• 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.

• 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.

• 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.

• 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.

• 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.

• Journal of Photoscience
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• 제5권1호
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• pp.23-26
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• 1998

Irradiation of diphenylbutadiyne (DPB) in methanol with 9,10-dicyanoanthracene (DCA) yields four methanol adducts, two more than the products obtained in the absence of DCA. Laser flash photolysis studies indicate the reaction to proceed through a photoinduced electron transfer mechanism involving DPB cation radical and DCA anion radical.

• Bulletin of the Korean Chemical Society
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• 제16권1호
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• pp.47-52
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• 1995

The mechanism of the photodecomposition of 2-methoxy-1,2-diphenyl diazoethane has been investigated in methanol and isoprene using time-resolved laser flash photolysis techniques. The reaction of triplet carbene which is generated from 2-methoxy-1,2-diphenyl diazoethane with methanol is believed to proceed via thermal excitation to the singlet state. The activation energy and enthalpy are consistent with a mechanism involving thermal equilibrium between the triplet and singlet state followed by the reaction of the singlet with methanol to give ether.

• 대한화학회지
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• 제39권4호
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• pp.237-243
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• 1995

Anthraquinone이 유기용매에서 광반으에 의하여 반응 중간체로 생성하는 짧은 수명의 중성 세미퀴논 라디칼과 음이온 라디칼을 시간분해 ESR법에 의하여 측정하였다. 2-2-propanol (PrOH)과 triethylamine (TEA) 10:1 혼합 용매에서 광반응에 의하여 생성하는 중성 anthrasemiquinone 라디칼(AQH${\cdot}$)과 음이온 라디칼 (AQH${\cdot}$)의 CIDEP 스펙트럼을 측정하였다. 생성한 AQH${\cdot}$은 반감기가 0.8 ${\mu}sec$로 수명이 아주 짧았으며, AQ${\cdot}$-은 안정하여 cwESR의 측정이 가능하였다. 스핀분극된 음이온 라디칼(AQ${\cdot}$-*)의 분극소멸 속도 상수는 $2.6{\times}10^5\; sec^{-1}$이고, 음이온 라디칼의 소멸은 1차 반응으로 속도상수가 $3.0{\times}10^2\; sec^{-1}$이다. 혼합용매에 TEA가 2% 미만일 때 CIDEP가 일어나지 않았다. 벤젠과 TEA 혼합용매에서는 반감기 3.0 ${\mu}sec$의 중성 anthrasemiquinone 라디칼의 CIDEP가 측정되었다. 그러나, cwESR은 측정되지 않았다. PrOH, TEA 또는 벤젠만의 용매로서는 CIDEP와 ESR을 측정할 수 없었다.

• 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.

• 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.