• Title/Summary/Keyword: Photochemical Reaction

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Azomethine Yilde Forming Photoreaction of N-(Tributylstannyl)methylphthalimide (N-(트리부틸스탄일)메틸프탈이미드의 아조메틴 일리드 형성 광화학 반응)

  • Jeong, Ho-Cheol;Park, Ki-Hyun;Park, Hea-Jung;Cho, Dae-Won;Yoon, Ung-Chan
    • Journal of the Korean Chemical Society
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    • v.53 no.3
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    • pp.302-307
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    • 2009
  • Investigation was conducted to examine whether photochemical reaction of N-(tributylstannyl)- methylphthalimide generates an azomethine ylide intermediate in its excited state as its silyl derivative N-(trimethylsilyl)methylphthalimide which has been observed to form an azomethine ylide. The irradiation of N-(tributylstannyl)methylphthalimide in $D_2O-CH_3$CN generates mono-deuterated N-methylphthalimide as an exclusive product which supports the efficient generation of azomethine ylide intermediate and its trapping by water molecule through a proto-destannylation pathway. However the generated tributylstannyl subsitiuted ylide was not observed to be trapped with a dipolarophile such as methyl acrylate and acrylonitrile present in the reactions which is in contrast with the ylide from N-(trimethylsilyl)methylphthalimide.

Artificial Photosynthesis System Containing CO2 Conversion Process (이산화탄소 변환 과정이 포함된 인공 광합성 시스템)

  • Kim, Kibum
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.1
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    • pp.63-68
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    • 2018
  • This paper presents an integrated photochemical reaction system (i.e., an artificial leaf) that uses earth-abundant catalysts for artificial photosynthesis with a carbon dioxide ($CO_2$) fixation process. The performance of the system was investigated in terms of the energy capture and conversion capabilities. A wireless configuration was achieved by directly doping cobalt oxide as an oxygen-evolving catalyst for water splitting reaction on the illuminated surface of photovoltaic (PV) cell, as well as molybdenum disulfide ($MoS_2$) as an efficient catalyst for $CO_2$ reduction on the back substrate surfaces of the PV cell. The system produces hydrogen and carbon monoxide (CO) as sustainable fuels (i.e., synthesis gas) at around 4.5% efficiency, which implies more than 75% catalytic efficiency at the cathode. The process of solar-driven $CO_2$ conversion and water-splitting reaction is contained in one system, which is one step closer to the successful realization of artificial photosynthesis.

Development of Photo-Fenton Method for Gaseous Peroxides Determination and Field Observations in Gwangju, South Korea

  • Chang, Won-Il;Shim, Jae-Bum;Hong, Sang-Bum;Lee, Jai H.
    • Journal of Korean Society for Atmospheric Environment
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    • v.23 no.E1
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    • pp.16-28
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    • 2007
  • An improved method was developed to determine gas-phase hydrogen peroxide($H_2O_2$) and organic hydro-peroxides (ROOH) in real-time, The analytical system for $H_2O_2$ is based on formation of hydroxybenzoic acid (OHBA), a strong fluorescent compound. OHBA is formed by a sequence of reactions, photoreduction of Fe(III)-EDTA to Fe(II)-EDTA, the Fenton reaction of Fe(II)-EDTA with $H_2O_2$, and hydroxylation of benzoic acid. By use of this analytical method rather than a previous similar method, Fenton reaction time was reduced from 2 min. to 30s. Air samples were collected by a surfaceless inlet to prevent inlet line losses. With a special arrangement of the sampling apparatus, sample delivery time was drastically reduced from ${\sim}5\;min\;to\;{\sim}20\;s$. The automated system was found to be sensitive, capable of continuous monitoring, and affordable to operate. A comparison of this method with a well-established one showed an excellent linear correlation, validating applicability of this technique to $H_2O_2$ determination. The system was applied to field measurements conducted during summertime of 2004 in Gwangju, South Korea. $H_2O_2$ was found to be a predominant species of peroxides. The diurnal variation of $H_2O_2$ displayed the maximum in early afternoon and the broad minimum throughout night. $H_2O_2$ was correlated positively with ozone, photochemical age, and temperature, however, negatively with $NO_x$ and relative humidity.

The Characteristics of Secondary Carbonaceous Species within PM10 and PM2.5 in Seoul and Incheon Area (서울과 인천지역 PM10 과 PM2.5 중 2차생성 탄소성분 추정)

  • Park Jin Soo;Kim Shin Do
    • Journal of Korean Society for Atmospheric Environment
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    • v.21 no.1
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    • pp.131-140
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    • 2005
  • To investigate secondary carbonaceous species within PM$_{10}$ and PM$_{2.5}$ in Seoul urban Metropolitan Area (SMA), Korea. atmospheric particulate matters samples were collected at two sites of SMA at UOS (The University Of Seoul station) sites and IHU (InHa University of Incheon station) during the period of 4 to 14 January and 12 to 22 May, 11 to 15 August 2004, and their characteristics were qualitatively discussed. during January and May and August of 2004. Daily average mass concentration 0.095 mg/㎥ in PM$_{10}$ and 0.053 mg/㎥ in PM$_{2.5}$ for mass respectively. were observed in SMA. The concentrations of carbonaceous species contributed 18.4% and 16.4% of PM$_{2.5}$ and PM$_{10}$ during the sampling period, respectively, of which OC accounted for 68% and 52% more of the total carbon (TC). OC and EC concentrations and their mass percentages were higher in PM$_{2.5}$ than in PM$_{10}$ which could be attributed to generation process. Organic aerosols would constitute up to 38% of PM$_{2.5}$ based on the evaluation of 1.6 for the ratio of OC to organic particulate. Secondary organic carbon (SOC) were estimated to be more than 13% and up to 68% of total OC based on the minimum OC/EC ratio of 1.06/1.11 using least square method. Comparisons of OC and EC with trace elements. As results of carbonaceous species analysis, the dominant factor in view of fine particle (PM$_{10}$/PM$_{2.5}$) is primary emission source such as mobile, fossil fuel combustion etc. during winter time in SMA. But in summer periods, remarkable fine particle increasing factor was secondary organic carbon dependent to photochemical reaction. reaction.n. reaction.

Photochemistry of Benzanilide I Photocyclization of Benzanilides (벤즈아닐리드류의 광화학 (제1보). 벤즈아닐리드류의 광고리화 반응)

  • Yong-Tae Park;Sang-Rok Do;Kap-Duk Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.426-436
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    • 1985
  • Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.

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Quality Control of Photosystem II during Photoinhibition

  • Yamamoto, Yasusi
    • 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.

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Design and Performance Evaluation of the KIST Indoor Smog Chamber (실내 스모그 챔버의 설계 및 성능평가)

  • 배귀남;김민철;이승복;송기범;진현철;문길주
    • Journal of Korean Society for Atmospheric Environment
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    • v.19 no.4
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    • pp.437-449
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    • 2003
  • A multi-functional indoor smog chamber was designed and evaluated to investigate photochemical or water vapor reaction mechanisms of air pollutants. Various smog chamber experiments could be conducted using ambient air or purified air in this smog chamber. The smog chamber consisted of a housing, a Teflon bag, blacklights, injection ports, sampling ports, and utility facilities. The characteristics of light source, the wall losses of air pollutants, and the quality of purified air were experimentally investigated. The maximum NO$_2$ photolysis rate was 1.10 min$^{-1}$ . In a 2.5-m$^3$ Teflon bag, the wall losses of ambient $O_3$, NO, and NO$_2$ were 1.2~2.4$\times$10$^{-3}$ min$^{-1}$ , 0.7~2.0$\times$10$^{-3}$ min$^{-1}$ , and 0.4~2.0$\times$10$^{-3}$ min$^{-1}$ , respectively. The wall loss of ambient particles ranging 0.05 to 0.2 ${\mu}{\textrm}{m}$ was 1.8~5.4$\times$10$^{-3}$ min$^{-1}$ , which was slightly higher than those of ambient gaseous species. The purified air supply system provided high quality of air with NO$_{x}$ < 1 ppb, and total hydrocarbons < 5 ppb.b.

Variations of NMHC and Fine Particles in Seoul in June 2001 (2001년 6월 서울에서의 비메탄계 탄화수소와 미세입자의 농도 변화)

  • 김영성;김진영
    • Journal of Korean Society for Atmospheric Environment
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    • v.20 no.1
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    • pp.87-97
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    • 2004
  • NMHC (non-methane hydrocarbons) and fine particles such as P $M_{10}$ and P $M_{2.5}$ were measured at KIST (Korea Institute of Science and Technology) in Seoul for a month from the end of May. At the beginning of June, peak ozones exceeded 100ppb both near KIST and in Seoul while ozone and fine particles decreased from the middle of June due to frequent precipitation. Because the measurement site was close to trees on a hill, isoprene concentration went up to 4.1ppb with an average of 0.76ppb. Toluene was the highest all day long, but particularly high concentration in the afternoon implied a contribution of emission from solvent use as well as vehicle exhaust. Eighty-five percent of P $M_{10}$ was P $M_{2.5}$ on an average since major ions except sea salt, including nitrate, were present within P $M_{2.5}$. Daily variations of pollutants were generally similar except for NMHC. One of major differences in NMHC variation was maintenance of a relative high concentration in rainy day, showing that NMHC were not effectively scavenged by precipitation.ion.ion.

Variations of Surface Ozone Concentration by Vertical Downward Mixing of Ozone in the Residual Layer of the Atmospheric Boundary Layer at the Busan Coastal Area (부산연안역의 대기경계층내 잔류 오존의 연직하향혼합에 의한 지표 오존농도의 변화 특성)

  • 전병일
    • Journal of Environmental Science International
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    • v.10 no.6
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    • pp.417-422
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    • 2001
  • The vertical structure of atmosphere was observed In investigate the variation of surface ozone concentration by vertical downward mixing of residual ozone in the atmospheric boundary layer at the Busan coastal area. Airsonde and pilot balloon measurements were made at Gamcheondong and the Kimhae airport for April 26~27, 1996. The vertical potential of potential temperature showed a residual layer between 510m and 1800m from 2100LST April 26 to 0900LST April 27. The downward mixing of ozone in the residual layer of the atmospheric boundary layer was confirmed from vertical profile of mixing ratio near 600m in the morning. The thickness of the sea breeze layer was 900m at 1500LST April 26. Thereafter, it become to be lowered with time A low level jet was measured near 900m at 0300LST on April 27 from a pibal measurement. Early morning sharp increase of surface ozone concentration at the Busan coastal area was caused by vertical downward mixing of ozone concentration rather than by photochemical reaction In the atmospheric boundary layer.

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Effect of Acid Rain on Vegetation (산성(酸性)비가 식생(植生)에 미치는 영향(影響))

  • Lee, Jong-Sik;Kim, Bok-Young
    • Korean Journal of Environmental Agriculture
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    • v.13 no.3
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    • pp.346-358
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    • 1994
  • In this paper, the current knowledge on the formation of acid rain and its effect on vegetation are reviewed. The pollutants which were emitted into the air are oxidized by photochemical reaction and affect the vegetation by dry and wet deposition. Acid rain at pH 4.0 affected sensitive plants and when it was below pH 3.0, visible symptoms developed in most of the crops. The acid rain treatment at pH 2.0 decreased dry weight, leaf area and chlorophyll contents in soybean but it increased rate of photosynthesis and respiration rate. Rain treatment at pH 2.8 increased ethylene production, but it’s not a suitable indicator of sensitivity to acid rain. At pH 2.0 treatment, the contents of soluble Mn and Al were increased but the cultivated soil pH at upper layer(0-5cm) was significantly decreased. The pertubation of glandular trichome which is existed along the vein was developed at all treatment except the control(pH 6.0) and non-treatment. Histological pertubation of spiked trichome and disintegration of chloroplast were developed only on the leaves of sesame treated with SAR(simulated acid rain) of pH 2.0.

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