Table of Content

24 December 1987, Volume 3 Issue 2

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Articles

A Study on The Interactions Between Coordination Compounds and Supports

Wang Xin, Xin Xinquan, Dai Anbang

1987, 3(2):  1-7. 

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In this study the viewpoint is taken that the supported complexes react with active groups on the surface of the support to form new entities which may be called surface complexes.Various interactions between the support and the solute in solution of impregnation have been found,and these interactions may be divided into four calsses: (1) there is no noticeable chemical interaction between the dissolved coordination compound and the support,except the physical adsorption;(2) the metal ion of the complex is anchored on the surface through the surface group as a ligand forming a surface complex,or the support provides the central ion for the formation of a surface polynuciear complex through the bridging ligand of the complex;(3) the surface of the support provides the central ion for ligands dissociated from the complex or for the solvent molecules;(4) the metal hydroxide might be formed,when the acidity of the cation of the support is weaker than that of the metal ion of the complex in a aqueous solution.

The Determination of Trace Amounts of Cadmium in Rice Samples by Dual-wave Length Spectrophotometry——cd(Ⅱ)-Cadion 2B-Tween 40System

Pu Binying, Wei Danyi

1987, 3(2):  8-13. 

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The optimal conditions of the Cd(Ⅱ)-Cadion 2B-Tween 40system have been studied.In the alkaline medium of NaOH,a red Cd(Ⅱ)-Cadion 2B-Tween 40 complex forms with e_510nm=9.80×10⁴ The K_a of Cadion 2B and Surface tension in the system was estimated.It was proved that Kwas increased and the reagent species with absorption maximum at 605nm formed.Using the dual-wave length method at 510—605nm the apparent molar absorptivity for cadmium measured was 2.60×10⁵ The molar ratio of cadmium to Cadion 2B is estimated to be 1:3 as estimated by the molar ratio method and continuous variation method.The Beer's law is obeyed in 0—6μg Cd/25ml.Using the proposed method with TEA,IDA and CIT masking mixture,the Cd content in rice samples was determined with satisfactory results.

Homogeneous Voltammetric Immunossesay of Diphtheria Toxoid and Diphtheria Antitoxin

Hu Yinhua, Tie Feng, Li Qingman

1987, 3(2):  14-18. 

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Diphtheria toxoid was denatured in 0.1M NH₄Cl-NH₃H₂O basal solution with pH 9.4,yielding a cathodic and an anodic polarographic peaks at -1.52 and -1.45V(vs.SCE),respectively.The cathodic and anodic peak heights varied linearly with diphtheria toxoid concentration over the range of 2.5 to 180μg/ml by single sweep polarography,and diphtheria toxoid even as low as 0.3μg/ml could be detected by differential pulse polarography.The decreased peak current value of diphtheria toxoid due to immunochemical binding reaction was proportional to diphtheria antitoxin in the range of 2.5×10^-6 to 5×10⁵ IU/ml,which determined diphtheria antitoxin level homogeneously.The assays are sensitive,specific,reproducible and simple in operation.The anodic peak was appl.ied to the determination of diphtheria toxoid in the triple vaccine.

Tartaric Acid Modified Electrodes and Studies on its Application for the Anodic striphing Voltammetry of cu(Ⅱ)

Fang Yuzhi, Li Yuansheng, Jin Litong

1987, 3(2):  19-25. 

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The preparation of tartaric acid modified electrode was studied.Reaction mechanism of copper(Ⅱ) on tartaric acid modified electrode was discussed and determination conditions for trace Cu(Ⅱ) by ASVwere also founded.

Synthesis of 2-Substituted-1,1,1-Trichloro-3-Nitropropane——A New Type of Fungicide

Chen Qijie, Liu Fengping, Xie Longguan

1987, 3(2):  26-31. 

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The syntheses of fourty-six 2-hydroxy-,2-amino-,2-hydrazino-,and 2-azacyclyl-1,1,1 -trichloro-3-nitropropane derivatives were described.Preliminary bioassays showed that the compounds exhibited fairly good fungistatic activity,among them 2-phenylhydrazino-1,1,l-trichloro-3-nitropropane was the most effective.

CIDNP of Diecyl Peroxides Studies on the Kinetics of Decomposition of Diacyl Peiroxides Ⅷ in the Decomposition of Diacyl Peroxides

Liu Youcheng, Guo Qingxiang, Liu Peiqi

1987, 3(2):  32-37. 

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¹H CIDNP spectra recorded during the decomposition of aliphatic diacyl peroxides ((RCOO)₂ R=n-C H (1),n-c₇H₁₁(2)) in ODCB in the presence of scavengers,such as I₂C₂H₅I,(CH₃)₂CHI,and CH₂=CHCH₂ Br show multiplet effect for the scavenged products,RX(X=Br,I) and for disproportionation products,R_-H.The reactionmechanism is discussed in terms of radical pair theory.

The Synthesis and Anticronvulsant Activity of Some α-Halo-m-Trif luoromethyl Cinnamamides

Ling Yangzhi, Xu Yanna, Li Anliang, Liu Weiqin

1987, 3(2):  38-43. 

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Nine a-halo-m-trifluoromethgl cinnamides were synthesized from trifluoromethyl benzene,via bromination,Grignard reaction,condensation,halogen addition reactions etc,as indicated in the synthetic scheme.Their configurations were confirmed by ¹H NMR.Their pharmacological results showed that the introduction of a-halogen group do not enhance their anticonvulsant activity as expected.

Studies on Cobalt-Carbon Cluster——Svntnesis of α-Naphthyl α-Thienyl and Substituted-Phonyl Phenylacetyene Dicobalt Hexacarbonyls

Song Licheng, Wang Zhongxia, Wang Jitao

1987, 3(2):  44-49. 

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12 new diarylacet ylenedicobalt hexacarbonyl complexes were synthesized by complexation reaction of a-naphthyl,a-thienyl or sub-stituted-phenyl phenylacetylene with Co₂CO)₈ and N-acetylation of p-aminophenyl phenylacetylenedicobalt hexacarbonyl.The structures of all the complexes were characterized by elemental analysis,IR and ¹H NMR spectroscopy.Making a comparison between the N-acetylation of p-aminophenyl phenylacetylenedicobalt hexacarbonyl and that of aniline under comparable conditions,we found that the clustercore PhC₂Co₂(CO)₆ para to an amino group attached to aromatic ring does not obviously affect the nucleophilicity of aniline.

The Thermal Stability and Adsorbability of the Mechylated Silica Gel

Zhao Zhenguo, Shao Changsheng, Qin Shoufeng, Lin Yao, Lin Zhenkun, Gu Tiren

1987, 3(2):  50-55. 

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The methylated silica gel has been produced by the reaction between the surface silanol groups and Clsi(CH₃)₃ vapor.The adsorption isotherms of acetic acid from carbon tetrachloride onto silica gel and emthylated silica gel heated at various temperatures have been determined at 25℃,and the above mentioned silica gels have been studied by TCand IR.The results indicate:(1) The adsorption of acetic acid from carbon tetrachloried onto methylated silica gel decreased greatly,probably because the concentration of the free hydroxyl groups for methylated silica gel decreased greatly as the IRshows.(2) As the methylated surface was destroyed at 450℃,the adsorption ability was restored when the methylated silica gel treated at>500℃.(3) So long as the methylated silica gel was treated at high temperature,the adsorption ability could be restored owing to that surface free hydroxyl groups were reproduced.

Several Conclusions Concerning Diffuse Functions

Liu Chengbu, Deng Conghao

1987, 3(2):  56-64. 

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Several conclutlons drawn from the using of diffuse functions in the ab initio study of molecular anions are discussed.The orbital exponents of the diffuse functions for some basis sets have been determined by using the method of linear fitting.These values are nearly identical with those obtained by method of optimization.

On the Rotational Invariance of the INDO Method Including f Orbitals into the Basis Set

Ren Jiangqing, Xu Guangxian(K. H. Hsu)

1987, 3(2):  65-72. 

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In order to ensure the rotational invariance of the one-center-two-electron integrals in the INDO method including for bitals into the basis set in our previous paper^[1], two methods are proposed in the present investigation to meet this requirement.The first one is to use the weighted average values J_μμ', K_μμ', and J_μμ'=J'_μμ+2K_μμ' for replacing the integrals (μμ|νν), (μν|μν) and (μμ|μμ), respectively.The second is a more stringent alternative,in which we have derived 690 nonzero hybrid one-center-two-electron integrals in addition to Coulomb and exchange types as expressions of Slater-Condon parameters.

Salt Effect of Vapor-Liquid Phase Equilibrium in the System Acetic Acid-Formic Acid-Water-Calcium Chloride

Li Xi, Jiang Fuming, Rang Hongye, Luo Ruyi, Xiu Qientang, Fua Shuguang

1987, 3(2):  73-77. 

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Vapor-liquid equilibrium data (VLE) were measured by usingotsudki-willlams still at 9.866×10⁴ (Pa) for the 3-component system AcOH-HCO₂H-H₂O and the 4-component system ACOH-HCO₂H-H₂O-CaCl₂ in the VLE,CaCl used was 0.5 (mol/kg solv.).The results show that the favorable effect of CaCl₂ is physical chemistry action,which relates to the phenomena of salting-out and salting-in.

Infrared Study on Interaction Between Methacrolein and Catalyst H₄PMo₁₁V₁O₄₀/SiO₂

Wu Tonghao, Yang Hongmao, Wang Guojia

1987, 3(2):  78-84. 

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In this paper,we report the results of an infrared study on methacrolein (MAL) adsorption on heteropoly acid catalyst,H₄-PMO₁₁V1O₄₀/SiO₂ Three surface species,CH₂=C(CH₃)-CHO^*(I),CH₂=C(CH₃)-CO(II) and CH₂=C(CH₃) were formed on the catalyst surface.We consider that they are the intermediates to form methacrylic acid (MAA).It was found that at 300℃ MALchemisorption did not occur on the catalyst surface treated with evacuation and v_P-O and v_Me-O-Me bands characterizing the heteropoly acid anion structure disappeared (Me: Mo or V)

A Study on the Gonductance of KBr. KSCN. KClO₄ and KI in the Mixed Solvent of Dimethylformamide and 1,4-Dioxane

Zhang Hong, Liu Ruilin, Li Zhifen

1987, 3(2):  85-94. 

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This paper reports the measured conductance of KBr,KSCN,KClO₄ and KIin the mixed solvent of DMF with 1,4-dioxane at various ratios,the viscosity of the mixed solvent and the density of the salt solution.According to the conductance equations,namely,Pitts equation,Fuoss-1978 equation and Lee-Wheaton equation,the experi-.mental data were fitted on computer to get the limit molar conductance of salt at infinite dilution Ao, the ionic association constant Ka,and the distance parameter between cation and anion R.The suitability of the theoretical equations and the interaction of ion-ion-solvent molecule were discussed.

Electrocatalytic Behavior of Metalloporphyrins(Ⅶ)——Kinetic Study of Cysteine Oxidation on Heat-Treated Cobalt Tetramethoxyphenyl Porphyrin Adsorbed on Graphite

Wang Zongli, Deng Zhongyi, Li Changming, Cha Chunsin

1987, 3(2):  95-102. 

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The metnoas or rotating ring-disc electrode(RRDE) ana cyclic voltammetry were used to study the oxidation of cgsteine on heat-treated cobalt tetramethoxyphenyl porphyrin adsorbed on graphite(Co-TMPP/graphite) in solutions of various pH.Experimental results showed that Co-TMPP/graphite exhibits significant catalytic activity for cysteine oxidation in solutions with various pH.The current efficiency of cysteine oxidation on Co-TMPP/graphite in basic media is more than 90%.It was found that the kinetics of cysteine oxidation on Co-TMPP/graphite is a simple irreversible reaction controlled by rate of charge transfer.The standard rate,constants(k°) of cysteine oxidation were calculated and the reaction mechanism of this reaction in solutions of various pH wes discussed.