Table of Content

24 December 1986, Volume 2 Issue 2

Previous Issue    Next Issue

Articles

THE ACTION MODE OF CISPLATIN ON DNA-SYNTHESIS AND CHARACTERIZATION OF N₇ N₁ CROSS-LINKAGE MODEL COMPOUND OF PLATINUM AND GUANOSINE

Qu Yun, Tang Wenxia, Dai Anbang

1986, 2(2):  1-6. 

Abstract ( )   PDF (384KB) ( )  

Related Articles | Metrics

The title Pt-Guo compound was synthesized and isolated by the reaction between cis-[Pt(NH₃)₂(H₂O)₂]·(NO₃)₂ and guanosine of mol ratio1:1 in a neutral aqueous solution followed by careful purification with partial crystalization and recrystallizatlon from water at 0℃.The compound was characterized by elemental analysis, molecular weight determination, DTA, and C NMRspectroscopy and its formulawas found to be [<Pt(NH₃)₂>8(GuoH_-1)₇ (OH)₂] (NO₃)₇ 8H₂O.The isolation of the compound provides direct evidence for the intrastrand cross-linkage between cisplatin and DNAthrough N₇, N₁ atoms of two adjacent guanines.

CRYSTAL AND MOLECULAR STRUCTURE OF SUEFATOAQUO-2, 3-DIMETHYL-2, 3-BUTYLDIAMINEPLATINUM

Guo Dongyao, Wang Fengshan, Qu Yun, Tang Wenxia, Dai Anbang

1986, 2(2):  7-11. 

Abstract ( )   PDF (277KB) ( )  

Related Articles | Metrics

[PtDMBA(SO₄)H₂O]·H₂Ocrystals belong to the orthorhombic system, a=11.073(3), b=9.672(2), c=21.156(7)A, space group C_2cb, z=8.The diffraction data (Moka) were collected with Nicolet R₃ four-circle di-ffractometer.The structure was determined by heavy atom method and refined by the least square program, R=0.0716.In the systematic study of anticancer action of a series of platinum compounds, our Coordination Chemistry Research Institute has synthesized Pt DMBASO₄·2H₂O(where DMBA=2, 3-dimethyl-2, 3-butyldiamino) and found it has antitumor activity against L-1210 in mice.In order to study the relationship between the structure and the anticancer effects of the platinum compounds, the crystal structure of the compound has been determined.

THE DETERMINATION OF INDIVIDUAL RARE EARTH IN THE BINARY MIXTURE OF Gd AND Y BY RATE DIFFERENTIAL KINETIC METHOD

Chen Danhua, Cai Ruxiu, Lin Zhixin, Zeng Yun'e

1986, 2(2):  12-17. 

Abstract ( )   PDF (341KB) ( )  

Related Articles | Metrics

The kinetic behaviour in the substitution reaction of RE(TCA)₂ [TCA=2-(2-arsenophenylazo)-7-(2, 4, 6, -trichlorophenylazo)-1, 8-dihy-droxy-naphthalene-3, 6-disulfonic acid] with CyDTAhas been studied and some kinetic parameters of the reaction system and kinetic equation for determination have been measured and established.Gd and Yin the binary mixture have been determined by using their rate difference in the ligand substitution reaction of RE(TCA)₂, with CyDTAat pH3.0. Anumber of synthesized samples are analysed by logarithmic extrapolation method with good sensitivity and high precision, and it is simple and rapid.

OSCILLOPOLAROGRAPHIC CHELOMETRIC TITRATIONS ON TWO SIMILAR MICRO Pt-ELECTRODES

Yang Zhaoliang, Gao Hong(H. Kao)

1986, 2(2):  18-22. 

Abstract ( )   PDF (306KB) ( )  

Related Articles | Metrics

Up to now, all oscillopolarographic titrations have been carried out in electrolytic cells with one micro electrode and one large electrode.Oscillopolarographic titrations on two similar micro indicator electrodes were studied and it was found that many substances such as EDTAand its related compounds giving no incisions at one micro Pt-electrode showed distinct incisions on two micro Pt-elec-trodes, for example, in the presence of KCl, EDTAand its related compounds yielded distinct incisions which can be used to indicate end-points of many chelometric titrations.Th⁴⁺, In³⁺, Ga³⁺, zn²⁺, Ni²⁺, Co²⁺, Mn²⁺, Cd²⁺ and rare earths can be directly titrated with EDTA, DTPA, CyDTAand HEDTA.Many new chelometric tieration procedures were developed.

STUDIES ON THE SYNTHESES OF RARE EARTH COLOR REAGENTS OF POLY-HALOGENATED BISAZO TYPE AND THE RELATIONSHIP BETWEEN THEIR MOLECULAR STRUCTURES AND PROPERTIES

Yu Ximao, Cai Ruxiu, Tian Shizong, Zeng Yun'e

1986, 2(2):  23-31. 

Abstract ( )   PDF (512KB) ( )  

Related Articles | Metrics

Asort of new rare earth color reagent-polyhalogenated bisazo chromotroplc acid derivants was designed and synthesized.They are easily soluble in water, alcohol and acetone, but insoluble in benzene, ethyl ether and chloroform.They are a kind of highly sensitive and excellently selective reagents for rare earth elements.The acidity of color reactions is strong (0.1N-4N) and the acidic range is wide.The relationship between the molecular structure and the reaction properties for rare earths was also studied.When the properties and positions of auxochromic groups are fixed, the sensitivities of reagents that have the complex functional groups-AsO₃H₂, -COOH and -PO₃H₂ are higher than others.

STUDIES ON SUBSTITUTION OF C=O IN BIS(μ-ALKYLTHIO)-HEXACARBONYLDI-IRONS----THE SYNTHESIS AND STRUCTURES OF(μ-RS)(μ-R'S)Fe₂(CO)₅Ph₃

Song Licheng, Hu Qingmei, Wang Jitao

1986, 2(2):  32-37. 

Abstract ( )   PDF (379KB) ( )  

Related Articles | Metrics

Fourteen new PPh₃ substituted Fe-Sclusters, with general formula (μ-RS)(μ-R'S)Fe₂(CO)₅ PPh₃, have been synthesized by reaction of unsymmetrical type of bis(μ-alkylthio ) hexacarbonyldiirons with triphenylphosphine.Based on the discussion of influence of PPh₃ on VCOand alkyl spacial orientation of PPh₃ in clusters has also been established.

THE SYNTHESIS OF PARAPHERCMONES OF THE RICE STEM BORER MOTH, CHILO SUPPRESSALIS WALKER

Li Zhengming, Liu Tianlin, Liu Ziping, Guo Husen, Yao Enyun

1986, 2(2):  38-43. 

Abstract ( )   PDF (406KB) ( )  

Related Articles | Metrics

(Z)-Hexadenes, their epoxides and arylanalogs were prepared s'tereo-specifically by Wittig reaction of alkylidenetriphenylphosphoranes with alkylaldehydes or arylaldehydes respectively.(E)-5-Hexadecene was obtained from the conversion of (Z)-5-hexadecene via addition of bromine, elimination-reduction with NaNH₂/NH₃ These compounds are active in EAGresponses.

A THEORETICAL STUDY OF MECHANISMS IN THE PHOTOCHEMICAL REACTIONS OF FORMING XETENE AFTER THE α-EOND RUPTURE IN CYCLCHEMANONE

Yu Hengtai, Sevin Alain

1986, 2(2):  44-50. 

Abstract ( )   PDF (473KB) ( )  

Related Articles | Metrics

ab initio, SCF+CIcalculations of the potential energy surfaces and barries in the various paths are presented for the chemical reactions of forming ketene after the a-bond rupture in cyclohexanone, using acetaldehyde as model.The possibilities of the various paths and thansition states of the important paths are discussed.

THE KINETICS OF THE DECOMPOSITION OF CYCLOHEXYL HYDROPEROXIDE IN THE PRESENCE OF VANADYL DIBENZOYLMETHANE

Zhan Zhengkun, Wan Xueshi

1986, 2(2):  51-58. 

Abstract ( )   PDF (519KB) ( )  

Related Articles | Metrics

The kinetics of the decomposition of cyclohexyl hydroperoxide(CHHP) in benzene catalyzed by vanadyl dibenzoylmethane[V0(DBM)₂, ] has been studied.It was found that the products of decomposition of CHHPwere cyclohexanol and cyclohexanone, which are produced in about equimolar amount, and the product cyclohexanol obviously inhibited the decomposition of CHHP.The kinetics data can be satisfactorily described by the following equation (with [CHHP]₀>>[VO(DBM)₂]₀)R₀=kK[CHHP]₀[VO(DBM)₂]₀/(¹⁺k[CHHP]₀) This is the kinetic evidence for the formation of a catalyst-hydro-peroxide intermediate.In the equation Kis the stability constant of the catalyst-hydroperoxide intermediate complex;k is the rate constant for the decomposition of the complex. The rate constant Kat 500℃ may be expressed as follows:k=1.9×10⁸exp(-53.7×10³/RT)S^-1 with the activation energy E_a=53.7kJ·mol^-1

MECHANISTIC STUDIES ON CATALYTIC DEHYDROGENATION OF ETHYL-BENZENE OVER IRON-OXIDE-BASED CATALYST SYSTEMS-I. ROLE OF LATTICE OXYGEN

Chen Huizheng, Ho Danyun, Xiao Zhangling, K. R. Tsai

1986, 2(2):  59-69. 

Abstract ( )   PDF (680KB) ( )  

Related Articles | Metrics

The role of lattice oxygen in the catalytic dehydrogenation of ethylbenzene over industrial iron-oxide-based catalysts has been investigated mainly by means of isotopic exchanges attending the dehydrogenation reaction.The results indicated that although the exchange of lattice oxygen with steam oxygen appeared to take place to an appreciable extent, the direct catalytic dehydrogenation of ethylbenzene appeared to be the major reaction pathway, with catalytic dehydrogenation by oxygen-transfer reaction pathway playing only a minor role, as revealed different extents of hydrogeh-deute-rium isotopic exchange between ethylbenzene and steam D₂Q at low and very high space velocities.The mechanisms of these two reaction pathways are discussed.For the oxygen-transfer dehydrogenation mechanism, electron transport between neighboring Active-sites operating cooperatively in opposite phases of their redox cycles may be a requisite factor.

STUDIES ON PROMOTION OF UPD OF. LEAD FOR ELECTRO-OXIDATION OF FORMIC ACID ON PLATINUM

Xu Zhengjiu, Li Zuojun

1986, 2(2):  70-78. 

Abstract ( )   PDF (550KB) ( )  

Related Articles | Metrics

Using potential sweep and potential-time sequence techniques, we have studied the promotion of the UPDof lead for the electrocata-lytic oxidation of formic aeid on platinum in the HClO₄ aqueous solution.The results show that the first oxidation peak in the anodic direction and the oxidation peak in the cathodic direction in the cyclic voitammogram are attributed to the oxid-ation of the same weakly adsorbed intermediate, while the second and third oxidation peaks in the anodic direction are attributed to the oxidation of the two different strongly adsorbed intermediates.Furthermore, all these intermediates appear as the linear adsorption on the platinum surface and they are probably single bonded species, Pt-HCOO, and multiple bonded species, Pt=COand Pt=COH, respectively.So the function of the UPDof lead for the electro-oxidation of formic acid is neither a third-body effect nor the decrease of nydrogen adsorption thus preventing the formation of poisoning species.The role of the UPDof lead should be an electronic effect, that is, it modifies the adsorption property of platinum in such a way that the oxidation of Intermediate, Pt-HCOO, becomes easier.

A STUDY ON THE BEHAVIOUR AND MECHANISM OF EXTRACTING GOLD(Ⅲ)USING PTSO

Li Lingying, Sun Yuanming, Pen Hongji, Di Ping

1986, 2(2):  79-84. 

Abstract ( )   PDF (352KB) ( )  

Related Articles | Metrics

PTSOis abbreviated from di-P-tolyl Eolphoxide having a>S=0 group and is a neutral extractant.We have studied the behaviour and conditions of the separation of Au(Ⅲ) from other elements on a column packed with the silica gel loaded with PTSOand have found that PTSOis a new stationary phase with extremely high selectivity for the separation and concentration of gold.However, the application of PTSOto the solvent extraction has not bean reported yet.We first studied the behaviour and mechanism using PTSOto extract gold by atomic-absorption spectrophotometry, ultra-violet spectrophotometry and infra-red spectrophotometry.The possible structure of the extractive formed from PTSOand Au(Ⅲ) is suggested.

QUANTUM CHEMICAL STUDIES ON THE ELECTROPHILIC ADDITIONS OF HALOGENS TO ETHYLENE AND SUBSTITUTED ETHYLENES

He Shaoren, Fu Xiaoyuan, Yu Jianguo

1986, 2(2):  85-91. 

Abstract ( )   PDF (439KB) ( )  

Related Articles | Metrics

The various intermediates of electrcphilic addition of F⁺, Cl⁺ to ethylene, propene, fluoroethylene were optimized by MNDOmethod with energy gradient technique.The most stable configurations were obtained. The substituted ethylenes tended to form the open intermediates more easily than ethylene, but Cl⁺as a reagent, tended to form the cyclic intermediate more easily than F⁺.The interaction energies △Eof the above three compounds with F⁺ as electrophile were studied further with ab initio method and △Ewere decomposed into their components by Morokuma's energy decomposition scheme.In these reactions, it was found that charge transfer is the most important interaction, while electrostatic interaction is the next.The effects of the substituting groups are also discussed.

ELECTRONIC STRUCTURE AND CHEMICAL BONDING OF TRISINDENYL SAMARIUM

Ren Jingqing, Xu Guangxian

1986, 2(2):  92-100. 

Abstract ( )   PDF (513KB) ( )  

Related Articles | Metrics

The electronic structure and chemical bonding of Sm(Ind)₃ were studied by using INDOcalculation method.The results showed that the 6s 6Pand 5d orbitals of Sm mixed with the atomic orbitals of ligands to some extent while the 4f orbital of Sm was strongly localized, participating in bonding less than 2%.The HOMO and the LUMO were of π-type.The chemical bond of Sm(Ind)₃ is considerably covalent in character.The net charge distribution on the carbon atoms of the indenyl group is unequal.The Some bonds in Sm(Ind)₃ THF is discussed.

KINETICS OF THE ZIEGLER-NATTA POLYMERIZATION OF 1-OCTENE(I)----THE KINETICS OF THE STATIONARY PERIOD

Yang Shilin, Fan Zhiqiang, Feng Linxian

1986, 2(2):  101-104. 

Abstract ( )   PDF (331KB) ( )  

Related Articles | Metrics

The kinetics of the Ziegler-Natta polymerization of C₆～C₂₀ α-defines has been seldom studied, which showed no apparent differences from the kinetics of the polymerization of ethylene and propylene.1-Octene polymerizes in alkanes in a solution state, differing from the slurry polymerization of ethylene.We have found and studied the inordinary kinetics of the polymerization of 1-octene on α-TiCl₃-AlEt₃[or-Al(i-Bu)₃, -AlEt₂Cl] catalysts in n-heptane, and have given a primary explanation to this phenomenon.