• Title/Summary/Keyword: 산화-환원 과정

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Electrochemical Characteristics at Copolymeric film Electrodes of [Ru(v-bpy)$_3$]$^{2+}$ and Vinylbenzoic Acid Modified with Dopamine (Dopamine으로 수식된 [Ru(v-bpy)$_3$$^{2+}$와 Vinylbenzoic Acid의 공중합 피막 전극의 전기화학 특성)

  • 차성극;박유철;임태곤
    • Polymer(Korea)
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    • v.25 no.6
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    • pp.782-788
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    • 2001
  • The $[Ru(v-bpy)_3]^{2+}$ and vinylbenzoic acid (vba) were electrochemically copolymerized to afford electrodes modified with dopamine to study their properties such as electropolymerization rate, redox process, and electron transfer. The optimum mole ratio of the monomers was 5:2, which gave $1.84{ imes}10^{-2}s^{-1}$ of rate constant for first order reaction, while the ratio of the substances on the copolymeric film produced was 5:1.68. The formal potential produced from the hydroquinone=quinone+$2H^+2e^-$reaction at the electrode of GC/p- $[Ru(v-bpy)_3]^{2+}$/vba-dopamine was 0.17 V in phosphate buffer (pH=7.10). The electrocatalytic rate was $2.58{ imes}10^5cms^{-1}$;2.41 times faster than that of non-modified one. The mass change measured by EQCM was $3.28{ imes}10^3$$gmol^{-1}$ which is larger than that of non-modified one.

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Redox Properties of Modified Poly-N,N'-bis(2-pyrrol-1-yl-propyl)-4,4'-Bipyridine Film Electrode (수식된 N,N'-bis(2-pyrrol-1-yl-propyl)-4,4'-bipyridine 고분자 피막전극의 산화-환원 특성)

  • Cha, Seong Keuck
    • Journal of the Korean Chemical Society
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    • v.45 no.5
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    • pp.429-435
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    • 2001
  • The monomer N,N'-bis(2-pyrrol-1-yl-propyl)-4,4'-bipyridine(bpb) was electrochemically polymerized on the glassy carbon electrode surface, which was modified with 1:1 ratio of erichrome black T(EBT) and glutathione(GSSG) to give a type of GC/poly-bpb, EBT, GSSG electrode for depositing Zn(II). The diffusion coefficients of the incorporated ions were 2.43${\times}10^{-15}$ and 9.14${\times}10^{-15} cm^2s^{-1}$ before taking Zn(II) ions and after them respectively. The modified electrodes are stable at the electrode process. The polymerized poly-bpb of 2.83${\times}10^4gmol^{-1}$ can deposit 2.15${\times}10^4gmol^{-1}$ of Zn(II). The number of pumping ions involving in the redox procedure at 0.77 V was 81.7% of the captured 180 ions into the polymer matrix, which was 3 times larger than that of the electrode modified with EBT alone.

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Electrochemical Properties of Pentadentate Binucleated Schiff Base Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes in Nonaqueous Solvent (비수용매에서 이핵성 다섯자리 Schiff Base Cobalt(Ⅱ) 및 Manganese(Ⅱ) 착물들의 전기화학적 성질)

  • Ki-Hyung Chjo;Yong-Kook Choi;Song-Ju Lee;Seong-Seop Seo
    • Journal of the Korean Chemical Society
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    • v.36 no.3
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    • pp.428-441
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    • 1992
  • We synthesized a series of binuclear pentadentate Schiff base complexes such as $Co(Ⅱ)_2$ (BSPP)($H_2O)_2$, $Co(Ⅱ)_2$ (BSPD)($H_2O)_2$, $Mn(Ⅱ)_2$ (BSPP)($H_2O)_2$ and $Mn(Ⅱ)_2$ (BSPD)($H_2O)_2$, mononuclear pentadentate Schiff base complexes such as Co(Ⅱ)(BSP)($H_2O)$ and Mn(Ⅱ)(BSP)($H_2O)$. The composition of these complexes identified by IR, UV-visible spectrum, T.G.A., DSC, and elemental analysis. The electrochemical redox processes have been examined by cyclic voltammetry and differential pulse polarography with glassy carbon electrode in 0.1M TEAP-Py(-DMSO and -DMF) as a supporting electrolyte solution. As a result of electrochemical measurements, the reduction processes for pentadentate binuclear Schiff base cobalt(Ⅱ) and manganese(Ⅱ) complexes occurred to four steps in $M(Ⅲ)_2$ / $Mn(Ⅱ)_2$ and $Mn(Ⅱ)_2$ / $M(Ⅰ)_2$ (M; Co, Mn) two processes through each two reduction steps with one electron, by contrast, the mononuclear pentadentate Schiff base cobalt(Ⅱ) and manganese(Ⅱ) complexes occurred to two steps in M(Ⅲ) / M(Ⅱ) and M(Ⅱ) / M(Ⅰ) (M; Co, Mn) two processes with one electron reduction steps.

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Reduction Efficiency of Cr(VI) in Aqueous Solution by Different Sources of Zero-Valent Irons (수용액 중 영가 철(Zero-Valent Iron)의 특성에 따른 Cr(VI)의 환원 효율 비교)

  • Yang, Jae-E.;Kim, Jong-Sung;Ok, Yong-Sik;Yoo, Kyung-Yoal
    • Korean Journal of Environmental Agriculture
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    • v.24 no.3
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    • pp.203-209
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    • 2005
  • Objective of this research was to assess the effectiveness of the different sources of the zero-valent irons (ZVIs) on the reduction of the toxic Cr(VI) to the nonhazardous Cr(III) in an aqueous solution. The physical and chemical properties of the six ZVIs were determined. Particle size and specific surface area of the ZVIs were in the ranges of $85.55{\sim}196.46{\mu}m\;and\;0.055{\sim}0.091m^2/g$, respectively. Most of the ZVIs contained Fe greater than 98% except for J (93%) and PU (88%). Reduction efficiencies of the ZVI for Cr(VI) reduction were varied with kinds of ZVIs. The J and PU ZVIs reduced 100% and 98% of Cr(VI) in the aqueous solution, respectively, within 3 hrs of reaction. However, PA, F, Sand J1 reduced 74, 65, 29 and 11% of Cr(VI), respectively, after 48 hrs. The pH of the reacting solution was rapidly increased from 3 to $4.34{\sim}9.04$ within 3 hrs. The oxidation-reduction potential (Eh) of the reacting solution was dropped from 600 to 319 mV within 3 hrs following addition of ZVIs to the Cr(VI) contaminated water. The capability of ZVIs for Cr(VI) reduction was the orders of PU > J > PA > F > S > J1, which coincided with the capacities to increase the pH and decrease the redox potentials. Results suggested that the reduction of Cr(VI) to Cr(III) was derived from the oxidation of the ZVI in the aqueous solution.

In-situ Precipitation of Arsenic and Copper in Soil by Microbiological Sulfate Reduction (미생물학적 황산염 환원에 의한 토양 내 비소와 구리의 원위치 침전)

  • Jang, Hae-Young;Chon, Hyo-Taek;Lee, Jong-Un
    • Economic and Environmental Geology
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    • v.42 no.5
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    • pp.445-455
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    • 2009
  • Microbiological sulfate reduction is the transformation of sulfate to sulfide catalyzed by the activity of sulfate-reducing bacteria using sulfate as an electron acceptor. Low solubility of metal sulfides leads to precipitation of the sulfides in solution. The effects of microbiological sulfate reduction on in-situ precipitation of arsenic and copper were investigated for the heavy metal-contaminated soil around the Songcheon Au-Ag mine site. Total concentrations of As, Cu, and Pb were 1,311 mg/kg, 146 mg/kg, and 294 mg/kg, respectively, after aqua regia digestion. In batch-type experiments, indigenous sulfate-reducing bacteria rapidly decreased sulfate concentration and redox potential and led to substantial removal of dissolved As and Cu from solution. Optimal concentrations of carbon source and sulfate for effective microbial sulfate reduction were 0.2~0.5% (w/v) and 100~200 mg/L, respectively. More than 98% of injected As and Cu were removed in the effluents from both microbial and chemical columns designed for metal sulfides to be precipitated. However, after the injection of oxygen-rich solution, the microbial column showed the enhanced long-term stability of in-situ precipitated metals when compared with the chemical column which showed immediate increase in dissolved As and Cu due to oxidative dissolution of the sulfides. Black precipitates formed in the microbial column during the experiments and were identified as iron sulfide and copper sulfide. Arsenic was observed to be adsorbed on surface of iron sulfide precipitate.

Microbial Community Composition Associated with Anaerobic Oxidation of Methane in Gas Hydrate-Bearing Sediments in the Ulleung Basin, East Sea (동해 울릉분지 가스 하이드레이트 매장 지역의 메탄산화 미생물 군집 조성 및 분포)

  • Cho, Hyeyoun;Kim, Sung-Han;Shin, Kyung-Hoon;Bahk, Jang-Jun;Hyun, Jung-Ho
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.20 no.1
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    • pp.53-62
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    • 2015
  • To elucidate the microbial consortia responsible for the anaerobic methane oxidation in the methane hydrate bearing sediments, we compared the geochemical constituents of the sediment, the rate of sulfate reduction, and microbial biomass and diversity using an analysis of functional genes associated with the anaerobic methane oxidation and sulfate reduction between chimney site (UBGH2-3) on the continental slope and non-chimney site (UBGH2-10) on the basin of the Ulleung Basin. From the vertical profiles of geochemical constituents, sulfate and methane transition zone (SMTZ) was clearly defined between 0.5 and 1.5 mbsf (meters below seafloor) in the UBGH2-3, and between 6 and 7 mbsf at the UBGH2-10. At the UBGH2-3, the sulfate reduction rate (SRR) in the SMTZ exhibited was appeared to be $1.82nmol\;cm^{-3}d^{-1}$ at the depth of 1.15 mbsf. The SRR in the UBHG2-10 showed a highest value ($4.29nmol\;cm^{-3}d^{-1}$) at the SMTZ. The 16S rRNA gene copy numbers of total Prokaryotes, mcrA, (methyl coenzyme M reductase subunit A), and dsrA (dissimilatory sulfite reductase subunit A) showed the peaks in the SMTZ at both sites, but the maximum mcrA gene copy number of the UBGH2-10 appeared below the SMTZ (9.8 mbsf). ANME-1 was a predominant ANME (Anaerobic MEthanotroph) group in both SMTZs of the UBGH2-3 and -10. However, The sequences of ANME-2 were detected only at 2.2 mbsf of the UBGH2-3 where high methane flux was observed because of massive amount of gas hydrate at shallow depth. And Desulfosarcina-Desulfococcus (DSS) that is associated with ANME-2 was detected in 2.2 mbsf of the UBHG2-3. Overall results demonstrate that ANME-1 and ANME-2 are considered as significant archaeal groups related to methane cycle in the subsurface sediment of the East Sea, and ANME-2/DSS consortia might be more responsible for methane oxidation in the methane seeping region than in non-seeping region.

A Case Study of Monitored Natural Attenuation at the Petroleum Hydrocarbon Contaminated Site : II. Evaluation of Natural Attenuation by Groundwater Monitoring (유류오염부지에서 자연저감기법 적용 사례연구 II. 지하수모니터링에 의한 자연저감 평가)

  • Yun Jeong Ki;Lee Min Hyo;Lee Suk Young;Noh Hoe Jung;Kim Moon Soo;Lee Kang Kun;Yang Chang Sool
    • Journal of Soil and Groundwater Environment
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    • v.9 no.3
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    • pp.38-48
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    • 2004
  • Natural attenuation of petroleum hydrocarbon was investigated at an industrial complex about 45 Km away from Seoul. The three-years monitoring results indicated that the concentrations of DO, nitrate, and sulfate in the contaminated area were significantly lower than the background monitoring groundwater under the non-contaminated area. The results also showed a higher ferrous iron concentration, a lower redox potential, and a higher (neutral) pH in the contaminated groundwater, suggesting that biodegradation of TEX(Toluene, Ethylbenzene, Xylene) is the major on-going process in the contaminated area. Groundwater in the contaminated area is anaerobic, and sulfate reduction is the dominant terminal electron accepting process in the area. The total attenuation rate was about 0.0017∼0.0224day$^{-1}$ and the estimated first-order degradation rate constant(λ) was 0.0008∼0.0106day$^{-1}$ . However, the reduction of TEX concentration in the groundwater was resulted from not only biodegradation but also dilution and reaeration through recharge of uncotaminated surface and groundwater. The natural attenuation was, therefore, found to be an effective, on-going remedial process at the site.

Comparison of the As(III) Oxidation Efficiency of the Manganese-coated Sand Prepared With Different Methods (망간코팅사 종류별 독성 3가 비소의 산화특성에 관한 비교 연구)

  • Kim, Byeong-Kwon;Lim, Jae-Woo;Chang, Yoon-Young;Yang, Jae-Kyu
    • Journal of Soil and Groundwater Environment
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    • v.13 no.2
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    • pp.62-69
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    • 2008
  • In this study physicochemical characteristics and stability of various manganese coated sands (MCS) prepared with different methods were evaluated. In addition, removal efficiencies of As(III) by each MCS were compared. Four different MCSs were used; B-MCS prepared by baking method, W&D-MCS prepared by wetting and dry method, NMCS prepared during the water treatment process and Birm which is a commercial MCS widely used for the removal iron and manganese. The manganese content in each MCS was following order: Birm (63,120 mg/kg) > N-MCS (10,400 mg/kg) >W&D-MCS (5,080 mg/kg) > B-MCS (2,220 mg/kg). Birm showed the least solubility (% basis) in acidic conditions. As(III) oxidation efficiency of B-MCS was continuously increased as the solution pH decreased. While As(III) oxidation efficiency of N-MCS and Birm was minimum around neutral pH. The increased As(III) oxidation efficiency above neutral pH for N-MCS and Birm could be due to the competitive adsorption of $Mn^{2+}$, which was produced from reduction of $MnO_2$, onto the surface of aluminum and manganese oxides.

Properties of Mononuclear and Binuclear Cu(II) Schiff Base Complexes and Oxidation of Ascorbic Acid (단핵 및 이핵성 시프염기리간드 Cu(II) 착물의 특성과 Ascorbic Acid에 대한 산화반응)

  • Kim, Sun Deuk;Lee, Young Seuk;Park, Jung Eun
    • Analytical Science and Technology
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    • v.13 no.5
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    • pp.558-564
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    • 2000
  • Mononuclear schiff base ligand N,N'-bissalicylidene-1,2-phenylenediamine(BSPD) and binuclear schiff base ligands N,N',N',N'''-tetrasalicylidene-3,3',4,4'-tetraaminodiphenyl-methane (TSTM), N,N',N'',N'''-tetrasalicylidene-3,3'-diaminobenzidine (TSDB) have been synthesized. Proton dissociation constants of the ligands were determined by potentiometric method. The synthesized ligands and complexes formed with Cu(II) ion. These complexes were investigated by cyclic voltammetry and differential pulse voltammetry. The results revealed two step diffusion controlled redox process. The mononuclear complex Cu(II)-BSPD and binuclear complexes $Cu(II)_2$-TSDB and $Cu(II)_2$-TSTM were used in the oxidation reaction of ascorbic acid. The reaction rates were in the order of $Cu(II)_2$-TSTM>$Cu(II)_2$-TSDB>Cu(II)-BSPD, indicating that the binuclear $Cu(II)_2$-TSTM complex had the fastest values.

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Oxidative Stress-dependent Structural and Functional Regulation of 2-cysteine Peroxiredoxins In Eukaryotes Including Plant Cells (산화 스트레스에 의존한 식물 및 진핵세포 2-시스테인 퍼록시레독신의 기능 조절)

  • Jang, Ho-Hee;Kim, Sun-Young;Lee, Sang-Yeol
    • Journal of Plant Biotechnology
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    • v.33 no.1
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    • pp.1-9
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    • 2006
  • Peroxiredoxins (Prxs) are ubiquitously distributed and play important functions in diverse cellular signaling systems. The proteins are largely classified into three groups, such as typical 2-Cys Prx, atypical 2-Cys Prx, and 1-Cys Prx, that are distinguished by their catalytic mechanisms and number of Cys residues. From the three classes of Prxs, the typical 2-Cys Prx containing the two-conserved Cys residues at its N-terminus and C-terminus catalyzes $H_2O_2$ with the use of thioredoxin (Trx) as an electron donor. During the catalytic cycle, the N-terminal Cys residue undergoes a peroxide-dependent oxidation to sulfenic acid, which can be further oxidized to sulfinic acid at the presence of high concentrations of $H_2O_2$ and a Trx system containing Trx, Trx reductase, and NADPH. The sulfinic acid form of 2-Cys Prx is reduced by the action of sulfiredoxin which requires ATP as an energy source. Under the strong oxidative or heat shock stress conditions, 2-Cys Prx in eukaryotes rapidly switches its protein structure from low-molecular-weight species to high-molecular-weight protein structures. In accordance with its structural changes, the protein concomitantly triggers functional switching from a peroxidase to a molecular chaperone, which can protect its substrate denaturation from external stress. In addition to its N-terminal active site, the C-terminal domain including 'YF-motif' of 2-Cys Prx plays a critical role in the structural changes. Therefore, the C-terminal truncated 2-Cys Prxs are not able to regulate their protein structures and highly resistant to $H_2O_2$-dependent hyperoxidation, suggesting that the reaction is guided by the peroxidatic Cys residue. Based on the results, it may be concluded that the peroxidatic Cys of 2-Cys Prx acts as an '$H_2O_2$-sensor' in the cells. The oxidative stress-dependent regulation of 2-Cys Prx provides a means of defense systems in cells to adapt stress conditions by activating intracellular defense signaling pathways. Particularly, 2-Cys Prxs in plants are localized in chloroplasts with a dynamic protein structure. The protein undergoes conformational changes again oxidative stress. Depending on a redox-potential of the chloroplasts, the plant 2-Cys Prx forms super-molecular weight protein structures, which attach to the thylakoid membranes in a reversible manner.