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        No Justice, No Peace? National Reconciliation and Local Conflict Resolution in Cambodia

        Mneesha Gellman 경남대학교 극동문제연구소 2008 ASIAN PERSPECTIVE Vol.32 No.2

        The Khmer Rouge Tribunal is expected by many in the international community to bring a sense of reconciliation to a nation still grappling with the aftermath of more than thirty years of civil war. Yet the gap between national and local reconciliation initiatives tests post-conflict reconstruction efforts to meet the needs of Cambodian citizens who feel unconnected to the tribunal. This article inquires into the interrelationship between national reconciliation processes and grassroots peacebuilding in the form of conflict resolution trainings. Noting that retributive justice processes cannot take the place of restorative justice, genuine reconciliation in Cambodia will need to incorporate culturally-based ritual derived from Buddhism in order to be relevant to local people. The Khmer Institute of Democracy (KID), a Cambodian NGO, serves as a case study for the successes and obstacles to local peacebuilding initiatives. The Khmer Rouge Tribunal is expected by many in the international community to bring a sense of reconciliation to a nation still grappling with the aftermath of more than thirty years of civil war. Yet the gap between national and local reconciliation initiatives tests post-conflict reconstruction efforts to meet the needs of Cambodian citizens who feel unconnected to the tribunal. This article inquires into the interrelationship between national reconciliation processes and grassroots peacebuilding in the form of conflict resolution trainings. Noting that retributive justice processes cannot take the place of restorative justice, genuine reconciliation in Cambodia will need to incorporate culturally-based ritual derived from Buddhism in order to be relevant to local people. The Khmer Institute of Democracy (KID), a Cambodian NGO, serves as a case study for the successes and obstacles to local peacebuilding initiatives.

      • Steady-State Catalytic Decomposition of Aspartic Acid on Cu(111)

        Yun, Yongju,Kondratyuk, Petro,Gellman, Andrew J. American Chemical Society 2019 JOURNAL OF PHYSICAL CHEMISTRY C - Vol.123 No.13

        <P>Decomposition of tartaric acid (TA, HO<SUB>2</SUB>CCH(OH)CH(OH)CO<SUB>2</SUB>H) and aspartic acid (Asp, HO<SUB>2</SUB>CCH(NH<SUB>2</SUB>)CH<SUB>2</SUB>CO<SUB>2</SUB>H) on Cu surfaces occurs via a vacancy-mediated surface explosion mechanism with nonlinear kinetics: <I>r</I><SUB>e</SUB> = <I>k</I><SUB>e</SUB>θ(1 - θ)<SUP>2</SUP>, where θ is the adsorbate coverage, and (1 - θ) is the vacancy coverage. During temperature-programmed reaction experiments on naturally chiral Cu(<I>hkl</I>)<SUP>R&S</SUP> surfaces, these kinetics, coupled with the chirality of the adsorbates, lead to highly enantiospecific decomposition rates. Herein, it is demonstrated that, in the presence of a thermal molecular beam with a constant Asp flux, <I>F</I><SUB>Asp</SUB>, the decomposition of Asp on Cu(111) occurs catalytically and in steady-state to turnover numbers >40 without contamination or deactivation of the surface. Moreover, the decomposition rates at a given (<I>T</I>, <I>F</I><SUB>Asp</SUB>) manifest the two different steady-states predicted by the nonlinearity of the decomposition kinetics. The unusual ability to catalytically decompose Asp on Cu, coupled with the ability to distinguish between <SMALL>D</SMALL>- and <SUP>13</SUP>C-<SMALL>L</SMALL>-Asp using mass spectrometry, opens an avenue for the future study of enantioselective catalysis on Cu(<I>hkl</I>)<SUP>R&S</SUP> surfaces.</P> [FIG OMISSION]</BR>

      • Initiation of Vacancy-Mediated, Surface Explosion Reactions: Tartaric and Aspartic Acid on Cu Surfaces

        Kondratyuk, Petro,Karagoz, Burcu,Yun, Yongju,Gellman, Andrew J. American Chemical Society 2019 The Journal of Physical Chemistry Part C Vol.123 No.31

        <P>Surface explosion reactions have highly nonlinear reaction kinetics that exhibit autoacceleration under isothermal conditions. These can lead to phenomena such as oscillatory surface reaction rates and to highly enantiospecific reactions of chiral adsorbates on chiral surfaces. Tartaric acid (TA) decomposes on Cu surfaces by an explosion mechanism that is propagated by vacancies, empty adsorption sites that self-replicate autocatalytically during TA decomposition. Surface explosion kinetics result from chain-branching steps in which one vacancy decomposes an adsorbate to yield two vacancies. In the absence of vacancies, surface explosions cannot occur; they require some initiation step that creates vacancies. By comparison with the chain-branching explosion step, little is known about the processes that initiate or nucleate surface explosion reactions. Time-resolved XPS measurements during the early stages of explosion initiation of TA/Cu(<I>hkl</I>) reveal a process that involves direct loss of TA from the surface to create the initial vacancies. In the presence of a gas phase flux to the surface, such vacancy nuclei can be repopulated to suppress the onset of explosion. Measurements on 18 different Cu(<I>hkl</I>) surface orientations demonstrate that the kinetics of the initiation process are structure-insensitive. This implies that the highly enantiospecific TA decomposition kinetics observed on chiral Cu(<I>hkl</I>) surfaces must arise from the structure sensitivity of the chain-branching explosion kinetics.</P> [FIG OMISSION]</BR>

      • Hydrophobic Variations of<i>N</i>-Oxide Amphiphiles for Membrane Protein Manipulation: Importance of Non-hydrocarbon Groups in the Hydrophobic Portion

        Chae, Pil Seok,Sadaf, Aiman,Gellman, Samuel H. Wiley (John WileySons) 2014 Chemistry - An Asian Journal Vol.9 No.1

        <P>Amphipathic agents called detergents serve as membrane-mimetic systems to maintain the native structures of membrane proteins during their manipulation. However, membrane proteins solubilized in conventional detergents tend to undergo denaturation and aggregation, necessitating the development of novel amphipathic agents with enhanced properties. Here we describe several new amphiphiles that contain an N-oxide group as the hydrophilic portion. The new amphiphiles have been evaluated for the ability to solubilize and stabilize a fragile multi-subunit assembly from biological membranes. We found that cholate-based agents were promising in supporting retention of the native protein quaternary structure, while deoxycholate-based amphiphiles were highly efficient in extracting/solubilizing the intact superassembly from the native membrane. Monitoring superassembly solubilization and stabilization as a function of variation in amphiphile structure led us to propose that a non-hydrocarbon moiety such as an amide, ether, or a hydroxy group present in the lipophilic regions can manifest distinctive effects in the context of membrane protein manipulation.</P>

      • SCIESCOPUS
      • Carbohydrate-containing Triton X-100 analogues for membrane protein solubilization and stabilization

        Chae, Pil Seok,Wander, Marc J.,Cho, Kyung Ho,Laible, Philip D.,Gellman, Samuel H. The Royal Society of Chemistry 2013 Molecular bioSystems Vol.9 No.4

        <P>Membrane protein manipulation is a challenging task owing to limited tertiary and quaternary structural stability once the protein has been removed from a lipid bilayer. Such instability can be overcome by embedding membrane proteins in detergent micelles formed from amphiphiles with carefully tuned properties. This study introduces a class of easy-to-synthesize amphiphiles, which are designated CGT (Chae's Glyco-Triton) detergents. Some of the agents are well suited for membrane protein solubilization and stabilization.</P> <P>Graphic Abstract</P><P>This study introduces a class of easy-to-synthesize amphiphiles that display favorable behaviour for membrane protein solubilization and stabilization. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c3mb25584k'> </P>

      • Conformation-specific spectroscopy of capped glutamine-containing peptides: role of a single glutamine residue on peptide backbone preferences

        Walsh, Patrick S.,Dean, Jacob C.,McBurney, Carl,Kang, Hyuk,Gellman, Samuel H.,Zwier, Timothy S. The Royal Society of Chemistry 2016 Physical chemistry chemical physics Vol.18 No.16

        <P>The conformational preferences of a series of short, aromatic-capped, glutamine-containing peptides have been studied under jet-cooled conditions in the gas phase. This work seeks a bottom-up understanding of the role played by glutamine residues in directing peptide structures that lead to neurodegenerative diseases. Resonant ion-dip infrared (RIDIR) spectroscopy is used to record single-conformation infrared spectra in the NH stretch, amide I and amide II regions. Comparison of the experimental spectra with the predictions of calculations carried out at the DFT M05-2X/6-31+G(d) level of theory lead to firm assignments for the H-bonding architectures of a total of eight conformers of four molecules, including three in Z-Gln-OH, one in Z-Gln-NHMe, three in Ac-Gln-NHBn, and one in Ac-Ala-Gln-NHBn. The Gln side chain engages actively in forming H-bonds with nearest-neighbor amide groups, forming C8 H-bonds to the C-terminal side, C9 H-bonds to the N-terminal side, and an amide-stacked geometry, all with an extended (C5) peptide backbone about the Gln residue. The Gln side chain also stabilizes an inverse gamma-turn in the peptide backbone by forming a pair of H-bonds that bridge the gamma-turn and stabilize it. Finally, the entire conformer population of Ac-Ala-Gln-NHBn is funneled into a single structure that incorporates the peptide backbone in a type I beta-turn, stabilized by the Gln side chain forming a C7 H-bond to the central amide group in the beta-turn not otherwise involved in a hydrogen bond. This beta-turn backbone structure is nearly identical to that observed in a series of X-(AQ)-Y beta-turns in the protein data bank, demonstrating that the gas-phase structure is robust to perturbations imposed by the crystalline protein environment.</P>

      • Surface and Internal Reactions of ZnO Nanowires: Etching and Bulk Defect Passivation by H Atoms

        Kim, Wooseok,Kwak, Geunjae,Jung, Minbok,Jo, Sam K.,Miller, James B.,Gellman, Andrew J.,Yong, Kijung American Chemical Society 2012 The Journal of Physical Chemistry Part C Vol.116 No.30

        <P>Reactions of ZnO nanowires (NWs) with atomic hydrogen were investigated with temperature-programmed desorption (TPD) mass spectrometry, scanning electron microscopy, and photoluminescence (PL) spectroscopy. During TPD, molecular H<SUB>2</SUB>, H<SUB>2</SUB>O, and atomic Zn desorbed from ZnO NWs pretreated with atomic H at 220 K. Three distinct H<SUB>2</SUB> TPD peaks, two from surface H states and one from a bulk H state, were identified. The TPD assignment of the bulk H state was corroborated by significantly suppressed emission at 564 nm and enhanced emission at 375 nm in PL experiments. Etching of ZnO NWs by atomic H was confirmed by desorption of molecular H<SUB>2</SUB>O and atomic Zn in TPD and by electron microscopic images of H-treated ZnO NWs. A mechanistic model for underlying H/ZnO NW reactions is proposed and discussed.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jpccck/2012/jpccck.2012.116.issue-30/jp304191m/production/images/medium/jp-2012-04191m_0006.gif'></P>

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