Table of Content

20 February 1991, Volume 9 Issue 1

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STUDY ON PHOTOSENSITIZED POLYMERIZATION IN MICELLAR SOLUTION Ⅴ. THE PHOTOCHEMICAL BEHAVIORS OF IONIC BENZOPHENONES IN THE DIFFERENT IONIC MICELLAR SOLUTIONS

FANG PEI-JI, WANG ER-JIAN

1991, 9(1):  1-7.  DOI: 10.7517/j.issn.1674-0475.1991.01.1

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Comparative study on the water-soluble photosensitizors, benzoylbenzyl sodium sulfonate (BP^-) and benzoylbenzyl trialkylammonium bromide (BP⁺) with benzophenone (BP) was carried out. The results of the transient and steady spectra indicate that both BP⁺ and BP^- locate in the stern layers of SDS anionic micelle and of CTAB cationic micelle respectively. Their photopysical and photochemical properties in homogeneous and heterogeneous systems are the same as that of BP. The photoreduction rates in the different ionic micellar systems were measured. The results obtained show that the photochemical reactivities of both ionic benzophenones BP⁺ and BP^- are much higher than that of neutral BP. Their photoreduction rates in the different ionic micellar systems are queit different due to the static electric interaction. Under the appropriate condition, the photoreduction rates of the ionic BP⁺ and BP^- are decades higher than that of neutral BP. The hydrophobic effect of amines was also examined.

THE PHOTOCHEMICAL CIS-TRANS-ISOMERIZATION OF AZOBENZENE AND ITS APPLICATION TO THE DETERMINATION OF LIGHT INTENSITY

HERMANN RAU, XIA PEI-JIE, SHEN YU-QUAN

1991, 9(1):  8-12.  DOI: 10.7517/j.issn.1674-0475.1991.01.8

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In this paper the principle of the azobenzene actinometer for the determination of light intensity was discussed. The method can also be used to determine the quantum yield of a photochemical isomerization of A<﹦>B type. A computer program was designed to calculate the data relevant to the determination of light intensity and quantum yield.

A STUDY ON THE PHOTOCHROMIC BEHAVIOR OF β-DIKETONE COMPOUNDS

ZHANG YI-FAN, Wu SHI-KANG

1991, 9(1):  13-21.  DOI: 10.7517/j.issn.1674-0475.1991.01.13

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The photochromic behavior of several kind of β-diketone compound with different structure has been studied. It was found that some compounds studied possess photochromic behavior, but for others listed in this paper, this phenomenon can not be observed. The mechanism of this phenomenon which was observed for some compounds was discussed in detail.

CYCLOVOLTAMMETRIC STUDIES ON THE DEAMINATION OF N-SUBSTITUTED QUINONE-IMINES

LIU CHUN-YAM, REN XIN-MIN

1991, 9(1):  22-28.  DOI: 10.7517/j.issn.1674-0475.1991.01.22

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The kinetics and mechanism of the deamination of N-substimted quinonediimines and N-substituted quinone monoimines were examined as a function of increasing pH. In this work, the rate constants of the deamination were determined with a semiempirical procedure of stationary electrode polarography.Deamination is initiated by nucleophilic attack on the most positively charged carbon atom of the benzene ring. Therefore, electron donating substituent has an effect on the rates of deamination and half-wave potential. Under the same condition, the half-wave potential of 2-methyl substituted compound is ca. 120 mV lower than the unsubstituted one. The absorption maximum of the dye formed by a methyl-substituted quinonediimine with the coupler would shift about 20-30 nm to the longer wavelength when compared with the unsubstituted compound.

PHOTOPHYSICS STUDIES OF ORGANIC COMPOUNDS Ⅷ. INVESTIGATION ON THE GROUND STATE DIMER AND EXCIMER FORMATION OF CETYL β-NAPHTHOATE IN L-B FILMS

MA XIAO-DONG, ZHU ZHI-QANG, CHEN FENG-QI, TUNG ZHEN-HO, FAN MEI-GONG

1991, 9(1):  29-35.  DOI: 10.7517/j.issn.1674-0475.1991.01.29

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The different types of cetyl β-naphthoate (NACE) molecule films were prepared by the Langmuir-Blodgett technique. The absorption and fluorescence spectra of the films were investigated. In chloroform solution and solid state of NACE monomer fluorescence was observed. The fluorescence of excimer and excited dimer of NACE were also observed, besides the monomer fluorescence, in L-B films. It was found that the environment of the hydrophilic region in L-B films is changed when the films are processed with heat and water. This makes that the chemical and physical properties of hydrophilic groups in hydrophilic region were changed. The formation mechanism of the ground state dimer and excimer of NACE in L-B films was supposed.

SENSITIZED PHOTOOXIDIZATION OF CHOLESTEROL AND L-CYSTEINE BY PHTHALOCYANINE SULFONATES

SONG JIN-HUA, AN JIN-YI, XU HUI-JUN

1991, 9(1):  36-43.  DOI: 10.7517/j.issn.1674-0475.1991.01.36

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Phthalocyanine sulfonates (H2SPC). chlorogallium phthalocyanine (CaClSPC) and chlor-oaluminum phthalocyanine (A1C1SPC) have been synthesized and their sensitized photooxid-ation of cholesterol and L-cysteine have been studied. Both aggregation of dyes and pH value of the solution affect the reaction rate. The results of enhancement of photooxidation rate observed when D₂O was used as the solvent and the quenching effect of NaN₂ indicate that sensitized photooxidation proceeds mainly via Type Ⅱ mechanism (involving singlet oxygen 2O2).

A NEW CYTOCHROME P-450 MODEL——PHOTOINDUCED OXYGEN TRANSFER FROM ACRIDINE N-OXIDE CATALYZED BY PHTHALOCYANINE IRON (Ⅱ)

LIN SHU-QUN, SHEN SU-YINO, LI LI, Xu HUI-JUN

1991, 9(1):  44-51.  DOI: 10.7517/j.issn.1674-0475.1991.01.44

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Photoinduced oxygen transfer from acriditae N-oxide to cyclohexene in the presence of catalytic amount of phthalocyanine iron(Ⅱ) giving cyclohexene epoxide as the main product can be considered to be one of the mechanisticc model systems of biological oxidation catalyzed by monooxygenase Cytochrome P-450. A new absorption peak at 710 nm indicating the formation of a complex between phthalocyanine iron (Ⅱ) with acridine N-oxide. The complex posseses oxidizing reactivity and is believed to be the active intermediate in the oxygen transfer reaction. The effect of substituent in acridine N-oxide on product distribution and the mechanism of photoinduced oxygen transfer from acridine N-oxide catalyzed by phthalocyanine iron (Ⅱ) are briefly discussed.

SYNTHESIS AND CHARACTERIZATION OF POLYVINYLOXYETHYL CINNAMATE

HUANG JIA-XIAN, LI SHENG, LI CHUN-RONG, LEI JIN-CHUN, CHEN GUO-HUA, LI HE

1991, 9(1):  52-57.  DOI: 10.7517/j.issn.1674-0475.1991.01.52

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In this paper a negative photoresist--polyvinyloxyethyl cinnamate, which has excellentproperties such as high resolution, high sensitivity, good adhesion, slight flagging after development, rare occurances of pin holes, high stability during storage and plasma incineration stripping was reported. Polyvinyloxyethyl cinnamate was polymerized by cationic polymerization, which was carried out at -75℃ and the boron trifluoride etherate was used as an initiator. Polyvinyloxyethyl cinnamate with high molecular weight and high yield can be obtained at low temperature, when purified monomer and coinitiator was used. The correlation Mark-Houwink equation for this polymer have been established by the measurement of frac-tionated samples with light scattering and viscometry methods. The finest line width of this photoresist is 0.5 μm and the useful line width in technique is≥1μm.

HYPOCRELLIN A SENSITIZED PHOTOOXIDATION OF BILIRUBIN IN APROTIC SOLVENT

MA JIN-SHI, WANG CHANG-QI, YAN FANG

1991, 9(1):  58-61.  DOI: 10.7517/j.issn.1674-0475.1991.01.58

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Hypocrellin A sensitized photooxidation of bilirubin in aprotic solvent, dichlorometh-ane, gave biliverdin and other degraded molecules. The yield of biliverdin was varied with concentration of bilirubin, irradiation time and light intensity. A highest yield was readied to 58%. The photooxidation pathway is ¹O₂ intermediated Type II, ‘ene addition’ of singlet oxygen at C10-C12 of bilirubin via bis-free radical intermediate may lead to formation of biliverdin.

PATHWAYS OF PHOTOOXIDATION REACTION OF LEUCO MALACHITE GREEN

LIU KUI-WEN, CHEN SHANG-XIAN

1991, 9(1):  62-66.  DOI: 10.7517/j.issn.1674-0475.1991.01.62

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The photooxidation reaction of leuco malachite green (LMG) was studied. As naphthalene was added into solution of LMG in dioxane, an emission spectrum of the exciplex formed between excited LMG and naphthalene was determined. When indole was put in solution of LMG in acetonitrile, the fluorescence of LMG did not change, but its phosphorescence was quenched by indole, and photochemical reaction rate of LMG was decreased simultaneously. It is concluded that in the absence of an electron acceptor the triplet of LMG plays an important role in the photochemical reaction.

ORGANOSILICONE PHOTOINITIATORY SYSTEM CONTAINING BENZOPHENONE GROUP

ZHANG XIAN-LIANG, ZHUO REN-XI, WANG QUAN

1991, 9(1):  67-70.  DOI: 10.7517/j.issn.1674-0475.1991.01.67

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2-Allyldxy-4-methoxy-bentzophenone (Ⅰ), γ-(4-methoxy-2-oxy-benzophenone) propylhep-tamethylcyclotetrasiloxane (Ⅱ) and polysiloxane containing pendent benzophenone group (Ⅲ) we’re synthesized. These photoinitiators have been used for the photoaddition of polymethylvin-ylsiloxane with 1, 10-dithioldecane. The organosilicone photoinitiators (Ⅱ, Ⅲ) are well compatible with polymethylvinlysiloxane. The effecacy of the photoinitiators has the following order Ⅱ>Ⅲ>Ⅰ.

DETERMINATION OF LEAD AND BISMUTH IN SILVER NITRATE BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

Wu XUE-HAN, PENG YUN, CUI GUANG-CHEN, ZHU ZI-YU

1991, 9(1):  71-75.  DOI: 10.7517/j.issn.1674-0475.1991.01.71

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A method for determination of trace quantities of lead and bismuth in silver nitrate was described. Lead and bismuth were separated from precipitated AgCl with NH₄Cl as a precipitant and EDTA as a complexing agent. The method is simple and convenient. The recoveries are up to more than 90%.

KINETICS AND MECHANISM OF IRON (Ⅲ) CATALYZED OXIDATION OF HYDROXYLAMINE BY 12-TUNGSTO-COBALT(Ⅲ)ATE

CHEN YU-CONG, ZHOU BEN-MAO, REN XIN-MIN

1991, 9(1):  76-80.  DOI: 10.7517/j.issn.1674-0475.1991.01.76

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Different from in HAc-NaAc (pH = 3.9-5.0), in HClO₄-NaClO₄ ([H+] - 0.1-0.4 mol/L) the reaction of the Fe (Ⅲ) catalyzed oxidation of hydroxylamine by 12-tungstocobalt (Ⅲ) ate obeys the following kinetic law:

This paper gives a description of the mechanism of the synergetic electron-proton transfer between NH₂OH and Fe³⁺(OH)^1- through a pentagonal model, considering that the active form of Fe (Ⅲ) is Fe³⁺(OH)^1-.