• Title, Summary, Keyword: photolysis

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Effects of NaOH and Humic Acid on the UV Photolysis of PCBs (PCBs의 광화학적 연구: NaOH 및 휴믹산 (humic acid, HA)에 의한 분해특성)

  • Shin, Hae Seung;Kim, Jae Hyoun
    • Journal of Environmental Health Sciences
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    • v.40 no.2
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    • pp.147-156
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    • 2014
  • Objectives: This study was carried out to examine whether the apparent photolysis with or without sensitizers [NaOH and humic acid (HA)] was prompted photodegradation of polychlorinated biphenyl (PCB) in aqueous solution. Methods: PCBs photodegradation occurred using fluorescence black lamps at ${\lambda}_{max}=300nm$. PCB congeners were exposed in 10 ppm HA or 0.05N NaOH solutions, to investigate the decreasing profile of PCB concentration with time. The PCBs were then analyzed by gas chromatography/mass spectrometry (GC-MS). Reductive degradation profile of PCB congeners in the presence of both sensitizers under oxygen-saturated protic conditions was described using the wind-rose diagrams. Results: Use of HA or NaOH decreased PCB concentration with time in the dark and on irradiation, indicating that photolysis underwent through reductive dechlorination through energy transfer and possibly with reactive oxygens. The dechlorination was marked by a chromatographic shift, observed in the GC-MS plots. Therefore it is logical to assume that increasing the dose of sensitizers would increase the photodegradation rates of PCBs. The half-lives of pentachloro-PCB (penta-3) in 0.05N NaOH and 10 ppm HA were estimated at about 47 hours and 39 hours, respectively, under the same experimental conditions of photolysis. It was found that the rate of photolysis of pentachloro-PCB in aqueous solution followed apparent first-order kinetics compared to other congeners. Conclusion: Photochemical degradation (using 328 nm UV light) of penta- and hexa-PCBs in HA or alkaline solution is a viable method for pretreatment method. The results are helpful for the further comprehension of the reaction mechanism for photolytic dechlorination of PCBs in aquatic system.

Structural Dynamics of Myoglobin Probed by Femtosecond Infrared Spectroscopy of the Amide Band

  • Kim, Seong-Heun;Jin, Geun-Young;Lim, Man-Ho
    • Bulletin of the Korean Chemical Society
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    • v.24 no.10
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    • pp.1470-1474
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    • 2003
  • The dynamics of the tertiary conformation of myoglobin (Mb) after photolysis of carbon monoxide was investigated at 283 K solution by probing amide I and II bands using femtosecond IR absorption spectroscopy. Time-resolved spectra in the amide region evolve with 6-12 ps time scale without noticeable subpicosecond dynamics. The spectra measured at 100 ps delay after photolysis is similar to the difference FTIR spectrum at equilibrium. Time-resolved spectra of photoexcited Mb evolve modestly and their amplitudes are less than 8% of those of photolyzed MbCO, indicating that thermal contribution to the spectral evolution in the amide region is negligible. These observations suggest that the conformational relaxation ensuing photolysis of MbCO be complex and the final deoxy protein conformation have been substantially formed by 100 ps, probably with 6- 12 ps time constant.

Quantitative Determination of Acetone formed in the Thermal and Photochemical Decompositions of Azobisisobutyronitrile

  • Yoon, Heung-Sick;Kim ,Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.284-287
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    • 1985
  • Cyanoisopropyl radical derived from azobisisobutyronitrile (AIBN) by either thermolysis or photolysis reacts with oxygen to give cyanoisopropylperoxy radical which then was converted to acetone and cyano radical and/or acetyl cyanide and methyl radical. Of these products, acetone formed was quantitatively determined by the addition of thianthrene cation radical perchlorate to the reaction mixture. The results showed that 55.7 mmol, 16.9 mmol, and 16.0 mmol of acetone were formed for 7 hours from 1 mol of AIBN at $82{\pm}1^{\circ}C$ in acetonitrile, carbon tetrachloride, and benzene, respectively. However, 22.2 mmol of acetone was formed from photolysis of 1 mmol of AIBN in acetonitrile. The value decreased to 13.2 mmol by bubbling argon into the solvent prior to photolysis.

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Photolysis of Tris(trimethylsilyl)methylsilane in the Presence of 2-Propenol

  • Bu, Bong Hyeon;Hong, Seung Gi;Gang, Seong Gwon
    • Bulletin of the Korean Chemical Society
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    • v.16 no.1
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    • pp.30-33
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    • 1995
  • UV photolysis of the titled polysilane (Me3Si)3SiMe (I) in the presence of a trapping agent of 2-propenol has been performed to investigate the interaction of short-lived silicon species formed from the photolysis of I with 2-propenol. Product studies show that the Me(Me3Si)Si: (II) and (Me3Si)3Si${\cdot}$(III) are primarily formed as the major reactive species which saturate their valencies via O-H insertion and H-abstraction, respectively. Some products are unstable toward further secondary reaction such as photodissociation and intermolecular reaction. The PM3 semiempirical calculations are performed to deduce the energetics of the photoinduced chemical reactions of I with the substrate.

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Photolysis of Diazotetracyanocyclopentadiene and Identification of Carbene Intermediate (디아오화합물의 광분해반응과 카르벤 중간체의 확인)

  • Kim, Min-Sik;Eom, Tae-Seop;Seong, Dae-Dong
    • The Korean Journal of Food And Nutrition
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    • v.7 no.1
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    • pp.29-35
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    • 1994
  • Photolysis of diazotetracyanocyclopentadiene has been investigated by means of IR and UV-vis spec troscopy in Ar matrix. Parent carbene is produced in low yield and could be detected by UV-vis spectroscopy and IR spectroscopy. The carbene produced from the diazo compound is very photolabile and also decay thermally at temperature as low as 10K. When the diazo compound is photolyzed the Arrhenius plots show a tunneling effect that is not shown as non linearity.

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Photochemistry of 1-(o-substituted -phenyl)-2-pentamethyldishilanyl Ethynes

  • Shim, Sang-Chul;Park, Seung-Ki
    • Journal of Photoscience
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    • v.6 no.1
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    • pp.13-19
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    • 1999
  • Irradiation of 1-(o-allyloxyphenyl)-2-pentamethyldisilanylenthyne 2a in methanol yields two 1 : 1 photoaddition products 3 and 4 via silacyclopropene intermediate. Photolysis of 2a with acetone in deaerated methylene chloride yields site specific and regioselective 1 : 1 adducts 6 ad 7 via silacyclopropene and 1-sila-1, 2-propdiene intermediate, respectively. Photolysis of 2a and 1-(o-(3', 3'-dimethyl-2'-propenylox)phenyl)-2-pen-tamethyldisilanylethyone 2b in benzene provides novel stereoselevtive intramolecular cyclization products 10 and 11, respectively. Irradiation of 1-(o-acetoxyphenyl)-2-pentamethyldisilanyl ethyne 2c in benzene yields the photo-Fries rearrangement products 18 and 19 and a photoproduct 17 via silacyclopropene intermediate. Photolysis of 1-(o-methoxycarbonlymethoxyphenyl)-2-pentamethyl disilanylenthyne 2d in benzene provides a novel intramolecular cycloaddition product 25 and 1-(o-methoxycarbonylemthoxiyphenyl)-2-trimethylsilylethyne 26 via silacyclopropene intermediate.

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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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Exchange Reaction Between Alkyl Iodides and $II^{131}$ in the Photolysis of Alkyl Iodides in Hydrocarbon (炭化水素內에서의 Alkyl Iodides의 光分解에서 $II^{131}$과 Alkyl Iodides 間의 交換反應)

  • Choi, Jae-Ho
    • Journal of the Korean Chemical Society
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    • v.10 no.1
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    • pp.43-45
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    • 1966
  • The rate of exchange of I atom between alkyl iodides(ethyl or methyl iodide) and $I_2$ in n-hexane have been determined using $II^{131}$. It is found that the escape of $CH_3$ radicals from a solvent cage is faster than $C_2H_5$ radicals and that photolysis of $C_2H_5I$ is almost identical to that in the case of $CH_3I$.

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Photochemistry of Conjugated Polyacethylenes: Photoaddition Reactions of 1-Phenyl-1,3,5-hexatriynes to Tetrahydrofuran

  • Shim, Sang Chul;Lee, Cheon Seok;Lee, Seong Taek
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.654-658
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    • 1992
  • Photolysis of 1-phenyl-1,3,5-hexatriynes in deaerated tetrahydrofuran gave photoreduction and photoaddition products, while photolysis of 1-phenyl-1,3,5-hexatriynes in deaerated alcoholic solvents (methanol, i-propanol) yielded dark red products, probably oligomers or decomposition products of reactants, as exclusive major products. A plausible mechanism for the reaction is proposed.

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Numerical Simulation of Fluorescent Whitening Agents (DAS1) in Tokyo Bay (동경만 형광표백제 성분물질(DAS1)의 거동 특성 시뮬레이션)

  • Kim, Dong-Myung
    • Journal of Environmental Science International
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    • v.20 no.4
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    • pp.519-525
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    • 2011
  • A three-dimensional ecological model(EMT-3D) was applied to DAS1 in Tokyo Bay. The simulated results of DAS1 were in good agreement with the observed values. The result of sensitivity analysis showed that photolysis coefficient and extinction coefficient were important factor for dissolved DAS1, and photolysis coefficient, extinction and POC partition coefficient for PAHs in particulate organic matter. Mass balance of DAS1 in Tokyo Bay was calculated by using the simulated results of EMT-3D.