• Title/Summary/Keyword: Singlet

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Photodecomposition Characteristics of Tetrabromobisphenol A (TBBPA) by Ultraviolet (UV-A) Irradiation (Ultraviolet-A (UV-A) 조사에 의한 Tetrabromobisphenol A (TBBPA)의 광분해 반응 특성)

  • Jang, Seok-Won;Han, Sang-Kuk
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.2
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    • pp.124-130
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    • 2013
  • Of all the brominated flame retardants (BFRs), TBBPA has the largest production volume (50% of the BFRs in current use). It is interest to investigate how they may degrade, because of it can pose an environmental hazard. By using UV-A (${\lambda}=352nm$ ), we have found that the UV-A irradiation increased the photodecomposition reaction rate of TBBPA in an intensity-dependent manner. We also observed 2,6-dibromo-p-benzosemiquinone radical ($a_{2H}=2.36G$, g = 2.0056) generated from TBBPA by reaction with singlet oxygen ($^1O_2$). On the other hand, when an aqueous preparation of HA was irradiated in the presence of TBBPA, the typical spectrum of semiquinone radical was detected by electron spin resonance (ESR). And then, we have found that the photodecomposition rate of TBBPA is decreased in depend on HA concentration. Radical formation and the reactive rate of TBBPA were inhibited by sodium azide used as a singlet oxygen quencher. Therefore we report that a similar $^1O_2$-induced oxidation can be initiate in aqueous solutions of TBBPA dissolved in humic acid (HA) by the UV-A irradiation (${\lambda}=352nm$). From these results, we suggest that the reaction rate of HA with $^1O_2$ is faster than that of TBBPA with $^1O_2$.

Photophysical and Photochemical Property of ATX-S10

  • Ito, Toshiaki;Okazaki, Shigetoshi;Kageyama, Kazumi;Hirohata, Toru;Kohno, Eiji;Hirano, Toru
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.527-529
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    • 2002
  • Photodynamic therapy (PDT) is a medical treatment using laser and photosensitizing drug taken up to destroy cancer cells. Singlet oxygen ($^1$0$_2$) generation is strongly related to this treatment. We have built a direct detection system monitoring feeble luminescence, in the near IR region, from $^1$0$_2$, We have comparatively studied the photophysical and photochemical properties in solution of a newly developed drug ATX-S10 and Photofrin already investigated clinically. We demonstrdted that ATX-S10 was capable of efficiently yielding $^1$0$_2$, which may lead to highly efficient PDT treatment. Successive laser excitation photobleached ATX -S10 readily in a dose-dependent manner. This result shows that ATX -S10 is useful in setting up suitable medical treatment conditions to minimize side effects.

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A Study on Generative Characteristics of Radicals in Aqueous Solutions of Humic Acids using Electron Spin Resonance (전자기공명기법을 이용한 Humic Acid 용액에서의 라디칼 발생 특성에 관한 연구)

  • Han, Sang-Kuk
    • Journal of Environmental Science International
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    • v.17 no.6
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    • pp.671-677
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    • 2008
  • We studied to determine quantitatively the radical species generated from humic acid (HA) solutions by irradiation(>400 mn). The formation of radical species from HA solutions was investigated with ESR spectroscopy. We gave ESR spectrum with g-value 2.0048 and line width 0.559mT, coincided with those of the semiquinone radical. 0.1 mg/L HA solution generated the radicals of $1.2{\times}10^{-6}M$, increased with increasing HA concentration. Also, pH and ionic strength effect of the amount of the semiquinone radical generate from HA solution. In this study, we have found that the singlet oxygen affects the semiquinone radicals generation in HA solution.

Energy Relaxation Dynamics of Excited Triplet States of Directly Linked Zn(II)Porphyrin Arrays

  • Song, Nam-Woong;Cho, Hyun-Sun;Yoon, Min-Chul;Aratani, Naoki;Osuka, Atsuhiro;Kim, Dong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.271-276
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    • 2002
  • The energy relaxation dynamics of the lowest excited singlet and triplet states of the Zn(II)porphyrin monomer and its directly linked arrays were comparatively investigated with increasing the number of porphyrin moieties. While the fluorescence decay rates and quantum yields of the porphyrin arrays increased with the increase of porphyrin units, their triplet-triplet (T-T) absorption spectra and decay times remained almost the same. The difference in the trends of energy relaxation dynamics between the excited singlet and triplet states has been discussed in view of the electronic orbital configurations.

PHOTOLYSIS OF [1.1.1]PROPELLANE : SYNTHESIS OF NEW COMPOUNDS AND MECHANISTIC STUDY

  • Lee, Woo-Bung;Oh, Dong-Won;Park, Mi-Sook;Hwang, Dug-Hea;Cheong, Chae-Joon;Moon, Hong-Young
    • Journal of Photoscience
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    • v.6 no.2
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    • pp.57-60
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    • 1999
  • The reaction of [1.1.1]propellane with singlet methylene afforded 1,3-dimethylenecyclobutane and [l.1.1.1]paddlane (3). Various minor products were also produced. The reaction of [1.1.1]propellane with triplet methylene afforded 1,3-dimethylenecyclobutane (2) and various minor products. But even trace of [1.1.1.1]paddlane was not detected. The mechanism for the addition of singlet methylene involved [1.1.1.1]paddlane intermediate The addition of triplet methylene led to diradical intermediate. In order to reveal the reaction pathway for generation of various ruiner products, various studies were carried out under the same condition.

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Interconversion of Electronic Spin State of p-Substituted Arylketocarbene Reactions

  • Sung, Dae-Dong;Jeong, Jin-Hee;Ryu, Zoon-Ha;Chin, Won-Bae;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.8
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    • pp.1231-1237
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    • 2004
  • Rate constants for photolytic reactions of p-substituted 2-diazopropiophenones were determined in acetonitrile. The reactions show a comparatively low value of activation energy and activation enthalpy to alkylcarbenes or other arylcarbenes. The transition state corresponds to the step of a new carbonyl bond formation. The high negative ρ -values are shown in Hammett plots. The kinetics results and EPR spectrum are in accord with a phenomenon that occurs in interconversion between singlet and triplet carbenes.

An Intramolecular Photosubstitution Reaction of N-(2,4-Dibromonaphthyl)- arenecarboxamide: Synthesis of 2-Arylnaphthoxazole

  • Bae, In-Soo;Kim, Yoo-Shin;Park, Yong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.24 no.7
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    • pp.916-920
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    • 2003
  • Photoreactions of N-(2,4-dibromonaphthyl)arenecarboxamides in basic medium result in the intramolecular substituted products, 2-aryl-8-bromonaphthoxazoles in moderate yields and further photoreactions of the products afford the reduced products, 2-arylnaphthoxazoles. These reactions are straightforward for syntheses of naphthoxazole derivatives. Since the intramolecular photosubstitution of the bromoarenecarboxamide by the oxygen of its amide group is more effective than the photoreduction of the substituted product, 2-aryl-8- bromonaphthoxazole in basic medium, the intramolecular substituted product, 2-aryl-8-bromonaphthoxazole can be isolated. A charge-transfered excited singlet state of an imidol form of the 2-bromoarenecarboxamide is involved in the photosubstitution, whereas an excited triplet state of the 2-aryl-8-bromonaphthoxzole is closely involved in the photoreduction.