• Title/Summary/Keyword: Oxidation Mechanism

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An Efficient and Mild Oxidation of α-Isophorone to Ketoisophorone Catalyzed by N-Hydroxyphthalimide and Copper Chloride

  • Chen, Lihua;Tang, Ruiren;Li, Zhongying;Liang, Shan
    • Bulletin of the Korean Chemical Society
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    • v.33 no.2
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    • pp.459-463
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    • 2012
  • N-hydroxyphthalimide (NHPI) and copper chloride ($CuCl_2$) were first utilized for aerobic oxidation of ${\alpha}$-isophorone (${\alpha}$-IP) to ketoisophorone (KIP) and the effects of co-catalysts, temperature, reaction time, solvent, amount of $CuCl_2$ and pressure of oxygen were investigated extensively. NHPI/$CuCl_2$ turned out to be highly efficient to this oxidation with up to 91.3% conversion and 81.0% selectivity under mild conditions. And various hydrocarbons including benzylic compounds, cycloalkene and its derivatives were also oxidized smoothly under optimized conditions. Moreover, the possible reaction mechanism was proposed and verified by FT-IR spectra.

Growth and Properties of Ultra-thin SiO2 Films by Rapid Thermal Dry Oxidation Technique (급속 건식 열산화 방법에 의한 초박막 SiO2의 성장과 특성)

  • 정상현;김광호;김용성;이수홍
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.1
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    • pp.21-26
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    • 2004
  • Ultra-thin silicon dioxides were grown on p-type(100) oriented silicon employing rapid thermal dry oxidation technique at the temperature range of 850∼1050 $^{\circ}C$. The growth rate of the ultra-thin film was fitted well with tile model which was proposed recently by da Silva & Stosic. The capacitance-voltage, current-voltage, characteristics were used to study the electrical properties of these thin oxides. The minimum interface state density around the midgap of the MOS capacitor having oxide thickness of 111.6 $\AA$ derived from the C-V curve was ranged from 6 to 10${\times}$10$^{10}$ /$\textrm{cm}^2$eV.

Oxidation Stability of Regenerated Lubricating Oils (II) Formation of anti-Oxidant Materials (潤滑再生油의 酸化安定性能 (第2報). 抗酸化性 物質의 生成)

  • Nah Yun Ho
    • Journal of the Korean Chemical Society
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    • v.19 no.1
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    • pp.50-52
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    • 1975
  • The oxidation stability of samples prepared by blending samples reported previously with diesel oil and diesel oil with additives(alkyl benzene and phenolic type of materials), was tested to study the mechanism of thermal oxidation stability of the regenerated lubricating oils. It was found that the improvement of thermal oxidation stability of such oils was caused by the formation of aromatic compounds, especially phenolic type of organic materials.

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Partial Oxidation of Methane over CeO2 Catalyst

  • Rho, Hyun-Seog;Jun, Ki-Won;Baek, Seung-Chan;Park, Sang-Eon
    • Bulletin of the Korean Chemical Society
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    • v.23 no.6
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    • pp.799-803
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    • 2002
  • Partial oxidation of methane has been conducted over $CeO_2$and it has been found that $CeO_2$has an extraordinary catalytic activity in the reaction. Its activity was strongly dependent on the $CH_4/CO_2$ ratio. Total combustion was dominant with stoichiometric feed ratio$(CH_4/O_2=$ 2.0) but partial oxidation was achieved between the $CH_4/O_2$ ration of 3.8 4.3 and the period depended upon the feed composition. The proposed raaction mechanism it that oxygen vacancies in raduced deria are supplied with oxygen molecules from the reactant, and then activate adsorbed oxygen, followed by releasing activated axygen species reacting with methane to produce $H_2$ and CO.

Tribological Characteristics of Silicon Nitride on Elevated Temperature (고온하에서 질화규소의 트라이볼로지적 특성)

  • 김대중;채영훈;김석삼
    • Tribology and Lubricants
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    • v.16 no.4
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    • pp.282-288
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    • 2000
  • A sliding friction and wear test for silicon nitride (Si,N4) was conducted using a ball-on-disk specimen configuration. The material used in this study was HIPed silicon nitride. The tests were carried out from room temperature to 1000$^{\circ}C$ using self-mated silicon nitride couples in laboratory air. The worn surfaces were observed by SEM and the debris particles from the worn surfaces were analyzed for oxidation by XPS. The normal load was found to have a more significant influence on the friction coefficient of the silicon nitride than an elevated temperature. The specific wear rate was found to decrease along with the sliding distance. The specific wear rate at 29.4 N and 1000$^{\circ}C$ was 292 times larger than that at room temperature. The main wear mechanism from room temperature to 750$^{\circ}C$ was caused by brittle fracture whereas from 750$^{\circ}C$ to 1000$^{\circ}C$ the wear mechanism was mainly influenced by the oxidation of silicon nitride due to the increased temperature. The oxidation of silicon nitride at a high temperature was a significant factor in the wear increase.

Kinetic Study of the Electrooxidation of Mefenamic Acid and Indomethacin Catalysed on Cobalt Hydroxide Modified Glassy Carbon Electrode

  • Saghatforoush, Lotfali.;Hasanzadeh, Mohammad.;Karim-Nezhad, Ghasem.;Ershad, Sohrab.;Shadjou, Nasrin.;Khalilzadeh, Balal.;Hajjizadeh, Maryam.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1341-1348
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    • 2009
  • Electrocatalytic oxidation of two anti-inflammatory drugs (Mefenamic acid and Indomethacin) was investigated on a cobalt hydroxide modified glassy carbon (CHM-GC) electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry and chronoamperometry techniques as well as steady state polarization measurements. Voltammetric studies indicated that in the presence of under study drugs, the anodic peak current of low-valence cobalt species increased, followed by a decrease in the corresponding cathodic current. This result indicates that the drugs were oxidized via cobalt hydroxide species immobilized on the electrode surface via an E$\acute{C}$ mechanism. A mechanism based on the electrochemical generation of Co (IV) active sites and their subsequent consumption by the drugs in question was also investigated. The constants rate of the catalytic oxidation of the drugs and the electron-transfer coefficients reported.

A study on the behavior of charge particles of $(SR.Ca)TiO_3$ ceramic ($(SR.Ca)TiO_3$세라믹의 하전입자 거동에 관한 연구)

  • 김진사;최운식;신철기;김성열;박현빈;김태성;이준응
    • Electrical & Electronic Materials
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    • v.10 no.2
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    • pp.97-104
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    • 1997
  • In this paper, in order to investigate the behavior of charged particles on (Sr.Ca)TiO$_{3}$ ceramics with paraelectric properties, the characteristics of electrical conduction and thermally stimulated current was measured respectively. As a result, the conduction mechanism is divided into three regions having different mechanism as the current increased. The region I below 200[V/Cm] shows the ohmic conduction. The region B between 200[V/cm] and 2000[V/cm] can be explained by the Poole-Frenkel emission theory, and the region III above 2000[V/cm] is dominated by the tunneling effect. The three peaks of TSC were obtained at the temperature of -20[.deg. C], 20[.deg. C] and 80[.deg. C], respectively. The origins of these peaks are that the .alpha. peak observed at -20[.deg. C] looks like to be ascribed to the ionization excitation from donor level in the grain, and the .alpha.' peak observed at 20 [.deg. C] appears to show up by hopping conduction of the trapped carrier of border between the oxidation layer and the grain, and the .betha. peak observed at 80[.deg. C] seems to be resulted from hopping conduction of existing carrier in the trap site of the border between the oxidation and second phase.

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The structures and catalytic activities of metallic nanoparticles on mixed oxide

  • Park, Jun-Beom
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.339-339
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    • 2010
  • The metallic nanoparticles (Pt, Au, Ag. Cu, etc.) supported on ceria-titania mixed oxide exhibit a high catalytic activity for the water gas shift reaction ($H_2O\;+\;CO\;{\leftrightarrow}\;H_2\;+\;CO_2$) and the CO oxidation ($O_2\;+\;2CO\;{\leftrightarrow}\;2CO_2$). It has been speculated that the high catalytic activity is related to the easy exchange of the oxidation states of ceria ($Ce^{3+}$ and $Ce^{4+}$) on titania, but very little is known about the ceria titanium interaction, the growth mode of metal on ceria titania complex, and the reaction mechanism. In this work, the growth of $CeO_x$ and Au/$CeO_x$ on rutile $TiO_2$(110) have been investigated by Scanning Tunneling Microscopy (STM), Photoelectron Spectroscopy (PES), and DFT calculation. In the $CeO_x/TiO_2$(110) systems, the titania substrate imposes on the ceria nanoparticles non-typical coordination modes, favoring a $Ce^{3+}$ oxidation state and enhancing their chemical activity. The deposition of metal on a $CeO_x/TiO_2$(110) substrate generates much smaller nanoparticles with an extremely high activity. We proposed a mechanism that there is a strong coupling of the chemical properties of the admetal and the mixed-metal oxide: The adsorption and dissociation of water probably take place on the oxide, CO adsorbs on the admetal nanoparticles, and all subsequent reaction steps occur at the oxide-admetal interface.

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Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

  • Li, Yan;Chang, Jie;Ouyang, Yong;Zheng, Xianwei
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1654-1658
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    • 2014
  • High value-added aromatic aldehydes (e.g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide ($H_2O_2$) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin ($Co(TPPS_4)$) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without $Co(TPPS_4)$. Moreover, a possible mechanism of HFBO oxidation using $Co(TPPS_4)/H_2O_2$ was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under $Co(TPPS_4)/H_2O_2$ system.

Enzymatic DNA oxidation: mechanisms and biological significance

  • Xu, Guo-Liang;Walsh, Colum P.
    • BMB Reports
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    • v.47 no.11
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    • pp.609-618
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    • 2014
  • DNA methylation at cytosines (5mC) is a major epigenetic modification involved in the regulation of multiple biological processes in mammals. How methylation is reversed was until recently poorly understood. The family of dioxygenases commonly known as Ten-eleven translocation (Tet) proteins are responsible for the oxidation of 5mC into three new forms, 5-hydroxymethylcytosine (5hmC), 5-formylcytosine (5fC) and 5-carboxylcytosine (5caC). Current models link Tet-mediated 5mC oxidation with active DNA demethylation. The higher oxidation products (5fC and 5caC) are recognized and excised by the DNA glycosylase TDG via the base excision repair pathway. Like DNA methyltransferases, Tet enzymes are important for embryonic development. We will examine the mechanism and biological significance of Tet-mediated 5mC oxidation in the context of pronuclear DNA demethylation in mouse early embryos. In contrast to its role in active demethylation in the germ cells and early embryo, a number of lines of evidence suggest that the intragenic 5hmC present in brain may act as a stable mark instead. This short review explores mechanistic aspects of TET oxidation activity, the impact Tet enzymes have on epigenome organization and their contribution to the regulation of early embryonic and neuronal development.