• Title/Summary/Keyword: In Situ $H_2O_2$ Generation

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Aromatization of 1,3,5-Trisubstituted of 4,5-Dihydro-1H-Pyrazoles by In-Situ Generation of I+ from Hydrogen Peroxide/Acids/Iodide Potassium or Sodium Systems

  • Maleki, Behrooz;Veisi, Hojat
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4366-4370
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    • 2011
  • A simple, green and cost-effective protocol was used for the aromatization of 1,3,5-trisubstituted-2-pyrazolines to the corresponding pyrazoles by in situ generation of iodine ($I^+$) from $H_2O_2$/AcOH or SSA or oxalic acid /KI or NaI system under thermal condition with moderate to good yields.

Direct Synthesis of H2O2 over Ti-Containing Molecular Sieves Supported Gold Catalysts: A Comparative Study for In-situ-H2O2-ODS of Fuel

  • Zhang, Han;Liu, Guangliang;Song, Haiyan;Chen, Chunxia;Han, Fuqin;Chen, Ping;Zhao, Zhixi;Hu, Shaozheng
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.3065-3072
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    • 2013
  • Direct synthesis of $H_2O_2$ and in situ oxidative desulfurization of model fuel over Au/Ti-HMS and Au/TS-1 catalysts has been comparatively investigated in water or methanol. Maximum amount (82%) of active $Au^0$ species for $H_2O_2$ synthesis was obtained. Au/Ti-HMS and Au/TS-1 exhibited the contrary performances in $H_2O_2$ synthesis as $CH_3OH/H_2O$ ratio of solvent changed. $H_2O_2$ decomposition and hydrogenation in water was inhibited by the introduction of methanol. Effect of $O_2/H_2$ ratio on $H_2O_2$ concentration, $H_2$ conversion and $H_2O_2$ selectivity revealed a relationship between $H_2O_2$ generation and $H_2$ consumption. The highest dibenzothiophene removal rate (83.2%) was obtained over Au/Ti-HMS in methanol at 1.5 of $O_2/H_2$ ratio and $60^{\circ}C$. But removal of thiophene over Au/TS-1 should be performed in water without heating to obtain a high removal rate (61.3%). Meanwhile, $H_2$ conversion and oxidative desulfurization selectivity of $H_2$ were presented.

Electrochemical Degradation of Phenol by Using Reticulated Vitreous Carbon Immobilized Horseradish Peroxidase (Horseradish Peroxidase가 고정화된 다공성 탄소 전극을 이용한 페놀의 전기화학적 분해)

  • Cho, Seung-Hee;Yeon, Kyeong-Ho;Kim, Gha-Young;Shim, Joon-Mok;Moon, Seung-Hyeon
    • Journal of Korean Society of Environmental Engineers
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    • v.27 no.12
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    • pp.1263-1269
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    • 2005
  • Horseradish peroxidase, had the phenol degradation rate of 95% in aqueous phase, was covalently immobilized on the surface of reticulated vitreous carbon(RVC) and the degradation of phenol was performed with in situ generated $H_2O_2$-immobilized HRP complex in an electrochemical reactor. The incorporation of carboxylic group on the RVC surface was confirmed by FT/IR spectrometry and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride(EDC) was used for peptide bonds between the carboxylic groups on the RVC surface and amine groups from HRP. The optimal conditions of in situ $H_2O_2$ generation such as concentration($10{\sim}200$ mM) and pH($5.0{\sim}8.0$) of electrolyte, supply of $O_2(10{\sim}50$ mL/min) and applied voltage($-0.2{\sim}-0.8$ volt, vs. Ag/AgCl) from potentiostat/galvanostat were determined by concentration of hydrogen peroxide and current efficiency. It was observed that the RVC immobilized HRP was stable maintaining 89% of the initial activity during 4 weeks. The phenol degradation rate of 86% was attained under the optimal condition of in situ $H_2O_2$ generation.

Kinetics of veratryl alcohol oxidation by lignin peroxidase and in-situ generated $H_2O_2$ in an electrochemical reactor

  • Lee, Gi-Beom;Gu, Man-Bok;Mun, Seung-Hyeon
    • 한국생물공학회:학술대회논문집
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    • 2000.11a
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    • pp.524-527
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    • 2000
  • An electroenzymatic system to oxidize veratryl alcohol of on electrodes with in-situ generated hydrogen peroxide was studied. We investigated hydrogen peroxide generation, current efficiency, and veratryl alcohol oxidation in the electrode system at various conditions. The reaction rates of veratryl alcohol oxidation were compared in an electrochemical, an electroenzymatic, and an usual biochemical systems to prove the concept of electroenzymatic oxidation.

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A Novel Method for Preparing of Oxoruthenates Complexes: trans-[RuO3(OH)2]2-, [RuO4]-, (n-Pr4N)+[RuO4]- and [RuO4 and Their Use as Catalytic Oxidants

  • Shoair, Abdel-Ghany F.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.10
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    • pp.1525-1528
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    • 2005
  • The synthesis and characterization of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O\;(C_2O_4}^{2-}$ = oxalato anoin) complex are described, and its redox properties (in buffer solution of pH = 12) have been investigated. This complex is used for in situ generation of oxoruthenates complexes which have been characterized by electronic spectroscopy. Reaction of ${K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${S_2O_8}^{2-}$ in molar KOH generates trans-${[RuO_3(OH)_2]^{2-}/S_2O_8}^{2-}$ reagent while with excess ${BrO_3}^-$ in molar $Na_2CO_3$ generates ${[RuO_4]^-/BrO_3}^-$ reagent. Avoiding the direct use of [$RuO_4$] the organic-soluble $(n-Pr_4N)^+[RuO_4]^-$, (TPAP) has been isolated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${BrO_3}^-$ in molar carbonate and n-$Pr_4$NOH. In a mixture of $H_2O/CCl_4$ ruthenium tetraoxide can be generated by reaction of $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ with excess ${IO_4}^-$. The catalytic activities of oxoruthenates that have been made from $K_3[Ru(C_2O_4)3]{\cdot}4H_2O$ towards the oxidation of benzyl alcohol, piperonyl alcohol, benzaldehyde and benzyl amine at room temperature have been studied.

Activation of persulfate by UV and Fe2+ for the defluorination of perfluorooctanoic acid

  • Song, Zhou;Tang, Heqing;Wang, Nan;Wang, Xiaobo;Zhu, Lihua
    • Advances in environmental research
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    • v.3 no.3
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    • pp.185-197
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    • 2014
  • Efficient defluorination of perfluorooctanoic acid (PFOA) was achieved by integrating UV irradiation and $Fe^{2+}$ activation of persulfate ($S_2O{_8}^{2-}$). It was found that the UV-$Fe^{2+}$, $Fe^{2+}-S_2O{_8}^{2-}$, and UV-$S_2O{_8}^{2-}$ processes caused defluorination efficiency of 6.4%, 1.6% and 23.2% for PFOA at pH 5.0 within 5 h, respectively, but a combined system of UV-$Fe^{2+}-S_2O{_8}^{2-}$ dramatically promoted the defluorination efficiency up to 63.3%. The beneficial synergistic behavior between $Fe^{2+}-S_2O{_8}^{2-}$ and UV-$S_2O{_8}^{2-}$ was demonstrated to be dependent on $Fe^{2+}$ dosage, initial $S_2O{_8}^{2-}$ concentration, and solution pH. The decomposition of PFOA resulted in generation of shorter-chain perfluorinated carboxylic acids (PFCAs), formic acid and fluoride ions. The generated PFCAs intermediates could be further defluorinated by adding supplementary $Fe^{2+}$ and, $S_2O{_8}^{2-}$ and re-adjusting solution pH in later reaction stage. The much enhanced PFOA defluorination in the UV-$Fe^{2+}-S_2O{_8}^{2-}$ system was attributed to the fact that the simultaneous employment of UV light and $Fe^{2+}$ not only greatly enhanced the activation of $S_2O{_8}^{2-}$ to form strong oxidizing sulfate radicals ($SO{_4}^{\cdot-}$), but also provided an additional decarboxylation pathway caused by electron transfer from PFOA to in situ generated $Fe^{3+}$.

Formation Behavior and Properties of PEO Films on AZ91 Mg Alloy in 0.1 M NaOH + 0.05 M NaF Solution Containing Various Na2SiO3 Concentrations (AZ91 마그네슘 합금의 플라즈마 전해산화 피막 형성 및 물성에 미치는 0.1 M NaOH + 0.05 M NaF 용액 중 Na2SiO3 농도의 영향)

  • Kwon, Duyoung;Song, Pung-Keun;Moon, Sungmo
    • Journal of the Korean institute of surface engineering
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    • v.53 no.2
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    • pp.59-66
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    • 2020
  • Effects of Na2SiO3 concentration added into 0.1 M NaOH + 0.05 M NaF solution on the formation behavior and properties of PEO films on AZ91 Mg alloy were investigated under 1200 Hz of alternating current (AC) by voltage-time curves, in-situ observation of arc generation behavior and measurements of film thickness, surface roughness and micro vickers hardness. In the absence of Na2SiO3 in the 0.1 M NaOH + 0.05 M NaF solution, about 4 ㎛ thick PEO film was formed within 1 min and then PEO film did not grow but white spots were formed by local burning. Addition of Na2SiO3 up to 0.2 M caused more increased formation voltage and growth of PEO film with uniform generation of arcs. Addition of Na2SiO3 from 0.2 M to 0.4 M showed nearly the same voltage-time behavior and uniform arc generation. Addition of Na2SiO3 more than 0.5 M resulted in a decrease of formation voltage and non-uniform arc generation due to local burning. PEO film growth rate increased with increasing added Na2SiO3 concentration but maximum PEO film thickness was limited by local burning if added Na2SiO3 concentration is higher than 0.5 M. Surface roughness of PEO film increased with increasing added Na2SiO3 concentration and appeared to be proportional to the PEO film thickness. PEO film hardness increased with increasing added Na2SiO3 concentration and reached a steady-state value of about 930 HV at more than 0.5 M of added Na2SiO3 concentration.

Genetic Screening for Plant Cell Death Suppressors and Their Functional Analysis in Plants

  • Yun, Dae-Jin
    • Proceedings of the Korean Society of Life Science Conference
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    • 2005.04a
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    • pp.23-36
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    • 2005
  • Bax, a mammalian pro-apoptotic member of the Bcl-2 family, induces cell death when expressed In yeast. To investigate whether .Bax expression can induce cell death in plant, we produced transgenic Arabidopsis plants that contained murine Bax cDNA under control of a glucocorticoid-inducible promoter. Transgenic plants treated with dexamethasone, a strong synthetic glucocorticoid, induced Bax accumulation and cell death, suggesting that some elements of cell death mechanism by Bax may be conserved among various orgarusms. Therefore, we developed novel yeast genetic system, and cloned several Plant Bax Inhibitors (PBIs). Here, we report the function of two PBIs In detail. PBIl is ascorbate peroxidase (sAPX). Fluorescence method of dihydrorhodamine123 oxidation revealed that expression of Bax in yeast cells generated reactive oxygen species (ROS), and which was greatly reduced by co-expression with sAPX. These results suggest that sAPX inhibits the generation of ROS by Bax, which in turn suppresses Bax-induced cell death in yeast. PBI2 encodes nucleoside diphosphate kinase (NDPK). ROS stress strongly induces the expression of the NDPK2 gene in Arabidopsis thaliana (AtNDPK2). Transgenic plants overexpressing AtNDPK2 have lower lovels of ROS than wildtype plants. Mutants lacking AtNDPK2 had higher levels of ROS than wildtype. H$_{2O2}$ treatment induced the phosphorylation of two endogenous proteins whose molecular weights suggested they are AtMPK3 and AtMPK6. In the absence of H2O2 treatment, phosphorylation of these proteins was slightly elevated in plants overexpressing AtNDPK2 but markedly decreased In the AtNDPK2 deletion mutant. Yeast two-hybrid and in vitro protein pull-down assays revealed that AtNDPK2 specifically interacts with AtMPK3 and AtMPK6. Furthermore, AtNDPK2 also enhances the MBP phosphorylation activity of AtMPK3 i'n vitro. Finally, constitutive overexpression of AtNDPK2 in Arabidopsis plants conferred an enhanced tolerance to multiple environmental stresses that elicit ROS accumulation In situ. Thus, AtNDPK2 appears to play a novel regulatory role in H2O2-mediated MAPK signaling in plants.

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Functional Screening for Cell Death Suppressors and Development of Multiple Stress-Tolerant Plants

  • Moon Hae-Jeong;Baek Dong-Won;Lee Ji-Young;Nam Jae-Sung;Yun Dae-Jin
    • Journal of Plant Biotechnology
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    • v.5 no.3
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    • pp.143-148
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    • 2003
  • Bax, a mammalian pro-apoptotic member of the Bcl-2 family induces cell death when expressed in yeast. To investigate whether Bax expression can induce cell death in plant, we produced transgenic Arabidopsis plants that contained murine Bax cDNA under control of a glucocorticoid-inducible promoter. Transgenic plants treated with dexamethasone, a strong synthetic glucocorticoid, induced Bax accumulation and cell death, suggesting that some elements of cell death mechanism by Bax may be conserved among various organisms. Therefore, we developed novel yeast genetic system, and cloned several Plant Bax Inhibitors (PBIs). Here, we report the function of two PBIs in detail. PBI1 is ascorbate peroxidase (sAPX). Fluorescence method of dihydrorhodamine123 oxidation revealed that expression of Bax in yeast cells generated reactive oxygen species (ROS), and which was greatly reduced by co-expression with sAPX. These results suggest that sAPX inhibits the generation of ROS by Bax, which in turn suppresses Baxinduced cell death in yeast. PBI2 encodes nucleoside diphosphate kinase (NDPK). ROS stress strongly induces the expression of the NDPK2 gene in Arabidopsis thaliana (AtNDPK2). Transgenic plants overexpressing AtNDPK2 have lower levels of ROS than wildtype plants. Mutants lacking AtNDPK2 had higher levels of ROS than wildtype. $H_2O_2$ treatment induced the phosphorylation of two endogenous proteins whose molecular weights suggested they are AtMPK3 and AtMPK6. In the absence of $H_2O_2$ treatment, phosphorylation of these proteins was slightly elevated in plants overexpressing AtNDPK2 but markedly decreased in the AtNDPK2 deletion mutant. Yeast two-hybrid and in vitro protein pull-down assays revealed that AtNDPK2 specifically interacts with AtMPK3 and AtMPK6. Furthermore, AtNDPK2 also enhances the MSP phosphorylation activity of AtMPK3 in vitro. Finally, constitutive overexpression of AtNDPK2 in Arabidopsis plants conferred an enhanced tolerance to multiple environmental stresses that elicit ROS accumulation in situ. Thus, AtNDPK2 appears to playa novel regulatory role in $H_2O_2$-mediated MAPK signaling in plants.

Functional Screening for Cell Death Suppressors and Development of Multiple Stress-Tolerant Plants

  • Moon, Hae-Jeong;Baek, Dong-Won;Lee, Ji-Young;Nam, Jae-Sung;Yun, Dae-Jin
    • Proceedings of the Korean Society of Plant Biotechnology Conference
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    • 2003.04a
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    • pp.65-71
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    • 2003
  • Bax, a mammalian pro-apoptotic member of the Bcl-2 family, induces cell death when expressed in yeast. To investigate whether Bax expression can induce cell death in plant, we produced transgenic Arabidopsis plants that contained murine Bax cDNA under control of a glucocorticoid-inducible promoter. Transgenic plants treated with dexamethasone, a strong synthetic glucocorticoid, induced Bax accumulation and cell death, suggesting that some elements of cell death mechanism by Bax may be conserved among various organisms. Therefore, we developed novel yeast genetic system, and cloned several Plant Bax Inhibitors (PBIs). Here, we report the function of two PBIs in detail. PBI1 is ascorbate peroxidase (sAPX). Fluorescence method of dihydrorho-damine 123 oxidation revealed that expression of Bax in yeast cells generated reactive oxygen species (ROS), and which was greatly reduced by co-expression with sAPX. These results suggest that sAPX inhibits the generation of ROS by Bax, which in turn suppresses Baxinduced cell death in yeast. PBI2 encodes nucleoside diphosphate kinase (NDPK). ROS stress strongly induces the expression of the NDPK2 gene in Arabidopsis thaliana (AtNDPK2). Transgenic plants overexpressing AtNDPK2 have lower levels of ROS than wildtype plants. Mutants lacking AtNDPK2 had higher levels of ROS than wildtype. $H_2O_2$ treatment induced the phosphorylation of two endogenous proteins whose molecular weights suggested they are AtMPK3 and AtMPK6. In the absence of $H_2O_2$ treatment, phosphorylation of these proteins was slightly elevated in plants overexpressing AtNDPK2 but markedly decreased in the AtNDPK2 deletion mutant. Yeast two-hybrid and in vitro protein pull-down assays revealed that AtNDPK2 specifically interacts with AtMPK3 and AtMPK6. Furthermore, AtNDPK2 also enhances the MBP phosphorylation activity of AtMPK3 in vitro. Finally, constitutive overexpression of AtNDPK2 in Arabidopsis plants conferred an enhanced tolerance to multiple environmental stresses that elicit ROS accumulation in situ. Thus, AtNDPK2 appears to play a novel regulatory role in $H_2O_2$-mediated MAPK signaling in plants.

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