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中文
Table of Content
24 November 1997, Volume 18 Issue 11
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Articles
Investigations on Various Structural Types and Valence States in Cerium Containing Hydrothermal Systems
LI Guang-She, XU Xiu-Ting, FENG Shou-Hua
1997, 18(11): 1737-1741.
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By means of XRD,1Rand XPSmeasurements, the structural types and valencestates of the products in cerium containing hydrothermal systems were investigated.Theresults show that, different starting species give different products with different stabilizedvalence states, such as direct formation of nanocrystalline CeO
2
and a novel phase CeOHCO
3
.No structural transformation was found for sample CeOHCO
3
after a cool pressure treatmentat 2 GPa.However, when CeOHCO
3
was calcinated at high temperatures in air, highcrystalline CeO
2
with brown color, different from that of commercial one, was obtained.
Solubilities Measurement of the Ternary Systems LaY
3
-
BAPHDCA-H
2
O(Y=NO
3
-
, Cl
-
) at 30℃
CUI Bin, TANG Zong-Xun, GUO Zhi-Zhen, CHEN Kai-Xun
1997, 18(11): 1742-1745.
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The solubilities and refractive indexes of saturated solutions of the ternarysystems LaY
3
-BAPHDCA--H
2
O (Y=NO
3
-
, Cl
-
) at 30℃ were studied and the correspondingequilibrium diagrams were constructed.The solubility curves and refractive index curves ofnitrate systems consist of three branches, corresponding to BAPHDCA, La (BAPHDCA)(NO
3
)
3
· 4H
2
Oand La(NO
3
)
3
· 6H
2
O.The complex is incongruently soluble in water.Theeutectic compositions (%) are: La (NO
3
)
3
25.25, BAPHDCA 0.91 and La (NO
3
)
3
, 60.15,BAPHDCA 0.45.The tenary complex was characterized by chemical analysis, elementaryanalysis, IRspectra,TG-DTGand X-ray power diffraction.The system of chloride is asimple one.The eutectic composition is LaCl
3
49.12%, BAPHDCA 0.82%.
Studies on Conductivity of Hydrotalcite [Cd
x
Mg
6-x
Al
2
(OH)
16
]
2+
[S·2H
2
O]
2-
Doped with Cu
2+
Ion
BAO Yu-Min, FU Ge-Yan, MA Shu-Jie, LI Lian-Sheng, FENG Shou-Hua, XU Ru-Ren
1997, 18(11): 1746-1749.
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Hydrotalcite [Cd
x
Mg
6-x
Al
2
(OH)
16
]
2+
[S·2H
2
O]
2-
doped with Cu
2+
ion wassynthesized hydrothermally and the influence of the Cu
2+
and Cd
2+
ionic content, sulphurationtime and calcination temperature on the conductivity was studied.The results show that theconductivity increases with the increases of Cu
2+
and Cd
2+
content and sulphuration time inthe given ranges, and decreases beyond the ranges.The activation energies calculated withequation σ=σ
0
exp (-E
a
/RT) in the ranges of temperatures from 323 Kto 363 Kand from383 Kto 523 Kare 76.55 kJ/mol and 7.18 kJ/mol, respectively.It is a good protonicconductor in the latter temperature range.
The Electrochemistry and Spectroelectrochemistry of the Co(Ⅱ)Substituted Derivatives of Cu, Zn-Superoxide Dismutase
QIAN Wen, ZHU Shi-Min, LUO Qin-Hui
1997, 18(11): 1750-1752.
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This paper reported the behavior of cyclic voltammetry (CV), differential pulsevoltammetry (DPV) and spectroelectrochemistry (SEC) of Co
2
Co
2
-superoxide dismutase.The results obtained by CVand DPVwere in agreement well with that obtained by SEC.The diffusion coefficient, the apparent number of electrons and oxidation-reductionpotentials were obtained.
Studies on Synthesis and Properties of Supermolecular Compound Involving Cobaltoximes with a Long Chain Alkyl and β-CD
XIANG Ping, LUO Lai-Bin, CHEN Ying, CHEN Hut-Lan
1997, 18(11): 1753-1755.
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Two supermolecular adducts involving p-cyclodextrin(β-CD) and long carbonchain alkyl (aqua) cobaltoximes (R= C
6
H
13
and C
8
H
17
) have been synthesized for the firsttime and characterized by elementary analysis, UV-Vis and
1
H NMR.We used the cyclicvoltammetry methods to characterize the electrochemical behaviour of the inclusion process.In addition, their formation constant K
a
was quantitatively determined by using UV-Vismethods.It has been shown that the longer the carbon chain of the alkyl groups are, themore stable the inclusion complexes are.furthermore, by adding n-C
8
H
17
Co (DH)
2
H
2
O/β-CDto the aqueous solution, it has been found that the formation constant decreased.
Studies on the Solid Complexes of RE(Ⅲ) with Phytic Acid
LI Xiao-Xia, YANG Ru-Dong, YANG Ying, LIU Jian-Min
1997, 18(11): 1756-1758.
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The solid complexes of phytic acid with trivalent rare earth metals in aqueoussolution were synthesized and characterized by means of elementary analysis, IRandanalysis.The composition of complexes [(C
6
H
6
) H
4
(PO
4
)
6
]
3
· RE (Ⅲ)
8
· C
2
H
5
OH· x H
2
O(x= 10～15, RE = Y, Pr, Gd, Tb, Er, Yb) was determined.The IRspecra of complexesclear polymer.In addition, the thermal cecomposition kinetics of the complexes wass investigatwed as well.
Crystal Structure of Dicarbonyl (η
5
-2, 4-Cyclopentadien-1-yl) tricyclohexylstannyliron
YAN Peng-Fei, LE Zheng-Yu, GAO Jin-Sheng, CHI Shu-Liang, BU Wei-Ming, FAN Yu-Guo, YE Ling, YANG Guang-Di
1997, 18(11): 1759-1761.
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The title complex Cp (CO)
2
FeSn(C
6
H
11
)
3
was synthesized and it's crystal structurewas determined by four-circle X-ray diffra tometer.The crystal belongs to monoclinic system, space group C
2
/c with parameters: a=1.9476 (4) nm, b=0.8826 (2) nm, c=2.9158(6) nm, β= 95.49(3)°, Z=4.The two carbonyl groups attached to iron atom lie inabout right angles to each other and to the tin-iron axis.The three-fold axis passing throughthe iron atom and relating these three ligand directions is almost perpendicular to the plane ofthe cyclopentadienyl ring.The co-ordination of ligands around the tin atom is close to tetrahedral.The cyclohexyls are all in stable chair-conformations.
Characterization of Solvent Polarity and Selectivity of Gas Chromatographic Liquid Phases
WANG Wen-Ling, ZHANG Xiang-Min, LU Pei-Zhang, DENG Jia-Qi
1997, 18(11): 1762-1768.
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An equation, I=AI' BN+C
1
∑n
1
R
Di
+C
2
μ
A
2
+C
3
α
α+C3
β
βA+C4,
was derivied to correlate the Kovats retention indices for solutes on different stationary phases.In thisequation, Ais determined by the interaction energy of a methylene group on two stationaryphases.Bis mainly determined by the relative intermolecular interaction energy of the carbonchain of a compound On two stationary phases.C1 is mainly determined by the dispersiveinteraction difference of the functional group(s) of a compound on two phases.C2 isdetermined by the difference of the dipole moment interaction energy of a compound on two phases C3
α
,C3
β
are determined by the differences of the relative hydrogen-bonding acceptor basicityor donor acidity of two phases.Therefore, we recommended Bto describe the polarity of astationary phases, the coefficient B,C3
α
,C3
β
to describe the selectivity of a stationary phase.These coefficients for 89 stationary phases were presented in present paper.
Separation of DNA Fragments by Capillary Electrophoresis with Non-gel Sieving Matrix of Hydroxyethyl Cellulose and Sucrose
CHEN Hong, SONG Li-Guo, XIONG Shao-Xiang, CHENG Jie-Ke
1997, 18(11): 1769-1773.
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We demonstrate that hydroxyethyl cellulose, sucrose and boric acid can formnongel sieving matrix with interpenetrating polymer networks (INPs).This kind of INPs mixednon-gel sieving matrix can greatly improve DNAseparation efficiency.While all elevenfragments of φX174/Hae Ⅲ DNAcan not be completely separated with a sieving matrix of 0.8%hydroxyethyl cellulose in 1×TBE buffer, they are successfully separated by a non-gelsieving matrix of 0.8% hydroxyethyl cellulose, 10% sucrose in 1×TBEbuffer.The reactionmechnism to form the INPs has been proposed.The length of a PCRmagnified DNAfragment from sex-related gene in rice-field cells is also determined, which is in good agreementwith slab gel electrophoresis.
Piezoelectric Immunosensor Based on the Agglutination of PEG for Determination of S. Japonicum Antibody
WU Zhao-Yang, SHEN Guo-Li, YU Ru-Qin, WANG Shi-Ping, ZENG Xian-Fang
1997, 18(11): 1774-1778.
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Anew liquid piezoelectric immunoassay was developed to determine infectionrabbit serum (IRS) by adult worm antigen (AWA) of S.japonicum, which is based on thetination of antibody and antigen-PEGcomplex by an immunoreaction.By examining thesurface appearances of the quartz crystal with scanning electronic microscopy(SEM) technologyand investigating the effect of the density and viscousity of the solution, it can be found thatthe absorption on the surfaces of the quartz crystal plays a dominant role in the frequencyresponse in the immunoassay.The influences including PEGconcentration, complexing time ofAWA-PEGcomplex and detection temperature on frequency responses were investigated indetail, respectively.The frequency shift was linear with the antibody concentration in therange of 3.6-42.0μg/mL.Five rabbit serum specimens were analyzed with this method andthe analytical results given by this approach show that the detection ratio of positive serumreaches 100% and the antibody concentration can be quantitatively determined.
Studies on the Electrochemical Oxidation of 1,4-Dihydrofpyridine and Its Derivatives
ZHANG Li-Xin, WANG Bing-Xiang, ZHU Shi-Min, CHEN Hong-Yuan, HU Hong-Wen
1997, 18(11): 1779-1782.
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The electrochemical oxidation of 1,4-dihydropyridine and its derivatives has beenstudied on Pt electrode in acetonitrile 0.1 mol/L TEAPsolution by cyclic voltammetry andbulk electrolysis.The results show that the electrode reaction is controlled by diffusion andchemical reaction with two successive one-electron oxidation irreversible process.Theelectrochemlcal oxidation mechanism of 1,4-dihydropyridine and its derivatives has beensuggested.The results of UVspectroelectrochemical experiment show that the electrochemicaloxidation gives the same products as in the chemical oxidation.
The Classification of Acidic Dyes with Artificial Neural Network
ZHANG Rui-Sheng, YAN Ai-Xia, LIU Man-Cang, HU Zhi-De
1997, 18(11): 1783-1787.
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The acidic dyes were classified by using Extented Delta-Bar-Delta (EDBD).Thebest structure of network was 4-6-5.The optimized learning times is about 5000.It isdifficult to classify these dyes because their structures are very similar.Compared with GCEDMand other methods which were applied formerly, the EDBDmethod have the advantanges ofmore stable classification standard, fewer parameters and quicker velocity.
Using ICP-AES to Investigate Adsorption Behavior of Quinine-Loaded Active Carbon on Metallic Anion WO
4
2-
LIU Huai-Zhi, JIANG Yi-Wan, HU Bin, LIAO Zhen-Huan, JIANG Zu-Cheng
1997, 18(11): 1788-1790.
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Anew metallic anion adsorbent quinine-loaded active carbon was prepared.ICP AESwas used to study its adsorptive property for metallic anion WO
4
2-
.The chemicalstability of the adsorbent was investigated.The effects of different concentrations of HCl andNH
3
· H
2
Osolution on adsorption rate and desorption rate as well as the interference effectsof some other ions were studied respectively.The method has been applied to thedetermination of trace tungsten in standard reference sample GSD-11.
Synthesis and Biological Activity of Pyrazole Derivatives
LI Zheng-Ming, CHEN Han-Song, ZHAO Wei-Guang, ZHANG Kai, HUANG Xing-Sheng
1997, 18(11): 1794-1799.
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Thirty new pyrazole acylhydrazine derivatives containing carboxylate,sulfonylate, hydrazone and dipyrazole ketone were synthesized from the intermediate 1, 3,4-substituted-5-pyrazole carboxylic hydrazide(7,8).Their structures were confirmed by
1
H NMRand elemental analysis.The preliminary biological tests showed that several compounds havesome fungicidal and herbicidal activity.
Quantitative Analysis of Prostaglandins in SD Rats by Capillary Zone Electrophoresis
HE Jin-Lan, LI Hui-Ping, Ll Xiao-Ge
1997, 18(11): 1797-1973.
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This paper reports an investigation of optimizing separation and detection foranimal prostaglanadins, i.e.prostaglandins E
2
(PGE
2
) and thromboxane B
2
(TXB
2
), bycapillary zone electrophoresis with indirect UVdetection at 254 nm.It was found that the addinon of 3 mmol/Lphosphomolybdic acid in 5 mmol/Lchromate chromate can lower the detectionlimits.The linear ranges for TXB2 and PGE2 were the same, i.e.5-80 μg/mL, theanalytical precisions (n=8) were 1.2%-1.4% and 3.5% for the measurement of the migrationtimes and for the determination with peak height, respectively.This approach wasdemonstrated in the lung of SDmouse and the results obtained agreed with those from references.
Synthesis of an Receptor Containing Chiral Bicyclic Guanidine for Amino Acids
HE Wei-Jiang, LU Guo-Yuan, HU Hong-Wen, JavierdeMendoza, PilarPrados
1997, 18(11): 1800-1803.
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An artificial receptor 1 for aromatic amino acids was prepared from a chiralbicycllc guanidine salt 2 by means of a new procedures.The deprotecting silylethers 2 and 4were selectively achieved in solutions of CH
3
COOH-THF-H
2
Oand HF-Pyridine respectively.Thus the receptor 1 was readily obtained upon reaction of the monosubstituted naphthoylester 5 with bromoacetic acid and then mono-azacrown ether.The total yield in five steps was40.5%.
Total Synthesis of Farnesyl Acetophenones and Farnesyl Flavanone
HUANG Chu-Sheng, LI Xiu-Ying, LI Ying, LI Yu-Lin
1997, 18(11): 1804-1808.
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Three novel natural compounds, 3-farnesyl-2, 4, 6-trihydroxy-acetophenone (1),4-farnesyloxy-2, 6-dihydroxyacetophenone(2) and 6-farnesyl-3', 4', 5, 7-tetrahydroxy-flavanone (3) isolated from the aerial part of Boronia ramosa in Australia, were firstlysynthesized by starting from 2,4, 6-trihydroxyacetophenone and farnesyl bromide with total yield52.0%, 6.5% and 19.8%, respectively.The synthetic steps of compound 3 contained sixreactions of C-farnesylation, hydroxy-protection, aldol-condesation, cyclization andgroupdeprotection all together.
Synthesis of Glycerophospholipid Conjugates of Uridine
ZHANG Cheng-Xiang, ZHANG Zhong-Biao, TANG Chu-Chi, CHEN Huan-Ming, CHI Guo-Chen, CHEN Ru-Yu
1997, 18(11): 1809-1813.
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New structural liponucleoside prodrugs were prepared in which uridine wascovalently attached to cyclic phospholipids.The strategy for the synthesis used hexaethylphosphorous triamide, activated by a catalytic amount of iodine, as the phosphorylating reagentin a one-pot reaction resulting in a number of phospholipid-uridine conjugates.The celltoxicity experiments show that the compounds have certain selective antitumor activities.
Microenvironmental Effect in the Synergistic Antioxidation of β-Carotene and α-Tocopherol
LI Zhao-Long, MA Lan-Ping, LIU You-Cheng, LIU Zhong-Li
1997, 18(11): 1814-1819.
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The antioxidation and antioxidant synergism of β-carotene(β-C) and α-tocopherol(VE) against free radical initiated peroxidation of linoleic acid have been studied by use ofoxygen uptake method in anionic , non-ionic and.cationic micelles, i.e., sodium dodecylsulfate (SDS), polyoxyethylene diisobutylphenol(Triton X-100) and cetyltrimethylammoniumbromide (CTAB), respectively.The peroxidation was initiated by an azo-initiator, eitherwater-soluble 2, 2' -azobis (2-amidinopropane) dihydrochloride(AAPH) or oil-soluble di-tert-butyl hyponitrite(DBHN).It was found that the antioxidant activity depends significantly onthe microenvironment of the reaction medium and the lipophilicity of the initiator.Althoughβ-carotene alone shows relatively weak antioxidant activity only in case of the DBHN-initiated peroxidastion of linoleic acid in SDSmicelle,it works very well synergistically with VEtosignificantly enhance the inhibition effect of VEfor either AAPHand DBHN-initiated peroxi-dation of linoleic acid in SDSand Triton X-100 micelles.The relationship between theantioxidant activity and the microenvironment is discussed.
Studies on the First Total Synthesis of (±)-Salvinolone
TIAN Yuan, CHEN Ning, QIN Bing-Chang, PAN Xin-Fu, HAO Xiao-Jiang, CHEN Chang-Xiang
1997, 18(11): 1820-1824.
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Salvinolone is a polyoxygenated aromatic tricyclic diterpene which was firstisolated from the roots of Salva prionitis.The assignment of its structure for compound 1 wasmostly made on the basis of spectral data.In order to confirm the assigned structure, aconvergent synthesis of Salvinolone(1) has been achieved in nine steps, starting with3-fisopropoxy-5, 5-dimethyl-2-cyclohexenone (4) and alcohol (2) which are readily available.Thekey steps are alkylation of carbonyl compound and intramolecular Friedel-Crafts reaction.This is the first total synthesis of (±)-salvinolone.
Studies on the Aggregation State of Hematoporphyrin in Surfactant Aqueous Solution
FENG Xi-Zeng, TIAN Fang, WANG Chen, BAI Chun-Li
1997, 18(11): 1825-1828.
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The aggregation state of hematoporphyrin(HP) in aqueous solution and insurfactant aqueous solution has been studied by spectrum analysis.In micellar media thedimerization effect is observed only in anionic sodium dodecyl sulfate(SDS).The monomer-dimerequilibrium is shifted toward the monomer side due to a high increase in the rate constant ofthe dimer dissociation than in the dimer formation with the SDSconcentration.Fromapplication of atomic force microscopy the relationship between the morphology variation andmicro structure of HP-SDSand the solution state is discussed.
On Convergence Patterns of the Hyperspherical Harmonic Expansion for the Excited
3
S Helium Atom
WANG Yi-Xuan, MI Yun-Jie, DENG Cong-Hao, HUANG Hai-Lan
1997, 18(11): 1829-1832.
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The convergence patterns of the hyperspherical harmonic expansion for theexcited
3
Sstates of the helium atom have been studied with the correlation function-hyperspherlcal harmonic-generalized Laguerre function method(CFHHGLF).The convergenteigenenergies at l=0, 1, 2 agree well with the s-limits, sp-limits and spd-limits of the configurationinteraction (CI) method.With only 44 hyperspherical harmonics, the eigenenergies of the 2
3
S,3
3
Sand 4
3
Sstates are the same as those from the exact Hylleraas variational method.
Quantum Chemistry Study on the Isopropylphosphonate Rare Earth Extractants
ZHANG Shao-Wen, SHEN Jian-Yun, FENG Wen-Lin, WANG Dian-Zuo
1997, 18(11): 1833-1837.
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Molecular dynamics method and semi-empirical quantum chemistry method havebeen used to study the geometric and electronic structure of seven isopropylphosphonate rareearth extractants.The geometry of each extractant was first obtained through MolecularAnnealing; then basd on the most stable structure optimized by Molecular Annealing, thegeometry was further optimized by using PM3 method.The results show that thesubstituent on the alkoxy group exhibits a stronger space obstacle effect than the main chain.The phosphonyl oxygen atom, which is the coordinate atom with the rare earth atom, hasthe largest component in HOMOorbitals.The LUMOorbitals consist of the contribution ofnon-coordinate orbitals.This results indicate that the HOMOof isopropylphosphonate mightplay an important role in the complex compound.The calculated atomic charges ofphosphorus atom, phosphoryl oxygen atom, hydroxy oxygen atom and hydroxy hydrogen atom varyregularly with the change of the size and position of substituents.We have found that thecharges of hydroxy oxygen atom and phosphorus atom have a linear relationship with theacid dissociation constants (pK
a
) of the extractants.
Ab Initio Study of B
4
C
2
, B
2
C
4
Clusters
GE Mao-Fa, HUANG Xu-Ri, FENG Ji-Kang, YANG Cheng, SUN Chia-Chong
1997, 18(11): 1838-1841.
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Various possible geometric configurations of B.C,, B
2
C
4
clusters were studied byusing quantum--chemical ah initio method, and their vibrational spectra were calculated.Thestable configurations of B
2
C
4
are linear or planar; while those of B
4
C
2
are linear, planar orthree-dimensional.Therefore, B.C, is similar to B
6
, B
2
C
4
is similar to C
6
. It is an importanteffect of stability that B
4
C
2
and B2C
4
have B-Cand C-Cmultiple-bond, and a strongconjugated effect.
Kinetics and Mechanism of Oxidation of iso-Propyl Amine by Diperiodatocuprate (Ⅲ) Complex Ion
SONG Wen-Yu, LI Zhen-Hua, WANG An-Zhou
1997, 18(11): 1842-1846.
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The kinetics of oxidation of iso-propyl amine(PA) by diperiodatocuprate(Ⅲ)complex ion was studied by spectrophotometry in alkaline medium in the temperature range of30～45℃ The reaction rate showed the first order dependence in oxidant, and 1.15-1.39order dependence in PA.It reveals that the pseudo first-order ([PA]
0
>[Cu (Ⅲ)
0
]) rateconstant, k
obs
, decreases with the increase in [OH
-
] and the increase in [IO
4
]
cx
(KIO
4
] addedexternally), which implicates that before the rate-determining step there is a pre-equilibriumin which one of the two periodate ligands of the oxidant is dissociated after the protonation toform a reactive monoperiodatocuprate (Ⅲ) ion.Under the protection of nitrogen the reactionsystem Induced the polymerization of acrylamide indicating the participation of free radicals.Anegative salt effect on rate was observed.Based on the observations a mechanism involving a pre-equilibration and an adduct formation between [Cu(HIO
6
)]
-
and PAwasproposed.The rate equation derived from the mechanism could be used to explain all the theexperimental observations and the pre-equilibration constants, rate constants of the rate-determining step together with the activation parameters were evaluated.
Theoretical Study of the Electronic Property of Phthalocyanine and Metal-phthalocyanine
WANG Xiu-Jun, HUANG Zong-Hao, SU Zhong-Min, WANG Rong-Shun
1997, 18(11): 1847-1850.
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Double-layer fragment was chosen as crystal cell model.By means of quantumchemistry EHMOmethod with crystal orbital, the conductive behavior of phthalocyanine(Pc) and metal-phthalocyanine (MPc, M=Ni, Fe) have been researched.The effect ofiodine doping has been discussed.The results show that iodine doping causes an obviouschange in the crystal structure, the interaction between the two layers of doping statebecomes greater, and the energy gap decreases and the conductivity of several crystals increasesrapidly.For the eigenstate, the change of central metal does not affect the energy gap, butfor the doping state, the effect is great.The orders of energy gap are E
g
(H
2
PcI) < E
g
(NipcI)<E
g
(FePcI), which coincides with the experiment results.From the energy bandstructure, Pc and Nipc are π-conductor, but the conductive band of FePc is relative tocentral metal (d
x
2
) obviously.
Theoretical Study on the Chemical Reaction of Metcars(Ⅰ)──Ab Initio Study of Ti
8
C
12
+
+CH
3
I→Ti
8
C
12
+
─I+CH
3
·
GE Mao-Fa, FENG Ji-Kang, TIAN Wei-Quan, LI Zhi-Ru, HUANG Xu-Ri, SUN Chia-Chong
1997, 18(11): 1851-1853.
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The reaction of Ti
8
C
1
2+
+CH
3
I→Ti
8
C
1
2+
——I+CH
3
. was studied by usingquantum-chemical ah initio method.Areasonable explaination was given to the experimentalobservations that the dominant reaction channel for Ti,Crs reacting with halogen-containingmolecules is that one halogen atom was abstracted.
The Dispersed States of Copper Species on CuO/ZrO
2
Catalysts and Its Influence on the Catalytic Performance
ZHOU Ren-Xian, JIANG Xiao-Yuan, LU Guang-Lie, ZHENG Xiao-Ming
1997, 18(11): 1854-1857.
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Copper/Zirconia catalysts were prepared by impregnation method andcharacterized by XRD, TPRand TPD-MS.It was concluded that four oxygen desorption peaks fromtwo different temperature ranges were related to oxygen species of surface adsorption,highly-dispersed copper oxide on ZrO
2
and CuOphase, respectively, and the highly-dispersedcopper oxide was easily reduced, which leads to a dramatic increase in oxidation activity.
Calorimetric Studies on the Microemulsion with Nonionic Surfactant
YU Xiu-Fang, ZHANG Hong-Ling, XUE Mei-Ling, XIN Yin-Chang, CHEN Zong-Qi
1997, 18(11): 1858-1861.
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The heat effect of microemulsion, which is composed of AEO
9
, hexadecane,hexanol and water was studied by using a 2277 Thermal Activity Monitor.Enthalpic studies onthe state of water microemulsion system have been carried out at 303 K.The resultsindicated that some modification of the three state modes was made.The heat effect of nonionicmicroemulsion was far lower than that of ionic microemulsion.In the unnormal rheologywater/oil ratio region, the thermal effect was determined.The △H
*
～T curves of differentwater and oil volume ratio were established.
Comparison of Alumina and Silica Supported Ni,Pd Catalysts in Synthesis of Methyl iso-Butylketone from Acetone and Hydrogen
GUAN Nai-Jia, SHAN Xue-Lei, ZHAO Dong, LIN Fu-Sheng
1997, 18(11): 1862-1865.
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Studies on the reaction of acetone and hydrogen to methyl iso-butylketone(MIBK)in one-step process over catalysts consisting of nickel and palladium loaded on alumina andsilica were performed.The effects of content of Ni and Pd on the reaction were investigated.Both Ni and Pd loaded catalysts.have exhibited good activity for this reaction, while higheractivity and better durability were achieved on the Pd-loaded catalysts.The addition of SiO
2
to Ni, Pd/Al
2
O
3
could enhance the activity and selectivity, and especially the durability ofthe catalysts.It is also found that Ni/Al
2
O
3
modified by rare earth metal of lanthanum andcerium could improve the activity of the catalysts.
Regioselective Hydroesterification of Styrene Catalyzed by PdCl
2
-NiCl
2
-PPh
3
/PVP
WAN Bo-Shun, LIAO Shi-Jian, XU Yun, YU Dao-Rong
1997, 18(11): 1866-1868.
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Polymer-supported bimetallic system of PdCl
2
-4NiCl
2
-PPH
3
/PVP [PVP= poly(N-vinyl-2-pyrrolidone)] provided an almost regiospecific conversion of styrene to thebranched methyl 2-propionate at a high conversion.Typical reaction conditions are: 353 K,2.1 MPa of COpressure (gauge pressure), 10h; styrene (1 mmol); methanol (0.8 mL) ;benzene (10 mL); PdCl
2
/PVP(0.04 mmol Pd, N/Pd= 20 in molar ratio); n (Pd): n(Ni): n(PPh
3
) = 1: 4:1.Aremarkable synergic effect of bimetallic catalyst can be observed.Effects of PVP, amount of triphenylphosphine and temperature on the reaction were studied.The system of PdCl
2
-4NiCl
2
-PPh
3
/PVPgave 100% conversion of styrene and 99% selectivityto the branched chain ester under the typical reaction conditions.
Digital Image Analysis Technique──2DFT and Its Application
ZHANG Jian-Wen, ZHANG Hong-Dong, YAN Dong, CHEN Zhi-Hao, YANG Yu-Liang
1997, 18(11): 1869-1874.
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Digital Image Analysis Technique(DIA) has been applied to extract various typesof physical information from an image of high-order structures in polymer systems.UsingDIA, we haye succeeded in obtaining the power spectrum of two-dimensional Fouriertransformation (2DFT) of an image in real space.By settinig up a time-resolved digital imageanalysis system, we managed to study the phase separation dynamics of poly(methylmathacrylate)/poly (vinyl acetate) via 2DFT.Even more, we made it practicable to study theelectronic microscopic picture with the help of a one-dimensional scanner.At the end of thispaper, remarks on getting rich information from DIAwere presented.
Studies on Block Copolymers of Isotactic Polystyrene and Poly(ethene-co-propene)(Ⅰ)──Synthesis of iPS-b-Poly(E-co-P) Block Copolymer
CHEN Tian-Hong, LIN Shang-An
1997, 18(11): 1875-1878.
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Sequential copolymerization of styrene with mixture of ethene and propene [iPS-b-Poly (E-co-P)] was carried out with NdClx (OR)y modified Ziegler-Natta Catalystdeveloped in our laboratory.The influence of concentration of catalyst and cocatalyst [Al(i-Bu)
3
], polymerization temperature, isospecific prepolymerization time of styrene and feedratio of ethene/propene on the copolymerizations was investigated in great details.Thecontent of lPSsegment in copolymerization product increases with the increasing time of styreneprepolymerization.
Synthesis and Characterization of Block Copolymers of Styrene and Methyl Methacrylate
LI Chun-Gang, ZHANG Bang-Hua, SONG Mou-Dao, ZHOU Qing-Ye, LI Ming, HE Bing-Lin
1997, 18(11): 1879-1883.
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Aseries of diblock copolymers of styrene and methyl methacrylate weresynthesized via sequential anionic polymerization.The products are diblock copolymers with highmolecular weight and narrow molecular weight distribution.The microphase-separatingstructure is proved by the information obtained from DMAand the solid state NMR.Themorphology structure is closely related to the ratio between X
PMMA
and X
PS
.
Mechanism of Bulk Copolymerization of Styrene and Maleic Anhydride
DONG Yu-Ping, FENG Lin-Xian, YANG Shi-Lin, SHEN Jia-Cong
1997, 18(11): 1884-1887.
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Because the interaction between the carbonyl groups of maleic anhydride (Man)and benzene ring of styrene(St) was the major part in the charge transfer complex (CTC)formed by St and Man, The unsaturated carbon--carbon double bond of Man was not in aadvantageous position in copolymerization with the ethyl group of St.The calculated data fromthe Complex-Dissociation Model were coincided well with experimental ones.It is reasonableconsidered that the bulk copolymerization of St and Man proceeded according to theComplex--Dissociation Model.The fitting data also showed that the probability of alternativecopolymerization increased with the increasing of temperature among 70～140℃.
Studies on Synthesis and Drug Release Properties of Aliphatic Polyester Anhydrides
HU Yun-Hua, ZHUO Ren-Xi
1997, 18(11): 1888-1892.
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Polyanhydrides are of particular interest as materials for controlled drug releasesystems due to their excellent surface erosion properties.In this paper, a series of aliphaticpolyester anhydrides -[COCH
2
CH
2
COO (CH
2
)
n
OCOCH
2
CH
2
COO]-
m
were prepared.The invitro degradation and drug release properties were also investigated.The results showed thatthe aliphatic polyester anhydrides had low melting temperature (
7
0℃).The in vitrodegradation rates of polyester anhydrides decreased with the increase of n, and degradationcompleted within
24
4
0h.The drug release rates from polyester anhydrides matrixes arerelated to the behavior of polyester anhydride degradation.
A New Synthetic Method of Liquid Crystalline Polyesters with Flexible Polymethylene Spacer
ZHANG Hai-Liang, TAN Song-Ting, ZHU Zhi-Qiang, WANG Xia-Yu
1997, 18(11): 1893-1896.
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Polymethylene his(p-hydroxybenzoates) (Ⅰ) were prepared from solbrol anddifferent dids by melted stated transesterification reaction with Ti (OC
4
H
9
-n)/N (n-C
4
H
9
)
3
asthe catalyst and (C
6
H
5
O)
3
Pas the heat-stable inhibitor.Six liquid crystalline polyesters weresynthesized from terephthalyl dichloride and (Ⅰ).Thermotropic liquid crystallineproperties of these polyesters were identified by DSCand polarizing microscope with a hot stage.
Pattern Recognition and Quantitative Characterization of Surface Shape of Microcapsulized Pigment Particles
YANG Gut-Qin, GUO Cong-Rong, WANG Xue-Song, CUI Jian-Zhong, YAN Le-Mei, ZHANG Wan-Dong
1997, 18(11): 1897-1898.
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Microcapsulized particles of ultramarine pigment were prepared, then theiracidresistant colour differences (ΔE) were determined and their images were processed as well asthe patterns were recognized with a computer, so that they were quantitatively characterizedvia the study of the surface fractional dimensionality(D).The results showed that the largerthe Dvalue of ultramarine particles, the less the ΔEof them.
Studies on Platelet-Resistance of Amphiphilic Polystyrenegraft-ω-stearyl-poly(ethylene oxide)
JI Jian, SUn Yong-Hog, Tong Feng-Oin, QIU Yong-Xing, FENG Lin-Xian
1997, 18(11): 1899-1901.
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The platelet adhesion and protein(Fibrinogen and albumin) adsorption ontoamphiphilic polystyrene-graft-poly(ethylene oxide) (PS-g-PEO) and polystyrene-graft -ω-stearyl-poly(ethyleneoxide) (PS-G-SPEO) were investigated.It was found that the plateletadhesion on PS-g-SPEOwas lower than that on PS-g-PEO.The PS-g-SPEOsurface shows apreference for Albumin, while the PS-g-PEOsurface absorbed Fibrinogen selectivelyu.Twoeffects of stearyl end group on PS-g-SPEOsurface: (1) the lower surface free energe leadsto SPEOenrich at surface; (2) the stearyl end group absorbed albumin selectively, seems tocontribute to resistant the platelet adhesion.So the polymer surface modificed by both stearylgroup and poly(ethylene oxide) chain may be a new ideal way to improve material's bloodcompatibility.
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