• 제목/요약/키워드: Hydrogen Transfer

검색결과 547건 처리시간 0.031초

Biochemical characterization of ferredoxin-NADP+ reductase interaction with flavodoxin in Pseudomonas putida

  • Yeom, Jin-Ki;Park, Woo-Jun
    • BMB Reports
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    • 제45권8호
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    • pp.476-481
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    • 2012
  • Flavodoxin (Fld) has been demonstrated to bind to ferredoxin-NADP$^+$ reductase A (FprA) in Pseudomonas putida. Two residues ($Phe^{256}$, $Lys^{259}$) of FprA are likely to be important for interacting with Fld based on homology modeling. Site-directed mutagenesis and pH-dependent enzyme kinetics were performed to further examine the role of these residues. The catalytic efficiencies of FprA-$Ala^{259}$ and FprA-$Asp^{259}$ proteins were two-fold lower than those of the wild-type FprA. Homology modeling also strongly suggested that these two residues are important for electron transfer. Thermodynamic properties such as entropy, enthalpy, and heat capacity changes of FprA-$Ala^{259}$ and FprA-$Asp^{259}$ were examined by isothermal titration calorimetry. We demonstrated, for the first time, that $Phe^{256}$ and $Lys^{259}$ are critical residues for the interaction between FprA and Fld. Van der Waals interactions and hydrogen bonding were also more important than ionic interactions for forming the FprA-Fld complex.

마이크로 리포머의 열 및 역학적 거동 분석 (A Study on Thermal and Mechanical Behaviors of Micro Reformer)

  • 황원재;장재혁;길재형;김상진;이로운;김성한;정기호;오용수
    • 한국정밀공학회:학술대회논문집
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    • 한국정밀공학회 2005년도 춘계학술대회 논문집
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    • pp.235-239
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    • 2005
  • We analyzed the thermal and mechanical behaviors of micro reformer for the purpose of design verifications and modification of micro channels. The reformer designed for hydrogen generation from methanol is essential to PEM(Proton Exchange Membrane) type fuel cell. For the mobile applications, the size and the simplicity would be the most critical issues. We utilized silicon process for micro reformer to obtain the thickness thinner than 2 mm thick. We have used commercial simulation software, IDEAS, to analyze the thermal and mechanical characteristics of micro reformer structure. The heat generation rates of heaters, heat transfer rates, and fluid temperatures are derived from thermal equilibrium relation and these values were used for thermal boundary conditions. We also analyzed the thermal stresses, thermal deformations to examine the possibility of failure.

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Kinetics and Mechanism of the Anilinolysis of Dicyclohexyl Phosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1997-2002
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    • 2011
  • The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; $cHex_2$P(=O)Cl] with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 60.0 $^{\circ}C$. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal ($k_H/k_D$ > 1; max $k_H/k_D$ = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse ($k_H/k_D$ < 1; min $k_H/k_D$ = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted $S_N2$ mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.

ASSESSMENT OF A NEW DESIGN FOR A REACTOR CAVITY COOLING SYSTEM IN A VERY HIGH TEMPERATURE GAS-COOLED REACTOR

  • PARK GOON-CHERL;CHO YUN-JE;CHO HYOUNGKYU
    • Nuclear Engineering and Technology
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    • 제38권1호
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    • pp.45-60
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    • 2006
  • Presently, the VHTGR (Very High Temperature Gas-cooled Reactor) is considered the most attractive candidate for a GEN-IV reactor to produce hydrogen, which will be a key resource for future energy production. A new concept for a reactor cavity cooling system (RCCS), a critical safety feature in the VHTGR, is proposed in the present study. The proposed RCCS consists of passive water pool and active air cooling systems. These are employed to overcome the poor cooling capability of the air-cooled RCCS and the complex cavity structures of the water-cooled RCCS. In order to estimate the licensibility of the proposed design, its performance and integrity were tested experimentally with a reduced-scale mock-up facility, as well as with a separate-effect test facility (SET) for the 1/4 water pool of the RCCS-SNU to examine the heat transfer and pressure drop and code capability. This paper presents the test results for SET and validation of MARS-GCR, a system code for the safety analysis of a HTGR. In addition, CFX5.7, a computational fluid dynamics code, was also used for the code-to-code benchmark of MARS-GCR. From the present experimental and numerical studies, the efficacy of MARS-GCR in application to determining the optimal design of complicated systems such as a RCCS and evaluation of their feasibility has been validated.

락트산 산증과 칼륨이동에 관한 실험적 연구 (An Experimental Study of Lactic Acidosis and Potassium Transfer in the Dog)

  • 박주철;이영균
    • Journal of Chest Surgery
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    • 제12권4호
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    • pp.395-402
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    • 1979
  • Intracellular pH was determined by distribution of 5.5-dimethyl-2,4-oxazolidlnedione [DMO]in the skeletal muscle of dogs before and after lactic acidosis induced by intravenous infusion of lactic acid solution. After infusion of lactic acid solution arterial pH decreased from 7.40 to around 7.12 [P<0.001]and metabolic acidosis was induced. However, dose-pH change response was not proportional as in the case of hydrochloric acid infusion. During lactic acidosis, intracellular pH changed very little except when venous blood $pCO_2$ increased significantly. The decrease of intracellular pH in lactic acidosis might be due primarily to the increase of intracellular $pCO_2$. And during lactic acidosis, change of extracellular pH was larger than that of intracellular pH, and this was also the case of change In hydrogen Ion concentration in extracellular and intracellular fluid. The fact was estimated that exogenous lactic acid transported into the cell does not contribute to pH change by the participation in the metabolism. Change in plasma potassium Ion concentration was not eminent as metabolic acid-base disturbances by other origin, and changing pattern of Hi/He ratio was not same as Ki/Ke ratio. In spite of no changes in extracellular potassium ion concentration after exogenous lactic acidosis total amount of potassium ion in extracellular fluid increased from 12.62mEg to 18.26mEg [P< 0.05].

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Oxidation of organic contaminants in water by iron-induced oxygen activation: A short review

  • Lee, Changha
    • Environmental Engineering Research
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    • 제20권3호
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    • pp.205-211
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    • 2015
  • Reduced forms of iron, such as zero-valent ion (ZVI) and ferrous ion (Fe[II]), can activate dissolved oxygen in water into reactive oxidants capable of oxidative water treatment. The corrosion of ZVI (or the oxidation of (Fe[II]) forms a hydrogen peroxide ($H_2O_2$) intermediate and the subsequent Fenton reaction generates reactive oxidants such as hydroxyl radical ($^{\bullet}OH$) and ferryl ion (Fe[IV]). However, the production of reactive oxidants is limited by multiple factors that restrict the electron transfer from iron to oxygen or that lead the reaction of $H_2O_2$ to undesired pathways. Several efforts have been made to enhance the production of reactive oxidants by iron-induced oxygen activation, such as the use of iron-chelating agents, electron-shuttles, and surface modification on ZVI. This article reviews the chemistry of oxygen activation by ZVI and Fe(II) and its application in oxidative degradation of organic contaminants. Also discussed are the issues which require further investigation to better understand the chemistry and develop practical environmental technologies.

THE MEMBRANE BIOFILM REACTOR IS A VERSA TILE PLATFORM FOR WATER AND WASTEWATER TREATMENT

  • Rittmann, Bruce E.
    • Environmental Engineering Research
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    • 제12권4호
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    • pp.157-175
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    • 2007
  • The membrane biofilm reactor (MBfR) creates a natural partnership of a membrane and biofilm, because a gas-transfer membrane delivers a gaseous substrate to the biofilm that grows on the membrane's outer wall. $O_2$-based MBfRs (called membrane aerated biofilm reactors, or MABRs) have existed for much longer than $H_2$-based MBfRs, but the $O_2$-based MBfR is a versatile platform for reducing oxidized contaminants in many water-treatment settings: drinking water, ground water, wastewater, and agricultural drainage. Extensive bench-scale experimentation has proven that the $H_2$-based MBfR can reduce many oxidized contaminant to harmless or easily removed forms: e.g., ${NO_3}^-$ to $N_2$, ${ClO_4}^-$ to $H_2O$ and $Cl^-$, ${SeO_4}^{2-}$ to $Se^0$, and trichloroethene (TCE) to ethene and $Cl^-$. The MBfR has been tested at the pilot scale for ${NO_3}^-$ and ${ClO_4}^-$ and is now entering field-testing for many of the oxidized contaminants alone or in mixtures. For the MBfR to attain its full promise, several issues must be addressed by bench and field research: understanding interactions with mixtures of oxidized contaminants, treating waters with a high TDS concentration, developing modules that can be used in situ to augment pre-denitrification of wastewater, and keeping the capital costs low.

카르복실산 합성전구체(合成前驅體)로서의 옥탄니트릴의 생성반응(生成反應)에 관(關한) 연구(硏究) (A Study on the Formation of Octanenitrile as a Precursor for Synthesis of Carboxylic Acid)

  • 김용인;오양환;김광식;이동우
    • 한국응용과학기술학회지
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    • 제6권2호
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    • pp.29-37
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    • 1989
  • Using the quarternary ammonium salts as phase transfer catalyst, the nucleophilic substitution reaction of 1-chlorooctane with sodium-cyanide was investigate kinetically with respect to the formation of octanenitrile. The product was analyzed with gas chromatograph, and quantity of octanenitrile was measured. The reaction condition was considered by the effect of the reaction temperature, of the species and the amount of catalyst, of the speed of strirring, and of the concentration of reactants. The reaction was carried out in the first order on the concentration of 1-chlorooctane and sodium cyanide, respectively. The over-all order was 2nd. The activation energies for the nucleophilic substitution reaction of 1-chlorooctane and 1-bromooctane under tetrabutylammonium hydrogen-sulfate were calculated as 2.05 and 10.08kcal/mol, respectively. The effect of various caltalysts was decreased in the order of tetrabutylammonium bromide, terabutylammonium, tetrabutylammonium hydrogensulfate, and tetrabutylammonium iodide. The reaction rate was dependent on the concentration of sodium-cyanide dissolved in the aqueous phase, and the good result was shown when the mol ratio between 1-chlorooctane and sodium cyanide was one per three.

Power control strategies of a DC-coupled hybrid power system for a building microgrid

  • Cho, Jea-Hoon;Hong, Won-Pyo
    • 조명전기설비학회논문지
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    • 제25권3호
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    • pp.50-64
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    • 2011
  • In this paper, a DC-coupled photovoltaic (PV), fuel cell (FC) and ultracapacitor hybrid power system is studied for building microgrid. In this proposed system, the PV system provides electric energy to the electrolyzer to produce hydrogen for future use and transfer to the load side, if possible. Whenever the PV system cannot completely meet load demands, the FC system provides power to meet the remaining load. The main weak point of the FC system is slow dynamics, because the power slope is limited to prevent fuel starvation problems, improve performance and increase lifetime. A power management and control algorithm is proposed for the hybrid power system by taking into account the characteristics of each power source. The main works of this paper are hybridization of alternate energy sources with FC systems using long and short storage strategies to build an autonomous system with pragmatic design, and a dynamic model proposed for a PV/FC/UC bank hybrid power generation system. A simulation model for the hybrid power system has been developed using Matlab/Simulink, SimPowerSystems and Matlab/Stateflow. The system performance under the different scenarios has been verified by carrying out simulation studies using a practical load demand profile, hybrid power management and control, and real weather data.

Transition State Variation in the Anilinolysis of O-Aryl Phenyl Phosphonochloridothioates in Acetonitrile

  • Adhikary, Keshab Kumar;Lumbiny, Bilkis Jahan;Dey, Shuchismita;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권8호
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    • pp.2628-2632
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    • 2011
  • The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.