• Title/Summary/Keyword: Redox complexes

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Electrochemical Immobilization of Osmium Complex onto the Carbon Nano-Tube Electrodes and its Application for Glucose sensor (전기화학적인 방법을 이용한 탄소나노튜브 전극상의 오스뮴 착물의 고정화 및 혈당센서에 관한 응용)

  • Choi, Young-Bong;Jeon, Won-Yong;Kim, Hyug-Han
    • Journal of the Korean Electrochemical Society
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    • v.13 no.1
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    • pp.50-56
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    • 2010
  • The multi-wall carbon nano-tube composite mixed with carbon paste electrode presented more sensitive and selective amperometric signals in the oxidation of glucose than general screen-printed carbon electrodes(SPCEs). Redox mediators to transport electrodes from enzyme to electrodes are very important part in the biosensor. A novel osmium redox complex was synthesized by the coordinating pyridine group containing primary amines which were electrochemically immobilized onto the MWCNT-SPCEs surface. Electrochemical studies of osmium complexes were investigated by cyclic voltammetry, chronoamperometry. The surface coverage of osmium complexes on the modified carbon nano-tube electrodes were significantly increased at 100 time (${\tau}_0=2.0\;{\times}\;10^{-9}\;mole/cm^2$) compared to that of the unmodified carbon electrodes. It's practical application of the glucose biosensor demonstrated that it shows good linear response to the glucose concentration in the range of 0-10 mM.

Template Synthesis of New Nickel(Ⅱ) Comlexes of 14-Membered Pentaaza Macrocyclic Ligands: Effects of C-Alkyl and N-Hydroxyalkyl Pendant Arms on the Solution Behaviors of the Complexes

  • 강신걸;최장식;김성진
    • Bulletin of the Korean Chemical Society
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    • v.16 no.6
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    • pp.518-523
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    • 1995
  • New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.

Electrochemical Properties of Binuclear Nickel(II) and Copper(II) Complexes with Tetradentate Schiff Base in Aprotic Solvents (1) (비수용매에서 이핵성 네자리 Schiff Base Nickel(II) 및 Copper(II) 착물들의 전기화학적 성질 (제 1 보))

  • Chjo Ki-Hyung;Choi Yong-Kook;Seo Seong-Seob;Lee Song-Ju
    • Journal of the Korean Chemical Society
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    • v.35 no.1
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    • pp.24-37
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    • 1991
  • We synthesized the binuclear Tetradentate Schiff base nickel(II) and copper(II) complexes ; [Ni(II)$_2$(SMPO)$_2$(L)$_2$], [Ni(II)$_2$(SPPD)$_2$(L)$_2$] and [Cu(II)$_2$(SMPD)$_2$] and [Cu(II)$_2$(SPPD)$_2$] (where, L : Py, DMSO and DMF). We identified the structure of these complexes by elemental analysis, IR-spectrum, T.G.A, D.S.C and ESR measurements. According to the results of cyclic voltammetry and DPP measurements in aprotic solvent included 0.1M TEAP as supporting electrolyte, we knew that diffusional controlled redox process of one step with one electron was irreversible process in 0.1M TEAP-Py solution. Also it was reversible or quasi reversible process in 0.1M TEAP-DMSO solution and reversible or E.C reaction mechanism in 0.1M TEAP-DMF solution at mononuclear complexes ; [Cu(II)(SOPD)] and [Ni(II)(SOPD)(L)$_2$]. But, we knew that diffusional controlled redox process of two step for one electron of binuclear complexes was as follows. The values of redox potential for dimeric complexes in 0.1M TEAP-L solution (where, L ; Py, DMSO and DMF) with scan rate 100mV/sec.

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Electrochemical Properties of Oxygen Adducts Pentadentate Schiff Base Cobalt (Ⅱ) Complexes in Aprotic Solvents (비수용매에서 다섯 자리 Schiff Base Cobalt (Ⅱ) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질)

  • Choe, Ju Hyeong;Jeong, Jin Sun;Choe, Yong Guk;Seo, Seong Seop
    • Journal of the Korean Chemical Society
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    • v.34 no.1
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    • pp.51-62
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    • 1990
  • Pentadentate Schiff base cobalt(II) complexes; Co(II)(Sal-DET) and Co(II)(Sal-DPT) were synthesized and these complexes were allowed to react with dry to form oxygen adducts of cobalt(II) complexes such as [Co(III)(Sal-DET)]$_2O_2$ and [Co(III)(DPT)]$_2O_2$ in aprotic solvents. These complexes have been identified by IR spectra, TGA, DSC, magnetic susceptibility measurements, and elemental analysis. It has been found that the oxygen adadduct complexes of $\mu$-peroxo type have hexaccordinated octahedral configuration with pentadentate schiff base cobalt(II) and oxygen, but the mole ratio of oxygen to cobalt(III) complexes of first step for oxygen adduct formation reaction of cobalt(II) complexes in aprotic solvents are 1:1. The redox reaction processes of Co(II)(Sal-DET), Co(II)(Sal-DPT), and oxygen adduct of cobalt(II) complexes were investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine. As a result the reduction reaction processes of Co(III)/Co(II) and Co(II)/Co(I) for cobalt(II) complexes and oxygen adducts of cobalt(II) complexes are two irreversible steps of one eletron process, and reaction processes of oxygen for oxygen adducts complexes were quasireversible and redox range of potential was $E_{pc}$ = -0.97V∼-0.86V and $E_{pa}$ = -0.87V ∼ 0.64V.

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Synthesis and Properties of Terdentates with Extra Pyridine Ring and Their Ru(II) Complexes

  • 장영동;문승욱;Randolph P. Thummel
    • Bulletin of the Korean Chemical Society
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    • v.18 no.2
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    • pp.174-179
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    • 1997
  • The synthesis and electronic as well as redox properties of four Ru(Ⅱ) complexes based on the ligand 4'-(4-pyridyl)-3,3';5',3"-bis-dimethylene-2,2';6',2"-terpyridine are reported. Each new complex is of the type [Ru(L)2]n+ and [Ru(tpy)(L)]n+, where L is the terdentate ligand with extra pyridine ring at 4'-position or is a N-methylated ligand and n=2, 3, or 4. Cyclic voltammetry indicates that the first electron added to the complex enters the viologen-type acceptor in N-methylated ligand.

Co-Electrodeposition of Bilirubin Oxidase with Redox Polymer through Ligand Substitution for Use as an Oxygen Reduction Cathode

  • Shin, Hyo-Sul;Kang, Chan
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3118-3122
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    • 2010
  • The water soluble redox polymer, poly(N-vinylimidazole) complexed with Os(4,4'-dichloro-2,2'-bipyridine)$_2Cl]^+$ (PVI-[Os(dCl-bpy)$_2Cl]^+$), was electrodeposited on the surface of a glassy carbon electrode by applying cycles of alternating square wave potentials between 0.2 V (2 s) and 0.7 V (2 s) to the electrode in a solution containing the redox polymer. The coordinating anionic ligand, $Cl^-$ of the osmium complex, became labile in the reduced state of the complex and was substituted by the imidazole of the PVI chain. The ligand substitution reactions resulted in crosslinking between the PVI chains, which made the redox polymer water insoluble and caused it to be deposited on the electrode surface. The deposited film was still electrically conducting and the continuous electrodeposition of the redox polymer was possible. When cycles of square wave potentials were applied to the electrode in a solution of bilirubin oxidase and the redox polymer, the enzyme was co-electrodeposited with the redox polymer, because the enzymes could be bound to the metal complexes through the ligand exchange reactions. The electrode with the film of the PVI-[Os(dCl-bpy)$_2Cl]^+$ redox polymer and the co-electrodeposited bilirubin oxidase was employed for the reduction of $O_2$ and a large increase of the currents was observed due to the electrocatalytic $O_2$ reduction with a half wave potential at 0.42 V vs. Ag/AgCl.

Studies on the Electrochemical Properties of Oxygen Adducts Tetradentate Schiff Base Cobalt (Ⅱ) Complexes in Aprotic Solvents (Ⅱ) (비수용매에서 네자리 Schiff Base Cobalt (II) 착물들의 산소첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 2 보))

  • Ki-Hyung Chjo;Jin-Soon Chung;Heui-Suk Ham;Seoing-Seob Seo
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.192-202
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    • 1989
  • Tetradentate schiff bases cabalt (II) complexes; Co(SED) and Co(ο-BSDT) were synthesized and these complexes allowed to reaction with dry oxygen to form oxygen adduct cobalt(III) complexes such as $[Co(o-BSDT)(DMSO)]_2O_2,\;[Co(SED)(Py)]_2O_2\;and\;[Co(o-BSDT)(Py)]_2O_2$ in DMSO and pyridine solutions. It has been found that the oxygen adduct cobalt(III) complexes have hexacoordinated octahedral configuration with tetradentate schiff base cobalt(II), DMSO or pyridine and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1:2. The redox processes, were investigated for Co(SEDT) and Co(ο-BSD) complexes in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine by cyclic voltammetry with glassy carbon electrode. As a result the redox processes of Co(II)/Co(III) and Co(II)/Co(I) found to be reversible or quasi-reversible for non uptake oxygen complexes but oxygen adduct complexes found to be irreversible processes and reaction processes of oxygen for oxygen adduct complexes are quasi-reversible process, the potential range was $E_{pc}=-0.85{\sim}-1.19V\;and\;E_{pa}=-0.74{\sim}-0.89V$.

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Polarograms of Uranium(VI) and Rare Earth(III) Metal Complexes with Macrocyclic Ligands in Dimethylsulfoxide Solvent (디메틸술폭시드 용매중에서 거대고리리간드를 포함한 우라늄(VI)과 희토류(III) 금속 착물의 폴라로그램)

  • Hak Jin Jung;Oh Jin Jung;Chilnam Choi
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.233-242
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    • 1988
  • The uranium(VI) complexes with new unsaturated macrocyclic ligands of cryptand types and the neodymium(III) complexes with cryptand 222 and DBC ligands have been investigated polarographically in dimethylsulfoxide solvent. The reduction states, electron numbers involved in the reduction process, effects of the added acid on the polarograms of complexes, and the mechanisms of the reduction electrode reactions have been examined. The stability constants and mole-ratio of new complexes were also obtained by polarographic method. The reaction of ligands was controlled by the diffusion in the reduction with four electrons at a step, whereas the redox reaction with six electrons at three steps in $UO_2\;^{2+}$ complexes with macrocyclic ligands and the redox reaction with one electron at a step in $Nd^{3+}$ complexes with cryptand 222 and DBC have been observed. The imine ligands formed stable complexes with uranium(VI) above pH 7.0, and the neodymium(III) complexes with cryptand 222 and DBC ligands were stable above pH 4.0.

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Polymer Electrolytes and their Application to Solar Cells and Separation Membranes (촉진수송 및 태양전지용 분리막)

  • 강용수
    • Proceedings of the Membrane Society of Korea Conference
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    • 2004.03a
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    • pp.13-35
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    • 2004
  • Metal Complexes in Macromolecules Applications of Polymer Electrolyte Membranes Facilitated Transport in Solid State Roles of Electrolytes in Solar Cells - Electrolytes :ㆍI- and $I_3$-conductor ㆍelectron barrier or hole conductor ㆍelectrochemical redox reaction media ㆍinterfacial contactor for dye, $TiO_2$ and electrode ㆍmechanical separator (omitted)

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Manipulation of Absorption Maxima by Controlling Oxidation Potentials in Bis(tridentate) Ru(II) N-Heterocyclic Carbene Complexes

  • Kim, Hyeong-Mook;Jeong, Daero;Noh, Hee Chang;Kang, Youn K.;Chung, Young Keun
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.448-456
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    • 2014
  • A series of seven Ru(II) complexes bearing NHC ligands have been synthesized. The electronic structures of these complexes were analysed by spectroscopic and electrochemical methods and further examined by theoretical calculations. Data show that absorption maxima are dependent on the HOMO level rather than the HOMO-LUMO gaps.