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Table of Content
24 June 1987, Volume 3 Issue 1
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Articles
Degradation Method for Preparing Organo-Arsenic and-Antimony Polytungstates and Comparative Study of Corresponding Polymolybdates
Gu Yidong(Yih-tong Ku), Liu Benyao
1987, 3(1): 1-7.
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In repeating and extending the syntheses of organo-arsenic polytungstates,we found that the "Degradation Method",taking sodium metatungstate as the starting material,was much more profita-ble.The known compound (CN
3
H
6
)
5
[(C
6
H
5
As)
2
W
6
O
25
H]·2H
2
O(1) was read-ily reproduced with a high yield.Anew compound (CN
3
H
6
)
6
[(p-OH,m-NO
2
C
6
H
3
As)
2
W
6
O
25
](2) was likewise synthesized.This "Degradation Method" using the reaction of sodium metatungstate with organo-anti-monate led to the isolation of four compounds with definite composition although amorphous in appearance.The preparations of organo-arsenic polymolybdates and organo-antimony polymolybdates were also studied and six new organo-arsenic polymolybdates were isolated: (CN
3
H
6
)
5
[(C
6
H
5
As)
2
MoO
25
H]H
2
O(3),(CN
3
H
6
)
4
[(n-C
3
H
7
As)
2
Mo
5
O
21
]·2H O (4),(CNH)
4
[(n-C
3
H
7
As)
2
Mo
6
O
24
](5),Cs
2
[(CH
3
)
2
AsMo
4
O
15
H](6),(NH
4
)
6
[(P-OH,m-NO
2
C
6
H
3
·As)
2
Mo
6
O
25
](7),and (CN
3
H
6
)
6
[(p-OH,m-NO
2
C
6
H
3
As)
2
Mo
6
O
25
](8).No definite corresponding organo-antimony polymo-lybdate with definite composition has been isolated yet.
New Techniques in Electrometric Titrations
Xu Weijian, Gao Hong(H. Kao)
1987, 3(1): 8-12.
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Five new techniques in electrometric titration are described: 1.Oscillopolarographic titration without incision at 1 micro and 1 macro Pt electrodes.2. Oscillopolarographic titration without in -cision at 3 electrodes.3.Oscillo potentiometric titration at 3 electrodes.4.Zero current oscillo bipotentiometric titration.5.Alternating current oscillo bipotentiometric at 2 similar electrodes.Among them methods 1,4,5 are very useful.
The Electrochemical Polymerization of Thiophene in Aqueous Sotations of an Acid
Ghen Yanzhon, huang Haitao, Tian Zhaowu
1987, 3(1): 13-20.
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People are more and more interested in polythiophene because of its night stability.At present,organic solvent system is still commonly used in electrochemical polymerization of thiophene and the related electrochemical studies.However,it is more practical to use aqueous solutions instead of organic solvents.The electrochemical polymerization of thiophene in aqueous solution of acid is discussed in this paper.In highly concentrated acidic solution,thiophene first undergoes low polymerization,and then the low polymer can be oxidized at the comparatively negative potential to form film.
The Study of the Reaction Mechanism for the Dehydrogenation of Ethylbenzene on Iron Oxide Catalysts (Ⅰ)——IR Spectra of Adspecies and Kinetic Isotope Effects
Chen Jianping, He Danyun, Cao Shoujing
1987, 3(1): 21-29.
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)
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In situ PT-IRspectroscopy was used to examine ethylbenzene adspecies on iron-oxide-besed catalysts,and the method of kinetic isotope effects was used to investigate the rate determining step of the dehydrogenation.Apossible reaction mechanism is proposed.
Two Conditions for Energy Sudden(ES) Theory
Ding Shiliang, Deng Conghao
1987, 3(1): 30-32.
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)
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Studies on Thermokinetics——Thermokinetic Method for Second Order Reactions
Wu Xiaoping, Qin Ziming, Deng Yu, Cai Ruzen
1987, 3(1): 33-37.
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On the theoretical basis of thermokinetics,the dimensionless parameter method for second-order reactions is suggested in this paper.Through thermokinetic studies of two reaction systems,the fundamental equations of thermokinetic method for second-order reactions were verified.
Synthesis and Application of Polyethylene Oxide Macromers (Ⅰ)——Synthesis and Characterization of Poly(Ethylene Oxide)Macromers with Allyl-End Group
Sun Fang, Wu Lanting, Yang Shilin
1987, 3(1): 38-46.
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)
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Polyethylene oxide(PEO) macromers with allyl-end group were synthesized by two different methods(initiating and deactivating).The products obtained were characterized accurately by means,of several techniques including
1
H NMR,IR,VPO,GPC and the double-bond titration,and the results show that such kinds of product possess expected structure.The macromers were copolymerized with small molecular acrylamide,and a series of copolymers with different composition,were obtained by adjusting copolymerization conditions.Moreover,some evidence concerning allyl-group rearrangement in synthesis of the macromers was observed and suitable condition for laboratorial preparation of the macromers is proposed.
The Glass Transition Temperature and Liquid
1
-Liquid
2
Relaxation of Star-Shaped Polystyrene
Wang Jian, Liu Jingjiang, Yang Meilin, Shen Jiacong
1987, 3(1): 47-51.
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The glass transition temperature T
g
and relaxation temperature T
11
of a series of regular star-shaped polystyrenes were measured by using torsional braid analyzer(TEA) and linear dilatometer.The results showed that T
g
for star-shaped polymer increases with increas-ing branching degree whan the molecular weights of branch chains arethe same,but it is lower than that of linear polystyrene with the same molecular weight.The liquid
1
— 1iquid
2
relaxation temperature T
11
and the intensity of loss peak of star polystyrene also depend on branching degree.Two-T
g
transitions in star polystyrenes with DVBmicrogel nodule were proved by comparing two types of star polystyrenes.
Studies on the Mechanism of the Photopofymerization of Acrylonitrib initiated by Aniline
Li Tong, Cao Weixiao, Feng Xinde
1987, 3(1): 52-59.
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We verified the formation of exciplex in the photopolymeriza-tion of acrylonitrile initiated with aniline.There are two routes to form exciplex,i.e.either through the excitation of the charge transfer complex of aniline with acrylonitrile or from the interaction of the excited singlet state aniline and the ground state acrylonitrile.Then it is followed by proton transfer proqess,leading to the generation of two kinds of radicals,which are responsible for the initiation.
Studies of Steroid Transformation Catalyzed by Polymer -Supported Liquid Membrane immobilized Cells
He Binglin, Li Naihong, Jiang Ping
1987, 3(1): 60-67.
Abstract
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This paper describes,the preparation and properties of polymer-supported liquid membrane immobilized cells of Arthrobacter simplex which catalyze the transformation of cortisol into predni-solone.The transforming activity of cells immobilized by this method was compared with that of cells immobilized by traditional entrapment method.The result showed that the transforming activity of the former was obviously higher than that of the latter,and there was no apparent difference of mechanical strength between che former and the latter under our working conditions.The various factors affecting the transformation were studied as well.
The Study of Steroid Transformation Catalyzed by Liquid Surfactant Encapsulated Cells
Jiang Ping, Li Naihong, He Binglin
1987, 3(1): 68-74.
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)
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The present paper describes the preparation and properties of the encapsulated Arthrobacter simplex cells by liquid surfactant membrane which catalyzes the transformation of biger steroid molecule,i.e.,cortisol into prednisolone.The experimental results indicated that the catalytic transformation took place very well and in some systems the encapsulated cells kept the initial rate of catalytic transformation as good as that of the free cells.The stability of storage is raised by encapsulation.We also investigated various factors which affect the biocatalytic transformation from which we know that the encapsulated cell system is not influenced by the contamination of Bacillus cells which inhibit the free cell system seriously.
2D NMR Studies on the Structure of Urushiol of Chinese Lacquer
Huang Zhaogeng, Qiu Feng, You Jiang, Qian Baogong, Li Liyun, Qiu Jianqing, Yuan Hanzhen, Shen Lianfang
1987, 3(1): 75-80.
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The urushiol diacetate was successfully separated by centrifugal rotation TLCon the silica gel coated with silver nitrate.The structure and configuration of key component of.urushiol (64.6%) were determined successfully by using
1
H and
13
C conventional method,DEPTtechnique,homo- and heteronuclear chemical shift correlation 2D-NMR,2D-J NMR,hftteronuclear relayed coherencetransfer 2D-NMR,and relaxation time T
1
investigation.The as-signment of resonances for
1
H and
13
C were confirmed.There is plentyof evidence which shows that the key component of urushiol is 3-(8'Z,11'E,13'Z-pentadecatrienyl)catechol.The results show that RELAY 2D-NMR new technique can be successfully applied to determining the structure of complicated unknown compounds.
The Ring-Chain Competition in Nonlinear Polycondensation (Ⅱ)——The Intramolecular Reaction Equations of the System Containing Two Dynamic Parameters
Zheng Fuan, Liu Fengqi, Zhao Donghui, Tang Xinyi
1987, 3(1): 81-89.
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Flory considered that the discrepancy between classical gelation theory and real reaction system was mainly attributed to the intramolecular reaction.On the basic principles of the probability we analysed the growing-disappearing of the groups in the even generations against a certain group statistically when three different reaction systems containing two dynamic parameters reached some degree of reaction.Furthermore,we obtained the intramolecular reaction equations in the form of analysis by means of introducing probability factor of cyclization bond.Using the equations obtained from this paper to deal with the critical condition of gelation,we found that the theoretical values agreed with the experimental ones.
Synthesis Structure and Behavbr of Polymeric Drugs Covalently Linked 5-Fluorouracil
Zhou Chaohua, Yang Fushun
1987, 3(1): 90-97.
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Four series of polymeric drugs with 5-Fluorouracil(5-FU) cova-lently linked in side chain were synthesized by the use of starch and carboxylmethylcellulose and two new 5-FUderivatives were also synthesized by using molecular sieve as a catalyst.Their structures were determined by IR,
1
H NMR and mass spectra.The changes in the Nitrogen content of polymeric drugs with reaction conditions and the influences of the Ncontent on their limiting viscosity were studied.The hydrolysis of 5-FU from starch and carboxylmethylcellulose derivatives in various of buffer were researched by simulating physiologically acid-alkali enviroment.In addition,anticancer activity(in vivo and in vitro) of some starch derivative has been preliminaryly observed.
Polymer Surfactants as Analytical Reagents——Synthesis of PPOTA and PPOCA and Their Analytical Properties
Liu Kunyuan, Xie Hui, Pan Gulan, Yu Ruqin
1987, 3(1): 98-103.
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)
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Two new polymer surfactants poly(propylene oxide)-a-tetradecyl-dimethylammonium chloride(PPOTA) and poly(propylene oxide)-a-cetyl-dimethylammonium chloride(PPOCA) were synthesized,which possess the characteristics of both cationic and nonionic surf actants.The properties of PPOTA and PPOCA were investigated.The synthesized surfactants can be used as sensitizing and solubilizing reagents for spectrophotometric analysis.Some examples of micellae improved by spectrophotometric systems such as Sc(Ⅲ)-CAS,Ge(Ⅳ)-PF and Ni(Ⅱ)-CAS were given.
Studies on Chemical Composition of Anemone Altaica C. A. May (Ⅱ)
Ju Yong, Jia Zhonqjian, Zhu Ziqing(Chu Tse-Tsing)
1987, 3(1): 104-105.
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A new dispirolactone compound,C
10
H
12
O
6
m.p.224-226℃,wasisolated from the ethyl acetate extract of the roots of anemone aJ-taica C.A.May,the Chinese medicinal herb,by using Si gel column chromatography.Its structure was determined as: 1,6,9,13-tetra-oxadispiro[4,2,4,2]tetradecane-2,10-dione by means of IR,NMR,MS spectra and X-ray diffraction analysis.
Editor-in-Chief:
Jihong YU
ISSN 1005-9040
CN 22-1183/O6
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