• Title/Summary/Keyword: Triplet state

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(Photosensitive Polymers VII) Mechanism of Photosensitized Curing Reaction of Cinnamoylated Polymers ((感光性 高分子에 關한 硏究 VII) Cinnamoylated Polymers의 光增感 硬化反應機構)

  • Kim, Kwang-Sup;Shim, Jyong-Sup
    • Journal of the Korean Chemical Society
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    • v.10 no.4
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    • pp.166-174
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    • 1966
  • The multistep mechanism of photosensitized curing reaction cinnamoylated photosensitive polymer is proposed from the energy level diagram of cinnamic acid and sensitizer, and from the fact that excess of sensitizer brings the sensitivity to a limiting value etc. Various factors which have effects on the ability of sensitizer are also discussed. The mechanism involves following steps: activation to the first excited singlet states of cinnamoyl group(C) and sensitizer(S) by their absorption of photon, their intersystem crossing to the lowest triplet state, bimolecular internal quenching by formation of excimer of sensitizer, triplet excitation energy transfer and intermolecular addition between cinnamoyl group in ground state and that in triplet state. The rate equation derived from this mechanism is $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ where $I^c_{abs}\;and\;I^s_{abs}$: the rates of absorption of photon by cinnamoyl group and sensitizer $K_n$: Constants. It is proved with the cinnamate of poly(glyceryl phthalate)(PGC) in the absence of sensitizer using the infrared analytical method and successfully applied for the experimental data reported on the effects of the degree of cinnamoyl esterification and the concentration of sensitizer upon the sensitivity.

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Characteristics of Photochemical Reaction of Pefloxacin Irradiated by UVB in an Aerobic Condition (산소 존재하에서 UVB에 의한 페플록사신의 광화학적 반응의 특성)

  • 최윤수;이경선
    • YAKHAK HOEJI
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    • v.44 no.1
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    • pp.36-40
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    • 2000
  • The photodegradation of pefloxacin, photolabile fluoroquinolone antibacterial agent, was studied. In the presence of $N_2$, photodegradation of pefloxacin was suppressed. The singlet oxygen and free radical generated in the reaction media proceeded photochemical reaction. The photodegradation of peflxacin was sensitized by benzophenone, a triplet state sensitizer.

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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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Photocyclodimerization of Maleimide

  • Shim, Sang-Chul;Bong, Pill-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.3 no.3
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    • pp.115-119
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    • 1982
  • The photoreaction of maleimide, one of the best model compounds of DNA molecules for psoralen-DNA photoreactions, is studied in order to investigate the photoreactivity and the mechanism of the maleimide-psoralen photoreaction. The (2+2) photocyclodimer of maleimide was obtained in solution state by direct or sensitized irradiation. The rate constant of dimerization is determined by quenching studies and found to be of the order of $10^9 M^{-1}sec^{-1}$. The direct dimerization of maleimide is found to undergo through the triplet excited state. The quantum yields of dimerization are dependent on the maleimide concentration.

The C$_4$ Photocycloadduct Formation of Khellin with Some Olefins

  • Ho Kwon Kang;Sang Chul Shim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.543-546
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    • 1989
  • The photocycloaddition reaction of khellin with several olefins has been investigated. The photocycloadducts are formed regioselectively on furanyl 4',5'-double bond of khellin probably due to the localization of excitation energy on the furanyl 4',5'-double bond in the reactive excited state. The photocycloaddition reaction proceeds through the excited triplet state and the same product was formed when khellin is irradiated with dimethylfumarate or dimethylmaleate indicating the formation of common intermediate. The quantum yields of photocycloadduct formation, fluorescence, and intersystem crossing are very sensitive to proton-donating ability of solvents.

Photo-Crosslinking of Poly(glycidyl methacrylate) Initiated by N-Hydroxyphthalimide Sulfonates

  • Kyu Ho Chae;Ik Ju Park;Min Ho Choi
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.614-618
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    • 1993
  • The photoacid generation efficiency of four N-hydroxyphthalimide sulfonate derivatives was studied by photo-crosslinking reaction of poly(glycidyl methacrylate) in solid film state. The relative photoacid generation efficiency was increased in the order of N-hydroxyphthalimide methanesulfonate > -toluenesulfonate > -nitrobenzenesulfonate > -dinitrobenzensulfonate, and the reaction was efficiently sensitized by benzophenone suggesting that this photoreactions is likely to proceed through its triplet excited state.

Exciton dissociation yields of semiconducting polymer thin film devices doped by various phosphorescent emitters

  • An, J.D.;Chang, J.Y.;Han, J.W.;Im, C.;Chin, B.D.
    • 한국정보디스플레이학회:학술대회논문집
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    • 2006.08a
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    • pp.1010-1013
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    • 2006
  • To understand the exact charge carrier photogeneration properties of photoactive thin films consisting of a ${\pi}-conjugated$ polymer matrix and a triplet dopant, we prepared two types of polymer, poly(9-vinylcarbazole) (PVK) and poly[9,9-bis(2- ethylhexyl)fluorene-2,7-diyl] (PF2/6) doped with triplet emitters for organic light-emitting diodes (OLED), either iridium(III)fac-tris(2-phenylpyridine) $(Ir(ppy)_3)$ or iridium(III)bis[(4,6-fluorophenyl)- $pyridinato-N,C^2'$]picolinate (FIrpic), as thin film devices by using the conventional method. Those doped film devices, as well as pristine film devices, on ITO substrates were characterized by means of steady state photocurrent measurement for a wide spectral range.

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Light-emitting diodes using gold nanoparticles (금 (gold) 나노 입자를 이용한 고분자 발광소자)

  • Park, Jong-Hyeok;Lim, Yong-Taik;Park, O-Ok;Kim, Jae-Kyeong;Yu, Jae-Woong;Kim, Young-Chul
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2003.04a
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    • pp.119-122
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    • 2003
  • We report a dramatic increase in the photo-stability of a blue-emitting polymer, poly(9,9-dioctylfluorene), achieved by the addition of gold nanoparticles to the polymer. The optical absorption band of gold nanoparticles is tuned to resonate the triplet exciton-ground state band gap energy of the polymer. The photo-oxidation rate of poly(9,9-dioctylfluorene) was drastically reduced by doping the polymer with a very small amount ($10^{-6}-10^{-5}$ volume fraction) of gold nanoparticles. The gold nanoparticles used herein act as the quenching agent of the triplet states and can be directly applied to various blue light emitting polymer thin film ( < 100 nm ) devices.

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Electronic Spectra and Quenching of Dimethylanilines (Dimethylanline의 Electronic Spectra와 消光)

  • Jung, Kyung-Hoon;Lee, Ik-Choon
    • Journal of the Korean Chemical Society
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    • v.8 no.4
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    • pp.158-163
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    • 1964
  • Electronic spectra and quenching constants for ten N,N-dimethylanilines (DMA) have been determined. The $250m{\mu}$ absorption band (C band) of DMA was shown to be mainly responsible for the quenching. This band was confirmed as an $n{\to}{\pi}^{\ast}$ band through substituent and medium effects on the spectra shifts. The energy absorbed by this band then transfers to triplet and down to the lowest triplet state, $^{3}La$, where the energy is lost by non-radiative collisions.

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Triplet Excitation Energy Transfer as a Function of Concentration in Glassy Methylbenzophenone

  • 한형순;이재광;남계준;최용국;국성근
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.923-926
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    • 1998
  • Spectral diffusion following direct triplet excitation from the ground state in glassy Methylbenzophenone as a function of transition energy has been studied. The concentrations of donor and acceptor have been determined for different transition energies. The geometrical distribution was determined by a computer simulation. The cluster size increases gradually with concentration and cluster percolation is observed at 0.31 mole fraction for a three dimensional system. The average distance between a donor and an acceptor also has been determined for different concentrations. The energy transfer efficiency changes abruptly at a critical concentration of 0.054, corresponding to a critical distance of 9.8 Å. The γvalue was evaluated to be 1.17.