• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.497-499
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• 1993

Irradiation of 4-biphenylyl-4-methyl-2-cyclohexenone (5) in benzene or methanol produced trans-6-biphenylyl-5-methylbicyclo[3,1,0]hexan-2-o ne (5a) and 3-biphenylyl-4-methylcyclohex-2-enone (5b). Electronic configurations of the excited states for 5a and 5b were assigned as n, ${\pi}^*$ and ${\pi}$, ${\pi}^*$ triplet states respectively. Irradiation of 4-methyl-4(${\beta}$-naphthyl)-2-cyclohexenone in benzene or methanol gave 4-methyl-3-(${\beta}$ -naphthyl)-2-cyclohexenone (6a), which is thought to arise from ${\pi}$, ${\pi}^*$ triplet state.

• Bulletin of the Korean Chemical Society
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• v.11 no.3
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• pp.241-244
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• 1990

The photochemistry of 1-Methyl-2-cyclohexenyl aryl ketones (phenyl ketone 7a, p-toluyl ketone 7b, biphenyl ketone 7c and -naphthyl ketone 7d) is reported. The aryl ketone 7a, 7b and 7c undergo photo-racemization with efficiencies of 0.75, 0.79 and 0.76 respectively on direct irradiation. Direct irradiation of the ketone 7d, however, undergoes 1,3-shift with an efficiency of 0.02. Triplet states are responsible for the racemizations and singlet state is responsible for 1,3-shift as in general. The ketone 7a, 7b and 7c are good example of a few ${\beta},{\gamma}$-unsaturated ketones which undergo efficient intersystem crossing on direct irradiation.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.857-860
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• 1994

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

• Journal of Photoscience
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• v.10 no.1
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• pp.9-20
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• 2003

Recent studies on the photoreactivity of l,4-unsaturated systems have changed some ideas that were firmly established in this area of research for many years. Thus, we have described the first examples of 2-aza-di-$\pi$-methane (2-ADPM) rearrangements promoted by triplet-sensitization and by single electron transfer (SET) using electron-acceptor sensitizers. These reactions afford N-vinylaziridine and cyclopropylimine photoproducts in the first examples of di-$\pi$-methane processes that yield three-membered ring heterocycles. l-Aza-1,4-dienes also undergo SET-promoted l-aza-di-$\pi$-methane (l-ADPM) rearrangements via radical-cation intermediates using electron acceptor sensitizers. In some cases, alternative cyclizations yielding different carbocycles and heterocycles have been observed. The l-ADPM and di-$\pi$-methane (DPM) reactions also occur via radical-anion intermediates on irradiation using electron donor sensitizers. On the other hand, the photoreactivity reported for $\beta$,${\gamma}$-unsaturated aldehydes for many years was decarbonylation to the corresponding alkenes. However, our studies demonstrate that these compounds undergo the oxa-di-$\pi$-methane (ODPM) rearrangement with high chemical and quantum efficiency. A comparison of the photochemical reactivity of $\beta$,${\gamma}$-unsaturated aldehydes and corresponding methyl ketones has shown that the ketones do not undergo the ODPM rearrangement while the corresponding aldehydes are reactive by this pathway. Monosubstituted $\beta$,${\gamma}$-unsaturated aldehydes at C-2 undergo the ODPM rearrangement yielding the corresponding cyclopropane carbaldehydes diastereoselectively. Finally, we have described the first examples of reactions, similar to the well know Norrish Type I process, which take place in the triplet excited state of $\beta$,${\gamma}$-unsaturated carbonyl compounds by excitation of the C-C double bond instead of the carbonyl group.

• 한국정보디스플레이학회:학술대회논문집
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• 2008.10a
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• pp.1509-1512
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• 2008

Monomer and aggregate of $Bebq_2$ give fluorescence at 492 and 511 nm at 12 K, respectively. Intense T1 emission with vibronic structure was observed from $Bebq_2$ and $Alq_3$ below 70 K by heavily doping with phosphorescent $Ir(ppy)_3$. Energy transfer from $Ir(ppy)_3$ was clarified by photoluminescence excitation spectra.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.202-205
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• 1987

The reduction of some cyclic conjugated enones with electron-donating substituent on C-3 by sodium borohydride was accelerated on irradiation. The photo-enhanced reduction seems to undergo through zwitterionic species formed from the (n, ${\pi}^{\ast}$) triplet state of conjugated enones, followed by hydride attack to yield unsaturated or saturated alcohols.

• Bulletin of the Korean Chemical Society
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• v.24 no.7
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• pp.916-920
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• 2003

Photoreactions of N-(2,4-dibromonaphthyl)arenecarboxamides in basic medium result in the intramolecular substituted products, 2-aryl-8-bromonaphthoxazoles in moderate yields and further photoreactions of the products afford the reduced products, 2-arylnaphthoxazoles. These reactions are straightforward for syntheses of naphthoxazole derivatives. Since the intramolecular photosubstitution of the bromoarenecarboxamide by the oxygen of its amide group is more effective than the photoreduction of the substituted product, 2-aryl-8- bromonaphthoxazole in basic medium, the intramolecular substituted product, 2-aryl-8-bromonaphthoxazole can be isolated. A charge-transfered excited singlet state of an imidol form of the 2-bromoarenecarboxamide is involved in the photosubstitution, whereas an excited triplet state of the 2-aryl-8-bromonaphthoxzole is closely involved in the photoreduction.

• KSII Transactions on Internet and Information Systems (TIIS)
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• v.13 no.9
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• pp.4665-4683
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• 2019

Previous methods build image annotation model by leveraging three basic dependencies: relations between image and label (image/label), between images (image/image) and between labels (label/label). Even though plenty of researches show that multiple dependencies can work jointly to improve annotation performance, different dependencies actually do not "work jointly" in their diagram, whose performance is largely depending on the result predicted by image/label section. To address this problem, we propose the adaptive attention annotation model (AAAM) to associate these dependencies with the prediction path, which is composed of a series of labels (tags) in the order they are detected. In particular, we optimize the prediction path by detecting the relevant labels from the easy-to-detect to the hard-to-detect, which are found using Binary Cross-Entropy (BCE) and Triplet Margin (TM) losses, respectively. Besides, in order to capture the inforamtion of each label, instead of explicitly extracting regional featutres, we propose the self-attention machanism to implicitly enhance the relevant region and restrain those irrelevant. To validate the effective of the model, we conduct experiments on three well-known public datasets, COCO 2014, IAPR TC-12 and NUSWIDE, and achieve better performance than the state-of-the-art methods.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.607-613
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• 1989

The chemical equilibria of Ni(II)-tetraamine (tetraamine = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene) complex ion in water, acetonitrile, acetone and nitromethane were investigated using spectrophotometric method, respectively. The equilibria between low-spin ($D_{4h}$) and high-spin ($O_h$) structures of Ni-tetraamine complex ion were presented in water, acetonitrile and acetone, but not in nitromethane. The eqilibrium constants, the reaction enthalpies and the reaction entropies were determined from analysis of the temperature dependence of the electronic spectra. The formation of the triplet species ($O_h$) was found to be exothermic. The solvent and electrolyte effects on the equilibrium constants could be explained by the dielectric constants of solvents and the reaction entropies.

• Journal of Photoscience
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• v.9 no.2
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• pp.515-517
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• 2002

Photodynamic therapy (PDT) is a cancer treatment modality which utilizes the cytotoxicity of the active singlet oxygen derived from irradiation of a tumor accumulated photosensitizer. As the oxygen in the singlet state radiates an emission of 1270nm wavelength when it decays to the triplet state, detection of the emission helps us to understand the mechanism of PDT or to evaluate photosensitizers. We detected the 1270nm emission from photosensitizers Photofrin and ATX-SI0 in vitro and in vivo by means of high sensitive NIR detectors. We obtained the maximum amount of singlet oxygen at irradiation wavelength of 665-670nm from a HeLa tumor in a nude mouse which is injected with ATX-S10.