Sensitization
    LIU Yu-Wen, XU Jian-Ping, WANG Xing-Qiao, CAO Xi-Zhang, LI Guang, GAO Ru-Gui
    1994, 15(1):  5-8. 
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    The metronidazole as a radio-sensitizer was chemically combined with protoporphyrin which has shown some orientating effects on cancer cells.The structure of this new compound was confirmed by the UV,IRspectra and elementary analysis.It is found that the porphyrin has shown some potential drug effect in aminal test and the decrease of dosage and reduction of toxicity.
    Studies on Phase Equilibrium of Ternary System Y(ClO4)3·3H2O-B15C5-CH3CN(20℃) by a Semimicro Method
    XUE Gang-Lin, REN De-Hou, SUN Ju-Chang
    1994, 15(1):  9-13. 
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    The solubilities of ternary system,Y(ClO4)3·3H2O-Bl5C5-CH3CN,have been investigated by a semimicro method at 20℃ for study of phase equilibrium,and the refractive indexes of saturated solutions have been determined.The results indicate that there are two kinds of complexes formed in the system , namely,Y(ClO4)3·Bl5C5·3H2O·2.5CH3CN and Y(ClO4)3·2Bl5C5·3H2O·CH3CN.Their compositions have been determined and properties have been characterized by IRspectra,conductivity measurements,DTG,TG and DSC.
    Studies on Phase Equilibrium of Ln(ClO4)3-DAPTU-H2O Ternary System at 30℃
    WANG Zhi-Yin, TANG Zong-Xun, CHEN Kai-Xun, GUO Zhi-Zhen
    1994, 15(1):  14-19. 
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    The solubilities and the refractive indexes of saturated solutions of the title systems at 30℃ have been studied and the corresponding equilibrium solubility diagrams and refractive index diagrams were drawn.All the solubility curves and refractive index curves of these systems consist of three branches,corresponding to DAPTU,Ln( DAPTU)2( ClO4)3·8H2O(Ln=La,Sm,Yb) and Ln( ClO4)3·mH2O(Ln=La,n=8;Sm,n=9;Yb,n=8),respectively.All the three ternary compounds formed in the title systems are new compounds reported for the first time in this paper.They are of incongruity in water.They were characterized by chemical analysis,elemental analysis,TG-DTG and IRspectra.
    Preparation and Structure Characterization of Pure Y-Type LB Films of Lead Stearate
    CHEN Hai-Yan, PENG Xiao-Gang, YU Lian-Xiang, ZHOU Yong-Liang, JIANG Yue-Shun, LI Tie-Jin, XU Yue, GAO Zhong-Min, WEI Quan
    1994, 15(1):  20-22. 
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    The collapse pressure of lead stearate(PbSt2)monolayer on the surface of 10-3mol/L PbCl2 solution(aq) is only 36 mN/m.And higher residual PbCl2 concentration was found within the PbSt2 LBfilms deposited on this subphase.However,the LBfilms with an acceptable composition and higher collapse pressure(about 60 Nm/m) was observed in the case of a lower PBCl2 concentration(<5×10-4mol/L).Pure Y-type transfer form for PbSt2 LBfilms was observed on the subphase with a lower PbCl2 concentration by the use of a faster dipping speed(10 cm/min).By X-ray diffraction measurements,it was determined that the pure Y-type PbSt2 LBfilms possess a certain layer mumber which is same to the value recorded during the deposition period.
    Catalytic Spectrophotometric Determination of Trace Molybdenum──A New Molybdenum(Ⅵ)-Diamine Hydrochloride Orange Ⅳ Catalytic Spectrophotometric System
    ZHENG Zhao-Sheng, WU He-Zhou, CHEN Zhi-Gui, HUANG Tian-Dong
    1994, 15(1):  23-26. 
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    A new catalytic spectrophotometric method for the determination of trace amount of Mo(Ⅵ) has been developed.The method is based on the catalytic effect of Mo(Ⅵ) on the reduction of orange Ⅳ with diamine hydrochloride. The effects of the solution PH,the reagent concentration and interfering ions on reaction rate have been studied.At.different temperatures,the linear range of determination is 0.025-1.8 μg/ mLfor molybdenum.The detection limit is 3.7×10-3 μg/mL,the relative standard deviation is 2.6%.The apparent activation energy of catalytic reaction is 46.0kJ/ mol.The method has been used to determine trace molybdenum in bean samples and the solubility product of both lead molybdate and barium molybdate.
    Studies on the Highly Sensitive and Selective Spectrophotometric Determination of Trace Osmium
    LI Ling-Ying, GUI Ming-De, ZHAO Ya-Qiu, ZHANG Shu-Roog
    1994, 15(1):  27-30. 
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    A new sensitive colour reaction of Os(Ⅳ) with 8-amino quinoline has been studied.The complex has an absorption peak at 600 nm and the reagent exhibits maximum absorptivity in the ultraviolet region,so that they show a strong colour contrast.The apparent molar absorptivity was found to be 1.32×105L/mol,cm.Beer's law is obeyed in the range of 0-10 μg of Os (Ⅳ)per l0 mL.It was also found that the complex reaction can be completed in 15-20 min,at 80-90℃ and pH 3.62 kept in a HAc-NaAc buffer solution,The colour of solution is stable at least 24 h.The molar ratio of Os(Ⅳ) to 8-amino quinoline was establislied to be 1:3 by two methods, All other noble metals except Ru(Ⅳ) which gives a slight absorption at 600 nm do not give colour reaction with 8-amino quinoline,even so 20 times amount of Ru(Ⅳ) can be tolerated.All common base metals reacting with 8-amino quinoline give no absorption at 600 nm,This paper is considered superior in terms of simplicity,stability,sensitivity and selectivity.
    Studies on the Polarographic Adsorptive Complex Wave of Germanium-Rutin
    ZHANG Cheng-Zhi, HE Wei-Jun, LI Nan-Qiang
    1994, 15(1):  31-34. 
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    In an acetate buffer solution,at pH 5.4,two sensitive adsorptive complex waves of Ge(Ⅳ)-rutin were obtained by using single-sweep polarography.They are stepewise reduction of Ge(Ⅳ) to Ge(Ⅱ) to Ge(0) in the complex,The detection limits of two waves are 8.0×10-8 mol/Land 4.0×10-8mol/L,respectively.The composition of the electroactive complex Ge(Ⅳ):Rt=1:3 was determined.The rate constants of surface electrode reaction(k)1=10.5s-1,(ks)2=1.9s-1 were determined.The proposed method was applied to the determination of germanium In organic gemanium tonic.
    Micelle-Sensitized Fluorometric Determination of Zirconium and Its Application
    ZHENG Yong-Xi, FAN Ying-Xin
    1994, 15(1):  35-38. 
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    The effect of surfactants on the fluorescence of the zirconium-morin system was described In 0.12 mol/L H2SO4 solution,the fluorescent intensity of this complex can be enhanced by cationic surfactant,cetyltrimethylammonium bromide(CTAB),but no effect in HCl medium.It was found that the mechanism of the effects of CTABon the absorbance and fluorescence were different.The absorptiometric measurement was favored with the formation of 1:3(Zr(Ⅳ):morin) complex in the proper CTABconcentration(near the critical micelle concentration,cmc,of CTAB).With the CTABconcentration increasing,a mixed-ligand complex was formed,and the intensity of fluorescence was enhanced dramatically.The role of CTABin the formation of the mixed-ligand complex and the enhancement of fluorescence was discussd.Anew analytical method for the fluorometric determination of Zr(Ⅳ)was described also.The detection limits of the method is 0.2ng/mL,calculated with S/N=6.The linear range of the calibration graph was 0.2ng/mL～0.5μg/mL.The intensity of fluorescence is stable for at least 24 hours.From the study of interfering ions,it was deduced that the selectivity of the method is high,This is one of the.best system for determination of traces of zirconium.
    Digital Signals Processing for Computerized Instrument in Electrochemistry(Ⅰ)──Piecewise Third-order Spline Function Method(PTSF)
    YU Jun-Sheng, ZHANG Zu-Xun
    1994, 15(1):  39-42. 
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    Smoothing of the digital data for computerized electrochem ical instrument by the piecewise third-order spline function technique is reported.The original digital signals in different noise levels measured from electrochemical experiments have been handled with the method.The results show that the processed digital signal waveforms are less distortion and signal- to-noise ratio enhancement.
    Intersection Point Rule for the Retention Value and Mobile Phase Composition of the Homologues in Reversed-Phase High-Performance Liquid Chromatography
    WANG Fu-An, YANG Chang-Sheng, JIANG Yuan-Li, JIANG Deng-Gao, LIU Da-Zhuang
    1994, 15(1):  43-46. 
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    Based on the intersection point rule for the retention value and normal boiling point of homologues in reversed-phase high-performance liquid chromatography,the intersection point rule for the retention value of homologues and mobile phase composition has been derived,and was testified by a lot of experimental data from the literature,With this newly proposed equation,we can use the retention value of the compound in one mobile phase composition to predict its retention value in any other mobile phase composition,For fourteen groups of homologues in five mobile phase on five kinds of columns,the overall average absolute error of 721 data sets is 2.8%.
    A Novel Method of Site Determination of Carbon Dioxide in Air
    YU Ai-Min, ANG Guang-De, WANG Rui, JIN Qin-Han
    1994, 15(1):  47-48. 
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    A home-designed portable gas chromatograph with a microwave induced plasma ionization detector(MIPID) has been developed.With Ar as carrier gas and support gas, a new method for the site determination of carbon dioxide(CO2) in air is described.The detection limit for CO2 is 3.5×10-8g.The method has been used to analyze the practical samples and the results are very satisfactory.
    Synthesis,Structure and Conformation of 1,4-Difluorotetraphenyl Benzene
    HUAN Zhen-Wei, ZHENG Zi-Rong, WANG Jing-Duan, LIU Wei-Guo, PAN Yin-Ming, LU Xiang-Jun, LIN Shao-Fan, LAI Cheng-Ming
    1994, 15(1):  49-52. 
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    By the method of electron transfer catalyzed reaction(ETC),the inert compound fluorotribromomethane can be activated by the electron donor 1,4-dilithioretraphenyl butadiene and the reaction will take place between them.The structure of the reaction product 1,4-difluorotetraphenyl benzene(Ⅰ) was determined by MS, NMR,and X-ray single crystal diffraction.Their comformations were calculated by molecular mechanics.
    Syntheses of Derivatives of 3-(1'-carbonyl)-Ferrocenyl-2-crotonic Ester with Amphipaphy
    ZHANG Cheng-Ru, YANG Kong-Zhang, YIN Rong-Jun
    1994, 15(1):  53-56. 
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    The acylation reaction of 3-ferrocenyl-2-crotonic ester has been investigated.When It reacted with alkyl acyl chloride or benzyl chloride,the substitution reaction took place in the unsubstituted cyclopentadiene ring and just one single new product was obtained.But as it reacted with α,β-unsaturated acyl chloride,two new products were obtained in each reaction.Ten new compounds with amphiphilic structure were prepared.All of them were characterized by 1H NMR,IRspectra and elemental analysis.
    An Exponent-type Homologous Linear Rule of Organic Homologs(Ⅰ)──The Verification by Using the UV Photo-electron Spectroscopy Data of Homologous Series
    LIU Feng-Ling, SHI Ming-Li, NING Shi-Guang
    1994, 15(1):  57-62. 
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    An exponent-type homologous linear rule has been first proposed here,the formula is as follows:P=a+bexp{(K+1)/(2(n+t)+3)} The new homologous linear rule was verified by using the UVphotoelectron spectroscopy data of conjugated and non-conjugated systems.As for organic conjugated homologs,69 sets of ionization potentials were verified.Among them,31 sets belong to two direction extending systems.As for organic non-conjugated homologs,60 sets of ionization potentials were verified.Among all the data,76.74%of the correlation is the"excellent"grades with correlation coefficient r≥0.99,and 20.16%,the"good"grades with r≥0. 95 and 3.10% with r≥0.90.
    H-Abstraction from p-Substituted Benzaldehydes by Bis-perfluoroalkyl Nitroxides──A New Attempt for Establishing Substituent Constants of Spin Delocalization σ by EPR Method
    ZHAO Cheng-Xue, QU Yan-Ling, ZHANG Wei-Xin, JIANG Xi-Kui, CHEN Guo-Fei
    1994, 15(1):  63-66. 
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    RFN(O·)RF and RFNO dissolved in F113 reacted with a series of p-substituted benzaldehydes at r,t.and ended up with very stable p-substituted benzoyl perfluoroalkyl nitroxides.Correlation analysis(△aN or △aFβ vis σ only;△aN vis σand σ both) disclosed that the polar effect is the major factor varying the spin density on the nitrtigen atom of the fluorinated acylnitroxides while the effect through spin delocalization is almost negligible.
    Studies on the Application of Lanthanoid Metal to Organic Reactions──The Reaction of NdCl3/Lithium Naphthalide System with Carbonyl Compounds
    BAO Jian-Chun, ZHANG Jin-Ju, BEI Mei-Zhi
    1994, 15(1):  67-71. 
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    The active neodymium metal(Nd*) prepared by the reduction of anhydrous NdCl3 with LiNp(LiNp=Lithium Naphthalide)shows a higher reactivity in its reaction with carbonyl compounds.The reaction of Nd* with carbonyl compounds followed by hydrolysis,produces the corresponding alcohols,pinacols and alkenes depending not only on the nature of the carbonyl compounds but also on the molar ratio of Nd*:RCOR' and the reaction time and temperature.The reaction of benzophenone with Nd* is studied in detail.The effect of.the different molar ratios of Nd*:RCOR' or adding the ligand or changing the solvent shows different selectivities of the reaction,The mechanism of the reaction of Nd* with benzophenone is discussed.
    Computer-Assisted Optimization of Separation of Amino Acids in Column Chromatography
    WANG Qin-Sun, YAN Bing-Wen, WANG Shou-Tin, TAO Xue
    1994, 15(1):  72-74. 
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    A computer-assisted method is presented for optimization of ICand pHselection of mobile phase in column chromatography.The optimization of expected separation is based on a polynomial estimation from 4-5preliminary runs.Satatical scanning technique is used for the optimization and computer simulation system(CSC) is established for chromatographic performance measurement in this method.By separation of three amino acids,excellent agreement is obtained between simulated and experimental results.
    The Electronic Structures and Spectra of Phthalocyanine and Copper Phthalocyanine
    LI Jun, FENG Ji-Kang, LI Zhi-Ru, SUN Jia-Zhong
    1994, 15(1):  75-78. 
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    The electronic structures and UV-Vis spectra of phthalocyanine(H2Pc) and copper phthalocyanine(CuPc) were studied by using INDO/CImethod.The shred hydrogen model has been used for H2Pc.The single electron located at the 11b1g(dx2-y2)MO for CuPc.From CuPc to H2Pc,as the D4h symmetry of molecule CuPc lowered to D2h of H2Pc,the lines of spectra splitted.The calculated results are consistent with the observed results.
    The Fundamental Effects of Triethanolamine in the Electrodeposition of Metals
    CAI Jia-Le, ZHOU Shao-Min
    1994, 15(1):  79-84. 
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    The behaviour of triethanolamine(TELA) at electrode/solution interface in alkaline solution with and without Zn2+、Cd2+、Cu2+、Fe3+ and Sn4+ ions has been studied by means of differential capacity,polarography,in-situ surface-enhanced Raman spectroscopy(SERS)and microdisc electrodes.The influence of TELA on the discharging process of above ions and the inhibition of TELAon the electrodeposition of zinc have been studied.The results are summarized as follows:TELAhas a stronger adsorptivity at the Hg(or Ag)/solution interface and adsorbs with·lat" orientation on Ag electrode at the potential of maximum adsorption(～-0. 60 V).TELAadsorption on Hg electrode obeys the Frumkin isotherm and possesses a linear relationship between(Ep-Em)2 and lgCTELA.Mixed ligand coordination compounds of metallic ions(such as Zn2+,Cd2+,Cu2+,Ni2+ and Fe3+) with TELAand OH- ions are formed,and these coordination compounds are surface-active. Their adsoption activities on Hg electrode are Ni(Ⅱ)>Fe(Ⅲ),Cu(Ⅱ)>Zn(Ⅱ)>Cd(Ⅱ).TELA affects the electroreduction of t he above metallic ions in different degree.The influences of TELAare the same in the sequence as adsoption activities corresponding to mixed ligand coordination compounds,The free energy of TELAadsorption in the presence of zinc ion has a more negative value than that in the absence of zinc ion.The interaction of adsorbed TELAmolecular changes from weak repellant to weak attraction in the presence of zinc ion.The observed rate constants for zinc electrodepositon(at-1.400 V)reduce according to the increase of TELAconcentration,and its inhibitive mechanism can be expressed by ks=k0(1-θ)+k1θ.
    The Interaction Between Clean/Hydrogenated Diamond(111) Surfaces and Methyl Radical
    LIU Bo, LI Yan-Xin, QIAN Xing-Zhong, PAN Shou-Fu
    1994, 15(1):  85-88. 
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    Interactive potential energy curves between methyl radical and the clean/hydrogenated diamond(111)surfaces are first calculated by Aml molecular orbital method.The effects of relaxation and reconstruction of the surface atoms and adsorbed hydrogen atoms on the potential energy curves have been found.It is concluded that the hydrogenated diamond(111) surface is more suitable for methyl radical to adsorbed and is therefore a better growth site for diamond than the clean surface,There is a strong interaction between methyl radical and the clean/hydrogenated diamond(111) surfaces within 5 nm above the surface.We suppose that the dynamic processes in the region is important for us to research.
    The Leaching Treatment of SDY Zeolite and Its Influence on Catalytic Properties
    FU Jun, BAO Shu-Lin, WU Peng, XU Qin-Hua
    1994, 15(1):  89-92. 
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    The extra-framework aluminum of SDYzeolite has been leached out with Na2H2EDTA,H4EDTA and HCl respectively.The structures,acidities and catalytic properties of these samples have been studied by using chemical analyses,XRD,N2 adsorption,NH3-TPD and n-heptane cracking reaction.It is found that Na2H2EDTA is a selective extractant which removes only amorphous extra-framework aluminum deposited in the zeolite pores without destroying the framework aluminum,Both the n-heptane cracking activity and nitrogen-resistance properties of SDY-NaE are higher than those of SDY.
    Studies on the Surface Acidity and Catalytic Properties of Pillared Ga-Substituted Saponite
    JIANG Ting-Shun, SUNT Tie, SHEN Jian-Ping, JIANG Da-Zhen, Min En-Ze
    1994, 15(1):  93-97. 
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    Two Ga-substituted saponites with different amount of gallium were synthesized by hydrothermal method.The pillared clays were prepared by cross-linking with hydroxyl aluminium oligomer,The results show that the amount of acidity of the samples increases with that of gallium in the tetrahedral sheet,and both Brnsted and Lewis acid sites are present on the surfaces of the samples,and the Bacid sites decrease after cross-linking with Al(13) oligomer.The studies on the catalytic properties show that the activity is correlative to the amount of gallium in the tetrahedral sheet.
    IR Spectra of Chemisorbed Species on MoSx-based Catalysts for Mixed Alcohols Synthesis from Syngas
    YANGY Yo-Quan, XU Jin-Lai, LIN Guo-Dong, LIAO Yuan-Yan, YUAN You-Zhu, ZHANG Hong-Bin
    1994, 15(1):  98-102. 
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    The IRspectra of chemisorbed species on SiO2 supported,or unsupported,alkali-promoted MoSx-based catalysts for the mixed alcohols synthesis from syngas were taken in-situ under the reaction conditions of 538 K,2.0 MPa,and flowing feed stream of syngas(CO/H2=1,V/V),and ex-situ at 323 K,atmospheric pressure and under the controlled atmosphere.The results indicate that the detectable surface intermediates of CO hydrogenation are and that the IRbands as the fingerprints of and are ambiguous,and too weak to be sure of assignments.Based upon the results of the present IR investigation,the major reaction pathways of the syngas conversion over the MoSx-K+ catalysts are suggested.
    Studies on the Redox Process of Silver Using Electrochemical Quartz Crystal Microbalance
    CHEN Sheng-Li, WU Bing-Liang, YANG Han-Xi
    1994, 15(1):  103-107. 
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    Combined with cyclic voltammetry,the Electrochemical Quartz Crystal Microbalance(EQCM) technique was used to study the redox behavior of silver in an alkaline solution.By insitu recording the change of mass in the process of polarization,the dependence of mass on voltage in accordance with the cyclic voltammogram was obtained.Before the formation of the bulk of Ag2O,a process of competition between the dissolution and the formation of AgOH(or hydrous Ag2O) surface-layer was detected.Alittle unexpected increase of mass was found at the beginning of the reduction of AgO to Ag2O,and the exceptional increase was discussed in terms of formation of a surface-compound and the change in the double layer structure.Acomparison was made between the measuring time derivative of the frequency and the calculating value based on current.According to this comparison,we valued the effectivity of EQCM in the study of the process of phase transfermation.
    Application of the Many-Body Expansion Potential Energy Functions to the Study of Group Ⅳ Atomic Microclusters(Ⅳ)──Structures and Stabilities of Si9-Si16 Microclusters
    LI Si-Dian
    1994, 15(1):  108-112. 
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    A many-body expansion potential energy function is used to study the structures and stabilities of silicon microclusters,suggesting that firstly,Si4-Si16 clusters can be constructed by successively adding two-or three-coordinated atoms,forming surfaces covered with four-membered butterfly rings(D2d);secondly,the trigonal bipyramid Si5(D3h) and D2d Si6 are the building blocks for most of these compact structures with a D4d cage Si10 added in for the clusters with over 10 atoms and both Si10 and Si16 are covered with three-or four-or five-coordinated atoms,predicting that Si5,Si6,Si10,and Si16 be the prominent peaks in the mass spectra of fragmentized silicon clusters,in agreement with experiments;and finally,these nondiamond compact structures have a maximum coordination number of five and the formation of six-coordinated silicon centres within half a sphere leads to destablization in energy.
    Direct Electrochemistry of Cytochrome C at Gold Electrode Modified with Pyridine or Its Polymer
    QU Xiao-Gang, ZHOU Cheng-Li, LU Tian-Hong, DONG Shao-Jun
    1994, 15(1):  113-116. 
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    In this paper,the direct electrochemistry of cytochrome Cat gold electrode modified with pyridine and its polymer(poly-pyridine) was studied.It was found that cytochrome Ccould undergo a rapid electron transfer reaction at pyridine-modified gold electrode.The promotion effect of pyridine was related to the adsorption time.With increasing the adsorption time,the separation between the cathodic and anodic peak potentials in the cyclic voltammogram of cytochrome Cbecame smaller and smaller.When the electrode was dipped into pyridine solution for 12 h,the separation got upmost.This result demonstrates that pyridine is also a good promoter for the direct electrochemical reaction of cytochrome Calthough it has only one functional group.Its polymer,poly-pyridine was also investigated in the experiment.The poly-pyridine modified gold electrode was prepared with electrochemical polymerization method.According to our electrochemical results,the promotion effect of poly-pyridine was much better than that of pyridine,indicating that a major requirement for an effective promoter was that it should be strongly adsorbed on the surface of the gold electrode.
    Preface
    The Ultrafine Amorphous Ni73P11B16 Alloy Particles with Higher Structural Stability
    FAN Yi-Ning, HU Zheng, XU Zhao-Yi, CHEN Yi
    1994, 15(1):  117-118. 
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    Ultrafine amorphous Ni73P11B16 alloy particles with the size in the range of 20-60 nm were prepared by the reaction of NiCl2 with KBH4 and NaH2PO2 in a aqueous solution.The fresh and heat-treated samples were characterized by TEM and XRD.It is shown that the NiPB alloy has a higher amorphous structural stability than NiP and NiB due to the coexistance of Pand B.
    Articles
    Photocatalytic Selective Oxidation and Hydrogen Transfer of SO2 Aqueous Solution
    WANG Zeng-Hua, HONG Jian-Bin, ZHUANG Qi-Xing
    1994, 15(1):  119-120. 
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    By changing initial concentration,reaction temperature,pHand irradiation time,the photocatalytic selective oxidation of SO2 aqueous solution is investigated.The experimental results show that both percentage oxidation of SO32- and selectivity of S2O62- dithionate are closely interrelated and assumption on the role of intermediates,atomic hydrogen H,which was produced prior to H2 formation,photospillover and participation in the mediated reduction of SO42- to form S2O62-,has been verified.In optimal conditions of H·formation,0.05 mol/L,80℃,pH 8.8 and irradiation time 4 h,the selectivity of the expensive S2O62- can be increased to 59.3% as the first oxidation product.
    Studies on Mass Spectra of Discharging Gas in Palladium Hollow Cathod Lamp Filled With Deuterium
    YANG Peng-Yuan, WANG Xiao-Ru
    1994, 15(1):  121-123. 
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    The behavior of a palladium hollow cathode lamp discharged in deuterium was reported.The lamp was operated at pulse mode with 1μs duration at 110 Hz,900 Vand >10 Acurrent.The oscillation of discharge was observed due to the absorption and desorption of deuterium on the palladium surface layer.The analysis of discharge gas by mass spectrometry showed there was trace amount of helium-4 after 30 hours of operation.
    The Study of Two Kinds of Methincyanines Bound Chemically to a Monocrystalline Silicon Surface and Their Spectral Response
    WANG Lan-Ying, HAO Ji-Xiang, ZHANG Zu-Xun, CAO Zi-Xiang
    1994, 15(1):  124-126. 
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    In the paper,two photosensitive dyes(thia-2'-cyanine dye and thiacyanine dye) were bound directly on monocrystalline silicon surface through chemical way respectively.Then the silicon wafer binding photosensitive dyes was examined by EPLP,LRS and XPS.The results show that the photosensitive dyes have been bound firmly to the monocrystalline silicon surface.And the spectral response curve of In/dye/n-Si(or p-Si) sandwich structure devices made of silicon wafers bound dye was determined.Compared with the spectral response curve of silicon p-n photocell of no covered antireflection coating it was found that there was a new response peak corresponding to the maximum absorption of photosensitive dye in the range of short wave,except the absorb peak at 650 nm.The short wave absorption of the silicon is increased and the spectral response range of the silicon is enlarged because of the binding of the dyes on the silicon surface.
    Studies on Morphological Structure of Low Molecular Weight PVC Prepared by Vibro-Milling Degradation
    GUO Shao-Yun, XU Xi
    1994, 15(1):  127-131. 
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    The effect of vibro-milling on particle size,crystalline structure,optical density and the plasticizer absorption of PVC were studied through FTIR,SEM and physical property tests.The experimental results show that the intensities of crystalline absorption bands on FTIRspectra at 635 cm-1,604-1 and 1427 cm-1 get weaker and the intensities of 635 cm-1 and 604 cm-1 bands tend to disappear during vibro-milling,while the intensity of the amorphous absorption band at 1435 cm-1 becomes stronger,indicating that the crystalline structure of PVCis changed somewhat and the crystallinity of PVC decreases during vibro-milling.The particle size and the molecular weight of PVCare decreased.The surface area and the amount of plasticizer absorption increase with the increase of vibro-milling time.The low molecular weight PVCso prepared has ultra-fine particle size,lower crystallinity and glass transition temperature,higher plasticizer absorption capacity,should have pretty good processability.
    Studies on the New Complexing Adsorbents(Ⅳ)──The Memorial Properties of Complexing Adsorbents Containing Polyethylene Polyamine and Copper(Ⅱ) or Nickel(Ⅱ) used as Template Ions
    HE Bing-Lin, WANG Bu-Sen, LI Wen-Lan, DING Ze-Ren, GUO Zhen-Liang
    1994, 15(1):  132-135. 
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    The behavior of kinetic adsorption and desorption of two kinds of complexing adsorbents containing polyethylene polyamine,with Cu(Ⅱ) or Ni(Ⅱ) as the template ion for Cu(Ⅱ) and Ni(Ⅱ) respectively,was studied.The results of five operating cycles show that the complexing adsorbents possess stationary sorption capacity for Cu(Ⅱ) or Ni(Ⅱ).Its saturated sorption capacities for Cu(Ⅱ) and Ni(Ⅱ) are 4. 357 mmol Cu(Ⅱ)/g and 3.153 mmol Ni(Ⅱ)/g respectively.The relative errors are±1.5%and±2.2%respectively.
    Synthesis of Side Chain LC Copolymer with NLO Unit and the Study of Its Poling Film by UV
    HUANG Zhi-Hua, YANG Chun-Cai, TANG Xin-Yi, WANG Hua-Bin, JING Xia-Bin
    1994, 15(1):  136-139. 
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    A zo-type nonmesogenic monomer and mesogenic monomer were synthesized.Copolymers were obtained using these monomers by radical polymerization.The phase transition temperatures of these copolymers were investigated by DSC,the result showed that the copolymer did not exhibit the mesomorphic nature in concentration of azo unit above 40 mol%.The polymeric film was poled by needle-electrode corona-onset poling at elevated temperature,the orientational order parameterφand its stability were estimated by UVmeasurement.This paper proceeded to an initial study for NLO property of liquid crystal polymer.
    Sequence Structure Characteristics of High Impact Polypropylenes
    MA De-Zhu, LI Xi-Qiang, HONG Kun-Lun, ZHANG Rui-Yun, LUO Xiao-Lie, ZHU Qing-Ren, HU Ke-Liang
    1994, 15(1):  140-144. 
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    Using FTIR,13C NMR etc.,we obtain the information of chain structure in composition and sequences distribution of high impact polypropylene.With DSC,WAXD etc.,we also study their crystalline behavior,transition of molten polymers and crystal structure.By various methods,we effectively characterize the sequences structure of high unimpact polypropylene.
    Studies on the Rigid-Rigid Block Copolymers(Ⅲ)──Synthesis and Properties of PEEK/HTA Block Copolymers
    CAO Jun-Kui, SU Wen-Cheng, ZHOU Wen-Sheng, ZHOU Feng-Qi, WU Zhong-Wen
    1994, 15(1):  145-149. 
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    A series of rigid-rigid block copolymers composed of poly(etheretherketone)(PEEK) and poly(arylethersulfone) with biphenyl structure(HTA) were synthesized by polycondensation.The characterization,thermal properties and crystallization behaviour of the block copolymers were investigated by DSC,TGA,WAXD,and dynamic viscoelastic measurement.The results show that for the copolymers no phase separation is observed.The copolymers are crystalline polymers similar to PEEK,the crystallinity measured by DSC decreases obviously with increasing HTA content.The Tg of the copolymer containing 37.24%HTA is 183℃,and is 40℃ higher than that of pure PEEK. The melting point of the copolymer is nearly as high as that of pure PEEK.The PEEK/HTA copolymers have very good high temperature mechanical property.
    Studies on High Permselective Gas Separation Membrane of Sulfur Dioxide(Ⅲ)──Michael Addition Reaction of Vinyl Sulfoxide with Poly(vinyl alcohol) and Structure Characterization
    JIANG Dong-Lin, ZHANG Yi-Feng, SHEN Zhi-Quan
    1994, 15(1):  150-153. 
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    Four kinds of alkyl vinyl sulfoxides were synthesized.The Michael addition reaction of vinyl sulfoxide with poly(vinyl alcohol) in the presence of NaOH as catalyst has been studied in detail.Polymers with various sulfoxide contents were prepared and characterized by means of 1H NMRand IR spectra.
    Studies on the Structure and Decolorization Properties of Cross-linked Polystyrene Amino Resins
    LIU Yong-Ning, SHI Zuo-Qing, FAN Yun-Ge, HE Bing-Lin
    1994, 15(1):  154-157. 
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    The authors prepared a series of macroreticular basic resins by using different kinds of aminating agents,percentage of crosslinker and porogenic agents.The resins were characterized and their capacities of decolorization were determined.In addition,the authors also investigated in detail the relation between the decolorization properties and the pore structure,nature of functional groups of resins.The results show that the nature and content of functional groups as well as pore structure of these resins has an important influence on their capacities of decolorization.
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