• Title/Summary/Keyword: Irreversible reaction

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Studies on The Electrochemical Properties of Oxygen adducts Tetradentate Schiff Base Cobalt(II) Complexes in DMSO (I) (DMSO용액에서 네자리 Schiff Base Cobalt(II) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질에 관한 연구 (제 1 보))

  • Chjo Ki-Hyung;Jin-Soon Chung;Heui-Suk Ham;Seoing-Seob Seo
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.542-554
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    • 1987
  • Tetradentate schiff base cobalt(II) complexes; Co(SED), Co(SND) and Co(SOPD) have been prepared, these complexes have react with dry oxygen in DMSO to form oxygen adducts cobalt(III) complexes; $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ and $[Co(SOPD)(DMSO)]_2O_2$. It seems to be that the oxygen adducts cobalt(Ⅲ) complexes have heexa coordinated octahedral configration with tetradentate schiff base cobalt (III), DMSO and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1 : 2, these complexes have been identified by IR-Spectra, T.G.A., magnetic susceptibilitis and elemental analysis of C.H.N. and Cobalt. The redox reaction process of Co(SED), Co(SND) and Co(SOPD) complexes was investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP-DMSO. The results of redox reaction process of Co(II) / Co(III) and Co(II) / Co(I) for cobalt(SED) and cobalt(SOPD) complexes and Co(II) / Co(III) process for cobalt(SND) complex are reversible process but Co(II) / Co(I) process of Cobalt(SND) complex is irreversible, and oxygen adduct complexes to quasi reversibly with oxygen should be very closed related to the redox potentials of range, $E_{pc}$ = -0.80~-0.89V and $E_{pa}$ = -0.70~-0.76V.

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Removal of Red Tide Organisms -1. flocculation of Red Tide Organisms by Using IOSP- (적조생물의 구제 -1. IOSP에 의한 적조생물의 응집제거-)

  • KIM Sung-Jae;CHO Kyu-Dae
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.33 no.5
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    • pp.448-454
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    • 2000
  • This study was to examine the physicochemical characteristics of coagulation reaction between ignited oyster shell powder (IOSP) and red tide organisms (RTO), and its feasibility, in developing a technology for the removal of RTO bloom in coastal sea,IOSP was made from oyster shell and its physicochemical characteristics were examined for particle size distribution, surface characteristic by scanning electron microscope, zeta potential, and alkalinity and pH variations in sea water. Two kinds of RTO that were used in this study, Cylindrotheca closterium and Skeletonema costatum, were sampled in Masan bay and were cultured in laboratory. Coagulation experiments were conducted using various c(Incentrations of IOSP, RTO, and a jar tester. The supernatant and RTO culture solution were analyzed for pH, alkalinity, RTO cell number, IOSP showed positive zeta potentials of $11.1{\~}50.1\;mV\;at\;pH\;6.2{\~}12.7$, A positive zeta potential of IOSP slowly decreased with decreasing pNa 4,0 to 2,0. When pNa reached zero, the zeta potential approached zero, When a pMg value was decreased, the positive zeta potential of IOSP increased until pMg 3.0 and decreased below pMg 3.0. IOSP showed 4.8 mV of positive zeta potential while RTO showed -9.2 mV of negative zeta potential in sea water. A positive-negative EDL (electrical double-layer) interaction occurred between $Mg(OH)_2$ adsorption layer of IOSP and RTO in sea water so that EDL attractive force always worked between them. Hence, their coagulation reaction occurred at primary minimum on which an extreme attractive force acted because of charge neutralization by $Mg(OH)_2$ adsorption layer of IOSP. As a result, the coagulation reaction was rapidly processed and was irreversible according to DLVO (Deriaguin-Landau-Verwey-Overbeek) theory. Removal rates of RTO were exponentially increased with increasing both IOSP concentration and G-value. The removal rates were steeply increased until 50 mg/l of IOSP and reached $100{\%}\;at\;400\;mg/l$ of IOSP. Removal rates of RTO were $70.5,\;70.5,\;81.7,\;85.3{\%}$ for G-values of $1,\;6,\;29,\;139\;sec^(-1)$at IOSP 100 mg/l, respectively. This indicated that mixing (i.e., collision among particles) was very important for a coagulation reaction.

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Electrochemical Reduction for trans-Complexes of Cobalt (III) with Bis(ethylenediamine) and Monodendate Ligands (한자리 리간드를 포함하는 트란스비스 (에틸렌디아민) 코발트 (III) 이온의 전극 환원반응)

  • Jung-Ui Hwang;Jong-Jae Chung;Jae-Duck Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.2
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    • pp.215-224
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    • 1989
  • Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

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Working Mechanism of Peroxiredoxins (Prxs) and Sulphiredoxin1 (Srx1) in Arabidopsis thaliana (애기장대 peroxiredoxins (Prxs)과 sulphiredoxin1 (Srx1)의 작용기작)

  • Kim, Min-Gab;Su'udi, Mukhamad;Park, Sang-Ryeol;Hwang, Duk-Ju;Bae, Shin-Chul
    • Journal of Life Science
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    • v.20 no.12
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    • pp.1777-1783
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    • 2010
  • Plants generate reactive oxygen species (ROS) as a by-product of normal aerobic metabolism or when exposed to a variety of stress conditions, which can cause widespread damage to biological macromolecules. To protect themselves from oxidative stress, plant cells are equipped with a wide range of antioxidant proteins. However, the detailed reaction mechanisms of these are still unknown. Peroxiredoxins (Prxs) are ubiquitous thiol-containing antioxidants that reduce hydrogen peroxide with an N-terminal cysteine. The active-site cysteine of peroxiredoxins is selectively oxidized to cysteine sulfinic acid during catalysis, which leads to inactivation of peroxidase activity. This oxidation was thought to be irreversible. Recently identified small protein sulphiredoxin (Srx1), which is conserved in higher eukaryotes, reduces cysteine.sulphinic acid in yeast peroxiredoxin. Srx1 is highly induced by $H_2O_2$-treatment and the deletion of its gene causes decreased yeast tolerance to $H_2O_2$, which suggest its involvement in the metabolism of oxidants. Moreover, Srx1 is required for heat shock and oxidative stress induced functional, as well as conformational switch of yeast cytosolic peroxiredoxins. This change enhances protein stability and peroxidase activity, indicating that Srx1 plays a crucial role in peroxiredoxin stability and its regulation mechanism. Thus, the understanding of the molecular basis of Srx1 and its regulation is critical for revealing the mechanism of peroxiredoxin action. We postulate here that Srx1 is involved in dealing with oxidative stress via controlling peroxiredoxin recycling in Arabidopsis. This review article thus will be describing the functions of Prxs and Srx in Arabidopsis thaliana. There will be a special focus on the possible role of Srx1 in interacting with and reducing hyperoxidized Cys-sulphenic acid of Prxs.

Determination of Estrone by Adsorptive Stripping Voltammetry (흡착 벗김 전압전류법에 의한 에스트론의 정량)

  • Hong, Taekee;Kyong, Jin Burm;Lee, Hyun Jung;Czae, Myung-Zoon
    • Analytical Science and Technology
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    • v.12 no.1
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    • pp.34-39
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    • 1999
  • Estrone such as estriol and estradiol can not be determined by votammetric methods, because these are electrochemically inactive in the potential windows for mercury drop electrode. Nitro-derivatives of estrone are electro active and nitration of estrone is accomplished by heating the solution involving estrone and sodium nitrite in a water-bath at $100^{\circ}C$ for 30 min. Such nitro-derivatives are determined directly by voltammetry. The electrochemical behavior for nitrated estrone was investigated by cyclic voltammetry. The trace estrone was determinated by differential pulse adsorptive cathodic stripping voltammetry. Nitrated estrone gives a well defined voltammetric wave at ca. - 0.61 V (vs. Ag/AgCl electrode). The electrochemical reaction was irreversible process in sodium borate buffer at pH 11 and nitrated estrone was strongly adsorbed on the surface of mercury electrode. The optimal experimental conditions for the determination of nitrated esterone were found to be 0.05 M sodium nitrate, 0.01 M sodium borate, pH 11.0, and an accumlation potential of 0.10 V (vs. Ag/AgCl). The detection limit was as low as $1{\times}10^{-9}M$ for estrone with 2 min accumulation time.

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Analysis on Isotherm, Kinetic and Thermodynamic Properties for Adsorption of Acid Fuchsin Dye by Activated Carbon (활성탄에 의한 Acid Fuchsin 염료의 흡착에 대한 등온선, 동력학 및 열역학 특성치에 대한 해석)

  • Lee, Jong Jib
    • Korean Chemical Engineering Research
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    • v.58 no.3
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    • pp.458-465
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    • 2020
  • Isotherms, kinetics and thermodynamic properties for adsorption of acid fuchsin (AF) dye by activated carbon were carried out using variables such as dose of adsorbent, pH, initial concentration and contact time and temperature. The effect of pH on adsorption of AF showed a bathtub with high adsorption percentage in acidic (pH 8). Isothermal adsorption data were fitted to the Freundlich, Langmuir, and Dubinin-Radushkevich isotherm models. Freundlich isothem model showed the highest agreement and confirmed that the adsorption mechanism was multilayer adsorption. It was found that adsorption capacity increased with increasing temperature. Freundlich's separation factor showed that this adsorption process was an favorable treatment process. Estimated adsorption energy by Dubinin-Radushkevich isotherm model indicated that the adsorption of AF by activated carbon is a physical adsorption. Adsorption kinetics was found to follow the pseudo-second-order kinetic model. Surface diffusion at adsorption site was evaluated as a rate controlling step by the intraparticle diffusion model. Thermodynamic parameters such as activation energy, Gibbs free energy, enthalpy entropy and isosteric heat of adsorption were investigated. The activation energy and enthalpy change of the adsorption process were 21.19 kJ / mol and 23.05 kJ / mol, respectively. Gibbs free energy was found that the adsorption reaction became more spontaneously with increasing temperature. Positive entropy was indicated that this process was irreversible. The isosteric heat of adsorption was indicated physical adsorption in nature.

고등식물에 미치는 항생물질의 영향 (제4보) - 대두 Aminoacid metabolism에 미치는 항생물질의 영향에 대하여

  • 이민재;이영록
    • YAKHAK HOEJI
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    • v.3 no.1
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    • pp.4-9
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    • 1957
  • Effects of antibioties on micro-organism have been reported by many scientists, such as Krampitz and Werkman, Fisher, Gale and Rodwell, Klimick Cavalito and Bailey, Umbreit, etc. On the mechanism by which penicillin act, Fisher(1947), Platt(1947), and Cavallito, considered that penicillin might act on bacteria by inhibiting with the normal function of SH-group of glutathione in the metabolism of the cell. Resenbrance of penicillin to gultathione in structure and the inactivation of penicillin by cysteine make us approve of the above inhibiting theory of SH-group. Galland (1947) and Schmidt (1947) reported that penicillin inhibited the activity of ribonuclease, Phosphatase, and mononucleotidase. Gale (1948) discovered that the gram positive bacteria had lost the power to uptake glutamic acid by ribonucleic acid in the medium contained penicillin: growth of gram positive organism was inhibited by the results that penicillin inhibited the uptake of amino acid byribonucleic acid, acting on ribonucleic acid of gram positive bacteria. Hotchkiss (1950) cultured S. aureus in the medium contained glucose and amino acids, and studied the effect of penicillin on protein synthesis. Peptide formation in living cells was inhibited by penicillin, while amono acid was utilized as before the addition of penicillin. On the otherhand, Binkley (1951) found penicillin interfered hydrolase of glutath one, and Hans (1950) reported penicillin inhibited the transpeptidation. On the machanism by which streptomycin acts. Cohen (1947) reported steptomycin made a irreversible complex with desoxyribonucleic acid, by the fact that desoxyribonucleic acid formed the precipitates with diguanide group of steptomycin. Zeller (1951) reported, on the other hand, streptomycin inhibited diamine oxidease. Geiger (1947) and Umbreit (1949) reported that steptomycin inhibited condensation of oxaloacetate and pyruvate in E. Coli and Oginsky et al (1949) reported steptomycin inhibited oxaloacetate-pyruvate reaction in Kreb's cycle. On the mechanism by which terramycin acts, Hahn & Wisseman (1951) reported that the formation of adaptive enzyme was inhibited by terramycin in E. Coli cultivated in the medium contained loctose, and that the protein synthesis was inhibited by terramycin. However, effects of antibiotics on amino acid metabolism have not been discussed much in spite of its important role in living cells. Especislly, effects of anitibiotics on higher plants have scarcely been reported. Here, to prove the effect of antibiotics on higher plants, and the mechanism by which, through amino acid metabolism, they promote or inhibit growth of plants, amino acids in bean plants treated with penicillin, streptomycin, and terramycin were analyzed by paper chromatography. And to clarify the antagonis of cysteine (as SH-group) against penicillin, through amino acid metabolism, amino acids in bean plants treated with cystene and penicillin, at the same time, were also analyzed.

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Comparative Studies on K2CO3-based Catalytic Gasification of Samhwa Raw Coal and Its Ash-free Coal (삼화 원탄과 무회분탄의 촉매(K2CO3) 가스화 반응성 비교 연구)

  • Kong, Yongjin;Lim, Junghwan;Rhim, Youngjoon;Chun, Donghyuk;Lee, Sihyun;Yoo, Jiho;Rhee, Young-Woo
    • Clean Technology
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    • v.20 no.3
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    • pp.218-225
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    • 2014
  • Catalytic gasification of raw coals at mild condition is not realized yet mainly due to deactivation of catalysts via their irreversible interaction with mineral matters in coal. In this work, the gasification behavior of ash-free coal (AFC) was compared with that of the parent raw coal. In order to modify the gasification conditions, the raw coal gasified with fixed variables (water supply, space velocity, temperature, catalysts) in a fixed bed reactor. When catalysts are added by physical mixing method with coal, $K_2CO_3$ was the most effective additives for steam gasification of coal. However, the activity of ash-free coal (AFC) was much less reactive than raw coal due to high temperature extraction in a 1-methylnaphthalene under 30bar at $370^{\circ}C$ for 1 h, almost removed oxygen functional groups, and increased carbonization. The addition of $K_2CO_3$ in AFC achieved higher conversion rate at low temperature ($700^{\circ}C$). At that time, the molar ratio of gases ($H_2/CO$ and $CO_2/CO$) was increased because of water-gas shift reaction (WGSR) by addition of catalysts. This shows that catalytic steam gasification of AFCs is achievable for economic improvement of gasification process at mild temperature.

The Cycling Performance of Graphite Electrode Coated with Tin Oxide for Lithium Ion Battery (리튬이온전지용 주석산화물이 도포된 흑연전극의 싸이클 성능)

  • Kang, Tae-Hyuk;Kim, Hyung-Sun;Cho, Won-Il;Cho, Byung-Won;Ju, Jeh-Beck
    • Journal of the Korean Electrochemical Society
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    • v.5 no.2
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    • pp.52-56
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    • 2002
  • Tin oxide was coated on graphite particle by sol-gel method and an electrode with this material having microcrystalline structure for lithium ion battery was obtained by heat treatment in the range $400-600^{\circ}C$. The content of tin oxide was controlled within the range of $2.25wt\%\~11.1wt\%$. The discharge capacity increased with the content of tin oxide and also initial irreversible capacity increased. The discharge capacity of tin oxide electrode showed more than 350 mAh/g at the initial cycle and 300 mAh/g after the 30th cycle in propylene carbonate(PC) based electrolyte whereas graphite electrode without surface modification showed 140 mAh/g. When the charge and discharge rate was changed from C/5 to C/2, The discharge capacity of tin oxide and graphite electrode showed $92\%\;and\;77\%$ of initial capacity, respectively. It has been considered that such an enhancement of electrode characteristics was caused because lithium $oxide(Li_2O)$ passive film formed from the reaction between tin oxide and lithium ion prevented the exfoliation of graphite electrode and also reduced tin enhanced the electrical conduction between graphite particles to improve the current distribution of electrode.

Mechanistic Studies for Electrochemical Oxidation of ${\iota}$-Sparteine (${\iota}$-Sparteine의 전기화학적 산화반응에 대한 메카니즘의 연구)

  • Jin-Hyo Park;Chang-Soo Jin;Sung-Nak Choi;Yoon-Bo Shim
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.711-716
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    • 1993
  • The mechanism for electrochemical oxidation of natural alkaloid, ${\iota}$-sparteine (SP) was studied in acetonitrile solvent. The cyclic voltammogram of SP shows two irreversible anodic peaks at +0.75 V and +1.45 V vs. Ag/AgCl (0.1M AgNO$_2$ in acetonitrile) electrode. Coulometry reveals that the number of electrons involved in each oxidation peaks is in the range of 1.2∼1.3 respectively. Neutral imine radical was produced by fast deprotonation of SP radical cation formed by oxidation of one nitrogen atom in SP. Two pathways are possible for the reaction of the neutral radical: Due to the disproportionation of the radical, SP and enamine were mainly produced. Also, the 1,2-dehydrosparteinium cation was formed as minor product through the second one electron transfer oxidation of this radical. The (+)-lupanine was produced by treatment of sparteinium cation with potassium hydroxide. We have isolated and confirmed the electrolysis products using IR, GC-MS, UV-Vis, and thin-layer spectroelectrochemical method.

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