• 제목/요약/키워드: singlet

검색결과 254건 처리시간 0.019초

자체증감작용으로 인한 옥소디피로메텐의 광산소화반응 (Self-Sensitized Photooxygenation of Oxodipyrromethene)

  • 박용태
    • 대한화학회지
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    • 제24권2호
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    • pp.146-149
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    • 1980
  • 빌리루빈의 경우와 같이 옥소디피로메텐도 자체증감작용으로 생긴 단일상태 산소와 반응하여 광분해 하였다. 단일상태 산소의 수명이 각각 다른 용매에서 시험한 결과, 수명이 더 긴 용매에서 옥소디피로메텐의 공산화반응이 빨랐으며, 단일상태 산소의 켄칭제가 존재하는데서는 광반응이 느렸다. 더우기, 증감제를 사용하지 않은 반응에서 생성물이 증감제를 사용한 반응에서 생성물과 같았다.

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The Effect of UV-A and Reactive Oxygen Species on Glycosylation and Fragmentation of Calf Skin Collagen

  • Wan Goo Cho;Sang Jin Kang;Seong Don Hong;Quse Chae
    • Bulletin of the Korean Chemical Society
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    • 제14권1호
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    • pp.107-109
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    • 1993
  • Non-enzymatic glycosylation and fragmentation of collagen molecule were investigated by irradiating Ultraviolet A(UV-A) with or without scavengers of reactive oxygen species (ROS) in the presence of glucose. Non-enzymatic glycosylation was increased by UV-A at high concentration of glucose. It was reduced in the presence of the scavengers of superoxide radical and singlet oxygen, but not reduced in the presence of hydroxy radical scavenger. Fragmentation of collagen was increased by UV-A, but it was decreased in the presence of all ROS scavengers tested. Superoxide radical and singlet oxygen produced by autoxidation of glucose without UV-A may encounter the initial phase of glycosylation. Data presented here suggest that UV-A affects only on the fragmentation process, but all ROS except hydroxy radical act on both processes. It appears that hydroxy radical does not act on the glycosylation process.

Mechanistic Studies on the Anormalous Photocycloaddition Reaction of 5-Styryl-1,3-dimethyluracil and 2,3-Dimethyl-2-butene: Formation of the “Apparent Forbidden” [$_\pi4_s + _\pi2_s$] Cycloadduct

  • Eun Ju Shin;Ho Kwon Kang;Sang Chul Shim
    • Bulletin of the Korean Chemical Society
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    • 제12권4호
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    • pp.434-437
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    • 1991
  • Irradiation of 5-styryl-1,3-dimethyluracil (5-SDU) with 2,3-dimethyl-2-butene (DMB) gives a [4+2] cycloadduct which is converted into a [2+2] cycloadduct on the prolonged irradiation. Triplet sensitization, quenching, and external heavy atom effect on the [4+2] photocycloaddition reaction demonstrate the singlet pathway and salt effect excludes a radical ion pair precursor possibility. Polar solvents increase the reaction efficiency implying a polar exciplex involvement in the [4+2] photocycloaddition reaction. Inverse temperature dependence both on the reaction and DMB fluorescence quenching of 5-SDU indicates the presence of a singlet exciplex intermediate.

Fluorescence Properties and Photoisomerization Behavior of 1-(9-Anthryl)-2-(2-quinolinyl)ethene

  • 신은주
    • Bulletin of the Korean Chemical Society
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    • 제20권11호
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    • pp.1263-1268
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    • 1999
  • The fluorescence properties and photoisomerization behavior of 1-(9-anthryl)-2-(2-quinolinyl)ethene (2-AQE) have been investigated in various solvents. Instead of phenyl ring in 1-(9-anthryl)-2-phenylethene, the intro-duction of quinoline ring reduces not only the fluorescence yield but also the photoisomerization yield, due to competition of efficient radiationless deactivation and an increase in the torsional barrier for twisting in the singlet manifold. The S1 decay parameters were found to be solvent-dependent due to the charge-transfer character of lowest S1 state. Polar solvents reduce the activation barrier to twisting, thus slight enhancing the isomerization of t-2-AQE in the singlet manifold. As solvent polarity is increased, Φf of c-2-AQE is greatly reduced, but Φc →t is practically independent of solvent polarity. Dual fluorescence in t-2-AQE was observed and two fluorescing species could be assigned t-2-AQE and c-2-AQE, where the ratio between two species was dependent on the solvent polarity. Interestingly, in the concentration above 1×10 -4 M, the shapes of the fluorescence excitation spectra of t- and c-2-AQE are significantly altered without spectral changes of their fluorescence and absorption, probably due to the formation of excimer.

Photodimerization of 5,7-Dimethoxycoumarin

  • Shim, Sang Chul;Jeong, Bong Mo;Paik Young Hee
    • Bulletin of the Korean Chemical Society
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    • 제13권6호
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    • pp.684-688
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    • 1992
  • Three photocyclodimers of 5,7-dimethoxycoumarin (DMC) were isolated and characterized from the photolysis of DMC in acetonitrile. The configuration of the dimers was found to be anti head-to-head, syn head-to-head and syn head-to-tail, respectively. The number and the ratio of the products are solvent dependent. The anti head-to-head dimer is favored in nonpolar solvents and the preference decreases as the solvent polarity increases giving almost 100${\%}$ syn dimers and less than 1${\%}$ anti dimer from methanol solution. The overall yields of dimers also increase with the solvent polarity. From sensitization and quenching experiments, anti dimer was found to be formed via excited singlet state while syn dimers were formed via both excited singlet and triplet states.

Singlet-Triplet Reactivity of 1-Methyl-2-Cyclohexenyl Aryl Ketones : Racemization vs 1,3-Acyl Shift in the Excited States

  • Woo Ki Chae;Mi Young Chae;Mi Kyung Park;Chung Hee Lee;Eun Hee You
    • Bulletin of the Korean Chemical Society
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    • 제11권3호
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    • pp.241-244
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    • 1990
  • The photochemistry of 1-Methyl-2-cyclohexenyl aryl ketones (phenyl ketone 7a, p-toluyl ketone 7b, biphenyl ketone 7c and -naphthyl ketone 7d) is reported. The aryl ketone 7a, 7b and 7c undergo photo-racemization with efficiencies of 0.75, 0.79 and 0.76 respectively on direct irradiation. Direct irradiation of the ketone 7d, however, undergoes 1,3-shift with an efficiency of 0.02. Triplet states are responsible for the racemizations and singlet state is responsible for 1,3-shift as in general. The ketone 7a, 7b and 7c are good example of a few ${\beta},{\gamma}$-unsaturated ketones which undergo efficient intersystem crossing on direct irradiation.

Methyl Linoleate Oxidation via Electron Transfer in Competition with $^1O_2$ Formation Photosensitized N-Acetyl-L-Tryptophan 3-Methyl Indole

  • Yoon, Min-Joong;Song, Moon-Young;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • 제6권5호
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    • pp.291-295
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    • 1985
  • The efficiency of photosensitization of methyl linoleate (ML) oxidation by N-acetyl-L-trypophan(NAT) and 3-methyl indole(scatole) was markedly enhanced by increased concentration of ML in ethanol solution. The fluorescence intensities of sensitizers were observed to be quenched by ML, indicating that ML interacts with the indole excited singlet state. The inhibition of photosensitization by azide demonstrated a possible role of singlet oxygen in the photosensitization. The steady state kinetic treatment of azide inhibition of photosensitization was expected to show linear increase of reciprocal yield of ML oxidation product vs. reciprocal ML concentration at constant azide concentration, but the actual slope was nonlinear. This indicates another competing reaction involved in the photosensitization, As a possible competing reaction, electron transfer from ML to the excited sensitizer was proposed, since the measured fluorescence quenching rate constant closely resembled electron transfer rate constant determined from ML concentration dependence of oxidation product formation.

SINGLET OXYGEN-MEDIATED PHOTOOXIDATION OF METHYL 11-HYDRO-13-(METHYLOXY)CARBONYLARTEMISINATE

  • Lee, Jung-Kul;Han, Jae-Hong;Kim, Jeong-Han;Lim, Yoong-Ho;Kim, Soo-Un
    • Journal of Photoscience
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    • 제1권2호
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    • pp.127-129
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    • 1994
  • Singlet oxygen-mediated photooxidation and subsequent triplet oxygen insertion of 11-hydro-13-(methyloxy)carbonylartemisinate (4) yielded a diketo compound 5 as the major product instead of the expected 11-hydro-13-(methyloxy)carbonylartemisinin (6). The formation of the unexpected product was in part consistent with the mechanism proposed by Acton and Roth and is the first isolation of the diketo compound from the photooxidation of artemisinate.

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