• 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.

• 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.

• 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.

• 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.

• 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.

• Journal of Photoscience
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• v.5 no.1
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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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• v.16 no.1
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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.

• Journal of the Korean Chemical Society
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• v.39 no.4
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• pp.237-243
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• 1995

The measurments of neutral semiquinone radicals, which were formed from the laser flash photolysis of anthraquinone (AQ) in the mixed solvents were carried out by the time resolved electron spin resonance (trESR) spectroscopy. The chemically induced dynamic electron polarization (CIDEP) spectra of the neutral semiquinone radical (AQH${\cdot}$) and semiquinone radical anion (AQ${\cdot}$-) were successively detected in the laser flash photolysis of AQ in the mixtures of 2-propanol (PrOH) and triethylamine (TEA). The neutral semiquinone radical was short-lived with the half-life of 0.8 ${\mu}sec$, whereas the semiquinone radical anion was relatively stable and then its cwESR could be observed. The rate constant of the spin-depolarization of semiquinone radical anion was $2.6{\times}10^5 sec^{-1}$ and the decay of the radical anion was the first order reaction with the rate constant of $3.0{\times}10^2\; sec^{-1}$. No CIDEP of semiquinone radical anion was observed in the mixture of PrOH and the lower concentration of TEA than 2 percent. The CIDEP spectrum of the neutral semiquinone radical was detected in the mixture of benzene and TEA with the half-life of 3.0 ${\mu}sec$. The neutral semiquinone radical could not be detected by cwESR. Neither CIDEP nor ESR absorption could be observed in PrOH, TEA or benzene only.

• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.404-412
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• 1990

The time resolved electron spin resonance spectroscopy are used to two measurement methods of chemically induced dynamic electron polarization (CIDEP) and absorption ESR. The spectra of the semiquinone radical anion were successively detected in the laser flash photolysis of anthraquinone in the mixtures of 2-propanol and triethylamine. The semiquinone radical anion was fairly stable and its cw ESR could be observed. The rate constant (T1$^{-1}$) of the spin-depolarization of polarized semiquinone radical anion was 2.6 ${\times}\;1-^5$ sec$^{-1}$ and the decay of the radical anion was the first order with the rate constant (K$_1}$) of 300.0 sec$^{-1}$. The intensity of CIDEP spectra increased with the increasing the microwave power, but the Torrey wiggles appeared following with decay curves.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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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.