• Title/Summary/Keyword: Photolysis

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Numerical Simulation of Fluorescent Whitening Agents (DAS1) in Tokyo Bay (동경만 형광표백제 성분물질(DAS1)의 거동 특성 시뮬레이션)

  • Kim, Dong-Myung
    • Journal of Environmental Science International
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    • v.20 no.4
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    • pp.519-525
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    • 2011
  • A three-dimensional ecological model(EMT-3D) was applied to DAS1 in Tokyo Bay. The simulated results of DAS1 were in good agreement with the observed values. The result of sensitivity analysis showed that photolysis coefficient and extinction coefficient were important factor for dissolved DAS1, and photolysis coefficient, extinction and POC partition coefficient for PAHs in particulate organic matter. Mass balance of DAS1 in Tokyo Bay was calculated by using the simulated results of EMT-3D.

N(2D) Product Velocity Mapped Imaging in the VUV Photolysis of Nitrous Oxide at 118.2 nm

  • Cosofret, Bogdan R.;Lambert, H. Mark;Houston, Paul L.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.179-183
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    • 2002
  • Resonance-enhanced multiphoton ionization with time-of-flight product imaging of the $N(^2D)$ atoms has been used to study the $N_2O$ photodissociation at 118.2 nm and the two-photon dissociation at 268.9 nm. These imaging experiments allowed the determination of the total kinetic energy distribution of the $NO(X^2{\prod})$ and $N(^2D_{5/2})$ products. The $NO(X^2{\prod})$ fragments resulting from the photodissociation processes are produced in highly vibrationally excited states. The two-photon photodissociation process yields a broad $NO(X^2{\prod})$ vibrational energy distribution, while the 118.2 nm dissociation appears to produce a vibrational distribution sharply peaked at $NO(X^2{\prod},\;{\nu}=14)$.

Conformational Dynamics of Heme Pocket in Myoglobin and Hemoglobin

  • Kim, Seong-Heun;Heo, Jeong-Hee;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.151-156
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    • 2005
  • The conformational dynamics of heme pocket, a small vacant site near the binding site of heme proteins -myoglobin (Mb) and hemoglobin (Hb), was investigated after photolysis of carbon monoxide from MbCO and HbCO in D$_2$O solution at 283 K by probing time-resolved vibrational spectra of photolyzed CO. Two absorption bands, arising from CO in the heme pocket, evolve nonexponentially in time. The band at higher energy side blue shifts and broadens with time and the one at lower energy side narrows significantly with a negligible shift. These spectral evolutions are induced by protein conformational changes following photolysis that modify structure and electric field of heme pocket, and ligand dynamics in it. The conformational changes affecting the spectrum of photolyzed CO in heme pocket likely modulates ligand-binding activity.

KINETICS OF ATRAZINE OXIDATION BY UV RADIATION AND OXALATE ASSISTED H2O2/UV PROCESSES

  • Choi, Hyun-Jin;Choi, Jong-Duck;Kim, Hyun-Kab;Lee, Tae-Jin
    • Environmental Engineering Research
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    • v.11 no.1
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    • pp.28-32
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    • 2006
  • The degradation of atrazine was explored using UV alone, $H_2O_2/UV$, oxalate/UV and oxalate-assisted $H_2O_2/UV$. The addition of oxalate to the $H_2O_2/UV$ (oxalate-assisted $H_2O_2/UV$) process was the most effective method for the degradation of atrazine. The overall kinetic rate constant was split into the direct oxidation due to photolysis and that by the radicals from hydrogen peroxide or oxalate. In semi-empirical terms, the initial concentration of hydrogen peroxide had a greater contribution than that of oxalate for atrazine oxidation.

PHOTOEVOLUTION OF HYDROGEN FROM AQUEOUS ALCOHOL WITH AGAROSE GEL SYSTEM CONTAINING CdS or $TiO_2$PARTICLES

  • Park,Yong-Tae;Lee, Sang-Gyun;Cheong, Jong-Jae;Lee, Jai-Young
    • Journal of Photoscience
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    • v.5 no.1
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    • pp.27-31
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    • 1998
  • An artificial photolysis system of water or aqueous alcohol is studied. Upon irradiation of agarose gel system containing colloidal CdS or TiO$_2$ particles with Rh catalyst, hydrogen and oxygen are produced from water. When an alcohol is used as an electron donor in the agarose system, hydrogen and oxidized form of alcohol, the corresponding an aldehyde, is produced. The photolysis mechanism of water or alcohol in the agarose system is proposed.

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PHOTOCHEMISTRY OF 1-PHENYL-4-(PENTAMETHYLDISILANYL)BUTA-1,2-DIYNE:$[PdCI_2(PPh_3)_2]$-CATALYZED REACTION

  • Lee, Seong-Taek;Baek, Eun-Kyung;Shim, Sang-Chul
    • Journal of Photoscience
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    • v.1 no.2
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    • pp.119-122
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    • 1994
  • $PdCI_2(PPh_3)_2$-catalyzed photolysis of 1-phenyl-4-(pentamethyldisilanyl)buta-1,3-diyne (1) in dry benzene gives 1,4-disilacyclohexa-2,5-diene type dimerization products(3-6) via silacyclopropene. The silacyclopropene is formed from the singlet excited state of 1 and this silacyclopropene reacts with $(PPh_3)_2Pd^0$to form palladasilacyclobutene. In this reaction, the silylene-palladium complex is generated and reacts with 1 to give another silacyclopropene. $PdCI_2(PPh_3)_2$catalyzed photolysis of 1 with other alkynes supports the involvement of this silylene complex.

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A Novel Photoreaction of (2-Hydroxyethoxyphenyl)pentamethyldisilane

  • Park, Seung Ki;Seong, Won-Je
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1331-1336
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    • 2009
  • Photolysis of (2-hydroxyethoxyphenyl)pentamethyldisilane 2 in benzene provides a novel intramolecular cyclization photoproduct 9 which was probably formed from the intramolecular reaction to form a seven-membered ring in silatriene intermediate 7 and then the photochemical disrotatory ring closure of 1,3-butadiene moiety to cyclobutene. Irradiation of 2 in methanol afforded photoproducts 5 and 6 which were formed by the nucleophilic attack of methanol to $\beta$ or $\alpha$ silicon atom in pentamethyldisilanyl group of the photoexcited state of 2. Compounds 10 and 11 were also formed by the same way as in the formation of the photoproducts 5 and 6 in the photolysis of (2-allyloxyethoxyphenyl)pentamethyldisilane 3 in methanol solvent. Photoreaction of (2-acetoxyethoxyphenyl) pentamethyldisilane 4 in methanol gave a photoproduct 12 which was formed via the elimination of dimethylsilylene species in the photoexcited state of 4.

A Study on the Degradation Characteristics of EPN (EPN의 분해특성에 관한 연구)

  • 이용두;김현희;김창영
    • Journal of Environmental Science International
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    • v.11 no.10
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    • pp.1103-1108
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    • 2002
  • In order to evaluate the degradation organophosphorus pesticide, EPN, in water environment, the effects of water temp.(10$^{circ}C,\;30^{\circ}C$), pH(3-11) and sunlight on its degradation were investigated during 10 days. The degradation rate of EPN(200 rpm) was faster at higher water temp. and higher pH, i.e., its degradation rate at pH 3, 5, 7, 9, 11 was 57, 63, 66, 69, 75%(1$0^{\circ}C$), and 70, 74, 79, 91, 97%(3$0^{\circ}C$) after 10 days, respectively. The effect of water temp. on its degradation was little in acidic condition, but was rather great in alkaline condition, with time. EPN was degraded fast at the alkaline condition by photolysis. At the condition of pH 11, EPN was degraded fast at the early stage in the first 2 days, but after that the degradation rate was weakened.

A Study on the Reaction of Icosahedral Carborane with Carbenes

  • Sung, Dae-Dong;Lee, Jae-Duck;Choi, Soon-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.8 no.2
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    • pp.63-68
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    • 1987
  • The photolysis and thermal reaction of hexafluorobenzene solution of icosahedral dicarba-closo-dodecaborane and various carbenes have been shown to lead to the formation of four isomeric insertion products to icosahedral molecules. The results showed the carbene insertion reaction to 1, 2-dicarba-closo-dodecaborane to occur at the positions of 4-, 5-, 7-, and 11-borons, 9-, and 12-borons 3-, and 6-borons and 8-, and 10-borons. The samples of 1, 7-, and 1, 12-dicarba-closo-dodecaborane with carbenes in hexafluorobenzene by photolysis showed no reaction. To find out the reactivities of carbenes to dicarba-closo-dodecaboranes, the total energies have been calculated and have been discussed the tendency for carbene insertion reactions to icosahedral carboranes.

Reaction of Triethylsilyl Radical with Sulfides, a Laser Flash Photolysis Study

  • Platz, M. S.;Lee, Woo-Bung
    • Bulletin of the Korean Chemical Society
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    • v.10 no.5
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    • pp.422-426
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    • 1989
  • Triethylsilyl radical was generated by laser flash photolysis of a 1:1 (v/v)solution of triethylsliance and di-tert-butyl peroxide. The silicon centered radical was reacted with sulfides to give carbon centered radicals by displacement at sulfar. The carbon radicals were readily detected by their transient absorption spectra. The absolute rate of reaction of triethylsilyl radical with 9-fluorenylphenylsulfide, di-n-butylsulfide, di-sec-butyl, di-tert-butyl sulfide and di-n-butyl disulfide are $2.40{\pm}0.12{\times}10^8M^{-1}s^{-1}$, $11.21{\pm}0.89{\times}10^6M^{-1}s^{-1}$, $8.79{\pm}0.73{\times}10^6M^{-1}s^{-1}$, $3.29{\pm}0.18{\times}10^6M^{-1}s^{-1}$, and $3.41{\pm}0.09{\times}10^8M^{-1}s^{-1}$, respectively.