• 제목/요약/키워드: Laser Photolysis

검색결과 33건 처리시간 0.019초

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

  • 심상철;신은주;채규호
    • Bulletin of the Korean Chemical Society
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    • 제6권4호
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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.

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

  • 김민식;채기수;김갑순;성대동
    • 한국식품영양학회지
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    • 제11권3호
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    • pp.267-271
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    • 1998
  • Seyferth 시약인 phenyl(tribromomethyl) mercury 및 diazomethane의 식품보존제인 dehydroacetic acid 및 coumarin과의 발암성과 그 반응기작을 분자 구조적 관점에서 알아보기 위하여 UV/vis 조건과 laser flash photolysis 시켰을 때의 결과는 다음과 같다. 1. Diazomethane과 Phenyl(tribromomethyl) mercury와 dehydroacetic acid와 diazomethane과의 반응은 광화학적 분해 반응에서 생성된 : CBr2와 : CH2 카르벤 중간체의 이탈기 효과에 따라 발암성이 크게 나타났다. 2. laser flash photolysis 상에서 반응시켰을 때 식품보존제의 발암성이 UV/vis 상에서의 photolysis 때보다 크게 나타났다.

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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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    • 제23권2호
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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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    • 제3권2호
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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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    • 제10권5호
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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.

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

  • 이기환;양준묵;윤민중
    • 대한화학회지
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    • 제34권3호
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    • pp.255-259
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    • 1990
  • Benoxaprofen (BXP)의 들뜬상태를 직접 검출하기 위하여, 질소 레이저 플래쉬 광분해 분광기를 제작하였다. 이 분광기의 성능을 확인하기 위하여 표준시료로써 안트라센을 사용하여 실험하였다. 에탄올에 녹은 BXP의 레이저 광들뜸을 질소기체 존재하에서 수행하였으며 파장범위 400-600 nm에 걸쳐 순간흡수 스펙트럼을 측정하고 이에 대한 산소 및 베타 카로틴의 효과를 조사하였다. 그 결과 415nm에서의 최대순간흡수띠는 BXP의 삼중항 상태에 기인하며 삼중항 에너지는 22 Kcal/mole 이상임을 확인하였다. 또한, BXP의 라디칼로 추정되는 중간체에 기인하는 최대순간 흡수띠가 520nm에 관측되었다. 이들 결과에 의해 BXP의 광증감 메카니즘을 논의하였다.

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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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    • 제21권6호
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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.

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

  • 김창현;임형순;조용재;정찬수;장동명;명윤;김한성;백승혁;임영록;박정희;송민섭;조원일;차은희
    • 전기화학회지
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    • 제15권3호
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    • pp.181-189
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    • 2012
  • ND-YAG 펄스 레이저를 사용하여 밀폐 반응기에서 가스상 $Ge(CH_3)_4$ (tetramethyl germanium, TMG)을 광분해하여 Ge (germanium) 나노입자를 합성하는 새로운 합성법을 개발하였다. 나노입자의 크기는 간단히 충돌이완가스를 사용하여 5-100 nm로 조절할 수 있었다. $Ge_{1-x}Si_x$ 합금 나노입자는 TMG와 $Si(CH_3)_4$ (tetramethyl silicon, TMS) 혼합가스를 광분해하여 합성하였으며, 이때 반응기 안의 가스 혼합비율에 따라 나노입자의 조성을 조절할 수 있었다. 합성된 나노입자는 얇은 탄소층(1-2 nm) 에 싸여있고, 안정한 콜로이드 용액형태로 잘 분산되어 있다. 합성된 Ge 나노입자와 Ge-RGO (reduced graphene oxide) 하이브리드 구조체 모두 리튬이온전지 특성이 50 사이클 이후 각각 800, 1,100 mAh/g의 높은 방전용량을 갖는 것을 확인하였고, 이 방법은 이전의 Ge 나노입자 합성법과 비교하여 높은 수득률, 우수한 재현성, 성분조절의 용이 하므로, 고성능 리튬 전지의 개발을 위한 음극소재로 기대된다. 이와 같은 Ge 나노입자의 새로운 대량 합성법은 고성능 에너지 변환 소재 실용화에 기여할 것으로 예상된다.

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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    • 제32권6호
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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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