• Title/Summary/Keyword: photolysis

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Accelerating effect of some photosensitizers on photodegradation of the herbicide quinclorac in aqueous solution and soil (감광제에 의한 수용액 및 토양 중 제초제 quinclorac의 광분해 촉진효과)

  • Ahn, Ki-Chang;Lee, Jae-Koo
    • The Korean Journal of Pesticide Science
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    • v.4 no.4
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    • pp.12-18
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    • 2000
  • In order to artificially reduce the quinclorac residue in aqueous solution and soil, six potential photosensitizers were screened for their effectiveness in enhancing the photodegradation. The degraded amount of quinclorac in distilled water by sunlight was minor compared to that in the dark, indicating that there was little direct photolysis. The photodegradation ratio of quinclorac in methanol was 40.3%. Whereas, the ratios in the presence of photosensitizers PS-1 (aromatic ketone), PS-3 (polycyclic quinone), and PS-6 (inorganic semiconductor) were 96.6, 72.7, and 95.7%, respectively, showing the most photosensitizing effects. In sand, PS-3 was more effective than any other photosensitizer PS-1 (19.6%), PS-3 (64.1%) and PS-6 ($17.9{\sim}19.4%$). five photoproducts of quinclorac in methanol were identified by GC-MS and quinclorac added with the photosensitizer PS-1 gave three photoproducts. Photoproducts with an aldehyde group formed in methanol were confirmed by the reduction of sodium 3,5-dinitrosalicylate in the Lindsay's method. E. crus-galli war. oryzicola was not controlled by the quinclorac residues photodegraded at tile concentrations higher than 30 ppm of the photosensitizer PS-3 in a flooded rice paddy soil. These results indicate that the quinclorac residues in aqueous solution and soil can be degraded efficiently by tile photosensitizers PS-1, PS-3, and PS-6.

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Initial Risk Assessment of Acetanilide with Respect to Ecological Integrity (아세트아닐리드의 초기 환경위해성 평가)

  • Lee, Su-Rae;Park, Seon-Ju;Lee, Mi-Kyung;Nam, U-Kyung;Chung, Sun-Hwa;Seog, Geum-Su;Park, Kwang-Sik;Kim, Kyun;Kim, Yong-Hwa
    • Environmental Analysis Health and Toxicology
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    • v.15 no.1_2
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    • pp.19-29
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    • 2000
  • Acetanilide may be released into the environment through air and wastewater from its production and use sites as an intermediate in the synthesis of pharmaceuticals and dyes. Acetanilide is biodegraded rapidly under aerobic conditions and decomposed by indirect photolysis in the presence of OH radicals. An estimated bioconcentration factor of 4.5 suggests that bioaccumulation in aquatic organisms is low. Ecotoxicological data on acetanilide exist on acute toxicity to fishes of 4 species only. According to the EUSES system, the lowest PNEC (Predicted no effect concentration) in fishes is 0.01 mg/1 and PEC (Predicted environmental concentration) for surface water on a regional scale is 9.1$\times$10$\^$-5/mg/l as the worst case. RCR (Risk characterization ratio) of acetanilide for surface water on a regional scale was estimated as 9.1$\times$10-3, which is safe enough for fishes, RCR on a local basis slightly exceeds the value 1 in water and sediment; that is, 1.3 and 1.6, respectively, which suggests the existence of ecotoxicological risk at the vicinity of the manufacturing site. For the refinement of environmental risk assessment on acetanilide, more data should be collected regarding prolonged fish toxicity, acute toxicity toward daphnia and algae. It is, therefore, recommended that acetanilide should be a candidate for further work to supplement the lacking data until it is proved to be safe in the ecotoxicological aspects.

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Possible Role of Nitric Oxide in Prevention of Atherosclerosis: Photo-induced adequate nitric oxide (PIANO)-mediated relaxation involves cyclic GMP increment (동맥경화 예방과 치료를 위한 연구시도: Nitric Oxide의 역활 -광 유도 nitric oxide(PIANO)의 혈관이완에 따른 cyclic GMP의 증가)

  • Chang, Ki-Churl;Chong, Won-Seog;Park, Byung-Wook;Lee, Seung-Youb;Ko, Hak-Joon
    • The Korean Journal of Pharmacology
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    • v.30 no.3
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    • pp.331-336
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    • 1994
  • Our purpose was to know whether photo-induced adequate nitric oxide (PIANO)-mediated relaxation of rat aorta is involved in cyclic GMP increment as well as inhibition of phosphatidylinositide hydrolysis due to phenylephrine (PE). Isometric tension was measured in vitro in response to either agents that modulate NO production or release NO by photolysis of photosensitizing agents in rat aorta that had been contracted with PE submaximally. PIANO-mediated relaxation was accompanied by increment of cyclic GMP, which was dependent on the intensity and duration of light exposure and concentration of photosensitizers. Phosphatidylinositide (PI) turnover augmented by PE was significantly inhibited by PIANO. These findings indiate that cGMP increment is responsible for PIANO-mediated relaxation and which may account for the inhibition of PI turnover due to ${\alpha}-adrenergic$ receptor stimulation.

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The Manufacture of Absorbents and Removal Characteristics of VOCs by Essential Oil and Photocatalyst (식물정유와 광촉매를 이용한 흡수제 제조 및 VOCs 제거특성에 관한 연구)

  • Jeong, Hae-Eun;Yang, Kyeong-Soon;Kang, Min-Kyoung;Cho, Joon-Hyung;Oh, Kwang-Joong
    • Clean Technology
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    • v.23 no.1
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    • pp.54-63
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    • 2017
  • Volatile organic compounds (VOCs) are widely used in both industrial and domestic activities. VOCs are one of the most unpleasant, frequently complaint-rousing factors of pollution around the world. It is now necessary to research and develop an alternative technology that could overcome the problems of the existing odor-control and VOC-eliminating techniques. In this study, essential oil and photocatalytic process was applied in the removal of benzene and toluene, typical VOCs in petrochemistry plant. therefore, this study conducted experiments on the selection of appropriate essential oil, photodegradation, hydroxyl radical generation capacity. The removal efficiency and reaction rate were performed to selecte the type and concentration of essential oil. As a result, removal efficiency of Hinoki Cypress oil was approximately 70% and reaction rate of Hinoki Cypress was high. The results of photolysis experiment, photocatalytic oxidation process showed that the decomposition efficiency of VOCs increased considerably with increasing UV lamp power. In addition, the conversion of VOCs was increased up to $0.1gL^{-1}$ photocatalysts. The hydroxyl radicals measure was performed to determine the ability to generate hydroxyl radicals. The analytical result showed that high $TiO_2$ concentration and lamp power was produced many hydroxyl radical. Experiments of the removal efficiency and reaction rate were performed using essential oil and photooxidation. As a result, the removal efficiency showed that the removal efficiency was increased high temperature and reaction time. The activation energy was calculated from the reaction rate equation at various temperature condition. Activation energy was approximately $18kJmol^{-1}$.

Effect of pH on UV Photodegradation of N-Nitrosamines in Water (수용액상 니트로스아민의 UV 광분해에서 pH 영향)

  • Shim, Jae-Goo;Aqeel, Afzal;Choi, Bo-Mi;Lee, Jung-Hyun;Kwak, No-Sang;Lim, Ho-Jin
    • Journal of Korean Society on Water Environment
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    • v.32 no.4
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    • pp.357-366
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    • 2016
  • N-nitrosamines are a class of carcinogenic chemicals that can pose significant hazards to the human life. Ultraviolet (UV) light irradiation is considered as one of the effective methods to reduce N-nitrosamines in the aqueous phase. This study aimed to investigate the pH influence on UV photodegradation of N-nitrosamines (i.e., N-nitrosodibutylamine (NDBA) and N-nitrosopyrrolidine (NPYR)) closely related to water treatment. Photodegradation rate constants of NDBA and NPYR remained between 3.26×10-2 L/W-min to 5.08×10-3 L/W-min and 1.14×10-2 L/W-min to 2.80×10-3 L/W-min at pH2-10, respectively. This study also focused on the formation of oxidized products (i.e., primarily NO2- and NO3-). Under slightly acidic and neutral conditions, NO2- formation was more prevalent than NO3- formation, while under strong acidic conditions, NO3- was more prevalent. There was no significant change in total organic carbon (TOC) and total nitrogen (TN), suggesting negligible loss of N-nitrosamines and degradation products from the system. NDBA was easily photodegraded than NPYR. This study also demonstrated that a lower pH is a favorable condition for photolytic degradation of N-nitrosamines in water.

Chemical Reaction of Solvated Electrons in Binary Mixture (이성분계 $(THF-H_2O)$에서 용매화전자의 화학반응속도)

  • Yu-Chul Park
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.201-207
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    • 1983
  • The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

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Photochemical Generation of Phenylsilylene and Its Chemistry (광분해 반응에 의한 Phenylsilylene의 생성과 그 반응성에 관한 연구)

  • Do Nam Lee;Han Seop Shin;Chang Hwan Kim;Myong Eui Lee
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.757-764
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    • 1993
  • The photochemical precursors, 1,1,1,3,3,3-hexamethyl-2-phenyltrisilane(2) and 2,3-dicarbomethoxy-1,4,5,6,7-pentaphenyl-7-silanorbornadiene(5) were synthesized in the yield of 10% and 73%, respectively. Irradiation of 2 at 254 nm in the presence of triethylsilane gave 1,1,1-triethyl-2-phenyldisilane (6) in 44% yield which was the product of phenylsilylene insertion into the Si-H bond. Irradiation of 2 in the presence of diphenylacetylene gave 1-phenyl-1-silacyclopenta-2,4-diene(4) in 68% yield together with 1,2-diphenyl-1,2-disilacyclohexa-2,5-diene(26%) which were formed from [2+2] addition of the silacyclopropene to diphenylacethylene and formed from dimerization of silacyclopropene, respectively. From the neat photolysis of precursor 2,1,5-dihydrosilanthrene(11), intermolecular C-H insertion product of phenylsilylene and 1,2-diphenyltrisilane(12), Si-H insertion product of phenylsilylene to the precursor were obtained in the yield of 5% and 7%, respectively. In the same experimental condition, both photolyses of 5 in the presence of triethylsilane and methanol showed that the intramolecular 1,5-sigmatropic rearrangement of precursor 5 to give the formation of silylenolether was more favorable process than the generation of phenylsilylene.

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Hydrogen Production from Photocatalytic Splitting of Water/Methanol Solution over a Mixture of P25-TiO2 and AgxO (산화은/이산화티타늄 혼합물을 광촉매로 활용한 물/메탄올 분해 수소제조)

  • Kim, Kang Min;Jeong, Kyung Mi;Park, No-Kuk;Lee, Tae Jin;Kang, Misook
    • Clean Technology
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    • v.21 no.4
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    • pp.271-277
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    • 2015
  • A photocatalyst which mixed by the commercialized P25-TiO2 and a synthesized AgxO was used in an appropriate weight ratio to effectively produce hydrogen gas in this study. The AgxOs were synthesized with the conventional sol-gel method, and tetramethylammonium hydroxides were added at the synthesis process in order to stabilize the solutions, and then the solutions were heat-treated at the temperatures of -5, 25, and 50 ℃, resulted to obtain the three types of silver oxides. Physicochemical properties of the synthesized AgxOs were identified through X-ray diffraction analysis (XRD), scanning emission microscopy (SEM), ultraviolet-visible spectroscopy, and X-ray photoelectron spectroscopy (XPS). In the photolysis results of water/methanol (weight ratio 1:1) solution, the mixture of P25-TiO2/AgxO exhibited a significantly higher hydrogen gases evolution, compared to that of pure P25-TiO2. Additionally, the addition of H2O2 as an supplement oxidant and in AgxO synthesized at 50 ℃ improved the hydrogen production efficiency. In particular, the emitted hydrogen gases reached to 13,000 μmol during 8 hours when a mixed catalyst, AgxO of 0.1 g and P25-TiO2 of 0.9 g, were used.

Kinetics of Photocatalytic Reactions with Porous Carriers Coated with Nano-$TiO_2$ Particles (나노-$TiO_2$ 입자로 코팅된 다공성 담체의 광촉매 반응에 관한 동력학)

  • Park, Seong-Jun;Rittmann, Bruce E.;Bae, Woo-Keun
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.10
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    • pp.927-932
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    • 2009
  • Toxic and recalcitrant organic pollutants in wastewaters can be effectively treated when advanced oxidation and biodegradation are combined, ideally with intimate coupling, in which both processes occur simultaneously in the same system. One means to achieve intimate coupling is to coat nanoscale $TiO_2$ on the outside of macroporous biofilm carriers. This study investigated the kinetics of photocatalysis with $TiO_2$-coated porous carriers. The carriers were made of polyvinyl alcohol (PVA) and coated with $TiO_2$ using a low-temperature sol-gel process. The $TiO_2$-coated carriers catalyzed the oxidation of methylene blue (MB) effectively under irradiation of UV light. The overall reaction rate with adsorption and photolysis saturated at high MB concentration, and approached the adsorption rate, which was first order for all MB concent rations. This result indicates that adsorbed MB may have slowed photocatalysis by blocking active sites for photocatalysis. The overall kinetics could be described by a quasi-Langmuir model. The estimated maximum specific (per unit mass of $TiO_2$) transformation rate of MB by the $TiO_2$-coated carriers was four times larger than that obtained from slurry-$TiO_2$ reactors. This observation demonstrated that the $TiO_2$ present as a coating on the carriers maintained high efficiency for transforming recalcitrant organic matter via photocatalysis. These findings serve as a foundation for advancement of an intimate coupling of photocatalysis to biodegradation.

A Photoreduction of Phenanthrenequinone by ESR and TRESR Spectroscopy(I)-Solvent Effect on Hyperfine-Splitting Constant of Radicals (ESR 및 TRESR 分光法에 의한 Phenanthrenequinone의 光環元反應(I). Radical의 超微細分離常數에 미치는 溶媒效果)

  • Daeil Hong;Chang Jin Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.3
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    • pp.271-278
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    • 1993
  • The hyperfine splitting constants of phenanthrenequinone anion radical have been determined for the solution of triethylamine with 2-propanol, 2-pentanol or benzene by cwESR and time-resolved ESR methods. The radical anion was produced by photolysis using a pulsed excimer laser. The resulting hyperfine splitting constant A$_{H1}$ and A$_{H2}$ are 1.662, 0.378 in 2-propanol, 1.602, 0.361 in 2-pentanol and 1.518 in benzene respectively. The hyperfine coupling constants decrease with the decreasing of polarity of the mixed solvent. The tendency of the variation depends on the polarity of the solvents, thus, making it in impossible to observe the magnetic equivalent proton in a mixed solvent of nonpolar benzene. Particularly, time-resolved ESR spectrum of triethylamine radical (TEA${\cdot}$) has been observed in 0.15∼0.30 ${\mu}s$ from the solvent of 3 : 1 with 2-pentanol and triethylamine. Thus from the results of solvent effect, we can suggest that the identification of the unstable short-lived spin polarized phenanthrenequinone anion radical(*PQ${\cdot}^-$) proceed through photochemistry.

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