• 제목/요약/키워드: Laser Photolysis

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이성분 혼합용매에서 화학변화에 미치는 용매의 영향 : THF-$H_2O$ (제1보). 용매화된 전자의 흡수스펙트럼 (The Solvent Effect on the Chemical Changes in Binary Mixture : i.e. THF-H2O System (Ⅰ))

  • 박유철;오상천
    • 대한화학회지
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    • 제24권5호
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    • pp.371-379
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    • 1980
  • 테트라히드로퓨란(THF)-물 혼합용매에서 용매화된 전자($e^-_s$)를 생성시켜 광흡수스펙트럼의 성질을 연구하였다. 본 연구에서 $e^-_s$는 nsec Q 스위치 Nd(YAG) 레이저 에너지 (265nm)를 이용한 광분해법으로 생성시켰다. 이 방법은 실험부분에서 도면으로 간단하게 기술되어 있다. 측정한 $e^-_s$의 최대흡수 파장은 THF의 함량과 온도에 따라 장파장쪽으로 이동하였고, 흡수스펙트럼의 폭 역시 THF에 따라 증가하였다. $e^-_s$의 반감기 또한 THF의 몰%에 따라 증가하였다. 혼합용매에서 최대 흡수파장은 순수한 물이나 THF에서 방사선 분해법을 측정한 흡수파장의 중간에서 모두 발견되었다. 이러한 실험 결과로부터 $e^-_s$의 체적과 최대흡수에너지 관계를 논의할 수 있었다.

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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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    • 제23권2호
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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.

Photochemical synthesis of diphenylphenanthrenes, and the photophysical properties studied by emission and transient absorption measurements

  • Yamaji, Minoru;Hakoda, Yuuma;Horimoto, Ami;Okamoto, Hideki
    • Rapid Communication in Photoscience
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    • 제3권4호
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    • pp.73-75
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    • 2014
  • Novel diphenylphenanthrenes (DPPs) were prepared by a photocyclization method, and the substituent effects of the phenyl groups on the photophysical properties of the phenanthrene chromophore were investigated based on measurements of fluorescence yields, lifetimes, and transient absorption. Fluorescence activities in DPPs are increased by introducing phenyl rings that can enhance the transition moment along the short axis of the phenanthrene skeleton. Intersystem crossing from the fluorescent states to the triplet manifolds is shown to be operative through the triplet-triplet absorption spectra obtained by laser photolysis techniques.

Formation and Properties of Enyne Radical Cation

  • Kim, Bang-Duk;Shim, Sang-Chul;Noboyuki Ichinose;Sachiko Tojo;Tetsuro Majima
    • Journal of Photoscience
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    • 제8권2호
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    • pp.67-69
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    • 2001
  • Radical cations of DPBEY and PPCB were generated by ${\gamma}$-radiolysis and pulse radiolysis in halogenated solvents. The radical cation PPCB+ shows 505 (shoulder) and 520 nm absorption peaks with 700 ns lifetime in agreement with the laser flash photolysis work and strongly support the exciplex mechanism proposed for the photoreaction of PPCB and dimethylfumarate.

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Photoinduced Electron- and Energy-Transfer Processes in Supramolecules using Imide Compounds

  • Fujitsuka, Mamoru;Majima, Tetsuro
    • Rapid Communication in Photoscience
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    • 제3권1호
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    • pp.1-15
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    • 2014
  • We summarize recent studies on photoinduced electron- and energy-transfer processes of various supramolecules including imide group(s) as a component. Recently, imides have been employed in various functional molecular systems, because of their excellent photophysical and electron accepting properties. Our research group also employed imides in various supramolecular systems such as donor-acceptor dyads, quantum dots, DNA, and so on. First, we summarize fundamental properties of imides such as photophysical and electrochemical properties. Then, photoinduced processes of imides in the supramolecular systems are described to show their applicability in the various fields.

Photoinduced Electron Transfer From Aromatic Amines to Triplet States of $C_{60}$

  • Yahata, Yukio;Sasaki, Yoshiko;Fujitsuka, Mamoru;Ito, Osamu
    • Journal of Photoscience
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    • 제6권3호
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    • pp.117-121
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    • 1999
  • Photoinduced electron transfer of C60 has been studied by the laser photolysis measuring the transient absorption bands in near-IR region. The electron transfer aromatic amines via the triplet state of C60 is confirmed by the decay of the transient absorption bands of the triplet state of C60 and the rise of the anion radical of C60 and the cation radicals of amines. The rate and efficiency of electron transfer are strongly affected by the donor ability of amines and polarity of solvents. Back electron-transfer kinetics is also strongly affected by the solvent polarity.

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Transient Absorption Spectra of Phenothiazine Derivative in the Vesicle System Containing Ru$^{2+}$ Complex as a Sensitizer

  • Park, Yong-Tae;Kim, Young-Doo;Burkhart, Richard D.;Caldwell, Norris J.
    • Bulletin of the Korean Chemical Society
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    • 제9권2호
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    • pp.84-87
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    • 1988
  • The Photophysical and photochemical properties of Ruthenium bipyridine with two long hydrocarbon chains, $[Ru(bipy)_2(dhbipy)]^{2+}$ and transient phenothiazine derivative cation radical $(PTD^+)$ in the cationic vesicle were studied. Transient absorption spectra of cation radical of phenothiazine derivative in the vesicle system containing the $Ru^{2+}$ complex, $[Ru(bipy)_2(dhbipy)]^{2+}$, (1) as sensitizer and phenothiazine derivative as electron donor was observed by XeCl excimer laser photolysis system. Thus the excited ruthenium complex would be quenched by phenothiazine derivative(PTD) reductively in the vesicle system. The quenching rate constant($K_Q$) of $Ru^{2+}$ with two long hydrocarbon chains in the vesicle by PTD was $9.6{\times}10^8M^{-1}S^{-1}$. The absorption decay kinetics showed that lifetime of phenothiazine derivative cation radical is a value in the 4-8m sec range.

SENSITIZED PHOTOINITIATING SYSTEM USED IN PHOTOPOLYMER FILMS

  • Liu, A.D;Trifunac, A.D;Krongauz, V.V.
    • 한국진공학회지
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    • 제7권s1호
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    • pp.20-24
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    • 1998
  • Photploymer films are widely used in printing and electronic industries, and their usage is expanding to encompass holography, data storage and data processing, optical waveguides and compact disks, etc. One of widely used photoplymerization initiator, 20chloro-hexaarylbiimidazole (o-Cl-HABI), is studied by laser flash photolysis in dichloromethane solution in the absence and presence of the visible light photosensitizing dye, 2, 5-bis[(2, 3, 6, 7 -tetrahydro- 1H, 5H -benzo [i, j,] quinolizin -1-yl) methylene]-cyclopenta-none, (JAW). In the presence of JAW, an increase in triarylimidazolyl radicals L.formation is observed in relative to the absence of JAW. The mechanism of this photosensitizing dissociation is concluded as the dissociation of the o-Cl-HABI radical anion formed by the electron transfer from excited singlet state of JAW to o-Cl-HABI. The observed formation of L.radicals exhibits a linear dependence on o-Cl-HABI concentration. The rate constant of electron transfer obtained from this dependence is equal to (1.0$\pm$0.2) x $10^9 M^{-1}s^{-1}$. No reaction between the excited triplet state of JAW and o-Cl-HABI is found.

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색소 첨가제에 의한 히드록시 라디칼의 광증감 생성반응 (Photosensitized Generation of ydroxyl Radical by Color Additive)

  • 김민식;성대동
    • 한국식품영양학회지
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    • 제10권1호
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    • pp.6-13
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    • 1997
  • 여러 종류의 coumarin 유도체가 광화학 반응에 의하여 OH·라디칼을 생성하는 반응을 ESR 및 레이저 섬광분해 반응으로 진행시키고 반응속도 상수를 구하여 반응성가 메카니즘을 알아보았다. 본 연구에서 사용된 9종류의 coumarin 유도체는 모두 OH·라디칼 생성반응 메카니즘으로 반응이 진행되었으나 1-ethy1-3-nitro-1-nitrosoguanidine은 광조사에 의해 OH·라디칼 생성반응이 일어나기 전에 분해하여 카르벤 중간체로 변하였다. 9개의 coumarin 유도체는 DMPO-OH 스핀부가 생성물에 해당하는 시그날을 나타내었다. OH·라디칼을 소진시키는 NaN3, EtOH, HCOONa 등은 강한 광증감제로 작용하였다. 수화된 전자의 소멸 THRE 상수는 N20을 첨가했을 때가 K3Fe(CN)6을 첨가했을 때보다 크게 나타났다.

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The Effect of S130A Mutant of pharaonis Halorhodopsin on Ability of Chloride Binding and Photocycle

  • Sato, Maki;Kikukawa, Takashi;Araiso, Tsunehisa;Okita, Hirotaka;Shimono, Kazumi;Kamo, Naoki;Demura, Makoto;Nitta, Katsutoshi
    • Journal of Photoscience
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    • 제9권2호
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    • pp.308-310
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    • 2002
  • Bacteriorhodopsin (bR) and halorhodopsin (hR), which exist in the membrane of Halobacterium salinarum, are light-driven ion pumps. In spite of high similarity of primary and tertiary structures between bR and hR, these membrane proteins transport different ions, proton and chloride, in the opposite direction. From alignment of the amino acid sequences, Thr-89 of bR is homologous to Ser-l15 of hR from Halobacterium salinarum (shR). X-ray structure of shR has revealed that OH group of this residue directly interacts with CI$\^$-/ Thus, Ser-lI5 of shR is expected to play an important role in CI$\^$-/ binding and transport. In this study, we expressed wild type hR from Natronobacterium pharaonis (PhR) and Sl30A, which corresponds to Ser-l15 of shR, in E. coli in order to clarify binding affinity of chloride ion and photocycle reactions. From the titration with CI$\^$-/, affinity of Sl30A became quite lower than that of WT (WT 6 mM, Sl30A 89 mM). Furthermore, from the flash photolysis with pulse laser of λ$\_$max/ at 532 nm, the reaction rate of SI30A from 0 intermediate to hR ground state was found to become apparently slower than that of WT. The singular value decomposition (SVD) and global fitting analyses of the photocycles were performed to identify all photointermediates and determine the reaction rates.

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