• Title/Summary/Keyword: Radical mechanism

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PARTIAL OXIDATION OF PROPANE ON NAFION SUPPORTED CATALYTIC MEMBRANE

  • F. Frusteri;C. Espro;F. Arena;F. Arena;E. Passalacqua;A.Patti;A. Parmaliana
    • Proceedings of the Membrane Society of Korea Conference
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    • 1999.07a
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    • pp.55-58
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    • 1999
  • Nafion supported catalytic membranes were found to be active, stable and selective in th partial oxidation of propane to oxygenates with H2O2 under mild condition. Addition of Fe2+ in liquid phase enhances the reaction rate. Reaction proceeds according to a radical mechanism based on th electrophilic activation of propane on superacid sites and subsequent reaction of the activated paraffin with OH radicals. The use of a catalytic membrane, which allow separation of the intermediate products from the liquid phase containing the oxidant, was found to be effective to perform selective partial oxidation of propane with high yields to oxygenated products.

Study of silicon deep via etching mechanism using in-situ temperature monitoring of silicon exposed to $SF_6/O_2$ plasma discharge

  • Im, Yeong-Dae;Lee, Seung-Hwan;Yu, Won-Jong;Jeong, Oh-Jin;Lee, Han-Chun
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2009.10a
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    • pp.116-117
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    • 2009
  • 식각 공정변화 즉 상부 ICP 파워, 반응기 압력, 실리콘 기판 온도변화에 따른 실리콘 딥 비어 (deep via) 의 형상 변화 메커니즘을 연구하였다. 메커니즘을 연구하기 위해 $SF_6/O_2$ 플라즈마에 노출된 실리콘 기판의 공정변화에 따른 표면 온도변화를 실시간으로 측정하여 플라즈마 내 positive ions의 거동을 분석하였다. 실리콘 기판의 표면온도를 상승시키는 주된 요인은 positive ions임을 확인할 수 있었으며 이는 기판에 적용된 negative voltage로 인하여 나타난 이온포격이 그 원인임을 알 수 있었다. 상대적으로 radical은 실리콘 표면온도 상승에 큰 역할을 하지 못하였다. 기판 표면온도가 상승 할수록 실리콘 딥 비어 구조에 undercut, local bowing과 같은 측벽 식각이 활성화됨을 확인할 수 있었으며 이는 기판에 들어오는 positive ions가 측벽식각을 유도하는 것으로 해석할 수 있었다.

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Mechanism and Products During the Homolytic Addition of CCl$_4$ and Cl$_3$CBr to $\beta$-Halostyrenes

  • Kim Sung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.1 no.2
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    • pp.45-49
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    • 1980
  • During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

The Photochemical Reactivities of Benzenes Tethered to Haloarene

  • 박용태;김영희;황철균;성대동
    • Bulletin of the Korean Chemical Society
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    • v.17 no.6
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    • pp.506-510
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    • 1996
  • The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.

Chemistry of Ruthenium Hydridonitrosyl Complexes Containing Chelating Triphosphines IV-Reactions between RuH(NO)(Cyttp) and Alkynes (Cyttp: Bis(dicyclohexylphosphino-propyl)phenylphosphine)

  • Ik-Mo Lee;Ook-Jae Cho;Devon W. Meek;Chan-Yong Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.625-631
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    • 1993
  • The types of the products of the reactions between RuH(NO)(Cyttp) and alkynes are sensitive to the nature of alkynes. Terminal, nonactivated alkynes (HC${\equiv}$CR, R=Ph, hexyl and $CH_2OH)$ produce acetylide complexes and terminal (HC${\equiv}$CR, R=C(O)Me, COOEt) or internal activated ones (RC${\equiv}$ CR, R=COOMe) lead to form alkenyl complexes. On the other hand, internal nonactivated alkynes (RC${\equiv}$CR, R=Ph) do not show reactivity toward RuH(NO)(Cyttp). These products can be rationalized by the cis-concerted mechanism but the radical pathway appears to work in the reaction of propargyl chloride. From the spectroscopic data, the trigonal bipyramidal structure with a linear NO group is proposed for these products.

Hydrodediazoniation of Arenediazonium Tetrafluoroborate with Triethylamine

  • 박군하;조윤환;장은주
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.179-182
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    • 1996
  • Hydrodediazoniation product (3a-d) was found to be the major product in the reaction of arenediazonium tetrafluoroborate (1a-d) with triethylamine (2) in methanol under nitrogen at room temperature. A quantitative study on the title reaction was investigated in detail and two remarks were noteworthy. One was the linear increase in the yield of 3a-d by increasing the molar concentration of 2 until equimolar concentration was reached between 1a-d and 2. The other was the suppression of the formation of 3a-d in the presence of oxygen. Based on these results, the title reaction was better understood by 1:1 electron transfer reaction between reactants (1a-d and 2) rather than by radical chain mechanism proposed in the reaction of arenediazonium tetrafluoroborate and triphenylphosphine.

Reactivity and Mechanism for Aryl Carbenic Anion Radicals

  • Sung, Dae-Dong;Uhm, Tae-Seop;Lee, Jong-Pal;Ryu, Zoon-Ha;Kim, Hyung-Tae
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.183-187
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    • 1993
  • Aryl carbenic anion radicals have been generated from the corresponding alkoxy-aryl diazo compounds by unimolecular decomposition reaction in various electrolyte/solvent systems. The electrochemical reductions of alkoxy-aryl diazo compounds in the electrolyte/solvent system are shown to initially be a one-electron process which affords the corresponding anion radicals. The unimolecular loss of nitrogen is favored at the propagation step and accelerated by the oxygen and carbon atoms of alkoxy group adjacent to the diazo function. The structure of the carbene anion radical in the termination is considered to be a resonance hybrid.

Mechanism on the Formation of Bis-9,9'-thioxanthenylmethane from the Reaction of Thioxanthylium Ion With Dimethylmercury(I)

  • Kim, Sung-Hoon;Kim, Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.157-162
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    • 1982
  • 9-Methylenethioxanthene(6) was synthesized and for the first time good mp and spectral data were taken. Reaction of (6) with thioxanthylium ion (1) in acetonitrile led to a carbenium addition adduct (8) which then was either attacked by a variety of nucleophiles subsequently added or underwent deprotonation reaction to give an olefin (13). From these reactions, was obtained bis-9,9'-thioxanthenylmethane (2). These results indicate clearly that (2) can be formed via (8) by accepting hydride. Isolation of (2) and (6) from the reaction of (1) with 9-methylthioxanthylium ion (18) also supports the involvement of (8) in the reaction of (1) with dimethylmercury. However, addition of thioxanthene radical (4) to (6) has not been ruled out.

Hijikia fusiforme Attenuate the Mast Cell-mediated Inflammatory Response through NF-kB Pathway Regulation

  • Su-Jin Kim
    • Korean Journal of Plant Resources
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    • v.36 no.6
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    • pp.549-555
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    • 2023
  • Hijikia fusiforme (HF), a member of brown algae family, exerts various pharmacological effects, including preventing arteriosclerosis and menopausal disorders. This study aimed to elucidate the ameliorative effect of HF on skin inflammation. We investigated the antioxidant and anti-inflammatory effect of HF extract to evaluate its potential as a functional materials. The antioxidant activity of HF was determined using 2,2-diphenyl-1-picrylhydrazy (DPPH) scavenging and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS+) scavenging. To determine the pharmacological mechanism of HF in inflammatory reaction, we evaluated the effects of HF on interleukin (IL)-8, IL-6 and tumor necrosis factor (TNF)-α production and nuclear factor-κB (NF-κB) activation in activated- human mast cells (HMC)-1. Results showed that HF had the high DPPH and ABTS+ radical scavenging activity, and it suppressed IL-8, IL-6 and TNF-α production in a concentration-dependent manner. Moreover, HF significantly ameliorated NF-kB activation in activated-HMC-1. Hence, these results provide evidence that HF's potential for skin inflammation therapy.

The Study of Free Radical Scavenging Effect of Lycii Fructus by Liver Injury of Rats (백서 간손상에 의한 구기자의 유리자유기 소거능에 관한 연구)

  • Yoon Sang Ju;Jung Sun Yeong;Kim Young Mi;Ha Ki Tae;Kim Cheorl Ho;Kim Dong Wook;Kim June Ki;Choi Dall Yeong
    • Journal of Physiology & Pathology in Korean Medicine
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    • v.17 no.1
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    • pp.91-100
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    • 2003
  • In the present study, we investigated the protective effect of the Lycii Fructus water extracts (LFE) against CCl4-induced hepatotoxicity and the mechanism underlying these protective effects in the rats. The pretreatment of LFE has shown to possess a significant protective effect by lowering the serum alanine and aspartate aminoteansferase (AST and ALT) and alkaline phosphatase (ALP). This hepatoprotective action was confirmed by histological observation, In addition, the pretreatment of LFE prevented the elevation of hepatic malondialdehyde (MDA) formation and the depletion of reduced glutathione (GSH) content and catalase activity in the liver of CC1₄-injected rats. The LFE also displayed hydroxide radical scavenging activity in a dose-dependent manner (IC50 = 83.6 μg/ml), as assayed by electron spin resonance (ESR) spin-trapping technique. Moreover, the expression of cytochrome P450 2E1 (CYP2E1) mRNA, as measured by reverse transcriptase-polymerase chain reaction (RT-PCR), was significantly decreased in the liver of LFE-pretreated rats when compared with that in the liver of control group. Based on these results, it was suggested that the hepatoprotective effects of the LFE may be related to antioxidant effects and regulation of CYP2E1 gene expression.