• Particle and aerosol research
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• v.4 no.1
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• pp.9-20
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• 2008

The effect of light intensity on the ozone formation and the aerosol number concentration during the photochemical reactions of ambient air was investigated in an indoor smog chamber. The smog chamber consists of a housing, 64 blacklights, and a $2.5-m^3$ reaction bag made of Teflon film. The bag was filled with the unfiltered ambient air in Seoul from January 10 to March 18, 2002. In this work, the photolysis rate of $NO_2$, $k_1$ was used as an index of light intensity. Three levels of light intensity were controlled by changing the number of blacklights turned on among 64 blacklights: $0.29min^{-1}$ (50%), $0.44min^{-1}$ (75%), $0.57min^{-1}$ (100%). The ozone concentration increased rapidly within 10 minutes after irradiation irrespective of light intensity, thereafter it increased linearly during the irradiation. The ozone production rate seems to be dependent on both the light intensity and the quality of ambient air introduced into the reaction bag. The change in aerosol number concentration also depended on both the light intensity and the ambient air quality, especially aerosol size distribution. Based on the initial ambient aerosol size distributions, the photochemical potential for aerosol formation and growth is classified into two cases. One is the case showing aerosol formation and growth processes, and the other is the case showing no apparent change in particle size distribution.

• Bulletin of the Korean Chemical Society
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• v.12 no.5
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• pp.554-559
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• 1991

The photophysical and photochemical properties of khellin were compared with those of 8-methoxypsoralen (8-MOP). Quantum yields of fluorescence and triplet formation decreases as solvent polarity increases, which is opposite to 8-MOP, and photocycloadditivity of khellin to olefins is much lower than that of 8-MOP. Electron ejection from khellin by laser flash was not observed, but observed from 8-MOP. As models of 4',5'-monoadducts of khellin or 8-MOP with thymine base, khellin<>dimethylfumarate 4',5'-monoadduct (KDF) was also compared with 8-MOP<>thymidine 4',5'-monoadduct (F-2) in those properties to give some insight on the second-step biadduct formation resulting in cross-links of DNA duplex. KDF and F-2 were very similar to khellin and 8-MOP in photophysical properties, respectively. However, KDF did not form adducts with various olefins, and thus it is thought that 2,3-double bond of chromone moiety in khellin is hardly reactive in contrast with 3,4-double bond of coumarin moiety in 8-MOP. These results indicate that khellin is fairly photostable compound, a poor type Ⅰ photodynamic sensitizer and producer of ${O_2}^{-}$ which is some cause of phototoxic erythemal reactions and undesirable side effects. Therefore khellin is safer to use than 8-MOP in photochemotherapy of some skin diseases. Although khellin is much less reactive than 8-MOP, khellin must be also a monofunctional drug. Since khellin is, however, as effective as 8-MOP in photochemotherapy of some skin diseases, it is suggested that khellin may be different from 8-MOP in the action mechanism.

• Journal of ILASS-Korea
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• v.23 no.4
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• pp.185-191
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• 2018

Benzene, toluene, ethylbenzene and xylene (BTEX) were well known as ozone precursors from photochemical reactions and contribute to the formation of photochemical smog which pose health hazards. Also, some of these compounds directly affect the human health due to their toxicity such as benzene. In this study, BTEX ratios and correlation of $C_2$-benzenes (xylenes, ethylbenzene) in vehicle exhaust from recreational vehicle (RV) and multi-purpose vehicle (MPV) were characterized using a chassis dynamometer. VOCs were collected by tedlar bag and a GC/MS system was used for their quantification. Among all of the BTEX, toluene has the highest concentration(more than 30% in composition of BTEX). The average ratio of toluene to benzene emissions (T/B ratio=2.2) was found in vehicle exhaust. The average m,p-xylene/ethylbenzene and m,p-xylene/o-xylene ratios were 1.0 and 3.0 respectively. As a result, it showed a good correlation between the $C_2$-benzenes ($R^2=0.98{\sim}0.99$). In the future, it can be used as a marker for effect evaluation to atmospheric environment by vehicle exhaust.

• Asian Journal of Atmospheric Environment
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• v.9 no.4
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• pp.237-246
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• 2015

We conducted intensive observations of ozone, CO, $NO_x$ (=NO and $NO_2$), $NO_y$ (total odd nitrogen species including particulate nitrate) and total nitrate (the sum of gaseous $HNO_3$ and particulate nitrate) at Cape Hedo, Okinawa, Japan, from 19 March to 3 April, 2009, to investigate ozone production during long-range transport from the Asian continent. Ozone production efficiency (OPE) was used to evaluate photochemical ozone production. OPE is defined as the number of molecules of ozone produced photochemically during the lifetime of a $NO_x$ molecule. OPE is calculated by the ratio of the concentration increase of ozone to that of $NO_z$ ($=NO_y-NO_x$). Average OPE during observation was estimated to be $12.6{\pm}0.5$, but concentrations of ozone increased nonlinearly with those of $NO_z$. This non-linearity suggests that OPE depends on air mass origin and $NO_z$ concentrations. There were very different values of OPE for the same air mass origin, so that only the air mass origin alone does not control OPE. OPE was low when $NO_z$ concentration was high. We examined the correlation between $NO_z$ and $CO/NO_y$ ratios, which we used instead of the ratio of non-methane hydrocarbons (NMHCs) to $NO_x$. The $CO/NO_y$ ratios decreased with increasing $NO_z$ concentrations. These results indicate that competition reactions of OH with NMHCs and $NO_2$ are the rate determining steps of photochemical ozone production during long-range transport from the Asian continent to Cape Hedo, for high concentrations of nitrogen oxides.

• Journal of Environmental Policy
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• v.4 no.1
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• pp.1-19
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• 2005

On January 1, 2005, the Special Act on Metropolitan Air Quality Improvement, known as the Blue Sky 21 Program, entered into force. This Special Act is aimed at reducing the annual average concentrations of $PM_{10}$ and $NO_2$ to $40{\mu}g/m^3$ and 22ppb, respectively, from their current levels of $76{\mu}g/m^3$ and 36ppb, within the next 10 years. While the main focus of the Act is to reduce $PM_{10}$ and $NO_2$ emissions, the government also anticipates that these reductions would lessen high ozone occurrences and improve visibility. However, reducing local PM emissions would not decrease $PM_{10}$ concentrations as much as expected since other significant sources, such as continental inflow and/or secondary formation from photochemical reactions, exist. This is corroborated by the fact that $PM_{10}$ in the greater Seoul Metropolitan area during the ozone season is mostly in the form of $PM_{2.5}$, which is secondarily formed on a regional scale. Furthermore, many modeling results indicate so-called '$NO_x$ disbenefits,' referring to the fostering of an increase in ozone concentrations from a decrease in $NO_x$ emissions, over an extensive area. In this paper, the current status of air quality in the Seoul Metropolitan area is reviewed, and several other issues, including the effect of long-range transport, photochemical characteristics, and tasks for successful implementation of the Special Act are discussed.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1218-1242
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• 2002

Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

• Journal of Photoscience
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• v.9 no.2
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• pp.382-384
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• 2002

When illuminated with strong visible light, the reaction center Dl protein of photo system II is photodamage and degraded. Reactive oxygen species and endogenous cationic radicals generated by photochemical reactions are the cause of the damage to the Dl protein. Recently we found that the photodamaged Dl protein cross-links with the surrounding polypeptides such as D2 and CP43 in photosystem II. As the cross-linking reaction is dependent on the presence of oxygen, reactive oxygen species are suggested to be involved. Among the reactive oxygen species examined, ？ OH was most effective in the formation of the cross-linked products. These results indicate that the cross-linking is mostly due to ？ OH generated at photosystem II. The cross-linking site of the Dl protein is not known. As several tyrosine residues exist at the D­E loop of the Dl protein, there is a possibility that di-Tyr is formed between the D­E loop of the Dl protein and surrounding polypeptides during the strong illumination. Therefore, we examined the formation of di-Tyr using the monoclonal antibody against di-Tyr under excess illumination of the photosystem II membranes. The results obtained here suggest that no di-Tyr is formed during the excess illumination of photosystem II.

• Journal of Photoscience
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• v.9 no.2
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• pp.55-58
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• 2002

The reaction center Dl protein of photosystem II is the target of photodamage by excess illumination. The Dl protein is damaged by reactive oxygen species generated by photochemical reactions and then degraded by specific proteolytic enzymes. We found that the Dl protein also cross-links with the surrounding polypeptides, such as D2 and CP43 in isolated thylakoids or photosystem II-enriched membranes from spinach under the illumination with strong visible light. The cross-linking was observed in spinach leaf discs as well when they were illuminated at higher temperature (40°C). It was also shown that the cross-linked products are digested efficiently by a protease(s) in the stroma. Thus the cross-linking/digestion processes of the Dl protein seem to comprise a new pathway in the turnover of the photodamaged Dl protein. It should be noted, however, that the cross-linked products of the Dl protein and CP43 induced by endogenous cationic radicals in the donor-side photoinhibition are resistant to proteolytic digestion. Accumulation of these cross-linked products in the thylakoids may lead to the decay of the function of chloroplasts and finally to the death of plant cells. Thus, we suggest that the quality control of photosystem II, especially removal of the cross-linked products of the Dl protein, is crucial for the survival of chloroplasts under the light stress.

• Journal of the Korean Chemical Society
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• v.41 no.12
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• pp.666-671
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• 1997

Photoreactions of pseudosaccharin pyridinemethyl ethers have been investigated. Pseudosaccharin 2-pyridinemethyl ether, pseudosaccharin 4-pyridinemethyl ether and pseudosaccharin 3-pyridinemethyl ether all undergo a facile photoreaction via reaction pathways involving homolysis of the bond between pseudosaccharyl oxygen and pyridinemethyl carbon, and excited nucleophilic substitution of pyridinemethoxy group by solvent, methanol which are not quenched by oxygen present in the reaction. Product yield demonstrates that the homolysis pathway predominates over the nucleophilic substitution.

• Journal of the Korean Applied Science and Technology
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• v.28 no.1
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• pp.102-108
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• 2011

The study of wave propagation and scattering in biological media has become increasingly important in recent years. The propagation of light within tissues is an important problem that confronts the dosimetry of therapeutic laser delivery and the development of diagnostic spectroscopy. In the clinical application of photodynamic therapy(PDT) and in photobiology, the photon deposition within a tissue determines the spatial distribution of photochemical reactions. Scattered light is measured as a function of the distance (r) between the axis of the incident beam and the detection spot. Consequently, knowledge of the photosensitizer(Chlorophyll-a) function that characterizes a phantom is measured. To obtain the results of scattering coefficients(${\mu}s$) of a turbid material from diffusion described by experimental approach. It was measured the energy fluency of photon radiation at the position of penetration depth. From fluorescence experimental method obtained the analytical expression for the scattered light as the values of $(I/I_o)_{wavelength}$ vs the distance between the center of the incident beam and optical fiber in terms of the condition of "in situ spectroscopy(optically thick)" and real time by fluorometric measurements. The result was compromised with transport of intensities though a random distribution of scatters.