• Title/Summary/Keyword: Photochemical Reaction Mechanism

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Photochemical and Thermal Reaction Mechanism for the Reaction of Carcinogenic Molecules and Food Reservatives (발암성 분자와 식품보존제의 광화학 및 열적 반응메카니즘)

  • 김민식;채기수;김갑순;성대동
    • The Korean Journal of Food And Nutrition
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    • v.11 no.3
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    • pp.267-271
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    • 1998
  • The photochemical carcinogenic reaction mechanism and molecular carcinogenic intensity through the reaction of dibromo carbene and diazomethane with dehydroacetic acid and coumarin have been studied under the two kinds of photolysis. The reaction intensities show the degree of carcinogenic activity. Under the condition of UV/vis light source, the yield of high toxic carcinogenetic carbene intermediate is produced less than those of the laser flash photolysis.

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A Study on the Mechanism for Photochemical Insertion of Methanol Into Aryl Ketocarbenes

  • Sung, Dae-Dong;Lee, Jong-Pal;Lee, Yong-Hee;Ryu, Worl-Sun;Ryu, Zoon-Ha
    • Journal of Photoscience
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    • v.7 no.1
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    • pp.15-19
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    • 2000
  • The photochemical reaction mechanism has been investigated for methanol insertion into the p-substituted phenylketo carbenes. The triplet spin state of phenyl koto carbene is stabilized by the neighbored carbonyl electrons. When the phenylketo carbene reacts with methanol, the ylied intermediate is formed, then moves to the activated transition state.

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Comparative Study on Photochemical Reactions of Aromatic Hydrocarbons in Indoor and Outdoor Smog Chambers (실내/외 스모그 챔버에서의 방향족계 탄화수소의 광화학 반응 비교 연구)

  • Dong Jong-In;Ahn Heung-Soon
    • Journal of Environmental Science International
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    • v.14 no.2
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    • pp.231-240
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    • 2005
  • The number of cases exceeding environmental standards of atmospheric ozone in the major cities in Korea has steadily increased during the past decades. In order to understand and analyze the atmospheric reactions in the atmosphere, especially the secondary photochemical reactions, smog chambers studies have been performed very actively by many research groups worldwide. However, these studies have focused on the mechanism of photochemical reactions in high concentration conditions, not at the ambient levels. Therefore, in-depth studies in these conditions are essentially needed to realize exact mechanism in the atmosphere near the earth surface, especially at Korean atmospheric conditions. In this experiment, the mechanism of photochemical smog was examined through a comparative experiment of smog chambers under sun light and black light conditions. The results of our study indicated that concentrations of ozone, aldehyde, and PAN increased as the radiation of light source increases. Photochemical reaction patterns can be considered quite similar for both black light and sun light experiments. Based on our experiments using toluene as a reactant which is present at significant high levels in ambient air relative to other VOCs, it was found that toluene could contribute notably to oxidize NO to $NO_2$, this reaction can eventually generate some other photochemical oxidants such as ozone, aldehyde, and PAN. The results of simulation and experiments generally showed a good agreement quite well except for the case of $O_3$. The restriction of oxidization of NO to $NO_2$ seems to cause this difference, which is mainly from the reaction of peroxy radical itself and other reactants in the real gas.

The investigation of photochemical reaction of phototoxic antimalarial compounds

  • Yoon, Ung-Chan;Epling, Gary-A.
    • Archives of Pharmacal Research
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    • v.3 no.2
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    • pp.87-88
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    • 1980
  • The goal of this research is to provide information that will lead to the development of new non-phototoxic antimalarial compounds. The goal was approached by first learning the chemical mechanism of phototoxicity of six representative compounds 1a-f: a[(diethyl-, -dihexyl-, and -dioctyl- aminomethyl)]-2-(3', 4' -dichlorophenyl)-6-methoxy-4-quinolinemethanol (1a, 1b, and 1c) and .alpha. [(diethyl-, -dibutyl-, and -dihexyl-aminomethyl)]-2-(-4'-methoxyphenyl-6-methoxy-7-chloro-4-quinolinemethan ol (1d, 1e, and 1f). The photochemical reaction of these compounds was investigated in 2-propanol. Similar photochemical fragmentation reactions accurred in all compounds.

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Numerical Simulation of Complicated Photochemical Reactions Occurring in the Atmosphere (대기내 발생하는 복잡한 광화학반응에 대한 수치실험)

  • Won Gyeong-Mee;Kim Yoo-Keun;Lee Haw-Woon;Kim Hee-Jeoung
    • Journal of Environmental Science International
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    • v.15 no.3
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    • pp.203-209
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    • 2006
  • In predicting oxidants concentration, the most important fact is to select a suitable photochemical reaction mechanism. Sensitivity analysis of $O_3$ and other important photochemical oxidants concentrations was conducted by using CBM-IV model. The predicted oxidants concentration was considerably related with the initial concentration of formaldehyde, $[NO_2]/[NO],\;NO_x$, RH and RCHO. As the initial concentration of formaldehyde increased, concentration of $NO_2$ increased. $O_3$ concentration was proportional to the $[NO_2]/[NO]$ ratio. When the initial concentrations of RH and RCHO were high, photochemical reaction was more reactive, including more rapid conversion of NO to $NO_2$ and increased oxidants. Also, the sensitivities of ozone formation to rate constants, $K_l,\;K_2\;and\;K_3$ in the $NO_2$ photolysis were studied.

Hula-twist, a Supramolecular Photoisomerization Reaction Mechanism in Reactions of Photosensitive Biopigments

  • Liu, Robert S.H.
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.1-4
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    • 2002
  • Hula-twist is a volume-conserving photoisomerization reaction mechanism postulated in 1985 to account for the rapid photoisomerization of the retinyl chromophore in rhodopsin. The requisite stereochemical consequence of simultaneous isomerization of a double bond and an adjacent single bond has recently been demonstrated in isomerization of pre-vitamin D in an organic glass and by many other examples of organic systems already reported in the literature This paper reports the consequence in applying the mechanism to the primary photochemical process of several photosensitive biopigments: bilirubin, photoactive yellow protein, bacteriorhodopsin and rhodopsin. It is shown that the anchored nature of the chromophores must first be taken into consideration.

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Fabrication of CuO/ZnO Nano-heterostructure by Photochemical Method and Their H2S Gas Sensing Properties

  • Kim, Jae-Hyun;Yong, Ki-Jung
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.359-359
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    • 2011
  • This study reports the H2S gas sensing properties of CuO / ZnO nano-hetero structure bundle and the investigation of gas sensing mechanism. The 1-Dimensional ZnO nano-structure was synthesized by hydrothermal method and CuO / ZnO nano-heterostructures were prepared by photo chemical reaction. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) spectra confirmed a well-crystalline ZnO of hexagonal structure. In order to improve the H2S gas sensing properties, simple type of gas sensor was fabricated with ZnO nano-heterostructures, which were prepared by photo-chemical deposition of CuO on the ZnO nanorods bundle. The furnace type gas sensing system was used to characterize sensing properties with diluted H2S gas (50 ppm) balanced air at various operating temperature up to 500$^{\circ}C$. The H2S gas response of ZnO nanorods bundle sensor increased with increasing temperature, which is thought to be due to chemical reaction of nanorods with gas molecules. Through analysis of X-ray photoelectron spectroscopy (XPS), the sensing mechanism of ZnO nanorods bundle sensor was explained by well-known surface reaction between ZnO surface atoms and hydrogen sulfide. However at high sensing temperature, chemical conversion of ZnO nanorods becomes a dominant sensing mechanism in current system. Photo-chemically fabricated CuO/ZnO heteronanostructures show higher gas response and higher current level than ZnO nanorods bundle. The gas sensing mechanism of the heteronanostructure can be explained by the chemical conversion of sensing material through the reaction with H2S gas.

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Determination of Reactivities by Molecular Orbital Theory (I) Theoretical Treatment on the Photochemical Reaction of Benzene and Maleic Anhydride (분자 궤도론에 의한 반응성 계산 (I) Benzene과 Maleic Anhydride 간의 광화학 반응)

  • Myung-Hwan Whangbo;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.273-280
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    • 1969
  • The MO's of maleic anhydride are calculated using the parameter values, $h_{o}$.= 1, $h_{o}$:= 2, $k_{c=o}$= 1, $k_{c-o}$= 0.8, and ${\delta}_{{\alpha}_n}=2{\times}(0.3)^n$. With these MO's the interaction energies of the photochemical reaction of maleic anhydride (MA) with benzene are calculated using intermolecular orbital theory. It is shown that there are cases where the interaction energy includes a constant term and this term takes a great role in the photochemical interaction energy, and that with the calculated interaction energies the reaction mechanism is quite well explained. And it is proved that the photochemical reaction is possible for the second addition step of MA to benzene, and that the MA-benzene adduct should have the well-known stereochemical structure.

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Phototoxic Potential Mechanism of Pefloxacin Irradiated by UVB (UVB 조사에 의한 페플록사신의 광독성 유발 기전)

  • 최윤수;이경선
    • YAKHAK HOEJI
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    • v.43 no.6
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    • pp.703-708
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    • 1999
  • The effect of antioxidants on photochemical reaction of pefloxacin by UVB (290~320 nm) was investigated and the possible mechanism of phototoxicity on the skin was also studied. The photo-degradation of pefloxacin by UVB was suppressed by cysteine, reduced glutathione and ascorbic acid, but was promoted by ${\alpha}-tocopherol$. Squalene, accounts for more than 10% of skin surface lipids, was peroxidized by pefloxacin through both radical and singlet oxygen mechanism.

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LASER FLASH PHOTOLYSIS STUDY ON THE PHOTOCYCLIZATION OF N-(O-HALOBENZYL) IMIDAZOLE

  • Park, Yong-Tae;Hwang, Young-Sun;Song, Woong Song;Kim, Dongho
    • Journal of Photoscience
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    • v.3 no.2
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    • pp.91-93
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    • 1996
  • In connection with our interest on the photochemical properties of heteroaryl halides, which are currently the subject of heterocyclic ring formation and haloarene degradation, we have studied the photochemistry of the haloarene linked to N-heteroarene compounds. Imidazo[5,1-a]isoindole was synthesized from N-(ochlorobenzyl)imidazole or N-(o-bromobenzyl) imidazole in acidic aqueous solution or acetonitrile via the intramolgcular photocyclization (Table 1). This type of reaction provides the synthetic methods for 5- and 6-membered polyheteroatomic heterocyclic ring compounds. However, the reaction mechanism for the intramolecular photocyclization of haloarene tethered heteroarenes has not yet been established. Grimshaw et al. suggested a mechanism for homolyric carbonhalogen bond fission assisted by radical complexation to explain their results in the photocyclization of 5-(2-chlorophenyl)-1,3-diphenylpyrazole. They also reported the detection of acyclohexadienyl intermediate involved in the above reaction. Park et al. reported several transient 'intermediates involved in the laser flash photolysis of N-(o-halobenzyl) pyridinium and N-benzyl-2-halopyridinium salts. Thus we performed the laser flash photolysis study on the photocyclization reaction of N-(o-chlorobenzyl) imidazole to identify the intermediate species involved in the reaction. Here, we report on the preliminary results in the photocyclization reaction of N-(o-halobenzyl)imidazole through the detection of reaction intermediates.

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