• 제목/요약/키워드: Electron transfer reaction

검색결과 258건 처리시간 0.027초

크롬(VI)-4-(Dimethylamino)pyridine에 의한 알코올류의 산화반응과 반응속도에 관한 연구 (A Study for Kinetics and Oxidation Reaction of Alcohols by Cr(VI)-4-(Dimethylamino)pyridine)

  • 김영식;박영조;김영준
    • 한국산학기술학회논문지
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    • 제14권1호
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    • pp.499-505
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    • 2013
  • 6M-HCl 용매 하에서 헤테로고리 화합물인 4-(dimethylamino)pyridine과 chromium(VI) trioxide의 반응을 통하여 4-(dimethylamino)pyridinium chlorochromate[$C_7H_{10}N_2HCrO_3Cl$] 착물을 합성하여, 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 4-(dimethylamino)pyridinium chlorochromate를 이용하여 벤질알코올의 산화반응을 측정한 결과 유전상수(${\varepsilon}$) 값이 큰 용매 즉, 시클로헥센<클로로포름<아세톤$H_2SO_4$)를 이용한 N,N'-디메틸포름아미드 용매 하에서 4-(dimethylamino)pyridinium chlorochromate는 벤질 알코올과 그의 유도체들(p-$OCH_3$, m-$CH_3$, H, m-$OCH_3$, m-Cl, m-$NO_2$)을 효과적으로 산화시켰다. 그리고 전자받개 그룹들은 반응속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰다. 또한 Hammett 반응상수(${\rho}$) 값은 -0.68(303K) 이었다. 그러므로 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어나는 메카니즘임을 알 수 있었다.

Study the Electrochemical Reduction of Some Triazines in N,N-Dimethylformamide at Glassy Carbon Electrode

  • Fotouhi, L.;Farzinnegad, N.;Heravi, M.M.;Khaleghi, Sh.
    • Bulletin of the Korean Chemical Society
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    • 제24권12호
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    • pp.1751-1756
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    • 2003
  • An electrochemical study related to the electroreduction of 4-amino-6-methyl-3-thio-1,2,4-triazin-5-one(I), 6-methyl-3-thio-1,2,4-triazin-5-one(II), and 2,4-dimetoxy-6-methyl-1,3,5-triazine(III) in dimethylformamide at glassy carbon electrode has been performed. A variety of electrochemical techniques, such as differential pulse voltammetry (DPV), cyclic voltammetry (CV), chronoamperometry, and coulometry were employed to clarify the mechanism of the electrode process. The compounds I and II with thiol group exhibited similar redox behavior. Both displayed two cathodic peaks, whereas the third compound, III, without thiol group showed only one cathodic peak in the same potential range of the second peak of I and II. The results of this study suggest that in the first step the one electron reduction of thiol produced a disulfide derivative and in the second reduction step the azomethane in the triazine ring was reduced in two electron processes. A reduction mechanism for all three compounds is proposed on this basis. In addition, some numerical constants, such as diffusion constant, transfer coefficient, and rate constant of coupled chemical reaction in the first reduction peak were also reported.

Improved Tri-iodide Reduction Reaction of Co-TMPP/C as a Non-Pt Counter Electrode in Dye-Sensitized Solar Cells

  • Kim, Jy-Yeon;Lee, Jin-Kyu;Han, Sang-Beom;Lee, Young-Woo;Park, Kyung-Won
    • Journal of Electrochemical Science and Technology
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    • 제1권2호
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    • pp.75-80
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    • 2010
  • We report Co-tetramethoxyphenylporphyrin on carbon particles (Co-TMPP/C) as a non-Pt catalyst for tri-iodide reduction in dye-sensitized solar cells (DSSCs). The presence of well-dispersed carbon and cobalt source in the catalyst surface is confirmed by transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray analysis. In the C 1s, Co 2p, and N 1s peaks measured by X-ray photoelectron spectroscopy, the C-N, Co-$N_4$, and N-C are assigned to the component at 285.7, 781.8, and 401 eV, respectively. Especially, the Co-TMPP/C shows improved current density, diffusion coefficient, and charge-transfer resistance in the ${I_3}^-/I^-$ redox reaction compared to conventional catalysts. Furthermore, in the DSSCs performance, the Co-TMPP/C shows increased short circuit current density, higher open circuit voltage, and improved cell efficieny in comparison with Pt/C.

Relaxation Process of the Photoexcited State and Singlet Oxygen Generating Activity of Water-soluble meso-Phenanthrylporphyrin in a DNA Microenvironment

  • Hirakawa, Kazutaka;Ito, Yusuke;Yamada, Takashi;Okazaki, Shigetoshi
    • Rapid Communication in Photoscience
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    • 제3권4호
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    • pp.81-84
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    • 2014
  • To examine the microenvironmental effect of DNA on the photosensitized reaction, the electron-donor-connecting porphyrin, meso-(9-phenanthryl)-tris(N-methyl-p-pyridinio) porphyrin (Phen-TMPyP), was synthesized. Phen-TMPyP can bind to oligonucleotides with two binding modes, depending on the DNA concentration. The fluorescence lifetime measurement of Phen-TMPyP shows a shorter component than that of the reference porphyrin without the phenanthryl moiety. However, the observed value is much longer than those of previously reported similar types of electron-donor-connecting porphyrins, suggesting that electron-transfer quenching by the phenanthryl moiety is not sufficient. The fluorescence quantum yield of Phen-TMPyP ($5{\mu}M$) decreased with an increase in DNA concentration of up to $5{\mu}M$ base pair (bp), possibly due to self-quenching through an aggregation along the DNA strand, increased with an increase in DNA concentration of more than $5{\mu}M$ bp and reached a plateau. The fluorescence quantum yield of Phen-TMPyP with a sufficient concentration of DNA was larger than that of the reference porphyrin. The singlet oxygen ($^1O_2$) generating activity of Phen-TMPyP was confirmed by the near-infrared emission spectrum measurement. The quantum yield of $^1O_2$ generation was decreased by a relatively small concentration of DNA, possibly due to the aggregation of Phen-TMPyP, and recovered with a sufficient concentration of DNA. The recovered quantum yield was rather smaller than that without DNA, indicating the quenching of $^1O_2$ by DNA. These results show that a DNA strand can stabilize the photoexcited state of a photosensitizer and, in a certain case, suppresses the $^1O_2$ generation.

$Mg_2$$SnO_4$:Mn 녹색 형광체의 저전압 음극선 발광 특성 (Cathodoluminescence of $Mg_2$$SnO_4$:Mn,:Mn Green Phosphor under Low-Voltage Electron Excitation)

  • 김경남;정하균;박희동;김도진
    • 한국재료학회지
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    • 제11권9호
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    • pp.759-762
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    • 2001
  • Mg$_2$SnO$_4$having an inverse spinel structure was selected as a new host material of $Mn^{2+}$ activator. The luminescence of the $Mg_2$SnO$_4$:Mn phosphor prepared by the solid-state reaction were investigated under ultraviolet and low-voltage electron excitation. The Mn-doped magnesium tin oxide exhibited strong green emission with the spectrum centered at 500nm wavelength. It was explained that the green emission in $Mg_2$SnO$_4$:Mn phosphor is due to energy transfer from $^4T_1to ^6A_1\;of\; Mn^{2+}$ ion at tetrahedral site in the spinel structure. The optimum concentration of $Mn^{2+}$/ion exhibiting maximum emission intensity by the low-voltage electron excitation was 0.6mol%. ?

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Micro Emulsion Synthesis of LaCoO3 Nanoparticles and their Electrochemical Catalytic Activity

  • Islam, Mobinul;Jeong, Min-Gi;Ghani, Faizan;Jung, Hun-Gi
    • Journal of Electrochemical Science and Technology
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    • 제6권4호
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    • pp.121-130
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    • 2015
  • The micro emulsion method has been successfully used for preparing perovskite LaCoO3 with uniform, fine-shaped nanoparticles showing high activity as electro catalysts in oxygen reduction reactions (ORRs). They are, therefore, promising candidates for the air-cathode in metal-air rechargeable batteries. Since the activity of a catalyst is highly dependent on its specific surface area, nanoparticles of the perovskite catalyst are desirable for catalyzing both oxygen reduction and evolution reactions. Herein, LaCoO3 powder was also prepared by sol-gel method for comparison, with a broad particle distribution and high agglomeration. The electro catalytic properties of LaCoO3 and LaCoO3-carbon Super P mixture layers toward the ORR were studied comparatively using the rotating disk electrode technique in 0.1 M KOH electrolyte to elucidate the effect of carbon Super P. Koutecky-Levich theory was applied to acquire the overall electron transfer number (n) during the ORR, calculated to be ~3.74 for the LaCoO3-Super P mixture, quite close to the theoretical value (4.0), and ~2.7 for carbon-free LaCoO3. A synergistic effect toward the ORR is observed when carbon is present in the LaCoO3 layer. Carbon is assumed to be more than an additive, enhancing the electronic conductivity of the oxide catalyst. It is suggested that ORRs, catalyzed by the LaCoO3-Super P mixture, are dominated by a 2+2-electron transfer pathway to form the final, hydroxyl ion product.

탄산 에틸렌계 용액 중에서 생성되는 흑연 음극 표면피막의 형상 및 저항에 미치는 충방전 속도의 영향 (Effects of Charge-discharge Rate on Morphology and Resistance of Surface Film on a Graphite Negative Electrode in an Ethylene Carbonate-based Solution)

  • 정순기;김보겸
    • 한국수소및신에너지학회논문집
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    • 제24권2호
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    • pp.179-185
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    • 2013
  • The behavior of surface film formation was greatly dependent on the speed of potential cycling. In $LiClO_4$ / EC + DEC, cyclic voltammetry results showed that the peaks originated from surface film formation on graphite electrode at the high charge-discharge rate was shifted to the lower potentials as the charge-discharge rate decrease. This indicates that surface films with different morphology and thickness were formed by different charge-discharge rate. Transmission electron microscopy (TEM) results indicated that the properties such as thickness and morphology of the surface film were greatly affected by the charge-discharge rate. Electrochemical impedance spectroscopy (EIS) showed that the resistance of surface film was affected by the speed of potential cycling. In addition, the charge transfer resistance was also dependent on the charge-discharge rate indicating that the charge transfer reaction was affected by the nature of surface film. TEM and EIS results suggested that the chemical property as well as the physical property of the surface film was affected by the charge-discharge rate.

Protective Effect Against Hydroxyl Radical-induced DNA Damage and Antioxidant Mechanism of [6]-gingerol: A Chemical Study

  • Lin, Jing;Li, Xican;Chen, Li;Lu, Weizhao;Chen, Xianwen;Han, Lu;Chen, Dongfeng
    • Bulletin of the Korean Chemical Society
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    • 제35권6호
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    • pp.1633-1638
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    • 2014
  • [6]-Gingerol is known as the major bioactive constituent of ginger. In the study, it was observed to effectively protect against ${\bullet}OH$-induced DNA damage ($IC_{50}$ $328.60{\pm}24.41{\mu}M$). Antioxidant assays indicated that [6]-gingerol could efficiently scavenge various free radicals, including ${\bullet}OH$ radical ($IC_{50}$ $70.39{\pm}1.23{\mu}M$), ${\bullet}O_2{^-}$ radical ($IC_{50}$ $228.40{\pm}9.20{\mu}M$), $DPPH{\bullet}$radical ($IC_{50}$ $27.35{\pm}1.44{\mu}M$), and $ABTS{^+}{\bullet}$radical ($IC_{50}$ $2.53{\pm}0.070{\mu}M$), and reduce $Cu^{2+}$ ion ($IC_{50}$ $11.97{\pm}0.68{\mu}M$). In order to investigate the possible mechanism, the reaction product of [6]-gingerol and $DPPH{\bullet}$ radical was further measured using HPLC combined mass spectrometry. The product showed a molecular ion peak at m/z 316 $[M+Na]^+$, and diagnostic fragment loss (m/z 28) for quinone. On this basis, it can be concluded that: (i) [6]-gingerol can effectively protect against ${\bullet}OH$-induced DNA damage; (ii) a possible mechanism for [6]-gingerol to protect against oxidative damage is ${\bullet}OH$ radical scavenging; (iii) [6]-gingerol scavenges ${\bullet}OH$ radical through hydrogen atom ($H{\bullet}$) transfer (HAT) and sequential electron (e) proton transfer (SEPT) mechanisms; and (iv) both mechanisms make [6]-gingerol be oxidized to semi-quinone or quinone forms.

2,6-Disubstituted Pyrylium Fluoroborates 화합물의 합성과 특성 (Synthesis and Characteristics of 2,6-disubstituted Pyrylium Fluoroborates)

  • 조성일
    • 공업화학
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    • 제20권3호
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    • pp.351-353
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    • 2009
  • Pyrylium염 화합물은 양전하를 띄고 있어 유용한 합성반응에 널리 이용되고 있다. 또한 전자를 받아들이는 특성을 갖고 있어 광유도전자전이(PET) 반응의 감광제 등에 응용되고 있다. 우리는 본 연구에서 몇몇 2,6-disubstituted pyrylium fluoroborate 염 화합물을 산성 매체(acetic anhydride/acid) 하에서 합성하였다. 합성한 화합물을 $^{1}H-NMR$, FT-IR과 TOF Mass로 그 구조를 확인하였다. 또한, 그 광특성을 UV-Vis를 통해 분석하였다.

Cathodoluminescence Properties of Novel $Mg_2SnO_4$:Mn Phosphor under Low-Voltage Electron Excitation

  • Kim, Kyung-Nam;Jung, Ha-Kyun;Park, Hee-Dong;Kim, Do-Jin
    • Journal of Information Display
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    • 제2권3호
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    • pp.13-17
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    • 2001
  • The manganese-doped magnesium tin oxide with spinel structure was selected as a green phosphor for FED application and was synthesized by the solid state reaction. Its luminescence properties were investigated under low-voltage electron excitation. The $Mg_2SnO_4$:Mn phosphor showed green emission with the spectrum centered at 500 nm due to energy transfer from $^4T_1$ to $^6A_1$ of $Mn^{2+}$ ion. Optimum Mn concentration was 0.6 mole % and the decay time was shorter than 10 ms.

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