• Title/Summary/Keyword: H/D exchange

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Excess proton catalyzed H/D exchange reaction at the ice surface

  • Moon, Eui-Seong;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.333-333
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    • 2011
  • We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.

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Protein Structural Characterization by Hydrogen/Deuterium Exchange Mass Spectrometry with Top-down Electron Capture Dissociation

  • Yu, Hai Dong;Ahn, Seonghee;Kim, Byungjoo
    • Bulletin of the Korean Chemical Society
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    • v.34 no.5
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    • pp.1401-1406
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    • 2013
  • This study tested the feasibility of observing H/D exchange of intact protein by top-down electron capture dissociation (ECD) mass spectrometry for the investigation of protein structure. Ubiquitin is selected as a model system. Local structural information was obtained from the deuteration levels of c and $z^{\cdot}$ ions generated from ECD. Our results showed that ${\alpha}$-helix region has the lowest deuteration level and the C-terminal fraction containing a highly mobile tail has the highest deuteration level, which correlates well with previous X-Ray and HDX/NMR analyses. We studied site-specific H/D exchange kinetics by monitoring H/D exchange rate of several structural motives of ubiquitin. Two hydrogen bonded ${\beta}$-strands showed similar HDX rates. However, the outer ${\beta}$-strand always has higher deuteration level than the inner ${\beta}$-strand. The HDX rate of the turn structure (residues 8-11) is lower than that of ${\beta}$-strands (residues 1-7 and residues 12-17) it connects. Although isotopic distribution gets broader after H/D exchange which results in a limited number of backbone cleavage sites detected, our results demonstrate that this method can provide valuable detailed structural information of proteins. This approach should also be suitable for the structural investigation of other unknown proteins, protein conformational changes, as well as protein-protein interactions and dynamics.

Reactive Ion Scattering Study of Ice Surfaces. Proton Transfer and H/D Exchange Reactions

  • Mun, Ui-Seong;Kim, Su-Yeon;Gang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.64-64
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    • 2010
  • Ice film surfaces were examined by using the reactive ion scattering (RIS) of low energy (<35 eV) cesium ion beams. Neutral molecules (X) on the surface were detected in the form of cesium-molecule ion clusters (CsX+). Ionic species on the surface were desorbed from the surface via a low energy sputtering (LES) process below the threshold energy of secondary ion emission. The RIS and LES methods allowed us to study the H/D exchange reactions between H2O and D2O molecules on the surface and the associated proton transfer mechanisms. Specifically, H/D exchange kinetics was examined for D2O ice films (~10 BL) covered with a small amount of H2O (<0.5 BL), in the presence or absence of HCl adsorbates which provided excess protons on the surface.

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Rates of Conformational Change of 3,3-Dimethylpiperidine and Solvent Effects on Its Conformation When Coordinated to the Paramagnetic Undecatungstocobalto(II)silicate Anion Studied by 1H NMR Spectroscopy

  • 현재원;소현수
    • Bulletin of the Korean Chemical Society
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    • v.18 no.9
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    • pp.961-965
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    • 1997
  • 1H NMR spectra of 3,3-dimethylpiperidine (1) at -70 to 30 ℃ exhibit gradual change from slow to rapid exchange between two alternate chair forms. The exchange rate constant was determined as a function of temperature by simulating the line shape of the signal from the two methyl groups using the modified Bloch equations. The resulting free energy of activation is ΔG* = 44.4±1.9 kJ mol-1 at 298 K. The 1H NMR spectrum of a D2O or dimethylsulfoxide-d6 (DMSO-d6) solution containing 1 and [SiW11CoⅡO39]6- exhibits separate signals for the free ligand and the complex, indicating that the ligand exchange is slow on the NMR time scale. In D2O the piperidine ring is frozen as a chair form even at room temperature with the cobalt ion bonded to the axial position of the nitrogen atom. When DMSO-d6 is added to the D2O solution, the NMR spectral change suggests that a rapid exchange occurs between the chair form and another conformer. It is proposed that the conformation of ^b1^b coordinated to [SiW11CoⅡO39]6- in DMSO-d6 is close to a twist form.

A Study on the Development of a Product Model-based Information Framework for AEC Products (AEC 시설물의 프로덕트 모델기반 정보공유 기술 개발에 관한 연구)

  • Kang, B.C.;Choi, S.R.;Kim, I.H.;Kim, H.D.;Kim, M.H.;Won, J.S.;Kwon, J.M.
    • Korean Journal of Computational Design and Engineering
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    • v.11 no.4
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    • pp.256-264
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    • 2006
  • Currently, it is necessary to share and exchange drawing information between 2D and 3D data in AEC(Architecture, Engineering & Construction) fields. The authors suggest an information model framework to express IFC(Industry Foundation Classes)-based drawing of 3D AEC products as 2D drawing. In this study, 1) an information framework has been developed to enable sharing and exchange of AEC product model by adding various information factors, 2) standardized APIs and an IFC2DBrowser are developed.

Local Laser Annealing in Exchange-Biased Films with Out-of-Plane and In-Plane Magnetic Anisotropy

  • Choi, S.D.;Kim, S.W.;Jin, D.H.;Yun, D.K.;Lee, M.S.;Ahn, J.H.;Joo, H.W.;Lee, K.A.;Lee, S.S.;Hwang, D.G.
    • Journal of Magnetics
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    • v.11 no.2
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    • pp.66-69
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    • 2006
  • Local magnetization reversal in the exchange-biased NiFe/FeMn and $[Pd/Co]_5/FeMn$ multilayers with in-plane and out-of-plane magnetic anisotropy was achieved by using laser annealing. The local annealed NiFe/FeMn film under the opposite magnetic field shows a magnetoresistance (MR) curve having two symmetric peaks at the positive and negative exchange biasing field (${\pm}H_{ex}$). The intensity of the nucleated MR peak rises as the exposed area extends during the laser annealing process, and the peak disappears under the reverse magnetic field. In the case of [Pd/Co]/FeMn films, the local magnetization reversal increased gradually as the laser power increases. The locally reversed magnetization was restored under the opposite magnetic field.

Exchange Coupling in NiFe/Ni Bilayer Fabricated By Electrodeposition

  • Kim, D.Y.;Jeon, S.J.;Kim, K.W.;Yoon, S.S.
    • Journal of Magnetics
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    • v.16 no.2
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    • pp.97-100
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    • 2011
  • Bilayers of soft NiFe (150 nm-420 nm) on hard Ni (150 nm) were prepared by electrodeposition. The process of magnetization reversal in the NiFe/Ni bilayers was then investigated. The hysteresis loop generated by a magnetization reversal of soft NiFe under a positive saturation state of a hard Ni layer shows a shift along the negative field axis, which is clear evidence for the exchange spring effect in the NiFe/Ni bilayers. The dependence of the coercive field $H_c$ and exchange bias field Hex on the thickness of the NiFe layer was also investigated. As the NiFe thickness increases from 150 nm to 420 nm, both $H_c$ and $H_{ex}$ decrease rapidly from $H_c$= 51.7 Oe and $H_{ex}$ = 12.2 Oe, and saturate to $H_c$ = 5.8 Oe and $H_{ex}$ = 3.5 Oe.

Room temperature ferromagnetism in diluted magnetic semiconductor $Zn_{l-x}Cr_xTe$

  • Ando, K.;Saito, H.;Zayets, V.;Yamagata, S.
    • Proceedings of the Korean Magnestics Society Conference
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    • 2003.06a
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    • pp.266-267
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    • 2003
  • The most distinguishing character of diluted magnetic semiconductors (DMSs) is a strong interaction between sp-carriers and localized d-spins (sp-d exchange interaction). Recently many "room-temperature (RT) ferromagnetic DMS" have been reported. However, it should be noted that their sp-d exchange interactions have not been confirmed yet. The lack of a clear evidence of the sp-d exchange interaction causes the controversy on the origin of the observed ferromagnetism. For the detection of the sp-d exchange interaction, magneto-optical spectroscopy such as a magnetic circular dichroism (MCD) measurement is the most powerful tool. By using the MCD spectroscopy, we have shown the sp-d exchange interactions in Zn$_{l-x}$Cr$_{x}$Te. Recently, we have obtained the RT ferromagnetism in a Zn$_{l-x}$Cr$_{x}$Te (x = 0.20) film.0) film.

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An implementation and security analysis on H.235 for VoIP security on embedded environments (임베디드 환경에서의 H.235 기반 VoIP 보안 단말 구현 및 안전성 분석에 관한 연구)

  • 김덕우;홍기훈;이상학;정수환
    • The Journal of Korean Institute of Communications and Information Sciences
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    • v.29 no.7C
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    • pp.1007-1014
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    • 2004
  • In this paper, H.235 based security mechanism for H.323 multimedia applications was implemented in embedded environment. H.235 covers authentication using HMAC-SHAI -96, authenticated Diffie-Hellman key exchange, security capability exchange, session key management for voice encryption, and encryption functions such as DES, 3DES, RC2. H.235-based mechanisms were also analyzed in terms of its security and possible attacks.

Perpendicular Exchange Bias and Thermal Stability of [Pd/Co]N/FeMn Films

  • Joo, H.W.;Kim, S.W.;An, J.H.;Choi, J.H.;Lee, M.S.;Lee, K.A.;Hwang, D.G.;Lee, S.S.
    • Journal of Magnetics
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    • v.10 no.1
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    • pp.33-35
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    • 2005
  • Perpendicular magnetization curves and crystal textures of $[Pd(0.8 nm)/Co(0.8 nm)]_5/FeMn$ multilayers having an exchange-biased perpendicular magnetic anisotropy as a function of FeMn thickness and annealing temperature were measured. As FeMn thickness increases from 0 to 21 nm, the perpendicular exchange biasing field ($H_{ex}$) obtained the maximum value of 130 Oe at FeMn thickness 12 nm. As the annealing temperature increases to $240^{\circ}C$, the Hex increased from 115 Oe to 190 Oe and the exchange-biased perpendicular magnetic anisotropy disappeared at $330^{\circ}C$.