Table of Content

24 June 1993, Volume 14 Issue 6

Previous Issue    Next Issue

Articles

Studies on the Solidification and Characterizations of USY Type Molecular Sieve-Kaolin by Hydrothermal Hot-Pressing Technique

MENG Xian-Ping, JI Tian-Hao, PANG Wen-Qin

1993, 14(6):  741-744. 

Asbtract ( )   PDF (324KB) ( )  

Related Articles | Metrics

Aseries of solidified bodies of kaolin, mixed with USYtype molecular sievs, were prepared by using the hydrothermai hot-pressing technique, The phase transformation, surface acidity, and catalytic cracking reaction of R- pentadecane were investigated.The results show that the temperature of solidification is one of the important factors which influence the properties of the solidified bodies under the condition of hydrothermai hot-pressing and that the solidified bodies of USY-kaolin have majority of Bronsted acid sites and few Lewis acid sites.The activity and gasolin conversion of the solidified bodies at 135℃ for n-pentadecane cracking are higher than those of the untreated sample.The surface acidity and catalytic characters of solidified bodies can be adjusted by means of changing compositions of the initial mixture and the conditions of solidification.

Synthesis, Crystal Structure and Properties of TAAB Nickel Adducts with Axial N-Base Ligands

LI Ming-Xing, XU Zheng, LI Jin-Yu, YOU Xiao-Zeng, WANG Hua-Qin, YANG Yue, YU Yun-Peng, ZHU Duo-Lin

1993, 14(6):  745-749. 

Asbtract ( )   PDF (376KB) ( )  

Related Articles | Metrics

Four adducts of Py, Im, DMFand 4,4'-bipy with Ni(TAAB)²⁺, where TAAB=tetraben-zo[b,f,j,R][1,5,9,13]tetraazacyclohexadecine, were synthesized and characterized by elementary analysis, IRand thermal analysis.The crystal structure of [Ni(TAAB)(Py)₂](BF₄)₂has been determined.The crystal belongs to a monoclinic system with space group P2₁/n, α=1.6465(6) nm, b=1.2486(5) nm, c=2.0219(1) nm,β=113.79°, V=3.8039 nm³, Z=4, R=0.068.TAABmacrocyclic ligand presents a decidedly saddle-shaped appearance.The planes of two pyridine molecules are perpendicular to each other.The bond distances of Ni-N(n)(n=10,20,30,40) are in the range of 0.1983-0.2043 nm while the bond distances of Ni-N(B)(n=5,6) are 0.2182-0.2189 nm, forming a distorted octahedron coordination geometry around nickel ion.The variable-temperature magnetic susceptibility of 4,4'-bipyridine-bridging nickel TAABcomplex obeys the Curi-er-Weiss law (θ=- 44 K) and indicates an antiferromagnetic exchange interaction between nickel ions.

Studies on the Solid State Reaction of Coordination.Compounds (LXI) --Solid State Synthesis of [Cu(SC(Ph)NHPh)(PPh₃)₂X](X=Cl, Br, I) and Crystal Structures of [Cu(SC(Ph)NHPh)(PPh₃)₂Cl]

LANG Jian-Ping, BAO Shi-An, XIN Xin-Quan, CAI Jin-Hua, KANG Bei-Sheng

1993, 14(6):  750-754. 

Asbtract ( )   PDF (371KB) ( )  

Related Articles | Metrics

Areddish-yellow solid was produced by the solid state reaction of SC(PH)NHPh, CuX(X=Cl,Br,I) and PPh₃.The products were extracted with CS₂ to obtain the reddish-yellow cubic crystals [Cu(SC(Ph)NHPh)(PPh₃)₂X].The crystal (X=Cl) is monoclinic with α=1.8013(5) nm, 6=1.4588(5) nm, c=1.7222(5) nm;β=105.54(3)°, space group P2₁/c, Z=-4.The geometry of the central Cu(Ⅰ) ion is distorted tetrahedron configuration.The average bond angle about the Cu(Ⅰ) ion is 109.4% Cu-S, Cu- Cl, Cu-P(1) and Cu--P(2) distances are 0.2352(3) nm, 0.2375(4) nm, 0.2297(4) nm and 0.2282(3) nm, respectively.

Intramolecular Ligand-Ligand Hydrophobic Interaction in Coordination Compounds (Ⅱ)--Systems of Cd²⁺(Co²⁺)-Phenanthroline-Amino-Acids System

GAO En-Jun, ZHU Ning, LIU Qi-Tao

1993, 14(6):  755-759. 

Asbtract ( )   PDF (382KB) ( )  

Related Articles | Metrics

The stabilities of binary complexes of type MB, MB₂ and the mixed ligand complexes of type MABhave been studied by potentiometric pHtitration technique at 37℃ and at ionic strength I=0.02(NaCI), where M=Cd(Ⅱ)orCo(Ⅱ); A=phenanthroline; B=glycine, alanine, valine, leucine, phenylalanine and tryptophan.The logarithm of stability constants IgK_MAB^M, the logarithm of equilibrium constants △lgKof reaction MA+MB=MAB+Mand the logarithm of equilibrium constants IgXof reaction M A₂ + MB₂=2MABhave been calculated.The results show that the six mixed ligand complexes containing leucine, phenylalanine or tryptophan as one of the ligands have an enhanced stability, because their △lgKand IgXare distinctly higher than the corresponding statistically expected values, even becoming positive values.The possible reasons that lead to these special results have been discussed from the viewpoints of π electronic back donation from the metal ions to the aromatic amine molecule and of the intramolecular ligand-ligand hydrophobic interactions presented in the mixed ligand complexes.After analysing the experimental data, we come to the conclusion that the major reason for the enhanced stability of above mentioned six mixed ligand complexes is the intramolecular hydrophobic interaction between the aromatical ring of phenanthroline and hydrophobic moieties of these amino-acids.The variation order of △lgKor IgXis Try>Phe>Leu, which is consistent with the size of hydrophobic moieties of amino-acids.The equilibrium constants, K₁ of transfer between the opened species (absence of ligand-ligand interaction) and the closed species (hydrophobic interaction having occured) and the percentage of the.closed species have been calculated for each of the six mixed ligand complexes (Table 3).The results show that the closed species of the mixed ligand complexes containing amino-acid with aromatical ring moiety as a ligand have become the major components in solution.

Studies on the Synthesis and Fluorescent Property of Alkaline Earth Stannates Doped Europium

LI Yuan-Ying, CHEN Huo-Yang, YANG Yan-Sheng

1993, 14(6):  760-763. 

Asbtract ( )   PDF (300KB) ( )  

Related Articles | Metrics

The synthesis and fluorescent property of MSnO₃:Eu³⁺ and M₂SnO₄:Eu³⁺(M=Ca,Sr, Ba) have been reported.The phosphors were prepared by mixing the solution of MCl₂(M=Ca,Sr, Ba) SnCl₂ and EuCl₃ according to stoichiometry.Their oxalates were coprecipitated and sintered at 1400-1500℃ for 5-6 h.Structures of the phosphors were confirmed by X-ray diffraction analysis, and CaSnO₃:Eu³⁺ and Ca₂SnO₄:Eu³⁺ belong to othorhomic system, SrSnO₃:Eu³⁺ and BaSnO₃:Eu³⁺ the cubic, Sr₂SnO₄:Eu³⁺ and Ba₂SnO₄:Eu³⁺ the tetragonal.The excited and emission spectra of the phosphors show that, the energy of charge transfer transition for Eu³⁺ shifts to the blue, and energy of f-f transition for Eu³⁺ shifts to the red.The CaSnO₃:Eu³⁺ and Ca₂SnO₄:Eu³⁺ show the major electric dipole transition.The other four phosphors show the major magnetic dipole transition.

Studies on the Synthesis and Property of Cr(CNCH₂C₆H₅)₃Cl₃ and Cr(CNCH₂C·H₅),Cl₂B(C₆H₅)₄ H₂O

GAO Yi-Ci, SHEN Feng-Jia, SHI Qi-Zhen

1993, 14(6):  764-765. 

Asbtract ( )   PDF (177KB) ( )  

Related Articles | Metrics

The title metal isocyanides were synthesized by the substitution reaction of Ugand.The reaction of CNCH₂C₆H₅ with CrCl₃(thf)₃ yielded Cr(CNCH₂C₆H₅)₃Cl₃.B(C₆H₅)₄^- anion was introduced into the reaction mixture only to form Cr(CNCH₂C₆H₅)₃Cl₂B(C₈H₅)₄.Two new compounds are all stable in air and unstable in chloroform, dichloromethane, acetone and other organic solvents.Their IRspectra and thermal stability have been investigated.

Spectrophotometry for Measuring Association Number and Association Degree in Solution State of the Species

HE Xi-Wen, SHI Chang-Hong, ZHANG Gui-Zhu, YANG Wan-Long, YU Gui-Ying

1993, 14(6):  766-770. 

Asbtract ( )   PDF (370KB) ( )  

Related Articles | Metrics

Anew approach for measuring association number (i) and associated degree (a) in species solution is presented.Selection of different values of i will yield curve with differing shape, but only the correct value of i will yield a straight line with slope p and intercept of ε_M.The value of a can be obtained from spectrophotometric data through the equation.The systems of bipyridine in cyclohexane and rhodamine 6Gin water are used to demonstrate the applicability of the method, it has been applied to the determination of i and α with satisfactory results.This paper describes the effect of rhodamine 6Gmonomer solution on recovering of fluorescence more effectively to the dimer solution.Rhodamine 6Gdimerizes in higher concentration range in aqueous solution and its fluorescence fades remarkably.In the case, the variation of R 6Gfluorescence intensity implies that the process from dimer to monomer is D→2M; M_i→M+(i-1.)Min water medium.

A Chemiluminescence Method for In-Line Monitor of Cr(Ⅵ) and Cr(Ⅲ) in Environmental Water

LU Jiu-Ru, ZHANG Xin-Rong, ZHANG Ba-He, QIN Wei, ZHANG Zhu-Jun

1993, 14(6):  771-774. 

Asbtract ( )   PDF (194KB) ( )  

Related Articles | Metrics

Achemiluminescenee method for in-line monitor of Cr(Ⅵ) and Cr(Ⅲ) in environmental water is proposed.The method is based on Cr(Ⅲ)-H₂O₂-luminoIchemiluminescence system.To determine Cr(Ⅲ) in sample, an anion-exchange column is used.Cr(Ⅲ) that passes through the column can be determined selectively by Cr(Ⅲ)-H₂O₂-luminol system.Cr(Ⅵ) can not be determined directly by this system because it can not react with H₂O₂ and luminol in alkaline medium.In order to determine Cr (Ⅵ), an cation-exchange column is used to separate Cr (Ⅵ) from Cr (Ⅲ) in sample.Cr (Ⅵ) that passes through the column is reduced into Cr(Ⅲ) by acidic H₂O₂ in the flow and determined subsequently with Cr(Ⅲ)-H₂O₂-luminol system in alkaline medium.By rotating the selecting-valve, Cr(Ⅲ) and Cr(Ⅵ) in sample can be determined alternatively.The method offers potential advantages of simplicity, selectivity and applicability to the determination of Cr(Ⅲ) and Cr(Ⅵ) in environmental water.The detection limit of the method is 4×10^-11 g/mL Cr.The linear range is 10^-5-10^-10g/mL Cr.

Pattern Recognition Application to ¹³C NMR Spectra of Flavone Compounds

ZHANG Liang, ZHANG Zheng-Xing, SHENG Long-Sheng, AN Deng-Kui

1993, 14(6):  775-777. 

Asbtract ( )   PDF (228KB) ( )  

Related Articles | Metrics

Aset of 64¹³C NMRspectra of flavone compounds were examined for information concerning chemical classes by pattern recognition.The Shannon information content for each chemical shift channel was calculated, the 14 channels with the highest information content were retained as a compressed basis set for SIMCA, LDAand KNNpattern recognition.The inherent class structure of the data showed two classes by NLM.Classification accuracy was 90.91%, 96.97% and 90.91% for two classes for SIMCA, LDAand KNN, respectively.

Studies on the Determination of Bisphenol A and Phenol with Reversed Phase High Performance Liquid Chromatography

LI Jin-Chang, SHI Jing, SHI Jun

1993, 14(6):  778-780. 

Asbtract ( )   PDF (217KB) ( )  

Related Articles | Metrics

Arapid and exact analysis method of bisphenol Aand phenol was established.It is necessary to control producing process and examine the quality of produts.Reversed phase high performance liquid chromatography was used to separate and determine bisphenol Aand phenol, under a selected optimum chromatography condition.This method is simple and convenient, and it also has a high sensitivity.It can be used to analyse the actual sample.The results are satisfactory.

Determination of Micro-osmium in the Anode Mud by Flow Injection Analysis

ZHOU Zhi-Fa, GU Jun, YE Shuai-Guan

1993, 14(6):  781-783. 

Asbtract ( )   PDF (218KB) ( )  

Related Articles | Metrics

Aprocedure was established for the determination of micro Os (Ⅷ) in the anode mud by flow injection analysis-integrated microconduit made by ourselves.This metnod is based on the velocity of γ-acid oxided by oxygen in air to form quinone(red) and the reaction is catalyzed by Os(Ⅷ).The proposed method is rapid, simple and low reagent consumption.The limit of detection for Os (Ⅷ) is 0.010 μg/mLand relative standard deviation is 2.1% in the concentration range of 0.010-0.100 μg/mL.Sampling frequency is 20 times per hour.

Simultaneous Determination of Thorium and Lanthanum in Waste Water with the Use of Kalman Filter-Spectrophotometry

ZHOU Wei-Liang, PAN Jiao-Mai, WANG Jian-Xing

1993, 14(6):  784-786. 

Asbtract ( )   PDF (269KB) ( )  

Related Articles | Metrics

The proper color-reaction condition of dibormocarboxyarsenazo with thorium (Ⅳ) are discussed.With the Kalman filter-spectrophotometry, thorium and lanthanum in waste water have been simultaneously determined by using the chromogenic reagent dibormocarboxyarsenazo with satisfactory-results.The average recovery of thorium and lanthanum are 100.68% and 99.62% respectively, the average deviation of determined results are less than +4.0%, and both with good reproducibility.

Syntheses and Biological Activities of Thiophosphoryl (Thiophosphonyl) Urea Derivatives

YANG Hua-Zheng, HUANG Zhan-Ao

1993, 14(6):  787-790. 

Asbtract ( )   PDF (304KB) ( )  

Related Articles | Metrics

The thiophosphoryl(thiophosphonyl) urea uerivatives, R(EtO)P(S)NHC(O)N (R¹)R², (R=EtO, Ph:R¹=alkyl, H; R²=alkyl, aryl and heterocyclic radical) were synthesized by the addition reaction of R(EtO)P(S)NCO (R=EtO, Ph) to various amines respectively and their structures were confirmed by means of elemental analysis, ¹H NMRand MS, Hie preliminary biological tests show that these compounds have herbicidal and anti-tumour activities and could inhibit the formation of chitin.

Studies on the Syntheses and Properties of N',N-(bis-(2-Chloroethyl))-O- (O',O'-dialkyl-phosphorylmethyl)-N', N'-dialkylphosphoryldiamide

CHEN Ru-Yu, ZHANG Ming, MAO Li-Juan

1993, 14(6):  791-794. 

Asbtract ( )   PDF (235KB) ( )  

Related Articles | Metrics

Anumber of compounds with the formula (ClCH₂CH₂)₂NP (O) NR₂¹ (OCHRP (O)OR₂²) have been synthesized.Their ¹H NMRspectra and some other properties are discussed.The antitumor properties of these compounds are being tested.It is found that some of them have positive results.

Studies on Stereochemistry of Adenosine 3', 5'-Cycloalkylphosphonate

YANG Xian-Bin, CHEN Xin, WANG Chun-Guang, ZHANG Li-He

1993, 14(6):  795-800. 

Asbtract ( )   PDF (462KB) ( )  

Related Articles | Metrics

The configuration of phosphorus in2'-toluenesulfonyl-adenosine-;3',5,'-cydlc methyl phos-phonate (Ⅰ) and cyciic-R-butylphosphonate (Ⅰ) were determined by using NOEtechnique, The data indicate that they are Sforms.The conformations of cyeloalkylphosphonate moieties were identified by two dimension HOM2 DJspectroscopy which shows that there exists an equilibrium between chair and twist forms in the solution.The population of chair conformation is higher than that of twist conformation and the ratio increased with increase of the polarity of solvent and temperature.The main hydrolysates of Ⅰ and Ⅱ in NH₄OHand CH₃OHare derivatives of nucleoside 5'-alkylphosphonate.

Synthetic and Spectroscopic Studies on N-Ferrocenoyl-N'-Aryl (alkyl) thioureas

WANG Ji-Tao, ZHANG Yun-Wen, XU Yu-Ming, YUAN Yao-Feng, GAO Sheng-Hua

1993, 14(6):  801-805. 

Asbtract ( )   PDF (393KB) ( )  

Related Articles | Metrics

In this paper, ferrocenoyl isothiocyanate is synthesized for the first time.Without being separated, it reacts with various amines, such as heterocyclic amines, aliphatic amines with lower molecular weight, α-naphthyl amine and aromatic amines containing various substituted groups.Twenty one N-ferrocenoyl-N'-Ary (alkyl) thiourea derivatives have been obtained in good yields.They can be conveniently isolated and purified.At a low temperature (- 5-0℃), ferrocenoyl-isoth-iocyanate reacts with aqueous solutions of free amines (i.e.33% ethyl amine, 25% methyl amine) to form corresponding derivatives in fairly good yields.All the compounds have not been reported so far and their structures have been confirmed by elemental analysis, ¹H NMRand IR.

Syntheses of 7,10-Diaryl-hexahydro(tetrahydro)benzo[C]acridin-8-ones

WANG Jin-Jun, HAN Guang-Fan, YIN Rong, JIANG Gui-Ji

1993, 14(6):  806-808. 

Asbtract ( )   PDF (226KB) ( )  

Related Articles | Metrics

Syntheses of 7, 10-diaryl-7,8,9,10,11, 12-hexahydro-benzo[C]acridin-8-ones (la-g) were achieved by reaction of 5-aryl-1, 3-cyclohexanedione, α-naphthylamine and the appropriate aromatic aldehydes in ethanol or benzene.The oxidation of compounds la-g with CrO₃ in acetic acid giving 7, 10-diaryl-8, 9, 10, 11-tetrahydrobenzo[C]-acridin-8-ones (2a-g) is also reported.The structures of 14 new compounds were characterized by elementary analysis, IR, and ¹H NMRspectra.The preliminary pharmacodynamic experiments show that compounds Ic, 1f, 2f possess a significant inhibition effect on the growth of KBcell.

The Selective Oxidation of Active Carbon-Hydrogen Bonds in Carbonyl Compounds, Benzylic Compounds and Fused Ring Aromatic Hydrocarbons with ACC

LIU Liang-Xian, CHEN Mi-Feng, CAI Kun

1993, 14(6):  809-811. 

Asbtract ( )   PDF (249KB) ( )  

Related Articles | Metrics

This paper reports a new oxidant--NH₄CrO₃Cl(ACC) which is the most inexpensive oxi-dant in oxochromium (Ⅵ)--amine oxidants and can be prepared easily.ACCis able to oxidate selectively active carbon-hydrogen bonds in carbonyl compounds, benzylic compounds and fused ring aromatic hydrocarbons.It is an efficient reagent with which the α-methyl or α-methylene groups in carbonyl compounds can be oxidized selectively into corresponding 1,2-dicarbonyl compounds by using ACC.The cycloketone can be oxidized into α, β-cyclic enone with a high efficiency; the benzylic methylene groups into benzylic ketones with good yield; and the fused ring aromatic hydrocarbons into quinones with a moderate yield.

Electronic Structure Analysis for Active Sites of Pig Insulin

YE Yuan-Jie

1993, 14(6):  812-816. 

Asbtract ( )   PDF (377KB) ( )  

Related Articles | Metrics

The quantum chemical calculation of the entire molecule of pig insulin is carried out by the extended negative factor counting method, in which the matrix elements are calculated in EHMOscheme.The concept of frontier orbitals is extended to involve those molecular orbitals with energies near to the Fermi level.The frontier orbitals localized at a few residues are simply named as "active orbitals".The results show that there are active orbitals at 70% of the active sites of pig insulin.The results show that there might be intrinsic relationship between the active orbitals of pig insulin and its biological activities but there is not 1-1 correspondance.The change of the three-dimensional conformation of pig insulin could result in the change of its electronic structures.The residues of the same kind may have different energy levels and distribution of active orbitals when they are in the different positions of the molecule.

Studies on Self-Association of n-AlcohoIs by Gas-Liquid Chromatography

ZHOU Xiao-Xian, WANG Yi-Lin, LI Song-Lin, ZHENG Guo-Kang

1993, 14(6):  817-820. 

Asbtract ( )   PDF (294KB) ( )  

Related Articles | Metrics

The finite concentration activity coefficients of n-alcohols (C₁-C₄) were measured in squalane at 313.15 Kby using gas-liquid chromatography.The data were treated with Kretschmer-Wiebe and Wiehe-Bagley two-parameter association model, respectively.The self-association equilibrium constants KAand the physical interaction parameters β were evaluated.It is found that the solute activity coefficients for ail systems decrease in the following order:methanol>ethanol>n-propanor> n-butanol.There exists a similar order for the constants KAand β.Both the studied two-parameter models can be fitted to the experimental results satisfactorily.

A Study of Molecular Design on the Second-Order Nonlinear Optical Properties of Dye-Type Organic Molecules

FENG Ji-Kang, YU Hong-Shi, LI Zhi-Ru

1993, 14(6):  821-825. 

Asbtract ( )   PDF (373KB) ( )  

Related Articles | Metrics

On the basis of AMIand INDO/CImethods, according to the sum-over-states expression, we devised a program for calculating nonlinear second-order optical susceptibilities β_ijk and performedrelevant study of molecular design, i.e., on the basis of(这里有图片19930622-821-1.gif) we examined theeffect of different substituents introduced into the phenyl and quinonoid rings, on the second-order optical nonlinearity.It was concluded that introducing a donor into the phenyl ring leads to the increase of β and introducing an acceptor into the phenyl ring leads to a reduction of β; in contrast with this, in troducing a donor in the quinonoid ring leads to the reduction of β and introducing an acceptor in quinonoid ring leads to the increas of β.The regularity summarized from above results has been explained micromechanically.Finally, two molecules having larger nonlinear second-order optical susceptibilities have been designed.

The Quantitative Relationship Between the Molecular Structures and the Hydrophobic Parameters of Halogenated Arenes

HUANG Qing-Guo, WANG Lian-Sheng, HAN Shuo-Kui, WANG Guo-Xiong, GAO Hong

1993, 14(6):  826-830. 

Asbtract ( )   PDF (384KB) ( )  

Related Articles | Metrics

The quantum chemical parameters including dipole moment and HOMOenergies of 46 halo-genated arenes are calculated by the HMOmethod.The total surface area (TSA) of each molecule is calculated too.Based on the Linear Solvation Energy Relationships (LSER) theory, the quantitative relationship between the molecular structures and the octanol/water partition coefficients is studied, and a successful partition model is proposed.This model can accurately calculate the difference of surface tension between the two solvents.

Ab initio Study on Transition Metal Binuclear Complexes MM'(O₂CH)₄(M,M'=Cr, Mo)

GONG Liang-Fa, ZHANG Ming-Yu

1993, 14(6):  831-835. 

Asbtract ( )   PDF (2552KB) ( )  

Related Articles | Metrics

In this paper, the ab initio calculations are performed on the metal-metal multiple bonds of the binuclear transition metal complexes MM'(O₂CH)₄, namely, Cr₂(O₂CH)₄, Mo₂(O₂CH)₄ and CrMo(O₂CH)₄. The optimized bond lengthes are in good agreement with the experimental values.The calculated results indicate that the Mo-Mo and Cr-Mo bonds are quadruple bonds which correspond to the configurations σ²π⁴δ² and σ²δ²π⁴ in Mo₂(O₂CH)₄ and CrMo(O₂CH)₄, respectively.For Cr₂(O₂CH)₄, the bonding property of Cr-Cr bond is explored by comparing the calculated results of three configurations.It is shown that a more rigorous theoretical calculation is needed in order to correctly describe the Cr-Cr multiple bonding essence.

Studies on Molecular Aromaticity by Means of Natural Bond Orbitals

SHAN Li-An, LI Le-Min

1993, 14(6):  836-840. 

Asbtract ( )   PDF (394KB) ( )  

Related Articles | Metrics

The method of natural bond orbitals is used to investigate the aromaticity of cyclic conjugated molecules.The pseudo-delocalization energy of the natural bond orbitals is defined and adopted as a criterion for measuring the aromaticity of molecules.The pseudo-delocalization energies of the natural bond orbitals of more than twenty organic or inorganic molecules were evaluated by INDOor DV-Xα method and a natural localization program respectively.It is shown that the aromaticity order of these molecules evaluated on basis of the pseudo-delocalization energies is essentially in accordance with those reported in the references, which shows the reasonableness and usableness of the aromaticity criterion proposed in this paper.

WO₃ Anodic Oxide Film (Ⅱ)--Effect of Media on- Electrochromic Process

LiN Zhong-Hua, LUO Jin, HUANG Fu-Min, CAI Xiu-Juan, TIAN Zhao-Wu

1993, 14(6):  841-844. 

Asbtract ( )   PDF (429KB) ( )  

Related Articles | Metrics

The effect of solvents and cations of H⁺ and Li⁺ on the- electrochromic stability and process at the WO₃ anodic, oxide film were investigated by using cyclic chronocoulometry, cyclic voltamme-try, in situ UV/Vis reflectance spectroscopy and photocurrent spectroscopy.The parameters of hydrogen or lithium accumulation amount in the film and the number of the transient perods which can be determined from the Q_t transient can be characteristic of the stability of the film, It can be found that the electrochromic system of W/WO₃/LiClO₄ solution in acetonilrile has a high stability.The in-terfacial electrochemical mechanism of the injection-extraction of Li ions in the electrochromic process is quite different from H⁺ ions.The color center for the anodic oxide film WO₃ is considered to be the free electrons whose density is over 10²¹/cm³ and the optical transition, i.e, coloring process, arises from the plasma oscillation.

Shape Selectivity of HZSM-5 in Disproportionation of β-Methylnaphthalene

SHEN Jian-Ping, MA Jun, JIANG Da-Zhen, MIN En-Ze

1993, 14(6):  845-848. 

Asbtract ( )   PDF (287KB) ( )  

Related Articles | Metrics

The disproportionation of β-methylnaphthalene(β-MN) was carried out over HZSM-5 catalysts.The external acid sites were eliminated by modification with P(C₆H₅)₃ and Si(Ph₂)Cl₂.The dis-proportionation and isomerization of β-MNoccur on different positions of the catalyst, the dispropor-tionation proceeds in the pore of HZSM-5 and yields 2,6-DMNselectively, whereas isomerization only proceeds on the external surface.The secondary reaction of DMNon the surface of HZSM-5 and isomerization are reduced by elimination of the external surface acid sites.

Effect of Adding ZrO₂ Methods on the Properties of CuO-ZnO-ZrO₂ Catalysts

XU Yong, WANG Ren

1993, 14(6):  849-852. 

Asbtract ( )   PDF (332KB) ( )  

Related Articles | Metrics

The influence of preparation methods for catsalyst CuO-ZnO-ZrO₂ on the activities for the reaction of rnethanol synthesis from CO₂ and hydrogen is studied.The optimum composition of the catalysts has been obtained.BET, XRD, TPRand XPSwere used to examine the crystal phases of catalysts and the state of active species.The adding methods of ZrO₂ affect the ratios of various component to catalytic activity.Adding ZrO₂ can increase the dispersion of active species and the surface area.The catalytic activities are not only related with the catalyst surface area, but also with the amount of bulky CuO, The activities and surface area of catalysts prepared from two solutions containing precipitate were higher than those of the catalysts made by adding ZrO₂ powder.And the former has 75% CuOin bulk phase in the catalyst, the latter just has only 69% CuOin bulk phase.The state of active component CuOand its effect is also studied.

Thermogram Reconstruction and Its Application to Thermokinetics

LIU Jing-Song, ZENG Xian-Cheng, DENG Yu, TIAN An-Min

1993, 14(6):  853-854. 

Asbtract ( )   PDF (153KB) ( )  

Related Articles | Metrics

The thermogram reconstruction method, which can be widely applied to the studies of thermokinetics of chemical reactions, has been proposed systematically in this paper, its reliability has been verified by experimental results.

The Cage Cluster of Carbon and Boron Elements and Their Relationship

TANG Ao-Qing, LT Qian-Shu

1993, 14(6):  855-856. 

Asbtract ( )   PDF (184KB) ( )  

Related Articles | Metrics

The conjugate relationship for elemental cage skeletons of carbon and boron clusters is discussed, and some symmetrical elemental cage skeletons and stability of cage clusters of boron element are studied.

Collinear Exact Quantum Scattering Study ——Vibrational Deactivation of H+ClH(v) on a Reactive Potential Energy Surface

BIAN Wen-Sheng, JU Guan-Zhi

1993, 14(6):  857-859. 

Asbtract ( )   PDF (222KB) ( )  

Related Articles | Metrics

Collinear exact quantum method is used to study the vibrational deactivation process of H+ClH(v≤3) on a newly-fitted ab initio potential energy surface.The reactive and nonreactive inelastic probabilities are obtained, which are found to oscillate with energy and exhibit some vibrationally nonadiabatic behavior.We conclude that, Hatoms are not very efficient deactivators of vibrationally excited HCl, and in the producing vibrational deactivation the nonreactive inelastic mechanism dominates over the reactive one at lower energies while reactive collisions become more important if the energy is high enough.Many conclusions from this work are shown to be in qualitative agreement with those from some previous literatures.

Studies on the Spectral Properties of Mg:Fe:LiNbO₃ Crystal

LI Ming-Hua, ZHAO Ye-Quan, XU Yu-Heng, LIU Cai-Xia, SHI Dong-Qi, WU Zhong-Kang

1993, 14(6):  860-862. 

Asbtract ( )   PDF (235KB) ( )  

Related Articles | Metrics

Mg:Fe:LiNbO₃ crystal sampls were prepared by melt-pulling method.Sample 1^# was reduced in Li₂CO₃ powders at 500oC for 24 h and sample 2^# was oxidized in Nb₂O₅ powders at 1000oCfor 20 h.The inclusion contents of MgOand Fe₂Os are 5 mol% and 0.08 mol% respectively.The absorption spectra of Mg:Fe:LiNbO₃, Fe:LiNbO₃ and Mg:LiNbO₃ crystals and the infrared transmission spectra of Mg:Fe:LiNbO₃ crystal were measured.There is an absorption peak at 480 nm in Mg:Fe:LiNbO₃ crystal, it is responed to Fe²⁺ absorption.There are two absorption peaks which lie at 500 nm and 1200 nm in Mg t LiNbO₃ crystal, they are responed to oxide vacancy Fcenter (V₀²⁺ + 2e^-) and Mg⁺ absorption, but the two absorption peaks in Mg:Fe:LiNbO₃ crystal are very weak and even vanish, this is due to that after Fe ions entered the crystal, Fe³⁺ will trap the electrons which are excited by treating the samples at high temperature and reduced condition, the electrons can't combine with oxide vacancy V₀²⁺ and Mg²⁺ to produce Fcenter and Mg⁺, The infrared transmission spectra of sample 1# show two OH^- absorption peaks at 2.83 μm and 2.85 μm, the absorption peak at 2.83 μm is stronger than that at 2.85 μm, the absorption peak at 2.83 μm is responed to the effect of Mg²⁺ on OH^- lonely, the absorption peak at 2.85 μm is responsed to the effect of Fe ions replacing Nb⁵⁺ on OH^- lonely or to the joint effect of Fe ions replacing Nb⁵⁺, and Mg²⁺ replacing Li⁺ on OH^-, consequently make the OH^- absorption red shift.It is concluded that Fe ions make the resistance of photorefraction decrease, but Mg ions make it increase.The joint effect of the two kinds of ions decides the photorefraction of the crystal.

Studies on Supported-Water-Soluble Phosphine Rhodium Complex Catalyst

YUAN You-Zhu, YANG Yi-Quan, ZHANG Hong-Bin, Cai Qi-Rui

1993, 14(6):  863-865. 

Asbtract ( )   PDF (2274KB) ( )  

Related Articles | Metrics

Much attention has been paid to the heterogenization of homogeneous rhodium complexes responsible for olefine hydroformylation catalysts in the literature.Many methods have been proposed, but no heterogeneous hydroformylation catalysts are commercially used so far for liquid-phase conversion, primarily because of problems arising from catalyst loss to the product-containing phase.The supported water-soluble phosphine-rhodium complex has been designed to facilitate hydroformylation at interface of two liquids.Immobilization of the catalyst is accomplished by means of the insolubility of the rhodium complex in the organic media.SiO₂ supported water-soluble sulfonated-triphenylphos-phine-rhodium complex shows an excellent catalytic activity for the hydroformylation of higher olefine of methyl 10-undeceoate.The reaction can be easily carried out in a fixed bed reaction system and it is found that the selectivity stabilized in the range of 98%-99% and n-/iso- ratios over 4.0 when P/ Rh molecular ratios in 10-15 under the testing period.This immobilized catalyst also shows significant water loss during the reaction based on IRdata of the catalyst, but non-effect on the catalytic activity has been observed.It is proposed that the ligands and central metal may be redistributed at the initial stage of the reaction to form active species with suitable water content in the fresh catalyst, and then the hydrophilic support holds the water-soluble phosphines by hydrogen bonding of the hydrated sodium-sulfonate group of the surface.

The lonization Potentials of Potassium Phenoxide and p-Substituted Phenoxides

YING Bai-Ning, WU Guo-Xiang

1993, 14(6):  866-867. 

Asbtract ( )   PDF (2286KB) ( )  

Related Articles | Metrics

t The interaction of phenol and its potassium salts as the electron donor with electron acceptor 7-nitro-5-phenyl-3H-1,4-benzodiazepin-2-(1H)one can form the charge transfer(CT) complexes in DMF.In this paper, with measuring the CTbands of CTcomplexes spectrophotometrically, the ionization potentials(I_P) of potassium phenoxide and p-substituted phenoxides(p-RC₆H₄OK) have been determined in the comparision method.

Studies on Radiation Effect of Chitosan (Ⅱ)--Some of the Chemical Changes Induced by Irradiation

ZHAO Wen-Wei, YU Li, ZHONG Xiao-Guang, ZHANG Yue-Fang, SUN Jia-Zhen, WANG Qiang

1993, 14(6):  868-871. 

Asbtract ( )   PDF (300KB) ( )  

Related Articles | Metrics

Partially deacetylated chitosan powders were subjected to γ-ray irradiation in the controlled volume of air.Thermogravimetric analyses indicate that the thermal stability of chitosan decreases after irradiation.The results of infrared spectrum investigation show that hydroxyl group increases with the increase of radiation dose while C-O-C group decreases, and the deacetylated moiety is more sensitive to irradiation than acetylated moiety.No evidence for carbonyl formation was observed.Main chain scission and reactions of amino group are the main chemical changes of chitosan under irradiation.

A Research on the Properties of Acetylized Sweet Potato Starches (Ⅰ)

CHEN Ung-Qiu, ZOU Xin-Xi

1993, 14(6):  872-875. 

Asbtract ( )   PDF (612KB) ( )  

Related Articles | Metrics

Acetylized sweet potato starches (ASPS) with various low degree of substitution (DS) prepared with Ac2Oand sweet potato starches (SPS) are very similiar to SPSaccording to the measurement of granular and surface structures by SEM, polarized light, X-rays diffraction.The surface structures of ASPSand SPSare observed really with the electro-conducting gum in the absence of the gold-plating method.Gelatinization temperatures of ASPSand SPSare (1) from 71.6-76.0-79.0 COto 65.5-67.0-70.0(℃) with DSfrom 0 to 0.1985; (2) increase firstly then decrease with NaCl concentration increasing from 0% to 25% ; (3) increase with glucose, sucrose, maltose concentration increasing from 0% to 25%; (4) decrease with the variation of pHvalues except neutral, particularly decrease sharp pHis under a strong base condition.For example, the gelatinization temperature is 10℃ when pH=13.3.Meanwhile the effects of glucose, sucrose, maltose, NaCl on gela-tinization temperature decrease with DSincreasing.

Quantum Chemical Study on the Stability Difference and Electronic Property of Poly(azovinylene) and Its Isomers

SU Zhong-Min, YU Xiao-Ping, WANG Rong-Shun, FU Yu-Jie

1993, 14(6):  876-878. 

Asbtract ( )   PDF (262KB) ( )  

Related Articles | Metrics

In this paper, the stabilities of poly (azovinylene), polymethineimine and polyisomethineimine which are isomers (C₂H₂N₂)_x, are calculated by using quantum chemistry MNDOand CNDO/2-COmathods and compared with each other.The poly (azovinylene) and polyisomethineimine are more stable than polymethineimine, the reason causing the difference between stabilities is that the interaction energies of PAV's C=N(N=N) and PIMl's C-Care larger.The atomic net charge distribution shows that the values in PAVand PIMl are smaller because of existing the symmetry i, and that in PM1 is larger, which may influence the conductivity.The comparison between band structures of isomers shows polyisomethineimine's conductive ability should be the best among them.

The ESR Study of PMMA Propagating Radical in Bulk Polymerization Process

MAO You-Gang, WANG Guo-Bin, ZHENG Ying-Guang, SHEN Jia-Cong

1993, 14(6):  879-882. 

Asbtract ( )   PDF (328KB) ( )  

Related Articles | Metrics

The ESRspectra of PMMAin bulk polymerization process have been obtained and simulated by using the models of Gaussian distribution about the two stable conformations Aand B.The results show that both the ratio of Aand Bconformations, and the average tilt angle of Bconformation decreased with half-height width of the Gaussian distribution as the indicative of the microviscosity of reaction system.The change was discussed with respect to the thermodynamics and dynamics.

The Ionic Interaction in lonomer Solution of Manganese Sulfonated EPDM

FENG Ke, OUYANG Wei, LI Zhuo-Mei, ZHANG Jian-Hui

1993, 14(6):  883-885. 

Asbtract ( )   PDF (260KB) ( )  

Related Articles | Metrics

The ionic interaction in ionomer solution of manganese sulfonated EPDMhas been investigated by viscometric method, as well as FTIRand ESRmethods.The results indicate there exists sol-vation between Mn²⁺ and alcohol cosolvent, the extent of which depends upon the concentration of Mn²⁺, alcohol content in the mixed solvent, molecular volume of alcohol and temperature.All these factors affect the aggregation state of Mn²⁺ in solution and the ionic interaction between the solvated Mn²⁺ and sulfonate anion SO₃^- in the ionomer macromolecule.

Structures and Properties of the Copolymers from Dialkyl Fumarates

SONG Zheng-Zhe, WEN Jiu-Mian, XU Ji-Ping

1993, 14(6):  886-888. 

Asbtract ( )   PDF (245KB) ( )  

Related Articles | Metrics

The structures and compositions of the copolymers of diaikyl fumarates such as PDiPF/ DnPF, PDiPF/DnBF, PDiPF/DnAF, PDiPF/DnHFand PDiPF/DEHFwere characterized by ¹H NMR.The effect of compositional ratio on the strength and strain as well as dynamic mechanical properties of these copolymers was investigated.The results show that the elongation of break of these copolymers increases significantly with increasing content of DRFs(DnPF, DnBF, DnAF, DnHF, DEHF), while tensile strength decreases.The a and β transition peaks shift to lower temperatures with increasing content of DRFs.The thermal properties and other properties of the copolymers were also clarified.