• Title/Summary/Keyword: Electron-transfer

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Electrochemical Behavior of Redox Proteins Immobilized on Nafion-Riboflavin Modified Gold Electrode

  • Rezaei-Zarchi, S.;Saboury, A.A.;Hong, J.;Norouzi, P.;Moghaddam, A.B.;Ghourchian, H.;Ganjali, M.R.;Moosavi-Movahedi, A.A.;Javed, A.;Mohammadian, A.
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2266-2270
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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.

Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy

  • Kim, Hyeong-Mook;Park, Jaeheung;Noh, Hee Chang;Lim, Manho;Chung, Young Keun;Kang, Youn K.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.587-596
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    • 2014
  • A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

Direct Electrochemistry and Electrocatalysis of Myoglobin with CoMoO4 Nanorods Modified Carbon Ionic Liquid Electrode

  • Zhao, Zengying;Cao, Lili;Hu, Anhui;Zhang, Weili;Ju, Xiaomei;Zhang, Yuanyuan;Sun, Wei
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.475-481
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    • 2013
  • By using ionic liquid 1-hexylpyridinium hexafluorophosphate ($HPPF_6$) based carbon ionic liquid electrode (CILE) as the substrate electrode, a $CoMoO_4$ nanorods and myoglobin (Mb) composite was casted on the surface of CILE with chitosan (CTS) as the film forming material to obtain the modified electrode (CTS/$CoMoO_4$-Mb/CILE). Spectroscopic results indicated that Mb retained its native structures without any conformational changes after mixed with $CoMoO_4$ nanorods and CTS. Electrochemical behaviors of Mb on the electrode were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks from the heme Fe(III)/Fe(II) redox center of Mb appeared, which indicated that direct electron transfer between Mb and CILE was realized. Electrochemical parameters such as the electron transfer number (n), charge transfer coefficient (${\alpha}$) and electron transfer rate constant ($k_s$) were estimated by cyclic voltammetry with the results as 1.09, 0.53 and 1.16 $s^{-1}$, respectively. The Mb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid in the concentration range from 0.1 to 32.0 mmol $L^{-1}$ with the detection limit as 0.036 mmol $L^{-1}$ ($3{\sigma}$), and the reduction of $H_2O_2$ in the concentration range from 0.12 to 397.0 ${\mu}mol\;L^{-1}$ with the detection limit as 0.0426 ${\mu}mol\;L^{-1}$ ($3{\sigma}$).

Theory of High Resolution TEM Image Formation: Coherence (1) (TEM 관련 이론해설 (6): 투과전자현미경의 고분해능 영상이론: 결맞음 (1))

  • Lee, Hwack-Joo
    • Applied Microscopy
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    • v.35 no.3
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    • pp.105-112
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    • 2005
  • In this review, the important ideas of coherence theory are introduced. The transfer function and damping envelopes of the microscope due to temporal and spatial coherence are described. The passbands and the condition of Scherzer focus are also disscussed in associated with the resolution of transmission electron microscope.

A study on the electron transport coefficients using monte carlo method in argon gas (몬테칼로법을 이용한 Ar기체의 전자수송계수에 관한 연구)

  • 하성철;전병훈
    • Electrical & Electronic Materials
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    • v.8 no.6
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    • pp.685-692
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    • 1995
  • The electron transport coefficients in argon gas is studied over the range of E/N values from 85 to 566 Td by the Monte Carlo method considering the latest cross section data. The result of the Monte Carlo method analysis shows that the value of the electron transport coefficients such as the electron drift velocity, the ratio of the longitudinal and transverse diffusion coefficients to the mobility. It is also found that the electron transport coefficients calculated by the two-term approximation analysis agree well with those by Monte Carlo calculation. The electron energy distributions function were analysed in argon at E/N=283, and 566 Td for a case of the equilibrium region in the mean electron energy. A momentum transfer cross section for the argon atom which was consistent with both of the present electron transport coefficients was derived over the range of mean electron energy from 10.3 to 14.5 eV, also suggested as a set of electron cross section for argon atom. The validity of the results obtained has been confirmed by a Monte Carlo simulation method.

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Reactivity and Reaction Mechanism for Reactions of 1, 1'-(Azodicarbonyl) dipiperidine with Triphenylphosphines

  • 성대동;최미정;하근문;엄태섭
    • Bulletin of the Korean Chemical Society
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    • v.20 no.8
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    • pp.935-938
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    • 1999
  • Reactivity and reaction mechanism for the reactions of 1,1'-(azodicarbonyl) dipiperidine with triphenylphosphines are investigated using kinetic method. The cation radical, Ph3P and the anion radical, -N-N - are produced during the course of the reaction. The cation radical is formed by the transfer of an electron from phosphorus to the nitrogen atom. The anion radical is formed by the addition of the one electron to the azo rad-ical. The rate constants are decreased by electron withdrawing groups while they are increased by electron donating groups present in triphenylphosphine. The electron density increases on nitrogen, while positive charge is developed on phosphorus in the transition state.

Quantum Mechanical Studies for Proton Transfer in HOCl + HCl and H2O + ClONO2 on Water Clusters

  • Kim, Yong-Ho;Park, Chea-Yong;Kim, Kyung-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.26 no.12
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    • pp.1953-1961
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    • 2005
  • We have performed high-level quantum mechanical calculation for multiple proton transfer in HOCl + HCl and $H_2O$ + $ClONO_2$ on water clusters, which can be used as a model of the reactions on ice surface in stratospheric clouds. Multiple proton transfer on ice surface plays crucial role in these reactions. The structures of the clusters with 0-3 water molecules and the transition state structures for the multiple proton transfer have been calculated. The energies and barrier heights of the proton transfer were calculated at various levels of theory including multi-coefficient correlated quantum mechanical methods (MCCM) that have recently been developed. The transition state structures and the predicted reaction mechanism depend very much on the level of theory. In particular, the HF level can not correctly predict the TS structure and barrier heights, so the electron correlation should be considered appropriately.

Transfer of Electronic Excitation Energy in Poltstyrene Films Doped with an Intramolecular Proton Transfer Compound

  • 강태종;김학진;정진갑
    • Bulletin of the Korean Chemical Society
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    • v.17 no.7
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    • pp.616-621
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    • 1996
  • The transfer of excitation energy from solvent to solute in polystyrene films doped with 2-(2'-hydroxyphenyl)benzothiazole (HBT) which undergoes intramolecular proton transfer in excited electronic state has been studied by employing steady state and time-resolved fluorescence measurements. The degree of Forster overlap between donor and acceptor molecule in this system is estimated to be moderate. Energy transfer efficiency increases with solute concentration at low concentration range and levels off at high concentration. It is observed that the excimer form of polystyrene is largely involved in energy transfer process. Photostability of HBT in polystyrene to UV light is also investigated to get insight into the long wavelength absorption band of HBT which was observed upon electron radiation.

Improved Electrical and Optical Properties of ITO Films by Using Electron Beam Irradiated Sputter

  • Wie, Sung Min;Kwak, Joon Seop
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.407-408
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    • 2013
  • Thin transparent conductive oxides (TCOs) having a thickness lower than 30 nm have been widely usedin touch screen panels. However the resistivity of the TCO films significantly increases as the thickness decreases, due to the poor crystallinity at very thin thickness of TCO films. In this study, we have investigated the effect of electron beam irradiation during the sputtering on the electrical properties and transmittance of 30 nm-thick ITO films, which have a different SnO2 atomic percent, prepared by magnetron sputtering at room temperature. Fig. 1 shows the variation of resistivity of ITO films with a different SnO2 atomic percent for both the normal ITO films and electron beam irradiated ITO films. As shows in Fig. 1, the electron beam irradiation to the ITO (SnO2 weight percent 10%) films during the sputtering resulted in a significantly decreased in resistivity from $7.4{\times}10^{-4}{\Omega}-cm$ to $1.5{\times}10^{-4}{\Omega}-cm$ and it also increased in transmittance from 84% to 88% at a wavelength of 550 nm. These results can be attributed to energy transfer from electron to ad-atoms of ITO films during the electron beam irradiated sputtering, which can enhance the crystallinity of 30 nm-thick ITO films. It is strongly indicate that electron beam irradiation can greatly improve the electrical properties and transmittance of very thin ITO films for touch screen panels, flexible displays and solar cells.

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