• 제목/요약/키워드: Electron transfer reaction

검색결과 258건 처리시간 0.026초

Triphenylphosphine Phenylimide의 전기화학적인 환원 (Electrochemical Reduction of Triphenylphosphine Phenylimide)

  • 박종민
    • 대한화학회지
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    • 제18권5호
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    • pp.341-353
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    • 1974
  • Triphenylphosphine phenylimide의 비수용액에서의 전기화학적인 환원반응을 polarography, cyclic voltammetry, controlled-potential coulometry 및 electron spin resonance 법을 써서 고찰하였다. 이 유기인화합물은 one-electon transfer에 따라서 anion radical이 형성되나 순간일 뿐이고 protonation과 재차 one-electon reduction 결과 인과 질소사이의 이중결합이 끊어진다. 그 결과 아닐린이 주요 반응생성물로서 발견되었다. 또 한편 동반하는 화학반응결과 생긴 주산물의 하나인 triphenylposphine oxide의 환원결과 인과 페닐 사이의 단일결합이 끊어지는 것도 관찰할 수 있었다.

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광학활성인${\Delta}-cis-[Co(en)_2(NO_2)_2]^+$과 라세미-$[CO(Y)^{2-}$(Y=EDTA. PDTA, CyDTA)간의 입체선택적 전자전달반응 (Stereoselective Electron Transfer Reactions between Optically Active${\Delta}-cis-[Co(en)_2(NO_2)_2]^+$and rac-$[CO(Y)^{2-}$(Y=EDTA. PDTA, CyDTA))

  • 이배욱;김동엽;이동진;오창은;도명기
    • 대한화학회지
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    • 제39권4호
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    • pp.275-280
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    • 1995
  • 수소이온 존재하에서 $cis-[Co(en)_2(NO_2)_2]^+$과 라세미-$[Co(Y)]^2-(Y=EDTA,\; PDTA,\; CyDTA)$간에 일어나는 전자전달반응속도를 조사하였다. 속도자료로부터 $cis-[Co(en)_2(NO_2)_2]^+$과 라세미-$[Co(Y)]^2$간에 일어나는 전자전달반응은 수소이온이 촉매로 작용하여 내부권으로 진행되는 것을 알 수 있었다. 한편, 광학활성인 △-cis-$[Co(en)_2(NO_2)_2]^+$과 라세미-$[Co(Y)]^2-(Y=EDTA,\; PDTA,\; CyDTA)$간의 입체선택적 전자전달반응에서는 △-[Co(EDTA)]-, △-[Co(PDTA)]- , △-[Co(CyDTA)]-가 각각 6.0, 2.9, 3.0% e.e.(e.e.=enantiomeric excess) 생성되었다. 이것은 두 착물이 접근하여 먼저 선택적 이온회합을 이루고 전자전달반응이 일어나는 것으로 볼 수 있다. 따라서 △-cis-$[Co(en)_2(NO_2)2_]^+$과 라세미-$[Co(Y)]^{2-}$간의 입체선택적 전자전달반응은 산촉매에 의한 내부적 반응과 입체선택적 이온회합에 따른 외부권 반응으로 진행된다고 추정할 수 있다.

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수정진동자를 이용한 자기조립된 Viologen 유도체의 계면전하이동 특성 (Surface Charge Transfer of Self-Assembled Viologen Derivative Using Quartz Crystal Microbalance)

  • 박상현;류길용;이동윤;권영수
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2005년도 추계학술대회 논문집 Vol.18
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    • pp.256-257
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    • 2005
  • We fabricated self-assembled monolayers(SAMs) onto quartz crystal microbalance(QCM) using viologen, which has been widely used as electron acceptor and electron transfer mediator. The viologen derivative exist in three redox states, namely. These redox reactions are highly reversible and can be cycled many times without significant side reactions, respectively. We studied the characteristics of charge transfer using different electrolyte solutions by electrochemical quartz crystal microbalance (EQCM). From the data, the redox peak currents were nearly equal charges during redox reaction and existed to an excellent linear interrelation between the scan rates and first redox peak currents. The redox reactions of viologen were highly reversible and the EQCM has been employed to monitor the electrochemically induced adsorption of SAMs during the redox reactions.

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3-Phenyl-4-Nitrosydnone의 전기화학적 연구 (Electrochemical Study on the 3-Phenyl-4-Nitrosydnone)

  • 김일광;김윤근;한순종
    • 대한화학회지
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    • 제32권3호
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    • pp.195-202
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    • 1988
  • Acetonitrile 용액중에서 3-phenyl-4-nitrosydnone의 전기화학전 환원을 direct current, differential pulse polarography, cyclic voltammetry 그리고 controlled potential coulometry 방법으로 연구하였다. Phenyl-N 단일 결합의 분리 이전에 nitro 기능기의 비가역적 전자 전달-화학반응(EC)기구의 진행으로 다전자 이동에 의한 amino(또한 hydroxylamino)기를 형성하고, 높은 음 전위 영역에서 2,3 비가역성 환원파의 일전자전달-화학반응에 의한 phenyl hydrazine을 생성하였다. 음극 반파 전위들은 cetyltrimethyl ammonium bromide의 억제 효과에 의해 음의 값으로 이동하였고 한편, sodium lauryl sulfate micelle은 높은 음전위 영역에서 제 2,3 환원파의 가역성산화 peaks를 보였다.

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Reaction between Gas-phase Hydrogen Atom and Chemisorbed Bromine Atoms on a Silicon(001)-(2X1) Surface

  • Park, Jong-Keun;Ree, Jong-Baik;Lee, Sang-Kwon;Kim, Yoo-Hang
    • Bulletin of the Korean Chemical Society
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    • 제28권12호
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    • pp.2271-2278
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    • 2007
  • Electron transfer of a redox protein at a bare gold electrode is too slow to observe the redox peaks. A novel Nafion-riboflavin functional membrane was constructed during this study and electron transfer of cytochrome c, superoxide dismutase, and hemoglobin were carried out on the functional membrane-modified gold electrode with good stability and repeatability. The immobilized protein-modified electrodes showed quasireversible electrochemical redox behaviors with formal potentials of 0.150, 0.175, and 0.202 V versus Ag/AgCl for the cytochrome c, superoxide dismutase and hemoglobin, respectively. Whole experiment was carried out in the 50 mM MOPS buffer solution with pH 6.0 at 25 oC. For the immobilized protein, the cathodic transfer coefficients were 0.67, 0.68 and 0.67 and electron transfer-rate constants were evaluated to be 2.25, 2.23 and 2.5 s?1, respectively. Hydrogen peroxide concentration was measured by the peroxidase activity of hemoglobin and our experiment revealed that the enzyme was fully functional while immobilized on the Nafion-riboflavin membrane.

Interaction Metal Ions with NADH Model Compounds. Cupric Ion Oxidation of Dihydronicotinamides

  • Park, Joon-Woo;Yun, Sung-Hoe;Koh Park, Kwang-Hee
    • Bulletin of the Korean Chemical Society
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    • 제9권5호
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    • pp.298-303
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    • 1988
  • Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

Nanoscale Protein Chip based on Electrical Detection

  • Choi, Jeong-Woo
    • 한국생물공학회:학술대회논문집
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    • 한국생물공학회 2005년도 생물공학의 동향(XVI)
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    • pp.18-18
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    • 2005
  • Photoinduced electron transport process in nature such as photoelectric conversion and long-range electron transfer in photosynthetic organisms are known to occur not only very efficiently but also unidirectionally through the functional groups of biomolecules. The basic principles in the development of new functional devices can be inspired from the biological systems such as molecular recognition, electron transfer chain, or photosynthetic reaction center. By mimicking the organization of the biological system, molecular electronic devices can be realized $artificially^{1)}$. The nano-fabrication technology of biomolecules was applied to the development of nano-protein chip for simultaneously analyzing many kinds of proteins as a rapid tool for proteome research. The results showed that the self-assembled protein layer had an influence on the sensitivity of the fabricated bio-surface to the target molecules, which would give us a way to fabricate the nano-protein chip with high sensitivity. The results implicate that the biosurface fabrication using self-assembled protein molecules could be successfully applied to the construction of nanoscale bio-photodiode and nano-protein chip based on electrical detection.

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WC/C 박막의 윤활접촉하의 마멸기구 (The Wear Mechanism of Carbon(WC/C) Thin Film in Lubricated Contact)

  • 안효석;김두인
    • Tribology and Lubricants
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    • 제24권6호
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    • pp.302-307
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    • 2008
  • The running-in behaviour of the metal carbon coating (WC/C) was evaluated with regard to its applicability as wear-resistant coating for key components in engines. Reciprocating wear tests under lubricated condition employing an oscillating friction wear tester were performed to investigate the tribological behaviors of the coatings in ambient environment. Confocal microscopy and scanning electron microscopy were used to observe worn surfaces and the wear scars on the steel balls. Elemental composition of the coating and worn surfaces were characterized using Auger electron spectroscopy. The friction behavior of WC/C coating was comparable to common carbon-based coatings. Thin tribofilm was formed on the worn surface of the steel ball due to material transfer and tribochemical reaction whereas there was no evidence of tribofilm generation on the coating surface. indicating the chemical innertness of WC/C coating.

Cr(VI)-6-Methylquinoline을 이용한 치환 벤질 알코올류의 산화반응과 속도론에 관한 연구 (A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using Cr(VI)-6-Methylquinoline)

  • 박영조;김영식
    • 공업화학
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    • 제26권3호
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    • pp.372-376
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    • 2015
  • 6M HCl 용매 하에서 6-메틸퀴놀린과 chromium(VI) trioxide의 반응을 통하여 6-MQCC(크롬(VI)-6-메틸퀴놀린) 착물을 합성하였다. 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 6-MQCC을 이용하여 벤질 알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 DMF > 아세톤 > 클로로포름 > 시클로헥센이었다. 산($H_2SO_4$) 촉매를 이용한 DMF 용매 하에서, 6-MQCC은 벤질 알코올(H)과 그의 유도체들($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$)을 효과적으로 산화시켰다. 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(${\rho}$) 값은 -0.69 (308 K)이었다. 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.

크롬(VI)-피라진 착물을 이용한 알코올류의 산화반응과 메카니즘 (Mechanism for the Oxidation Reaction of Alcohols Using Cr(VI)-Pyrazine Complex)

  • 박영조;김영식
    • 공업화학
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    • 제27권1호
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    • pp.110-114
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    • 2016
  • 6M HCl 용매 하에서 피라진과 chromium (VI) trioxide의 반응을 통하여 PZCC (크롬 (VI)-피라진 착물)을 합성하였다. 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 PZCC을 이용하여 벤질알코올의 산화반응을 측정한 결과, 용매의 유전상수 값이 증가함에 따라 반응수율이 증가했다. 그 순서는 N,N'-디메틸포름아미드 > 아세톤 > 클로로포름 > 시클로헥센이었다. 산($H_2SO_4$) 촉매를 이용한 N,N'-디메틸포름아미드 용매 하에서, PZCC은 벤질알코올(H)과 그의 유도체들($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$)을 효과적으로 산화시켰다. 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰고, Hammett 반응상수(${\rho}$)값은 -0.70 (308 K)이었다. 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어났다.