• Journal of Photoscience
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• v.12 no.1
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• pp.47-50
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• 2005

Mediumeffects have been explored on the competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl-substituted phenyl ketones. The chemical selectivities of photochemical reactions of silylalkyl phenyl ketones appear to depend on medium polarity, medium silophilicity, added metal cation and alkyl length. Irradiations of silylalkylketones in aqueous solvent system and in presence of metal cation such as $Li^+$ and $Mg^{+2} $lead to formation of acetophenone predominantly by the sequential SET-silyl transfer route.

• Bulletin of the Korean Chemical Society
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• v.26 no.5
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• pp.791-794
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• 2005

A visible photochemistry of maleic to fumaric acid adsorbed on silver nanoparticle surfaces was investigated as probed by SERS using a simple flow method. Photoisomerization of maleic to fumaric acid was consecutively observed in the condition of various flow rates, which varied the exposure time of laser beam. The sequential SERS spectra of maleic acid indicated that the photochemical isomerization and desorption took place simultaneously on silver nanoparticle surfaces as a function of laser fluency and wavelength. For 530.9nm laser line excitation, the rate constant coefficients were obtained with a = 5.9 $sec^{-1}$ mW for isomerization and b = 13.9 $sec^{-1}$ mW for desorption, which $k_1\;=\;aI^n\;and\;k_2\;=\;bI^m$. Both reactions were one photon process (n = 1, m = 1) of a visible light and relatively fast process whose decay time was in the range of milli-second for 50 mW laser power. The rate of photochemical reaction increased on going toward the blue and photodesorption was a dominant process. A simple flow method used in this study was very useful to study a relatively fast photochemical reaction of molecules adsorbed on silver nanoparticle surfaces.

• Journal of Photoscience
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• v.10 no.1
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• pp.89-96
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• 2003

Two important types of $\alpha$-heterolytic fragmentation reactions of aminium radicals are discussed. In these fragmentation processes, transfer of electrofugal groups from the aminium radicals to either Lowry-Bronsted or Lewis bases produces $\alpha$-amino radicals. The results of recent studies that provided key information about the dynamics of the important aminium radical fragmentation reactions, deprotonation, desilylation, are summarized. Finally, selected examples, which demonstrate how knowledge of the relative rates of aminium radical cleavage can be used to design synthetically relevant SET-promoted photocyclization reactions, are presented.

• Proceedings of the Korea Air Pollution Research Association Conference
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• 2006.04a
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• pp.257-258
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• 2006

• Journal of Photoscience
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• v.1 no.2
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• pp.123-126
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• 1994

Irradiation of aromatic $\alpha$-diketones, such as benzil, 4,4'-dimethylbenzil, 4-chlorobenzil, 4,4'-diisopropylbenzil, 3,3,'-dimethylbenzil, in methanol gives rise to xanthone derivatives, in addition to $\alpha$-hydroxyketones. Irradiation of 4,4'-dibromobenzil, 2,2'-pyridil, 2,2'-naphthil and 9,9'-anthril yields only $\alpha$-hydroxyketones, whereas 4,4'-dimethoxybenzil yields methyl 4-methoxybenzoate.

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.42-44
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• 2004

Valerophenones containing a substituent at alpha position to the carbonyl group show the remarkable substituent effects on their photochemical reactions. ${\alpha}$-Bromovalerophenone gives only the C-Br bond cleavage products, but the ${\alpha}$-chlorovalerophenone follows the classical Norrish/Yang reaction pathway predominantly.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.743-748
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• 1994

Photochemical reactions of saccharin with tertiary amines were explored. Saccharin was found to undergo an acid-base reaction with N-trimethylsilylmethyl-N,N-diethyl amine to form N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin salt which is in equilibrium with free saccharin and N-trimethylsilylmethyl-N,N-diethyl amine insolution. Photoreaction of N-trimethylsilylmethyl-N,N-diethyl ammonium saccharin in $CH_3OH\;or\;CH_3CN$ results in the generation of desilylmethylated product, N,N-diethyl ammonium saccharin mainly along with benzamide. Photoreaction of N-methylsaccharin with N-trimethylsilylmethyl-N,N-diethyl amine in $CH_3OH$ leads to the production of o-(N-methylcarbamoyl)-N-ethylbenzenesulfonamid e as the major product along with N-methylbenzamide as the minor product. On the other hand, photoreaction of N,N,N-triethyl ammonium saccharin, generated from saccharin and triethylamine, produces N-methylbenzamide as the exclusive product. These photoreactions are quenched by oxygen indicating that triplets of saccharin and N-methylsaccharin are the reactive excited states. Based on the consideration of the redox potentials of saccharin and N-trimethylsilylmethyl-N,N-diethyl amine, and the nature of photoproducts, pathways involving initial triplet state single electron transfer are proposed for photoreactions of the saccharins with the ${\alpha}$-silylamine.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2453-2458
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• 2010

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.

• Journal of Environmental Science International
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• v.17 no.10
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• pp.1169-1182
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• 2008

The chemical and meteorological effects on the concentration variations of air pollutants ($O_3$ and its precursors) were evaluated based on ground observation data in coastal and inland regions, Busan during springs and summers of 2005-2006. For the purpose of this study, study areas were classified into 5 categories: coastal area (CA), industrial area (IA), downtown area (DA), residential area (RA), and suburban area (SA). Two sites of Dongsam (DS) and Yeonsan (YS) were selected for the comparison purpose between the coastal and inland regions. $O_3$ concentrations in CA and SA were observed to be highest during spring (e.g., 40 ppb), whereas those in DA and RA were relatively low during summer (e.g., $22\sim24$ ppb). It was found that $O_3$ concentrations in IA were not significantly high although high VOCs (especially toluene of about 40 ppb) and $NO_x$ ($\geq$ 35 ppb) were observed. On the other hand, the concentration levels of $O_3$ and $PM_{10}$ at the DS site were significantly higher than those at the YS site, but $NO_x$ was slightly lower than that at the YS site. This might be caused by the photochemical activity and meteorological conditions (e.g., sea-land breeze and atmospheric stagnance). When maximum $O_3$ (an index of photochemical activity) exceeds 100 ppb, the contribution of secondary $PM_{10}\;((PM_{10})_{SEC})$ to total observed $PM_{10}$ concentrations was estimated up to 32% and 17% at the DS and YS sites, respectively. In addition, the diurnal variations of $(PM_{10})_{SEC}$ at the DS site were similar to those of $O_3$ regardless of season, which suggests that they are mostly secondary $PM_{10}$ produced from photochemical reactions.

• Proceedings of the Korean Institute of IIIuminating and Electrical Installation Engineers Conference
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• 2004.11a
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• pp.131-135
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• 2004

The molecules of the substance absorbing a light obtains the radiant energy to the wavelength of the light to make thermal reactions or photochemical reactions. Specially, thermal reactions by infrared radiation brings about physical damage by temperature rise process or temperature drop process of the material. In this study, a measuring system was set up to measure the temperature rise and temperature drop of each sample by infrared radiation from light source. And a physical demage of samples by infrared radiation were measured using the measuring system.