• 제목/요약/키워드: Hydrogen Transfer

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Lipid Film에 수식된 헤모글로빈의 전기화학적 특성과 $H_{2}O_{2}$응답특성 (Direct electrochemistry of hemoglobin at carbon electrode modified with lipid film and its application as a $H_{2}O_{2}$ sensor)

  • 이동윤;박상현;최용성;권영수
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 2006년도 추계학술대회 논문집 전기물성,응용부문
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    • pp.93-94
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    • 2006
  • In this research, the enhancement of electron-transfer activity of hemoglobin (Hb) in dodecanoic acid film was investigated for the first time. This type of composite film was made on glassy carbon electrode by casting method. Cyclic voltammetric result of the modified electrode displays a well defined redox peaks which was attributed to the direct electrochemical response of Rb. Our results illustrate that Rb exchange electrons directly with electrode and exhibits the characteristics of peroxidase. When we apply this modified electrode as a biosensor, it gives excellent performances in the electrocatalytic reduction of hydrogen peroxide ($H_{2}O_{2}$). Through the optimal conditions, the proposed biosensor shows the linear range for H2O2 determination was from $1{\times}10^{-5}$ to $1.25{\times}10^{-4}mol/L$ with a detection limit of $1{\times}10^{-7}mol/L$. The biosensor retained more than 90% of the initial response after 14 days.

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Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorophosphate in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제33권6호
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    • pp.1879-1884
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    • 2012
  • The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.09-1.01) with the strongly basic anilines while secondary inverse ($k_H/k_D$ = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the ($R_1O$)($R_2O$)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.

A Multiagent-Based Hybrid Power Control and Management of Distributed Power Sources

  • Yoon, Gi-Gab;Hong, Won-Pyo;Lee, Ki-Hong
    • 조명전기설비학회논문지
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    • 제25권8호
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    • pp.70-81
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    • 2011
  • In this paper, a multi-agent control system for DC-coupled photovoltaic (PV), fuel cell (FC), ultracapacitor(UC) and battery hybrid power system is studied for commercial buildings & apartment buildings 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. A multi-agent system based-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 the multi-agent control system with pragmatic design, and a dynamic model proposed for a PV/FC/UC/battery bank hybrid power generation system. A dynamic simulation model for the hybrid power system has been developed using Matlab/Simulink, SimPowerSystems and Stateflow. Simulation results are also presented to demonstrate the effectiveness of the proposed multi-agent control and management system for building microgrid.

Binder-Free Synthesis of NiCo2S4 Nanowires Grown on Ni Foam as an Efficient Electrocatalyst for Oxygen Evolution Reaction

  • Patil, Komal;Babar, Pravin;Kim, Jin Hyeok
    • 한국재료학회지
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    • 제30권5호
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    • pp.217-222
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    • 2020
  • The design and fabrication of catalysts with low-cost and high electrocatalytic activity for the oxygen evolution reaction (OER) have remained challenging because of the sluggish kinetics of this reaction. The key to the pursuit of efficient electrocatalysts is to design them with high surface area and more active sites. In this work, we have successfully synthesized a highly stable and active NiCo2S4 nanowire array on a Ni-foam substrate (NiCo2S4 NW/NF) via a two-step hydrothermal synthesis approach. This NiCo2S4 NW/NF exhibits overpotential as low as 275 mV, delivering a current density of 20 mA cm-2 (versus reversible hydrogen electrode) with a low Tafel slope of 89 mV dec-1 and superior long-term stability for 20 h in 1 M KOH electrolyte. The outstanding performance is ascribed to the inherent activity of the binder-free deposited, vertically aligned nanowire structure, which provides a large number of electrochemically active surface sites, accelerating electron transfer, and simultaneously enhancing the diffusion of electrolyte.

Development of diverse fluorides source for applicable F-18 radiofluorination method

  • Park, Su Hong;Kim, Dong Wook
    • 대한방사성의약품학회지
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    • 제2권1호
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    • pp.17-21
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    • 2016
  • Alkali metal fluoride sources (MFs) such as potassium fluoride (KF) have been widely used as a fluoride source in the nucleophilic displacement reaction. However, they have low solubility and nucleophilicity in most of the organic solvents. Bulky fluoride sources such as tetrabutylammonium fluoride (TBAF) were substituted for MFs to improve these properties. However, hygroscopic property of TBAF makes it less convenient for handling as well as its strong basic property can make the side-reaction occur. Recently, novel fluoride sources have been developed to solve these problems. In this paper, we would like to introduce coordinated fluoride sources as a new fluoride sources such as tetrabutylammonium tetra(t-butyl alcohol)-coordinated fluoride, crown ether metal complex fluoride, and various bulky alcohols coordinated fluoride complexes. In particular, bulky alcohol coordinated fluoride source could generated by the controlled hydrogen-bonded of fluoride with alcohols and these fluoride sources have better stability and reactivity with showing low hygroscopic property. The study of these fluoride sources will help to understand the characteristic of [$^{18}F$]fluoride for increasing the radiochemical yield in the [$^{18}F$]radiofluorination.

Src Redox Regulation: There Is More Than Meets the Eye

  • Chiarugi, Paola
    • Molecules and Cells
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    • 제26권4호
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    • pp.329-337
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    • 2008
  • Src-family kinases are critically involved in the control of cytoskeleton organization and in the generation of integrin-dependent signaling responses, inducing tyrosine phosphorylation of many signaling and cytoskeletal proteins. Activity of the Src family of tyrosine kinases is tightly controlled by inhibitory phosphorylation of a carboxy-terminal tyrosine residue, inducing an inactive conformation through binding with its SH2 domain. Dephosphorylation of C-ter tyrosine, as well as its deletion of substitution with phenylalanine in oncogenic Src kinases, leads to autophosphorylation at a tyrosine in the activation loop, thereby leading to enhanced Src activity. Beside this phophorylation/dephosphorylation circuitry, cysteine oxidation has been recently reported as a further mechanism of enzyme activation. Mounting evidence describes Src activation via its redox regulation as a key outcome in several circumstances, including growth factor and cytokines signaling, integrin-mediated cell adhesion and motility, membrane receptor cross-talk as well in cell transformation and tumor progression. Among the plethora of data involving Src kinase in physiological and pathophysiological processes, this review will give emphasis to the redox component of the regulation of this master kinase.

Efficiency Factors of Singlet Oxygen Generation from Core-Modified Expanded Porphyric : Tetrathiarubyrin in Ethanol

  • 하정현;정국영;김민선;이양훈;신구;김용록
    • Bulletin of the Korean Chemical Society
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    • 제22권1호
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    • pp.63-67
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    • 2001
  • The photophysical properties and the singlet oxygen generation efficiency of tetrathiarubyrin have been investigated to elucidate the possibility of its use as a photodynamic therapy (PDT) photosensitizer by steady-state and time-resolved spectroscopic methods. The observed photophysical properties were affected by various molecular aspects, such as extended ${\pi}conjugation$, structural distortion, and internal heavy atom. The steady-state electronic absorption spectrum was red-shifted due to the extended $\pi-conjugation$, and the spin orbital coupling was enhanced by the structural distortion and the internal heavy atom effect. As a result of the enhanced spin orbital coupling, the triplet quantum yield increased to 0.90 $\pm$ 0.10 and the triplet state lifetime was shortened to 7.0 $\pm$ 1.2 ${\mu}s$. Since the triplet state decays at a relatively faster rate, the efficiency of the oxygen quenching of the triplet state decreases. The singlet oxygen quantum yield was estimated to be 0.52 $\pm$ 0.02, which is somewhat lower than expected. On the other hand, the efficiency of singlet oxygen generation during the oxygen quenching of triplet state, $f{\Delta}^T$, is near unity. Such high efficiency of singlet oxygen generation can be explained by the following two possible factors: The hydrogen bonding of ethanol which impedes the deactivation pathway of the charge transfer complex with oxygen to the ground state, the less probability of the aggregation formation.

Exploratory Study of Photocyclization Reactions of N-(Trimethylsilylmethylthioalkyl)phthalimides

  • Ung Chan Yoon;Sang Jin Lee;Kyung Ja Lee;Sung Ju Cho;Chan Woo Lee;Patrick S. Mariano
    • Bulletin of the Korean Chemical Society
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    • 제15권2호
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    • pp.154-161
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    • 1994
  • Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethylthioalkyl)phthalimides (alkyl=ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl). Photocyclizations occur in methanol in modest to high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from sulfur in the ${\alpha}$-silylmethylthioalkyl groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate ${\alpha}$ -silylmethylthio cation radicals and cyclization by radical coupling is proposed. In contrast, photoreactions of N-(trimethylsilylmethylthioalkyl)phthalimides in acetone follow different reaction routes to produce another cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon ${\alpha}$ to silicon and sulfur atoms via triplet carbonyl hydrogen abstraction pathway. The normal singlet SET pathway dominates this triplet process for photoreactions of these substances in methanol while the triplet process dominates the singlet SET pathway for those in acetone. The efficient and regioselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Photocyclization Reactions of N-(Trimethylsilylmethoxyalkyl)Phthalimides. Efficient and Regioselective Route to Heterocycles

  • Yoon Ung Chan;Oh Ju Hee;Lee, Sang Jin;Kim, Dong Uk;Lee, Jong Gun;Kang Kyung-Tae;Mariano Patrick S.
    • Bulletin of the Korean Chemical Society
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    • 제13권2호
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    • pp.166-172
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    • 1992
  • Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethoxyalkyl)phthalimides(alkyl=E thyl, n-propyl, n-butyl, n-pentyl, and n-octyl). Photocyclizations occur in methanol in high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from oxygen in the $\alpha-silylmethoxy$ groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate $\alpha-silylmethoxy$ cation radicals and cyclization by radical coupling are proposed. In contrast, photoreaction of N-(trimethylsilylmethoxyethyl) phthalimide in acetone follows different reaction routes to produce two cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon $\alpha$ to silicon and oxygen atoms via triplet carbonyl hydrogen abstraction triplet carbonyl silyl group abstraction pathways. The normal singlet SET pathway dominates these triplet processes for photoreaction of this substance in methanol. The efficient and regioselective cyclization reactions observed for photolysis in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.

Rational Design of Binder-Free Fe-Doped CuCo(OH)2 Nanosheets for High-Performance Water Oxidation

  • Patil, Komal;Jang, Su Young;Kim, Jin Hyeok
    • 한국재료학회지
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    • 제32권5호
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    • pp.237-242
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    • 2022
  • Designing and producing a low-cost, high-current-density electrode with good electrocatalytic activity for the oxygen evolution reaction (OER) is still a major challenge for the industrial hydrogen energy economy. In this study, nanostructured Fe-doped CuCo(OH)2 was discovered to be a precedent electrocatalyst for OER with low overpotential, low Tafel slope, good durability, and high electrochemically active surface sites at reduced mass loadings. Fe-doped CuCo(OH)2 nanosheets are made using a hydrothermal synthesis process. These nanosheets are clumped together to form a highly open hierarchical structure. When used as an electrocatalyst, the Fe-doped CuCo(OH)2 nanosheets required an overpotential of 260 mV to reach a current density of 50 mA cm-2. Also, it showed a small Tafel slope of 72.9 mV dec-1, and superior stability while catalyzing the generation of O2 continuously for 20 hours. The Fe-doped CuCo(OH)2 was found to have a large number of active sites which provide hierarchical and stable transfer routes for both electrolyte ions and electrons, resulting in exceptional OER performance.