• Title/Summary/Keyword: C-H activation

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Density Functional Study on the C-H Bond Cleavage of Aldimine by a Rhodium(I) Catalyst

  • Yoo, Kyung-Hwa;Jun, Chul-Ho;Choi, Cheol-Ho;Sim, Eun-Ji
    • Bulletin of the Korean Chemical Society
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    • 제29권10호
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    • pp.1920-1926
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    • 2008
  • We investigated the C-H bond activation mechanism of aldimine by the [RhCl$(PPH_3)_3$] model catalyst using DFT B3LYP//SBKJC/6-31G*/6-31G on GAMESS. Due to their potential utility in organic synthesis, C-H bond activation is one of the most active research fields in organic and organometallic chemistry. C-H bond activation by a transition metal catalyst can be classified into two types of mechanisms: direct C-H bond cleavage by the metal catalyst or a multi-step mechanism via a tetrahedral transition state. There are three structural isomers of [RhCl$(PH_3)_2$] coordinated aldimine that differ in the position of chloride with respect to the molecular plane. By comparing activation energies of the overall reaction pathways that the three isomeric structures follow in each mechanism, we found that the C-H bond activation of aldimine by the [RhCl$(PH_3)_3$] catalyst occurs through the tetrahedral intermediate.

Culturability of Clostridium botulinum Spores under Different Germination Conditions, Sublethal Heat Treatments, and in the Presence of Nisin

  • Chung, Yoon-Kyung;Yousef, Ahmed E.
    • Preventive Nutrition and Food Science
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    • 제12권4호
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    • pp.251-258
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    • 2007
  • Thermal resistance and heat activation characteristics of Clostridium botulinum ATCC 25763 spores were evaluated. The effects of nisin and pH on the activation and subsequent germination were also investigated. Spores of C. botulinum were not inactivated by heat treatments up to $92^{\circ}C$ for 2 hr. Heat treatment at $85^{\circ}C$ for 90 min was selected as the optimal activation condition based on monitoring subsequent germination. L-alanine alone or in combination with L-cysteine was not sufficient to germinate the spores of this strain. Tryptone-Peptone- Glucose-Yeast extract (TPGY) broth supplemented with L-alanine was used as a suitable germination medium. Decreasing pH of activation suspension increased the degree of phase darkening, i.e., germination. In addition, the presence of nisin during activation increased the degree of phase darkening. The majority of spore populations were dormant at a pH of less than 2.8, and these populations required heat activation to increase the culturability on TPGY agar medium. However, extended heating in the presence of nisin at pH 2.8 decreased the spore count; however, heat activation was less necessary at pH 3.4, compared at pH 2.8.

Theoretical Study of C-H σ-Bond Activation and Related Reactions

  • Sakaki, Shigeyoshi
    • Bulletin of the Korean Chemical Society
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    • 제24권6호
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    • pp.829-831
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    • 2003
  • Various theoretical studies of σ-bond activation of organic molecules by transition metal complexes arereviewed. In the homolytic σ-bond activation, the d orbital energy level of the central metal is an importantfactor, as well known. At the same time, the electron-withdrawing substituent which stabilizes the sp3 orbitalaccelerates the homolytic σ-bond activation. In the heterolytic C-H σ-bond activation of RH by $MXL_n$, the XHbond formation is an important driving force, where $MRL_n$ and HX are formed as products. The heterolytic σ-bond activation is also understood in terms of the electrophilic attack of the metal center to the substrate.

SiC 웨이퍼의 이온 주입 손상 회복을 통한 Macrostep 형성 억제 (Suppression of Macrostep Formation Using Damage Relaxation Process in Implanted SiC Wafer)

  • 송근호;김남균;방욱;김상철;서길수;김은동
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2002년도 하계학술대회 논문집
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    • pp.346-349
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    • 2002
  • High Power and high dose ion implantation is essentially needed to make power MOSFET devices based on SiC wafers, because the diffusivities of the impurities such as Al, N, p, B in SiC crystal are very low. In addition, it is needed high temperature annealing for electrical activation of the implanted species. Due to the very high annealing temperature, the surface morphology after electrical activation annealing becomes very rough. We have found the different surface morphologies between implanted and unimplanted region. The unimplanted region showed smoother surface morphology It implies that the damage induced by high energy ion implantation affects the roughening mechanism. Some parts of Si-C bonding are broken in the damaged layer, s\ulcorner the surface migration and sublimation become easy. Therefore the macrostep formation will be promoted. N-type 4H-SiC wafers, which were Al ion implanted at acceleration energy ranged from 30kev to 360kev, were activated at 1600$^{\circ}C$ for 30min. The pre-activation annealing for damage relaxation was performed at 1100-1500$^{\circ}C$ for 30min. The surface morphologies of pre-activation annealed and activation annealed were characterized by atomic force microscopy(AFM).

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Activation of JNK and c-Jun Is Involved in Glucose Oxidase-Mediated Cell Death of Human Lymphoma Cells

  • Son, Young-Ok;Jang, Yong-Suk;Shi, Xianglin;Lee, Jeong-Chae
    • Molecules and Cells
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    • 제28권6호
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    • pp.545-551
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    • 2009
  • Mitogen-activated protein kinases (MAPK) affect the activation of activator protein-1 (AP-1), which plays an important role in regulating a range of cellular processes. However, the roles of these signaling factors on hydrogen peroxide ($H_2O_2$)-induced cell death are unclear. This study examined the effects of $H_2O_2$ on the activation of MAPK and AP-1 by exposing the cells to $H_2O_2$ generated by either glucose oxidase or a bolus addition. Exposing BJAB or Jurkat cells to $H_2O_2$ affected the activities of MAPK differently according to the method of $H_2O_2$ exposure. $H_2O_2$ increased the AP-1-DNA binding activity in these cells, where continuously generated $H_2O_2$ led to an increase in mainly the c-Fos, FosB and c-Jun proteins. The c-Jun-$NH_2$-terminal kinase (JNK)-mediated activation of c-Jun was shown to be related to the $H_2O_2$-induced cell death. However, the suppression of $H_2O_2$-induced oxidative stress by either JNK inhibitor or c-Jun specific antisense transfection was temporary in the cells exposed to glucose oxidase but not to a bolus $H_2O_2$. This was associated with the disruption of death signaling according to the severe and prolonged depletion of reduced glutathione. Overall, these results suggest that $H_2O_2$ may decide differently the mode of cell death by affecting the intracellular redox state of thiol-containing antioxidants, and this depends more closely on the duration exposed to $H_2O_2$ than the concentration of this agent.

CH3OH/H2O 가스의 기상활성법을 이용한 다이아몬드 박막성장 과정에서의 OES분석 (OES Analysis for Diamond Film Growth by Vapor Activation Method Using CH3OH/H2O Gas)

  • 이권재;고재귀;신재수
    • 한국재료학회지
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    • 제13권1호
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    • pp.31-35
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    • 2003
  • The intensity is measured as functions of both distance from filament to substrate and $CH_3$OH/($CH_3$OH+$H_2$O) ratio by OES(Optical Emission Spectroscopy) to investigate the effects of activation species such as $H_{\alpha}$, $H_{\beta}$, H$\Upsilon\;C_3$, CH on diamond film growth.$ H_{\alpha}$ increases as $CH_3$OH composition decreases, while CH increases as $CH_3$OH composition increases. The intensity of $H_{\alpha}$ decreases as the distance increases and that of CH increases as the distance increases. The intensities of other activation species of $H_{\beta}$, H$\Upsilon\;C_3$, do not vary as a function of measured position distance. It varies randomly. It means that various parameters for depositing diamond thin film can be explained by the intensity(density) change of activation species, as a function of the distance of the filament.

Papaya Latex에 있는 단백질분해효소(蛋白質分解酪素)들의 열불활성(熱不活性)에 관하여 (Heat Inactivation of Proteolytic Enzymes in Papaya Latex)

  • 노봉수;박관화
    • 한국식품과학회지
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    • 제12권3호
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    • pp.209-215
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    • 1980
  • 파파이야 라텍스를 $(NH_4)_2SO_4$,분획 및 CM-cellulose column을 통과시켜 두개의 획분으로 분리하고 각 획분 별로 pH 7.0, $60{\sim}90^{\circ}C$에서 열 불활성 실험을 행하고 다음과 같은 열역학적인 자료를 얻었다. 1. fraction I 의 z-value는 $25^{\circ}C$이었고 $70^{\circ}C$에서 활성화 엔탈피 (enthalpy of activation) 89.5 kJ/mol, 활성화엔트로피 (entropy of activation) -44.0 kJ/mol K, 활성화 자유에너지(free energy of activation) 104.6 kJ/mol이었다. 2. fraction II 의 z-value는 $23^{\circ}C$이고 $70^{\circ}C$에서 활성화 엔트로피 -22.0 kJ/mol K, 활성화 자유에너지 104.2 kJ/mol이었다. 3. fraction I과 fraction II를 혼합한 경우의 z-value는 $24.6^{\circ}C$, $70^{\circ}C$에서 활성화 엔탈피 90.9 kJ/mol, 활성화 앤트로피 -38.8 J/mol K, 활성화 자유에너지 104.2 kJ/mol이었다. 4. 조 추출액의 z-value는 $23.2^{\circ}C$이고 $70^{\circ}C$에서 활성화 엔트로피 113.8 kJ/mol, 활성화 엔트로피 22.0 kJ/mol K, 활성화자유에너지 106.2 kJ/mol이었다. 이상의 결과에서 fraction I 이 fraction II 보다 열에 안정하다고 볼 수 있었고 파파이야 라텍스에 있는 단백질 분해 효소의 열 안정성은 주로 fraction I 에 기인하는 것 을 알 수 있었다.

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시멘트종류에 따른 압축강도와 등가재령 관계에 관한 실험적 연구 (An Experimental Study on the Relation of Compressive Strength and the Equivalent Age according to the Kind of Cement)

  • 나철성;장종호;길배수;김정일;남재현;김무한
    • 한국건축시공학회:학술대회논문집
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    • 한국건축시공학회 2003년도 학술.기술논문 발표회
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    • pp.13-16
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    • 2003
  • There is no study that application of the maturity using H.B.C and H.S.C. Also activation energy has different values according to the cement, admixture and water-cement ratio. Therefore to make accurate explanation for the effect of temperature on concrete strength development properties, it is necessary that activation energy value according to the kind of cement is reviewed. This study compares and estimates equivalent age using activation energy value obtained by this experiment and Freiesleben activation energy value with compressive strength of concrete. As the result of this study, activation energy value obtained by this study has more accurate explanation of temperature's influence on concrete strength development than Freiesleben activation energy value.

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