• Title/Summary/Keyword: cyclic peroxide

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Preparation of LiCoO$_2$from Used Lithium Ion Battery by Hydrometallurgical Processes

  • Lee, Churl-Kyoung;Rhee, Kang-In;Yang, Dong-Hyo;Yu, Hyo-Shin
    • Proceedings of the IEEK Conference
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    • 2001.10a
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    • pp.240-244
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    • 2001
  • Recycling process involving mechanical, thermal, hydrometallurgical, and sol-gel step has been applied to recover cobalt and lithium from spent lithium ion batteries and to synthesize LiCoO$_2$from leach liquor as cathodic active materials. Electrode materials containing lithium and cobalt could be concentrated with 2-step thermal and mechanical treatment. Leaching behaviors of the lithium and cobalt in nitric acid media was investigated in terms of reaction variables. Hydrogen peroxide in 1 M HNO$_3$solution turned out to be an effective reducing agent by enhancing the leaching efficiency. O f many possible processes to produce LiCoO$_2$, the amorphous citrate precursor process (ACP) has been applied to synthesize powders with a large specific surface area and an exact stoichiometry. After leaching used LiCoO$_2$with nitric acid, the molar ratio of Li/Co in the leach liquor was adjusted at 1.1 by adding a fresh LiNO$_3$solution. Then, 1 M citric acid solution at a 100% stoichiometry was also added to prepare a gelatinous precursor. When the precursor was calcined at 95$0^{\circ}C$ for 24 hr, purely crystalline LiCoO$_2$was successfully obtained. The particle size and specific surface area of the resulting crystalline powders were 20 пm and 30 $\textrm{cm}^2$/g, respectively The LiCoO$_2$powder was proved to have good characteristics as cathode active materials in charge/discharge capacity and cyclic performance.

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The Electrocatalytic Reduction of Oxygen by Bis-Cobalt Phenylporphyrins in Various pH Solutions (여러 가지 pH 수용액에서 Bis-Cobalt Phenylporphyrin 유도체들에 의한 산소의 전극 촉매적 환원)

  • Yong-Kook Choi;Ki-Hyung Chjo;Jong-Ki Park
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.735-743
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    • 1993
  • The electrocatalytic reduction of oxygen is investigated by cyclic voltammetry and chronoamperometry at glassy carbon electrode and carbon microelectrode coated with a variety of cobalt phenylprophyrins in various pH solutions. Oxygen reduction catalyzed by the monomeric porphyrin Co(Ⅱ)-TPP mainly occurs through the 2e$^-$ reduction pathway resulting in the formation of hydrogen peroxide whereas electrocatalytic process carried out 4e$^-$ reduction pathway of oxygen to H$_2$O at the electrodes coated with cofacial bis-cobalt phenylporphyrins in acidic solution. The electrocatalytic reduction of oxygen is irreversible and diffusion controlled. The reduction potentials of oxygen in various pH solutions have a straight line from pH 4 to pH 13, but level off in strong acidic solution. The reduction potentials of oxygen shift to positive potential more 400 mV at the electrode coated with monomer Co-TPP compound than bare glassy carbon electrode while 750 mV at the electrode coated with dimer Co-TPP compound.

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The Electrocatalytic Reduction of Dioxygen by Bis-Cobalt Phenylporphyrins in Alkaline Solution (알칼리 수용액에서 Bis-Cobalt Phenylporphyrin 유도체들에 의한 산소의 전극 촉매적 환원)

  • Yong-Kook ChoI;Hyun-Ju Moon;Seung-Won Jeon;Ki-Hyung Chjo
    • Journal of the Korean Chemical Society
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    • v.37 no.4
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    • pp.462-469
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    • 1993
  • The electrocatalytic reduction of dioxygen is investigated by cyclic voltammetry and chronoamperometry at glassy carbon electrode and carbon microelectrode coated with a variety of cobalt phenylporphyrins. The n value obtained at carbon microelectrode is slightly different from that determined at glassy carbon electrode. Dioxygen reduction catalyzed by the monormeric porphyrin Co(II)-TPP mainly occurs through the $2e^-$ reduction pathway resulting in the formation of hydrogen peroxide, electrocatalytic process carries out $4e^-$ reduction pathway of dioxygen to $H_2O$ at the electrodes coated with bis-cobalt phenylporphyrins. The electrocatalytic reduction of dioxygen is irreversible and diffusion controlled.

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Effects of Shut-down Process on Degradation of Polymer Electrolyte Membrane Fuel Cells I. Effects of Hydrogen Removal on the Degradation (운전 정지 시 보관방법이 고분자 전해질 연료전지의 열화에 미치는 영향 I. 잔류 수소 제거 방법의 영향)

  • Lim, Sang-Jin;Cho, Eun-Ae;Lee, Sang-Yeop;Kim, Hyoung-Juhn;Lim, Tae-Hoon;Lee, Kwan-Young
    • Journal of the Korean Electrochemical Society
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    • v.9 no.3
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    • pp.118-123
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    • 2006
  • Degradation of polymer electrolyte membrane fuel cell (PEMFC) that is facilitated by on/off cycles is one of the most important issues for commercialization of fuel cell vehicles. When a PEMFC stack is shut down, residual hydrogen and induce high voltage equivalent to open circuit voltage to the cathode side that might cause sintering of Pt catalyst and facilitate formation of hydrogen peroxide at the anode side that might decompose $Nafionc\'{A}$ membrane. In this study, degradation of PEMFC exposed to repetitive on/off cycles was investigated by measuring i-V characteristics, ac impedance, cyclic voltammograms, gas leak, cross-sectional SEM images, and TEM images. To prevent degradation of PEMFC caused by the residual gases, hydrogen was removed from anode gas channel by gas-purging and by using a dummy resistance, that were found to be a very effective method.

Mutation in clpxoo4158 Reduces Virulence and Resistance to Oxidative Stress in Xanthomonas oryzae pv. oryzae KACC10859

  • Cho, Jung-Hee;Jeong, Kyu-Sik;Han, Jong-Woo;Kim, Woo-Jae;Cha, Jae-Soon
    • The Plant Pathology Journal
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    • v.27 no.1
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    • pp.89-92
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    • 2011
  • Cyclic AMP receptor-like protein (Clp), is known to be a global transcriptional regulator for the expression of virulence factors in Xanthomonas campestris pv. campestris (Xcc). Sequence analysis showed that Xanthomonas oryzae pv. oryzae (Xoo) contains a gene that is strongly homologous to the Xcc clp. In order to determine the role of the Clp homolog in Xoo, a marker exchange mutant of $clp_{xoo4158}$ was generated. Virulence and virulence factors, such as the production of cellulase, xylanase, and extracellular polysaccharides (EPS) and swarming motility were significantly decreased in the $clp_{xoo4158}$ mutant. Moreover, the mutation caused the strain to be more sensitive to hydrogen peroxide and to over-produce siderophores. Complementation of the mutant restored the mutation-related phenotypes. Expression of $clp_{xoo4158}$, assessed by reverse-transcription realtime PCR and clp promoter activity, was significantly reduced in the rpfB, rpfF, rpfC, and rpfG mutants. These results suggest that the clp homolog, $clp_{xoo4158}$, is involved in the control of virulence and resistance against oxidative stress, and that expression of the gene is controlled by RpfC and RpfG through a diffusible signal factor (DSF) signal in Xanthomonas oryzae pv. oryzae KACC10859.

Effect of Monomers and Initiators on Electrochemical Properties of Gel Polymer Electrolytes (젤 고분자 전해질의 전기화학적 특성에 대한 단량체 및 개시제의 영향)

  • Park, Hyoun-Gyu;Ryu, Sang-Woog
    • Polymer(Korea)
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    • v.34 no.4
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    • pp.357-362
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    • 2010
  • Poly(ethyleneglycol diacrylate)(PEGDA) or 2-ethylhexyl acrylate(2EHA)-based gel polymer electrolytes(GPEs) which have a solid content in the range of 8~54 wt% were synthesized and their ionic conductivity and electrochemical properties were measured at room temperature. It was observed that the ionic conductivity over $1\times10^{-3}$ S/cm was obtained in a homogeneous PEGDA-based GPE with 21 wt% of solid content. However the electrochemical stability of the GPE was lower than that of a liquid electrolyte. The presence of AIBN initiator which can produce a N2 gas during polymerization process might be the reason of this low oxidation decomposition potential. As an alternative, benzoyl peroxide was used as an initiator and GPE with enhanced electrochemical stability was obtained. Finally, the formation of stable solid electrolyte interphase on a graphite anode was evidenced by cyclic voltammetry measurement.

Effect of Terephthalaldehyde to Facilitate Electron Transfer in Heme-mimic Catalyst and Its Use in Membraneless Hydrogen Peroxide Fuel Cell (테레프탈알데하이드의 전자전달 강화효과에 따른 헴 단백질 모방 촉매의 성능 향상 및 이를 이용한 비분리막형 과산화수소 연료전지)

  • Jeon, Sieun;An, Heeyeon;Chung, Yongjin
    • Korean Chemical Engineering Research
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    • v.60 no.4
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    • pp.588-593
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    • 2022
  • Terephthalaldehyde (TPA) is introduced as a cross liker to enhance electron transfer of hemin-based cathodic catalyst consisting of polyethyleneimine (PEI), carbon nanotube (CNT) for hydrogen peroxide reduction reaction (HPRR). In the cyclic voltammetry (CV) test with 10 mM H2O2 in phosphate buffer solution (pH 7.4), the current density for HPRR of the suggested catalyst (CNT/PEI/hemin/PEI/TPA) shows 0.2813 mA cm-2 (at 0.2 V vs. Ag/AgCl), which is 2.43 and 1.87 times of non-cross-linked (CNT/PEI/hemin/PEI) and conventional cross liker (glutaraldehyde, GA) used catalyst (CNT/PEI/hemin/PEI/GA), respectively. In the case of onset potential for HPRR, that of CNT/PEI/hemin/PEI/TPA is observed at 0.544 V, while those of CNT/PEI/hemin/PEI and CNT/PEI/hemin/PEI/GA are 0.511 and 0.471 V, respectively. These results indicate that TPA plays a role in facilitating electron transfer between the electrodes and substrates due to the π-conjugated cross-linking bonds, whereas conventional GA cross-linker increases the overpotential by interrupting electron and mass transfer. Electrochemical impedance spectroscopy (EIS) results also display the same tendency. The charge transfer resistance (Rct) of CNT/PEI/hemin/PEI/TPA decreases about 6.2% from that of CNT/PEI/hemin/PEI, while CNT/PEI/hemin/PEI/GA shows the highest Rct. The polarization curve using each catalyst also supports the superiority of TPA cross liker. The maximum power density of CNT/PEI/hemin/PEI/TPA (36.34±1.41 μWcm-2) is significantly higher than those of CNT/PEI/hemin/PEI (27.87±0.95 μWcm-2) and CNT/PEI/hemin/PEI/GA (25.57±1.32 μWcm-2), demonstrating again that the cathode using TPA has the best performance in HPRR.

Electrochemical Characteristic on Hydrogen Intercalation into the Interface between Electrolyte of the 0.1N H2SO4and Amorphous Tungsten Oxides Thin Film Fabricated by Sol-Gel Method (졸-겔법으로 제조된 비정질의 텅스텐 산화물 박막과 황산 전해질 계면에서 일어나는 수소의 층간 반응에 대한 전기화학적 특성)

  • Kang, Tae-Hyuk;Min, Byoung-Chul;Ju, Jeh-Beck;Sohn, Tae-Won;Cho, Won-Il
    • Applied Chemistry for Engineering
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    • v.7 no.6
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    • pp.1078-1086
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    • 1996
  • The peroxo-polytungstic acid was formed by the direct reaction of tungsten powder with the hydrogen peroxide solution. Peroxo-polytungstic powder were prepared by rotary evaporator using the fabricated on to ITO coated glass as substrate by dip-coating method using $2g/10mL(W-IPA/H_2O)$ sol solution. A substrate was dipped into the sol solution and after a meniscus had settled, the substrate was withdrawn at a constant rate of the 3mm/sec. Thicker layer could be built up by repeated dipping/post-treatment 15 times cycles. The layers dried at the temperature of $65{\sim}70^{\circ}C$ during the withdrawn process, and then tungsten oxides thin film was formed by final heating treatment at the temperature of $230{\sim}240^{\circ}C$ for 30min. A linear rotation between the thickness of thin film and the number of dipping/post-treatment cycles for tungsten oxides thin films made by dip-coating was found. The thickness of thin film had $60{\AA}$ after one dipping. From the patterns of XRD, the structure of tungsten oxides thin film identified as amorphous one and from the photographs of SEM, the defects and the moderate cracks were observed on the tungsten oxides thin film, but the homogeneous surface of thin films were mostly appeared. The electrochemical characteristic of the $ITO/WO_3$ thin film electrode were confirmed by the cyclic voltammetry and the cathodic Tafel polaization method. The coloring bleaching processes were clearly repeated up to several hundreds cycles by multiple cyclic voltammetry, but the dissolved phenomenon of thin film revealed in $H_2SO_4$ solution was observed due to the decrease of the current densities. The diffusion coefficient was calculated from irreversible Randles-Sevick equation from the data obtained by the cyclic voltammetry with various scan rates.

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Up-regulation of Heme Oxygenase-1 Expression by cAMP-elevating Agents in RAW 264.7 cells

  • Ko, Young-Shin;Park, Min-Kyu;Kang, Young-Jin;Lee, Young-Soo;Seo, Han-Geuk;Lee, Duck-Hyung;Yunchoi, Hye-Sook;Chong, Won-Seog;Chang, Ki-Churl
    • Biomolecules & Therapeutics
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    • v.10 no.2
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    • pp.71-77
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    • 2002
  • Heme oxygenase-1 (HO-1) is the inducible from of the rate-limiting enzyme of heme degradation; it regulates the cellular contents of heme. HO-1 is up-regulated by various stimuli including oxidative stress so that it is thought to participate in general cellular defense mechanisms against oxidative stress in mammalian cells. To investigate the role of the cAMP-dependent protein kinase A (PKA) signaling pathway on nitrogen oxidative stress-induced HO-1 gene expression, RAW 264.7 cell cultures were treated with sodium nitroprusside (SNP). SNP increased the expression of HO-1 mRNA and protein, time- and concentration-dependently. Treatment with H89, PKA inhibitor, but not LY83583, guanylate cyclase inhibitor, significantly diminished the HO-1 expression by SNP, indicating that cAMP plays a crucial role in the induction of HO-1. Incubation with cAMP-elevating agents, such as forskolin or isoproterenol resulted in up-regulation of the expression of HO-1. Forskolin-induced expression of HO-1 was inhibited by H89. Furthermore, propranolol, $\beta$-adrenoceptor blocker, inhibited the isoproterenol-induced HO-1 expression, supporting the importance of cAMP in the induction of HO-1 expression. Higenamine-S, but not higenamineR, enhanced the HO-1 expression induced by SNP. Furthermore, cellular toxicity induced by hydrogen peroxide was attenuated by the presence of SNP, which was further increased by the presence of ZnPPIX, HO-1 inhibitor. Collectively, these results strongly suggest that up-regulation of HO-1 expression in RAW 264.7 cells involves PKA signal pathway.

Expression and Localization of ATF4 Gene on Oxidative Stress in Preimplantation Mouse Embryo (생쥐 착상전 배아에서 산화적 스트레스에 의한 ATF4 유전자의 발현과 존재 부위)

  • Na, Won-Heum;Kang, Han-Seung;Eo, Jin-Won;Gye, Myung-Chan;Kim, Moon-Kyoo
    • Development and Reproduction
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    • v.10 no.2
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    • pp.105-113
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    • 2006
  • Reactive oxygen species(ROS) generated in cellular metabolism have an effect on cell maturation and development. In human reproductive tract, oxidative injury by ROS may induce female infertility. Also, oxidative injury may be responsible for developmental retardation and arrest of mammalian preimplantation embryos. Activating transcription factor 4(ATF4) is a member of the cyclic-AMP response element-binding(CREB) familiy of basic region- leucine zipper(bZip). ATF4 is known to regulate stress response to protect cell from various stress factors and inducer of apoptisis. The purpose of this study was to investigate whether ATF4 is involved in the defensive mechanism in oxidative stress condition during the development of mouse preimplantation embryos. To verify the expression of ATF4 in oxidative stress condition, 2-cell stage embryos were cultured in HTF media containing 0.1mM, 0.5mM or 1mM hydrogen peroxide($H_2O_2$) for 1hr(2-cell), 8hr(4-cell), 17hr(8-cell), 24hr(morula), 48hr(early blastocyst) or 64hr(late blastocyst). The developmental rate decreased in the 0.1mM $H_2O_2$ treated group compared with control group. In embryos treated with 0.5mM and 1mM $H_2O_2$ showed 2-cell block. As a results of the semi-quantitative RT-PCR analysis of SOD1, ATF4 and Bax gene expression, SOD1, ATF4 and Bax genes were increased in 0.1mM, 0.5mM, 1mM $H_2O_2$ treated groups compared with control group. In 2-cell embryos, expression of SOD1, ATF4 and Bax genes were notably increased in 0.1mM, 0.5mM, 1mM $H_2O_2$ treated groups compared with control group. Immunofluorescence analysis showed that ATF4 protein was localized at the cytoplasm of preimplantation embryos. The increase in ATF4 immunoreactivety was observed in the 0.1mM, 0.5mM, 1mM $H_2O_2$ treated groups compared with control group. It suggests that oxidative stress by $H_2O_2$ induces expression of ATF4 and may be involved in protection mechanism in preimplantation embryos from oxidative injury.

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