• Title/Summary/Keyword: Catalytic cycle

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Photocatalytic Oxidation of 2-Mercaptoethanol to Disulfide using Sb(V)-, P(V)-, and Ge(IV)-porphyrin Complexes

  • Shiragami, Tsutomu;Onitsuka, Dai;Matsumoto, Jin;Yasuda, Masahide
    • Rapid Communication in Photoscience
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    • v.3 no.4
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    • pp.70-72
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    • 2014
  • Visible-light irradiation of MeCN solution containing di(hydroxo)metallo(tetraphenyl)porphyrin complex $(tppM(OH)_2$: 1a; $M=Sb(V)^+Br^-$, 1b; $M=P(V)^+Cl^-$, 1c; M=Ge(IV)) and 2-mercaptoethanol (2-ME) as a substrate under aerated condition gave bis(2-hydroxyethyl)disulfide (2-HEDS) as an oxidative product of 2-ME. It is indicated that the oxidation of 2-ME should proceed with a photocatalytic process by 1, because the turn over number (TON) for the formation of 2-HEDS was over unit. The TON was determined to be 642 as a maximum value when 1a was used as a sensitizer. The formation of 2-HDES was extremely slow under argon atmosphere. The fluorescence of 1 was not quenched by 2-ME at all, and the free energy change (${\Delta}G$) with electron transfer (ET) from 2-ME to excited triplet state of $1(^31^*)$ was estimated as a negative value. The quenching rate constant ($k_r$) of $^31^*$ by 2-ME, obtained by the kinetics for the formation of 2-HEDS, strongly depends on ${\Delta}G$. These findings indicate that 1-sensitized oxidation was initiated by photoinduced ET from 2-ME to $^31^*$ to generate both radical cation of 2-ME ($2-ME^{+\bulle}$) and porphyrin radical anion ($1^{-\bulle}$), resulting that the formation of 2-HEDS can be proceeded by the dimerization of $2-ME^{+\bulle}$, and through a catalytic cycle due to returning to 1 by the ET from $1^{-\bulle}$ to molecular oxygen.

Evaluation of Hydrogenation Properties on Ti-Nb-Cr Alloys by Single-Roll Melt Spinning (단롤주조법에 의한 Ti-Nb-Cr 합금의 제조와 수소화 특성 평가)

  • Kim, Kyeong-Il;Hong, Tae-Whan
    • Korean Journal of Metals and Materials
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    • v.47 no.7
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    • pp.433-439
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    • 2009
  • Ti and Ti based hydrogen storage alloys have been thought to be the third generation of alloys with a high hydrogen capacity, which makes it difficult to handle because of high reactivity. In order to solve the problem, the activation of a wide range of hysteresis of hydriding/dehydriding and without degradation of hydrogen capacity due to the hydriding/dehydriding cycle have to be improved in order to be aplied. Ti-Cr alloys have a high capacity about 0.8 wt.% in an ambient atmosphere. When the Ti-Cr alloys are added to Nb and Ta elements, they formed a laves phase in the alloy system. The Nb element was expected to make easy diffuse hydrogen in the Ti-Cr storage alloy, which was a catalytic element. In this study, the Ti-Nb-Cr ternary alloy was prepared by melt spinning. As-received specimens were characterized using XRD (X-ray Diffraction), SEM (Scanning Electron Microscopy) with EDX (Energy Dispersive X-ray) and TG/DSC (Thermo Gravimetric Analysis/Differential Scanning Calorimetry). In order to examine hydrogenation behavior, the PCI (Pressure-Composition-Isotherm) was performed at 293, 323, 373 and 423 K.

Electron Transfer to Hydroxylase through Component Interactions in Soluble Methane Monooxygenase

  • Lee, Chaemin;Hwang, Yunha;Kang, Hyun Goo;Lee, Seung Jae
    • Journal of Microbiology and Biotechnology
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    • v.32 no.3
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    • pp.287-293
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    • 2022
  • The hydroxylation of methane (CH4) is crucial to the field of environmental microbiology, owing to the heat capacity of methane, which is much higher than that of carbon dioxide (CO2). Soluble methane monooxygenase (sMMO), a member of the bacterial multicomponent monooxygenase (BMM) superfamily, is essential for the hydroxylation of specific substrates, including hydroxylase (MMOH), regulatory component (MMOB), and reductase (MMOR). The diiron active site positioned in the MMOH α-subunit is reduced through the interaction of MMOR in the catalytic cycle. The electron transfer pathway, however, is not yet fully understood due to the absence of complex structures with reductases. A type II methanotroph, Methylosinus sporium 5, successfully expressed sMMO and hydroxylase, which were purified for the study of the mechanisms. Studies on the MMOH-MMOB interaction have demonstrated that Tyr76 and Trp78 induce hydrophobic interactions through π-π stacking. Structural analysis and sequencing of the ferredoxin domain in MMOR (MMOR-Fd) suggested that Tyr93 and Tyr95 could be key residues for electron transfer. Mutational studies of these residues have shown that the concentrations of flavin adenine dinucleotide (FAD) and iron ions are changed. The measurements of dissociation constants (Kds) between hydroxylase and mutated reductases confirmed that the binding affinities were not significantly changed, although the specific enzyme activities were significantly reduced by MMOR-Y93A. This result shows that Tyr93 could be a crucial residue for the electron transfer route at the interface between hydroxylase and reductase.

Separation of 2,6-dimethylnaphthalene in Dimethylnaphthalene Isomers Mixture by Crystallization Operation (결정화 조작에 의한 Dimethylnaphthalene 이성체 혼합물 중의 2,6-dimethylnaphthalene의 분리)

  • Kang, Ho-Cheol;Kim, Su Jin
    • Applied Chemistry for Engineering
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    • v.25 no.1
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    • pp.116-120
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    • 2014
  • Light cycle oil (LCO), one of the by-products of the catalytic cracking gasoline manufacturing process, contains a lot of valuable aromatics. In particular, 2,6-dimethylnaphthalene (2,6-DMN) contained in LCO has been becoming important as the basic material of polyethylene naphthalate plastic and liquid crystal polymer, etc. If it were possible to separate and purify the valuable aromatic hydrocarbons (such as 2,6-DMN) from LCO, which have only been used as fuel mixed with heavy oil, it would be very meaningful in terms of the efficient use of resources. We investigated the high-purity purification of 2,6-DMN by the combined method of melt crystallization (MC) and solute crystallization (SC). The enriched DMN isomer mixtures (concentration of 2,6-DMN : 10.43%) recovered from LCO by distillation-extraction combination and the crystal recovered by MC used as raw materials of MC and SC, respectively. The solvent of SC used was a mixture of methanol and acetone (60 : 40 wt%). The crystal of 2,6-DMN with a high-purity of 99.5% was recovered by MC-SC combination. We confirmed that the MC-SC combination was one of the very useful combinations for the high-purity purification of 2,6-DMN contained in the enriched DMN isomer mixtures.

Magnetite Dissolution by Copper Catalyzed Reductive Decontamination (촉매제로 구리이온을 이용한 환원성 제염에 의한 마그네타이트 용해)

  • Kim, Seonbyeong;Park, Sangyoon;Choi, Wangkyu;Won, Huijun;Park, Jungsun;Seo, Bumkyoung
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.16 no.4
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    • pp.421-429
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    • 2018
  • Hydrazine based reductive dissolution applied on magnetite oxide was investigated. Dissolution of Fe(II) and Fe(III) from magnetite takes place either by protonation, surface complexation, or reduction. Solution containing hydrazine and sulfuric acid provides hydrogen to break bonds between Fe and oxygen by protonation and electrons for the reduction of insoluble Fe(III) to soluble Fe(II) in acidic solution of pH 3. In terms of dissolution rate, numerous transition metal ions were examined and Cu(II) ion was found to be the most effective to speed up the dissolution. During the cycle of Cu(I) ions to Cu(II) ions, the released electron promoted the reduction of Fe(III) and Cu(II) ions returned to Cu(I) ion due to the oxidation of hydrazine. In the experimental results, the addition of a very low amount of cupric ion (about 0.5 mM) to the solution increased the dissolution rate about 40% on average and up to 70% for certain specific conditions. It is confirmed that even though the coordination structure of copper ions with hydrazine is not clear, the $Cu(II)/H^+/N_2H_4$ system is acceptable regarding the dissolution performance as a decontamination reagent.

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.

Differences in Gene Expression Profiles Reflecting Differences in Drug Sensitivity to Acetaminophen in Normal and Transformed Hepatic Cell Lines In vitro

  • Jeong, Youn-Kyoung;Kang, Jin-Seok;Kim, Joo-Whan;Suh, Soo-Kyung;Lee, Michael;Kim, Seung-Hee;Lee, Sang-Kook;Park, Sue-Nie
    • Molecular & Cellular Toxicology
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    • v.5 no.1
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    • pp.32-43
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    • 2009
  • Acetaminophen (APAP) overdose is known to cause severe hepatotoxicity mainly through the depletion of glutathione. In this study, we compared the cytotoxic effects of APAP on both a normal murine hepatic cell line, BNL CL.2, and its SV40-transformed cell line, BNL SV A.8. Gene expression profiles for APAP-treated cells were also obtained using microarray and analyzed to identify differences in genes or profiles that may explain the differences of susceptibility to APAP in these cell lines. These two cell lines exhibited different susceptibilities to APAP (0-$5,000{\mu}M$); BNL SV A.8 cells were more susceptible to APAP treatment compared to BNL CL.2 cells. A dose of $625{\mu}M$ APAP, which produced significant differences in cytotoxicity in these cell lines, was tested. Microarray analysis was performed to identify significant differentially expressed genes (DEGs) irrespective of APAP treatment. Genes up-regulated in BNL SV A.8 cells were associated with immune response, defense response, and apoptosis, while down-regulated genes were associated with catalytic activity, cell adhesion and the cytochrome P450 family. Consistent with the cytotoxicity data, no significant DEGs were found in BNL CL.2 cells after treatment with $625{\mu}M$ APAP, while cell cycle arrest and apoptosis-related genes were up-regulated in BNL SV A.8 cells. Based on the significant fold-changes in their expression, a genes were selected and their expressions were confirmed by quantitative real-time RT-PCR; there was a high correlation between them. These results suggest that gene expression profiles may provide a useful method for evaluating drug sensitivity of cell lines and eliciting the underlying molecular mechanism. We further compared the genes identified from our current in vitro studies to the genes previously identified in our lab as regulated by APAP in both C57BL/6 and ICR mice in vivo. We found that a few genes are regulated in a similar pattern both in vivo and in vitro. These genes might be useful to develop as in vitro biomarkers for predicting in vivo hepatotoxicity. Based on our results, we suggest that gene expression profiles may provide useful information for elucidating the underlying molecular mechanisms of drug susceptibility and for evaluating drug sensitivity in vitro for extrapolation to in vivo.

Knocking Down Nucleolin Expression Enhances the Radiosensitivity of Non-Small Cell Lung Cancer by Influencing DNA-PKcs Activity

  • Xu, Jian-Yu;Lu, Shan;Xu, Xiang-Ying;Hu, Song-Liu;Li, Bin;Qi, Rui-Xue;Chen, Lin;Chang, Joe Y.
    • Asian Pacific Journal of Cancer Prevention
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    • v.16 no.8
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    • pp.3301-3306
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    • 2015
  • Nucleolin (C23) is an important anti-apoptotic protein that is ubiquitously expressed in exponentially growing eukaryotic cells. In order to understand the impact of C23 in radiation therapy, we attempted to investigate the relationship of C23 expression with the radiosensitivity of human non-small cell lung cancer (NSCLC) cells. We investigated the role of C23 in activating the catalytic subunit of DNA-dependent protein kinase (DNA-PKcs), which is a critical protein for DNA double-strand breaks (DSBs) repair. As a result, we found that the expression of C23 was negatively correlated with the radiosensitivity of NSCLC cell lines. In vitro clonogenic survival assays revealed that C23 knockdown increased the radiosensitivity of a human lung adenocarcinoma cell line, potentially through the promotion of radiation-induced apoptosis and adjusting the cell cycle to a more radiosensitive stage. Immunofluorescence data revealed an increasing quantity of ${gamma}$-H2AX foci and decreasing radiation-induced DNA damage repair following knockdown of C23. To further clarify the mechanism of C23 in DNA DSBs repair, we detected the expression of DNA-PKcs and C23 proteins in NSCLC cell lines. C23 might participate in DNA DSBs repair for the reason that the expression of DNA-PKcs decreased at 30, 60, 120 and 360 minutes after irradiation in C23 knockdown cells. Especially, the activity of DNA-PKcs phosphorylation sites at the S2056 and T2609 was significantly suppressed. Therefore we concluded that C23 knockdown can inhibit DNA-PKcs phosphorylation activity at the S2056 and T2609 sites, thus reducing the radiation damage repair and increasing the radiosensitivity of NSCLC cells. Taken together, the inhibition of C23 expression was shown to increase the radiosensitivity of NSCLC cells, as implied by the relevance to the notably decreased DNA-PKcs phosphorylation activity at the S2056 and T2609 clusters. Further research on targeted C23 treatment may promote effectiveness of radiotherapy and provide new targets for NSCLC patients.

Internal Flow Analysis of Urea-SCR System for Passenger Cars Considering Actual Driving Conditions (운전 조건을 고려한 승용차용 요소첨가 선택적 촉매환원장치의 내부 유동 해석에 관한 연구)

  • Moon, Seong Joon;Jo, Nak Won;Oh, Se Doo;Lee, Ho Kil;Park, Kyoung Woo
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.40 no.3
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    • pp.127-138
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    • 2016
  • Diesel vehicles should be equipped with urea-selective catalytic reduction(SCR) system as a high-performance catalyst, in order to reduce harmful nitrogen oxide emissions. In this study, a three-dimensional Eulerian-Lagrangian CFD analysis was used to numerically predict the multiphase flow characteristics of the urea-SCR system, coupled with the chemical reactions of the system's transport phenomena. Then, the numerical spray structure was modified by comparing the results with the measured values from spray visualization, such as the injection velocity, penentration length, spray radius, and sauter mean diameter. In addition, the analysis results were verified by comparison with the removal efficiency of the nitrogen oxide emissions during engine and chassis tests, resulting in accuracy of the relative error of less than 5%. Finally, a verified CFD analysis was used to calculate the interanl flow of the urea-SCR system, thereby analyzing the characteristics of pressure drop and velocity increase, and predicting the uniformity index and overdistribution positions of ammonia.

Fabrication and the Electrochemical Characteristics of Petroleum Residue-Based Anode Materials (석유계 잔사유 기반 음극재 제조 및 그 전기화학적 특성)

  • Kim, Daesup;Lim, Chaehun;Kim, Seokjin;Lee, Young-Seak
    • Applied Chemistry for Engineering
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    • v.33 no.5
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    • pp.496-501
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    • 2022
  • In this study, an anode material for lithium secondary batteries was manufactured using petroleum-based residual oil, which is a petroleum refining by-product. Among petroleum-based residual oils, pyrolysis fuel oil (PFO), fluidized catalyst cracking-decant oil (FCC-DO), and vacuum residue (VR) were used as carbon precursors. The physicochemical characteristics of petroleum-based residual oil were confirmed through Matrix-assisted laser desorption/ionization Time-of-Flight (MALDI-TOF) and elemental analysis (EA), and the structural characteristics of anode materials manufactured from residual oil were evaluated using X-ray crystallography (XRD) and Raman spectroscopic techniques. VR was found to contain a wide range of molecular weight distributions and large amounts of impurities compared to PFO and FCC-DO, and PFO and FCC-DO exhibited almost similar physicochemical characteristics. From the XRD analysis results, carbonized PFO and FCC-DO showed similar d002 values. However, it was confirmed that FCC-DO had a more developed layered structure than PFO in Lc (Length of a and c axes in the crystal system) and La values. In addition, FCC-DO showed the best cycle characteristics in electrochemical characteristics evaluation. According to the physicochemical and electrochemical results of the petroleum-based residual oil, FCC-DO is a better carbon precursor for a lithium secondary battery than PFO and VR.