• Title/Summary/Keyword: Photochemical Reaction

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A novel method with photochemical reaction for LK immobilization on the polyurethane surface (폴리우레탄 표면의 광화학적 공유결합을 이용한 새로운 LK 고정화 방법에 관한 연구)

  • Kim, H.J.;Nakayama, Yasuhide;Shim, J.H.;Ryu, G.H.;Kim, J.;Matsuda, Takehisa;Min, B.G.
    • Proceedings of the KOSOMBE Conference
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    • v.1996 no.05
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    • pp.91-96
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    • 1996
  • 광반응을 이용하여 fibrinolytic 활성을 보이는 LK (lumbrokinase)를 생체재료인 PU (polyurethane) 표면에 고정화하는 방법에 관하여 연구하였다. 먼저 PU표면에 amino 작용기를 도입하기 위하여 side chain 작용기로 phenylazide 와 amino작용기를 갖는 AzPhPAL을 이용하였으며 광반응은 266nm 이상의 UV light을 약 1분간 조사시키는 방법을 이용하였다. LK를 amino작용기가 유도된 PU 표면에 공유결합시키기 위하여 amide결합 형성시 사용되는 수용성 carbodiimide인 EDC를 이용하였다. ESCA측정시, AzPhPAL으로 공유결합시킨 경우 반응하지 않은 PU표면에 비하여 N/C가 0.1717로, LK 고정시 S/C가 0.0043로 증가된것을 알 수 있었다. 이것으로부터 AzPhPAL과 LK가 PU표면에 공유결합된 것을 확인할 수 있었으며 static contact angle 측정으로 표면개질된 PU표면이 소수성에서 친수성으로 변화된 것을 확인 할 수 있었다. 또한 공유결합된 LK의 활성을 확인하기 위하여 fibrin plate test를 실시하였는데 그 결과 고정화된 후에도 LK의 활성이 존재함을 알 수 있었다.

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Photochemical Reaction and Characterization of TiO2 Thin Film Photocatalyst Fabricated by Sol-Gel Method (졸-겔 방법으로 제조한 TiO2박막 광촉매의 물성 분석과 광화학 반응)

  • Lim, Hee-Sup;Lee, Yong-Hee;Son, Jong-Yun;Yu, Yun-Sik;Lee, Dong-Hwan;Sung, Dae-Dong
    • Applied Chemistry for Engineering
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    • v.16 no.2
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    • pp.187-193
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    • 2005
  • The photocatalyst $TiO_2$ thin film was made from titanium (IV) isopropoxide, ethanol, and HCl by sol-gel method. The surface observation by SEM showed the sample that was coated 5 times at $500^{\circ}C$ had good properties. The component ratio, in atom% of O : Ti by EDX analysis, of 61 : 39 by spin coating was superior than dip coating. It was found that crystal structure changed from anatase phase to rutile phase as a function of the temperature of thin film fabrication, and this was measured by XRD. The photolysis efficiency of total organic compounds (TOC) by lighting UV beam on $TiO_2$ thin film showed 20%~65% within 1 h, and decreased slowly thereafter.

The Mechanism of the Photocyclization of N-(2-Haloarylmethyl)Pyridinium and N-(arylmethyl)-2-Halopyridinium Salts

  • Yong-Tae Park;Chang-Han Joo;Chung-Do Choi;Kum-Soo Park
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.163-169
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    • 1991
  • The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.

Electrochemical Behavior of Light Lanthanide Ions in Nonaqueous Solution, Flow Injection Determination and Photochemical Characterization of Eight Coordinated Chelates of Heavy Metal Ions (Part I) Electrochemical Behavior of Light Lanthanide Ions in Nonaqueous Solution (물아닌용매에서 가벼운 란탄족 이온의 전기화학적 거동, 흐름주입에 의한 정량 및 중금속이온의 킬레이트형 8-배위 착물의 광화학적 특성 (제 1 보) 물아닌용매에서 가벼운 란탄족이온의 전기화학적 거동)

  • Kang, Sam-Woo;Pak, Chong-Min;Do, Lee-Mi;Song, Myoung-Kyu;Kim, Il-Kwang
    • Analytical Science and Technology
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    • v.7 no.3
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    • pp.361-369
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    • 1994
  • Voltammetric behavior of some light lanthanide ions($La^{3+}$, $Pr^{3+}$, $Nd^{3+}$, $Sm^{3+}$ and $Eu^{3+}$) in acetonitrile(AN) and dimethylformamide(DMF) has been investigated by direct current, differential pulse polarography and cyclic voltammetry. The reduction of $La^{3+}$, $Pr^{3+}$ and $Nd^{3+}$ in 0.1M TEAP proceeded directly to the metallic state through three-electron charge transfer of irreversible process where as $Sm^{3+}$ and $Eu^{3+}$ proceeded by charge transfer of two steps. As the results of the cyclic voltammetric investigation, the first step reduction of $Sm^{3+}$ and $Eu^{3+}$ were a quasireversible reaction, the second step reductions were an irreversible reaction. The cathodic peak currents of the differential pulse polarogram showed adsorptive properties at lower sweep rates and high concentrations of these metal ions. The peak potenital was shifted to a negative petential and the peak current decreased with the increase of percentage of water in AN. On the other hand, the peak potential was shifted to a positive potential and the peak current decreased with an increased percentage of water in DMF.

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CdS-Titania-Nanotube Composite Films for Photocatalytic Hydrogen Production (CdS/Titania-나노튜브 복합 막을 이용한 광촉매적 수소제조)

  • Lee, Hyun-Mi;So, Won-Wook;Baeg, Jin-Ook;Kong, Ki-Jeong;Moon, Sang-Jin
    • Transactions of the Korean hydrogen and new energy society
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    • v.18 no.3
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    • pp.230-237
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    • 2007
  • Titania nanotube(TiNT) and CdS sol were synthesized by hydrothermal reaction under strongly basic condition and by precipitation reaction of $Cd(N0_3)_2$ and $Na_2S$ aqueous solutions, respectively. After preparing a series of CdS-TiNT composite films on $F:SnO_2$ conducting glass with variation of the mole ratio (r) of TiNT/(CdS+TiNT), their visible light absorption, photocatalytic activities for hydrogen production, and the photocurrent generation were examined. In general, this CdS-TiNT series showed lower photocatalytic activities and photocurrent generation under Xe light irradiation compared to their counterparts, i.e., CdS-$TiO_2$ particulate series. It appeared that TiNTs are not so effective photocatalyic material in spite of their larger specific surface areas compared to $TiO_2$ nanoparticles, because they indicate a poor crystallinity and less intimate interaction or contact with CdS particles owing to the tubular morphology and an easy agglomeration among themselves.

Solution Phase Photolyses of Substituted Diphenyl Ether Herbicides under Simulated Environmental Conditions (모조(模造) 환경조건하(環境條件下)에서의 치환(置換) Diphenyl Ether 제초제(除草劑)의 광분해(光分解)에 관(關)한 연구(硏究))

  • Lee, Jae-Koo
    • Applied Biological Chemistry
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    • v.17 no.3
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    • pp.149-176
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    • 1974
  • Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

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Characteristics of Vertical Ozone Distributions in the Pohang Area, Korea (포항지역 오존의 수직분포 특성)

  • Kim, Ji-Young;Youn, Yong-Hoon;Song, Ki-Bum;Kim, Ki-Hyun
    • Journal of the Korean earth science society
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    • v.21 no.3
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    • pp.287-301
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    • 2000
  • In order to investigate the factors and processes affecting the vertical distributions of ozone, we analyzed the ozone profile data measured using ozonesonde from 1995 to 1997 at Pohang city, Korea. In the course of our study, we analyzed temporal and spatial distribution characteristics of ozone at four different heights: surface (100m), troposphere (10km), lower stratosphere (20km), and middle stratosphere (30km). Despite its proximity to a local, but major, industrial complex known as Pohang Iron and Steel Co. (POSCO), the concentrations of surface ozone in the study area were comparable to those typically observed from rural and/or unpolluted area. In addition, the findings of relative enhancement of ozone at this height, especially between spring and summer may be accounted for by the prevalence of photochemical reactions during that period of year. The temporal distribution patterns for both 10 and 20km heights were quite compatible despite large differences in their altitudes with such consistency as spring maxima and summer minima. Explanations for these phenomena may be sought by the mixed effects of various processes including: ozone transport across two heights, photochemical reaction, the formation of inversion layer, and so on. However, the temporal distribution pattern for the middle stratosphere (30km) was rather comparable to that of the surface. We also evaluated total ozone concentration of the study area using Brewer spectrophotometer. The total ozone concentration data were compared with those derived by combining the data representing stratospheric layers via Umkehr method. The results of correlation analysis showed that total ozone is negatively correlated with cloud cover but not with such parameter as UV-B. Based on our study, we conclude that areal characteristics of Pohang which represents a typical coastal area may be quite important in explaining the distribution patterns of ozone not only from surface but also from upper atmosphere.

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Chlorophyll Fluorescence and $CO_2$ Fixation Capacity in Leaves of Camellia sinensis, Camellia japonica, and Citrus unshiu (차나무, 동백나무, 귤나무 잎에서 엽록소 형광 및 $CO_2$ 흡수능의 비교 분석)

  • Oh, Soonja;Lee, Jin-Ho;Ko, Kwang-Sup;Koh, Seok Chan
    • Korean Journal of Environmental Biology
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    • v.30 no.2
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    • pp.98-106
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    • 2012
  • The chlorophyll fluorescence and photosynthetic $CO_2$ fixation capacity of leaves from three major crop trees found on Jeju Island, Camellia sinensis L., Camellia japonica L., and Citrus unshiu M., were analyzed. The photosynthetic $CO_2$ fixation rate of C. sinensis was similar to that of C. unshiu, and much higher than that of C. japonica which belongs to the same genus. Stomatal conductance in the three species was high at dawn and low during daytime. The intercellular $CO_2$ concentration of the three species was also high at dawn and decreased at midday. The transpiration rate showed an opposite trend from the intercellular $CO_2$ concentration. The photochemical efficiencies of PSII (Fv/Fm) in C. sinensis were slightly lower at midday compared to the level at dawn and/or dusk. The decline in Fv/Fm of C. sinensis at midday was much smaller than that of C. japonica. These results indicate that C. sinensis is better acclimated to high levels of radiation under natural conditions in late summer, although its PSII reaction center was inhibited by strong radiation. Of the chlorophyll fluorescence parameters in the species, the RC/CS decreased significantly while the ABS/RC, TRo/RC, ETo/RC, and DIo/RC increased significantly at midday in late summer. However, C. unshiu did not show significant changes in these values depending on the time of day. Among the three species, the daily $CO_2$ fixation rate in C. sinensis ($320.1mmol\;m^{-2}d^{-1}$) was the highest, followed by that of C. unshiu ($292.5mmol\;m^{-2}d^{-1}$) and C. japonica ($244.8mmol\;m^{-2}d^{-1}$). Thus, C. sinensis may be a valuable crop tree in terms of the uptake of $CO_2$ under natural field conditions.

Seasonal Variation of PM2.5 Components Observed in an Industrial Area of Chiba Prefecture, Japan

  • Ichikawa, Yujiro;Naito, Suekazu;Ishii, Katsumi;Oohashi, Hideaki
    • Asian Journal of Atmospheric Environment
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    • v.9 no.1
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    • pp.66-77
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    • 2015
  • In order to survey the seasonal variation of the chemical composition of particulate matter of $2.5{\mu}m$ or less ($PM_{2.5}$), $PM_{2.5}$ was sampled from 8 February 2013 to 31 March 2014 in an industrial area of Chiba Prefecture, Japan. Chemical measurements of the sample included: ionic components ($Na^+$, $NH_4{^+}$, $Ca^{2+}$, $Mg^{2+}$, $K^+$, $Cl^-$, $NO_3{^-}$ and $SO_4{^{2-}}$), carbonaceous components - organic carbon (OC) and elemental carbon (EC), and water-soluble organic carbon (WSOC). Also, secondary organic carbon (SOC) was measured based using the EC tracer method, and char-EC and soot-EC were calculated from the analytical results. The data obtained were interpreted in terms of temporal variation. Of the overall mean value of $PM_{2.5}$ mass concentration obtained during the study period, ionic components, OC and EC accounted for 45.3%, 19.7%, and 8.0%, respectively. $NO_3{^-}$ showed a unique seasonal distribution pattern due to a dependence on temperature and absolute humidity. It was estimated that an approximate temperature of $14^{\circ}C$, and absolute humidity of $7g/m^3$ were critical for the reversible reaction of $NH_4NO_3(p){\leftrightharpoons}NH_3(g)+HNO_3(g)$. The amount of OC and EC contributing to the monthly $PM_{2.5}$ mass concentration was higher in autumn and winter compared to spring and summer. This result could be attributed to the impact of burning biomass, since WSOC and the ratio of char-EC/soot-EC showed a similar pattern during the corresponding period. From the comparison of monthly WSOC/OC values, a maximum ratio of 83% was obtained in August (summer). The WSOC and estimated SOC levels derived from the EC tracer method correlated (R=0.77) in summer. The high occurrence of WSOC during summer was mainly due to the formation of SOC by photochemical reactions. Through long-term observation of $PM_{2.5}$ chemical components, we established that the degree to which the above-mentioned factors influence $PM_{2.5}$ composition, fluctuates with seasonal changes.

Potential Source of PM10, PM2.5, and OC and EC in Seoul During Spring 2016 (2016년 봄철 서울의 PM10, PM2.5 및 OC와 EC 배출원 기여도 추정)

  • Ham, Jeeyoung;Lee, Hae Jung;Cha, Joo Wan;Ryoo, Sang-Boom
    • Atmosphere
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    • v.27 no.1
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    • pp.41-54
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    • 2017
  • Organic carbon (OC) and elemental carbon (EC) in $PM_{2.5}$ were measured using Sunset OC/EC Field Analyzer at Seoul Hwangsa Monitoring Center from March to April, 2016. The mean concentrations of OC and EC during the entire period were $4.4{\pm}2.0{\mu}gC\;m^{-3}$ and $1.4{\pm}0.6{\mu}gC\;m^{-3}$, respectively. OC/EC ratio was $3.4{\pm}1.0$. The average concentrations of $PM_{10}$ and $PM_{2.5}$ were $57.4{\pm}25.9$ and $39.7{\pm}19.8{\mu}g\;m^{-3}$, respectively, which were detected by an optical particle counter. The OC and EC peaks were observed in the morning, which were impacted by vehicle emission, however, their diurnal variations were not noticeable. This is determined to be contributed by the long-range transported OC or secondary formation via photochemical reaction by volatile organic compounds at afternoon. A conditional probability function (CPF) model was used to identify the local source of pollution. High concentrations of $PM_{10}$ and $PM_{2.5}$ were observed from the westerly wind, regardless of wind speed. When wind velocity was high, a mixing plume of dust and pollution during long-range transport from China in spring was observed. In contrast, pollution in low wind velocity was from local source, regardless of direction. To know the effect of long-range transport on pollution, a concentration weighted trajectory (CWT) model was analyzed based on a potential source contribution function (PSCF) model in which 75 percentiles high concentration was picked out for CWT analysis. $PM_{10}$, $PM_{2.5}$, OC, and EC were dominantly contributed from China in spring, and EC results were similar in both PSCF and CWT. In conclusion, Seoul air quality in spring was mainly affected by a mixture of local pollution and anthropogenic pollutants originated in China than the Asian dust.