• Title/Summary/Keyword: Homolysis

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PHOTOCHEMICAL REACTIONS OF PSEUDOSACCHARIN 3-ALLYL ETHER (PROBENAZOLE) AND ITS ALKYL ETHER

  • Yoon, Ung-Chan
    • Journal of Photoscience
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    • v.2 no.2
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    • pp.77-81
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    • 1995
  • Photoreactions of pseudosaccharin ethers have been investigated. Pseudosaccharin 3-allyl ether undergoes a facile photoreaction via reaction pathways involving homolysis of bond between pseudosaccharyl oxygen and 3-allyl carbon, and excited nucleophilic substitution of allyloxy group by solvent which are not quenched by oxygen present in the reaction. Product yield demonstrates that the homolysis pathway predominates over the nucleophilic substitution in ca. 7:1 ratio. In contrast, pseudosaccharin alkyl ethers follow different reaction routes to produce two products, solvent-substituted pseudosaccharin alkyl ethers and reduction products, 3-alkoxy-1, 2-benzisothiazoles. The formations of reduction products, 3-alkoxy-1, 2-benzisothiazoles are completely quenched by oxygen.

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Photochemical Reactions of Pseudosaccharin Pyridinemethyl Ethers (Pseudosaccharin Pyridinemethyl Ether들의 광화학반응)

  • Yoon, Ung Chan;Kim, Jeong Hie;Lee, Sang Jin;Kim, Hyun Jin;Oh, Sun Wha;Park, Won Woo
    • 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.

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MEK-PO 분해 폭발사고 사례 연구

  • 김관응;이근원;김기영;박상현
    • Proceedings of the Korean Institute of Industrial Safety Conference
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    • 2003.10a
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    • pp.54-59
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    • 2003
  • 유기과산화물은 분자구조내에 과산화결합(Peroxy, -O-O-)을 갖고 있는 유기화합물로서 매우 불안정한 과산화수소(H-O-O-H)의 유도체이다. 과산화물을 특징짓는 산소-산소(-O-O-) 과산화결합은 C-H, C-O, C-C 등의 결합에 비하여 결합에너지가 작아서 열이나 빛에 의해서 쉽게 균형분해(Homolysis)가 일어나 두 개의 유리기인 라디칼(Free radical)을 생성하게 되는데, 이때 생성된 라디칼은 비닐중합반응을 개시시킬 수 있고, 또한 다른 자유 라디칼 반응을 유발시킬 수 있다.(중략)

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Experimental study on antioxidant action of Kyungoktang (경옥탕(瓊玉湯)의 항산화작용(抗酸化作用)에 대한 실험적(實驗的) 연구(硏究))

  • Kim, Byung-Tak;Kim, Sung-Hoon
    • Journal of Haehwa Medicine
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    • v.7 no.1
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    • pp.741-748
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    • 1998
  • In order to evaluate the effectiveness of KOK(kyungokko) experimentally used for longevity hematology, erythrocyte hemolysis and TBA(thiobarbituric acid) were measured, after LKOK(low concentration KOK) and HKOK(high concentration KOK) were administrated to mice pretreated with AAPH (2,2'-Azobis(2-amidinopropane), hydrocholoride, free radical inducer. In hematology WBC and hemoglobin were reduced significantly, while the number of platelet was significantly incresed as compared with control. Erythrocyte hemolysis by damage of free radical on cell membrane of RBC and TBA(Thiobarbituric acid) were significantly inhibited in both sample groups as compared with control. These results suggest KOK had antioxidant effect.

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The Study of DEP Degradation Properties by Combination US and UV Lamp of Different Wavelength (초음파 (US)와 다양한 파장범위의 자외선 (UV) 조사에 따른 DEP 분해특성에 관한 연구)

  • Na, Seung-Min;Cai, Jinhua;Shin, Dong-Hoon;Cui, Mingcan;Khim, Jee-Hyeong
    • Journal of Environmental Science International
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    • v.21 no.7
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    • pp.845-853
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    • 2012
  • Diethyl phthalate (DEP) is widely spread in the natural environment as an endocrine disruption chemicals (EDs). Therefore, in this study, ultrasound (US) and ultraviolet (UVC), including various applied power density (10-40 W/L), UV wavelengths (365 nm, 254 nm and 185 nm) and frequencies (283 kHz, 935 kHz) were applied to a DEP contaminated solution. The pseudo-first order degradation rate constants were in the order of $10^{-1}$ to $10^{-4}\;min^{-1}$ depending on the processes. Photolytic and sonophotolytic DEP degradation rate also were high at shortest UV wavelength (VUV) due to the higher energy of photons, higher molar absorption coefficient of DEP and increased hydroxyl radical generation from homolysis of water. Sonolytic DEP degradation rate increased with increase of applied input power and the dominant reaction mechanism of DEP in sonolysis was estimated as hydroxyl radical reaction by the addition of t-BuOH, which is a common hydroxyl radical scavenger. Moreover, synergistic effect of were also observed for sonophotolytic degradation with various UV irradiation.

Synthesis of Star-like Random Copolymers from Resorcinarene-Based Octa-Functional Alkoxyamine Initiator via Nitroxide Mediated Free Radical Polymerization

  • Abraham, Sinoj;Choi, Jae-Ho;Lee, Jin-Kyu;Ha, Chang-Sik;Kim, Il
    • Macromolecular Research
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    • v.15 no.4
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    • pp.324-329
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    • 2007
  • An octa-functional alkoxyamine initiator, with the 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO) free radical, was synthesized based on resorcinarene, with its efficiency to initiate the nitroxide-mediated free radical copolymerization of styrene and methyl methacrylate (MMA) described. A difunctional analogue of this initiator was also synthesized, using resorcinol as the core molecule. The structures of the resulting initiators were confirmed by homolysis studies based on electron spin resonance spectroscopy and molecular modeling. The polymerization behavior and characteristics of the polymers obtained using these two initiators were also compared. Well-defined star-shaped and linear random copolymers, with low polydispersities and controlled molecular weights, were prepared. The efficiencies of these initiators towards copolymerization, as well as the parameters permitting the formation of well-defined polymers, were also investigated. The reactivity ratios were $r_a=0.42(a=styrene)\;and\;r_b=0.33(b=MMA)$ for the octa-functional initiator system and $r_a=0.45\;and\;r_b=0.39$ for the difunctional initiator system.

Peroxyl Radical Scavenging Capacity of the Flavonolignan Silybin, Ginkgo Biloba Extract EGb 761, American Green Tea and a Series of Germacranolides

  • Winston, Gary W.;Kim, Young Chul;Dugas, Alton J.;Castaneda-Acosta, Jose;Fischer, Nikolaus H.
    • Toxicological Research
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    • v.17
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    • pp.271-280
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    • 2001
  • We report on the applicability oj a method recently developed in our laboratory for measuring the antioxidant potential of isolated chemicals and extracts derived from natural products. Peroxyl radicals generated by thermal homolysis of 2,2'-azobis-amidinopropane (ABAP) oxidize $\alpha$-keto-${\gamma}$-methiolbutyric acid (KMBA) to ethylene, which is monitored by gas chromatography. Inhibition of ethylene formation in the presence of antioxidants that compete with KMBA for peroxyl radicals is the basis of the Total Oxyradical Scavenging Capacity Assay (TOSCA; Winston et al., 1998). Antioxidative activities of water-soluble extracts of American green tea, the anti-hepatotoxic flavonolignan from milk thistle (Silybum marianum) silybin, Ginkgo biloba extract EGb 761, and a series of naturally occuring sesquiterpene lactones (all ger-macranolides found in in fungi, liverworts, and plants) were studied. The specific TOSC value per $\mu$M silybin was 5.2, which is essentially comparable to that of Trolo $x^{ⓡ}$, a water-soluble vitamine E analog. Tea and Ginkgo extracts exhibited potent peroxyl radical scavenging capacity with values, respectively of =1700 and 1000 $\mu$mols Trolo $x^{ⓡ}$ equivalent per gram dry matter. The known anti-inflammatory activity of some germacranolides prompted study of their antioxidant capacity. None of the lactones exhibited antioxidant capacity toward peroxyl radicals comparable to Trolo $x^{ⓡ}$; costunilide, the most lipophilic, had a TOSC value = to glutathione. The potential role of peroxyl radicals in lipidperoxidation, other cellular damage, and var-ious disease states suggest a possible preventive role for silybin, green tea and Ginkgo biloba in oxidative stress caused by these free radical species.ecies.

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Comparison of Hydroxyl Radical, Peroxyl Radical, and Peroxynitrite Scavenging Capacity of Extracts and Active Components from Selected Medicinal Plants

  • Kwon, Do-Young;Kim, Sun-Ju;Lee, Ju-Won;Kim, Young-Chul
    • Toxicological Research
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    • v.26 no.4
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    • pp.321-327
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    • 2010
  • The ability of 80% ethanol extracts from five medicinal plants, Aralia continentalis, Paeonia suffruticosa, Magnolia denudata, Anemarrhena asphodeloides, and Schizonepeta tenuifolia, to neutralize hydroxyl radical, peroxyl radical and peroxynitrite was examined using the total oxyradical scavenging capacity (TOSC) assay. Peroxyl radical was generated from thermal homolysis of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (ABAP); hydroxyl radical by an iron-ascorbate Fenton reaction; peroxynitrite by spontaneous decomposition of 3-morpholinosydnonimine N-ethylcarbamide (SIN-1). The oxidants generated react with $\alpha$-keto-$\gamma$-methiolbutyric acid (KMBA) to yield ethylene, and the TOSC of the substances tested is quantified from their ability to inhibit ethylene formation. Extracts from P. suffruticosa, M. denudata, and S. tenuifolia were determined to be potent peroxyl radical scavenging agents with a specific TOSC (sTOSC) being at least six-fold greater than that of glutathione (GSH). These three plants also showed sTOSCs toward peroxynitrite markedly greater than sTOSC of GSH, however, only P. suffruticosa revealed a significant hydroxyl radical scavenging capacity. Seven major active constituents isolated from P. suffruticosa, quercetin, (+)-catechin, methyl gallate, gallic acid, benzoic acid, benzoyl paeoniflorin and paeoniflorin, were determined for their antioxidant potential toward peroxynitrite, peroxyl and hydroxyl radicals. Quercetin, (+)-catechin, methyl gallate, and gallic acid exhibited sTOSCs 40~85 times greater than sTOSC of GSH. These four components also showed a peroxynitrite scavenging capacity higher than at least 10-fold of GSH. For antioxidant activity against hydroxyl radical, methyl gallate was greatest followed by gallic acid and quercetin. Further studies need to be conducted to substantiate the significance of scavenging a specific oxidant in the prevention of cellular injury and disease states caused by the reactive free radical species.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

  • Cho, Dae-Won;Oh, Sun-Wha;Kim, Dong-Uk;Park, Hea-Jung;Xue, Jin-Ying;Yoon, Ung-Chan;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2453-2458
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    • 2010
  • Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.