• Title/Summary/Keyword: Photoproduct

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Relationship between Singlet Oxygen Formation and Photolysis of Phloxine B in Aqueous Solutions

  • Keum, Young-Soo;Kim, Jeong-Han;Li, Qing-Xiao
    • Journal of Photoscience
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    • v.10 no.3
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    • pp.219-223
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    • 2003
  • Phloxine B (2,4,5,7-tetrabromo-4,5,6,7-tetrachlorofluorescein disodium salt), also referred as D&C red dye no. 28, is phototoxic to many insects such as Tephritidae fruit flies. Sunlight photolysis of phloxine B in aqueous solutions was a first order kinetic reaction at low concentrations. But it turned to be more complex reactions with the increase of phloxine B concentration. The half-lives of phloxine B (6-120 ${\mu}$M) were 18-41 and 52-289 hours in oxygenated and deaerated distilled water, respectively. The photolysis rate constants increased as the phloxine B concentrations increased. The singlet oxygen formation positively correlated with the concentrations of phloxine B and humic acid in oxygenated distilled water. The formation of singlet oxygen did not stop even after the complete degradation of phloxine B, which suggested an involvement of photoproduct-mediated reactions. The results showed that singlet oxygen mediated photooxidation was a dominant reaction for phloxine B dissipation in an aqueous solution, and the self-sensitized and photoproduct-mediated reactions were also involved at the higher concentrations. Iodide and bromide ions significantly decreased phloxine B photolysis rate constants, which were in relation to the decrease of singlet oxygen formation.

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Photochemical Reactions of Some Carbonyl Compounds with N, Nv-Dimethylaniline: Formation of $\beta- and \gamma-Hydroxynmines$

  • Kim, Sung-Sik;Change, Ji-Ae;Mah, Yoon-Jung
    • Journal of Photoscience
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    • v.9 no.1
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    • pp.5-7
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    • 2002
  • Direct irradiation of carbonyl compounds such as some aldehydes, ketones and anthraquinone in N,N-dimethylamiline(DMA), without using other solvents, gave $\beta$-hydroxyamines as the major products. Irradiation of anthrone and DMA in methanol afforded ${\gamma}$-hydroxyamine. The structure of the photoproduct was confirmed by treatment with an acid to give a bicyclic compound.

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Dicyanoanthracene and Biphenyl Co-sensitized Photooxygenation of 1,1-Diphenyl-2-vinylcyclopropane

  • Shim, Sang-Chul;Song, Jeong-Sup
    • Bulletin of the Korean Chemical Society
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    • v.7 no.2
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    • pp.150-153
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    • 1986
  • Co-sensitized photooxygenation of 1,1-diphenyl-2-vinylcyclopropane (VCP-DPh) with 9,10-dicyanoanthracene and biphenyl in oxygen-saturated acetonitrile solution produced 3,3-diphenyl-5-vinyl-1,2-dioxolane as the major product. The same photoproduct was obtained by acetone sensitized photooxygenation in oxygen-saturated acetone solution. However, VCP-DPh remained intact when directly irradiated with DCA or irradiated with Rose Bengal to generate singlet oxygen. A mechanism involving a cosensitizer radical cation and sensitizer radical anion is proposed.

"KALEIDOSCOPIC" TOPOCHEMICAL PHOTOPOLYMERIZATION BEHAVIOR OF DIOLEFIN COMPOUNDS

  • Hasegawa, Masaki;Chung, Chan-Moon;Kinbara, Kazushi
    • Journal of Photoscience
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    • v.4 no.3
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    • pp.147-160
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    • 1997
  • INTRODUCTION : Various types of organic reactions in the crystalline state, so-called "topochemical reaction", have been reported in this century." Among the reactions, [2+2] photocycloaddition of diolefin crystals are one of the most intensively investigated examples. In the topochemical reaction in a pure sense, the space group symmetry is perfectly preserved throughout the reaction as were demonstrated by the crystalline-state photopolymerization of 2,5-distyrylpyrazine (2,5-DSP) and photodimerization of propyl $\alpha$-cyano-4-[2-(4-pyridyl) ethenyl]cinnamate. 2,5-DSP was initially prepared by Franke and in 1958 Koelsch and Gumprecht described briefly in their article of diazine-derivatives that it was found that the compound (2,5-DsP) was converted into a colorless insoluble polymer (\ulcorner) dec. 331~331$\circ$ when the solid was exposed for a few hours to ultraviolet light. Wright described in his book as if Koelsch and Gumprecht had investigated both the structure of the photoproduct and the crystal structure 2,5-DSP in detail. However, in the paper, they have not described any study on chemically correct analysis and crystallography of the resulting photoproduct at all. In 1967, one of present authors (M. H.) independently made the same observation as Franke that brilliant yellow crystal of 2,5-DSP was converted into powdery white substance under the sunlight in the course of a preparative study of pyrazine-2,5-dicarboxylic acid from 2,5-DSP. He investigated this phenomenon and concluded for the first time that a linear highmolecular-weight polymer crystal ([$\eta$] > 3.0 in $CF_3COOH$ solution) with recurring cyclobutane units in the main chain, had been produced from 2,5-DSP crystal by the action of sunlight.on of sunlight.

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A study on the photodegradiation of 4-hydroxy-biphenylcarboxylic acid by $TiO_2$ ($TiO_2$에 의한 4-hydroxy-biphenylcarboxylic acid의 광분해 연구)

  • 유수창;이상희;임정훈;김동희;전형탁;김복희
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.12 no.2
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    • pp.110-114
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    • 2002
  • The relationship between the orientation of molecules adsorbed on $_TiO2$ and their photoproducts was examined by employing HBPCA (4-hydroxy-biphenylcarboxylic acid) as a model organic pollutant. For this purpose, the Photoproducts after irradiation with UV radiation at various pH were compared by utilizing UV and Raman spectroscopies. It was found from these studies that pH affected the photoproducts probably due to the different orientations of the adsorbed molecules, and that the orientation of the adsorbed molecules and their photoproducts were closely correlated.

Photochemistry of 1-(o-substituted -phenyl)-2-pentamethyldishilanyl Ethynes

  • Shim, Sang-Chul;Park, Seung-Ki
    • Journal of Photoscience
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    • v.6 no.1
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    • pp.13-19
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    • 1999
  • Irradiation of 1-(o-allyloxyphenyl)-2-pentamethyldisilanylenthyne 2a in methanol yields two 1 : 1 photoaddition products 3 and 4 via silacyclopropene intermediate. Photolysis of 2a with acetone in deaerated methylene chloride yields site specific and regioselective 1 : 1 adducts 6 ad 7 via silacyclopropene and 1-sila-1, 2-propdiene intermediate, respectively. Photolysis of 2a and 1-(o-(3', 3'-dimethyl-2'-propenylox)phenyl)-2-pen-tamethyldisilanylethyone 2b in benzene provides novel stereoselevtive intramolecular cyclization products 10 and 11, respectively. Irradiation of 1-(o-acetoxyphenyl)-2-pentamethyldisilanyl ethyne 2c in benzene yields the photo-Fries rearrangement products 18 and 19 and a photoproduct 17 via silacyclopropene intermediate. Photolysis of 1-(o-methoxycarbonlymethoxyphenyl)-2-pentamethyl disilanylenthyne 2d in benzene provides a novel intramolecular cycloaddition product 25 and 1-(o-methoxycarbonylemthoxiyphenyl)-2-trimethylsilylethyne 26 via silacyclopropene intermediate.

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Gene-Specific Repair of 6-4 Photoproducts in Trichothiodystrophy Cells

  • Nathan, Sheila;Van Hoffen, Anneke;Mullenders, Leon H.F.;Mayne, Lynne V.
    • BMB Reports
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    • v.32 no.6
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    • pp.554-560
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    • 1999
  • TTD1BI cells are non-hypersensitive to UV irradiation and perform normal genome repair of pyrimidine dimers but fail to excise 6-4 photoproducts and, concomitantly, are unable to restore RNA synthesis levels following UV irradiation. This pointed to a detect in gene-specific repair and this study was undertaken to examine repair of 6-4 photoproducts at the gene-level. The results indicated a defect in gene-specific repair of 6-4 photoproducts in active genes, although strand-specificity of 6-4 photoproduct removal was essentially similar to that of normal cells. These findings indicate that the near normal UV resistance of TTD1BI cells may be due to the inability of these cells to remove DNA lesions preferentially, as well as to the cells opting out of the cell cycle to repair damage before resuming replication.

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A New Asymmetric Photoisomerization of 2,3-Dihydropyrrolo[1,2-b]benzisothiazole 5,5-Dioxides (2,3-Dihydropyrrolo[1,2-b]benzisothiazole 5,5-Dioxide들의 비대칭성 광이성질화 반응)

  • Elghamry, Ibrahim;Dopp, Dietrich
    • Journal of the Korean Chemical Society
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    • v.54 no.6
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    • pp.727-730
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    • 2010
  • A tricyclic ring system bearing new stereogenic center namely 2,3-dihydro[1]benzothieno[3,2-b]pyrrole 4,4-dioxide was synthesized by asymmetric photoisomerization of 2,3-dihydropyrrolo[1,2-b]benzisothiazole 5,5-dioxide by irradiation with 245 nm emission of the low-pressure mercury lamp. The chemical structure and the purity of the photoproduct were delineated preliminarily by IR, NMR, and MS and finally confirmed by single crystal X-ray crystallography.

Photoinduced Enolization of 2-(Ortho-tolyl)benzofuran-3-one

  • Park, Bong-Ser;Eunsook Koh;Hyojeong Yoon;Chae, Woo-Ki
    • Journal of Photoscience
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    • v.9 no.1
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    • pp.13-15
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    • 2002
  • The structurally rigid $\alpha$-(o-alkylphenyl) acetophenone derivatives lacking $\beta$-hydrogens, 3,3-dimethyl-2-o-tolylibdan-1-one and 2-o-tolyl-benzofuran-3-one, were prepared and their photochemical behaviors were examined. The former did not give any photoproduct while the latter turned into its enol tautomer. The difference of reactivity of two ketones was attributed to aromatic character of the extol of the benzofuranone. It was concluded that the reaction occurred via photoinduced 1,3-H transfer.

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Effect on Growth of Yeasts and Photosynthetic Bacteria by Photochemical Product of Harmaline with N-Methylmaleimide (Harmaline과 N-Methylrnaleimide의 광화학반응 생성물이 효모 및 광합성 세균의 성장에 미치는 영향)

  • Ham, Heui-Suk;Kang, Dae-Gil;Choi, Won-Ki
    • The Korean Journal of Mycology
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    • v.17 no.4
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    • pp.202-208
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    • 1989
  • The photochemical reaction of harmaline and N-methylmaleimide has been investigated by spectroscopic methods. A photoproduct was isolated from the irradiation mixture of harmaline and N-methylmaleimide. Spectroscopic results suggested that the amine group of harmaline was added photochemically to the double C=C bond of N-methylmaleimide. This synthesized harmaline derivative has a biological toxicity, because it inhibits the growth of some yeasts and photosynthetic bacteria.

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