• Title/Summary/Keyword: Laser Photolysis

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Nanosecond Laser Flash Photolysis Study of 5-Styryl-1,3-dimethyluracil

  • Shim Sang Chul;Shin Eun Ju;Chae Kyu Ho
    • Bulletin of the Korean Chemical Society
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    • v.6 no.4
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    • pp.234-238
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    • 1985
  • The photoisomerization of 5-styryl-1,3-dimethyluracil is studied with nanosecond laser flash photolysis technique at room temperature. The laser flash photolysis of E-isomer produces the transient absorption spectrum regarded as the triplet-triplet absorption, but the transient absorption of Z-isomer does not show the typical decay curve, probably due to the facile photocyclization reaction during the laser flash photolysis. Using the energy transfer method on nanosecond laser spectroscopy, the energy of the lowest triplet state for E isomer is estimated to lie between 41.8 and 47 kcal/mol. The triplet lifetime for E-isomer obtained from the decay curve of the transient absorption is ca. 93ns. The $S_1 → T_1$ intersystem crossing of E-isomer on direct excitation is relatively inefficient at room temperature supporting the singlet mechanism for direct photoisomerization.

Photochemical and Thermal Reaction Mechanism for the Reaction of Carcinogenic Molecules and Food Reservatives (발암성 분자와 식품보존제의 광화학 및 열적 반응메카니즘)

  • 김민식;채기수;김갑순;성대동
    • The Korean Journal of Food And Nutrition
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    • v.11 no.3
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    • pp.267-271
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    • 1998
  • The photochemical carcinogenic reaction mechanism and molecular carcinogenic intensity through the reaction of dibromo carbene and diazomethane with dehydroacetic acid and coumarin have been studied under the two kinds of photolysis. The reaction intensities show the degree of carcinogenic activity. Under the condition of UV/vis light source, the yield of high toxic carcinogenetic carbene intermediate is produced less than those of the laser flash photolysis.

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Depletion Kinetics of the Ground State CrO Generated from the Reaction of Unsaturated Cr(CO)x with O2 and N2O

  • Son, H.S.;Ku, J.K.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.2
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    • pp.184-188
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    • 2002
  • Unsaturated $Cr(CO)_x(1{\leq}x{\leq}5)$molecules were generated in the gas phase from photolysis of $Cr(CO)_6$vapor in He using an unfocussed weak UV laser pulse and their reactions with $O_2$ and $N_2O$ have been studied. The formation and disappearance of the ground state CrO molecules were identified by monitoring laser-induced fluorescence(LIF) intensities vs delay time between the photolysis and probe pulses. The photolysis laser power dependence as well as the delay time dependence of LIF intensities from the CrO orange system showed different behavior as those from ground state Cr atoms, suggesting that the ground state CrO molecules were generated from the reaction between $O_2/N_2O$ and photo-fragments of $Cr(CO)_6$ by one photon absorption. The depletion rate constants for the ground state CrO by $O_2$ and $N_2O$ are $5.4{\pm}0.2{\times}10^{-11}$ and $6.5{\pm}0.4{\times}10^{-12}cm^3molecule^{-1}s^{-1}$, respectively.

LASER FLASH PHOTOLYSIS STUDY ON THE PHOTOCYCLIZATION OF N-(O-HALOBENZYL) IMIDAZOLE

  • Park, Yong-Tae;Hwang, Young-Sun;Song, Woong Song;Kim, Dongho
    • Journal of Photoscience
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    • v.3 no.2
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    • pp.91-93
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    • 1996
  • In connection with our interest on the photochemical properties of heteroaryl halides, which are currently the subject of heterocyclic ring formation and haloarene degradation, we have studied the photochemistry of the haloarene linked to N-heteroarene compounds. Imidazo[5,1-a]isoindole was synthesized from N-(ochlorobenzyl)imidazole or N-(o-bromobenzyl) imidazole in acidic aqueous solution or acetonitrile via the intramolgcular photocyclization (Table 1). This type of reaction provides the synthetic methods for 5- and 6-membered polyheteroatomic heterocyclic ring compounds. However, the reaction mechanism for the intramolecular photocyclization of haloarene tethered heteroarenes has not yet been established. Grimshaw et al. suggested a mechanism for homolyric carbonhalogen bond fission assisted by radical complexation to explain their results in the photocyclization of 5-(2-chlorophenyl)-1,3-diphenylpyrazole. They also reported the detection of acyclohexadienyl intermediate involved in the above reaction. Park et al. reported several transient 'intermediates involved in the laser flash photolysis of N-(o-halobenzyl) pyridinium and N-benzyl-2-halopyridinium salts. Thus we performed the laser flash photolysis study on the photocyclization reaction of N-(o-chlorobenzyl) imidazole to identify the intermediate species involved in the reaction. Here, we report on the preliminary results in the photocyclization reaction of N-(o-halobenzyl)imidazole through the detection of reaction intermediates.

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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.

$N_2$-Laser Flash Photolysis study of Photosensitizing Properties of Benoxaprofen ($N_2$-레이저 플래쉬 광분해 방법에 의한 Benoxaprofen의 광증감 작용에 관한 연구)

  • Lee, Gi Hwan;Yang, Jun Muk;Yun, Min Jung
    • Journal of the Korean Chemical Society
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    • v.34 no.3
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    • pp.255-259
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    • 1990
  • The nitrogen-laser flash photolysis apparatus has been set up to detect directly the transient produced from the excited Benoxaprofen (BXP). The function of the instrument has been tested by using anthracene as a standard sample. The laser photoexcitation of BXP in ethanol has been carried out under a constant stream of $N_2$ gas and a transient absorption spectrurn has been recorded over the 400-600 nm. The effects of oxygen and ${\beta}-carotene$ on the transient spectrum reveal that thee maximum transient absorption at 415 nm is attributed to the triplet state of BXP and the triplet energy of BXP is above 22 Kcal/mole. In addition to the triplet state, another transient species has been observed to be produced, which is probably a radical form of BXP. The photosensitization mechanism of BXP is discussed based on these results.

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Depletion Kinetics of Ground State FeO Molecules by $O_2, N_2O, and \;N_2$

  • Son, H. S.
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.583-587
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    • 2000
  • Depletion kinetics of ground state FeO molecules by $0_2$, $N_2O$ and $N_2$ has been studied at room temperature. The ground state FeO molecules were generated by photolysis of a $Fe$(CO)_5$/M(O_2$, $N_2O)/He$ mixture using an unfocused weak UV laser beam. The formation of ground state FeO molecules was identified by a laser-induced fluorescence (LIF) method. The intensity distribution of those undisturbed rotational lines suggests that the rotational temperature of the ground state FeO molecules is lower than room temperature. The LIF intensities of FeO molecules at different partial pressures of $0_2$, $N_2O$ and $N_2$ were monitored as a function of the time delay between the photolysis and probe laser pulses to obtain the depletion rate constants for the ground state FeO. They were 1.7+ 0.2x $10^{-12}$, 4.8 $\pm0.4$ x $10^{-12}$, and $1.4\pm$ 0.2x $10^{-12}cm^3$molecule^{-1}s^{-1}$$ by $0_2$, $N_20$, and $N_2$, respectively.

High-Yield Gas-Phase Laser Photolysis Synthesis of Germanium Nanocrystals for High-Performance Lithium Ion Batteries (고성능 리튬이온 전지를 위한 저마늄 나노입자의 가스상 레이저 광분해 대량 합성법 개발)

  • Kim, Cang-Hyun;Im, Hyung-Soon;Cho, Yong-Jae;Chung, Chan-Su;Jang, Dong-Myung;Myung, Yoon;Kim, Han-Sung;Back, Seung-Hyuk;Im, Young-Rok;Park, Jeung-Hee;Song, Min-Seob;Cho, Won-Il;Cha, Eun-Hee
    • Journal of the Korean Electrochemical Society
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    • v.15 no.3
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    • pp.181-189
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    • 2012
  • We developed a new high-yield synthesis method of free-standing germanium nanocrystals (Ge NCs) by means of the gas-phase photolysis of tetramethyl germanium in a closed reactor using an Nd-YAG pulsed laser. Size control (5-100 nm) can be simply achieved using a quenching gas. The $Ge_{1-x}Si_x$ NCs were synthesized by the photolysis of a tetramethyl silicon gas mixture and their composition was controlled by the partial pressure of precursors. The as-grown NCs are sheathed with thin (1-2 nm) carbon layers, and well dispersed to form a stable colloidal solution. Both Ge NC and Ge-RGO hybrids exhibit excellent cycling performance and high capacity of the lithium ion battery (800 and 1100 mAh/g after 50 cycles, respectively) as promising anode materials for the development of high-performance lithium batteries. This novel synthesis method of Ge NCs is expected to contribute to expand their applications in high-performance energy conversion systems.

Study on A Laser-induced Photoredox Reaction for the Extraction of Precious Elements from Aqueous Solutions

  • Kyuseok Song;Hyungki Cha;Lee, Jongmin;Park, Jongsoo;Lee, Yong-Ill
    • Nuclear Engineering and Technology
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    • v.32 no.6
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    • pp.531-536
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    • 2000
  • The extraction of precious metals from aqueous solutions is performed by using a photoredox reaction with a Q-switched Nd:YAG laser. The metallic silver was efficiently precipitated and extracted from the silver nitrate solution by laser photolysis. An optimum reaction condition for silver extraction was determined by adjusting various experimental factors such as type of reducing agent, type of acids and reaction time. The composition of the reaction product was analyzed and it was identified as metallic silver, not other molecular types. The photoreaction of chromium(III) chloride in an acidic aqueous solution was also investigated. The 355 nm laser light was better suited for the reaction of silver nitrate as well as chromium(III) chloride in an acidic solution compared to the 532 nm light.

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