• Title/Summary/Keyword: Laser flash photolysis

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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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    • v.8 no.2
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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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    • v.3 no.1
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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.

SENSITIZED PHOTOINITIATING SYSTEM USED IN PHOTOPOLYMER FILMS

  • Liu, A.D;Trifunac, A.D;Krongauz, V.V.
    • Journal of the Korean Vacuum Society
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    • v.7 no.s1
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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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Photosensitized Generation of ydroxyl Radical by Color Additive (색소 첨가제에 의한 히드록시 라디칼의 광증감 생성반응)

  • 김민식;성대동
    • The Korean Journal of Food And Nutrition
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    • v.10 no.1
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    • pp.6-13
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    • 1997
  • Reactivity and reaction mechanism for the photosensitized generation of hydroxyl radical by various coumarin derivatives are investigated by means of ESR and laser flash photolysis methods. The nine kinds of coumarin derivatives show to be proceeded through the OH·radical generation mechanism, however 1-ethyl-3-nitro-1-nitrosoguanidine decomposes and produces the carbene intermediate before OH·radical generation reaction occurs. The nine coumarin derivatives show the signals, which are corresponded to DMPO-OH spin adducts. NaN3, EtOH and HCOONa act as a strong photosensitizer to quench OH·radical. The decay rate constants of the hydrated electrons in the case of added N2O show higher than added K3Fe(CN)6.

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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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    • v.9 no.2
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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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A Gas-Phase Investigation of Oxygen-Hydrogen Exchange Reaction of O(3P) + C2H5 → H(2S) + C2H4O

  • Jang, Su-Chan;Park, Min-Jin;Choi, Jong-Ho
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.839-844
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    • 2014
  • The gas-phase radical-radical reaction $O(^3P)$ + $C_2H_5$ (ethyl) ${\rightarrow}$ $H(^2S)$ + $CH_3CHO$(acetaldehyde) was investigated by applying a combination of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration and ab initio calculations. The two radical reactants $O(^3P)$ and $C_2H_5$ were respectively produced by photolysis of $NO_2$ and supersonic flash pyrolysis of the synthesized precursor azoethane. Doppler profile analysis of the nascent H-atom products in the Lyman-${\alpha}$ region revealed that the average translational energy of the products and the average fraction of the total available energy released as translational energy were $5.01{\pm}0.72kcalmol^{-1}$ and 6.1%, respectively. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title exchange reaction is a major channel and proceeds via an addition-elimination mechanism through the formation of a short-lived, dynamical addition complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed small kinetic energy release can be explained in terms of the loose transition state with a product-like geometry and a small reverse activation barrier along the reaction coordinate.