• Title/Summary/Keyword: proton reaction

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Improved Microstructural Homogeneity of Ni-BCY Cermets Membrane via High-Energy Milling (고에너지 밀링을 통한 Ni-BaCe0.9Y0.1O3-δ 서멧 멤브레인의 미세구조 균질성 향상)

  • Kim, Hyejin;Ahn, Kiyong;Kim, Boyoung;Lee, Jongheun;Chung, Yong-Chae;Kim, Hae-Ryoung;Lee, Jong-Ho
    • Journal of the Korean Ceramic Society
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    • v.49 no.6
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    • pp.648-653
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    • 2012
  • Hybridization of dense ceramic membranes for hydrogen separation with an electronically conductive metallic phase is normally utilized to enhance the hydrogen permeation flux and thereby to increase the production efficiency of hydrogen. In this study, we developed a nickel and proton conducting oxide ($BaCe_{0.9}Y_{0.1}O_{3-{\delta}}$: BCY) based cermet (ceramic-metal composites) membrane. Focused on the general criteria in that the hydrogen permeation properties of a cermet membrane depend on its microstructural features, such as the grain size and the homogeneity of the mix, we tried to optimize the microstructure of Ni-BCY cermets by controlling the fabrication condition. The Ni-BCY composite powder was synthesized via a solid-state reaction using $2NiCO_3{\cdot}3Ni(OH)_2{\cdot}4H_2O$, $BaCeO_3$, $CeO_2$ and $Y_2O_3$ as a starting material. To optimize the mixing scale and homogeneity of the composite powder, we employed a high-energy milling process. With this high-energy milled composite powder, we could fabricate a fine-grained dense membrane with an excellent level of mixing homogeneity. This controlled Ni-BCY cermet membrane showed higher hydrogen permeability compared to uncontrolled Ni-BCY cermets created with a conventionally ball-milled composite powder.

Modulation of Inwardly Rectifying $K^+$ Channel by Intracellular and Extracellular pH in Bovine Aortic Endothelial Cells

  • Park, Kyu-Sang;Kong, In-Deok;Lee, Joong-Woo;Rhim, Hye-Whon;Kim, Young-Chul;So, In-Suk;Kim, Ki-Whan
    • The Korean Journal of Physiology and Pharmacology
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    • v.6 no.5
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    • pp.255-260
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    • 2002
  • The effects of intracellular and extracellular pH on the inwardly rectifying $K^+$ (IRK) channel of the bovine aortic endothelial cells (BAECs) were examined using whole-cell patch-clamp technique. The IRK current, efficiently blocked by $Ba^{2+}\;(200{\mu}M),$ is the most prominent membrane current in BAECs, which mainly determines the resting membrane potential. The expression of Kir2.1 was observed in BAECs using reverse transcriptase-polymerase chain reaction (RT-PCR) analysis. Intracellular alkalinization, elicited by the extracellular substitution of NaCl with $NH_4Cl$ (30 mM), significantly augmented the amplitude of IRK current. On the contrary, the amplitude of IRK current was attenuated by the Na-acetate (30 mM)-induced intracellular acidification. The changes in extracellular pH also closely modulated the amplitude of IRK current, which was decreased to $40.2{\pm}1.3%$ of control upon switching the extracellular pH to 4.0 from 7.4. The extracellular pH value for half-maximal inhibition (pK) of IRK current was 5.11. These results demonstrate that the activity of IRK channel in BAECs, probably Kir2.1, was suppressed by proton at both sides of plasma membrane.

Reaction Mechanism of Acetylcholinesterase Catalyzed Hydrolysis of Thiocholine Esters (아세틸콜린에스터라제 촉매에 의한 티오에스테르의 가수분해 반응 메카니즘 연구)

  • 정대일;최순규;이용균;박유미;곽문정;신영주;최병욱;이봉호;한정태
    • Journal of Life Science
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    • v.12 no.1
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    • pp.32-42
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    • 2002
  • It was researched to react horse serum-BChE with hefanoylthiocholine chosen among choline esters. According as number of carbon of acyl group in choline esters was increased, reactivity was decreased but strength of ES complex was increased (Km=0,140mM). The pH-V/K profile for BChE-catalyzed hydrolysis of hexanoylthiocholine yields a p $K_{a}$ =4.974$\pm$0.028. This value is equal to recent literature that shows systematic shift from dependence of activity on the basic form fo a residue that huts a p $K_{a}$ =6.2~6.4 to catalysis by a residue or residues that has a p $K_{a}$ =4.7~5.0. The resulting kinetic solvent isotope effect of hexanoylthiocholine is $^{D/V}$K=1.18. The magnitude of the isotope effect suggests that proton transfer is not an element of transition-state stabilization.n.

The Effects of Hexamethylenetetramine Concentration on the Structural and Electrochemical Performances of Ni(OH)2 Powder for Pseudocapacitor Applications (헥사메틸렌테트라민 농도에 따른 수산화니켈 입자의 특성 분석 및 의사커패시터 응용)

  • Kim, Dong Yeon;Jeong, Young-Min;Baek, Seong-Ho;Son, Injoon
    • Journal of Powder Materials
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    • v.26 no.3
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    • pp.231-236
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    • 2019
  • Ni hydroxides ($Ni(OH)_2$) are synthesized on Ni foam by varying the hexamethylenetetramine (HMT) concentration using an electrodeposition process for pseudocapacitor (PC) applications. In addition, the effects of HMT concentration on the $Ni(OH)_2$ structure and the electrochemical properties of the PCs are investigated. HMT is the source of amine-based $OH^-$ in the solution; thus, the growth rate and morphological structure of $Ni(OH)_2$ are influenced by HMT concentration. When $Ni(OH)_2$ is electrodeposited at a constant voltage mode of -0.85 V vs. Ag/AgCl, the cathodic current and the number of nucleations are significantly reduced with increasing concentration of HMT from 0 to 10 mM. Therefore, $Ni(OH)_2$ is sparsely formed on the Ni foam with increasing HMT concentration, showing a layered double-hydroxide structure. However, loosely packed $Ni(OH)_2$ grains that are spread on Ni foam maintain a much greater surface area for reaction and result in the effective utilization of the electrode material due to the steric hindrance effect. It is suggested that the $Ni(OH)_2$ electrodes with HMT concentration of 7.5 mM have the maximum specific capacitance (1023 F/g), which is attributed to the facile electrolyte penetration and fast proton exchange via optimized surface areas.

Onion peel extract and its constituent, quercetin inhibits human Slo3 in a pH and calcium dependent manner

  • Wijerathne, Tharaka Darshana;Kim, Ji Hyun;Kim, Min Ji;Kim, Chul Young;Chae, Mee Ree;Lee, Sung Won;Lee, Kyu Pil
    • The Korean Journal of Physiology and Pharmacology
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    • v.23 no.5
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    • pp.381-392
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    • 2019
  • Sperm function and male fertility are closely related to pH dependent $K^+$ current (KSper) in human sperm, which is most likely composed of Slo3 and its auxiliary subunit leucine-rich repeat-containing protein 52 (LRRC52). Onion peel extract (OPE) and its major active ingredient quercetin are widely used as fertility enhancers; however, the effect of OPE and quercetin on Slo3 has not been elucidated. The purpose of this study is to investigate the effect of quercetin on human Slo3 channels. Human Slo3 and LRRC52 were co-transfected into HEK293 cells and pharmacological properties were studied with the whole cell patch clamp technique. We successfully expressed and measured pH sensitive and calcium insensitive Slo3 currents in HEK293 cells. We found that OPE and its key ingredient quercetin inhibit Slo3 currents. Inhibition by quercetin is dose dependent and this degree of inhibition decreases with elevating internal alkalization and internal free calcium concentrations. Functional moieties in the quercetin polyphenolic ring govern the degree of inhibition of Slo3 by quercetin, and the composition of such functional moieties are sensitive to the pH of the medium. These results suggest that quercetin inhibits Slo3 in a pH and calcium dependent manner. Therefore, we surmise that quercetin induced depolarization in spermatozoa may enhance the voltage gated proton channel (Hv1), and activate non-selective cation channels of sperm (CatSper) dependent calcium influx to trigger sperm capacitation and acrosome reaction.

Conductance Study on the Characteristics of Solution Containing Crown Ethers and Univalent Cation Perchlorates

  • Lee, Shim-Sung;Park, Sung-Oh;Jung, Jong-Hwa;Lee, Bu-Yong;Kim, Si-Joong
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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    • pp.276-281
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    • 1990
  • The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

A Study on Oxygen Reduction Reaction of PtM Electrocatalysts Synthesized by a Modified Polyol Process (수정된 폴리올 방법을 적용하여 합성한 PtM 촉매들의 산소환원반응성 연구)

  • Yang, Jongwon;Hyun, Kyuwhan;Chu, Cheunho;Kwon, Yongchai
    • Applied Chemistry for Engineering
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    • v.25 no.1
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    • pp.78-83
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    • 2014
  • In this research, we evaluated the performance and characteristics of carbon supported PtM (M = Ni and Y) alloy catalysts (PtM/Cs) synthesized by a modified polyol method. With the PtM/Cs employed as a catalyst for the oxygen reduction reaction (ORR) of cathodes in proton exchange membrane fuel cells (PEMFCs), their catalytic and ORR activities and electrical performance were investigated and compared with those of commercial Pt/C. Their particle sizes, particle distributions and electrochemically active surface areas (EAS) were measured by TEM and cyclic voltammetry (CV), while their ORR activity and electrical performance were explored using linear sweeping voltammetries with rotating disk electrodes and rotating ring-disk electrodes as well as PEMFC single cell tests. TEM and CV measurements show that PtM/Cs have the compatible particle size and EAS with Pt/C. When it comes to ORR activity, PtM/C showed the equivalent or better half-wave potential, kinetic current density, transferred electron number per oxygen molecule and $H_2O_2$ production(%) to or than commerical Pt/C. Based on results gained by the three electrode tests, when the PEMFC single cell tests were carried out, the current density measured at 0.6 V and maximum power density of PEMFC single cell adopting PtM/C catalysts were better than those adopting Pt/C catalyst. It is therefore concluded that PtM/C catalysts synthesized by modified polyol can result in the equivalent or better ORR catalytic capability and PEMFC performance to or than commercial Pt/C catalyst.

Production of $[^{18}F]F_2$ Gas for Electrophilic Substitution Reaction (친전자성 치환반응을 위한 $[^{18}F]F_2$ Gas의 생산 연구)

  • Moon, Byung-Seok;Kim, Jae-Hong;Lee, Kyo-Chul;An, Gwang-Il;Cheon, Gi-Jeong;Chun, Kwon-Soo
    • Nuclear Medicine and Molecular Imaging
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    • v.40 no.4
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    • pp.228-232
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    • 2006
  • Purpose: electrophilic $^{18}F(T_{1/2}=110\;min)$ radionuclide in the form of $[^{18}F]F_2$ gas is of great significance for labeling radiopharmaceuticals for positron omission tomography (PET). However, its production In high yield and with high specific radioactivity is still a challenge to overcome several problems on targetry. The aim of the present study was to develop a method suitable for the routine production of $[^{18}F]F_2$ for the electrophilic substitution reaction. Materials and Methods: The target was designed water-cooled aluminum target chamber system with a conical bore shape. Production of the elemental fluorine was carried out via the $^{18}O(p,n)^{18}F$ reaction using a two-step irradiation protocol. In the first irradiation, the target filled with highly enriched $^{18}O_2$ was irradiated with protons for $^{18}F$ production, which were adsorbed on the inner surface of target body. In the second irradiation, the mixed gas ($1%[^{19}F]F_2/Ar$) was leaded into the target chamber, fellowing a short irradiation of proton for isotopic exchange between the carrier-fluorine and the radiofluorine absorbed in the target chamber. Optimization of production was performed as the function of irradiation time, the beam current and $^{18}O_2$ loading pressure. Results: Production runs was performed under the following optimum conditions: The 1st irradiation for the nuclear reaction (15.0 bar of 97% enriched $^{18}O_2$, 13.2 MeV protons, 30 ${\mu}A$, 60-90 min irradiation), the recovery of enriched oxygen via cryogenic pumping; The 2nd irradiation for the recovery of absorbed radiofluorine (12.0 bar of 1% $[^{19}F]fluorine/argon$ gas, 13.2 MeV protons, 30 ${\mu}A$, 20-30 min irradiation) the recovery of $[^{18}F]fluorine$ for synthesis. The yield of $[^{18}F]fluorine$ at EOB (end of bombardment) was achieved around $34{\pm}6.0$ GBq (n>10). Conclusion: The production of $^{18}F$ electrophilic agent via $^{18}O(p,n)^{18}F$ reaction was much under investigation. Especially, an aluminum gas target was very advantageous for routine production of $[^{18}F]fluorine$. These results suggest the possibility to use $[^{18}F]F_2$ gas as a electrophilic substitution agent.

Observation of Secondary Organic Aerosol and New Particle Formation at a Remote Site in Baengnyeong Island, Korea

  • Choi, Jinsoo;Choi, Yongjoo;Ahn, Junyoung;Park, Jinsoo;Oh, Jun;Lee, Gangwoong;Park, Taehyun;Park, Gyutae;Owen, Jeffrey S.;Lee, Taehyoung
    • Asian Journal of Atmospheric Environment
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    • v.11 no.4
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    • pp.300-312
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    • 2017
  • To improve the understanding of secondary organic aerosol (SOA) formation from the photo-oxidation of anthropogenic and biogenic precursors at the regional background station on Baengnyeong Island, Korea, gas phase and aerosol chemistries were investigated using the Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-ToF-MS) and the Aerodyne High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS), respectively. HR-ToF-AMS measured fine particles ($PM_1$; diameter of particle matter less than $1{\mu}m$) at a 6-minute time resolution from February to November 2012, while PTR-ToF-MS was deployed during an intensive period from September 21 to 29, 2012. The one-minute time-resolution and high mass resolution (up to $4000m{\Delta}m^{-1}$) data from the PTR-ToF-MS provided the basis for calculations of the concentrations of anthropogenic and biogenic volatile organic compounds (BVOCs) including oxygenated VOCs (OVOCs). The dominant BVOCs from the site are isoprene (0.23 ppb), dimethyl sulphide (DMS, 0.20 ppb), and monoterpenes (0.38 ppb). Toluene (0.45 ppb) and benzene (0.32 ppb) accounted for the majority of anthropogenic VOCs (AVOCs). OVOCs including acetone (3.98 ppb), acetaldehyde (2.67 ppb), acetic acid (1.68 ppb), and formic acid (2.24 ppb) were measured. The OVOCs comprise approximately 75% of total measured VOCs, suggesting the occurrence of strong oxidation processes and/or long-range transported at the site. A strong photochemical aging and oxidation of the atmospheric pollutants were also observed in aerosol measured by HR-ToF-AMS, whereby a high $f_{44}:f_{43}$ value is shown for organic aerosols (OAs); however, relatively low $f_{44}:f_{43}$ values were observed when high concentrations of BVOCs and AVOCs were available, providing evidence of the formation of SOA from VOC precursors at the site. Overall, the results of this study revealed several different SOA formation mechanisms, and new particle formation and particle growth events were identified using the powerful tools scanning mobility particle sizer (SMPS), PTR-ToF-MS, and HR-ToF-AMS.

Contribution of a Low-Barrier Hydrogen Bond to Catalysis Is Not Significant in Ketosteroid Isomerase

  • Jang, Do Soo;Choi, Gildon;Cha, Hyung Jin;Shin, Sejeong;Hong, Bee Hak;Lee, Hyeong Ju;Lee, Hee Cheon;Choi, Kwan Yong
    • Molecules and Cells
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    • v.38 no.5
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    • pp.409-415
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    • 2015
  • Low-barrier hydrogen bonds (LBHBs) have been proposed to have important influences on the enormous reaction rate increases achieved by many enzymes. ${\Delta}^5$-3-ketosteroi isomerase (KSI) catalyzes the allylic isomerization of ${\Delta}^5$-3-ketosteroid to its conjugated ${\Delta}^4$-isomers at a rate that approache the diffusion limit. Tyr14, a catalytic residue of KSI, has been hypothesized to form an LBHB with the oxyanion of a dienolate steroid intermediate generated during the catalysis. The unusual chemical shift of a proton at 16.8 ppm in the nuclear magnetic resonance spectrum has been attributed to an LBHB between Tyr14 $O{\eta}$ and C3-O of equilenin an intermediate analogue, in the active site of D38N KSI. This shift in the spectrum was not observed in Y30F/Y55F/D38N and Y30F/Y55F/Y115F/D38N mutant KSIs when each mutant was complexed with equilenin, suggesting that Tyr14 could not form LBHB with the intermediate analogue in these mutant KSIs. The crystal structure of Y30F/Y55F/Y115F/D38N-equilenin complex revealed that the distance between Tyr14 $O{\eta}$ and C3-O of the bound steroi was within a direct hydrogen bond. The conversion of LBHB to an ordinary hydrogen bond in the mutant KSI reduced the binding affinity for the steroid inhibitors by a factor of 8.1-11. In addition, the absence of LBHB reduced the catalytic activity by only a factor of 1.7-2. These results suggest that the amount of stabilization energy of the reaction intermediate provided by LBHB is small compared with that provided by an ordinary hydrogen bond in KSI.