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Sample records for active surface site

  1. Mimicking enzymatic active sites on surfaces for energy conversion chemistry.

    PubMed

    Gutzler, Rico; Stepanow, Sebastian; Grumelli, Doris; Lingenfelder, Magalí; Kern, Klaus

    2015-07-21

    Metal-organic supramolecular chemistry on surfaces has matured to a point where its underlying growth mechanisms are well understood and structures of defined coordination environments of metal atoms can be synthesized in a controlled and reproducible procedure. With surface-confined molecular self-assembly, scientists have a tool box at hand which can be used to prepare structures with desired properties, as for example a defined oxidation number and spin state of the transition metal atoms within the organic matrix. From a structural point of view, these coordination sites in the supramolecular structure resemble the catalytically active sites of metallo-enzymes, both characterized by metal centers coordinated to organic ligands. Several chemical reactions take place at these embedded metal ions in enzymes and the question arises whether these reactions also take place using metal-organic networks as catalysts. Mimicking the active site of metal atoms and organic ligands of enzymes in artificial systems is the key to understanding the selectivity and efficiency of enzymatic reactions. Their catalytic activity depends on various parameters including the charge and spin configuration in the metal ion, but also on the organic environment, which can stabilize intermediate reaction products, inhibits catalytic deactivation, and serves mostly as a transport channel for the reactants and products and therefore ensures the selectivity of the enzyme. Charge and spin on the transition metal in enzymes depend on the one hand on the specific metal element, and on the other hand on its organic coordination environment. These two parameters can carefully be adjusted in surface confined metal-organic networks, which can be synthesized by virtue of combinatorial mixing of building synthons. Different organic ligands with varying functional groups can be combined with several transition metals and spontaneously assemble into ordered networks. The catalytically active metal

  2. A proposed definition of the 'activity' of surface sites on lactose carriers for dry powder inhalation.

    PubMed

    Grasmeijer, Floris; Frijlink, Henderik W; de Boer, Anne H

    2014-06-01

    A new definition of the activity of surface sites on lactose carriers for dry powder inhalation is proposed which relates to drug detachment during dispersion. The new definition is expected to improve the understanding of 'carrier surface site activity', which stimulates the unambiguous communication about this subject and may aid in the rational design and interpretation of future formulation studies. In contrast to the currently prevailing view on carrier surface site activity, it follows from the newly proposed definition that carrier surface site activity depends on more variables than just the physicochemical properties of the carrier surface. Because the term 'active sites' is ambiguous, it is recommended to use the term 'highly active sites' instead to denote carrier surface sites with a relatively high activity. PMID:24613490

  3. The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.; Cole, F.

    1992-11-01

    An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  4. The calculation of surface orbital energies for specific types of active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.; Cole, F.

    1992-01-01

    An angular overlap calculation has been used to determine the s, p, and d orbital energy levels of the different types of surface sites present on dispersed metal catalysts. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  5. Extending the Diffuse Layer Model of Surface Acidity Behavior: III. Estimating Bound Site Activity Coefficients

    EPA Science Inventory

    Although detailed thermodynamic analyses of the 2-pK diffuse layer surface complexation model generally specify bound site activity coefficients for the purpose of accounting for those non-ideal excess free energies contributing to bound site electrochemical potentials, in applic...

  6. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability.

    PubMed

    Stamenkovic, Vojislav R; Fowler, Ben; Mun, Bongjin Simon; Wang, Guofeng; Ross, Philip N; Lucas, Christopher A; Marković, Nenad M

    2007-01-26

    The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption. PMID:17218494

  7. From single crystal surfaces to single atoms: investigating active sites in electrocatalysis.

    PubMed

    O'Mullane, Anthony P

    2014-04-21

    Electrocatalytic processes will undoubtedly be at the heart of energising future transportation and technology with the added importance of being able to create the necessary fuels required to do so in an environmentally friendly and cost effective manner. For this to be successful two almost mutually exclusive surface properties need to be reconciled, namely producing highly active/reactive surface sites that exhibit long term stability. This article reviews the various approaches which have been undertaken to study the elusive nature of these active sites on metal surfaces which are considered as adatoms or clusters of adatoms with low coordination number. This includes the pioneering studies at extended well defined stepped single crystal surfaces using cyclic voltammetry up to the highly sophisticated in situ electrochemical imaging techniques used to study chemically synthesised nanomaterials. By combining the information attained from single crystal surfaces, individual nanoparticles of defined size and shape, density functional theory calculations and new concepts such as mesoporous multimetallic thin films and single atom electrocatalysts new insights into the design and fabrication of materials with highly active but stable active sites can be achieved. The area of electrocatalysis is therefore not only a fascinating and exciting field in terms of realistic technological and economical benefits but also from the fundamental understanding that can be acquired by studying such an array of interesting materials. PMID:24599277

  8. Active-site titration analysis of surface influence on immobilized Candida antarctica Lipase B activity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Matrix morphology and surface polarity effects were investigated for Candida antarctica lipase B immobilization. Measurements of the amount of lipase immobilized (bicinchoninic acid method) and the catalyst’s tributyrin hydrolysis activity, coupled with a determination of the lipase’s functional fr...

  9. Testing the applicability of rapid on-site enzymatic activity detection for surface water monitoring

    NASA Astrophysics Data System (ADS)

    Stadler, Philipp; Vogl, Wolfgang; Juri, Koschelnik; Markus, Epp; Maximilian, Lackner; Markus, Oismüller; Monika, Kumpan; Peter, Strauss; Regina, Sommer; Gabriela, Ryzinska-Paier; Farnleitner Andreas, H.; Matthias, Zessner

    2015-04-01

    bacteria. Therefore the applicability of on-site enzymatic activity determination as a direct surrogate or proxy parameter for microbiological standard assays and quantification of fecal indicator bacteria (FIB) concentration could not be approved and further research in this field is necessary. Presently we conclude that rapid on-site detection of enzymatic activity is applicable for surface water monitoring and that it constitutes a complementary on-site monitoring parameter with high potential. Selection of the type of measured enzymatic activities has to be done on a catchment-specific basis and further work is needed to learn more about its detailed information characteristics in different habitats. The accomplishment of this method detecting continuous data of enzymatic activity in high temporal resolution caused by a target bacterial member is on the way of becoming a powerful tool for water quality monitoring, health related water quality- and early warning requirements.

  10. A facile reflux procedure to increase active surface sites form highly active and durable supported palladium@platinum bimetallic nanodendrites

    NASA Astrophysics Data System (ADS)

    Wang, Qin; Li, Yingjun; Liu, Baocang; Xu, Guangran; Zhang, Geng; Zhao, Qi; Zhang, Jun

    2015-11-01

    A series of well-dispersed bimetallic Pd@Pt nanodendrites uniformly supported on XC-72 carbon black are fabricated by using different capping agents. These capping agents are essential for the branched morphology control. However, the surfactant adsorbed on the nanodendrites surface blocks the access of reactant molecules to the active surface sites, and the catalytic activities of these bimetallic nanodendrites are significantly restricted. Herein, a facile reflux procedure to effectively remove the capping agent molecules without significantly affecting their sizes is reported for activating supported nanocatalysts. More significantly, the structure and morphology of the nanodendrites can also be retained, enhancing the numbers of active surface sites, catalytic activity and stability toward methanol and ethanol electro-oxidation reactions. The as-obtained hot water reflux-treated Pd@Pt/C catalyst manifests superior catalytic activity and stability both in terms of surface and mass specific activities, as compared to the untreated catalysts and the commercial Pt/C and Pd/C catalysts. We anticipate that this effective and facile removal method has more general applicability to highly active nanocatalysts prepared with various surfactants, and should lead to improvements in environmental protection and energy production.

  11. Nature of Catalytic Active Sites Present on the Surface of Advanced Bulk Tantalum Mixed Oxide Photocatalysts

    SciTech Connect

    Phivilay, Somphonh; Puretzky, Alexander A; Domen, Kazunari Domen; Wachs, Israel

    2013-01-01

    The most active photocatalyst system for water splitting under UV irradiation (270 nm) is the promoted 0.2%NiO/NaTaO3:2%La photocatalyst with optimized photonic efficiency (P.E.) of 56%, but fundamental issues about the nature of the surface catalytic active sites and their involvement in the photocatalytic process still need to be clarified. This is the first study to apply cutting edge surface spectroscopic analyses to determine the surface nature of tantalum mixed oxide photocatalysts. Surface analysis with HR-XPS (1-3nm) and HS-LEIS (0.3nm) spectroscopy indicates that the NiO and La2O3 promoters are concentrated in the surface region of the bulk NaTaO3 phase. The La2O3 is concentrated on the NaTaO3 outermost surface layers while NiO is distributed throughout the NaTaO3 surface region (1-3nm). Raman and UV-vis spectroscopy revealed that the bulk molecular and electronic structures, respectively, of NaTaO3 were not modified by the addition of the La2O3 and NiO promoters, with La2O3 resulting in a slightly more ordered structure. Photoluminescence (PL) spectroscopy reveals that the addition of La2O3 and NiO produces a greater number of electron traps resulting in the suppression of the recombination of excited electrons/holes. In contrast to earlier reports, the La2O3 is only a textural promoter (increasing the BET surface area ~7x by stabilizing smaller NaTaO3 particles), but causes a ~3x decrease in the specific photocatalytic TORs ( mol H2/m2/h) rate because surface La2O3 blocks exposed catalytic active NaTaO3 sites. The NiO promoter was found to be a potent electronic promoter that enhances the NaTaO3 surface normalized TORs by a factor of ~10-50 and TOF by a factor of ~10. The level of NiO promotion is the same in the absence and presence of La2O3 demonstrating that there is no promotional synergistic interaction between the NiO and La2O3 promoters. This study demonstrates the important contributions of the photocatalyst surface properties to the fundamental

  12. Analysis of structural changes in active site of luciferase adsorbed on nanofabricated hydrophilic Si surface by molecular-dynamics simulations

    SciTech Connect

    Nishiyama, Katsuhiko; Hoshino, Tadatsugu

    2007-05-21

    Interactions between luciferase and a nanofabricated hydrophilic Si surface were explored by molecular-dynamics simulations. The structural changes in the active-site residues, the residues affecting the luciferin binding, and the residues affecting the bioluminescence color were smaller on the nanofabricated hydrophilic Si surface than on both a hydrophobic Si surface and a hydrophilic Si surface. The nanofabrication and wet-treatment techniques are expected to prevent the decrease in activity of luciferase on the Si surface.

  13. Near-Surface Site Characterization Using a Combination of Active and Passive Seismic Arrays

    NASA Astrophysics Data System (ADS)

    Lane, J. W.; Liu, L.; Chen, Y.; White, E. A.

    2007-12-01

    Seismic surveys with an active source are commonly used to characterize the subsurface. Increasingly, passive seismic surveys utilizing ambient seismic frequencies (microtremors) are being used to support geotechnical and hazards engineering studies. In this study, we use a combination of active and passive seismic methods to characterize a watershed site at Haddam Meadows State Park, Haddam, Connecticut. At Haddam Meadows, we employed a number of seismic arrays using both active and passive approaches to estimate the depth to rock and the seismic velocity structure of the unconsolidated sediments. The active seismic surveys included seismic refraction and multi-channel analysis of surface waves (MASW) using an accelerated weight-drop seismic source. The passive seismic surveys consisted of MASW techniques using both linear and circular geophone arrays, and a survey using a 3-component seismometer. The active seismic data were processed using conventional algorithms; the passive seismic data were processed using both the spatial autocorrelation method (SPAC) and the horizontal to vertical spectral ratio (H/V) method. The interpretations of subsurface structure from the active and passive surveys are generally in good agreement and compare favorably with ground truth information provided by adjacent boreholes. Our results suggest that a combination of active and passive seismic methods can be used to rapidly characterize the subsurface at the watershed scale.

  14. Extension of polyphenolics by CWPO-C peroxidase mutant containing radical-robust surface active site.

    PubMed

    Pham, L T Mai; Kim, S Jin; Ahn, U Suk; Choi, J Weon; Song, B Keun; Kim, Y Hwan

    2014-01-01

    Expressed as insoluble forms in Escherichia coli, native cationic cell wall peroxidase (CWPO-C) from the poplar tree and mutant variants were successfully reactivated via refolding experiments and used to elucidate the previously presumed existence of an electron transfer (ET) pathway in the CWPO-C structure. Their catalytic properties were fully characterized through various analyses including steady-state kinetic, direct oxidation of lignin macromolecules and their respective stabilities during the polymerization reactions. The analysis results proved that the 74th residue on the CWPO-C surface plays an important role in catalyzing the macromolecules via supposed ET mechanism. By comparing the residual activities of wild-type CWPO-C and mutant 74W CWPO-C after 3 min, mutation of tyrosine 74 residue to tryptophan increased the radical resistance of peroxidase up to ten times dramatically while maintaining its capability to oxidize lignin macromolecules. Furthermore, extension of poly(catechin) as well as lignin macromolecules with CWPO-C Y74W mutant clearly showed that this radical-resistant peroxidase mutant can increase the molecular weight of various kinds of polyphenolics by using surface-located active site. The anti-oxidation activity of the synthesized poly(catechin) was confirmed by xanthine oxidase assay. The elucidation of a uniquely catalytic mechanism in CWPO-C may improve the applicability of the peroxidase/H2O2 catalyst to green polymer chemistry. PMID:24122664

  15. Detection analysis of surface hydroxyl active sites and simulation calculation of the surface dissociation constants of aqueous diatomite suspensions

    NASA Astrophysics Data System (ADS)

    Ma, Shu-Cui; Wang, Zhi-Gang; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-02-01

    The surface properties of the diatomite were investigated using nitrogen adsorption/deadsorption isotherms, TG-DSC, FTIR, and XPS, and surface protonation-deprotonation behavior was determined by continuous acid-base potentiometric titration technique. The diatomite sample with porous honeycomb structure has a BET specific surface area of 10.21 m2/g and large numbers of surface hydroxyl functional groups (i.e. tbnd Si-OH, tbnd Fe-OH, and tbnd Al-OH). These surface hydroxyls can be protonated or deprotonated depending on the pH of the suspension. The experimental potentiometric data in two different ionic strength solutions (0.1 and 0.05 mol/L NaCl) were fitted using ProtoFit GUI V2.1 program by applying diffuse double layer model (DLM) with three amphoteric sites and minimizing the sum of squares between a dataset derivative function and a model derivative function. The optimized surface parameters (i.e. surface dissociation constants (log K1, log K2) and surface site concentrations (log C)) of the sample were obtained. Based on the optimized surface parameters, the surface species distribution was calculated using Program-free PHREEQC 3.1.2. Thus, this work reveals considerable new information about surface protonation-deprotonation processes and surface adsorptive behaviors of the diatomite, which helps us to effectively use the cheap and cheerful diatomite clay adsorbent.

  16. The Role of OOH Binding Site and Pt Surface Structure on ORR Activities

    PubMed Central

    Jia, Qingying; Caldwell, Keegan; Ziegelbauer, Joseph M.; Kongkanand, Anusorn; Wagner, Frederick T.; Mukerjee, Sanjeev; Ramaker, David E.

    2015-01-01

    We present experimentally observed molecular adsorbate coverages (e.g., O(H), OOH and HOOH) on real operating dealloyed bimetallic PtMx (M = Ni or Co) catalysts under oxygen reduction reaction (ORR) conditions obtained using X-ray absorption near edge spectroscopy (XANES). The results reveal a complex Sabatier catalysis behavior and indicate the active ORR mechanism changes with Pt–O bond weakening from the O2 dissociative mechanism, to the peroxyl mechanism, and finally to the hydrogen peroxide mechanism. An important rearrangement of the OOH binding site, an intermediate in the ORR, enables facile H addition to OOH and faster O–O bond breaking on 111 faces at optimal Pt–O bonding strength, such as that occurring in dealloyed PtM core-shell nanoparticles. This rearrangement is identified by previous DFT calculations and confirmed from in situ measured OOH adsorption coverages during the ORR. The importance of surface structural effects and 111 ordered faces is confirmed by the higher specific ORR rates on solid core vs porous multi-core nanoparticles. PMID:26190857

  17. Switching on the Metathesis Activity of Re Oxo Alkylidene Surface Sites through a Tailor-Made Silica-Alumina Support.

    PubMed

    Valla, Maxence; Stadler, David; Mougel, Victor; Copéret, Christophe

    2016-01-18

    Re oxo alkylidene surface species are putative active sites in classical heterogeneous Re-based alkene-metathesis catalysts. However, the lack of evidence for such species questions their existence and/or relevance as reaction intermediates. Using Re(O)(=CH-CH=CPh2)(OtBuF6)3(THF), the corresponding well-defined Re oxo alkylidene surface species can be generated on both silica and silica-alumina supports. While inactive on the silica support, it displays very good activity, even for functionalized olefins, on the silica-alumina support. PMID:26756446

  18. Long-term active layer and ground surface temperature trends: results of 12 years of observations at Alaskan CALM sites

    NASA Astrophysics Data System (ADS)

    Shiklomanov, N. I.; Nelson, F. E.; Streletskyi, D. A.; Klene, A. E.; Schimek, M.; Little, J.

    2006-12-01

    The uppermost layer of seasonal thawing above permafrost (the active layer) is an important regulator of energy and mass fluxes between the surface and the atmosphere in the polar regions. The Circumpolar Active Layer Monitoring (CALM) program is a network of sites at which data about active-layer thickness (ALT) and dynamics are collected. CALM was established in the 1990s to observe and detect the long-term response of the active layer and near-surface permafrost to changes in climate. Active layer monitoring is an important component of efforts to assess the effects of global change in permafrost environments. CALM strategies are evolving; this presentation showcases some additions to CALM observation procedures designed to monitor processes and detect changes not anticipated in the original CALM protocol of the early 1990s. In this study we used data from 12 (1995-2006) years of extensive, spatially oriented field observations at CALM sites in northern Alaska to examine landscape-specific spatial and temporal trends in active-layer thickness and air and ground surface temperature. Despite an observed increase in air temperature, active-layer thickness exhibited a decreasing trend over the study period. This result indicates that soil consolidation accompanying penetration of thaw into an ice-rich stratum at the base of the active layer has resulted in subsidence of the surface with little or no apparent thickening of the active layer, as traditionally defined. Differential Global Positioning Systems (DGPS) technology was used to detect frost heave and thaw settlement within representative landscapes. Preliminary results indicate that heave and settlement follow patterns of spatial variation similar to those of active-layer thickness. To evaluate the effect of vegetation on ground surface temperature, several heat-transfer coefficients were estimated, including land cover specific thermal diffusivity and empirical n-factors.

  19. Endocrine disrupting activities of surface water associated with a West Virginia oil and gas industry wastewater disposal site

    USGS Publications Warehouse

    Kassotis, Christopher D.; Iwanowicz, Luke; Akob, Denise M.; Cozzarelli, Isabelle M.; Mumford, Adam; Orem, William H.; Nagel, Susan C.

    2016-01-01

    Currently, >95% of end disposal of hydraulic fracturing wastewater from unconventional oil and gas operations in the US occurs via injection wells. Key data gaps exist in understanding the potential impact of underground injection on surface water quality and environmental health. The goal of this study was to assess endocrine disrupting activity in surface water at a West Virginia injection well disposal site. Water samples were collected from a background site in the area and upstream, on, and downstream of the disposal facility. Samples were solid-phase extracted, and extracts assessed for agonist and antagonist hormonal activities for five hormone receptors in mammalian and yeast reporter gene assays. Compared to reference water extracts upstream and distal to the disposal well, samples collected adjacent and downstream exhibited considerably higher antagonist activity for the estrogen, androgen, progesterone, glucocorticoid and thyroid hormone receptors. In contrast, low levels of agonist activity were measured in upstream/distal sites, and were inhibited or absent at downstream sites with significant antagonism. Concurrent analyses by partner laboratories (published separately) describe the analytical and geochemical profiling of the water; elevated conductivity as well as high sodium, chloride, strontium, and barium concentrations indicate impacts due to handling of unconventional oil and gas wastewater. Notably, antagonist activities in downstream samples were at equivalent authentic standard concentrations known to disrupt reproduction and/or development in aquatic animals. Given the widespread use of injection wells for end-disposal of hydraulic fracturing wastewater, these data raise concerns for human and animal health nearby.

  20. Endocrine disrupting activities of surface water associated with a West Virginia oil and gas industry wastewater disposal site.

    PubMed

    Kassotis, Christopher D; Iwanowicz, Luke R; Akob, Denise M; Cozzarelli, Isabelle M; Mumford, Adam C; Orem, William H; Nagel, Susan C

    2016-07-01

    Currently, >95% of end disposal of hydraulic fracturing wastewater from unconventional oil and gas operations in the US occurs via injection wells. Key data gaps exist in understanding the potential impact of underground injection on surface water quality and environmental health. The goal of this study was to assess endocrine disrupting activity in surface water at a West Virginia injection well disposal site. Water samples were collected from a background site in the area and upstream, on, and downstream of the disposal facility. Samples were solid-phase extracted, and extracts assessed for agonist and antagonist hormonal activities for five hormone receptors in mammalian and yeast reporter gene assays. Compared to reference water extracts upstream and distal to the disposal well, samples collected adjacent and downstream exhibited considerably higher antagonist activity for the estrogen, androgen, progesterone, glucocorticoid and thyroid hormone receptors. In contrast, low levels of agonist activity were measured in upstream/distal sites, and were inhibited or absent at downstream sites with significant antagonism. Concurrent analyses by partner laboratories (published separately) describe the analytical and geochemical profiling of the water; elevated conductivity as well as high sodium, chloride, strontium, and barium concentrations indicate impacts due to handling of unconventional oil and gas wastewater. Notably, antagonist activities in downstream samples were at equivalent authentic standard concentrations known to disrupt reproduction and/or development in aquatic animals. Given the widespread use of injection wells for end-disposal of hydraulic fracturing wastewater, these data raise concerns for human and animal health nearby. PMID:27073166

  1. Adsorption of cadmium ions on oxygen surface sites in activated carbon

    SciTech Connect

    Jia, Y.F.; Thomas, K.M.

    2000-02-08

    Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon by oxidation using nitric acid. Fourier-transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), and selective neutralization were used to characterize the surface oxygen functional groups. The oxidized carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stabilities were varied progressively. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released protons to adsorbed cadmium ions on oxidized carbon was approximately 2, indicating cation exchange was involved in the process of adsorption. Na{sup +} exchange studies with the oxidized carbon gave a similar ratio. After heat treatment of the oxidized carbons to remove oxygen functional groups, the ratio of H{sup +} released to Cd{sup 2+} adsorbed and the adsorption capacity decreased significantly. Both reversible and irreversible processes were involved in cadmium ion adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups, whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion.

  2. A Conserved Surface Loop in Type I Dehydroquinate Dehydratases Positions an Active Site Arginine and Functions in Substrate Binding

    SciTech Connect

    Light, Samuel H.; Minasov, George; Shuvalova, Ludmilla; Peterson, Scott N.; Caffrey, Michael; Anderson, Wayne F.; Lavie, Arnon

    2012-04-18

    Dehydroquinate dehydratase (DHQD) catalyzes the third step in the biosynthetic shikimate pathway. We present three crystal structures of the Salmonella enterica type I DHQD that address the functionality of a surface loop that is observed to close over the active site following substrate binding. Two wild-type structures with differing loop conformations and kinetic and structural studies of a mutant provide evidence of both direct and indirect mechanisms of involvement of the loop in substrate binding. In addition to allowing amino acid side chains to establish a direct interaction with the substrate, closure of the loop necessitates a conformational change of a key active site arginine, which in turn positions the substrate productively. The absence of DHQD in humans and its essentiality in many pathogenic bacteria make the enzyme a target for the development of nontoxic antimicrobials. The structures and ligand binding insights presented here may inform the design of novel type I DHQD inhibiting molecules.

  3. Can we define an asymptotic value for the ice active surface site density for heterogeneous ice nucleation?

    NASA Astrophysics Data System (ADS)

    Niedermeier, Dennis; Augustin-Bauditz, Stefanie; Hartmann, Susan; Wex, Heike; Ignatius, Karoliina; Stratmann, Frank

    2015-05-01

    The immersion freezing behavior of droplets containing size-segregated, monodisperse feldspar particles was investigated. For all particle sizes investigated, a leveling off of the frozen droplet fraction was observed reaching a plateau within the heterogeneous freezing temperature regime (T >- 38°C). The frozen fraction in the plateau region was proportional to the particle surface area. Based on these findings, an asymptotic value for ice active surface site density ns, which we named ns⋆, could be determined for the investigated feldspar sample. The comparison of these results with those of other studies not only elucidates the general feasibility of determining such an asymptotic value but also shows that the value of ns⋆ strongly depends on the method of the particle surface area determination. However, such an asymptotic value might be an important input parameter for atmospheric modeling applications. At least it shows that care should be taken when ns is extrapolated to lower or higher temperature.

  4. Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

    DOE PAGESBeta

    Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; Nash, Connor; Steirer, K. Xerxes; Clark, Jared; Robichaud, David J.; Ruddy, Daniel A.

    2016-01-21

    Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo2C) for the deoxygenation of acetic acid, anmore » abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

  5. Effects of Al(3+) Ions on Formation of Silica Framework and Surface Active Sites for SO4(2-) Ions.

    PubMed

    Sasahara, Shigeo; Ozeki, Sumio

    2016-07-19

    Al(3+) ions were introduced into silica framework at 318 K in order to make active Al sites for SO4(2-) by the addition of aqueous sodium silicate solution to aqueous sulfuric acid solution of Al2(SO4)3. The (27)Al and (29)Si NMR spectra of aluminosilicates were measured at 278 K with reaction time. (29)Si NMR spectra were analyzed by the multivariate curve resolution. The addition of Al(3+) ions to aqueous silicate solution promoted gel formation. Small amounts of Al(3+) ions were incorporated as a four-coordinated complex at early stage of polymerization reaction of silicates and during subsequent reaction six-coordinated Al complex increased, suggesting reversible conversion between 4- and 6-coordinated complexes. SO4(2-) ions interact with positive surfaces of aluminosilicates and are specifically adsorbed on the surface sites of 6-coordinated Al(3+) species, which may be stabilized on silicate surfaces as [Al(H2O)5SO4](+). PMID:27352046

  6. Recent characterization activities of Midway Valley as a potential repository surface facility site

    SciTech Connect

    Gibson, J.D.; Wesling, J.R.; Swan, F.H.; Bullard, T.F.

    1992-01-31

    Midway Valley, located at the eastern base of Yucca Mountain, Nye County, Nevada, has been identified as a possible location for the surface facilities of a potential high-level nuclear-waste repository. This structural and topographic valley is bounded by two north- trending, down-to-the-west normal faults: the Paintbrush Canyon fault on the east and the Bow Ridge fault on the west. Surface and near-surface geological data have been acquired from Midway Valley during the past three years with particular emphasis on evaluating the existence of Quaternary faults. A detailed (1:6000) surficial geological map has been prepared based on interpretation of new and existing aerial photographs, field mapping, soil pits, and trenches. No evidence was found that would indicate displacement of these surficial deposits along previously unrecognized faults. However, given the low rates of Quaternary faulting and the extensive areas that are covered by late Pleistocene to Holocene deposits south of Sever Wash, Quaternary faulting between known faults cannot be precluded based on surface evidence alone. Middle to late Pleistocene alluvial fan deposits (Unit Q3) exist at or near the surface throughout Midway Valley. Confidence is increased that the potential for surface fault rupture in Midway Valley can be assessed by excavations that expose the deposits and soils associated with Unit Q3 or older units (middle Pleistocene or earlier).

  7. Mg2+ binds to the surface of thymidylate synthase and affects hydride transfer at the interior active site

    PubMed Central

    Wang, Zhen; Sapienza, Paul J.; Abeysinghe, Thelma; Luzum, Calvin; Lee, Andrew L.; Finer-Moore, Janet S.; Stroud, Robert M.; Kohen, Amnon

    2013-01-01

    Thymidylate synthase (TSase) produces the sole intracellular de novo source of thymidine (i.e. the DNA base T) and thus is a common target for antibiotic and anticancer drugs. Mg2+ has been reported to affect TSase activity, but the mechanism of this interaction has not been investigated. Here we show that Mg2+ binds to the surface of Escherichia coli TSase and affects the kinetics of hydride transfer at the interior active site (16 Å away). Examination of the crystal structures identifies a Mg2+ near the glutamyl moiety of the folate cofactor, providing the first structural evidence for Mg2+ binding to TSase. The kinetics and NMR relaxation experiments suggest that the weak binding of Mg2+ to the protein surface stabilizes the closed conformation of the ternary enzyme complex and reduces the entropy of activation on the hydride transfer step. Mg2+ accelerates the hydride transfer by ca. 7-fold but does not affect the magnitude or temperature-dependence of the intrinsic kinetic isotope effect. These results suggest that Mg2+ facilitates the protein motions that bring the hydride donor and acceptor together, but it does not change the tunneling ready state of the hydride transfer. These findings highlight how variations in cellular Mg2+ concentration can modulate enzyme activity through long-range interactions in the protein, rather than binding at the active site. The interaction of Mg2+ with the glutamyl-tail of the folate cofactor and nonconserved residues of bacterial TSase may assist in designing antifolates with poly-glutamyl substitutes as species-specific antibiotic drugs. PMID:23611499

  8. Surface carbon transformations at a site of active continental serpentinization: the Tablelands, Newfoundland, Canada

    NASA Astrophysics Data System (ADS)

    Rietze, A.; Szponar, N.; Lang, S. Q.; Kohl, L.; Morrill, P. L.

    2013-12-01

    The Tablelands in Newfoundland, Canada contain terrestrial peridotite-hosted groundwater springs associated with serpentinization. These springs act as windows into subsurface systems and provide insight into their biogeochemistry. However, at sites where ultra-basic water pools and mixes with overland flow the reactions in the pools must be considered when trying to source organic compounds. We will present data from a pool (WHC2) located in the Tablelands to determine the biogeochemical carbon transformations at this mixing site. The ultra-basic, reducing groundwater springs had higher concentrations of alkanes (C1-C4) and organic acids (acetate and formate) than the overland flow, suggesting that these organics originated from the groundwater source. A two component mixing model was developed to predict what the concentrations of alkanes and organic acids would be in the WHC2 pool based on physical mixing of groundwater and overland flow. Acetate and C2-C4 alkane concentrations were fairly well predicted by the mixing model, suggesting little consumption or production of this organic acid and these alkanes in the pool. However, methane concentrations were under predicted by the model at two sampling points in the pool, suggesting production of methane at these sites. At the same two sampling locations formate concentrations were over predicted by the model, suggesting that formate was being consumed in the pool. The water at these sampling times was highly reducing; therefore oxidation of formate was not likely responsible for the consumption of formate. Organic acid fermentation using formate is one possible sink for formate and source for methane. However, the genomic data from the site has shown little evidence for microbial methanogenesis (1). Geochemical measurements of the carbon in the pool can help elucidate the most dominant source of methane. On a Bernard plot (C1/C2+ vs. δ13CCH4 (‰)) the alkanes measured at the springs plot in the thermogenic

  9. Applicability of rapid and on-site measured enzyme activity for surface water quality monitoring in an agricultural catchment

    NASA Astrophysics Data System (ADS)

    Stadler, Philipp; Farnleitner, Andreas H.; Sommer, Regina; Kumpan, Monika; Zessner, Matthias

    2014-05-01

    For the near real time and on-site detection of microbiological fecal pollution of water, the measurement of beta-D- Glucuronidase (GLUC) enzymatic activity has been suggested as a surrogate parameter and has been already successfully operated for water quality monitoring of ground water resources (Ryzinska-Paier et al. 2014). Due to possible short measure intervals of three hours, this method has high potential as a water quality monitoring tool. While cultivation based standard determination takes more than one working day (Cabral 2010) the potential advantage of detecting the GLUC activity is the high temporal measuring resolution. Yet, there is still a big gap of knowledge on the fecal indication capacity of GLUC (specificity, sensitivity, persistence, etc.) in relation to potential pollution sources and catchment conditions (Cabral 2010, Ryzinska-Paier et al. 2014). Furthermore surface waters are a big challenge for automated detection devices in a technical point of view due to the high sediment load during event conditions. This presentation shows results gained form two years of monitoring in an experimental catchment (HOAL) dominated by agricultural land use. Two enzymatic measurement devices are operated parallel at the catchment outlet to test the reproducibility and precision of the method. Data from continuous GLUC monitoring under both base flow and event conditions is compared with reference samples analyzed by standardized laboratory methods for fecal pollution detection (e.g. ISO 16649-1, Colilert18). It is shown that rapid enzymatic on-site GLUC determination can successfully be operated from a technical point of view for surface water quality monitoring under the observed catchment conditions. The comparison of enzyme activity with microbiological standard analytics reveals distinct differences in the dynamic of the signals during event conditions. Cabral J. P. S. (2010) "Water Microbiology. Bacterial Pathogens and Water" International Journal of

  10. Can we define an asymptotic value for the ice active surface site density for heterogeneous ice nucleation?

    NASA Astrophysics Data System (ADS)

    Niedermeier, Dennis; Augustin-Bauditz, Stefanie; Hartmann, Susan; Wex, Heike; Ignatius, Karoliina; Stratmann, Frank

    2015-04-01

    The formation of ice in atmospheric clouds has a substantial influence on the radiative properties of clouds as well as on the formation of precipitation. Therefore much effort has been made to understand and quantify the major ice formation processes in clouds. Immersion freezing has been suggested to be a dominant primary ice formation process in low and mid-level clouds (mixed-phase cloud conditions). It also has been shown that mineral dust particles are the most abundant ice nucleating particles in the atmosphere and thus may play an important role for atmospheric ice nucleation (Murray et al., 2012). Additionally, biological particles like bacteria and pollen are suggested to be potentially involved in atmospheric ice formation, at least on a regional scale (Murray et al., 2012). In recent studies for biological particles (SNOMAX and birch pollen), it has been demonstrated that freezing is induced by ice nucleating macromolecules and that an asymptotic value for the mass density of these ice nucleating macromolecules can be determined (Hartmann et al., 2013; Augustin et al., 2013, Wex et al., 2014). The question arises whether such an asymptotic value can also be determined for the ice active surface site density ns, a parameter which is commonly used to describe the ice nucleation activity of e.g., mineral dust. Such an asymptotic value for ns could be an important input parameter for atmospheric modeling applications. In the presented study, we therefore investigated the immersion freezing behavior of droplets containing size-segregated, monodisperse feldspar particles utilizing the Leipzig Aerosol Cloud Interaction Simulator (LACIS). For all particle sizes considered in the experiments, we observed a leveling off of the frozen droplet fraction reaching a plateau within the heterogeneous freezing temperature regime (T > -38°C) which was proportional to the particle surface area. Based on these findings, we could determine an asymptotic value for the ice

  11. ROLE OF C AND P SITES ON THE CHEMICAL ACTIVITY OF METAL CARBIDE AND PHOSPHIDES: FROM CLUSTERS TO SINGLE-CRYSTAL SURFACES

    SciTech Connect

    RODRIGUEZ,J.A.; VINES, F.; LIU, P.; ILLAS, F.

    2007-07-01

    Transition metal carbides and phosphides have shown tremendous potential as highly active catalysts. At a microscopic level, it is not well understood how these new catalysts work. Their high activity is usually attributed to ligand or/and ensemble effects. Here, we review recent studies that examine the chemical activity of metal carbide and phosphides as a function of size, from clusters to extended surfaces, and metal/carbon or metal/phosphorous ratio. These studies reveal that the C and P sites in these compounds cannot be considered as simple spectators. They moderate the reactivity of the metal centers and provide bonding sites for adsorbates.

  12. Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

    SciTech Connect

    Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L.

    2015-03-14

    Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

  13. Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

    NASA Astrophysics Data System (ADS)

    Skomski, Daniel; Tempas, Christopher D.; Bukowski, Gregory S.; Smith, Kevin A.; Tait, Steven L.

    2015-03-01

    Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

  14. Examination of metals from aerospace-related activity in surface water samples from sites surrounding the Kennedy Space Center (KSC), Florida.

    PubMed

    Bowden, John A; Cantu, Theresa M; Scheidt, Douglas M; Lowers, Russell H; Nocito, Brian A; Young, Vaneica Y; Guillette, Louis J

    2014-05-01

    Metal contamination from Space Shuttle launch activity was examined using inductively coupled plasma-atomic emission spectroscopy in a two-tier study sampling surface water collected from several sites at the Kennedy Space Center (KSC) and associated Merritt Island National Wildlife Refuge in east central Florida. The primary study examined both temporal changes in baseline metal concentrations (19 metals) in surface water (1996 to 2009, 11 sites) samples collected at specific long-term monitoring sites and metal deposition directly associated with Space Shuttle launch activity at two Launch Complexes (LC39A and LC39B). A secondary study examined metal concentrations at additional sites and increased the amount of elements measured to 48 elements. Our examination places a heavy focus on those metals commonly associated with launch operations (e.g., Al, Fe, Mn, and Zn), but a brief discussion of other metals (As, Cu, Mo, Ni, and Pb) is also included. While no observable accumulation of metals occurred during the time period of the study, the data obtained postlaunch demonstrated a dramatic increase for Al, Fe, Mn, and Zn. Comparing overall trends between the primary and secondary baseline surface water concentrations, elevated concentrations were generally observed at sampling stations located near the launch complexes and from sites isolated from major water systems. While there could be several natural and anthropogenic sources for metal deposition at KSC, the data in this report indicate that shuttle launch events are a significant source. PMID:24738662

  15. Identical Location Transmission Electron Microscopy Imaging of Site-Selective Pt Nanocatalysts: Electrochemical Activation and Surface Disordering.

    PubMed

    Arán-Ais, Rosa M; Yu, Yingchao; Hovden, Robert; Solla-Gullón, Jose; Herrero, Enrique; Feliu, Juan M; Abruña, Héctor D

    2015-12-01

    We have employed identical location transmission electron microscopy (IL-TEM) to study changes in the shape and morphology of faceted Pt nanoparticles as a result of electrochemical cycling; a procedure typically employed for activating platinum surfaces. We find that the shape and morphology of the as-prepared hexagonal nanoparticles are rapidly degraded as a result of potential cycling up to +1.3 V. As few as 25 potential cycles are sufficient to cause significant degradation, and after about 500-1000 cycles the particles are dramatically degraded. We also see clear evidence of particle migration during potential cycling. These finding suggest that great care must be exercised in the use and study of shaped Pt nanoparticles (and related systems) as electrocatlysts, especially for the oxygen reduction reaction where high positive potentials are typically employed. PMID:26524187

  16. Construction of manned lunar surface sites

    NASA Astrophysics Data System (ADS)

    Yuzawa, Yoshinori; Horie, Michihiko; Nakamura, Tetsuya; Amagata, Raita; Honda, Tetsuya

    1991-07-01

    A review is conducted on manned lunar surface sites to be constructed in around 2010 to conduct various experiments and observations on the lunar surface in a short time prior to developing permanent lunar bases. Methods of construction and operation of manned lunar surface sites are established, taking requirements from the mission parts and shipping mean constraints. Review results of mission requirements and operation profiles are presented. Experiment subjects, structures and outlines of subsystems, weight balance, electric power balance and functional block diagram of the manned lunar surface sites are presented. Conceptual drawings of air-lock and roving vehicle, operation profiles and conceptual drawing of lunar surface sites are shown.

  17. New Surface-Enhanced Raman Sensing Chip Designed for On-Site Detection of Active Ricin in Complex Matrices Based on Specific Depurination.

    PubMed

    Tang, Ji-Jun; Sun, Jie-Fang; Lui, Rui; Zhang, Zong-Mian; Liu, Jing-Fu; Xie, Jian-Wei

    2016-01-27

    Quick and accurate on-site detection of active ricin has very important realistic significance in view of national security and defense. In this paper, optimized single-stranded oligodeoxynucleotides named poly(21dA), which function as a depurination substrate of active ricin, were screened and chemically attached on gold nanoparticles (AuNPs, ∼100 nm) via the Au-S bond [poly(21dA)-AuNPs]. Subsequently, poly(21dA)-AuNPs were assembled on a dihydrogen lipoic-acid-modified Si wafer (SH-Si), thus forming the specific surface-enhanced Raman spectroscopy (SERS) chip [poly(21dA)-AuNPs@SH-Si] for depurination of active ricin. Under optimized conditions, active ricin could specifically hydrolyze multiple adenines from poly(21dA) on the chip. This depurination-induced composition change could be conveniently monitored by measuring the distinct attenuation of the SERS signature corresponding to adenine. To improve sensitivity of this method, a silver nanoshell was deposited on post-reacted poly(21dA)-AuNPs, which lowered the limit of detection to 8.9 ng mL(-1). The utility of this well-controlled SERS chip was successfully demonstrated in food and biological matrices spiked with different concentrations of active ricin, thus showing to be very promising assay for reliable and rapid on-site detection of active ricin. PMID:26719952

  18. Active surface faulting or landsliding in the Lower Tagus Valley (Portugal)? A solved controversy concerning the Vila Chã de Ourique site

    NASA Astrophysics Data System (ADS)

    Cabral, João Manuel; Marques, Fernando; Figueiredo, Paula; Matias, Luís

    2011-04-01

    The Lower Tagus Valley has experienced significant (M 6-7) historical seismicity, evidencing the presence of seismogenic faults. These are still deficiently known due to the low strain rates and the recent alluvial sedimentation of the Tagus River that buries most of the structures, though Paleoseismic evidence was allegedly found by a research team in the Tagus valley, at a site 60 km N of Lisbon, near Vila Chã de Ourique (VCO). According to this team, trenching at the VCO site exposed an active thrust fault, evidencing the surface rupture of a large earthquake that occurred in 1531. Our studies performed at this site, comprising field observations with a reappraisal of the trench outcrops previously excavated, borehole drilling, soil mechanics laboratory testing, and seismic reflection acquisition, pointed to the alternative interpretation that the outcropping structures are gravitational and not of tectonic origin. The interpretation of new outcrops crosscutting the structures exposed at the trenches, as well as newly acquired high-resolution seismic reflection data, definitely exclude the active thrust fault explanation and support a gravitational slip model for all the observed structures. Gravitational slip in the river bank slope was promoted by low shear strength clays and high pore water pressure coupled with slope toe river erosion. Gravitational slides must have occurred prior to development of the present sedimentation level of the Tagus alluvial plain, which was attained in the last few thousand years as indicated by borehole data and estimations of sedimentation rates.

  19. Surface barrier research at the Hanford Site

    SciTech Connect

    Gee, G.W.; Ward, A.L.; Fayer, M.J.

    1997-12-31

    At the DOE Hanford Site, a field-scale prototype surface barrier was constructed in 1994 over an existing waste site as a part of a CERCLA treatability test. The above-grade barrier consists of a fine-soil layer overlying coarse layers of sands, gravels, basalt rock (riprap), and a low permeability asphalt layer. Two sideslope configurations, clean-fill gravel on a 10:1 slope and basalt riprap on a 2:1 slope, were built and are being tested. Design considerations included: constructability; drainage and water balance monitoring, wind and water erosion control and monitoring; surface revegetation and biotic intrusion; subsidence and sideslope stability, and durability of the asphalt layer. The barrier is currently in the final year of a three-year test designed to answer specific questions related to stability and long-term performance. One half of the barrier is irrigated such that the total water applied, including precipitation, is 480 mm/yr (three times the long-term annual average). Each year for the past two years, an extreme precipitation event (71 mm in 8 hr) representing a 1,000-yr return storm was applied in late March, when soil water storage was at a maximum. While the protective sideslopes have drained significant amounts of water, the soil cover (2-m of silt-loam soil overlying coarse sand and rock) has never drained. During the past year there was no measurable surface runoff or wind erosion. This is attributed to extensive revegetation of the surface. In addition, the barrier elevation has shown a small increase of 2 to 3 cm that is attributed to a combination of root proliferation and freeze/thaw activity. Testing will continue through September 1997. Performance data from the prototype barrier will be used by DOE in site-closure decisions at Hanford.

  20. Five-fold twinned Pd2NiAg nanocrystals with increased surface Ni site availability to improve oxygen reduction activity.

    PubMed

    Liu, Suli; Zhang, Qinghua; Li, Yafei; Han, Min; Gu, Lin; Nan, Cewen; Bao, Jianchun; Dai, Zhihui

    2015-03-01

    The synthesis of highly active oxygen reduction reaction (ORR) catalysts with good durability and low cost is highly desirable but still remains a significant challenge. In this work, we present the synthesis of five-fold twinned Pd2NiAg nanocrystals (NCs) with a Ni-terminal surface which exhibit excellent electrocatalytic performance for ORR in alkaline media, even better than the performance of the commercial Pt/C catalyst. Using high-angle annular-dark-field imaging together with density functional theory calculations, it is found that the surfaces of the five-fold twinned Pd2NiAg NCs exhibit an unusual valence electron density. The maximum catalytic activity originates from the increased availability of surface Ni sites in five-fold twinned Pd2NiAg NCs and the features of twinned structural defects. This study provides an explanation of the enhanced ORR from the special structure of this novel material, which opens up new avenues for the design of novel classes of electrocatalysts for fuel cells and metal-air batteries. PMID:25626352

  1. Site-directed immobilization of antibody using EDC-NHS-activated protein A on a bimetallic-based surface plasmon resonance chip

    NASA Astrophysics Data System (ADS)

    Sohn, Young-Soo; Lee, Yeon Kyung

    2014-05-01

    The characteristics of a waveguide-coupled bimetallic surface plasmon resonance (WcBiM SPR) sensor using (3-dimethylaminopropyl)-3-ethylcarbodiimide(EDC)-N-hydroxysuccinimide(NHS)-activated protein A was investigated, and the detection of IgG using the EDC-NHS-activated protein A was studied in comparison with protein A and a self-assembled monolayer (SAM). The WcBiM sensor, which has a narrower full width at half maximum (FWHM) and a steeper slope, was selected since it leads to a larger change in the reflectance in the intensity detection mode. A preparation of the EDC-NHS-activated protein A for site-directed immobilization of antibodies was relative easily compared to the engineered protein G and A. In antigen-antibody interactions, the response to IgG at the concentrations of 50, 100, and 150 ng/ml was investigated. The results showed that the sensitivity of the WcBiM sensor using the EDC-NHS-activated protein A, protein A, and SAM was 0.0185 [%/(ng/ml)], 0.0065 [%/(ng/ml)], and 0.0101 [%/(ng/ml)], respectively. The lowest detectable concentrations of IgG with the EDC-NHS-activated protein A, protein A, and SAM were 4.27, 12.83, and 8.24 ng/ml, respectively. Therefore, the increased sensitivity and lower detection capability of the WcBiM SPR chip with the EDC-NHS-activated protein A suggests that it could be used in early diagnosis where the trace level concentrations of biomolecules should be detected.

  2. Improving surface coal refuse disposal site inspections

    SciTech Connect

    Meister, R.A.; Hoffman, R.L.

    1980-06-01

    The study on improving surface coal refuse disposal site inspections included surface inspections of 15 refuse disposal sites. Monthly aerial photos were taken of the sites and computer methods were used to determine elevation changes. Photogrammetric techniques that were used are described in detail. A comparison of the results of each of these inspection techniques is included. A detailed evaluation of the photogrammetric techniques was made and conclusions were drawn concerning the advantages and disadvantages of using aerial photography and photogrammetry as part of the inspection procedure. Operators' opinions of the aerial photography methods are included.

  3. Active frequency selective surfaces

    NASA Astrophysics Data System (ADS)

    Buchwald, Walter R.; Hendrickson, Joshua; Cleary, Justin W.; Guo, Junpeng

    2013-05-01

    Split ring resonator arrays are investigated for use as active elements for the realization of voltage controllable frequency selective surfaces. Finite difference time domain simulations suggest the absorptive and reflective properties of such surfaces can be externally controlled through modifications of the split ring resonator gap impedance. In this work, such voltage-controlled resonance tuning is obtained through the addition of an appropriately designed high electron mobility transistor positioned across the split ring resonator gap. It is shown that a 0.5μm gate length high electron mobility transistor allows voltage controllable switching between the two resonant conditions associated with a split ring resonator and that of a closed loop geometry when the surface is illuminated with THz radiation. Partial switching between these two resonant conditions is observed at larger gate lengths. Such active frequency selective surfaces are proposed, for example, for use as modulators in THz detection schemes and as RF filters in radar applications when scaled to operate at GHz frequencies.

  4. Salt site performance assessment activities

    SciTech Connect

    Kircher, J.F.; Gupta, S.K.

    1983-01-01

    During this year the first selection of the tools (codes) for performance assessments of potential salt sites have been tentatively selected and documented; the emphasis has shifted from code development to applications. During this period prior to detailed characterization of a salt site, the focus is on bounding calculations, sensitivity and with the data available. The development and application of improved methods for sensitivity and uncertainty analysis is a focus for the coming years activities and the subject of a following paper in these proceedings. Although the assessments to date are preliminary and based on admittedly scant data, the results indicate that suitable salt sites can be identified and repository subsystems designed which will meet the established criteria for protecting the health and safety of the public. 36 references, 5 figures, 2 tables.

  5. Microstructure of surface cerium hydride growth sites

    SciTech Connect

    Brierley, Martin; Knowles, John; Montgomery, Neil; Preuss, Michael

    2014-05-15

    Samples of cerium were exposed to hydrogen under controlled conditions causing cerium hydride sites to nucleate and grow on the surface. The hydriding rate was measured in situ, and the hydrides were characterised using secondary ion mass spectrometry, scanning electron microscopy, and optical microscopy. The results show that the hydriding rate proceeded more quickly than earlier studies. Characterisation confirmed that the hydrogen is confined to the sites. The morphology of the hydrides was confirmed to be oblate, and stressed material was observed surrounding the hydride, in a number of cases lathlike features were observed surrounding the hydride sites laterally with cracking in the surface oxide above them. It is proposed that during growth the increased lattice parameter of the CeH{sub 2} induces a lateral compressive stress around the hydride, which relieves by the ca. 16% volume collapse of the γ-Ce to α-Ce pressure induced phase transition. Cracking of the surface oxide above the laths reduces the diffusion barrier to hydrogen reaching the metal/oxide interface surrounding the hydride site and contributes to the anisotropic growth of the hydrides.

  6. Hanford Site surface soil radioactive contamination control plan, March 1993

    SciTech Connect

    Mix, P.D.; Winship, R.A.

    1993-04-01

    The Decommissioning and Resource Conservation and Recovery Act Closure Program is responsible to the US Department of Energy Richland Field Office, for the safe and cost-effective surveillance, maintenance, and decommissioning of surplus facilities and Resource Conservation and Recovery Act of 1976 closures at the Hanford Site. This program also manages the Radiation Area Remedial Action that includes the surveillance, maintenance, decontamination, and/or interim stabilization of inactive burial grounds, cribs, ponds, trenches, and unplanned release sites. This plan addresses only the Radiation Area Remedial Action activity requirements for managing and controlling the contaminated surface soil areas associated with these inactive sites until they are remediated as part of the Hanford Site environmental restoration process. All officially numbered Radiation Area Remedial Action and non-Radiation Area Remedial Action contaminated surface soil areas are listed in this document so that a complete list of the sites requiring remediation is contained in one document.

  7. Vibrational Spectroscopic Observation of Atomic-Scale Local Surface Sites Using Site-Selective Signal Enhancement.

    PubMed

    Hu, Jian; Hoshi, Nagahiro; Uosaki, Kohei; Ikeda, Katsuyoshi

    2015-12-01

    Molecule-substrate interactions are sensitively affected by atomic-scale surface structures. Unique activity in heterogeneous catalysts or electrocatalysts is often related with local surface sites with specific structures. We demonstrate that adsorption geometry of a model molecule with an isocyanide anchor is drastically varied among one-fold atop, two-fold bridge, and three-fold hollow configurations with increasing the size of atomic-scale local surface sites of Pd islands on an Au(111) model surface. The vibrational spectroscopic observation of such local information is realized by site-selective and self-assembled formation of hotspots, where Raman scattering intensity is significantly enhanced via excitation of localized surface plasmons. PMID:26551000

  8. Identification of protein functions from a molecular surface database, eF-site.

    PubMed

    Kinoshita, Kengo; Furui, Jun'ichi; Nakamura, Haruki

    2002-01-01

    A bioinformatics method was developed to identify the protein surface around the functional site and to estimate the biochemical function, using a newly constructed molecular surface database named the eF-site (electrostatic surface of Functional site. Molecular surfaces of protein molecules were computed based on the atom coordinates, and the eF-site database was prepared by adding the physical properties on the constructed molecular surfaces. The electrostatic potential on each molecular surface was individually calculated solving the Poisson-Boltzmann equation numerically for the precise continuum model, and the hydrophobicity information of each residue was also included. The eF-site database is accessed by the internet (http://pi.protein.osaka-u.ac.jp/eF-site/). We have prepared four different databases, eF-site/antibody, eF-site/prosite, eF-site/P-site, and eF-site/ActiveSite, corresponding to the antigen binding sites of antibodies with the same orientations, the molecular surfaces for the individual motifs in PROSITE database, the phosphate binding sites, and the active site surfaces for the representatives of the individual protein family, respectively. An algorithm using the clique detection method as an applied graph theory was developed to search of the eF-site database, so as to recognize and discriminate the characteristic molecular surfaces of the proteins. The method identifies the active site having the similar function to those of the known proteins. PMID:12836670

  9. Repository surface design site layout analysis

    SciTech Connect

    Montalvo, H.R.

    1998-02-27

    The purpose of this analysis is to establish the arrangement of the Yucca Mountain Repository surface facilities and features near the North Portal. The analysis updates and expands the North Portal area site layout concept presented in the ACD, including changes to reflect the resizing of the Waste Handling Building (WHB), Waste Treatment Building (WTB), Carrier Preparation Building (CPB), and site parking areas; the addition of the Carrier Washdown Buildings (CWBs); the elimination of the Cask Maintenance Facility (CMF); and the development of a concept for site grading and flood control. The analysis also establishes the layout of the surface features (e.g., roads and utilities) that connect all the repository surface areas (North Portal Operations Area, South Portal Development Operations Area, Emplacement Shaft Surface Operations Area, and Development Shaft Surface Operations Area) and locates an area for a potential lag storage facility. Details of South Portal and shaft layouts will be covered in separate design analyses. The objective of this analysis is to provide a suitable level of design for the Viability Assessment (VA). The analysis was revised to incorporate additional material developed since the issuance of Revision 01. This material includes safeguards and security input, utility system input (size and location of fire water tanks and pump houses, potable water and sanitary sewage rates, size of wastewater evaporation pond, size and location of the utility building, size of the bulk fuel storage tank, and size and location of other exterior process equipment), main electrical substation information, redundancy of water supply and storage for the fire support system, and additional information on the storm water retention pond.

  10. The active site behaviour of electrochemically synthesised gold nanomaterials.

    PubMed

    Plowman, Blake J; O'Mullane, Anthony P; Bhargava, Suresh K

    2011-01-01

    Even though gold is the noblest of metals, a weak chemisorber and is regarded as being quite inert, it demonstrates significant electrocatalytic activity in its nanostructured form. It is demonstrated here that nanostructured and even evaporated thin films of gold are covered with active sites which are responsible for such activity. The identification of these sites is demonstrated with conventional electrochemical techniques such as cyclic voltammetry as well as a large amplitude Fourier transformed alternating current (FT-ac) method under acidic and alkaline conditions. The latter technique is beneficial in determining if an electrode process is either Faradaic or capacitive in nature. The observed behaviour is analogous to that observed for activated gold electrodes whose surfaces have been severely disrupted by cathodic polarisation in the hydrogen evolution region. It is shown that significant electrochemical oxidation responses occur at discrete potential values well below that for the formation of the compact monolayer oxide of bulk gold and are attributed to the facile oxidation of surface active sites. Several electrocatalytic reactions are explored in which the onset potential is determined by the presence of such sites on the surface. Significantly, the facile oxidation of active sites is used to drive the electroless deposition of metals such as platinum, palladium and silver from their aqueous salts on the surface of gold nanostructures. The resultant surface decoration of gold with secondary metal nanoparticles not only indicates regions on the surface which are rich in active sites but also provides a method to form interesting bimetallic surfaces. PMID:22455038

  11. Surface Sites in Cu-Nanoparticles: Chemical Reactivity or Microscopy?

    PubMed

    Larmier, Kim; Tada, Shohei; Comas-Vives, Aleix; Copéret, Christophe

    2016-08-18

    Copper nanoparticles are widely used in catalysis and electrocatalysis, and the fundamental understanding of their activity requires reliable methods to assess the number of potentially reactive atoms exposed on the surface. Herein, we provide a molecular understanding of the difference observed in addressing surface site titration using prototypical methods: transmission electron micrscopy (TEM), H2 chemisorption, and N2O titration by a combination of experimental and theoretical study. We show in particular that microscopy does not allow assessing the amount of reactive surface sites, while H2 and N2O chemisorptions can, albeit with slightly different stoichiometries (1 O/2CuS and 1 H2/2.2CuS), which can be rationalized by density functional theory calculations. High-resolution TEM shows that the origin of the observed difference between microscopy and titration methods is due to the strong metal support interaction experienced by small copper nanoparticles with the silica surface. PMID:27490121

  12. Processes Impacting Atmosphere-Surface Exchanges at Arctic Terrestrial Sites

    NASA Astrophysics Data System (ADS)

    Persson, Ola; Grachev, Andrey; Konopleva, Elena; Cox, Chris; Stone, Robert; Crepinsek, Sara; Shupe, Matthew; Uttal, Taneil

    2015-04-01

    Surface energy fluxes are key to the annual cycle of near-surface and soil temperature and biologic activity in the Arctic. While these energy fluxes are undoubtedly changing to produce the changes observed in the Arctic ecosystem over the last few decades, measurements have generally not been available to quantify what processes are regulating these fluxes and what is determining the characteristics of these annual cycles. The U.S. National Oceanic and Atmospheric Administration has established, or contributed to the establishment of, several terrestrial "supersites" around the perimeter of the Arctic Ocean at which detailed measurements of atmospheric structure, surface fluxes, and soil thermal properties are being made. These sites include Barrow, Alaska; Eureka and Alert, Canada; and Tiksi, Russia. Atmospheric structure measurements vary, but include radiosoundings at all sites and remote sensing of clouds at two sites. Additionally, fluxes of sensible heat and momentum are made at all of the sites, while fluxes of moisture and CO2 are made at two of the sites. Soil temperatures are also measured in the upper 120 cm at all sites, which is deep enough to define the soil active layer. The sites have been operating between 3 years (Tiksi) and 24 years (Barrow). While all sites are located north of 71° N, the summer vegetation range from lush tundra grasses to rocky soils with little vegetation. This presentation will illustrate some of the atmospheric processes that are key for determining the annual energy and temperature cycles at these sites, and some of the key characteristics that lead to differences in, for instance, the length of the summer soil active layer between the sites. Atmospheric features and processes such as cloud characteristics, snowfall, downslope wind events, and sea-breezes have impacts on the annual energy cycle. The presence of a "zero curtain" period, when autumn surface temperature remains approximately constant at the freezing point

  13. Site Characterization of Marine Clay Deposits in South Seberang Prai, Penang using Combined Active and Passive Multichannel Analysis of Surface Wave (MASW)

    NASA Astrophysics Data System (ADS)

    Ariffin, J.; Ismail, M. A. M.; Tan, C. G.; Murtadza, N. M.

    2016-07-01

    The multichannel analysis of surface wave (MASW) has drawn considerable interest in subsoil investigation and characterization. This method has been studied and improved in the last few decades, thereby leading to several combinations of existing active and passive methods. This study aims to identify the presence of marine clay layer using combined active and passive MASW methods. The shear wave velocity profile obtained interpreting clay layer within the range of 70-150 m/s and sand layer within the range of 100-300 m/s. Results suggest that the combined MASW method significantly improves shear wave velocity profiling in shallow and deep soil layers and the results are validated using the cone resistance and shear wave velocity estimated from cone penetration test.Introduction

  14. ColiSense, today's sample today: A rapid on-site detection of β-D-Glucuronidase activity in surface water as a surrogate for E. coli.

    PubMed

    Heery, Brendan; Briciu-Burghina, Ciprian; Zhang, Dian; Duffy, Gillian; Brabazon, Dermot; O'Connor, Noel; Regan, Fiona

    2016-02-01

    A sensitive field-portable fluorimeter with incubating capability and triplicate sample chambers was designed and built. The system was optimised for the on-site analysis of E. coli in recreational waters using fluorescent based enzyme assays. The target analyte was β-D-Glucuronidase (GUS) which hydrolyses a synthetic substrate 6-Chloro-4-Methyl-Umbelliferyl-β-D-Glucuronide (6-CMUG) to release the fluorescent molecule 6-Chloro-4-Methyl-Umbelliferyl (6-CMU). The system was calibrated with 6-CMU standards. A LOD of 5 nM and a resolution of less than 1 nM was determined while enzyme kinetic tests showed detection of activities below 1 pmol min(-1) mL(-1) of sample. A field portable sample preparation, enzyme extraction protocol and continuous assay were applied with the system to analyse freshwater and marine samples. Results from a one day field trial are shown which demonstrated the ability of the system to deliver results on-site within a 75 min period. PMID:26653426

  15. Site selective surface enhanced Raman on nanostructured cavities

    NASA Astrophysics Data System (ADS)

    Lordan, Frances; Rice, James H.; Jose, Bincy; Forster, Robert J.; Keyes, Tia E.

    2011-07-01

    Presented here are angle dependence studies on the surface enhanced Raman (SER) signal obtained from dye placed on plasmon active nanocavity arrays. A comparative study was carried out between two modified array supports. One array had dye placed only on the interior walls of the cavities in the array. The other array had dye placed only on its top flat surface. Results show that Raman intensities as a function of angle depend on the location of the dye on the array; this was interpreted to arise from the presence of different plasmon polariton modes in these sites.

  16. Europa's Active Surface

    NASA Technical Reports Server (NTRS)

    1996-01-01

    A newly discovered impact crater can be seen just right of the center of this image of Jupiter's moon Europa returned by NASA's Galileo spacecraft camera. The crater is about 30 kilometers (18.5 miles) in diameter. The impact excavated into Europa's icy crust, throwing debris (seen as whitish material) across the surrounding terrain. Also visible is a dark band, named Belus Linea, extending east-west across the image. This type of feature, which scientists call a 'triple band,' is characterized by a bright stripe down the middle. The outer margins of this and other triple bands are diffuse, suggesting that the dark material was put there as a result of possible geyser-like activity which shot gas and rocky debris from Europa's interior. The curving 'X' pattern seen in the lower left corner of the image appears to represent fracturing of the icy crust and infilling by slush which froze in place. The crater is centered at about 2 degrees north latitude by 239 degrees west longitude. The image was taken from a distance of 156,000 kilometers (about 96,300 miles) on June 27, 1996, during Galileo's first orbit around Jupiter. The area shown is 860 by 700 kilometers (530 by 430 miles), or about the size of Oregon and Washington combined. The Galileo mission is managed by NASA's Jet Propulsion Laboratory.

  17. Active Sites Environmental Monitoring Program: Program plan

    SciTech Connect

    Ashwood, T.L.; Wickliff, D.S.; Morrissey, C.M.

    1990-10-01

    DOE Order 5820.2A requires that low-level waste (LLW) disposal sites active on or after September 1988 and all transuranic (TRU) waste storage sites be monitored periodically to assure that radioactive contamination does not escape from the waste sites and pose a threat to the public or to the environment. This plan describes such a monitoring program for the active LLW disposal sites in SWSA 6 and the TRU waste storage sites in SWSA 5 North. 14 refs., 8 figs.

  18. Active particles on curved surfaces

    NASA Astrophysics Data System (ADS)

    Fily, Yaouen; Baskaran, Aparna; Hagan, Michael

    Active systems have proved to be very sensitive to the geometry of their environment. This is often achieved by spending significant time at the boundary, probing its shape by gliding along it. I will discuss coarse graining the microscopic dynamics of self-propelled particles on a general curved surface to predict the way the density profile on the surface depends on its geometry. Beyond confined active particles, this formalism is a natural starting point to study objects that cannot leave the boundary at all, such as cells crawling on a curved substrate, animals running on uneven ground, or active colloids trapped at an interface.

  19. Method for measuring surface activity of silicon nitride powder

    NASA Technical Reports Server (NTRS)

    Kanno, Y.; Imai, H.

    1985-01-01

    Amorphous, alpha-, and beta-Si3N4 powders were activated by vibration ball milling in purified MeOH, and the surface activity of ground powders was determined by the temperature programmed desorption (TPD) method using NH3 gas. The concentration of active sites with a potential energy equivalent to the peak temperature in the spectrum increased was markedly by ball milling the amorphous Si3N4. The alpha- and beta-Si3N4 also had active sites produced by ball milling. The concentration of active site increased with increased ball milling time. A method for measuring surface activity of ceramic raw materials by TPD is proposed.

  20. A non-active-site SET domain surface crucial for the interaction of MLL1 and the RbBP5/Ash2L heterodimer within MLL family core complexes.

    PubMed

    Shinsky, Stephen A; Hu, Michael; Vought, Valarie E; Ng, Sarah B; Bamshad, Michael J; Shendure, Jay; Cosgrove, Michael S

    2014-06-12

    The mixed lineage leukemia-1 (MLL1) enzyme is a histone H3 lysine 4 (H3K4) monomethyltransferase and has served as a paradigm for understanding the mechanism of action of the human SET1 family of enzymes that include MLL1-MLL4 and SETd1a,b. Dimethylation of H3K4 requires a sub-complex including WRAD (WDR5, RbBP5, Ash2L, and DPY-30), which binds to each SET1 family member forming a minimal core complex that is required for multiple lysine methylation. We recently demonstrated that WRAD is a novel histone methyltransferase that preferentially catalyzes H3K4 dimethylation in a manner that is dependent on an unknown non-active-site surface from the MLL1 SET domain. Recent genome sequencing studies have identified a number of human disease-associated missense mutations that localize to the SET domains of several MLL family members. In this investigation, we mapped many of these mutations onto the three-dimensional structure of the SET domain and noticed that a subset of MLL2 (KMT2D, ALR, MLL4)-associated Kabuki syndrome missense mutations map to a common solvent-exposed surface that is not expected to alter enzymatic activity. We introduced these mutations into the MLL1 SET domain and observed that all are defective for H3K4 dimethylation by the MLL1 core complex, which is associated with a loss of the ability of MLL1 to interact with WRAD or with the RbBP5/Ash2L heterodimer. Our results suggest that amino acids from this surface, which we term the Kabuki interaction surface or KIS, are required for formation of a second active site within SET1 family core complexes. PMID:24680668

  1. A non-active site SET domain surface crucial for the interaction of MLL1 and the RbBP5-ASH2L heterodimer within MLL family core complexes

    PubMed Central

    Shinsky, Stephen A.; Hu, Michael; Vought, Valarie E.; Ng, Sarah B.; Bamshad, Michael J.; Shendure, Jay; Cosgrove, Michael S.

    2014-01-01

    The Mixed Lineage Leukemia-1 (MLL1) enzyme is a histone H3 lysine 4 (H3K4) monomethyltransferase and has served as a paradigm for understanding the mechanism of action of the human SET1 family of enzymes that include MLL1–4, and SET1d1a,b. Dimethylation of H3K4 requires a sub-complex including WDR5, RbBP5, Ash2L, and DPY-30 (WRAD), which binds to each SET1 family member forming a minimal core complex that is required for multiple lysine methylation. We recently demonstrated that WRAD is a novel histone methyltransferase that preferentially catalyzes H3K4 dimethylation in a manner that is dependent on an unknown non-active site surface from the MLL1 SET domain. Recent genome sequencing studies have identified a number of human disease-associated missense mutations that localize to the SET domains of several MLL family members. In this investigation, we mapped many of these mutations onto the three-dimensional structure of the SET domain and noticed that a subset of MLL2 (KMT2D, ALR, MLL4)-associated Kabuki syndrome (KS) missense mutations map to a common solvent-exposed surface that is not expected to alter enzymatic activity. We introduced these mutations into the MLL1 SET domain and observed that all are defective for H3K4 dimethylation by the MLL1 core complex, which is associated with a loss of the ability of MLL1 to interact with WRAD or with the RbBP5-Ash2L heterodimer. Our results suggest that amino acids from this surface, which we term the Kabuki interaction surface or (KIS), are required for formation of a second active site within SET1 family core complexes. PMID:24680668

  2. Educational Activity Sites for High School Students

    ERIC Educational Resources Information Center

    Troutner, Joanne

    2005-01-01

    Finding quality Internet resources for high school students is a continuing challenge. Several high-quality web sites are presented for educators and students. These sites offer activities to learn how an art conservator looks at paintings, create a newspaper, research and develop an end product, build geometry and physics skills, explore science…

  3. Human Mars Landing Site and Impacts on Mars Surface Operations

    NASA Technical Reports Server (NTRS)

    Bussey, Ben; Hoffman, Stephen J.

    2016-01-01

    NASA has begun a process to identify and discuss candidate locations where humans could land, live and work on the Martian surface. These locations are referred to as Exploration Zones (EZs). Given current mission concepts, an EZ is a collection of Regions of Interest (ROIs) that are located within approximately 100 kilometers of a centralized landing site. ROIs are areas that are relevant for scientific investigation and/or development/maturation of capabilities and resources necessary for a sustainable human presence. The EZ also contains a landing site and a habitation site that will be used by multiple human crews during missions to explore and utilize the ROIs within the EZ. These candidate EZs will be used by NASA as part of a multi-year process of determining where and how humans could explore Mars. In the near term this process includes: (a) identifying locations that would maximize the potential science return from future human exploration missions, (b) identifying locations with the potential for resources required to support humans, (c) developing concepts and engineering systems needed by future human crews to conduct operations within an EZ, and (d) identifying key characteristics of the proposed candidate EZs that cannot be evaluated using existing data sets, thus helping to define precursor measurements needed in advance of human missions. Existing and future robotic spacecraft will be tasked to gather data from specific Mars surface sites within the representative EZs to support these NASA activities. The proposed paper will describe NASA's initial steps for identifying and evaluating candidate EZs and ROIs. This includes plans for the "First Landing Site/Exploration Zone Workshop for Human Missions to the Surface of Mars" to be held in October 2015 at which proposals for EZs and ROIs will be presented and discussed. It will also include a discussion of how these considerations are (or will be) taken into account as future robotic Mars missions are

  4. Surface Landing Site Weather Analysis for Constellation Program

    NASA Technical Reports Server (NTRS)

    Altino, Karen M.; Burns, K. Lee

    2008-01-01

    Weather information is an important asset for NASA's Constellation Program in developing the next generation space transportation system to fly to the International Space Station, the Moon and, eventually, to Mars. Weather conditions can affect vehicle safety and performance during multiple mission phases ranging from pre-launch ground processing to landing and recovery operations, including all potential abort scenarios. Meteorological analysis is an important contributor, not only to the development and verification of system design requirements but also to mission planning and active ground operations. Of particular interest are the surface atmospheric conditions at both nominal and abort landing sites for the manned Orion capsule. Weather parameters such as wind, rain, and fog all play critical roles in the safe landing of the vehicle and subsequent crew and vehicle recovery. The Marshall Space Flight Center Natural Environments Branch has been tasked by the Constellation Program with defining the natural environments at potential landing zones. Climatological time series of operational surface weather observations are used to calculate probabilities of occurrence of various sets of hypothetical vehicle constraint thresholds, Data are available for numerous geographical locations such that statistical analysis can be performed for single sites as well as multiple-site network configurations. Results provide statistical descriptions of how often certain weather conditions are observed at the site(s) and the percentage that specified criteria thresholds are matched or exceeded. Outputs are tabulated by month and hour of day to show both seasonal and diurnal variation. This paper will describe the methodology used for data collection and quality control, detail the types of analyses performed, and provide a sample of the results that can be obtained,

  5. Single-site surface-enhanced Raman scattering beyond spectroscopy

    NASA Astrophysics Data System (ADS)

    Takase, Mai; Yasuda, Satoshi; Murakoshi, Kei

    2016-04-01

    Recent progress in the observation of surface-enhanced Raman scattering (SERS) is reviewed to examine the possibility of finding a novel route for the effective photoexcitation of materials. The importance of well-controlled SERS experiments on a single molecule at a single site is discussed based on the difference in the information obtained from ensemble SERS measurements using multiple active sites with an uncontrolled number of molecules. A single-molecule SERS observation performed at a mechanically controllable breaking junction with a simultaneous conductivity measurement provides clear evidence of the drastic changes both in the intensity and in the Raman mode selectivity of the electromagnetic field generated by localized surface plasmon resonance. Careful control of the field at a few-nanometer-wide gap of a metal nanodimer results in the modification of the selection rule of electronic excitation of an isolated single-walled carbon nanotube. The examples shown in this review suggest that a single-site SERS observation could be used as a novel tool to find, develop, and implement applications of plasmon-induced photoexcitation of materials.

  6. Oxidative dissolution of pyrite surfaces by hexavalent chromium: Surface site saturation and surface renewal

    NASA Astrophysics Data System (ADS)

    Graham, Andrew M.; Bouwer, Edward J.

    2012-04-01

    In-situ reduction of toxic Cr(VI) to nontoxic Cr(III) represents an important natural attenuation process for Cr(VI)-impacted environments. This study investigates the stoichiometry and kinetics of Cr(VI) reduction by pyrite, a reduced iron-sulfur mineral ubiquitous in recent estuarine and marine sediments. Pyrite suspensions at surface loadings of 0.28-2.10 m2/L (typical of estuarine or marine sediments) were capable of completely reducing 7-120 μM Cr(VI) on the timescale of minutes to days, with the time to reaction completion decreasing with increasing pyrite loading, decreasing initial Cr(VI) concentration, and decreasing suspension pH. Analysis of metal species (Cr and Fe) and sulfur species in solution and at the mineral surface indicated that Cr(VI) oxidatively dissolved the pyrite surface, releasing ferrous iron and sulfate into solution as the reaction progressed. Surface disulfide groups were postulated as the Cr(VI)-reactive surface entity. Net production or consumption of aqueous Fe(II) was shown to depend upon the relative rates of proton-promoted Fe(II) release, Fe(II) release due to oxidative dissolution of pyrite in the presence of Cr(VI), and Fe(II) consumption due to homogeneous reaction with Cr(VI). Kinetics of Cr(VI) reduction by pyrite displayed a biphasic pattern, and the time to reaction completion increased dramatically with increasing initial Cr(VI) concentration. Rapid Cr(VI) removal occurred early in the reaction progress, attributable to Cr(VI) loss under an adsorption-limited regime. Slow, approximately zero-order, Cr(VI) removal occurred over the bulk of the time courses, and corresponded to Cr(VI) removal under surface site saturation conditions. Stoichiometric Cr(VI) reduction was able to proceed under surface site limited conditions owing to regeneration of reactive surface sites following desorption/dissolution of oxidized surface products, as demonstrated in repeat Cr(VI)-spiking experiments. The role of surface passivation was

  7. The active sites of supported silver particle catalysts in formaldehyde oxidation.

    PubMed

    Chen, Yaxin; Huang, Zhiwei; Zhou, Meijuan; Hu, Pingping; Du, Chengtian; Kong, Lingdong; Chen, Jianmin; Tang, Xingfu

    2016-08-01

    Surface silver atoms with upshifted d-orbitals are identified as the catalytically active sites in formaldehyde oxidation by correlating their activity with the number of surface silver atoms, and the degree of the d-orbital upshift governs the catalytic performance of the active sites. PMID:27406403

  8. Low dielectric response in enzyme active site

    PubMed Central

    Mertz, Edward L.; Krishtalik, Lev I.

    2000-01-01

    The kinetics of charge transfer depend crucially on the dielectric reorganization of the medium. In enzymatic reactions that involve charge transfer, atomic dielectric response of the active site and of its surroundings determines the efficiency of the protein as a catalyst. We report direct spectroscopic measurements of the reorganization energy associated with the dielectric response in the active site of α-chymotrypsin. A chromophoric inhibitor of the enzyme is used as a spectroscopic probe. We find that water strongly affects the dielectric reorganization in the active site of the enzyme in solution. The reorganization energy of the protein matrix in the vicinity of the active site is similar to that of low-polarity solvents. Surprisingly, water exhibits an anomalously high dielectric response that cannot be described in terms of the dielectric continuum theory. As a result, sequestering the active site from the aqueous environment inside low-dielectric enzyme body dramatically reduces the dielectric reorganization. This reduction is particularly important for controlling the rate of enzymatic reactions. PMID:10681440

  9. GIS Surface Effects Map Archive, Nevada Test Site, Nevada

    SciTech Connect

    Grasso, Dennis N.

    2003-08-28

    The GIS Surface Effects Map Archive contains a comprehensive collection of maps showing the surface effects produced by underground nuclear testing at the Nevada Test Site. From 1951 to 1992, scientists with the U.S. Geological Survey and agencies of the U.S. Department of Energy used field and aerial-photo mapping techniques to painstakingly map such surface effects as collapse sinks, craters, cracks, fractures, faults, and pressure ridges. Shortly after each test, a complex surface effects map was produced. Of the more than 920 underground detonations conducted at the Nevada Test Site, 688 were mapped for surface effects. This archive preserves these original maps in digital format. A Geographic Information System (GIS) was used to digitally reproduce each original, hand-drawn surface effects map and to assemble these maps into the digital data sets of this archive. The archive was designed to allow easy access to the maps, while preserving the original maps for perpetuity. Users can query the detonation sites database; prepare, view, and print individual or composite maps; and perform various types of scientific analysis and management tasks. Spatial analyses and queries can be performed on detonation sites and related surface effects in conjunction with other chronological, geographical, geological, or hydrological information via links to external maps and databases. This browser interface provides information about the archive, the history of surface effects mapping at the Nevada Test Site, the methods used to produce the digital surface effects maps, and links to published reports, data tables, and maps. Location maps show testing areas, operational areas, and detonation sites. Demonstration maps illustrate the methods used to produce the digital surface effects maps and exhibit some of the characteristics and uses for these data. Use the links below to view and print individual surface effects maps, retrieve information about the detonations and types of

  10. Benzene derivatives adsorbed to the Ag(111) surface: Binding sites and electronic structure

    SciTech Connect

    Miller, Daniel P.; Tymińska, Nina; Zurek, Eva; Simpson, Scott

    2015-03-14

    Dispersion corrected Density Functional Theory calculations were employed to study the adsorption of benzenes derivatized with functional groups encompassing a large region of the activated/deactivated spectrum to the Ag(111) surface. Benzenes substituted with weak activating or deactivating groups, such as methyl and fluoro, do not have a strong preference for adsorbing to a particular site on the substrate, with the corrugations in the potential energy surface being similar to those of benzene. Strong activating (N(CH{sub 3}){sub 2}) and deactivating (NO{sub 2}) groups, on the other hand, possess a distinct site preference. The nitrogen in the former prefers to lie above a silver atom (top site), but in the latter a hollow hexagonal-closed-packed (H{sub hcp}) site of the Ag(111) surface is favored instead. Benzenes derivatized with classic activating groups donate electron density from their highest occupied molecular orbital to the surface, and those functionalized with deactivating groups withdraw electron density from the surface into orbitals that are unoccupied in the gas phase. For benzenes functionalized with two substituents, the groups that are strongly activating or deactivating control the site preference and the other groups assume sites that are, to a large degree, dictated by their positions on the benzene ring. The relative stabilities of the ortho, meta, and para positional isomers of disubstituted benzenes can, in some cases, be modified by adsorption to the surface.

  11. Chemisorption and diffusion of hydrogen on surface and subsurface sites of flat and stepped nickel surfaces

    NASA Astrophysics Data System (ADS)

    Bhatia, Bhawna; Sholl, David S.

    2005-05-01

    Plane-wave density functional theory calculations were performed to investigate the binding and diffusion of hydrogen on three flat Ni surfaces, Ni(100), Ni(110), and Ni(111), and two stepped Ni surfaces, Ni(210) and Ni(531). On each surface, the favored adsorption sites were identified by considering the energy and stability of various binding sites and zero-point energy corrections were computed. Binding energies are compared with experimental and theoretical results from the literature. Good agreement with experimental and previous theoretical data is found. At surface coverages where adsorbate-adsorbate interactions are relatively weak, the binding energy of H is similar on the five Ni surfaces studied. Favorable binding energies are observed for stable surface sites, while subsurface sites have unfavorable values relative to the gas phase molecular hydrogen. Minimum energy paths for hydrogen diffusion on Ni surfaces and into subsurface sites were constructed.

  12. Systemic Loxoscelism Confirmation by Bite-Site Skin Surface ELISA

    PubMed Central

    Wasserman, Gary S.; Calcara, David A.; Green, Jonathan A.; Stoecker, William V.; Larkin, Karen

    2011-01-01

    We report here a case of systemic loxoscelism, confirmed by bite-site skin surface swab. Features of systemic loxoscelism present in this case included debilitating symptoms, a classic local bite-site reaction, hemolysis causing loss of approximately 15% of the blood volume within 72 hours, and a symptomatic exanthem. A skin surface ELISA test was used to confirm the presence of venom. This test enables confirmation of cases of loxoscelism for which no spider is found. PMID:20063514

  13. Mars Polar Lander Site Surface Details

    NASA Technical Reports Server (NTRS)

    1999-01-01

    This picture is an enlargement of a portion of a MOC image taken in late July 1999, showing the onset of defrosting of the seasonal carbon dioxide frost cap (small, occasionally fan-shaped dark spots seen throughout this image). Two craters are seen in this image, a very rare occurrence on the south polar layered deposits. Shown for comparison at the same scale is a picture of Jack Murphy (now Qualcomm) Stadium in San Diego, California. Clearly visible in the inset is the baseball diamond and pitcher's mound; less clear but certainly visible are a number of automobiles (small light dots) in the parking lot west (to the left) of the stadium. The elevation of the sun in the Mars image is about 10o; the sunlight is coming from the bottom (north) in this image. The shadow of the rims of the craters can be used to determine their depths. The smaller crater in the bottom right corner is about 60 m (197 feet) across and 7 m (23 feet) deep; the large crater just below the inset is 175 m (574 feet) across and 17 m (56 feet) deep. Similar calculations for other features in the images indicate that much of the surface is smooth and flat. Relief is typically much less than 1-2 meters (3-7 feet) in height over areas of 10-15 meters across (33-49 feet).

    Malin Space Science Systems and the California Institute of Technology built the MOC using spare hardware from the Mars Observer mission. MSSS operates the camera from its facilities in San Diego, CA. The Jet Propulsion Laboratory's Mars Surveyor Operations Project operates the Mars Global Surveyor spacecraft with its industrial partner, Lockheed Martin Astronautics, from facilities in Pasadena, CA and Denver, CO.

  14. Identification of Ice Nucleation Active Sites on Silicate Dust Particles

    NASA Astrophysics Data System (ADS)

    Zolles, Tobias; Burkart, Julia; Häusler, Thomas; Pummer, Bernhard; Hitzenberger, Regina; Grothe, Hinrich

    2015-04-01

    Mineral dusts originating from Earth's crust are known to be important atmospheric ice nuclei. In agreement with earlier studies, feldspar was found as the most active of the tested natural mineral dusts [1-3]. Nevertheless, among those structures K-feldspar showed by far the highest ice nucleation activity. In this study, the reasons for its activity and the difference in the activity of the different feldspars were investigated in closer details. Conclusions are drawn from scanning electron microscopy, X-ray powder diffraction, infrared spectroscopy, and oil-immersion freezing experiments. We give a potential explanation of the increased ice nucleation activity of K-feldspar. The ice nucleating sites are very much dependent on the alkali ion present by altering the water structure and the feldspar surface. The higher activity of K-feldspar can be attributed to the presence of potassium ions on the surface and surface bilayer. The alkali-ions have different hydration shells and thus an influence on the ice nucleation activity of feldspar. Chaotropic behavior of Calcium and Sodium ions are lowering the ice nucleation potential of the other feldspars, while kosmotropic Potassium has a neutral or even positive effect. Furthermore we investigated the influence of milling onto the ice nucleation of quartz particles. The ice nucleation activity can be increased by mechanical milling, by introducing more molecular, nucleation active defects to the particle surface. This effect is larger than expected by plane surface increase. [1] Atkinson et al. The Importance of Feldspar for Ice Nucleation by Mineral Dust in Mixed-Phase Clouds. Nature 2013, 498, 355-358. [2] Yakobi-Hancock et al.. Feldspar Minerals as Efficient Deposition Ice Nuclei. Atmos. Chem. Phys. 2013, 13, 11175-11185. [3] Zolles et al. Identification of Ice Nucleation Active Sites on Feldspar Dust Particles. J. Phys. Chem. A 2015 accepted.

  15. Resonant active sites in catalytic ammonia synthesis: A structural model

    NASA Astrophysics Data System (ADS)

    Cholach, Alexander R.; Bryliakova, Anna A.; Matveev, Andrey V.; Bulgakov, Nikolai N.

    2016-03-01

    Adsorption sites Mn consisted of n adjacent atoms M, each bound to the adsorbed species, are considered within a realistic model. The sum of bonds Σ lost by atoms in a site in comparison with the bulk atoms was used for evaluation of the local surface imperfection, while the reaction enthalpy at that site was used as a measure of activity. The comparative study of Mn sites (n = 1-5) at basal planes of Pt, Rh, Ir, Fe, Re and Ru with respect to heat of N2 dissociative adsorption QN and heat of Nad + Had → NHad reaction QNH was performed using semi-empirical calculations. Linear QN(Σ) increase and QNH(Σ) decrease allowed to specify the resonant Σ for each surface in catalytic ammonia synthesis at equilibrium Nad coverage. Optimal Σ are realizable for Ru2, Re2 and Ir4 only, whereas other centers meet steric inhibition or unreal crystal structure. Relative activity of the most active sites in proportion 5.0 × 10- 5: 4.5 × 10- 3: 1: 2.5: 3.0: 1080: 2270 for a sequence of Pt4, Rh4, Fe4(fcc), Ir4, Fe2-5(bcc), Ru2, Re2, respectively, is in agreement with relevant experimental data. Similar approach can be applied to other adsorption or catalytic processes exhibiting structure sensitivity.

  16. Active site specificity of plasmepsin II.

    PubMed Central

    Westling, J.; Cipullo, P.; Hung, S. H.; Saft, H.; Dame, J. B.; Dunn, B. M.

    1999-01-01

    Members of the aspartic proteinase family of enzymes have very similar three-dimensional structures and catalytic mechanisms. Each, however, has unique substrate specificity. These distinctions arise from variations in amino acid residues that line the active site subsites and interact with the side chains of the amino acids of the peptides that bind to the active site. To understand the unique binding preferences of plasmepsin II, an enzyme of the aspartic proteinase class from the malaria parasite, Plasmodium falciparum, chromogenic octapeptides having systematic substitutions at various positions in the sequence were analyzed. This enabled the design of new, improved substrates for this enzyme (Lys-Pro-Ile-Leu-Phe*Nph-Ala/Glu-Leu-Lys, where * indicates the cleavage point). Additionally, the crystal structure of plasmepsin II was analyzed to explain the binding characteristics. Specific amino acids (Met13, Ser77, and Ile287) that were suspected of contributing to active site binding and specificity were chosen for site-directed mutagenesis experiments. The Met13Glu and Ile287Glu single mutants and the Met13Glu/Ile287Glu double mutant gain the ability to cleave substrates containing Lys residues. PMID:10548045

  17. Do surface active parenteral formulations cause inflammation?

    PubMed

    Söderberg, Lars; Engblom, Johan; Lanbeck, Peter; Wahlgren, Marie

    2015-04-30

    Local irritation and inflammation at the site of administration are a common side effect following administration of parenteral formulations. Biological effects of surface (interfacial) activity in solutions are less well investigated than effects caused by other physico-chemical parameters such as pH and osmolality. The interfacial activity in different systems, including human plasma, typical amphiphilic substances with fundamental biological relevance such as free fatty acids, anesthetic depot formulations and six different antibiotics was measured. The relative interfacial pressure, and/or concentration of active substance, required to obtain 50% of the maximal attainable effect in terms of interfacial pressure were calculated. The aim was to test the hypothesis that these parameters would allow comparison to biological effects reported in in vivo studies on the investigated substances. The highest interfacial activity was found in a triglyceride/plasma system. Among the antibiotic tested, the highest interfacial activities were found in erythromycin and dicloxacillin, which is in accordance with previous clinical findings of a high tendency of infusion phlebitis and cell toxicity. Independently of investigated system, biological effects were minimal below a 15% relative increase of interfacial activity. Above 35-45% the effects were severe. Interfacial activity in parenteral formulations may well cause damages to tissues followed by inflammation. PMID:25708007

  18. Artist's rendering of Lunar Surface Activities

    NASA Technical Reports Server (NTRS)

    1969-01-01

    Lunar Surface Activities: Instruments erected on the surface are a seismometer to record any subsurface activity of the Moon, a laser reflector, a solar wind collector, and possibly an antenna for improving communications and television picture transmission.

  19. 43 CFR 3271.12 - What do I need to start preliminary site investigations that may disturb the surface?

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... investigations that may disturb the surface? 3271.12 Section 3271.12 Public Lands: Interior Regulations Relating... start preliminary site investigations that may disturb the surface? (a) You must: (1) Fully describe... not begin the site investigation or surface disturbing activity until BLM approves your Sundry...

  20. 43 CFR 3271.12 - What do I need to start preliminary site investigations that may disturb the surface?

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... investigations that may disturb the surface? 3271.12 Section 3271.12 Public Lands: Interior Regulations Relating... start preliminary site investigations that may disturb the surface? (a) You must: (1) Fully describe... not begin the site investigation or surface disturbing activity until BLM approves your Sundry...

  1. 43 CFR 3271.12 - What do I need to start preliminary site investigations that may disturb the surface?

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... investigations that may disturb the surface? 3271.12 Section 3271.12 Public Lands: Interior Regulations Relating... start preliminary site investigations that may disturb the surface? (a) You must: (1) Fully describe... not begin the site investigation or surface disturbing activity until BLM approves your Sundry...

  2. 43 CFR 3271.12 - What do I need to start preliminary site investigations that may disturb the surface?

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... investigations that may disturb the surface? 3271.12 Section 3271.12 Public Lands: Interior Regulations Relating... start preliminary site investigations that may disturb the surface? (a) You must: (1) Fully describe... not begin the site investigation or surface disturbing activity until BLM approves your Sundry...

  3. Molecular Imprint of Enzyme Active Site by Camel Nanobodies

    PubMed Central

    Li, Jiang-Wei; Xia, Lijie; Su, Youhong; Liu, Hongchun; Xia, Xueqing; Lu, Qinxia; Yang, Chunjin; Reheman, Kalbinur

    2012-01-01

    Screening of inhibitory Ab1 antibodies is a critical step for producing catalytic antibodies in the anti-idiotypic approach. However, the incompatible surface of the active site of the enzyme and the antigen-binding site of heterotetrameric conventional antibodies become the limiting step. Because camelid-derived nanobodies possess the potential to preferentially bind to the active site of enzymes due to their small size and long CDR3, we have developed a novel approach to produce antibodies with alliinase activities by exploiting the molecular mimicry of camel nanobodies. By screening the camelid-derived variable region of the heavy chain cDNA phage display library with alliinase, we obtained an inhibitory nanobody VHHA4 that recognizes the active site. Further screening with VHHA4 from the same variable domain of the heavy chain of a heavy-chain antibody library led to a higher incidence of anti-idiotypic Ab2 abzymes with alliinase activities. One of the abzymes, VHHC10, showed the highest activity that can be inhibited by Ab1 VHHA4 and alliinase competitive inhibitor penicillamine and significantly suppressed the B16 tumor cell growth in the presence of alliin in vitro. The results highlight the feasibility of producing abzymes via anti-idiotypic nanobody approach. PMID:22374998

  4. Corrosion Research And Web Site Activities

    NASA Technical Reports Server (NTRS)

    Heidersbach, Robert H.

    2001-01-01

    This report covers corrosion-related activities at the NASA Kennedy Space Center during the summer of 2000. The NASA Kennedy Space Center's corrosion web site, corrosion.ksc.nasa.gov, was updated with new information based on feedback over the past two years. The methodology for a two-year atmospheric exposure testing program to study the effectiveness of commercial chemicals sold for rinsing aircraft and other equipment was developed and some preliminary laboratory chemical analyses are presented.

  5. Corrosion Research and Web Site Activities

    NASA Technical Reports Server (NTRS)

    Heidersbach, Robert H.

    2002-01-01

    This report covers corrosion-related activities at the NASA Kennedy Space Center during the summer of 2000. The NASA Kennedy Space Center's corrosion web site, corrosion.ksc.nasa.gov, was updated with new information based on feedback over the past two years. The methodology for a two-year atmospheric exposure testing program to study the effectiveness of commercial chemicals sold for rinsing aircraft and other equipment was developed and some preliminary laboratory chemical analyses are presented.

  6. First principles characterization of silicate sites in clay surfaces.

    PubMed

    Alvim, Raphael S; Miranda, Caetano R

    2015-02-21

    Aluminosilicate clays like Montmorillonite (MMT) and Muscovite Mica (MT) have siloxane cavities on the basal plane. The hydroxyl groups localized in these cavities and van der Waals (vdW) forces contribute significantly to adsorption processes. However, the basal sites are found to be difficult to characterize experimentally. Here, (001) surfaces of MMT and MT clays were investigated using first-principles calculations to understand how these silicate surface sites are influenced by hydroxyl groups and the effective role of inner layer vdW interactions. Based on density-functional theory (DFT) within the generalized gradient approximation (GGA), different types of exchange-correlation functionals were tested to check the effect of vdW dispersion correction. Noncontact atomic force microscopy (nc-AFM), X-ray absorption spectroscopy (XAS) in the near-edge region and solid-state nuclear magnetic resonance (SS-NMR) spectroscopy were simulated. In both clays, the oxygen surface sites are directly affected by the intralayer interaction through hydroxyl groups. Our results indicated that the chemical environment of the hydroxyl groups is distinct in the MMT and MT structures. The vdW correction was essential for a better description of the surface oxygen sites and correctly describes the similarity between both clays. Particularly, the bulk apical oxygen sites in the MT structure are less influenced by vdW interaction. Compared to MMT, the silicon surface sites of MT are more sensitive to the intralayer changes in Si-Oapical-Al and with less effect of the hydroxyl groups. These results provide a clear understanding of influence of the siloxane cavity on the oxygen and silicon surface sites in aluminosilicates. PMID:25592132

  7. Control of Eolian soil erosion from waste site surface barriers

    SciTech Connect

    Ligotke, M.W.

    1994-11-01

    Physical models were tested in a wind tunnel to determine optimum surface-ravel admixtures for protecting silt-loam soil from erosion by, wind and saltating, sand stresses. The tests were performed to support the development of a natural-material surface barrier for and waste sites. Plans call for a 2-m deep silt-loam soil reservoir to retain infiltrating water from rainfall and snowmelt. The objective of the study was to develop a gravel admixture that would produce an erosion-resistant surface layer during, periods of extended dry climatic stress. Thus, tests were performed using simulated surfaces representing dry, unvegetated conditions present just after construction, after a wildfire, or during an extended drought. Surfaces were prepared using silt-loam soil mixed with various grades of sand and Travel. Wind-induced surface shear stresses were controlled over the test surfaces, as were saltating, sand mass flow rates and intensities. Tests were performed at wind speeds that approximated and exceeded local 100-year peak gust intensities. Surface armors produced by pea gravel admixtures were shown to provide the best protection from wind and saltating sand stresses. Compared with unprotected silt-loam surfaces, armored surfaces reduced erosion rates by more than 96%. Based in part on wind tunnel results, a pea gravel admixture of 15% will be added to the top 1 in of soil in a prototype barrier under construction in 1994. Field tests are planned at the prototype site to provide data for comparison with wind tunnel results.

  8. Protein Function Annotation By Local Binding Site Surface Similarity

    PubMed Central

    Spitzer, Russell; Cleves, Ann E.; Varela, Rocco; Jain, Ajay N.

    2013-01-01

    Hundreds of protein crystal structures exist for proteins whose function cannot be confidently determined from sequence similarity. Surflex-PSIM, a previously reported surface-based protein similarity algorithm, provides an alternative method for hypothesizing function for such proteins. The method now supports fully automatic binding site detection and is fast enough to screen comprehensive databases of protein binding sites. The binding site detection methodology was validated on apo/holo cognate protein pairs, correctly identifying 91% of ligand binding sites in holo structures and 88% in apo structures where corresponding sites existed. For correctly detected apo binding sites, the cognate holo site was the most similar binding site 87% of the time. PSIM was used to screen a set of proteins that had poorly characterized functions at the time of crystallization, but were later biochemically annotated. Using a fully automated protocol, this set of 8 proteins was screened against approximately 60,000 ligand binding sites from the PDB. PSIM correctly identified functional matches that pre-dated query protein biochemical annotation for five out of the eight query proteins. A panel of twelve currently unannotated proteins was also screened, resulting in a large number of statistically significant binding site matches, some of which suggest likely functions for the poorly characterized proteins. PMID:24166661

  9. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    PubMed Central

    Guo, Wei; Vlachos, Dionisios G.

    2015-01-01

    Ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material's structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N−H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design. PMID:26443525

  10. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    SciTech Connect

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-H bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.

  11. The impact of the competitive adsorption of ions at surface sites on surface free energies and surface forces

    NASA Astrophysics Data System (ADS)

    Parsons, Drew F.; Salis, Andrea

    2015-04-01

    The relationship between surface charge and surface potential at the solid-liquid interface is often determined by a charge regulation process, the chemisorption of a potential determining ion such as H+. A subtle ion-specific effect can be observed when other ions compete with the primary potential determining ion to bind to a surface site. Site competition may involve alternative ions competing for a first binding site, e.g., metals ions competing with H+ to bind to a negatively charged oxide or carboxyl site. Second-binding sites with site competition may also be found, including amphoteric OH2+ sites, or anion binding to amine groups. In this work, a general theoretical model is developed to describe the competitive adsorption of ions at surface sites. Applied to the calculation of forces, the theory predicts a 20% increase in repulsion between titania surfaces in 1 mM NaCl, and a 25% reduction in repulsion between silica surfaces in 0.1M NaCl compared to calculations neglecting ion site competition.

  12. The impact of the competitive adsorption of ions at surface sites on surface free energies and surface forces.

    PubMed

    Parsons, Drew F; Salis, Andrea

    2015-04-01

    The relationship between surface charge and surface potential at the solid-liquid interface is often determined by a charge regulation process, the chemisorption of a potential determining ion such as H(+). A subtle ion-specific effect can be observed when other ions compete with the primary potential determining ion to bind to a surface site. Site competition may involve alternative ions competing for a first binding site, e.g., metals ions competing with H(+) to bind to a negatively charged oxide or carboxyl site. Second-binding sites with site competition may also be found, including amphoteric OH2 (+) sites, or anion binding to amine groups. In this work, a general theoretical model is developed to describe the competitive adsorption of ions at surface sites. Applied to the calculation of forces, the theory predicts a 20% increase in repulsion between titania surfaces in 1 mM NaCl, and a 25% reduction in repulsion between silica surfaces in 0.1M NaCl compared to calculations neglecting ion site competition. PMID:25854258

  13. Binding of oxygen on vacuum fractured pyrite surfaces: Reactivity of iron and sulfur surface sites

    NASA Astrophysics Data System (ADS)

    Berlich, A. G.; Nesbitt, H. W.; Bancroft, G. M.; Szargan, R.

    2013-05-01

    Synchrotron radiation excited photoelectron spectroscopy (SXPS) has been used to study the interaction of oxygen with vacuum fractured pyrite surfaces. Especially valence band spectra obtained with 30 eV photon energy were analyzed to provide a mechanism of the incipient steps of pyrite oxidation. These spectra are far more sensitive to the oxidation than sulfur or iron core level spectra. It is shown that oxygen is adsorbed on Fe(II) surface sites restoring the octahedral coordination of the Fe(II) sites. This process leads to the removal of two surface states in the valence band which are located at the low and high binding energy sides of the outer valence band, respectively. The existence of these surface states which have been proposed by calculations is experimentally proven. Furthermore, it is shown, that the sulfur sites are more reactive than expected. Sulfite like species are already formed after the lowest oxygen exposure of 10 L. This oxidation occurs at sulfur sites neighboring the Fe(II) surface sites. Oxidation of the S2 - surface sites which were considered as the most reactive species in former studies is second. No iron(III) oxides are formed during oxygen exposure, supporting the assumption that water plays an important role in the oxidation mechanism of pyrite surfaces.

  14. Surface Landing Site Weather Analysis for NASA's Constellation Program

    NASA Technical Reports Server (NTRS)

    Altino, Karen M.; Burns, K. L.

    2008-01-01

    Weather information is an important asset for NASA's Constellation Program in developing the next generation space transportation system to fly to the International Space Station, the Moon and, eventually, to Mars. Weather conditions can affect vehicle safety and performance during multiple mission phases ranging from pre-launch ground processing of the Ares vehicles to landing and recovery operations, including all potential abort scenarios. Meteorological analysis is art important contributor, not only to the development and verification of system design requirements but also to mission planning and active ground operations. Of particular interest are the surface weather conditions at both nominal and abort landing sites for the manned Orion capsule. Weather parameters such as wind, rain, and fog all play critical roles in the safe landing of the vehicle and subsequent crew and vehicle recovery. The Marshall Space Flight Center (MSFC) Natural Environments Branch has been tasked by the Constellation Program with defining the natural environments at potential landing zones. This paper wiI1 describe the methodology used for data collection and quality control, detail the types of analyses performed, and provide a sample of the results that cab be obtained.

  15. Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

    SciTech Connect

    Bruhn, Thomas; Fimland, Bjørn-Ove; Vogt, Patrick

    2015-03-14

    We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. On the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces.

  16. Active site of ribulosebisphosphate carboxylase/oxygenase

    SciTech Connect

    Hartman, F.C.; Stringer, C.D.; Milanez, S.; Lee, E.H.

    1985-01-01

    Previous affinity labeling studies and comparative sequence analyses have identified two different lysines at the active site of ribulosebisphosphate carboxylase/oxygenase and have suggested their essentiality to function. The essential lysines occupy positions 166 and 329 in the Rhodospirillum rubrum enzyme and positions 175 and 334 in the spinach enzyme. Based on the pH-dependencies of inactivations of the two enzymes by trinitrobenzene sulfonate, Lys-166 (R. rubrum enzyme) exhibits a pK/sub a/ of 7.9 and Lys-334 (spinach enzyme) exhibits a pK/sub a/ of 9.0. These low pK/sub a/ values as well as the enhanced nucleophilicities of the lysyl residues argue that both are important to catalysis rather than to substrate binding. Lys-166 may correspond to the essential base that initiates catalysis and that displays a pK/sub a/ of 7.5 in the pH-curve for V/sub max//K/sub m/. Cross-linking experiments with 4,4'-diisothiocyano-2,2'-disulfonate stilbene demonstrate that the two active-site lysines are within 12 A. 50 refs., 7 figs., 1 tab.

  17. Site-directed, on-surface assembly of DNA nanostructures.

    PubMed

    Meyer, Rebecca; Saccà, Barbara; Niemeyer, Christof M

    2015-10-01

    Two-dimensional DNA lattices have been assembled from DNA double-crossover (DX) motifs on DNA-encoded surfaces in a site-specific manner. The lattices contained two types of single-stranded protruding arms pointing into opposite directions of the plane. One type of these protruding arms served to anchor the DNA lattice on the solid support through specific hybridization with surface-bound, complementary capture oligomers. The other type of arms allowed for further attachment of DNA-tethered probe molecules on the opposite side of the lattices exposed to the solution. Site-specific lattice assembly and attachment of fluorophore-labeled oligonucleotides and DNA-protein conjugates was demonstrated using DNA microarrays on flat, transparent mica substrates. Owing to their programmable orientation and addressability over a broad dynamic range from the nanometer to the millimeter length scale, such supramolecular architecture might be used for presenting biomolecules on surfaces, for instance, in biosensor applications. PMID:26306556

  18. Modeling Near-Surface Temperatures at Martian Landing Sites

    NASA Technical Reports Server (NTRS)

    Martin, T. Z.; Bridges, N. T.; Murphy, J. R.

    2003-01-01

    We have developed a process for deriving near-surface (approx. 1m) temperatures for potential landing sites, based on observational parameters from MGS TES, Odyssey THEMIS, and a boundary layer model developed by Murphy for fitting Pathfinder meteorological measurements. Minimum nighttime temperatures at the MER landing sites can limit power available, and thus mission lifetime. Temperatures are derived based on thermal inertia, albedo, and opacity estimated for the Hematite site in Sinus Meridiani, using predictions of 1-m air temperatures from a one-dimensional atmospheric model. The Hematite site shows 9 % probability of landing at a location with nighttime temperatures below the 97 C value considered to be a practical limit for operations.

  19. Active Sites Environmental Monitoring Program: Program plan

    SciTech Connect

    Ashwood, T.L.; Wickliff, D.S.; Morrissey, C.M.

    1992-02-01

    The Active Sites Environmental Monitoring Program (ASEMP), initiated in 1989, provides early detection and performance monitoring of transuranic (TRU) waste and active low-level waste (LLW) facilities at Oak Ridge National Laboratory (ORNL) in accordance with US Department of Energy (DOE) Order 5820.2A. Active LLW facilities in Solid Waste Storage Area (SWSA) 6 include Tumulus I and Tumulus II, the Interim Waste Management Facility (IWMF), LLW silos, high-range wells, asbestos silos, and fissile wells. The tumulus pads and IWMF are aboveground, high-strength concrete pads on which concrete vaults containing metal boxes of LLW are placed; the void space between the boxes and vaults is filled with grout. Eventually, these pads and vaults will be covered by an engineered multilayered cap. All other LLW facilities in SWSA 6 are below ground. In addition, this plan includes monitoring of the Hillcut Disposal Test Facility (HDTF) in SWSA 6, even though this facility was completed prior to the data of the DOE order. In SWSA 5 North, the TRU facilities include below-grade engineered caves, high-range wells, and unlined trenches. All samples from SWSA 6 are screened for alpha and beta activity, counted for gamma-emitting isotopes, and analyzed for tritium. In addition to these analytes, samples from SWSA 5 North are analyzed for specific transuranic elements.

  20. Prediction of allosteric sites on protein surfaces with an elastic-network-model-based thermodynamic method

    NASA Astrophysics Data System (ADS)

    Su, Ji Guo; Qi, Li Sheng; Li, Chun Hua; Zhu, Yan Ying; Du, Hui Jing; Hou, Yan Xue; Hao, Rui; Wang, Ji Hua

    2014-08-01

    Allostery is a rapid and efficient way in many biological processes to regulate protein functions, where binding of an effector at the allosteric site alters the activity and function at a distant active site. Allosteric regulation of protein biological functions provides a promising strategy for novel drug design. However, how to effectively identify the allosteric sites remains one of the major challenges for allosteric drug design. In the present work, a thermodynamic method based on the elastic network model was proposed to predict the allosteric sites on the protein surface. In our method, the thermodynamic coupling between the allosteric and active sites was considered, and then the allosteric sites were identified as those where the binding of an effector molecule induces a large change in the binding free energy of the protein with its ligand. Using the proposed method, two proteins, i.e., the 70 kD heat shock protein (Hsp70) and GluA2 alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptor, were studied and the allosteric sites on the protein surface were successfully identified. The predicted results are consistent with the available experimental data, which indicates that our method is a simple yet effective approach for the identification of allosteric sites on proteins.

  1. Prediction of allosteric sites on protein surfaces with an elastic-network-model-based thermodynamic method.

    PubMed

    Su, Ji Guo; Qi, Li Sheng; Li, Chun Hua; Zhu, Yan Ying; Du, Hui Jing; Hou, Yan Xue; Hao, Rui; Wang, Ji Hua

    2014-08-01

    Allostery is a rapid and efficient way in many biological processes to regulate protein functions, where binding of an effector at the allosteric site alters the activity and function at a distant active site. Allosteric regulation of protein biological functions provides a promising strategy for novel drug design. However, how to effectively identify the allosteric sites remains one of the major challenges for allosteric drug design. In the present work, a thermodynamic method based on the elastic network model was proposed to predict the allosteric sites on the protein surface. In our method, the thermodynamic coupling between the allosteric and active sites was considered, and then the allosteric sites were identified as those where the binding of an effector molecule induces a large change in the binding free energy of the protein with its ligand. Using the proposed method, two proteins, i.e., the 70 kD heat shock protein (Hsp70) and GluA2 alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptor, were studied and the allosteric sites on the protein surface were successfully identified. The predicted results are consistent with the available experimental data, which indicates that our method is a simple yet effective approach for the identification of allosteric sites on proteins. PMID:25215770

  2. Surface sites and unrelaxed surface energies of tetrahedral silica polymorphs and silicate

    NASA Astrophysics Data System (ADS)

    Murashov, Vladimir V.; Demchuk, Eugene

    2005-12-01

    Surface properties of respirable silica, which represents a major occupational safety concern, were investigated computationally, and a model for quantitative characterization of crystalline silica surface sites was developed. It was found that the surface energy of crystalline solids, such as silica and silicates, can be calculated as a product of the surface site density and site energy. The energies of sites formed by faceting tetrahedral silica polymorphs and aluminosilicate were determined by parametric fitting ab initio surface energies to site densities. Boltzmann's statistics was used to describe the distribution of faces as an exponential function of unrelaxed surface energy in the comminuted crystalline solids. Using these findings, crystallographic face distributions on fractured quartz, coesite, tridymite, and cristobalite were derived and average silanol hydroxyl densities in fractured particulate of these materials were estimated as 0.070, 0.059, 0.058, and 0.055 Å -2, respectively. The proposed method of quantitative characterization of the surface bridges the gap between microscopic simulations and measurable observables, such as cytotoxicity of respirable silica.

  3. Ozone measurements from a global network of surface sites

    NASA Technical Reports Server (NTRS)

    Oltmans, Samuel J.; Levy, Hiram, II

    1994-01-01

    From a network of surface ozone monitoring sites distributed primarily over the Atlantic and Pacific Oceans, the seasonal, day-to-day, and diurnal patterns are delineated. At most of the NH (Northern Hemisphere) sites there is a spring maximum and late summer or autumn minimum. At Barrow, AK (70 deg N) and Barbados (14 deg N), however, there is a winter maximum, but the mechanisms producing the maximum are quite different. All the sites in the SH (Southern Hemisphere) show winter maxima and summer minima. At the subtropical and tropical sites, there are large day-to-day variations that reflect the changes in flow patterns. Air of tropical origin has much lower ozone concentrations than air from higher latitudes. At the two tropical sites (Barbados and Samoa), there is a marked diurnal ozone variation with highest amounts in the early morning and lowest values in the afternoon. At four of the locations (Barrow, AK; Mauna Loa, HI; American Samoa; and South Pole), there are 15- through 20-year records which allow us to look at longer term changes. At Barrow there has been a large summer increase over the 20 years of measurements. At South Pole, on the other hand, summer decreases have led to an overall decline in surface ozone amounts.

  4. Surface soil variability and stratigraphy at the Apollo 16 site

    NASA Technical Reports Server (NTRS)

    Mitchell, J. K.; Houston, W. N.; Carrier, W. D., III; Costes, N. C.; Scott, R. F.

    1973-01-01

    The results of penetration tests, analyses of footprint and Lunar Roving Vehicle track depths, and core tube sample data have been used to deduce details of near-surface stratigraphy (to depths of several tens of cm) and lateral variability in soil conditions. Local variations (meter scale) in penetration resistance and porosity may be large, and soil stratigraphy may be complex. Since average properties are about the same at all sites, these variations probably reflect individual cratering and depositional events. These local variations cannot be anticipated on the basis of surface appearance or behavior.

  5. Direct epoxidation of propylene over stabilized Cu(+) surface sites on titanium-modified Cu2O.

    PubMed

    Yang, Xiaofang; Kattel, Shyam; Xiong, Ke; Mudiyanselage, Kumudu; Rykov, Sergei; Senanayake, Sanjaya D; Rodriguez, José A; Liu, Ping; Stacchiola, Dario J; Chen, Jingguang G

    2015-10-01

    Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate that by generating highly dispersed and stabilized Cu(+) active sites in a TiCuOx mixed oxide the epoxidation selectivity can be tuned. The TiCuOx surface anchors the key surface intermediate, an oxametallacycle, leading to higher selectivity for epoxidation of propylene. PMID:26215635

  6. Direct Epoxidation of Propylene over Stabilized Cu+ Surface Sites on Ti Modified Cu2O

    DOE PAGESBeta

    Yang, X.; Kattel, S.; Xiong, K.; Mudiyanselage, K.; Rykov, S.; Senanayake, S. D.; Rodriguez, J. A.; Liu, P.; Stacchiola, D. J.; Chen, J. G.

    2015-07-17

    Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu+ active sites in a TiCuOx mixed oxide. The TiCuOx surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

  7. FINAL CLOSURE PLAN SURFACE IMPOUNDMENTS CLOSURE, SITE 300

    SciTech Connect

    Lane, J E; Scott, J E; Mathews, S E

    2004-09-29

    Lawrence Livermore National Laboratory of the University of California (LLNL) operates two Class II surface impoundments that store wastewater that is discharged from a number of buildings located on the Site 300 Facility (Site 300). The wastewater is the by-product of explosives processing. Reduction in the volume of water discharged from these buildings over the past several years has significantly reduced the wastewater storage needs. In addition, the impoundments were constructed in 1984, and the high-density polyethylene (HDPE) geomembrane liners are nearing the end of their service life. The purpose of this project is to clean close the surface impoundments and provide new wastewater storage using portable, above ground storage tanks at six locations. The tanks will be installed prior to closure of the impoundments and will include heaters for allowing evaporation during relatively cool weather. Golder Associates (Golder) has prepared this Final Closure Plan (Closure Plan) on behalf of LLNL to address construction associated with the clean closure of the impoundments. This Closure Plan complies with State Water Resources Control Board (SWRCB) Section 21400 of the California Code of Regulations Title 27 (27 CCR {section}21400). As required by these regulations and guidance, this Plan provides the following information: (1) A site characterization, including the site location, history, current operations, and geology and hydrogeology; (2) The regulatory requirements relevant to clean closure of the impoundments; (3) The closure procedures; and, (4) The procedures for validation and documentation of clean closure.

  8. Site descriptive modeling as a part of site characterization in Sweden - Concluding the surface based investigations

    SciTech Connect

    Andersson, Johan; Winberg, Anders; Skagius, Kristina; Stroem, Anders; Lindborg, Tobias

    2007-07-01

    The Swedish Nuclear Fuel and Waste Management Co., SKB, is currently finalizing its surface based site investigations for the final repository for spent nuclear fuel in the municipalities of Oestharmnar (the Forsmark area) and Oskarshamn (the Simpevar/Laxemar area). The investigation data are assessed into a Site Descriptive Model, constituting a synthesis of geology, rock mechanics, thermal properties, hydrogeology, hydro-geochemistry, transport properties and a surface system description. Site data constitute a wide range of different measurement results. These data both need to be checked for consistency and to be interpreted into a format more amenable for three-dimensional modeling. The three-dimensional modeling (i.e. estimating the distribution of parameter values in space) is made in a sequence where the geometrical framework is taken from the geological models and in turn used by the rock mechanics, thermal and hydrogeological modeling. These disciplines in turn are partly interrelated, and also provide feedback to the geological modeling, especially if the geological description appears unreasonable when assessed together with the other data. Procedures for assessing the uncertainties and the confidence in the modeling have been developed during the course of the site modeling. These assessments also provide key input to the completion of the site investigation program. (authors)

  9. Titanium surface hydrophilicity enhances platelet activation.

    PubMed

    Alfarsi, Mohammed A; Hamlet, Stephen M; Ivanovski, Saso

    2014-01-01

    Titanium implant surface modification is a key strategy used to enhance osseointegration. Platelets are the first cells that interact with the implant surface whereupon they release a wide array of proteins that influence the subsequent healing process. This study therefore investigated the effect of titanium surface modification on the attachment and activation of human platelets. The surface characteristics of three titanium surfaces: smooth (SMO), micro-rough (SLA) and hydrophilic micro-rough (SLActive) and the subsequent attachment and activation of platelets following exposure to these surfaces were determined. The SLActive surface showed the presence of significant nanoscale topographical features. While attached platelets appeared to be morphologically similar, significantly fewer platelets attached to the SLActive surface compared to both the SMO and SLA surfaces. The SLActive surface however induced the release of the higher levels of chemokines β-thromboglobulin and platelet factor 4 from platelets. This study shows that titanium surface topography and chemistry have a significant effect on platelet activation and chemokine release. PMID:25311339

  10. Human Mars Landing Site and Impacts on Mars Surface Operations

    NASA Technical Reports Server (NTRS)

    Bussey, Ben; Hoffman, Stephen J.

    2016-01-01

    This paper describes NASA's initial steps for identifying and evaluating candidate Exploration Zones (EZs) and Regions of Interests (ROIs) for the first human crews that will explore the surface of Mars. NASA's current effort to define the exploration of this planet by human crews, known as the Evolvable Mars Campaign (EMC), provides the context in which these EZs and ROIs are being considered. The EMC spans all aspects of a human Mars mission including launch from Earth, transit to and from Mars, and operations on the surface of Mars. Studies related to Mars surface operations and related system capabilities have led to the current definition of an EZ as well as ROIs. An EZ is a collection of ROIs that are located within approximately 100 kilometers of a centralized landing site. ROIs are areas that are relevant for scientific investigation and/or development/maturation of capabilities and resources necessary for a sustainable human presence. The EZ also contains one or more landing sites and a habitation site that will be used by multiple human crews during missions to explore and utilize the ROIs within the EZ. With the EMC as a conceptual basis, the EZ model has been refined to a point where specific site selection criteria for scientific exploration and in situ resource utilization can be defined. In 2015 these criteria were distributed to the planetary sciences community and the in situ resource utilization and civil engineering communities as part of a call for EZ proposals. The resulting "First Landing Site/Exploration Zone Workshop for Human Missions to the Surface of Mars" was held in October 2015 during which 47 proposals for EZs and ROIs were presented and discussed. Proposed locations spanned all longitudes and all allowable latitudes (+/- 50 degrees). Proposed justification for selecting one of these EZs also spanned a significant portion of the scientific and resource criteria provided to the community. Workshop results will be used to prepare for

  11. Investigations of adsorption sites on oxide surfaces using solid-state NMR and TPD-IGC

    NASA Astrophysics Data System (ADS)

    Golombeck, Rebecca A.

    diameters and thermal histories. The bulk structural features in both compositions of glass fibers were identified using high-resolution 29Si, 27Al, and 11B magic-angle spinning (MAS) NMR spectroscopic measurements. In multi-component glasses, the determination of silicon, aluminum, and boron distributions becomes difficult due to the competitive nature of the network-modifying oxides among the network-forming oxides. In pure silicates, 29Si MAS NMR can often resolve resonances arising from silicate tetrahedron having varying numbers of bridging oxygens. In aluminoborosilicate glasses, aluminum is present in four-, five-, and six- coordination with oxygen as neighbors. The speciation of the aluminum can be determined using 27Al MAS NMR. The fraction of tetrahedral boron species in the glass fibers were measured using 11B MAS NMR, which is typically used to study the short-range structure of borate containing glasses such as alkali borate, borosilicate, and aluminoborosilicate glasses. While solid-state NMR is a powerful tool for elucidating bonding environments and coordination changes in the glass structure, it cannot quantitatively probe low to moderate surface area samples due to insufficient spins. Chemical probes either physisorbed or chemisorbed to the fiber's surface can increase the surface selectivity of NMR for analysis of samples with low surface areas and provide information about the local molecular structure of the reactive surface site. Common chemical probe molecules contain NMR active nuclei such as 19F or may be enriched with 13C. A silyating agent, (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS), reacts with reactive surface hydroxyls, which can be quantified by utilizing the NMR active nucleus (19F) contained in the probe molecule. The observed 19F MAS NMR peak area is integrated and compared against a standard of known fluorine spins (concentration), allowing the number of reactive hydroxyl sites to be quantified. IGC is a method used to study the

  12. A biologically active surface enzyme assembly that attenuates thrombus formation

    PubMed Central

    Qu, Zheng; Muthukrishnan, Sharmila; Urlam, Murali K.; Haller, Carolyn A.; Jordan, Sumanas W.; Kumar, Vivek A.; Marzec, Ulla M.; Elkasabi, Yaseen; Lahann, Joerg; Hanson, Stephen R.

    2013-01-01

    Activation of hemostatic pathways by blood-contacting materials remains a major hurdle in the development of clinically durable artificial organs and implantable devices. We postulate that surface-induced thrombosis may be attenuated by the reconstitution onto blood contacting surfaces of bioactive enzymes that regulate the production of thrombin, a central mediator of both clotting and platelet activation cascades. Thrombomodulin (TM), a transmembrane protein expressed by endothelial cells, is an established negative regulator of thrombin generation in the circulatory system. Traditional techniques to covalently immobilize enzymes on solid supports may modify residues contained within or near the catalytic site, thus reducing the bioactivity of surface enzyme assemblies. In this report, we present a molecular engineering and bioorthogonal chemistry approach to site-specifically immobilize a biologically active recombinant human TM fragment onto the luminal surface of small diameter prosthetic vascular grafts. Bioactivity and biostability of TM modified grafts is confirmed in vitro and the capacity of modified grafts to reduce platelet activation is demonstrated using a non-human primate model. These studies indicate that molecularly engineered interfaces that display TM actively limit surface-induced thrombus formation. PMID:23532366

  13. Surface-material maps of Viking landing sites on Mars

    NASA Technical Reports Server (NTRS)

    Moore, H. J.; Keller, J. M.

    1991-01-01

    Researchers mapped the surface materials at the Viking landing sites on Mars to gain a better understanding of the materials and rock populations at the sites and to provide information for future exploration. The maps extent to about 9 m in front of each lander and are about 15 m wide - an area comparable to the area of a pixel in high resolution Viking Orbiter images. The maps are divided into the near and far fields. Data for the near fields are from 1/10 scale maps, umpublished maps, and lander images. Data for the far fields are from 1/20 scale contour maps, contoured lander camera mosaics, and lander images. Rocks are located on these maps using stereometric measurements and the contour maps. Frequency size distribution of rocks and the responses of soil-like materials to erosion by engine exhausts during landings are discussed.

  14. Seismic Surface-Wave Tomography of Waste Sites - Final Report

    SciTech Connect

    Long, Timothy L.

    2000-09-14

    The objective of this study was to develop analysis programs for surface-wave group-velocity tomography, and apply these to three test areas. We succeeded by obtaining data covering two square areas that were 30 meters on a side, and a third area that was 16 meters on a side, in addition to a collaborative effort wherein we processed data from the Oak Ridge National Laboratory site. At all sites, usable group velocities were obtained for frequencies from 16 to 50 Hz using a sledgehammer source. The resulting tomographic images and velocity anomalies were sufficient to delineate suspected burial trenches (one 4-meters deep) and anomalous velocity structure related to rocks and disturbed soil. The success was not uniform because in portions of one area the inversion for shear-wave structure became unstable. More research is needed to establish a more robust inversion technique.

  15. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts.

    PubMed

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and (57)Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  16. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    NASA Astrophysics Data System (ADS)

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-10-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity.

  17. Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts

    PubMed Central

    Sahraie, Nastaran Ranjbar; Kramm, Ulrike I.; Steinberg, Julian; Zhang, Yuanjian; Thomas, Arne; Reier, Tobias; Paraknowitsch, Jens-Peter; Strasser, Peter

    2015-01-01

    Carbon materials doped with transition metal and nitrogen are highly active, non-precious metal catalysts for the electrochemical conversion of molecular oxygen in fuel cells, metal air batteries, and electrolytic processes. However, accurate measurement of their intrinsic turn-over frequency and active-site density based on metal centres in bulk and surface has remained difficult to date, which has hampered a more rational catalyst design. Here we report a successful quantification of bulk and surface-based active-site density and associated turn-over frequency values of mono- and bimetallic Fe/N-doped carbons using a combination of chemisorption, desorption and 57Fe Mössbauer spectroscopy techniques. Our general approach yields an experimental descriptor for the intrinsic activity and the active-site utilization, aiding in the catalyst development process and enabling a previously unachieved level of understanding of reactivity trends owing to a deconvolution of site density and intrinsic activity. PMID:26486465

  18. Immobilization of Active Bacteriophages on Polyhydroxyalkanoate Surfaces.

    PubMed

    Wang, Chanchan; Sauvageau, Dominic; Elias, Anastasia

    2016-01-20

    A rapid, efficient technique for the attachment of bacteriophages (phages) onto polyhydroxyalkanoate (PHA) surfaces has been developed and compared to three reported methods for phage immobilization. Polymer surfaces were modified to facilitate phage attachment using (1) plasma treatment alone, (2) plasma treatment followed by activation by 1-ethyl-3-(3-(dimethylamino)propyl)carbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (sulfo-NHS), (3) plasma-initiated acrylic acid grafting, or (4) plasma-initiated acrylic acid grafting with activation by EDC and sulfo-NHS. The impact of each method on the surface chemistry of PHA was investigated using contact angle analysis and X-ray photoelectron spectroscopy. Each of the four treatments was shown to result in both increased hydrophilicity and in the modification of the surface functional groups. Modified surfaces were immersed in suspensions of phage T4 for immobilization. The highest level of phage binding was observed for the surfaces modified by plasma treatment alone. The change in chemical bond states observed for surfaces that underwent plasma treatment is suspected to be the cause of the increased binding of active phages. Plasma-treated surfaces were further analyzed through phage-staining and fluorescence microscopy to assess the surface density of immobilized phages and their capacity to capture hosts. The infective capability of attached phages was confirmed by exposing the phage-immobilized surfaces to the host bacteria Escherichia coli in both plaque and infection dynamic assays. Plasma-treated surfaces with immobilized phages displayed higher infectivity than surfaces treated with other methods; in fact, the equivalent initial multiplicity of infection was 2 orders of magnitude greater than with other methods. Control samples - prepared by immersing polymer surfaces in phage suspensions (without prior plasma treatment) - did not show any bacterial growth inhibition, suggesting they did not bind

  19. Surface Plasma Source Electrode Activation by Surface Impurities

    SciTech Connect

    Dudnikov, Vadim; Johnson, Rolland P.; Han, B.; Murray, S. N.; Pennisi, T. R.; Santana, M.; Stockli, Martin P.; Welton, R. F.

    2011-09-26

    In experiments with RF saddle antenna surface plasma sources (SPS), the efficiency of H{sup -} ion generation was increased by up to a factor of 5 by plasma electrode 'activation', without supplying additional Cs, by heating the collar to high temperature for several hours using hot air flow and plasma discharge. Without cracking or heating the cesium ampoule, but likely with Cs recovery from impurities, the achieved energy efficiency was comparable to that of conventionally cesiated SNS RF sources with an external or internal Cs supply. In the experiments, optimum cesiation was produced (without additional Cs) by the collection and trapping of traces of remnant cesium compounds from SPS surfaces. Such activation by accumulation of impurities on electrode surfaces can be a reason for H{sup -} emission enhancement in other so-called 'volume' negative ion sources.

  20. Dissecting the active site of a photoreceptor protein

    NASA Astrophysics Data System (ADS)

    Hoff, Wouter; Hara, Miwa; Ren, Jie; Moghadam, Farzaneh; Xie, Aihua; Kumauchi, Masato

    While enzymes are quite large molecules, functionally important chemical events are often limited to a small region of the protein: the active site. The physical and chemical properties of residues at such active sites are often strongly altered compared to the same groups dissolved in water. Understanding such effects is important for unraveling the mechanisms underlying protein function and for protein engineering, but has proven challenging. Here we report on our ongoing efforts on using photoactive yellow protein (PYP), a bacterial photoreceptor, as a model system for such effects. We will report on the following questions: How many residues affect active site properties? Are these residues in direct physical contact with the active site? Can functionally important residues be recognized in the crystal structure of a protein? What structural resolution is needed to understand active sites? What spectroscopic techniques are most informative? Which weak interactions dominate active site properties?

  1. Adjoint active surfaces for localization and imaging.

    PubMed

    Cook, Daniel A; Mueller, Martin Fritz; Fedele, Francesco; Yezzi, Anthony J

    2015-01-01

    This paper addresses the problem of localizing and segmenting regions embedded within a surrounding medium by characterizing their boundaries, as opposed to imaging the entirety of the volume. Active surfaces are used to directly reconstruct the shape of the region of interest. We describe the procedure for finding the optimal surface, which is computed iteratively via gradient descent that exploits the sensitivity of an error minimization functional to changes of the active surface. In doing so, we introduce the adjoint model to compute the sensitivity, and in this respect, the method shares common ground with several other disciplines, such as optimal control. Finally, we illustrate the proposed active surface technique in the framework of wave propagation governed by the scalar Helmholtz equation. Potential applications include electromagnetics, acoustics, geophysics, nondestructive testing, and medical imaging. PMID:25438311

  2. Active micromixer using surface acoustic wave streaming

    DOEpatents

    Branch; Darren W. , Meyer; Grant D. , Craighead; Harold G.

    2011-05-17

    An active micromixer uses a surface acoustic wave, preferably a Rayleigh wave, propagating on a piezoelectric substrate to induce acoustic streaming in a fluid in a microfluidic channel. The surface acoustic wave can be generated by applying an RF excitation signal to at least one interdigital transducer on the piezoelectric substrate. The active micromixer can rapidly mix quiescent fluids or laminar streams in low Reynolds number flows. The active micromixer has no moving parts (other than the SAW transducer) and is, therefore, more reliable, less damaging to sensitive fluids, and less susceptible to fouling and channel clogging than other types of active and passive micromixers. The active micromixer is adaptable to a wide range of geometries, can be easily fabricated, and can be integrated in a microfluidic system, reducing dead volume. Finally, the active micromixer has on-demand on/off mixing capability and can be operated at low power.

  3. Surface Plasma Source Electrode Activation by Surface Impurities

    SciTech Connect

    Dudnikov, Vadim; Han, Baoxi; Johnson, Rolland P.; Murray Jr, S N; Pennisi, Terry R; Santana, Manuel; Stockli, Martin P; Welton, Robert F

    2011-01-01

    In experiments with RF saddle antenna surface plasma sources (SPS), the efficiency of H- ion generation was increased by up to a factor of 5 by long time plasma electrode activation, without adding Cs from Cs supply, by heating the collar to high temperature using hot air flow and plasma discharge. Without cracking or heating the cesium ampoule, but likely with Cs recovery from impurities, the achieved energy efficiency was comparable to that of conventionally cesiated SNS RF sources with an external or internal Cs supply. In the experiments, perfect cesiation was produced (without additional Cs supply) by the collection and trapping of traces of remnant cesium compounds from SPS surfaces.

  4. Human Mars Landing Site and Impacts on Mars Surface Operations

    NASA Technical Reports Server (NTRS)

    Hoffman, Stephen J.; Bussey, Ben

    2016-01-01

    This paper describes NASA's initial steps for identifying and evaluating candidate Exploration Zones (EZs) and Regions of Interests (ROIs) for the first human crews that will explore the surface of Mars. NASA's current effort to define the exploration of this planet by human crews, known as the Evolvable Mars Campaign (EMC), provides the context in which these EZs and ROIs are being considered. The EMC spans all aspects of a human Mars mission including launch from Earth, transit to and from Mars, and operations on the surface of Mars. An EZ is a collection of ROIs located within approximately 100 kilometers of a centralized landing site. ROIs are areas relevant for scientific investigation and/or development/maturation of capabilities and resources necessary for a sustainable human presence. The EZ also contains one or more landing sites and a habitation site that will be used by multiple human crews during missions to explore and utilize the ROIs within the EZ. With the EMC as a conceptual basis, the EZ model has been refined to a point where specific site selection criteria for scientific exploration and in situ resource utilization can be defined. In 2015 these criteria were distributed to the planetary sciences community and the in situ resource utilization and civil engineering communities as part of a call for EZ proposals. The resulting "First Landing Site/Exploration Zone Workshop for Human Missions to the Surface of Mars" was held in October 2015 during which 47 proposals for EZs and ROIs were presented and discussed. Proposed locations spanned all longitudes and all allowable latitudes (+/- 50 degrees). Proposed justification for selecting one of these EZs also spanned a significant portion of the scientific and resource criteria provided to the community. Several important findings resulted from this Workshop including: (a) a strong consensus that, at a scale of 100 km (radius), multiple places on Mars exist that have both sufficient scientific interest

  5. Mars Surveyor Project Landing Site Activities

    NASA Technical Reports Server (NTRS)

    Gulick, Virginia C.; Briggs, Geoffrey; Saunders, R. Stephen; Gilmore, Martha; Soderblom, Larry

    1999-01-01

    The Mars Surveyor Program --now a cooperative program led by NASA and CNES along with other international partners -- is underway. It has the primary science objective of furthering our understanding of the biological potential and possible biological history of Mars and has the complementary objective of improving our understanding of martian climate evolution and planetary history The missions will develop technology and acquire data necessary for eventual human Exploration. Launches of orbiters, landers and rovers will take place in 2001 and in 2003; in 2005 a complete system will be launched capable of returning samples to Earth by 2008. A key aspect of the program is the selection of landing sites. This abstract 1) reports on the status of the landing site selection process that begins with the 2001 lander mission and 2) outlines be opportunities for the Mars community to provide input into the landing site selection process.

  6. Mars Surveyor Project Landing Site Activities

    NASA Technical Reports Server (NTRS)

    Gulick, V. C.; Briggs, Geoffrey; Saunders, R. Stephen; Gilmore, Martha; Soderblom, Larry

    1999-01-01

    The Mars Surveyor Program -- now a cooperative program led by NASA and CNES along with other international partners -- is underway. It has the primary science objective of furthering our understanding of the biological potential and possible biological history of Mars and has the complementary objective of improving our understanding of martian climate evolution and planetary history. The missions will develop technology and acquire data necessary for eventual human exploration. Launches of orbiters, landers and rovers will take place in 2001 and in 2003; in 2005 a complete system will be launched capable of returning samples to Earth by 2008. A key aspect of the program is the selection of landing sites. This abstract 1) reports on the status of the landing site selection process that begins with the 2001 lander mission and 2) outlines the opportunities for the Mars community to provide input into the landing site selection process.

  7. The bifunctional active site of s-adenosylmethionine synthetase. Roles of the active site aspartates.

    PubMed

    Taylor, J C; Markham, G D

    1999-11-12

    S-Adenosylmethionine (AdoMet) synthetase catalyzes the biosynthesis of AdoMet in a unique enzymatic reaction. Initially the sulfur of methionine displaces the intact tripolyphosphate chain (PPP(i)) from ATP, and subsequently PPP(i) is hydrolyzed to PP(i) and P(i) before product release. The crystal structure of Escherichia coli AdoMet synthetase shows that the active site contains four aspartate residues. Aspartate residues Asp-16* and Asp-271 individually provide the sole protein ligand to one of the two required Mg(2+) ions (* denotes a residue from a second subunit); aspartates Asp-118 and Asp-238* are proposed to interact with methionine. Each aspartate has been changed to an uncharged asparagine, and the metal binding residues were also changed to alanine, to assess the roles of charge and ligation ability on catalytic efficiency. The resultant enzyme variants all structurally resemble the wild type enzyme as indicated by circular dichroism spectra and are tetramers. However, all have k(cat) reductions of approximately 10(3)-fold in AdoMet synthesis, whereas the MgATP and methionine K(m) values change by less than 3- and 8-fold, respectively. In the partial reaction of PPP(i) hydrolysis, mutants of the Mg(2+) binding residues have >700-fold reduced catalytic efficiency (k(cat)/K(m)), whereas the D118N and D238*N mutants are impaired less than 35-fold. The catalytic efficiency for PPP(i) hydrolysis by Mg(2+) site mutants is improved by AdoMet, like the wild type enzyme. In contrast AdoMet reduces the catalytic efficiency for PPP(i) hydrolysis by the D118N and D238*N mutants, indicating that the events involved in AdoMet activation are hindered in these methionyl binding site mutants. Ca(2+) uniquely activates the D271A mutant enzyme to 15% of the level of Mg(2+), in contrast to the approximately 1% Ca(2+) activation of the wild type enzyme. This indicates that the Asp-271 side chain size is a discriminator between the activating ability of Ca(2+) and the

  8. Communication: Methane dissociation on Ni(111) surface: Importance of azimuth and surface impact site

    NASA Astrophysics Data System (ADS)

    Shen, Xiangjian; Zhang, Zhaojun; Zhang, Dong H.

    2016-03-01

    Understanding the role of reactant ro-vibrational degrees of freedom (DOFs) in reaction dynamics of polyatomic molecular dissociation on metal surfaces is of great importance to explore the complex chemical reaction mechanism. Here, we present an expensive quantum dynamics study of the dissociative chemisorption of CH4 on a rigid Ni(111) surface by developing an accurate nine-dimensional quantum dynamical model including the DOF of azimuth. Based on a highly accurate fifteen-dimensional potential energy surface built from first principles, our simulations elucidate that the dissociation probability of CH4 has the strong dependence on azimuth and surface impact site. Some improvements are suggested to obtain the accurate dissociation probability from quantum dynamics simulations.

  9. Communication: Methane dissociation on Ni(111) surface: Importance of azimuth and surface impact site.

    PubMed

    Shen, Xiangjian; Zhang, Zhaojun; Zhang, Dong H

    2016-03-14

    Understanding the role of reactant ro-vibrational degrees of freedom (DOFs) in reaction dynamics of polyatomic molecular dissociation on metal surfaces is of great importance to explore the complex chemical reaction mechanism. Here, we present an expensive quantum dynamics study of the dissociative chemisorption of CH4 on a rigid Ni(111) surface by developing an accurate nine-dimensional quantum dynamical model including the DOF of azimuth. Based on a highly accurate fifteen-dimensional potential energy surface built from first principles, our simulations elucidate that the dissociation probability of CH4 has the strong dependence on azimuth and surface impact site. Some improvements are suggested to obtain the accurate dissociation probability from quantum dynamics simulations. PMID:26979673

  10. Patched bimetallic surfaces are active catalysts for ammonia decomposition

    DOE PAGESBeta

    Guo, Wei; Vlachos, Dionisios G.

    2015-10-07

    In this study, ammonia decomposition is often used as an archetypical reaction for predicting new catalytic materials and understanding the very reason of why some reactions are sensitive on material’s structure. Core–shell or surface-segregated bimetallic nanoparticles expose outstanding activity for many heterogeneously catalysed reactions but the reasons remain elusive owing to the difficulties in experimentally characterizing active sites. Here by performing multiscale simulations in ammonia decomposition on various nickel loadings on platinum (111), we show that the very high activity of core–shell structures requires patches of the guest metal to create and sustain dual active sites: nickel terraces catalyse N-Hmore » bond breaking and nickel edge sites drive atomic nitrogen association. The structure sensitivity on these active catalysts depends profoundly on reaction conditions due to kinetically competing relevant elementary reaction steps. We expose a remarkable difference in active sites between transient and steady-state studies and provide insights into optimal material design.« less

  11. Boltzmann active walkers and rough surfaces

    NASA Astrophysics Data System (ADS)

    Pochy, R. D.; Kayser, D. R.; Aberle, L. K.; Lam, L.

    1993-06-01

    An active walker model (AWM) was recently proposed by Freimuth and Lam for the generation of various filamentary patterns. In an AWM, the walker changes the landscape as it walks, and its steps are in turn influenced by the changing landscape. The landscape so obtained is a rough surface. In this paper, the properties of such a rough surface (with average height conserved) generated by a Boltzmann active walker in 1 + 1 dimensions is investigated in detail. The scaling properties of the surface thickness σ T is found to belong to a new class quite different from other types of fractal surfaces. For example, σ T is independent of the system size L, but is a function of the “temperature” T. Soliton propagation is found when T = 0.

  12. Active Flow Control Stator With Coanda Surface

    NASA Technical Reports Server (NTRS)

    Guendogdu; Vorreiter; Seume

    2010-01-01

    Active Flow Control increases the permissible aerodynamic loading. Curved surface near the trailing edge ("Coanda surface"): a) increases turning -> higher pressure ratio. b) controls boundary layer separation -> increased surge margin. Objective: Reduce the number of vanes or compressor stages. Constraints: 1. In a real compressor, the vane must still function entirely without blowing. 2. Maintain the flow exit angle of the reference stator despite the resulting increase in stator loading.

  13. Downward shortwave surface irradiance from 17 sites for the FIRE/SRB Wisconsin experiment

    NASA Technical Reports Server (NTRS)

    Whitlock, Charles H.; Hay, John E.; Robinson, David A.; Cox, Stephen K.; Wardle, David I.; Lecroy, Stuart R.

    1990-01-01

    A field experiment was conducted in Wisconsin during Oct. to Nov. 1986 for purposes of both intensive cirrus cloud measurments and SRB algorithm validation activities. The cirrus cloud measurements were part of the FIRE. Tables are presented which show data from 17 sites in the First ISCCP (International Satellite Cloud Climatology Project) Regional Experiment/Surface Radiation Budget (FIRE/SRB) Wisconsin experiment region. A discussion of intercomparison results and calibration inconsistencies is also included.

  14. Photoinduced Charge Transfer from Titania to Surface Doping Site

    PubMed Central

    Inerbaev, Talgat; Hoefelmeyer, James D.; Kilin, Dmitri S.

    2013-01-01

    We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting. PMID:23795229

  15. Photoinduced Charge Transfer from Titania to Surface Doping Site.

    PubMed

    Inerbaev, Talgat; Hoefelmeyer, James D; Kilin, Dmitri S

    2013-05-16

    We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting. PMID:23795229

  16. Optical Activity of Anisotropic Achiral Surfaces

    SciTech Connect

    Verbiest, T.; Kauranen, M.; Van Rompaey, Y.; Persoons, A. |

    1996-08-01

    Anisotropic achiral surfaces respond differently to left- and right-hand circularly polarized light. This occurs when the orientation of the surface with respect to an otherwise achiral experimental setup makes the total geometry chiral. Such optical activity is demonstrated in second-harmonic generation from an anisotropic thin molecular film. The circular-difference response reverses sign as the handedness of the geometry is reversed and vanishes when the setup possesses a mirror plane. The results are explained within the electric-dipole-allowed second-order surface nonlinearity. {copyright} {ital 1996 The American Physical Society.}

  17. The active site of ribulose-bisphosphate carboxylase/oxygenase

    SciTech Connect

    Hartman, F.C.

    1991-01-01

    The active site of ribulose-bisphosphate carboxylase/oxygenase requires interacting domains of adjacent, identical subunits. Most active-site residues are located within the loop regions of an eight-stranded {beta}/{alpha}-barrel which constitutes the larger C-terminal domain; additional key residues are located within a segment of the smaller N-terminal domain which partially covers the mouth of the barrel. Site-directed mutagenesis of the gene encoding the enzyme from Rhodospirillum rubrum has been used to delineate functions of active-site residues. 6 refs., 2 figs.

  18. Surface-mediated synthesis of dimeric rhodium catalysts on MgO: tracking changes in the nuclearity and ligand environment of the catalytically active sites by X-ray absorption and infrared spectroscopies.

    PubMed

    Yardimci, Dicle; Serna, Pedro; Gates, Bruce C

    2013-01-21

    The preparation of dinuclear rhodium clusters and their use as catalysts is challenging because these clusters are unstable, evolving readily into species with higher nuclearities. We now present a novel synthetic route to generate rhodium dimers on the surface of MgO by a stoichiometrically simple surface-mediated reaction involving [Rh(C(2)H(4))(2)] species and H(2). X-ray absorption and IR spectra were used to characterize the changes in the nuclearity of the essentially molecular surface species as they formed, including the ligands on the rhodium and the metal-support interactions. The support plays a key role in stabilizing the dinuclear rhodium species, allowing the incorporation of small ligands (ethyl, hydride, and/or CO) and enabling a characterization of the catalytic performance of the supported species for the hydrogenation of ethylene as a function of the metal nuclearity and ligand environment. A change in the nuclearity from one to two Rh atoms leads to a 58-fold increase in the catalytic activity for ethylene hydrogenation, a reaction involving unsaturated, but stable, dimeric rhodium species. PMID:23208893

  19. A study on the flexibility of enzyme active sites

    PubMed Central

    2011-01-01

    Background A common assumption about enzyme active sites is that their structures are highly conserved to specifically distinguish between closely similar compounds. However, with the discovery of distinct enzymes with similar reaction chemistries, more and more studies discussing the structural flexibility of the active site have been conducted. Results Most of the existing works on the flexibility of active sites focuses on a set of pre-selected active sites that were already known to be flexible. This study, on the other hand, proposes an analysis framework composed of a new data collecting strategy, a local structure alignment tool and several physicochemical measures derived from the alignments. The method proposed to identify flexible active sites is highly automated and robust so that more extensive studies will be feasible in the future. The experimental results show the proposed method is (a) consistent with previous works based on manually identified flexible active sites and (b) capable of identifying potentially new flexible active sites. Conclusions This proposed analysis framework and the former analyses on flexibility have their own advantages and disadvantage, depending on the cause of the flexibility. In this regard, this study proposes an alternative that complements previous studies and helps to construct a more comprehensive view of the flexibility of enzyme active sites. PMID:21342563

  20. The surface energy balance at the Huygens landing site and the moist surface conditions on Titan

    NASA Astrophysics Data System (ADS)

    Williams, Kaj E.; McKay, Christopher P.; Persson, Fredrik

    2012-01-01

    The Huygens Probe provided a wealth of data concerning the atmosphere of Titan. It also provided tantalizing evidence of a small amount of surface liquid. We have developed a detailed surface energy balance for the Probe landing site. We find that the daily averaged non-radiative fluxes at the surface are 0.7 W m-2, much larger than the global average value predicted by McKay et al. (1991) of 0.037 W m-2. Considering the moist surface, the methane and ethane detected by the Probe from the surface is consistent with a ternary liquid of ethane, methane, and nitrogen present on the surface with mole fractions of methane, ethane, and nitrogen of 0.44, 0.34, and 0.22, respectively, and a total mass load of ∼0.05 kg m-2. If this liquid is included in the surface energy balance, only a small fraction of the non-radiative energy is due to latent heat release (∼10-3 W m-2). If the amount of atmospheric ethane is less than 0.6×10-5, the surface liquid is most likely evaporating over timescales of 5 Titan days, and the moist surface is probably a remnant of a recent precipitation event. If the surface liquid mass loading is increased to 0.5 kg m-2, then the liquid lifetime increases to ∼56 Titan days. Our modeling results indicate a dew cycle is unlikely, given that even when the diurnal variation of liquid is in equilibrium, the diurnal mass variation is only 3% of the total liquid. If we assume a high atmospheric mixing ratio of ethane (>0.6×10-5), the precipitation of liquid is large (38 cm/Titan year for an ethane mixing ratio of 2×10-5). Such a flux is many orders of magnitude in excess of the photochemical production rate of ethane.

  1. Safety Oversight of Decommissioning Activities at DOE Nuclear Sites

    SciTech Connect

    Zull, Lawrence M.; Yeniscavich, William

    2008-01-15

    The Defense Nuclear Facilities Safety Board (Board) is an independent federal agency established by Congress in 1988 to provide nuclear safety oversight of activities at U.S. Department of Energy (DOE) defense nuclear facilities. The activities under the Board's jurisdiction include the design, construction, startup, operation, and decommissioning of defense nuclear facilities at DOE sites. This paper reviews the Board's safety oversight of decommissioning activities at DOE sites, identifies the safety problems observed, and discusses Board initiatives to improve the safety of decommissioning activities at DOE sites. The decommissioning of former defense nuclear facilities has reduced the risk of radioactive material contamination and exposure to the public and site workers. In general, efforts to perform decommissioning work at DOE defense nuclear sites have been successful, and contractors performing decommissioning work have a good safety record. Decommissioning activities have recently been completed at sites identified for closure, including the Rocky Flats Environmental Technology Site, the Fernald Closure Project, and the Miamisburg Closure Project (the Mound site). The Rocky Flats and Fernald sites, which produced plutonium parts and uranium materials for defense needs (respectively), have been turned into wildlife refuges. The Mound site, which performed R and D activities on nuclear materials, has been converted into an industrial and technology park called the Mound Advanced Technology Center. The DOE Office of Legacy Management is responsible for the long term stewardship of these former EM sites. The Board has reviewed many decommissioning activities, and noted that there are valuable lessons learned that can benefit both DOE and the contractor. As part of its ongoing safety oversight responsibilities, the Board and its staff will continue to review the safety of DOE and contractor decommissioning activities at DOE defense nuclear sites.

  2. Source effects on surface waves from Nevada Test Site explosions

    SciTech Connect

    Patton, H.J.; Vergino, E.S.

    1981-11-01

    Surface waves recorded on the Lawrence Livermore National Laboratory (LLNL) digital network have been used to study five underground nuclear explosions detonated in Yucca Valley at the Nevada Test Site. The purpose of this study is to characterize the reduced displacement potential (RDP) at low frequencies and to test secondary source models of underground explosions. The observations consist of Rayleigh- and Love-wave amplitude and phase spectra in the frequency range 0.03 to 0.16 Hz. We have found that Rayleigh-wave spectral amplitudes are modeled well by a RDP with little or no overshoot for explosions detonated in alluvium and tuff. On the basis of comparisons between observed and predicted source phase, the spall closure source proposed by Viecelli does not appear to be a significant source of Rayleigh waves that reach the far field. We tested two other secondary source models, the strike-slip, tectonic strain release model proposed by Toksoez and Kehrer and the dip-slip thrust model of Masse. The surface-wave observations do not provide sufficient information to discriminate between these models at the low F-values (0.2 to 0.8) obtained for these explosions. In the case of the strike-slip model, the principal stress axes inferred from the fault slip angle and strike angle are in good agreement with the regional tectonic stress field for all but one explosion, Nessel. The results of the Nessel explosion suggest a mechanism other than tectonic strain release.

  3. DOE site performance assessment activities. Radioactive Waste Technical Support Program

    SciTech Connect

    Not Available

    1990-07-01

    Information on performance assessment capabilities and activities was collected from eight DOE sites. All eight sites either currently dispose of low-level radioactive waste (LLW) or plan to dispose of LLW in the near future. A survey questionnaire was developed and sent to key individuals involved in DOE Order 5820.2A performance assessment activities at each site. The sites surveyed included: Hanford Site (Hanford), Idaho National Engineering Laboratory (INEL), Los Alamos National Laboratory (LANL), Nevada Test Site (NTS), Oak Ridge National Laboratory (ORNL), Paducah Gaseous Diffusion Plant (Paducah), Portsmouth Gaseous Diffusion Plant (Portsmouth), and Savannah River Site (SRS). The questionnaire addressed all aspects of the performance assessment process; from waste source term to dose conversion factors. This report presents the information developed from the site questionnaire and provides a comparison of site-specific performance assessment approaches, data needs, and ongoing and planned activities. All sites are engaged in completing the radioactive waste disposal facility performance assessment required by DOE Order 5820.2A. Each site has achieved various degrees of progress and have identified a set of critical needs. Within several areas, however, the sites identified common needs and questions.

  4. Savannah River Site prioritization of transition activities

    SciTech Connect

    Finley, R.H.

    1993-11-01

    Effective management of SRS conversion from primarily a production facility to other missions (or Decontamination and Decommissioning (D&D)) requires a systematic and consistent method of prioritizing the transition activities. This report discusses the design of a prioritizing method developed to achieve systematic and consistent methods of prioritizing these activities.

  5. Green Bank Telescope active surface system

    NASA Astrophysics Data System (ADS)

    Lacasse, Richard J.

    1998-05-01

    During the design phase of the Green Bank Telescope (GBT), various means of providing an accurate surface on a large aperture paraboloid, were considered. Automated jacks supporting the primary reflector were selected as the appropriate technology since they promised greater performance and potentially lower costs than a homologous or carbon fiber design, and had certain advantages over an active secondary. The design of the active surface has presented many challenges. Since the actuators are mounted on a tipping structure, it was required that they support a significant side-load. Such devices were not readily available commercially so they had to be developed. Additional actuator requirements include low backlash, repeatable positioning, and an operational life of at least 230 years. Similarly, no control system capable of controlling the 2209 actuators was commercially available. Again a prime requirement was reliability. Maintaining was also a very important consideration. The system architecture is tree-like. An active surface 'master-computer' controls interaction with the telescope control system, and controls ancillary equipment such as power supplies and temperature monitors. Two slave computers interface with the master- computer, and each closes approximately 1100 position loops. For simplicity, the servo is an 'on/off' type, yet achieves a positioning resolution of 25 microns. Each slave computer interfaces with 4 VME I/O cards, which in turn communicate with 140 control modules. The control modules read out the positions of the actuators every 0.1 sec and control the actuators' DC motors. Initial control of the active surface will be based on an elevation dependant structural model. Later, the model will be improved by holographic observations.Surface accuracy will be improved further by using laser ranging system which will actively measure the surface figure. Several tests have been conducted to assure that the system will perform as desired when

  6. Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts.

    PubMed

    Wang, Lu-Cun; Friend, C M; Fushimi, Rebecca; Madix, Robert J

    2016-07-01

    The activation of molecular O2 as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O2 activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O2 dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O2 dissociation is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O2 dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction. PMID:27376884

  7. Identification of Glycosylation Sites Essential for Surface Expression of the CaVα2δ1 Subunit and Modulation of the Cardiac CaV1.2 Channel Activity.

    PubMed

    Tétreault, Marie-Philippe; Bourdin, Benoîte; Briot, Julie; Segura, Emilie; Lesage, Sylvie; Fiset, Céline; Parent, Lucie

    2016-02-26

    Alteration in the L-type current density is one aspect of the electrical remodeling observed in patients suffering from cardiac arrhythmias. Changes in channel function could result from variations in the protein biogenesis, stability, post-translational modification, and/or trafficking in any of the regulatory subunits forming cardiac L-type Ca(2+) channel complexes. CaVα2δ1 is potentially the most heavily N-glycosylated subunit in the cardiac L-type CaV1.2 channel complex. Here, we show that enzymatic removal of N-glycans produced a 50-kDa shift in the mobility of cardiac and recombinant CaVα2δ1 proteins. This change was also observed upon simultaneous mutation of the 16 Asn sites. Nonetheless, the mutation of only 6/16 sites was sufficient to significantly 1) reduce the steady-state cell surface fluorescence of CaVα2δ1 as characterized by two-color flow cytometry assays and confocal imaging; 2) decrease protein stability estimated from cycloheximide chase assays; and 3) prevent the CaVα2δ1-mediated increase in the peak current density and voltage-dependent gating of CaV1.2. Reversing the N348Q and N812Q mutations in the non-operational sextuplet Asn mutant protein partially restored CaVα2δ1 function. Single mutation N663Q and double mutations N348Q/N468Q, N348Q/N812Q, and N468Q/N812Q decreased protein stability/synthesis and nearly abolished steady-state cell surface density of CaVα2δ1 as well as the CaVα2δ1-induced up-regulation of L-type currents. These results demonstrate that Asn-663 and to a lesser extent Asn-348, Asn-468, and Asn-812 contribute to protein stability/synthesis of CaVα2δ1, and furthermore that N-glycosylation of CaVα2δ1 is essential to produce functional L-type Ca(2+) channels. PMID:26742847

  8. Ionizable Side Chains at Catalytic Active Sites of Enzymes

    PubMed Central

    Jimenez-Morales, David; Liang, Jie

    2012-01-01

    Catalytic active sites of enzymes of known structure can be well defined by a modern program of computational geometry. The CASTp program was used to define and measure the volume of the catalytic active sites of 573 enzymes in the Catalytic Site Atlas database. The active sites are identified as catalytic because the amino acids they contain are known to participate in the chemical reaction catalyzed by the enzyme. Acid and base side chains are reliable markers of catalytic active sites. The catalytic active sites have 4 acid and 5 base side chains, in an average volume of 1072 Å3. The number density of acid side chains is 8.3 M (in chemical units); the number density of basic side chains is 10.6 M. The catalytic active site of these enzymes is an unusual electrostatic and steric environment in which side chains and reactants are crowded together in a mixture more like an ionic liquid than an ideal infinitely dilute solution. The electrostatics and crowding of reactants and side chains seems likely to be important for catalytic function. In three types of analogous ion channels, simulation of crowded charges accounts for the main properties of selectivity measured in a wide range of solutions and concentrations. It seems wise to use mathematics designed to study interacting complex fluids when making models of the catalytic active sites of enzymes. PMID:22484856

  9. Nanovalve Activation by Surface-Attached Photoacids

    PubMed Central

    Guardado-Alvarez, T. M.; Russell, M. M.

    2015-01-01

    Proton transfer caused by excitation of a photoacid attached to the surface of a mesoporous silica nanoparticle activates a nanovalve and causes release of trapped molecules. The protonation of an aniline- based stalk releases a noncovalently bound cyclodextrin molecule that blocked a pore. The results show that pH-responsive molecular delivery systems can be externally controlled using light. PMID:24942753

  10. Analysis of Binding Site Hot Spots on the Surface of Ras GTPase

    PubMed Central

    Buhrman, Greg; O’Connor, Casey; Zerbe, Brandon; Kearney, Bradley M.; Napoleon, Raeanne; Kovrigina, Elizaveta A.; Vajda, Sandor; Kozakov, Dima; Kovrigin, Evgenii L.; Mattos, Carla

    2011-01-01

    We have recently discovered an allosteric switch in Ras, bringing an additional level of complexity to this GTPase whose mutants are involved in nearly 30% of cancers. Upon activation of the allosteric switch, there is a shift in helix 3/loop 7 associated with a disorder to order transition in the active site. Here, we use a combination of multiple solvent crystal structures and computational solvent mapping (FTMap) to determine binding site hot spots in the “off” and “on” allosteric states of the GTP-bound form of H-Ras. Thirteen sites are revealed, expanding possible target sites for ligand binding well beyond the active site. Comparison of FTMaps for the H and K isoforms reveals essentially identical hot spots. Furthermore, using NMR measurements of spin relaxation, we determined that K-Ras exhibits global conformational dynamics very similar to those we previously reported for H-Ras. We thus hypothesize that the global conformational rearrangement serves as a mechanism for allosteric coupling between the effector interface and remote hot spots in all Ras isoforms. At least with respect to the binding sites involving the G domain, H-Ras is an excellent model for K-Ras and probably N-Ras as well. Ras has so far been elusive as a target for drug design. The present work identifies various unexplored hot spots throughout the entire surface of Ras, extending the focus from the disordered active site to well-ordered locations that should be easier to target. PMID:21945529

  11. Bactericidal activity of biomimetic diamond nanocone surfaces.

    PubMed

    Fisher, Leanne E; Yang, Yang; Yuen, Muk-Fung; Zhang, Wenjun; Nobbs, Angela H; Su, Bo

    2016-03-01

    The formation of biofilms on implant surfaces and the subsequent development of medical device-associated infections are difficult to resolve and can cause considerable morbidity to the patient. Over the past decade, there has been growing recognition that physical cues, such as surface topography, can regulate biological responses and possess bactericidal activity. In this study, diamond nanocone-patterned surfaces, representing biomimetic analogs of the naturally bactericidal cicada fly wing, were fabricated using microwave plasma chemical vapor deposition, followed by bias-assisted reactive ion etching. Two structurally distinct nanocone surfaces were produced, characterized, and the bactericidal ability examined. The sharp diamond nanocone features were found to have bactericidal capabilities with the surface possessing the more varying cone dimension, nonuniform array, and decreased density, showing enhanced bactericidal ability over the more uniform, highly dense nanocone surface. Future research will focus on using the fabrication process to tailor surface nanotopographies on clinically relevant materials that promote both effective killing of a broader range of microorganisms and the desired mammalian cell response. This study serves to introduce a technology that may launch a new and innovative direction in the design of biomaterials with capacity to reduce the risk of medical device-associated infections. PMID:26992656

  12. Ag/Au mixed sites promote oxidative coupling of methanol on the alloy surface.

    PubMed

    Xu, Bingjun; Siler, Cassandra G F; Madix, Robert J; Friend, Cynthia M

    2014-04-14

    Nanoporous gold, a dilute alloy of Ag in Au, activates molecular oxygen and promotes the oxygen-assisted catalytic coupling of methanol. Because this trace amount of Ag inherent to nanoporous gold has been proposed as the source of oxygen activation, a thin film Ag/Au alloy surface was studied as a model system for probing the origin of this reactivity. Thin alloy layers of Ag(x)Au(1-x), with 0.15≤x≤0.40, were examined for dioxygen activation and methanol self-coupling. These alloy surfaces recombine atomic oxygen at different temperatures depending on the alloy composition. Total conversion of methanol to selective oxidation products, that is, formaldehyde and methyl formate, was achieved at low initial oxygen coverage and at low temperature. Reaction channels for methyl formate formation occurred on both Au and Au/Ag mixed sites with a ratio, as was predicted from the local 2-dimensional composition. PMID:24633724

  13. Enzymatic activity induced by interactions with a nanofabricated hydrophobic Si surface

    NASA Astrophysics Data System (ADS)

    Nishiyama, Katsuhiko

    2013-07-01

    The binding of peptides of 2-10 glycine residues (2-10Gly) to papain on nanofabricated hydrophobic Si surfaces was investigated by molecular dynamics and docking simulations. 5Gly, 7Gly, 9Gly, and 10Gly were distributed on sites near the active center of papain on the Si surface, while 6-10Gly were distributed on sites near the active center of free papain. The Si surface changed the substrate specificity of papain, and modification of this surface should allow full control of substrate specificity. Molecular surgery of proteins in cells may be realized using papain on specially designed surfaces.

  14. Dual active surface heat flux gage probe

    NASA Astrophysics Data System (ADS)

    Liebert, Curt H.; Kolodziej, Paul

    1995-02-01

    A unique plug-type heat flux gage probe was tested in the NASA Ames Research Center 2x9 turbulent flow duct facility. The probe was fabricated by welding a miniature dual active surface heat flux gage body to the end of a hollow metal cylindrical bolt containing a metal inner tube. Cooling air flows through the inner tube, impinges onto the back of the gage body and then flows out through the annulus formed between the inner tube and the hollow bolt wall. Heat flux was generated in the duct facility with a Huels arc heater. The duct had a rectangular cross section and one wall was fabricated from 2.54 centimeter thick thermal insulation rigid surface material mounted onto an aluminum plate. To measure heat flux, the probe was inserted through the plate and insulating materials with the from of the gage located flush with the hot gas-side insulation surface. Absorbed heat fluxes measured with the probe were compared with absorbed heat fluxes measured with six water-cooled reference calorimeters. These calorimeters were located in a water-cooled metal duct wall which was located across from the probe position. Correspondence of transient and steady heat fluxes measured with the reference calorimeters and heat flux gage probe was generally within a satisfactory plus or minus 10 percent. This good correspondence was achieved even though the much cooler probe caused a large surface temperature disruption of 1000K between the metal gage and the insulation. However, this temperature disruption did not seriously effect the accuracy of the heat flux measurement. A current application for dual active surface heat flux gages is for transient and steady absorbed heat flux, surface temperature and heat transfer coefficient measurements on the surface of an oxidizer turbine inlet deflector operating in a space shuttle test bed engine.

  15. Land surface cleanup of plutonium at the Nevada Test Site

    SciTech Connect

    Ebeling, L.L.; Evans, R.B.; Walsh, E.J.

    1991-01-01

    The Nevada Test Site (NTS) covers approximately 3300 km{sup 2} of high desert and is located approximately 100 km northwest of Las Vegas, Nevada. Soil contaminated by plutonium exists on the NTS and surrounding areas from safety tests conducted in the 1950s and 1960s. About 150 curies of contamination have been measured over 1200 hectares of land surface. Most contamination is found in the top 5 cm of soil but may be found deep as 25 cm. The cost of conventional removal and disposal of the full soil volume has been estimated at over $500,000,000. This study is directed toward minimizing the volume of waste which must be further processed and disposed of by precisely controlling soil removal depth. The following soil removal machines were demonstrated at the NTS: (1) a CMI Corporation Model PR-500FL pavement profiler, (2) a CMI Corporation Model Tr-225B trimmer reclaimer, (3) a Caterpillar Model 623 elevating scraper equipped with laser depth control, (4) a Caterpillar Model 14G motor grader equipped with laser depth control, (5) a Caterpillar Model 637 auger scraper, and (6) a XCR Series Guzzler vacuum truck. 5 refs., 5 figs.

  16. Active Sites Environmental Monitoring Program FY 1996 annual report

    SciTech Connect

    Morrissey, C.M.; Marshall, D.S.; Cunningham, G.R.

    1997-11-01

    This report summarizes the activities of the Active Sites Environmental Monitoring Program (ASEMP) from October 1995 through September 1996. The Radioactive Solid Waste Operations Group (RSWOG) of the Waste Management and Remedial Action Division (WMRAD) and the Environmental Sciences Division (ESD) at Oak Ridge National Laboratory (ORNL) established ASEMP in 1989. The purpose of the program is to provide early detection and performance monitoring at active low-level waste (LLW) disposal sites in Solid Waste Storage Area (SWSA) 6 and transuranic (TRU) waste storage sites in SWSA 5 North as required by Chapters 2 and 3 of US Department of Energy Order 5820.2A.

  17. Active sites environmental monitoring Program - Program Plan: Revision 2

    SciTech Connect

    Morrissey, C.M.; Hicks, D.S.; Ashwood, T.L.; Cunningham, G.R.

    1994-05-01

    The Active Sites Environmental Monitoring Program (ASEMP), initiated in 1989, provides early detection and performance monitoring of active low-level-waste (LLW) and transuranic (TRU) waste facilities at Oak Ridge National Laboratory (ORNL). Several changes have recently occurred in regard to the sites that are currently used for waste storage and disposal. These changes require a second set of revisions to the ASEMP program plan. This document incorporates those revisions. This program plan presents the organization and procedures for monitoring the active sites. The program plan also provides internal reporting levels to guide the evaluation of monitoring results.

  18. Asphaltenes as a surface active agent

    SciTech Connect

    Sheu, E.Y.; Shields, M.B.; Storm, D.A.

    1995-12-31

    Asphaltene represents the heavy-end materials of the crude oil, conventionally defined via solvent solubility (either heptane or pentane). Chemically, it consists of polynuclear aromatics with the H/C ratio close to unity. Additionally, it contains a great deal of heteroatoms, such as sulfur, nitrogen, nickel, vanadium, etc. Several experiments have revealed the surface activity of asphaltenes in some selected solvents through measurements of their rheology or critical micelle concentrations in these solvents. The asphaltene micelles were found thermodynamically reversible. In a two phase asphaltene/water system, asphaltenes appear to vary their surface activities depending upon the polarity of the aqueous phase. Our recent experiment further showed that asphaltene/water/toluene may form, water-in-oil emulsion under certain conditions.

  19. Nicotinamide Cofactors Suppress Active-Site Labeling of Aldehyde Dehydrogenases.

    PubMed

    Stiti, Naim; Chandrasekar, Balakumaran; Strubl, Laura; Mohammed, Shabaz; Bartels, Dorothea; van der Hoorn, Renier A L

    2016-06-17

    Active site labeling by (re)activity-based probes is a powerful chemical proteomic tool to globally map active sites in native proteomes without using substrates. Active site labeling is usually taken as a readout for the active state of the enzyme because labeling reflects the availability and reactivity of active sites, which are hallmarks for enzyme activities. Here, we show that this relationship holds tightly, but we also reveal an important exception to this rule. Labeling of Arabidopsis ALDH3H1 with a chloroacetamide probe occurs at the catalytic Cys, and labeling is suppressed upon nitrosylation and oxidation, and upon treatment with other Cys modifiers. These experiments display a consistent and strong correlation between active site labeling and enzymatic activity. Surprisingly, however, labeling is suppressed by the cofactor NAD(+), and this property is shared with other members of the ALDH superfamily and also detected for unrelated GAPDH enzymes with an unrelated hydantoin-based probe in crude extracts of plant cell cultures. Suppression requires cofactor binding to its binding pocket. Labeling is also suppressed by ALDH modulators that bind at the substrate entrance tunnel, confirming that labeling occurs through the substrate-binding cavity. Our data indicate that cofactor binding adjusts the catalytic Cys into a conformation that reduces the reactivity toward chloroacetamide probes. PMID:26990764

  20. Active surfaces: Ferrofluid-impregnated surfaces for active manipulation of droplets

    NASA Astrophysics Data System (ADS)

    Khalil, Karim; Mahmoudi, Seyed Reza; Abu-Dheir, Numan; Varanasi, Kripa

    2014-11-01

    Droplet manipulation and mobility on non-wetting surfaces is of practical importance for diverse applications ranging from micro-fluidic devices, anti-icing, dropwise condensation, and biomedical devices. The use of active external fields has been explored via electric, acoustic, and vibrational, yet moving highly conductive and viscous fluids remains a challenge. Magnetic fields have been used for droplet manipulation; however, usually, the fluid is functionalized to be magnetic, and requires enormous fields of superconducting magnets when transitioning to diamagnetic materials such as water. Here we present a class of active surfaces by stably impregnating active fluids such as ferrofluids into a textured surface. Droplets on such ferrofluid-impregnated surfaces have extremely low hysteresis and high mobility such that they can be propelled by applying relatively low magnetic fields. Our surface is able to manipulate a variety of materials including diamagnetic, conductive and highly viscous fluids, and additionally solid particles.

  1. Active surfaces: Ferrofluid-impregnated surfaces for active manipulation of droplets

    NASA Astrophysics Data System (ADS)

    Khalil, Karim S.; Mahmoudi, Seyed Reza; Abu-dheir, Numan; Varanasi, Kripa K.

    2014-07-01

    Droplet manipulation and mobility on non-wetting surfaces is of practical importance for diverse applications ranging from micro-fluidic devices, anti-icing, dropwise condensation, and biomedical devices. The use of active external fields has been explored via electric, acoustic, and vibrational, yet moving highly conductive and viscous fluids remains a challenge. Magnetic fields have been used for droplet manipulation; however, usually, the fluid is functionalized to be magnetic, and requires enormous fields of superconducting magnets when transitioning to diamagnetic materials such as water. Here we present a class of active surfaces by stably impregnating active fluids such as ferrofluids into a textured surface. Droplets on such ferrofluid-impregnated surfaces have extremely low hysteresis and high mobility such that they can be propelled by applying relatively low magnetic fields. Our surface is able to manipulate a variety of materials including diamagnetic, conductive and highly viscous fluids, and additionally solid particles.

  2. 30 CFR 71.500 - Sanitary toilet facilities at surface work sites; installation requirements.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Sanitary toilet facilities at surface work... SURFACE WORK AREAS OF UNDERGROUND COAL MINES Sanitary Toilet Facilities at Surface Worksites of Surface Coal Mines § 71.500 Sanitary toilet facilities at surface work sites; installation requirements....

  3. 30 CFR 71.500 - Sanitary toilet facilities at surface work sites; installation requirements.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Sanitary toilet facilities at surface work... SURFACE WORK AREAS OF UNDERGROUND COAL MINES Sanitary Toilet Facilities at Surface Worksites of Surface Coal Mines § 71.500 Sanitary toilet facilities at surface work sites; installation requirements....

  4. Pinning effect for photoisomerization of a dicationic azobenzene derivative by anionic sites of the clay surface.

    PubMed

    Umemoto, Tetsuro; Ohtani, Yuta; Tsukamoto, Takamasa; Shimada, Tetsuya; Takagi, Shinsuke

    2014-01-11

    The photoisomerization behaviour of a dicationic azobenzene derivative on the inorganic surface was examined. The isomerization reaction was controlled by the charged array of the inorganic surface due to the "pinning effect" because of the electrostatic interaction between anionic charged sites on the inorganic surface and cationic charged sites in dye molecules. PMID:24226932

  5. Active site - a site of binding of affinity inhibitors in baker's yeast inorganic pyrophosphatase

    SciTech Connect

    Svyato, I.E.; Sklyankina, V.A.; Avaeva, S.M.

    1986-03-20

    The interaction of the enzyme-substrate complex with methyl phosphate, O-phosphoethanolamine, O-phosphopropanolamine, N-acetylphosphoserine, and phosphoglyolic acid, as well as pyrophosphatase, modified by monoesters of phosphoric acid, with pyrophosphate and tripolyphosphate, was investigated. It was shown that the enzyme containing the substrate in the active site does not react with monophosphates, but modified pyrophosphatase entirely retains the ability to bind polyanions to the regulatory site. It is concluded that the inactivation of baker's yeast inorganic pyrophosphatase by monoesters of phosphoric acid, which are affinity inhibitors of it, is the result of modification of the active site of the enzyme.

  6. Vibrating surface actuators for active flow control

    NASA Astrophysics Data System (ADS)

    Calkins, Frederick T.; Clingman, Dan J.

    2002-07-01

    Current research has shown that aircraft can gain significant aerodynamic performance benefits from active flow control (AFC). AFC seeks to control large scale flows by exploiting natural response triggered by small energy inputs. The principal target application is download alleviation of the V-22 Osprey under the DARPA sponsored Boeing Active Flow Control System program. One method of injecting energy into the flow over the V22 wings is to use an active vibrating surface on the passive seal between the wing and flapperon. The active surface is an oscillating cantilevered beam which injects fluid into the flow, similar to a synthetic jet, and interacts with the flow field. Two types of actuators, or flipperons, are explored. The first is a multilayer piezoelectric polyvinylidene fluoride cantilevered bender. The second is a single crystal piezoelectric (SCP)d31 poled wafer mounted on a cantilevered spring steel substrate. This paper details the development effort including fabrication, mechanical and electrical testing, and modeling for both types of actuators. Both flipperons were mounted on the passive seal between a 1/10th scale V22 wing and flapperon and the aerodynamic performance evaluated in low speed wind tunnel. The SCP flipperon demonstrated significant cruise benefits, with increase of 10 percent lift and 20 percent angle of attack capability. The PVDF flipperon provided a 16 percent drag reduction in the hover mode.

  7. A small ribozyme with dual-site kinase activity

    PubMed Central

    Biondi, Elisa; Maxwell, Adam W.R.; Burke, Donald H.

    2012-01-01

    Phosphoryl transfer onto backbone hydroxyls is a recognized catalytic activity of nucleic acids. We find that kinase ribozyme K28 possesses an unusually complex active site that promotes (thio)phosphorylation of two residues widely separated in primary sequence. After allowing the ribozyme to radiolabel itself by phosphoryl transfer from [γ-32P]GTP, DNAzyme-mediated cleavage yielded two radiolabeled cleavage fragments, indicating phosphorylation sites within each of the two cleavage fragments. These sites were mapped by alkaline digestion and primer extension pausing. Enzymatic digestion and mutational analysis identified nucleotides important for activity and established the active structure as being a constrained pseudoknot with unusual connectivity that may juxtapose the two reactive sites. Nuclease sensitivities for nucleotides near the pseudoknot core were altered in the presence of GTPγS, indicating donor-induced folding. The 5′ target site was more strongly favored in full-length ribozyme K28 (128 nt) than in truncated RNAs (58 nt). Electrophoretic mobilities of self-thiophosphorylated products on organomercurial gels are distinct from the 5′ mono-thiophosphorylated product produced by reaction with polynucleotide kinase, potentially indicating simultaneous labeling of both sites within individual RNA strands. Our evidence supports a single, compact structure with local dynamics, rather than global rearrangement, as being responsible for dual-site phosphorylation. PMID:22618879

  8. Effect of soil erosion on the long-term stability of FUSRAP near-surface waste-burial sites

    SciTech Connect

    Knight, M.J.

    1983-04-01

    Decontamination of FUSRAP sites could result in the generation of large volumes (in excess of 400,000 m/sup 3/) of low-activity radioactive wastes (primarily contaminated soil and building materials) requiring subsequent disposal. It is likely that near-surface burial will be seriously considered as an option for disposal of these materials. A number of factors - including soil erosion - could adversely affect the long-term stability of a near-surface waste-burial site. The majority of FUSRAP sites are located in the humid eastern United States, where the principal cause of erosion is the action of water. This report examines the effect of soil erosion by water on burial-site stability based on analysis of four hypothetical near-surface burial sites. The Universal Soil Loss Equation was employed to estimate average annual soil loss from burial sites and the 1000-year effects of soil loss on the soil barrier (burial trench cap) placed over low-activity wastes. Results suggest that the land use of the burial site and the slope gradient of the burial trench cap significantly affect the rate of soil erosion. The development of measures limiting the potential land use of a burial site (e.g., mixing large rocks into the burial trench cap) may be required to preserve the integrity of a burial trench for long periods of time.

  9. Fluctuating sea surface temperatures in the subtropical North Atlantic during Oceanic Anoxic Event 1a at DSDP Site 398 and ODP Site 641

    NASA Astrophysics Data System (ADS)

    Hofmann, P.; Wiegand, R.; Handley, L.; Wagner, T.; Talbot, H. M.; Mcanena, A.

    2012-04-01

    The early Aptian is characterized by a perturbation of the global carbon cycle which occurred during Oceanic Anoxic Event 1a (OAE 1a, Selli-Event, ca. 120 Ma). OAE 1a is well documented by organic carbon-rich sediments from marine and terrestrial localities worldwide. The trigger mechanism and the environmental consequences of OAE 1a are still under dispute. Here we present sea surface temperature estimates based on TEX 86 measurements (tetraether index of tetraethers containing 86 carbons) from the Galicia Margin (subtropical North Atlantic) at DSDP Site 398 and ODP Site 641C. The investigated sites are approximately 350 km apart and located on the slope of the Vigo seamount (Site 398) and the Galicia Bank (Site 641). Sea surface temperature (SST) records at both Sites suggest a significant and sustained warming of the Galica Margin surface waters during OAE 1a. The observed warming during OAE 1a is disrupted by several SST decreases which vary in magnitude from site to site. Similar surface water cooling episodes but with different magnitudes have been reported from the central Pacific region. The exact nature and timing of these intermittent cooling periods remains to be discovered but the occurrence in both the North Atlantic and Pacific may point towards a global trigger mechanism. We speculate that the thermal development of the surface waters of the subtropical North Atlantic during OAE 1a may reflect global fluctuations in pCO2 in response to variations in the intensity of Pacific volcanic activity in the Pacific Ontong Java area with superimposed local adjustments in the oceanic circulation pattern of the North Atlantic.

  10. PTHrP regulates the modeling of cortical bone surfaces at fibrous insertion sites during growth.

    PubMed

    Wang, Meina; VanHouten, Joshua N; Nasiri, Ali R; Johnson, Randy L; Broadus, Arthur E

    2013-03-01

    The sites that receive ligament and tendon insertions (entheses) on the cortical surfaces of long bones are poorly understood, particularly regarding modeling and regulation. Entheses are classified as either fibrocartilaginous or fibrous based on their structures. Fibrous entheses typically insert into the metaphysis or diaphysis of a long bone, bear a periosteal component, and are modeled during long-bone growth. This modeling forms a root system by which the insertions attach to the cortical surface. In the case of the medial collateral ligament, modeling drives actual migration of the ligament along the cortical surface in order to accommodate linear growth, whereas in other sites modeling may excavate a deep cortical root system (eg, the teres major insertion) or a shallow root system with a large footprint (eg, the latissimus dorsi insertion). We report here that conditionally deleting parathyroid hormone-related protein (PTHrP) in fibrous entheses via Scleraxis-Cre targeting causes modeling to fail in these three iterations of osteoclast-driven enthesis excavation or migration. These iterations appear to represent formes frustes of a common modeling strategy, presumably differing from each other as a consequence of differences in biomechanical control. In sites in which PTHrP is not induced, either physiologically or because of conditional deletion, modeling does not take place and fibrocartilage is induced. These findings represent the initial genetic evidence that PTHrP regulates periosteal/intramembranous bone cell activity on cortical bone surfaces and indicate that PTHrP serves as a load-induced modeling tool in fibrous insertion sites during linear growth. PMID:23109045

  11. Active site density and reactivity for the photocatalytic dehydrogenation of 2-propanol on TiO 2 (110)

    NASA Astrophysics Data System (ADS)

    Brinkley, David; Engel, Thomas

    1998-10-01

    By combining molecular beam experiments at 350 K with low temperature experiments on an immobile adlayer, we determine the fraction of surface sites active for the photocatalytic dehydrogenation of 2-propanol to acetone to be 0.08 on a fully oxidized surface. We also find that the reaction probability at these sites is essentially unity. The presence of oxygen vacancies (≈0.1 monolayer) increases the fraction of active sites to 0.15 without changing the reaction probability, reaction kinetics, or product distribution. From this, we conclude that only sites which can bind O 2 strongly are active for the reaction. Candidates for such sites include steps and kinks on fully oxidized surfaces and oxygen lattice vacancies on reduced surfaces.

  12. Secondary ion mass spectrometry (SIMS) analysis of hypervelocity microparticle impact sites on LDEF surfaces

    NASA Technical Reports Server (NTRS)

    Simon, C. G.; Buonaquisti, A. J.; Batchelor, D. A.; Hunter, J. L.; Griffis, D. P.; Misra, V.; Ricks, D. R.; Wortman, J. J.; Brownlee, D. E.; Best, S. R.

    1995-01-01

    Two dimensional elemental ion maps have been recorded for hundreds of microparticle impact sites and contamination features on LDEF surfaces. Since the majority of the analyzed surfaces were metal-oxide-silicon (MOS) impact detectors from the Interplanetary Dust Experiment, a series of 'standard' and 'blank' analyses of these surfaces are included. Hypervelocity impacts of forsterite olivine microparticles on activated flight sensors served as standards while stylus and pulsed laser simulated 'impacts' served as analytical blanks. Results showed that despite serious contamination issues, impactor residues can be identified in greater than 1/3 of the impact sites. While aluminum oxide particles could not be detected on aluminum surfaces, they were detected on germanium surfaces from row 12. Remnants of manmade debris impactors consisting of paint chips and bits of metal were identified on surfaces from LDEF Rows 3 (west or trailing side), 6 (south), 9 (ram or leading side), 12 (north) and the space end. Higher than expected ratios of manmade microparticle impacts to total microparticle impacts were found on the space end and the trailing side. These results were consistent with time-tagged and time-segregated microparticle impact data from the IDE and other LDEF experiments. A myriad of contamination interferences were identified and their effects on impactor debris identification mitigated during the course of this study. These interferences include pre-, post and inflight deposited surface contaminants as well as indigenous heterogeneous material contaminants. Non-flight contaminations traced to human origins, including spittle and skin oils, contributed significant levels of alkali-rich carbonaceous interferences. A ubiquitous layer of in-flight deposited silicaceous contamination varied in thickness with location on LDEF, even on a micro scale. In-flight deposited (low velocity) contaminants include urine droplets and bits of metal film from eroded thermal

  13. Hanford Site environmental data for calendar year 1993--surface and Columbia River

    SciTech Connect

    Bisping, L.E.

    1994-06-01

    Environmental monitoring at the Hanford Site, located in southeastern Washington State, is conducted by Battelle Memorial Institute, Pacific Northwest Division, as part of its contract to operate the Pacific Northwest Laboratory (PNL) for the U.S. Department of Energy. The data collected provide a historical record of radionuclide and radiation levels attributable to natural causes, worldwide fallout, and Hanford operations. Data are also collected to monitor several chemicals. Pacific Northwest Laboratory publishes an annual environmental report for the Hanford Site each calendar year. The Hanford Site Environmental Report for Calendar Year 1993 describes the Site mission and activities, general environmental features, radiological and chemical releases from operations, status of compliance with environmental regulations, status of programs to accomplish compliance, and environmental monitoring activities and results. The report includes a summary of offsite and onsite environmental monitoring data collected during 1993 by PNL`s Environmental Monitoring Program. Appendix A of that report contains data summaries created from raw surface and river monitoring data. This volume contains the actual raw data used to create the summaries.

  14. Hanford Site environmental data for calendar year 1994: Surface and Columbia River

    SciTech Connect

    Bisping, L.E.

    1995-07-01

    Environmental monitoring at the Hanford Site, located in southeastern Washington State, is conducted by Battelle Memorial Institute, Pacific Northwest Division, as part of its contract to operate the Pacific Northwest Laboratory (PNL) for the US Department of Energy. The data collected provide a historical record of radionuclide and radiation levels attributable to natural causes, worldwide fallout, and Hanford operations. Data are also collected to monitor several chemicals. Pacific Northwest Laboratory publishes an annual environmental report for the Hanford Site each calendar year. The Hanford Site Environmental Report for Calendar Year 1994 describes the Site mission and activities, general environmental features, radiological and chemical releases from operations, status of compliance with environmental regulations, status of programs to accomplish compliance, and environmental monitoring activities and results. The report includes a summary of offsite and onsite environmental monitoring data collected during 1994 b PNL`s Environmental Monitoring Program. Appendix A of that report contains data summaries created from raw surface and river monitoring data. This volume contains the actual raw data used to create the summaries.

  15. Motility of active fluid drops on surfaces

    NASA Astrophysics Data System (ADS)

    Khoromskaia, Diana; Alexander, Gareth P.

    2015-12-01

    Drops of active liquid crystal have recently shown the ability to self-propel, which was associated with topological defects in the orientation of active filaments [Sanchez et al., Nature 491, 431 (2013), 10.1038/nature11591]. Here, we study the onset and different aspects of motility of a three-dimensional drop of active fluid on a planar surface. We analyze theoretically how motility is affected by orientation profiles with defects of various types and locations, by the shape of the drop, and by surface friction at the substrate. In the scope of a thin drop approximation, we derive exact expressions for the flow in the drop that is generated by a given orientation profile. The flow has a natural decomposition into terms that depend entirely on the geometrical properties of the orientation profile, i.e., its bend and splay, and a term coupling the orientation to the shape of the drop. We find that asymmetric splay or bend generates a directed bulk flow and enables the drop to move, with maximal speeds achieved when the splay or bend is induced by a topological defect in the interior of the drop. In motile drops the direction and speed of self-propulsion is controlled by friction at the substrate.

  16. A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.

    1992-01-01

    An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ligands'' with localized surface orbitals perturbed only by these ligands''. These complexes'' are based on a twelve coordinate species with the ligands'' attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  17. A Frontier Molecular Orbital determination of the active sites on dispersed metal catalysts

    SciTech Connect

    Augustine, R.L.; Lahanas, K.M.

    1992-11-01

    An angular overlap calculation has been used to determine the s, p and d orbital energy levels of the different types of surface sites present on a dispersed metal catalysts. The basis for these calculations is the reported finding that a large number of catalyzed reactions take place on single atom active sites on the metal surface. Thus, these sites can be considered as surface complexes made up of the central active atom surrounded by near-neighbor metal atom ``ligands`` with localized surface orbitals perturbed only by these ``ligands``. These ``complexes`` are based on a twelve coordinate species with the ``ligands`` attached to the t{sub 2g} orbitals and the coordinate axes coincident with the direction of the e{sub g} orbitals on the central atom. These data can permit a Frontier Molecular Orbital treatment of specific site activities as long as the surface orbital availability for overlap with adsorbed substrates is considered along with its energy value and symmetry.

  18. Dashboard applications to monitor experiment activities at sites

    NASA Astrophysics Data System (ADS)

    Andreeva, Julia; Belforte, Stefano; Boehm, Max; Casajus, Adrian; Flix, Josep; Gaidioz, Benjamin; Grigoras, Costin; Kokoszkiewicz, Lukasz; Lanciotti, Elisa; Rocha, Ricardo; Saiz, Pablo; Santinelli, Roberto; Sidorova, Irina; Sciabà, Andrea; Tsaregorodtsev, Andrei

    2010-04-01

    In the framework of a distributed computing environment, such as WLCG, monitoring has a key role in order to keep under control activities going on in sites located in different countries and involving people based in many different sites. To be able to cope with such a large scale heterogeneous infrastructure, it is necessary to have monitoring tools providing a complete and reliable view of the overall performance of the sites. Moreover, the structure of a monitoring system critically depends on the object to monitor and on the users it is addressed to. In this article we will describe two different monitoring systems both aimed to monitor activities and services provided in the WLCG framework, but designed in order to meet the requirements of different users: Site Status Board has an overall view of the services available in all the sites supporting an experiment, whereas Siteview provides a complete view of all the activities going on at a site, for all the experiments supported by the site.

  19. Architecture and active site of particulate methane monooxygenase

    PubMed Central

    Culpepper, Megen A.; Rosenzweig, Amy C.

    2012-01-01

    Particulate methane monooxygenase (pMMO) is an integral membrane metalloenzyme that oxidizes methane to methanol in methanotrophic bacteria, organisms that live on methane gas as their sole carbon source. Understanding pMMO function has important implications for bioremediation applications and for the development of new, environmentally friendly catalysts for the direct conversion of methane to methanol. Crystal structures of pMMOs from three different methanotrophs reveal a trimeric architecture, consisting of three copies each of the pmoB, pmoA, and pmoC subunits. There are three distinct metal centers in each protomer of the trimer, mononuclear and dinuclear copper sites in the periplasmic regions of pmoB and a mononuclear site within the membrane that can be occupied by copper or zinc. Various models for the pMMO active site have been proposed within these structural constraints, including dicopper, tricopper, and diiron centers. Biochemical and spectroscopic data on pMMO and recombinant soluble fragments, denoted spmoB proteins, indicate that the active site involves copper and is located at the site of the dicopper center in the pmoB subunit. Initial spectroscopic evidence for O2 binding at this site has been obtained. Despite these findings, questions remain about the active site identity and nuclearity and will be the focus of future studies. PMID:22725967

  20. Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity.

    PubMed

    Matsubu, John C; Yang, Vanessa N; Christopher, Phillip

    2015-03-01

    CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability. PMID:25671686

  1. Methanopyrus kandleri topoisomerase V contains three distinct AP lyase active sites in addition to the topoisomerase active site.

    PubMed

    Rajan, Rakhi; Osterman, Amy; Mondragón, Alfonso

    2016-04-20

    Topoisomerase V (Topo-V) is the only topoisomerase with both topoisomerase and DNA repair activities. The topoisomerase activity is conferred by a small alpha-helical domain, whereas the AP lyase activity is found in a region formed by 12 tandem helix-hairpin-helix ((HhH)2) domains. Although it was known that Topo-V has multiple repair sites, only one had been mapped. Here, we show that Topo-V has three AP lyase sites. The atomic structure and Small Angle X-ray Scattering studies of a 97 kDa fragment spanning the topoisomerase and 10 (HhH)2domains reveal that the (HhH)2domains extend away from the topoisomerase domain. A combination of biochemical and structural observations allow the mapping of the second repair site to the junction of the 9th and 10th (HhH)2domains. The second site is structurally similar to the first one and to the sites found in other AP lyases. The 3rd AP lyase site is located in the 12th (HhH)2domain. The results show that Topo-V is an unusual protein: it is the only known protein with more than one (HhH)2domain, the only known topoisomerase with dual activities and is also unique by having three AP lyase repair sites in the same polypeptide. PMID:26908655

  2. Methanopyrus kandleri topoisomerase V contains three distinct AP lyase active sites in addition to the topoisomerase active site

    PubMed Central

    Rajan, Rakhi; Osterman, Amy; Mondragón, Alfonso

    2016-01-01

    Topoisomerase V (Topo-V) is the only topoisomerase with both topoisomerase and DNA repair activities. The topoisomerase activity is conferred by a small alpha-helical domain, whereas the AP lyase activity is found in a region formed by 12 tandem helix-hairpin-helix ((HhH)2) domains. Although it was known that Topo-V has multiple repair sites, only one had been mapped. Here, we show that Topo-V has three AP lyase sites. The atomic structure and Small Angle X-ray Scattering studies of a 97 kDa fragment spanning the topoisomerase and 10 (HhH)2 domains reveal that the (HhH)2 domains extend away from the topoisomerase domain. A combination of biochemical and structural observations allow the mapping of the second repair site to the junction of the 9th and 10th (HhH)2 domains. The second site is structurally similar to the first one and to the sites found in other AP lyases. The 3rd AP lyase site is located in the 12th (HhH)2 domain. The results show that Topo-V is an unusual protein: it is the only known protein with more than one (HhH)2 domain, the only known topoisomerase with dual activities and is also unique by having three AP lyase repair sites in the same polypeptide. PMID:26908655

  3. Detection limit for activation measurements in ultralow background sites

    NASA Astrophysics Data System (ADS)

    Trache, Livius; Chesneanu, D.; Margineanu, R.; Pantelica, A.; Ghita, D. G.; Burducea, I.; Straticiuc, M.; Tang, X. D.

    2014-09-01

    We used 12C +13C fusion at the beam energies E = 6, 7 and 8 MeV to determine the sensitivity and the limits of activation method measurements in ultralow background sites. A 13C beam of 0.5 μA from the 3 MV Tandem accelerator of the Horia Hulubei National Institute of Physics and Nuclear Engineering - IFIN HH impinged on thick graphite targets. After about 24 hrs of irradiation targets were measured in two different laboratories: one with a heavy shielded Ge detector in the institute (at the surface) and one located underground in the microBequerel laboratory, in the salt mine of Slanic-Prahova, Romania. The 1369- and 2754 keV peaks from 24Na deactivation were clearly observed in the γ-ray spectra obtained for acquisitions lasting a few hours, or a few days. Determination of the detection limit in evaluating the cross sections for the target irradiated at Ec . m = 3 MeV indicates the fact that it is possible to measure gamma spectrum in underground laboratory down to Ec . m = 2 . 6 MeV. Cleaning the spectra with beta-gamma coincidences and increasing beam intensity 20 times will take as further down. The measurements are motivated by the study of the 12 C +12 C reaction at astrophysical energies.

  4. Using Carbohydrate Interaction Assays to Reveal Novel Binding Sites in Carbohydrate Active Enzymes.

    PubMed

    Cockburn, Darrell; Wilkens, Casper; Dilokpimol, Adiphol; Nakai, Hiroyuki; Lewińska, Anna; Abou Hachem, Maher; Svensson, Birte

    2016-01-01

    Carbohydrate active enzymes often contain auxiliary binding sites located either on independent domains termed carbohydrate binding modules (CBMs) or as so-called surface binding sites (SBSs) on the catalytic module at a certain distance from the active site. The SBSs are usually critical for the activity of their cognate enzyme, though they are not readily detected in the sequence of a protein, but normally require a crystal structure of a complex for their identification. A variety of methods, including affinity electrophoresis (AE), insoluble polysaccharide pulldown (IPP) and surface plasmon resonance (SPR) have been used to study auxiliary binding sites. These techniques are complementary as AE allows monitoring of binding to soluble polysaccharides, IPP to insoluble polysaccharides and SPR to oligosaccharides. Here we show that these methods are useful not only for analyzing known binding sites, but also for identifying new ones, even without structural data available. We further verify the chosen assays discriminate between known SBS/CBM containing enzymes and negative controls. Altogether 35 enzymes are screened for the presence of SBSs or CBMs and several novel binding sites are identified, including the first SBS ever reported in a cellulase. This work demonstrates that combinations of these methods can be used as a part of routine enzyme characterization to identify new binding sites and advance the study of SBSs and CBMs, allowing them to be detected in the absence of structural data. PMID:27504624

  5. Using Carbohydrate Interaction Assays to Reveal Novel Binding Sites in Carbohydrate Active Enzymes

    PubMed Central

    Wilkens, Casper; Dilokpimol, Adiphol; Nakai, Hiroyuki; Lewińska, Anna; Abou Hachem, Maher; Svensson, Birte

    2016-01-01

    Carbohydrate active enzymes often contain auxiliary binding sites located either on independent domains termed carbohydrate binding modules (CBMs) or as so-called surface binding sites (SBSs) on the catalytic module at a certain distance from the active site. The SBSs are usually critical for the activity of their cognate enzyme, though they are not readily detected in the sequence of a protein, but normally require a crystal structure of a complex for their identification. A variety of methods, including affinity electrophoresis (AE), insoluble polysaccharide pulldown (IPP) and surface plasmon resonance (SPR) have been used to study auxiliary binding sites. These techniques are complementary as AE allows monitoring of binding to soluble polysaccharides, IPP to insoluble polysaccharides and SPR to oligosaccharides. Here we show that these methods are useful not only for analyzing known binding sites, but also for identifying new ones, even without structural data available. We further verify the chosen assays discriminate between known SBS/CBM containing enzymes and negative controls. Altogether 35 enzymes are screened for the presence of SBSs or CBMs and several novel binding sites are identified, including the first SBS ever reported in a cellulase. This work demonstrates that combinations of these methods can be used as a part of routine enzyme characterization to identify new binding sites and advance the study of SBSs and CBMs, allowing them to be detected in the absence of structural data. PMID:27504624

  6. Near surface characterisation of a limestone site using borehole and surface geophysics.

    NASA Astrophysics Data System (ADS)

    Sénéchal, G.; Hollender, F.; Rousset, D.

    2003-04-01

    The paper deals with the analysis of the respective performances and the optimization of geophysical methods used for the non-destructive imagery of rocks, from the surface to a depth of approximately 100 m. Different techniques, carried out from the surface or from boreholes, have been tested on the \\char`&{uml;}Médecin Hill\\char`&{uml;} (Centre d'Etude de Cadarache - 13108 St. Paul lez Durance - France). This test site consists in a low fractured limestone, crossed by several faults characterized by a near-vertical dip. The site was previously investigated by numerous other characterization methods (boreholes, surface geology, structural analysis, well logging, etc.): a well known structural 3D model is available. Each tested geophysical method is based on the determination of different physical parameters (elastic parameters, density, electrical resistivity, dielectric permittivity, etc.). In terms of resolution and depth of investigation, every geophysical method has its own drawbacks and advantages. High resolution seismic focuses between 20 and some hundred of meters of depth with a metric to decametric vertical resolution. GPR has a decimetric resolution but electromagnetic waves are strongly attenuated after a few meters of propagation. DC resistivity is a potential method so, resolution dramatically decreases with depth of investigation. The acquisition pattern of this last study leads to a depth of investigation around 15 m and a resolution of one to several meters. Several surface acquisitions have been performed within a 400 m line along which seven boreholes are located. From the high resolution reflection seismic data, we calculated a depth migrated section which displays the main interfaces affected by some near vertical faults. These results are compared to seismic data obtained from a borehole survey interpreted with the help of log data. A radar borehole survey, using tomographic and reflection pattern surveys provided improved information but

  7. Viking landing sites, remote-sensing observations, and physical properties of Martian surface materials

    NASA Technical Reports Server (NTRS)

    Moore, Henry J.; Jakosky, Bruce M.

    1989-01-01

    Consideration is given to the relations between the physical properties of the surface materials at Viking landing sites, the physical properties of other Martian surfaces inferred from radar observations from earth and thermal observations from orbit, and the geological processes that formed the materials and shaped the surfaces. The radar and thermal remote-sensing signatures of the landing site surface materials are estimated and compared with the thermal and radar measurements for the entire planet. It is shown that the surface materials at the landing sites are good analogs for the materials in most of the Martian equatorial regions.

  8. Viking landing sites, remote-sensing observations, and physical properties of Martian surface materials

    NASA Astrophysics Data System (ADS)

    Moore, H. J.; Jakosky, B. M.

    1989-09-01

    Consideration is given to the relations between the physical properties of the surface materials at Viking landing sites, the physical properties of other Martian surfaces inferred from radar observations from earth and thermal observations from orbit, and the geological processes that formed the materials and shaped the surfaces. The radar and thermal remote-sensing signatures of the landing site surface materials are estimated and compared with the thermal and radar measurements for the entire planet. It is shown that the surface materials at the landing sites are good analogs for the materials in most of the Martian equatorial regions.

  9. New NSO Solar Surface Activity Maps

    NASA Astrophysics Data System (ADS)

    Henney, C. J.; Harvey, J. W.

    2001-05-01

    Using NSO-Kitt Peak Vacuum Telescope (KPVT) synoptic data, we present several new solar surface activity maps. The motivation is to test conventional wisdom about conditions that are likely to produce solar activity such as flares, coronal mass ejections and high speed solar wind streams. The ultimate goal is to improve real-time, observation-based models for the purpose of predicting solar activity. A large number of maps will eventually be produced based on the wide range of ideas and models of the conditions thought to lead to solar activity events. When data from the new SOLIS instruments becomes available, the range of possible models that can be tested will be greatly expanded. At present, the daily maps include ones that show magnetic field complexity, emerging flux and high speed solar wind sources. As a proxy for local magnetic potential energy, each element of the magnetic complexity map is the distance-weighted rms of the opposing ambient magnetic field. The flux emergence map is the difference between the two most recent absolute magnetic flux images. The solar wind source map is produced from coronal hole area data. The new maps are available on the NSO-Kitt Peak World Wide Web page. This research was supported in part by the Office of Navel Research Grant N00014-91-J-1040. The NSO-Kitt Peak data used here are produced cooperatively by NSF/AURA, NASA/GSFC, and NOAA/SEC.

  10. Surface refractivity measurements at NASA spacecraft tracking sites

    NASA Technical Reports Server (NTRS)

    Schmid, P. E.

    1972-01-01

    High-accuracy spacecraft tracking requires tropospheric modeling which is generally scaled by either estimated or measured values of surface refractivity. This report summarizes the results of a worldwide surface-refractivity test conducted in 1968 in support of the Apollo program. The results are directly applicable to all NASA radio-tracking systems.

  11. SEISMIC SURFACE-WAVE TOMOGRAPHY OF WASTE SITES

    EPA Science Inventory

    Studies of the earth using surface waves are extensive. The early targets were crustal thickness and upper mantle structure because surface waves are well recorded on the early long period instrumentation and because the velocity contrast between the crust and mantle exhibits pro...

  12. Correlations between surface structure and catalytic activity/selectivity

    SciTech Connect

    Goodman, D.W.

    1992-10-01

    Objective is to address the keys to understanding the relation between surface structure and catalytic activity/selectivity. Of concern are questions related to enhanced catalytic properties of mixed-metal catalysts and critical active site requirements for molecular synthesis and rearrangement. The experimental approach utilizes a microcatalytic reactor contiguous to a surface analysis system, an arrangement which allows in vacuo transfer of the catalyst from one chamber to the other. Surface techniques being used include Auger (AES), UV and X-ray photoemission spectroscopy (UPS and XPS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), high resolution electron energy loss spectroscopy (HREELS) and infrared reflection-absorption spectroscopy (IRAS). Our research program builds upon our previous experience relating the results of single crystal kinetic measurements with the results obtained with supported analogs. As well we are exploiting our recent work on the preparation, the characterization, and the determination of the catalytic properties of ultra-thin metal and metal oxide films. The program is proceeding toward the study of the unique catalytic properties of ultrathin metal films; the investigation of the critical ensemble size requirements for principal catalytic reaction types; and the modelling of supported catalysts using ultra-thin planar oxide surfaces.

  13. Surface and Near-surface Investigations of a Legacy Test Site

    NASA Astrophysics Data System (ADS)

    Sussman, A. J.; Schultz-Fellenz, E. S.; Chipman, V.; Cogbill, A. H.; Conklin, G.; Townsend, M.

    2012-12-01

    Salut, one of 82 underground U.S. nuclear tests conducted at Pahute Mesa, was detonated on June 12, 1985, in rhyolitic lava 608 m below the surface and with announced yield of 20-150 kt. One of the objectives of the Comprehensive Inspection Technologies (CIT) team, a component of the National Center for Nuclear Security is to evaluate Salut and other legacy sites as a test bed for use in treaty monitoring, verification, and other national security applications. As opposed to a surface collapse resulting in a crater, Salut experienced a subsurface collapse such that the most obvious feature associated with nuclear testing was not produced, giving the CIT team an opportunity to test a number of inspection technologies in a broad context. Ground-based visual observation, ground-based LiDAR, gravity and magnetics data were collected during a field campaign in the summer of 2012. Visual observations were performed using different approaches which were assessed for accuracy and efficiency. The complete set of visual observation data was integrated with the LiDAR. The primary purpose of the Salut gravity survey was to attempt to detect a possible subsurface collapse zone which might be located as little as 200 meters below the surface. The Salut survey was conducted along radial lines centered upon the location of the Salut vertical borehole; lines were 45° apart and 800 long. A residual gravity map of the area was calculated by subtracting a least-squares' planar surface from the observed Bouguer gravity data, which were calculated using a reduction density of 2450 kg/m^3. The residual map shows a gravity low of -150 to -190 mGal centered about 50 m west of the Salut borehole. In addition, a gravity anomaly of about -40 mGal is centered over the nearby (460 m to the west) Tenabo event: the Tenabo event, like Salut, did not collapse to the surface. Work by Los Alamos National Laboratory was sponsored by the National Nuclear Security AdministrationAward No. DE-AC52-06NA

  14. Active Sites Environmental Monitoring Program: Mid-FY 1991 report

    SciTech Connect

    Ashwood, T.L.; Wickliff, D.S.; Morrissey, C.M.

    1991-10-01

    This report summarizes the activities of the Active Sites Environmental Monitoring Program (ASEMP) from October 1990 through March 1991. The ASEMP was established in 1989 by Solid Waste Operations and the Environmental Sciences Division to provide early detection and performance monitoring at active low-level radioactive waste (LLW) disposal sites in Solid Waste Storage Area (SWSA) 6 and transuranic (TRU) waste storage sites in SWSA 5 as required by chapters II and III of US Department of Energy Order 5820.2A. Monitoring results continue to demonstrate the no LLW is being leached from the storage vaults on the tumulus pads. Loading of vaults on Tumulus II began during this reporting period and 115 vaults had been loaded by the end of March 1991.

  15. An active-site peptide from pepsin C

    PubMed Central

    Kay, J.; Ryle, A. P.

    1971-01-01

    Porcine pepsin C is inactivated rapidly and irreversibly by diazoacetyl-dl-norleucine methyl ester in the presence of cupric ions at pH values above 4.5. The inactivation is specific in that complete inactivation accompanies the incorporation of 1mol of inhibitor residue/mol of enzyme and evidence has been obtained to suggest that the reaction occurs with an active site residue. The site of reaction is the β-carboxyl group of an aspartic acid residue in the sequence Ile-Val-Asp-Thr. This sequence is identical with the active-site sequence in pepsin and the significance of this in terms of the different activities of the two enzymes is discussed. PMID:4942834

  16. Does Titan have an Active Surface?

    NASA Astrophysics Data System (ADS)

    Nelson, R.

    2009-12-01

    ammonia, a compound expected in Titan’s interior. This, combined with the previous evidence from VIMS and RADAR images, creates a strong case for Titan having a presently active surface, possibly due to cryovolcanism. Cassini encountered Titan at very close range on 2008-11-19-13:58 and again on 2008-12-05-12:38. These epochs are called T47 and T48. Comparison of earlier lower resolution data (T5) with the recent T47 and T48 data reveal changes of the surface reflectance and morphology in the Hotei region. This is the first evidence from VIMS that confirms the RADAR report that Hotei Reggio has morphology consistent with volcanic terrain. It has not escaped our attention that ammonia, in association with methane and nitrogen, the principal species of Titan’s atmosphere, closely replicates the environment at the time that live first emerged on earth. If Titan is currently active then these results raise the following questions: What is the full extent of current geologic activity? What are the ongoing processes? Are Titan’s chemical processes today supporting a prebiotic chemistry similar to that under which life evolved on Earth? This work done at JPL under contract with NASA. Refs: [1]R. M. Nelson et al., Icarus 199 (2009) 429-441. [2]R. M. Nelson et al., GRL, VOL. 36, L04202, doi:10.1029/2008GL036206, 2009. [3]S. D. Wall GRL, VOL. 36, L04203, doi:10.1029/2008GL036415, 2009

  17. Active chemisorption sites in functionalized ionic liquids for carbon capture.

    PubMed

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

    Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined. PMID:27243042

  18. Cyclic silicate active site and stereochemical match for apatite nucleation on pseudowollastonite bioceramic-bone interfaces.

    PubMed

    Sahai, Nita; Anseau, Michel

    2005-10-01

    Hydroxyapatite (Ca5(PO4)3(OH)) forms on pseudowollastonite (psW) (alpha-CaSiO3) in vitro in simulated body fluid, human parotid saliva and cell-culture medium, and in vivo in implanted rat tibias. We used crystallographic constraints with ab initio molecular orbital calculations to identify the active site and reaction mechanism for heterogeneous nucleation of the earliest calcium phosphate oligomer/phase. The active site is the planar, cyclic, silicate trimer (Si3O9) on the (001) face of psW. The trimer has three silanol groups (>SiOH) arranged at 60 degrees from each other, providing a stereochemical match for O atoms bonded to Ca2+ on the (001) face of hydroxyapatite. Calcium phosphate nucleation is modeled in steps as hydrolysis of surface Ca-O bonds with leaching of Ca2+ into solution, protonation of the surface Si-O groups to form silanols, calcium sorption as an inner-sphere surface complex and, attachment of HPO4(2-). Our model explains the experimental solution and high resolution transmission electron microscopy data for epitaxial hydroxyapatite growth on psW in vitro and in vivo. We propose that the cyclic silicate trimer is the universal active site for heterogeneous, stereochemically promoted nucleation on silicate-based bioactive ceramics. A critical active site-density and a point of zero charge of the bioceramic less than physiological pH are required for bioactivity. PMID:15949543

  19. Rat intestinal trehalase. Studies of the active site.

    PubMed

    Chen, C C; Guo, W J; Isselbacher, K J

    1987-11-01

    Rat intestinal trehalase was solubilized, purified and reconstituted into proteoliposomes. With octyl glucoside as the solubilizing detergent, the purified protein appeared as a single band on SDS/polyacrylamide-gel electrophoresis with an apparent molecular mass of 67 kDa. Kinetic studies indicated that the active site of this enzyme can be functionally divided into two adjacent regions, namely a binding site (with pKa 4.8) and a catalytic site (with pKa 7.2). Other findings suggested that the catalytic site contains a functional thiol group, which is sensitive to inhibition by N-ethylmaleimide, Hg2+ and iodoacetate. Substrate protection and iodoacetate labelling of the thiol group demonstrated that only a protein of 67 kDa was labelled. Furthermore, sucrose and phlorizin protected the thiol group, but Tris-like inhibitors did not. Structure-inhibition analysis of Tris-like inhibitors, the pH effect of Tris inhibition and Tris protection of 1-(3-dimethylaminopropyl)-3-ethylcarbodi-imide inactivation permitted characterization and location of a separate site containing a carboxy group for Tris binding, which may also be the binding region. On the basis of these findings, a possible structure for the active site of trehalase is proposed. PMID:3426558

  20. Active Site and Remote Contributions to Catalysis in Methylthioadenosine Nucleosidases

    PubMed Central

    Thomas, Keisha; Cameron, Scott A.; Almo, Steven C.; Burgos, Emmanuel S.; Gulab, Shivali A.; Schramm, Vern L.

    2015-01-01

    5′-Methylthioadenosine/S-adenosyl-L-homocysteine nucleosidases (MTANs) catalyze the hydrolysis of 5′-methylthioadenosine to adenine and 5-methylthioribose. The amino acid sequences of the MTANs from Vibrio cholerae (VcMTAN) and Escherichia coli (EcMTAN) are 60% identical and 75% similar. Protein structure folds and kinetic properties are similar. However, binding of transition-state analogues is dominated by favorable entropy in VcMTAN and by enthalpy in EcMTAN. Catalytic sites of VcMTAN and EcMTAN in contact with reactants differ by two residues; Ala113 and Val153 in VcMTAN are Pro113 and Ile152, respectively, in EcMTAN. We mutated the VcMTAN catalytic site residues to match those of EcMTAN in anticipation of altering its properties toward EcMTAN. Inhibition of VcMTAN by transition-state analogues required filling both active sites of the homodimer. However, in the Val153Ile mutant or double mutants, transition-state analogue binding at one site caused complete inhibition. Therefore, a single amino acid, Val153, alters the catalytic site cooperativity in VcMTAN. The transition-state analogue affinity and thermodynamics in mutant VcMTAN became even more unlike those of EcMTAN, the opposite of expectations from catalytic site similarity; thus, catalytic site contacts in VcMTAN are unable to recapitulate the properties of EcMTAN. X-ray crystal structures of EcMTAN, VcMTAN, and a multiple-site mutant of VcMTAN most closely resembling EcMTAN in catalytic site contacts show no major protein conformational differences. The overall protein architectures of these closely related proteins are implicated in contributing to the catalytic site differences. PMID:25806409

  1. Surface Forcing from CH4 at the North Slope of Alaska and Southern Great Plains Sites

    NASA Astrophysics Data System (ADS)

    Collins, W.; Feldman, D.; Turner, D. D.

    2014-12-01

    Recent increases in atmospheric CH4 have been spatially heterogeneous as indicated by in situ flask measurements and space-borne remote-sensing retrievals from the AIRS instrument, potentially leading to increased radiative forcing. We present detailed, specialized measurements at the DOE ARM North Slope of Alaska (NSA) and Southern Great Plains (SGP) sites to derive the time-series of both CH4 atmospheric concentrations and associated radiative implications at highly-contrasting natural and anthropogenic sources. Using a combination of spectroscopic measurements, in situ observations, and ancillary data for the atmospheric thermodynamic state from radiosondes and cloud-clearing from active sounders, we can separate out the contribution of CH4 to clear-sky downwelling radiance spectra and its infrared surface forcing. The time-series indicates year-to-year variation in shoulder season increases of CH4 concentration and forcing at NSA and large signals from anthropogenic activity at SGP.

  2. Water in the Active Site of Ketosteroid Isomerase

    PubMed Central

    Hanoian, Philip; Hammes-Schiffer, Sharon

    2011-01-01

    Classical molecular dynamics simulations were utilized to investigate the structural and dynamical properties of water in the active site of ketosteroid isomerase (KSI) to provide insight into the role of these water molecules in the enzyme-catalyzed reaction. This reaction is thought to proceed via a dienolate intermediate that is stabilized by hydrogen bonding with residues Tyr16 and Asp103. A comparative study was performed for the wild-type (WT) KSI and the Y16F, Y16S, and Y16F/Y32F/Y57F (FFF) mutants. These systems were studied with three different bound ligands: equilenin, which is an intermediate analog, and the intermediate states of two steroid substrates. Several distinct water occupation sites were identified in the active site of KSI for the WT and mutant systems. Three additional sites were identified in the Y16S mutant that were not occupied in WT KSI or the other mutants studied. The number of water molecules directly hydrogen bonded to the ligand oxygen was approximately two waters in the Y16S mutant, one water in the Y16F and FFF mutants, and intermittent hydrogen bonding of one water molecule in WT KSI. The molecular dynamics trajectories of the Y16F and FFF mutants reproduced the small conformational changes of residue 16 observed in the crystal structures of these two mutants. Quantum mechanical/molecular mechanical calculations of 1H NMR chemical shifts of the protons in the active site hydrogen-bonding network suggest that the presence of water in the active site does not prevent the formation of short hydrogen bonds with far-downfield chemical shifts. The molecular dynamics simulations indicate that the active site water molecules exchange much more frequently for WT KSI and the FFF mutant than for the Y16F and Y16S mutants. This difference is most likely due to the hydrogen-bonding interaction between Tyr57 and an active site water molecule that is persistent in the Y16F and Y16S mutants but absent in the FFF mutant and significantly less

  3. Surface active properties of chitosan and its derivatives.

    PubMed

    Elsabee, Maher Z; Morsi, Rania Elsayed; Al-Sabagh, A M

    2009-11-01

    This review discusses the definition of surface active agents and specifically natural polymeric surface active agents. Chitosan by itself was found to have weak surface activity since it has no hydrophobic segments. Chemical modifications of chitosan could improve such surface activity. This is achieved by introducing hydrophobic substituents in its glucosidic group. Several examples of chitosan derivatives with surfactant activity have been surveyed. The surface active polymers form micelles and aggregates which have enormous importance in the entrapment of water-insoluble drugs and consequently applications in the controlled drug delivery and many biomedical fields. Chitosan also interacts with several substrates by electrostatic and hydrophobic interactions with considerable biomedical applications. PMID:19682870

  4. Energy transfer at the active sites of heme proteins

    SciTech Connect

    Dlott, D.D.; Hill, J.R.

    1995-12-31

    Experiments using a picosecond pump-probe apparatus at the Picosecond Free-electron Laser Center at Stanford University, were performed to investigate the relaxation of carbon monoxide bound to the active sites of heme proteins. The significance of these experiments is two-fold: (1) they provide detailed information about molecular dynamics occurring at the active sites of proteins; and (2) they provide insight into the nature of vibrational relaxation processes in condensed matter. Molecular engineering is used to construct various molecular systems which are studied with the FEL. We have studied native proteins, mainly myoglobin obtained from different species, mutant proteins produced by genetic engineering using recombinant DNA techniques, and a variety of model systems which mimic the structures of the active sites of native proteins, which are produced using molecular synthesis. Use of these different systems permits us to investigate how specific molecular structural changes affect dynamical processes occurring at the active sites. This research provides insight into the problems of how different species needs are fulfilled by heme proteins which have greatly different functionality, which is induced by rather small structural changes.

  5. Chemical Modification of Papain and Subtilisin: An Active Site Comparison

    ERIC Educational Resources Information Center

    St-Vincent, Mireille; Dickman, Michael

    2004-01-01

    An experiment using methyle methanethiosulfonate (MMTS) and phenylmethylsulfonyl flouride (PMSF) to specifically modify the cysteine and serine residues in the active sites of papain and subtilism respectively is demonstrated. The covalent modification of these enzymes and subsequent rescue of papain shows the beginning biochemist that proteins…

  6. Changes in active site histidine hydrogen bonding trigger cryptochrome activation.

    PubMed

    Ganguly, Abir; Manahan, Craig C; Top, Deniz; Yee, Estella F; Lin, Changfan; Young, Michael W; Thiel, Walter; Crane, Brian R

    2016-09-01

    Cryptochrome (CRY) is the principal light sensor of the insect circadian clock. Photoreduction of the Drosophila CRY (dCRY) flavin cofactor to the anionic semiquinone (ASQ) restructures a C-terminal tail helix (CTT) that otherwise inhibits interactions with targets that include the clock protein Timeless (TIM). All-atom molecular dynamics (MD) simulations indicate that flavin reduction destabilizes the CTT, which undergoes large-scale conformational changes (the CTT release) on short (25 ns) timescales. The CTT release correlates with the conformation and protonation state of conserved His378, which resides between the CTT and the flavin cofactor. Poisson-Boltzmann calculations indicate that flavin reduction substantially increases the His378 pKa Consistent with coupling between ASQ formation and His378 protonation, dCRY displays reduced photoreduction rates with increasing pH; however, His378Asn/Arg variants show no such pH dependence. Replica-exchange MD simulations also support CTT release mediated by changes in His378 hydrogen bonding and verify other responsive regions of the protein previously identified by proteolytic sensitivity assays. His378 dCRY variants show varying abilities to light-activate TIM and undergo self-degradation in cellular assays. Surprisingly, His378Arg/Lys variants do not degrade in light despite maintaining reactivity toward TIM, thereby implicating different conformational responses in these two functions. Thus, the dCRY photosensory mechanism involves flavin photoreduction coupled to protonation of His378, whose perturbed hydrogen-bonding pattern alters the CTT and surrounding regions. PMID:27551082

  7. Near-surface gas mapping studies of salt geologic features at Weeks Island and other sites

    SciTech Connect

    Molecke, M.A.; Carney, K.R.; Autin, W.J.; Overton, E.B.

    1996-10-01

    Field sampling and rapid gas analysis techniques were used to survey near-surface soil gases for geotechnical diagnostic purposes at the Weeks Island Strategic Petroleum Reserve (SPR) site and other salt dome locations in southern Louisiana. This report presents the complete data, results and interpretations obtained during 1995. Weeks Island 1994 gas survey results are also briefly summarized; this earlier study did not find a definitive correlation between sinkhole No. 1 and soil gases. During 1995, several hundred soil gas samples were obtained and analyzed in the field by gas chromatography, for profiling low concentrations and gas anomalies at ppm to percent levels. The target gases included hydrogen, methane, ethane and ethylene. To supplement the field data, additional gas samples were collected at various site locations for laboratory analysis of target gases at ppb levels. Gases in the near-surface soil originate predominantly from the oil, from petrogenic sources within the salt, or from surface microbial activity. Surveys were conducted across two Weeks Island sinkholes, several mapped anomalous zones in the salt, and over the SPR repository site and its perimeter. Samples were also taken at other south Louisiana salt dome locations for comparative purposes. Notable results from these studies are that elevated levels of hydrogen and methane (1) were positively associated with anomalous gassy or shear zones in the salt dome(s) and (2) are also associated with suspected salt fracture (dilatant) zones over the edges of the SPR repository. Significantly elevated areas of hydrogen, methane, plus some ethane, were found over anomalous shear zones in the salt, particularly in a location over high pressure gas pockets in the salt, identified in the mine prior to SPR operations. Limited stable isotope ratio analyses, SIRA, were also conducted and determined that methane samples were of petrogenic origin, not biogenic.

  8. FINAL REPORT. SEISMIC SURFACE-WAVE TOMOGRAPHY OF WASTE SITES

    EPA Science Inventory

    The objective of this study was to develop analysis programs for surface-wave group-velocity tomography and apply these to three test areas. We succeeded by obtaining data covering two square areas that were 30 meters on a side and one that was 16 meters on a side, in addition to...

  9. Active sites environmental monitoring program. Annual report FY 1992

    SciTech Connect

    Morrissey, C.M.; Ashwood, T.L.; Hicks, D.S.

    1994-04-01

    This report summarizes the activities of the Active Sites Environmental Monitoring Program (ASEMP) at ORNL from October 1991 through September 1992. Solid Waste Operations and the Environmental Sciences Division established ASEMP in 1989 to provide early detection and performance monitoring at active low-level waste (LLW) disposal sites in Solid Waste Storage Area (SWSA) 6 and transuranic (TRU) waste storage sites in SWSA 5 as required by Chapter 2 and 3 of US Department of Energy Order 5820.2A. The Interim Waste Management Facility (IWMF) began operation in December 1991. Monitoring results from the tumulus and IWMF disposal pads continue to indicate that no LLW is leaching from the storage vaults. Storm water falling on the IWMF active pad was collected and transported to the Process Waste Treatment Plant while operators awaited approval of the National Pollutant Discharge Elimination System (NPDES) permit. Several of the recent samples collected from the active IWMF pad had pH levels above the NPDES limit of 9.0 because of alkali leached from the concrete. The increase in gross beta activity has been slight; only 1 of the 21 samples collected contained activity above the 5.0 Bq/L action level. Automated sample-collection and flow-measurement equipment has been installed at IWMF and is being tested. The flume designed to electronically measure flow from the IWMF pads and underpads is too large to be of practical value for measuring most flows at this site. Modification of this system will be necessary. A CO{sub 2} bubbler system designed to reduce the pH of water from the pads is being tested at IWMF.

  10. Effect of Surface-Active Pseudomonas spp. on Leaf Wettability

    PubMed Central

    Bunster, Lillian; Fokkema, Nyckle J.; Schippers, Bob

    1989-01-01

    Different strains of Pseudomonas putida and P. fluorescens isolated from the rhizosphere and phyllosphere were tested for surface activity in droplet cultures on polystyrene. Droplets of 6 of the 12 wild types tested spread over the surface during incubation, and these strains were considered surface active; strains not showing this reaction were considered non-surface active. Similar reactions were observed on pieces of wheat leaves. Supernatants from centrifuged broth cultures behaved like droplets of suspensions in broth; exposure to 100°C destroyed the activity. Average contact angles of the supernatants of surface-active and non-surface-active strains on polystyrene were 24° and 72°, respectively. The minimal surface tension of supernatants of the surface-active strains was about 46 mN/m, whereas that of the non-surface-active strains was 64 mN/m (estimations from Zisman plots). After 6 days of incubation, wheat flag leaves sprayed with a dilute suspension of a surface-active strain of P. putida (WCS 358RR) showed a significant increase in leaf wettability, which was determined by contact angle measurements. Increasing the initial concentration of bacteria and the amount of nutrients in the inoculum sprayed on leaves reduced the contact angles from 138° on leaves treated with antibiotics (control) to 43° on leaves treated with surface-active bacteria. A closely related strain with no surface activity on polystyrene did not affect leaf wettability, although it was present in densities similar to those of the surface-active strain. Nutrients alone could occasionally also increase leaf wettability, apparently by stimulating naturally occurring surface-active bacteria. When estimating densities of Pseudomonas spp. underneath droplets with low contact angles, it appeared that populations on leaves treated with a surface-active strain could vary from about 104 to 106 CFU cm−2, suggesting that the surface effect may be prolonged after a decline of the

  11. C¹ Positive Surface over Positive Scattered Data Sites.

    PubMed

    Ibraheem, Farheen; Hussain, Malik Zawwar; Bhatti, Akhlaq Ahmad

    2015-01-01

    The aim of this paper is to develop a local positivity preserving scheme when the data amassed from different sources is positioned at sparse points. The proposed algorithm first triangulates the irregular data using Delauny triangulation method, therewith interpolates each boundary and radial curve of the triangle by C¹ rational trigonometric cubic function. Half of the parameters in the description of the interpolant are constrained to keep up the positive shape of data while the remaining half are set free for users' requirement. Orthogonality of trigonometric function assures much smoother surface as compared to polynomial functions. The proposed scheme can be of great use in areas of surface reconstruction and deformation, signal processing, CAD/CAM design, solving differential equations, and image restoration. PMID:26057122

  12. C¹ Positive Surface over Positive Scattered Data Sites

    PubMed Central

    Ibraheem, Farheen; Hussain, Malik Zawwar; Bhatti, Akhlaq Ahmad

    2015-01-01

    The aim of this paper is to develop a local positivity preserving scheme when the data amassed from different sources is positioned at sparse points. The proposed algorithm first triangulates the irregular data using Delauny triangulation method, therewith interpolates each boundary and radial curve of the triangle by C¹ rational trigonometric cubic function. Half of the parameters in the description of the interpolant are constrained to keep up the positive shape of data while the remaining half are set free for users’ requirement. Orthogonality of trigonometric function assures much smoother surface as compared to polynomial functions. The proposed scheme can be of great use in areas of surface reconstruction and deformation, signal processing, CAD/CAM design, solving differential equations, and image restoration. PMID:26057122

  13. Probing the promiscuous active site of myo-inositol dehydrogenase using synthetic substrates, homology modeling, and active site modification.

    PubMed

    Daniellou, Richard; Zheng, Hongyan; Langill, David M; Sanders, David A R; Palmer, David R J

    2007-06-26

    The active site of myo-inositol dehydrogenase (IDH, EC 1.1.1.18) from Bacillus subtilis recognizes a variety of mono- and disaccharides, as well as 1l-4-O-substituted inositol derivatives. It catalyzes the NAD+-dependent oxidation of the axial alcohol of these substrates with comparable kinetic constants. We have found that 4-O-p-toluenesulfonyl-myo-inositol does not act as a substrate for IDH, in contrast to structurally similar compounds such as those bearing substituted benzyl substituents in the same position. X-ray crystallographic analysis of 4-O-p-toluenesulfonyl-myo-inositol and 4-O-(2-naphthyl)methyl-myo-inositol, which is a substrate for IDH, shows a distinct difference in the preferred conformation of the aryl substituent. Conformational analysis of known substrates of IDH suggests that this conformational difference may account for the difference in reactivity of 4-O-p-toluenesulfonyl-myo-inositol in the presence of IDH. A sequence alignment of IDH with the homologous glucose-fructose oxidoreductase allowed the construction of an homology model of inositol dehydrogenase, to which NADH and 4-O-benzyl-scyllo-inosose were docked and the active site energy minimized. The active site model is consistent with all experimental results and suggests that a conserved tyrosine-glycine-tyrosine motif forms the hydrophobic pocket adjoining the site of inositol recognition. Y233F and Y235F retain activity, while Y233R and Y235R do not. A histidine-aspartate pair, H176 and D172, are proposed to act as a dyad in which H176 is the active site acid/base. The enzyme is inactivated by diethyl pyrocarbonate, and the mutants H176A and D172N show a marked loss of activity. Kinetic isotope effect experiments with D172N indicate that chemistry is rate-determining for this mutant. PMID:17539607

  14. Enhanced oxygen evolution activity of IrO2 and RuO2 (100) surfaces

    SciTech Connect

    Stoerzinger, Kelsey; Qiao, Liang; Biegalski, Michael D; Christen, Hans M; Shao-Horn, Yang

    2014-01-01

    The activities of the oxygen evolution reaction (OER) on IrO2 and RuO2 catalysts are among the highest known to date. However, the intrinsic OER activities of surfaces with defined crystallographic orientations are not well established experimentally. Here we report that the (100) surface of IrO2 and RuO2 is more active than the (110) surface that has been traditionally explored by density functional theory studies. The relation between the OER activity and density of coordinatively undersaturated metal sites exposed on each rutile crystallographic facet is discussed. The surface-orientation dependent activities can guide the design of high-surface-area catalysts with increased activity for electrolyzers, metal-air batteries, and photoelectrochemical water splitting applications.

  15. PEP-SiteFinder: a tool for the blind identification of peptide binding sites on protein surfaces.

    PubMed

    Saladin, Adrien; Rey, Julien; Thévenet, Pierre; Zacharias, Martin; Moroy, Gautier; Tufféry, Pierre

    2014-07-01

    Peptide-protein interactions are important to many processes of life, particularly for signal transmission or regulatory mechanisms. When no information is known about the interaction between a protein and a peptide, it is of interest to propose candidate sites of interaction at the protein surface, to assist the design of biological experiments to probe the interaction, or to serve as a starting point for more focused in silico approaches. PEP-SiteFinder is a tool that will, given the structure of a protein and the sequence of a peptide, identify protein residues predicted to be at peptide-protein interface. PEP-SiteFinder relies on the 3D de novo generation of peptide conformations given its sequence. These conformations then undergo a fast blind rigid docking on the complete protein surface, and we have found, as the result of a benchmark over 41 complexes, that the best poses overlap to some extent the experimental patch of interaction for close to 90% complexes. In addition, PEP-SiteFinder also returns a propensity index we have found informative about the confidence of the prediction. The PEP-SiteFinder web server is available at http://bioserv.rpbs.univ-paris-diderot.fr/PEP-SiteFinder. PMID:24803671

  16. INORGANIC PLUME DELINEATION USING SURFACE HIGH RESOLUTION ELECTRICAL RESISTIVITY AT THE BC CRIBS & TRENCHES SITE HANFORD

    SciTech Connect

    BENECKE, M.W.

    2007-05-29

    A surface resistivity survey was conducted on the Hanford Site over a waste disposal trench that received a large volume of liquid inorganic waste. The objective of the survey was to map the extent of the plume that resulted from the disposal activities approximately 50 years earlier. The survey included six resistivity transects of at least 200m, where each transect provided two-dimensional profile information of subsurface electrical properties. The results of the survey indicated that a low resistivity plume resides at a depth of approximately 25-44 m below ground surface. The target depth was calibrated with borehole data of pore-water electrical conductivity. Due to the high correlation of the pore-water electrical conductivity to nitrate concentration and the high correlation of measured apparent resistivity to pore-water electrical conductivity, inferences were made that proposed the spatial distribution of the apparent resistivity was due to the distribution of nitrate. Therefore, apparent resistivities were related to nitrate, which was subsequently rendered in three dimensions to show that the nitrate likely did not reach the water table and the bounds of the highest concentrations are directly beneath the collection of waste sites.

  17. Surface Radiation Survey at the Shepley’s Hill Remediation Site, Devens, Massachusettes

    SciTech Connect

    J. R. Giles; C. P. Oertel; L. G. Roybal

    2009-09-01

    The Idaho National Laboratory (INL) provided technical support for ongoing environmental remediation activities at the Shepley’s Hill remediation site, near Devens, MA. The technical support included the completion of a radiation survey of naturally occurring radioactive materials (NORM) at Shepley’s Hill, Shepley’s Hill landfill cover, and Red Cove areas. The objective of the radiation survey was to assess the ability of the INL backpack sodium iodide spectroscopy (BaSIS) system to detect elevated levels of NORM that may be associated with radon-222 emanation from near surface and subsurface fractures in the area. It is postulated that these fracture zones provide subsurface conduits for the transport of environmental contaminants. As such, location of these fracture sets will proved EPA Region 1 with the means for completing the development of an accurate site conceptual model. The results of the radiological survey show that some of the radiological anomalies correlate with currently mapped rock outcrops; however, not all of the rock outcrops in the surveyed area have been mapped. As such, it is not conclusive that all of the radiological anomalies correspond with surface rock outcrops. EPA Region 1 intends to perform a more comprehensive correlation of the radiation data collected with the BaSIS system with additional data sets such as detailed bedrock structural mapping, 2-dimensional resistivity profiling, and high-resolution topographic mapping. The results of this effort will be used in consideration of designing a potential follow-on effort for mapping of radon.

  18. Remaining Sites Verification Package for the 100-B-23, 100-B/C Area Surface Debris, Waste Site, Waste Site Reclassification Form 2008-027

    SciTech Connect

    J. M. Capron

    2008-06-16

    The 100-B-23, 100-B/C Surface Debris, waste consisted of multiple locations of surface debris and chemical stains that were identified during an Orphan Site Evaluation of the 100-B/C Area. Evaluation of the collected information for the surface debris features yielded four generic waste groupings: asbestos-containing material, lead debris, oil and oil filters, and treated wood. Focused verification sampling was performed concurrently with remediation. Site remediation was accomplished by selective removal of the suspect hazardous items and potentially impacted soils. In accordance with this evaluation, the verification sampling results support a reclassification of this site to Interim Closed Out. The results of verification sampling show that residual contaminant concentrations do not preclude any future uses and allow for unrestricted use of shallow zone soils. The results also demonstrate that residual contaminant concentrations are protective of groundwater and the Columbia River.

  19. Activated wetting dynamics in the presence of mesoscopic surface disorder

    NASA Astrophysics Data System (ADS)

    Davitt, Kristina; Pettersen, Michael; Rolley, Etienne

    2012-02-01

    Although disorder is commonly used to explain contact angle hysteresis, it is often neglected when considering wetting dynamics. When viscous forces are negligible, contact-line velocity is modelled by the Molecular Kinetic Theory [1], which predicts an activated motion driven by molecular jumps on preferential adsorption sites. We believe that in the presence of mesoscopic disorder, this model can be reinterpreted and that the activation length is no longer molecular-sized but is related to depinning events on the surface. This hypothesis is supported by a study of the wetting of cesium by liquid hydrogen in which it was shown that the activation length is of the order of the expected roughness [2]. However, no systematic study between the activation area and the length scale of the disorder has previously been made. We study wetting dynamics on metal films evaporated under different conditions, allowing us to obtain films with lateral grain sizes ranging from 10 to 200 nm. We find that the activation area deduced from wetting experiments is coherent with these sizes; however, its precise relation to the scale of disorder is not clear.[1] T.D. Blake and J.M. Haynes, J. Colloid Interface Sci. 30, 421 (1969)[2] E. Rolley and C. Guthmann, PRL 98, 166105 (2007)

  20. Near-surface wave velocity structure of Faial (Azores - Portugal) Island for site effect studies

    NASA Astrophysics Data System (ADS)

    Borges, José; Neves, Samuel; Caldeira, Bento; Bezzeghoud, Mourad; Carvalho, João; Carvalho, Alexandra

    2015-04-01

    Throughout history, the life of the Azorean people has been marked by earthquakes that have had different effects depending on their proximity and magnitude. This seismic activity, which may have volcanic or tectonic origins, has affected the population of these islands by destroying infrastructure and claiming lives. The social and economic impacts of these phenomena are enormous. The last significant event affecting the Azores (Portugal) was the July 1998 Mw=6.2 earthquake causing major destruction affecting more than 5000 people, causing 8 deaths, 150 persons injured and 1500 homeless. Ground motion simulations are mainly based on source characteristics and are heavily dependent on the medium, which is still poorly understood. Subsurface soil condition can amplify the seismic waves, so, for seismic response analysis, it is necessary to know the shallow soil properties and its spatial variability. For this purpose, we applied P and S-wave refraction, Multichannel Analysis of Surface Waves (MASW) to characterize shear wave velocity at different sites in the Faial Island, in particular, in sites where already occurred amplification. Ambient vibrations can also be used to estimate physical properties of the shallower geological formations. With this goal, the obtained velocity models were confirmed by comparison between real H/V curves with synthetic ones. We concluded that the anomalous intensities observed in some sites are strongly related to thick layers of soft sediments of pyroclastic deposits produced by old volcanic eruptions occurred in the Faial Island.

  1. Anisotropic capillary barrier for waste site surface covers

    DOEpatents

    Stormont, J.C.

    1996-08-27

    Waste sites are capped or covered upon closure. The cover structure incorporates a number of different layers each having a contributory function. One such layer is the barrier layer. Traditionally the barriers have been compacted soil and geosynthetics. These types of barriers have not been successfully implemented in unsaturated ground conditions like those found in dry climates. Capillary barriers have been proposed as barrier layers in dry environments, but the divergence length of these barriers has been found to be inadequate. An alternative to the capillary barrier is a anisotropic capillary barrier. An anisotropic capillary barrier has an increased divergence length which results in more water being diverted laterally preventing the majority of water from percolating in a downward direction through the barrier. 10 figs.

  2. Anisotropic capillary barrier for waste site surface covers

    DOEpatents

    Stormont, John C.

    1996-01-01

    Waste sites are capped or covered upon closure. The cover structure incorporates a number of different layers each having a contributory function. One such layer is the barrier layer. Traditionally the barriers have been compacted soil and geosynthetics. These types of barriers have not been successfully implemented in unsaturated ground conditions like those found in dry climates. Capillary barriers have been proposed as barrier layers in dry environments, but the divergence length of these barriers has been found to be inadequate. An alternative to the capillary barrier is a anisotropic capillary barrier. An anisotropic capillary barrier has an increased divergence length which results in more water being diverted laterally preventing the majority of water from percolating in a downward direction through the barrier.

  3. Active-Site-Accessible, Porphyrinic Metal;#8722;Organic Framework Materials

    SciTech Connect

    Farha, Omar K.; Shultz, Abraham M.; Sarjeant, Amy A.; Nguyen, SonBinh T.; Hupp, Joseph T.

    2012-02-06

    On account of their structural similarity to cofactors found in many metallo-enzymes, metalloporphyrins are obvious potential building blocks for catalytically active, metal-organic framework (MOF) materials. While numerous porphyrin-based MOFs have already been described, versions featuring highly accessible active sites and permanent microporosity are remarkably scarce. Indeed, of the more than 70 previously reported porphyrinic MOFs, only one has been shown to be both permanently microporous and contain internally accessible active sites for chemical catalysis. Attempts to generalize the design approach used in this single successful case have failed. Reported here, however, is the synthesis of an extended family of MOFs that directly incorporate a variety of metalloporphyrins (specifically Al{sup 3+}, Zn{sup 2+}, Pd{sup 2+}, Mn{sup 3+}, and Fe{sup 3+} complexes). These robust porphyrinic materials (RPMs) feature large channels and readily accessible active sites. As an illustrative example, one of the manganese-containing RPMs is shown to be catalytically competent for the oxidation of alkenes and alkanes.

  4. Identification of active sites in gold-catalyzed hydrogenation of acrolein.

    PubMed

    Mohr, Christian; Hofmeister, Herbert; Radnik, Jörg; Claus, Peter

    2003-02-19

    The active sites of supported gold catalysts, favoring the adsorption of C=O groups of acrolein and subsequent reaction to allyl alcohol, have been identified as edges of gold nanoparticles. After our recent finding that this reaction preferentially occurs on single crystalline particles rather than multiply twinned ones, this paper reports on a new approach to distinguish different features of the gold particle morphology. Elucidation of the active site issue cannot be simply done by varying the size of gold particles, since the effects of faceting and multiply twinned particles may interfere. Therefore, modification of the gold particle surface by indium has been used to vary the active site characteristics of a suitable catalyst, and a selective decoration of gold particle faces has been observed, leaving edges free. This is in contradiction to theoretical predictions, suggesting a preferred occupation of the low-coordinated edges of the gold particles. On the bimetallic catalyst, the desired allyl alcohol is the main product (selectivity 63%; temperature 593 K, total pressure p(total) = 2 MPa). From the experimentally proven correlation between surface structure and catalytic behavior, the edges of single crystalline gold particles have been identified as active sites for the preferred C=O hydrogenation. PMID:12580618

  5. Nest predation increases with parental activity: Separating nest site and parental activity effects

    USGS Publications Warehouse

    Martin, T.E.; Scott, J.; Menge, C.

    2000-01-01

    Alexander Skutch hypothesized that increased parental activity can increase the risk of nest predation. We tested this hypothesis using ten open-nesting bird species in Arizona, USA. Parental activity was greater during the nestling than incubation stage because parents visited the nest frequently to feed their young during the nestling stage. However, nest predation did not generally increase with parental activity between nesting stages across the ten study species. Previous investigators have found similar results. We tested whether nest site effects might yield higher predation during incubation because the most obvious sites are depredated most rapidly. We conducted experiments using nest sites from the previous year to remove parental activity. Our results showed that nest sites have highly repeatable effects on nest predation risk; poor nest sites incurred rapid predation and caused predation rates to be greater during the incubation than nestling stage. This pattern also was exhibited in a bird species with similar (i.e. controlled) parental activity between nesting stages. Once nest site effects are taken into account, nest predation shows a strong proximate increase with parental activity during the nestling stage within and across species. Parental activity and nest sites exert antagonistic influences on current estimates of nest predation between nesting stages and both must be considered in order to understand current patterns of nest predation, which is an important source of natural selection.

  6. Nest predation increases with parental activity: separating nest site and parental activity effects.

    PubMed Central

    Martin, T E; Scott, J; Menge, C

    2000-01-01

    Alexander Skutch hypothesized that increased parental activity can increase the risk of nest predation. We tested this hypothesis using ten open-nesting bird species in Arizona, USA. Parental activity was greater during the nestling than incubation stage because parents visited the nest frequently to feed their young during the nestling stage. However, nest predation did not generally increase with parental activity between nesting stages across the ten study species. Previous investigators have found similar results. We tested whether nest site effects might yield higher predation during incubation because the most obvious sites are depredated most rapidly. We conducted experiments using nest sites from the previous year to remove parental activity. Our results showed that nest sites have highly repeatable effects on nest predation risk; poor nest sites incurred rapid predation and caused predation rates to be greater during the incubation than nestling stage. This pattern also was exhibited in a bird species with similar (i.e. controlled) parental activity between nesting stages. Once nest site effects are taken into account, nest predation shows a strong proximate increase with parental activity during the nestling stage within and across species. Parental activity and nest sites exert antagonistic influences on current estimates of nest predation between nesting stages and both must be considered in order to understand current patterns of nest predation, which is an important source of natural selection. PMID:11413645

  7. Single-molecule catalysis mapping quantifies site-specific activity and uncovers radial activity gradient on single 2D nanocrystals.

    PubMed

    Andoy, Nesha May; Zhou, Xiaochun; Choudhary, Eric; Shen, Hao; Liu, Guokun; Chen, Peng

    2013-02-01

    Shape-controlled metal nanocrystals are a new generation of nanoscale catalysts. Depending on their shapes, these nanocrystals exhibit various surface facets, and the assignments of their surface facets have routinely been used to rationalize or predict their catalytic activity in a variety of chemical transformations. Recently we discovered that for 1-dimensional (1D) nanocrystals (Au nanorods), the catalytic activity is not constant along the same side facets of single nanorods but rather differs significantly and further shows a gradient along its length, which we attributed to an underlying gradient of surface defect density resulting from their linear decay in growth rate during synthesis (Nat. Nanotechnol.2012, 7, 237-241). Here we report that this behavior also extends to 2D nanocrystals, even for a different catalytic reaction. By using super-resolution fluorescence microscopy to map out the locations of catalytic events within individual triangular and hexagonal Au nanoplates in correlation with scanning electron microscopy, we find that the catalytic activity within the flat {111} surface facet of a Au nanoplate exhibits a 2D radial gradient from the center toward the edges. We propose that this activity gradient results from a growth-dependent surface defect distribution. We also quantify the site-specific activity at different regions within a nanoplate: The corner regions have the highest activity, followed by the edge regions and then the flat surface facets. These discoveries highlight the spatial complexity of catalytic activity at the nanoscale as well as the interplay amid nanocrystal growth, morphology, and surface defects in determining nanocatalyst properties. PMID:23320465

  8. Closure Report for Corrective Action Unit 300: Surface Release Areas Nevada Test Site, Nevada

    SciTech Connect

    NSTec Environmental Restoration

    2007-07-01

    Corrective Action Unit (CAU) 300 is located in Areas 23, 25, and 26 of the Nevada Test Site, which is located approximately 65 miles northwest of Las Vegas, Nevada. CAU 300 is listed in the Federal Facility Agreement and Consent Order of 1996 as Surface Release Areas and is comprised of the following seven Corrective Action Sites (CASs), which are associated with the identified Building (Bldg): {sm_bullet} CAS 23-21-03, Bldg 750 Surface Discharge {sm_bullet} CAS 23-25-02, Bldg 750 Outfall {sm_bullet} CAS 23-25-03, Bldg 751 Outfall {sm_bullet} CAS 25-60-01, Bldg 3113A Outfall {sm_bullet} CAS 25-60-02, Bldg 3901 Outfall {sm_bullet} CAS 25-62-01, Bldg 3124 Contaminated Soil {sm_bullet} CAS 26-60-01, Bldg 2105 Outfall and Decon Pad The Nevada Division of Environmental Protection (NDEP)-approved corrective action alternative for CASs 23-21-03, 23-25-02, and 23-25-03 is no further action. As a best management practice, approximately 48 feet of metal piping was removed from CAS 23-25-02 and disposed of as sanitary waste. The NDEP-approved corrective action alternative for CASs 25-60-01, 25-60-02, 25-62-01, and 26-60-01, is clean closure. Closure activities for these CASs included removing and disposing of soil impacted with total petroleum hydrocarbons-diesel range organics (TPH-DRO), polychlorinated biphenyls (PCBs), semivolatile organic compounds (SVOCs), and cesium (Cs)-137, concrete impacted with TPH-DRO, and associated piping impacted with TPH-DRO. CAU 300 was closed in accordance with the NDEP-approved CAU 300 Corrective Action Plan (CAP) (U.S. Department of Energy, National Nuclear Security Administration Nevada Site Office [NNSA/NSO], 2006). The closure activities specified in the CAP were based on the recommendations presented in the CAU 300 Corrective Action Decision Document (NNSA/NSO, 2005). This Closure Report documents CAU 300 closure activities. During closure activities, approximately 40 cubic yards (yd3) of low-level waste consisting of TPH-DRO-, PCB

  9. Elemental analyses of hypervelocity micro-particle impact sites on interplanetary dust experiment sensor surfaces

    NASA Technical Reports Server (NTRS)

    Simon, Charles G.; Hunter, J. L.; Griffis, D. P.; Misra, V.; Ricks, D. R.; Wortman, Jim J.

    1992-01-01

    The Interplanetary Dust Experiment (IDE) had over 450 electrically active ultra-high purity metal-oxide-silicon impact detectors located on the six primary sides of the Long Duration Exposure Facility (LDEF). Hypervelocity micro-particles that struck the active sensors with enough energy to breakdown the 0.4 to 1.0 micron thick SiO2 insulator layer separating the silicon base (the negative electrode), and the 1000 A thick surface layer of aluminum (the positive electrode) caused electrical discharges that were recorded for the first year of orbit. These discharge features, which include 50 micron diameter areas where the aluminum top layer has been vaporized, facilitate the location of the impacts. The high purity Al-SiO2-Si substrates allow detection of trace (ppm) amounts of hypervelocity impactor residues. After sputtering through a layer of surface contamination, secondary ion mass spectrometry (SIMS) is used to create two-dimensional elemental ion intensity maps of micro-particle impact sites on the IDE sensors. The element intensities in the central craters of the impacts are corrected for relative ion yields and instrumental conditions and then normalized to silicon. The results are used to classify the particles' origins as 'manmade', 'natural' or 'indeterminate'. The last classification results from the presence of too little impactor residue (a frequent occurrence on leading edge impacts), analytical interference from high background contamination, the lack of information on silicon residue, the limited usefulness of data on aluminum in the central craters, or a combination of these circumstances. Several analytical 'blank' discharges were induced on flight sensors by pressing down on the sensor surface with a pure silicon shard. Analyses of these blank discharges showed that the discharge energy blasts away the layer of surface contamination. Only Si and Al were detected inside the discharge zones, including the central craters, of these features. A

  10. Active Sites Environmental Monitoring Program. FY 1993: Annual report

    SciTech Connect

    Morrissey, C.M.; Ashwood, T.L.; Hicks, D.S.; Marsh, J.D.

    1994-08-01

    This report continues a series of annual and semiannual reports that present the results of the Active Sites Environmental Monitoring Program (ASEMP) monitoring activities. The report details monitoring data for fiscal year (FY) 1993 and is divided into three major areas: SWSA 6 [including tumulus pads, Interim Waste Management Facility (IWMF), and other sites], the low-level Liquid-Waste Solidification Project (LWSP), and TRU-waste storage facilities in SWSA 5 N. The detailed monitoring methodology is described in the second revision of the ASEMP program plan. This report also presents a summary of the methodology used to gather data for each major area along with the results obtained during FY 1993.

  11. Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold.

    PubMed

    Krajčí, Marian; Kameoka, Satoshi; Tsai, An-Pang

    2016-08-28

    We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al2Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped {211} surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir-Hinshelwood mechanism with the activation energy of 37 kJ/mol or via the CO-OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy. PMID:27586937

  12. Comparison of surface fluxes and conductances at two contrasting sites within the FIFE area

    NASA Technical Reports Server (NTRS)

    Stewart, J. B.; Verma, S. B.

    1992-01-01

    Surface flux measurements from two contrasting sites within the FIFE study area are analyzed. The seasonal variation of midday latent heat fluxes and surface conductances at the two sites was found to be very similar even though the ratio of their average total leaf area indices was greater than two to one. Concurrent measurements made at another six flat sites within the FIFE area confirmed the independence of latent heat flux with respect to leaf area index. The surface conductance stress function related to specific humidity deficit was the same for the two sites, whereas the solar radiation stress function showed a difference of 30 percent at a solar radiation input of 300 W/sq m and the soil moisture stress function showed a difference of 16 percent when half the extractable soil moisture had been taken up. However, when the stress functions were combined to determine the surface conductance, these differences virtually canceled out.

  13. Improving the neutral phytase activity from Bacillus amyloliquefaciens DSM 1061 by site-directed mutagenesis.

    PubMed

    Xu, Wei; Shao, Rong; Wang, Zupeng; Yan, Xiuhua

    2015-03-01

    Neutral phytase is used as a feed additive for degradation of anti-nutritional phytate in aquatic feed industry. Site-directed mutagenesis of Bacillus amyloliquefaciens DSM 1061 phytase was performed with an aim to increase its activity. Mutation residues were chosen based on multiple sequence alignments and structure analysis of neutral phytsaes from different microorganisms. The mutation sites on surface (D148E, S197E and N156E) and around the active site (D52E) of phytase were selected. Analysis of the phytase variants showed that the specific activities of mutants D148E and S197E remarkably increased by about 35 and 13% over a temperature range of 40-75 °C at pH 7.0, respectively. The k cat of mutants D148E and S197E were 1.50 and 1.25 times than that of the wild-type phytase, respectively. Both D148E and S197E showed much higher thermostability than that of the wild-type phytase. However, mutants N156E and D52E led to significant loss of specific activity of the enzyme. Structural analysis revealed that these mutations may affect conformation of the active site of phytase. The present mutant phytases D148E and S197E with increased activities and thermostabilities have application potential as additives in aquaculture feed. PMID:25613522

  14. Active sites in char gasification: Final technical report

    SciTech Connect

    Wojtowicz, M.; Lilly, W.D.; Perkins, M.T.; Hradil, G.; Calo, J.M.; Suuberg, E.M.

    1987-09-01

    Among the key variables in the design of gasifiers and combustors is the reactivity of the chars which must be gasified or combusted. Significant loss of unburned char is unacceptable in virtually any process; the provision of sufficient residence time for complete conversion is essential. A very wide range of reactivities are observed, depending upon the nature of the char in a process. The current work focuses on furthering the understanding of gasification reactivities of chars. It has been well established that the reactivity of char to gasification generally depends upon three principal factors: (1) the concentration of ''active sites'' in the char; (2) mass transfer within the char; and (3) the type and concentration of catalytic impurities in the char. The present study primarily addresses the first factor. The subject of this research is the origin, nature, and fate of active sites in chars derived from parent hydrocarbons with coal-like structure. The nature and number of the active sites and their reactivity towards oxygen are examined in ''model'' chars derived from phenol-formaldehyde type resins. How the active sites are lost by the process of thermal annealing during heat treatment of chars are studied, and actual rate for the annealing process is derived. Since intrinsic char reactivities are of primary interest in the present study, a fair amount of attention was given to the model char synthesis and handling so that the effect of catalytic impurities and oxygen-containing functional groups in the chemical structure of the material were minimized, if not completely eliminated. The project would not be considered complete without comparing characteristic features of synthetic chars with kinetic behavior exhibited by natural chars, including coal chars.

  15. Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

    PubMed

    Pang, Simon H; Schoenbaum, Carolyn A; Schwartz, Daniel K; Medlin, J Will

    2013-01-01

    One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism. PMID:24025780

  16. Biological surface-active compounds from marine bacteria.

    PubMed

    Dang, Nga Phuong; Landfald, Bjarne; Willassen, Nils Peder

    2016-01-01

    Surface-active compounds (SACs) are widely used in different industries as well as in many daily consumption products. However, with the increasing concern for their environmental acceptability, attention has turned towards biological SACs which are biodegradable, less toxic and more environmentally friendly. In this work, 176 marine hydrocarbon-degrading bacterial isolates from petroleum-contaminated sites along the Norwegian coastline were isolated and screened for their capacity to produce biological SACs. Among them, 18 isolates were capable of reducing the surface tension of the culture medium by at least 20 mN m(-1) and/or capable of maintaining more than 40% of the emulsion volume after 24 h when growing on glucose or kerosene as carbon and energy source. These isolates were members of the genera Pseudomonas, Pseudoalteromonas, Rhodococcus, Catenovulum, Cobetia, Glaciecola, Serratia, Marinomonas and Psychromonas. Two isolates, Rhodococcus sp. LF-13 and Rhodococcus sp. LF-22, reduced surface tension of culture medium by more than 40 mN m(-1) when growing on kerosene, n-hexadecane or rapeseed oil. The biosurfactants were produced by resting cells of the two Rhodococcus strains suggesting the biosynthesis of the biosurfactants was not necessarily associated with their growth on hydrocarbons. PMID:26506920

  17. Potential sites of CFTR activation by tyrosine kinases.

    PubMed

    Billet, Arnaud; Jia, Yanlin; Jensen, Timothy J; Hou, Yue-Xian; Chang, Xiu-Bao; Riordan, John R; Hanrahan, John W

    2016-05-01

    The CFTR chloride channel is tightly regulated by phosphorylation at multiple serine residues. Recently it has been proposed that its activity is also regulated by tyrosine kinases, however the tyrosine phosphorylation sites remain to be identified. In this study we examined 2 candidate tyrosine residues near the boundary between the first nucleotide binding domain and the R domain, a region which is important for channel function but devoid of PKA consensus sequences. Mutating tyrosines at positions 625 and 627 dramatically reduced responses to Src or Pyk2 without altering the activation by PKA, suggesting they may contribute to CFTR regulation. PMID:26645934

  18. Brownian aggregation rate of colloid particles with several active sites

    SciTech Connect

    Nekrasov, Vyacheslav M.; Yurkin, Maxim A.; Chernyshev, Andrei V.; Polshchitsin, Alexey A.; Yakovleva, Galina E.; Maltsev, Valeri P.

    2014-08-14

    We theoretically analyze the aggregation kinetics of colloid particles with several active sites. Such particles (so-called “patchy particles”) are well known as chemically anisotropic reactants, but the corresponding rate constant of their aggregation has not yet been established in a convenient analytical form. Using kinematic approximation for the diffusion problem, we derived an analytical formula for the diffusion-controlled reaction rate constant between two colloid particles (or clusters) with several small active sites under the following assumptions: the relative translational motion is Brownian diffusion, and the isotropic stochastic reorientation of each particle is Markovian and arbitrarily correlated. This formula was shown to produce accurate results in comparison with more sophisticated approaches. Also, to account for the case of a low number of active sites per particle we used Monte Carlo stochastic algorithm based on Gillespie method. Simulations showed that such discrete model is required when this number is less than 10. Finally, we applied the developed approach to the simulation of immunoagglutination, assuming that the formed clusters have fractal structure.

  19. Market-based control of active surfaces

    NASA Astrophysics Data System (ADS)

    Berlin, Andrew A.; Hogg, Tad; Jackson, Warren B.

    1998-12-01

    This paper describes a market-based approach to controlling a smart matter-based object transport system, in which an array of distributed air jets applies forces to levitate and control the motion of a planar object. In the smart matter regime, the effects of spatial and temporal variation of operating parameters among a multiplicity of sensor, actuators, and controllers make it desirable for a control strategy to exhibit a minimal dependence on system models, and to be able to arbitrate among conflicting goals. A market-based strategy is introduced that aggregates the control requirements of multiple relatively simple local controllers, each of which seeks to optimize the performance of the system within a limited spatial and temporal range. These local controllers act as the market's consumers, and two sets of distributed air jets act as the producers. Experiments are performed comparing the performance of the market-based strategy to a near-optimal model-derived benchmark, as well as to a hand-tuned PD controller. Results indicate that even though the local controllers in the market are not based on a detailed model of the system dynamics, the market is able to effectively approximate the performance of the model-based benchmark. In certain specialized cases, such as tracking a step trajectory, the performance of the market surpasses the performance of the model-based benchmark by balancing the needs of conflicting control goals. A brief overview of the active surface smart matter prototype being developed at Xerox PARC that is the motivation behind this work is also presented.

  20. Data-Driven Surface Traversability Analysis for Mars 2020 Landing Site Selection

    NASA Technical Reports Server (NTRS)

    Ono, Masahiro; Rothrock, Brandon; Almeida, Eduardo; Ansar, Adnan; Otero, Richard; Huertas, Andres; Heverly, Matthew

    2015-01-01

    The objective of this paper is three-fold: 1) to describe the engineering challenges in the surface mobility of the Mars 2020 Rover mission that are considered in the landing site selection processs, 2) to introduce new automated traversability analysis capabilities, and 3) to present the preliminary analysis results for top candidate landing sites. The analysis capabilities presented in this paper include automated terrain classification, automated rock detection, digital elevation model (DEM) generation, and multi-ROI (region of interest) route planning. These analysis capabilities enable to fully utilize the vast volume of high-resolution orbiter imagery, quantitatively evaluate surface mobility requirements for each candidate site, and reject subjectivity in the comparison between sites in terms of engineering considerations. The analysis results supported the discussion in the Second Landing Site Workshop held in August 2015, which resulted in selecting eight candidate sites that will be considered in the third workshop.

  1. Pioneering Objectives and Activities on the Surface of Mars

    NASA Technical Reports Server (NTRS)

    Toups, Larry; Hoffman, Stephen J.

    2015-01-01

    Human Mars missions have been a topic of sustained interest within NASA, which continues to use its resources to examine many different mission objectives, trajectories, vehicles, and technologies, the combinations of which are often referred to as reference missions or architectures. The current investigative effort, known as the Evolvable Mars Campaign (EMC), is examining alternatives that can pioneer an extended human presence on Mars that is Earth independent. These alternatives involve combinations of all the factors just mentioned. This paper is focused on the subset of these factors involved with objectives and activities that take place on the surface of Mars. "Pioneering" is a useful phrase to encapsulate the current approach being used to address this situation - one of its primary definitions is "a person or group that originates or helps open up a new line of thought or activity or a new method or technical development". Thus, in this scenario, NASA would be embarking on a path to "pioneer" a suite of technologies and operations that will result in an Earth independent, extended stay capability for humans on Mars. This paper will describe (a) the concept of operation determined to be best suited for the initial emplacement, (b) the functional capabilities determined to be necessary for this emplacement, with representative examples of systems that could carry out these functional capabilities and one implementation example (i.e., delivery sequence) at a representative landing site, and will (c) discuss possible capabilities and operations during subsequent surface missions.

  2. Seismic Surface-Wave Tomography of Waste Sites

    SciTech Connect

    Leland Timothy Long

    2002-12-17

    Surface-wave group-velocity tomography is an efficient way to obtain images of the group velocity over a test area. Because Rayleigh-wave group velocity depends on frequency, there are separate images for each frequency. Thus, at each point in these images the group velocities define a dispersion curve, a curve that relates group velocity to frequency. The objective of this study has been to find an accurate and efficient way to find the shear-wave structure from these dispersion curves. The conventional inversion techniques match theoretical and observed dispersion curves to determine the structure. These conventional methods do not always succeed in correctly differentiating the fundamental and higher modes, and for some velocity structures can become unstable. In this research a perturbation technique was developed. The perturbation method allows the pre-computation of a global inversion matrix which improves efficiency in obtaining solutions for the structure. Perturbation methods are stable and mimic the averaging process in wave propagation; hence. leading to more accurate solutions. Finite difference techniques and synthetic trace generation techniques were developed to define the perturbations. A new differential trace technique was developed for slight variations in dispersion. The improvements in analysis speed and the accuracy of the solution could lead to real-time field analysis systems, making it possible to obtain immediate results or to monitor temporal change in structure, such as might develop in using fluids for soil remediation.

  3. Counting Active Sites on Titanium Oxide-Silica Catalysts for Hydrogen Peroxide Activation through In Situ Poisoning with Phenylphosphonic Acid

    SciTech Connect

    Eaton, Todd R.; Boston, Andrew M.; Thompson, Anthony B.; Gray, Kimberly A.; Notestein, Justin M.

    2015-06-04

    Quantifying specific active sites in supported catalysts improves our understanding and assists in rational design. Supported oxides can undergo significant structural changes as surface densities increase from site-isolated cations to monolayers and crystallites, which changes the number of kinetically relevant sites. Herein, TiOx domains are titrated on TiOx–SiO2 selectively with phenylphosphonic acid (PPA). An ex situ method quantifies all fluid-accessible TiOx, whereas an in situ titration during cis-cyclooctene epoxidation provides previously unavailable values for the number of tetrahedral Ti sites on which H2O2 activation occurs. We use this method to determine the active site densities of 22 different catalysts with different synthesis methods, loadings, and characteristic spectra and find a single intrinsic turnover frequency for cis-cyclooctene epoxidation of (40±7) h-1. This simple method gives molecular-level insight into catalyst structure that is otherwise hidden when bulk techniques are used.

  4. Identification of Ice Nucleation Active Sites on Feldspar Dust Particles

    PubMed Central

    2015-01-01

    Mineral dusts originating from Earth’s crust are known to be important atmospheric ice nuclei. In agreement with earlier studies, feldspar was found as the most active of the tested natural mineral dusts. Here we investigated in closer detail the reasons for its activity and the difference in the activity of the different feldspars. Conclusions are drawn from scanning electron microscopy, X-ray powder diffraction, infrared spectroscopy, and oil-immersion freezing experiments. K-feldspar showed by far the highest ice nucleation activity. Finally, we give a potential explanation of this effect, finding alkali-metal ions having different hydration shells and thus an influence on the ice nucleation activity of feldspar surfaces. PMID:25584435

  5. Surface Complexation Modeling of U(VI) Adsorption onto Savannah River Site Sediments

    NASA Astrophysics Data System (ADS)

    Dong, W.; Wan, J.; Tokunaga, T. K.; Denham, M.; Davis, J.; Hubbard, S. S.

    2011-12-01

    The Savannah River Site (SRS) was a U.S. Department of Energy facility for plutonium production during the Cold War. Waste plumes containing low-level radioactivity and acidic waste solutions were discharged to a series of unlined seepage basins in the F-Area of the SRS from 1955 to 1988. Although the site has undergone many years of active remediation, the groundwater remains acidic, and the concentrations of U and other radionuclides are still significantly higher than their Maximum Contaminant Levels (MCLs). The objective of this effort is to understand and predict U(VI) mobility in acidic waste plumes through developing surface complexation models (SCMs). Laboratory batch experiments were conducted to evaluate U adsorption behavior over the pH range of 3.0 to 9.5. Ten sorbent samples were selected including six contaminated sediment samples from three boreholes drilled within the plume and along the groundwater flow direction, two uncontaminated (pristine) sediment samples from a borehole outside of the plume, and two reference minerals, goethite and kaolinite (identified as the dominant minerals in the clay size fraction of the F-Area sediments). The results show that goethite and kaolinite largely control U partitioning behavior. In comparison with the pristine sediment, U(VI) adsorption onto contaminated sediments exhibits adsorption edges shifted toward lower pH by about 1.0 unit (e.g., from pH≈4.5 to pH≈3.5). We developed a SCMs based component additivity (CA) approach, which can successfully predict U(VI) adsorption onto uncontaminated SRS sediments. However, application of the same SCMs based CA approach to contaminated sediments resulted in underestimates of U(VI) adsorption at acidic pH conditions. The model sensitivity analyses indicate that both goethite and kaolinite surfaces co-contributed to U(VI) adsorption under acidic pH conditions. In particular, the exchange sites of clay minerals might play an important role in adsorption of U(VI) at p

  6. JPL field measurements at the Finney County, Kansas, test site, October 1976: Meteorological variables, surface reflectivity, surface and subsurface temperatures

    NASA Technical Reports Server (NTRS)

    Kahle, A. B.; Schieldge, J.; Paley, H. N.

    1977-01-01

    Data collected at the Finney County, Kansas test site as part of the Joint Soil Moisture Experiment (JSME) are presented here, prior to analysis, to provide all JSME investigators with an immediate source of primary information. The ground-truth measurements were taken to verify and complement soil moisture data taken by microwave and infrared sensors during aircraft overflights. Measurements were made of meteorological variables (air speed, temperature, relative humidity, and rainfall), surface reflectivity, and temperatures at and below the surface.

  7. Site-Specific Scaling Relations for Hydrocarbon Adsorption on Hexagonal Transition Metal Surfaces

    SciTech Connect

    Montemore, Matthew M.; Medlin, James W.

    2013-10-03

    Screening a large number of surfaces for their catalytic performance remains a challenge, leading to the need for simple models to predict adsorption properties. To facilitate rapid prediction of hydrocarbon adsorption energies, scaling relations that allow for calculation of the adsorption energy of any intermediate attached to any symmetric site on any hexagonal metal surface through a carbon atom were developed. For input, these relations require only simple electronic properties of the surface and of the gas-phase reactant molecules. Determining adsorption energies consists of up to four steps: (i) calculating the adsorption energy of methyl in the top site using density functional theory or by simple relations based on the electronic structure of the surface; (ii) using modified versions of classical scaling relations to scale between methyl in the top site and C₁ species with more metal-surface bonds (i.e., C, CH, CH₂) in sites that complete adsorbate tetravalency; (iii) using gas-phase bond energies to predict adsorption energies of longer hydrocarbons (i.e., CR, CR₂, CR₃); and (iv) expressing energetic changes upon translation of hydrocarbons to various sites in terms of the number of agostic interactions and the change in the number of carbon-metal bonds. Combining all of these relations allows accurate scaling over a wide range of adsorbates and surfaces, resulting in efficient screening of catalytic surfaces and a clear elucidation of adsorption trends. The relations are used to explain trends in methane reforming, hydrocarbon chain growth, and propane dehydrogenation.

  8. Elemental analyses of hypervelocity microparticle impact sites on Interplanetary Dust Experiment sensor surfaces

    NASA Technical Reports Server (NTRS)

    Simon, Charles G.; Hunter, J. L.; Griffis, D. P.; Misra, V.; Ricks, D. A.; Wortman, Jim J.; Brownlee, D. E.

    1993-01-01

    The Interplanetary Dust Experiment (IDE) had over 450 electrically active ultra-high purity metal-oxide-silicon impact detectors located on the six primary sides of the Long Duration Exposure Facility (LDEF). Hypervelocity microparticles (approximately 0.2 to approximately 100 micron diameter) that struck the active sensors with enough energy to break down the 0.4 or 1.0 micron thick SIO2 insulator layer separating the silicon base (the negative electrode), and the 1000 A thick surface layer of aluminum (the positive electrode) caused electrical discharges that were recorded for the first year of orbit. The high purity Al-SiO2-Si substrates allowed detection of trace (ppm) amounts of hypervelocity impactor residues. After sputtering through a layer of surface contamination, secondary ion mass spectrometry (SIMS) was used to create two-dimensional elemental ion intensity maps of microparticle impact sites on the IDE sensors. The element intensities in the central craters of the impacts were corrected for relative ion yields and instrumental conditions and then normalized to silicon. The results were used to classify the particles' origins as 'manmade,' 'natural,' or 'indeterminate.' The last classification resulted from the presence of too little impactor residue, analytical interference from high background contamination, the lack of information on silicon and aluminum residues, or a combination of these circumstances. Several analytical 'blank' discharges were induced on flight sensors by pressing down on the sensor surface with a pure silicon shard. Analyses of these blank discharges showed that the discharge energy blasts away the layer of surface contamination. Only Si and Al were detected inside the discharge zones, including the central craters of these features. Thus far a total of 79 randomly selected microparticle impact sites from the six primary sides of the LDEF have been analyzed: 36 from tray C-9 (Leading (ram), or East, side), 18 from tray C-3

  9. Elemental Analyses of Hypervelocity Microparticle Impact Sites on Interplanetary Dust Experiment Sensor Surfaces

    NASA Technical Reports Server (NTRS)

    Simon, C. G.; Hunter, J. L.; Griffis, D. P.; Misra, V.; Ricks, D. A.; Wortman, J. J.; Brownlee, D. E.

    1992-01-01

    The Interplanetary Dust Experiment (IDE) had over 450 electrically active ultra-high purity metal-oxide-silicon impact detectors located on the six primary sides of the Long Duration Exposure Facility (LDEF). Hypervelocity microparticles (approximately 0.2 to approximately 100 micron diameter) that struck the active sensors with enough energy to breakdown the 0.4 or 1.0 micron thick SiO2 insulator layer separating the silicon base (the negative electrode), and the 1000 A thick surface layer of aluminum (the positive electrode) caused electrical discharges that were recorded for the first year of orbit. The high purity Al-SiO2-Si substrates allowed detection of trace (ppm) amounts of hypervelocity impactor residues. After sputtering through a layer of surface contamination, secondary ion mass spectrometry (SIMS) was used to create two-dimensional elemental ion intensity maps of microparticle sites on the IDE sensors. The element intensities in the central craters of the impacts were corrected for relative ion yields and instrumental conditions and then normalized to silicon. The results classification resulted from the particles' origins as 'manmade', 'natural', or 'indeterminate'. The last classification resulted from the presence of too little impactor residue, analytical interference from high background contamination, the lack of information on silicon and aluminum residues, or a combination of these circumstances. Several analytical 'blank' discharges were induced on flight sensors by pressing down on the sensor surface with a pure silicon shard. Analyses of these blank discharges showed that the discharge energy blasts away the layer of surface contamination. Only Si and Al were detected inside the discharge zones, including the central craters, of these features. Thus far, a total of 79 randomly selected microparticle impact sites from the six primary sides of the LDEF were analyzed: 36 from tray C-9 (Leading (ram), or east, side), 18 from tray C-3 (Trailing

  10. VARIABLE BOUND-SITE CHARGING CONTRIBUTIONS TO SURFACE COMPLEXATION MASS ACTION EXPRESSIONS

    EPA Science Inventory

    One and two pK models of surface complexation reactions between reactive surface sites (>SOH) and the proton (H+) use mass action expressions of the form: Ka={[>SOHn-1z-1]g>SOH(0-1)aH+EXP(-xeY/kT)}/{[>SOHnz]g>SOH(n)} where Ka=the acidity constant, [ ]=reactive species concentrati...

  11. Basement Surface Faulting and Topography for Savannah River Site and Vicinity

    SciTech Connect

    Cumbest, R.J.

    1998-12-17

    This report integrates the data from more than 60 basement borings and over 100 miles of seismic reflection profiling acquired on the Savannah River Site to map the topography of the basement (unweathered rock) surface and faulting recorded on this surface.

  12. Active control of compressible flows on a curved surface

    NASA Technical Reports Server (NTRS)

    Maestrello, L.; Parikh, P.; Bayliss, A.; Turkel, E.

    1985-01-01

    The effect of localized, time periodic surface heating and cooling over a curved surface is studied. This is a mechanism for the active control of unstable disturbances by phase cancellation and reinforcement. It is shown that the pressure gradient induced by the curvature significantly enhances the effectiveness of this form of active control. In particular, by appropriate choice of phase, active surface heating can completely stabilize and unstable wave.

  13. Seismic site characterization of an urban dedimentary basin, Livermore Valley, California: Site tesponse, basin-edge-induced surface waves, and 3D simulations

    USGS Publications Warehouse

    Hartzell, Stephen; Leeds, Alena L.; Ramirez-Guzman, Leonardo; Allen, James P.; Schmitt, Robert G.

    2016-01-01

    Thirty‐two accelerometers were deployed in the Livermore Valley, California, for approximately one year to study sedimentary basin effects. Many local and near‐regional earthquakes were recorded, including the 24 August 2014 Mw 6.0 Napa, California, earthquake. The resulting ground‐motion data set is used to quantify the seismic response of the Livermore basin, a major structural depression in the California Coast Range Province bounded by active faults. Site response is calculated by two methods: the reference‐site spectral ratio method and a source‐site spectral inversion method. Longer‐period (≥1  s) amplification factors follow the same general pattern as Bouguer gravity anomaly contours. Site response spectra are inverted for shallow shear‐wave velocity profiles, which are consistent with independent information. Frequency–wavenumber analysis is used to analyze plane‐wave propagation across the Livermore Valley and to identify basin‐edge‐induced surface waves with back azimuths different from the source back azimuth. Finite‐element simulations in a 3D velocity model of the region illustrate the generation of basin‐edge‐induced surface waves and point out strips of elevated ground velocities along the margins of the basin.

  14. Recent Experience Using Active Love Wave Techniques to Characterize Seismographic Station Sites

    NASA Astrophysics Data System (ADS)

    Martin, A. J.; Yong, A.; Salomone, L.

    2014-12-01

    Active-source Love waves recorded by the multi-channel analysis of surface wave (MASLW) technique were recently analyzed in two site characterization projects. Between 2010 and 2011, the 2009 American Recovery and Reinvestment Act (ARRA) funded GEOVision to conduct geophysical investigations at 189 seismographic stations—185 in California and 4 in the Central Eastern U.S. (CEUS). The original project plan was to utilize active and passive Rayleigh wave-based techniques to obtain shear-wave velocity (VS) profiles to a minimum depth of 30 m and the time-averaged VS of the upper 30 meters (VS30). Early in the investigation it became evident that Rayleigh wave techniques, such as multi-channel analysis of surface waves (MASRW), were not effective at characterizing all sites. Shear-wave seismic refraction and MASLW techniques were therefore applied. The MASLW technique was deployed at a total of 38 sites, in addition to other methods, and used as the primary technique to characterize 22 sites, 5 of which were also characterized using Rayleigh wave techniques. In 2012, the Electric Power Research Institute funded characterization of 33 CEUS station sites. Based on experience from the ARRA investigation, both MASRW and MASLW data were acquired by GEOVision at 24 CEUS sites—the remaining 9 sites and 2 overlapping sites were characterized by University of Texas, Austin. Of the 24 sites characterized by GEOVision, 16 were characterized using MASLW data, 4 using both MASLW and MASRW data and 4 using MASRW data. Love wave techniques were often found to perform better, or at least yield phase velocity data that could be more readily modeled using the fundamental mode assumption, at shallow rock sites, sites with steep velocity gradients, and, sites with a thin, low velocity, surficial soil layer overlying stiffer sediments. These types of velocity structure often excite dominant higher modes in Rayleigh wave data, but not in Love wave data. At such sites, it may be possible

  15. Site-dependent catalytic activity of graphene oxides towards oxidative dehydrogenation of propane.

    PubMed

    Tang, Shaobin; Cao, Zexing

    2012-12-28

    Graphene oxides (GOs) may offer extraordinary potential in the design of novel catalytic systems due to the presence of various oxygen functional groups and their unique electronic and structural properties. Using first-principles calculations, we explore the plausible mechanisms for the oxidative dehydrogenation (ODH) of propane to propene by GOs and the diffusion of the surface oxygen-containing groups under an external electric field. The present results show that GOs with modified oxygen-containing groups may afford high catalytic activity for the ODH of propane to propene. The presence of hydroxyl groups around the active sites provided by epoxides can remarkably enhance the C-H bond activation of propane and the activity enhancement exhibits strong site dependence. The sites of oxygen functional groups on the GO surface can be easily tuned by the diffusion of these groups under an external electric field, which increases the reactivity of GOs towards ODH of propane. The chemically modified GOs are thus quite promising in the design of metal-free catalysis. PMID:22801590

  16. Controlled Release of Biologically Active Silver from Nanosilver Surfaces

    PubMed Central

    Liu, Jingyu; Sonshine, David A.; Shervani, Saira; Hurt, Robert H.

    2010-01-01

    Major pathways in the antibacterial activity and eukaryotic toxicity of nano-silver involve the silver cation and its soluble complexes, which are well established thiol toxicants. Through these pathways, nano-silver behaves in analogy to a drug delivery system, in which the particle contains a concentrated inventory of an active species, the ion, which is transported to and released near biological target sites. Although the importance of silver ion in the biological response to nano-silver is widely recognized, the drug delivery paradigm has not been well developed for this system, and there is significant potential to improve nano-silver technologies through controlled release formulations. This article applies elements of the drug delivery paradigm to nano-silver dissolution and presents a systematic study of chemical concepts for controlled release. After presenting thermodynamic calculations of silver species partitioning in biological media, the rates of oxidative silver dissolution are measured for nanoparticles and macroscopic foils and used to derive unified area-based release kinetics. A variety of competing chemical approaches are demonstrated for controlling the ion release rate over four orders of magnitude. Release can be systematically slowed by thiol and citrate ligand binding, formation of sulfidic coatings, or the scavenging of peroxy-intermediates. Release can be accelerated by pre-oxidation or particle size reduction, while polymer coatings with complexation sites alter the release profile by storing and release inventories of surface-bound silver. Finally, the ability to tune biological activity is demonstrated through bacterial inhibition zone assay carried out on selected formulations of controlled release nano-silver. PMID:20968290

  17. Current activities handbook: formerly utilized sites remedial action program

    SciTech Connect

    1981-02-27

    This volume is one of a series produced under contract with the DOE, by Politech Corporation to develop a legislative and regulatory data base to assist the FUSRAP management in addressing the institutional and socioeconomic issues involved in carrying out the Formerly Utilized Sites Remedial Action Program. This Information Handbook series contains information about all relevant government agencies at the Federal and state levels, the pertinent programs they administer, each affected state legislature, and current Federal and state legislative and regulatory initiatives. This volume is a compilation of information about the activities each of the thirteen state legislatures potentially affected by the Formerly Utilized Sites Remedial Action Program. It contains a description of the state legislative procedural rules and a schedule of each legislative session; a summary of pending relevant legislation; the name and telephone number of legislative and state agency contacts; and the full text of all bills identified.

  18. Molecular dioxygen enters the active site of 12/15-lipoxygenase via dynamic oxygen access channels.

    PubMed

    Saam, Jan; Ivanov, Igor; Walther, Matthias; Holzhütter, Hermann-Georg; Kuhn, Hartmut

    2007-08-14

    Cells contain numerous enzymes that use molecular oxygen for their reactions. Often, their active sites are buried deeply inside the protein, which raises the question whether there are specific access channels guiding oxygen to the site of catalysis. Choosing 12/15-lipoxygenase as a typical example for such oxygen-dependent enzymes, we determined the oxygen distribution within the protein and defined potential routes for oxygen access. For this purpose, we have applied an integrated strategy of structural modeling, molecular dynamics simulations, site-directed mutagenesis, and kinetic measurements. First, we computed the 3D free-energy distribution for oxygen, which led to identification of four oxygen channels in the protein. All channels connect the protein surface with a region of high oxygen affinity at the active site. This region is localized opposite to the nonheme iron providing a structural explanation for the reaction specificity of this lipoxygenase isoform. The catalytically most relevant path can be obstructed by L367F exchange, which leads to a strongly increased Michaelis constant for oxygen. The blocking mechanism is explained in detail by reordering the hydrogen-bonding network of water molecules. Our results provide strong evidence that the main route for oxygen access to the active site of the enzyme follows a channel formed by transiently interconnected cavities whereby the opening and closure are governed by side chain dynamics. PMID:17675410

  19. CO Oxidation on Au/TiO2: Condition-Dependent Active Sites and Mechanistic Pathways.

    PubMed

    Wang, Yang-Gang; Cantu, David C; Lee, Mal-Soon; Li, Jun; Glezakou, Vassiliki-Alexandra; Rousseau, Roger

    2016-08-24

    We present results of ab initio electronic structure and molecular dynamics simulations (AIMD), as well as a microkinetic model of CO oxidation catalyzed by TiO2 supported Au nanocatalysts. A coverage-dependent microkinetic analysis, based on energetics obtained with density functional methods, shows that the dominant kinetic pathway, activated oxygen species, and catalytic active sites are all strongly depended on both temperature and oxygen partial pressure. Under oxidizing conditions and T < 400 K, the prevalent pathway involves a dynamic single atom catalytic mechanism. This reaction is catalyzed by a transient Au-CO species that migrates from the Au-cluster onto a surface oxygen adatom. It subsequently reacts with the TiO2 support via a Mars van Krevelen mechanism to form CO2 and finally the Au atom reintegrates back into the gold cluster to complete the catalytic cycle. At 300 ≤ T ≤ 600 K, oxygen-bound single Oad-Au(+)-CO sites and the perimeter Au-sites of the nanoparticle work in tandem to optimally catalyze the reaction. Above 600 K, a variety of alternate pathways associated with both single-atom and the perimeter sites of the Au nanoparticle are found to be active. Under low oxygen pressures, Oad-Au(+)-CO species can be a source of catalyst deactivation and the dominant pathway involves only Au-perimeter sites. A detailed comparison of the current model and the existing literature resolves many apparent inconsistencies in the mechanistic interpretations. PMID:27480512

  20. Surface Structure Dependent Electrocatalytic Activity of Co3O4 Anchored on Graphene Sheets toward Oxygen Reduction Reaction

    PubMed Central

    Xiao, Junwu; Kuang, Qin; Yang, Shihe; Xiao, Fei; Wang, Shuai; Guo, Lin

    2013-01-01

    Catalytic activity is primarily a surface phenomenon, however, little is known about Co3O4 nanocrystals in terms of the relationship between the oxygen reduction reaction (ORR) catalytic activity and surface structure, especially when dispersed on a highly conducting support to improve the electrical conductivity and so to enhance the catalytic activity. Herein, we report a controllable synthesis of Co3O4 nanorods (NR), nanocubes (NC) and nano-octahedrons (OC) with the different exposed nanocrystalline surfaces ({110}, {100}, and {111}), uniformly anchored on graphene sheets, which has allowed us to investigate the effects of the surface structure on the ORR activity. Results show that the catalytically active sites for ORR should be the surface Co2+ ions, whereas the surface Co3+ ions catalyze CO oxidation, and the catalytic ability is closely related to the density of the catalytically active sites. These results underscore the importance of morphological control in the design of highly efficient ORR catalysts. PMID:23892418

  1. Hanford Site Permanent Isolation Surface Barrier Development Program: Fiscal year 1992 and 1993 highlights

    SciTech Connect

    Cadwell, L.L.; Link, S.O.; Gee, G.W.

    1993-09-01

    The Hanford Site Permanent Isolation Surface Barrier Development Program was jointly developed by the Pacific Northwest Laboratory and Westinghouse Hanford Company to design and test an earthen cover system that can be used to inhibit water infiltration; plant, animal, and human intrusion; and wind and water erosion. Kaiser Engineers Hanford Company provided engineering design support for the program. Work on barrier design has been under way at Hanford for nearly 10 years. The comprehensive development of a long-term barrier, formerly the Hanford Site Protective Barrier Development Program, was initiated in FY 1986, and a general field-tested design is expected to be completed by FY 1998. Highlights of efforts in FY 1992 and FY 1993 included the resumption of field testing, the completion of the prototype barrier design, and the convening of an external peer review panel, which met twice with the barrier development team. The review panel provided helpful guidance on current and future barrier development activities, while commending the program for its significant technical contributions to innovative barrier technology development.

  2. Vitronectin-binding staphylococci enhance surface-associated complement activation.

    PubMed Central

    Lundberg, F; Lea, T; Ljungh, A

    1997-01-01

    Coagulase-negative staphylococci are well recognized in medical device-associated infections. Complement activation is known to occur at the biomaterial surface, resulting in unspecific inflammation around the biomaterial. The human serum protein vitronectin (Vn), a potent inhibitor of complement activation by formation of an inactive terminal complement complex, adsorbs to biomaterial surfaces in contact with blood. In this report, we discuss the possibility that surface-immobilized Vn inhibits complement activation and the effect of Vn-binding staphylococci on complement activation on surfaces precoated with Vn. The extent of complement activation was measured with a rabbit anti-human C3c antibody and a mouse anti-human C9 antibody, raised against the neoepitope of C9. Our data show that Vn immobilized on a biomaterial surface retains its ability to inhibit complement activation. The additive complement activation-inhibitory effect of Vn on a heparinized surface is very small. In the presence of Vn-binding strain, Staphylococcus hemolyticus SM131, complement activation on a surface precoated with Vn occurred as it did in the absence of Vn precoating. For S. epidermidis 3380, which does not express binding of Vn, complement activation on a Vn-precoated surface was significantly decreased. The results could be repeated on heparinized surfaces. These data suggest that Vn adsorbed to a biomaterial surface may serve to protect against surface-associated complement activation. Furthermore, Vn-binding staphylococcal cells may enhance surface-associated complement activation by blocking the inhibitory effect of preadsorbed Vn. PMID:9038294

  3. Identification of covalent active site inhibitors of dengue virus protease

    PubMed Central

    Koh-Stenta, Xiaoying; Joy, Joma; Wang, Si Fang; Kwek, Perlyn Zekui; Wee, John Liang Kuan; Wan, Kah Fei; Gayen, Shovanlal; Chen, Angela Shuyi; Kang, CongBao; Lee, May Ann; Poulsen, Anders; Vasudevan, Subhash G; Hill, Jeffrey; Nacro, Kassoum

    2015-01-01

    Dengue virus (DENV) protease is an attractive target for drug development; however, no compounds have reached clinical development to date. In this study, we utilized a potent West Nile virus protease inhibitor of the pyrazole ester derivative class as a chemical starting point for DENV protease drug development. Compound potency and selectivity for DENV protease were improved through structure-guided small molecule optimization, and protease-inhibitor binding interactions were validated biophysically using nuclear magnetic resonance. Our work strongly suggests that this class of compounds inhibits flavivirus protease through targeted covalent modification of active site serine, contrary to an allosteric binding mechanism as previously described. PMID:26677315

  4. Active Site Dependent Reaction Mechanism over Ru/CeO2 Catalyst toward CO2 Methanation.

    PubMed

    Wang, Fei; He, Shan; Chen, Hao; Wang, Bin; Zheng, Lirong; Wei, Min; Evans, David G; Duan, Xue

    2016-05-18

    Oxygen vacancy on the surface of metal oxides is one of the most important defects which acts as the reactive site in a variety of catalytic reactions. In this work, operando spectroscopy methodology was employed to study the CO2 methanation reaction catalyzed by Ru/CeO2 (with oxygen vacancy in CeO2) and Ru/α-Al2O3 (without oxygen vacancy), respectively, so as to give a thorough understanding on active site dependent reaction mechanism. In Ru/CeO2 catalyst, operando XANES, IR, and Raman were used to reveal the generation process of Ce(3+), surface hydroxyl, and oxygen vacancy as well as their structural evolvements under practical reaction conditions. The steady-state isotope transient kinetic analysis (SSITKA)-type in situ DRIFT infrared spectroscopy undoubtedly substantiates that CO2 methanation undergoes formate route over Ru/CeO2 catalyst, and the formate dissociation to methanol catalyzed by oxygen vacancy is the rate-determining step. In contrast, CO2 methanation undergoes CO route over Ru surface in Ru/α-Al2O3 with the absence of oxygen vacancy, demonstrating active site dependent catalytic mechanism toward CO2 methanation. In addition, the catalytic activity evaluation and the oscillating reaction over Ru/CeO2 catalyst further prove that the oxygen vacancy catalyzes the rate-determining step with a much lower activation temperature compared with Ru surface in Ru/α-Al2O3 (125 vs 250 °C). PMID:27135417

  5. Comparison of Grab, Air, and Surface Results for Radiation Site Characterization

    NASA Astrophysics Data System (ADS)

    Glassford, Eric Keith

    2011-12-01

    The use of proper sampling methods and sample types for evaluating sites believed to be contaminated with radioactive materials is necessary to avoid misrepresenting conditions at the site. This study was designed to investigate if the site characterization, based upon uranium contamination measured in different types of samples, is dependent upon the mass of the sample collected. A bulk sample of potentially contaminated interior dirt was collected from an abandoned metal processing mill that rolled uranium between 1948 and 1956. The original mill dates from 1910 and has a dirt floor. The bulk sample was a mixture of dirt, black and yellow particles of metal dust, and small fragments of natural debris. Small mass (approximately 0.75 grams (g)) and large mass (approximately 70g) grab samples were prepared from the bulk sample material to simulate collection of a "grab" type sample. Air sampling was performed by re-suspending a portion of the bulk sample material using a vibration table to simulate airborne contamination that might be present during site remediation. Additionally, samples of removable contaminated surface dust were collected on 47 mm diameter filter paper by wiping the surfaces of the exposure chamber used to resuspend the bulk material. Certified reference materials, one containing a precisely known quantity of U 3O8 and one containing a known quantity of natural uranium, were utilized to calibrate the gamma spectrometry measurement system. Non-destructive gamma spectrometry measurements were used to determine the content of uranium-235 (235U) at 185 keV and 143 keV, thorium-234 (234Th) at 63 keV, and protactinium-234m (234mPa) at 1001 keV in each sample. Measurement of natural uranium in small, 1 g samples is usually accomplished by radiochemical analysis in order to measure alpha particles emitted by 238U, 235U, and 234U. However, uranium in larger bulk samples can also be measured non-destructively using gamma spectrometry to detect the low

  6. Polarizability of the active site of cytochrome c reduces the activation barrier for electron transfer.

    PubMed

    Dinpajooh, Mohammadhasan; Martin, Daniel R; Matyushov, Dmitry V

    2016-01-01

    Enzymes in biology's energy chains operate with low energy input distributed through multiple electron transfer steps between protein active sites. The general challenge of biological design is how to lower the activation barrier without sacrificing a large negative reaction free energy. We show that this goal is achieved through a large polarizability of the active site. It is polarized by allowing a large number of excited states, which are populated quantum mechanically by electrostatic fluctuations of the protein and hydration water shells. This perspective is achieved by extensive mixed quantum mechanical/molecular dynamics simulations of the half reaction of reduction of cytochrome c. The barrier for electron transfer is consistently lowered by increasing the number of excited states included in the Hamiltonian of the active site diagonalized along the classical trajectory. We suggest that molecular polarizability, in addition to much studied electrostatics of permanent charges, is a key parameter to consider in order to understand how enzymes work. PMID:27306204

  7. Polarizability of the active site of cytochrome c reduces the activation barrier for electron transfer

    NASA Astrophysics Data System (ADS)

    Dinpajooh, Mohammadhasan; Martin, Daniel R.; Matyushov, Dmitry V.

    2016-06-01

    Enzymes in biology’s energy chains operate with low energy input distributed through multiple electron transfer steps between protein active sites. The general challenge of biological design is how to lower the activation barrier without sacrificing a large negative reaction free energy. We show that this goal is achieved through a large polarizability of the active site. It is polarized by allowing a large number of excited states, which are populated quantum mechanically by electrostatic fluctuations of the protein and hydration water shells. This perspective is achieved by extensive mixed quantum mechanical/molecular dynamics simulations of the half reaction of reduction of cytochrome c. The barrier for electron transfer is consistently lowered by increasing the number of excited states included in the Hamiltonian of the active site diagonalized along the classical trajectory. We suggest that molecular polarizability, in addition to much studied electrostatics of permanent charges, is a key parameter to consider in order to understand how enzymes work.

  8. Polarizability of the active site of cytochrome c reduces the activation barrier for electron transfer

    PubMed Central

    Dinpajooh, Mohammadhasan; Martin, Daniel R.; Matyushov, Dmitry V.

    2016-01-01

    Enzymes in biology’s energy chains operate with low energy input distributed through multiple electron transfer steps between protein active sites. The general challenge of biological design is how to lower the activation barrier without sacrificing a large negative reaction free energy. We show that this goal is achieved through a large polarizability of the active site. It is polarized by allowing a large number of excited states, which are populated quantum mechanically by electrostatic fluctuations of the protein and hydration water shells. This perspective is achieved by extensive mixed quantum mechanical/molecular dynamics simulations of the half reaction of reduction of cytochrome c. The barrier for electron transfer is consistently lowered by increasing the number of excited states included in the Hamiltonian of the active site diagonalized along the classical trajectory. We suggest that molecular polarizability, in addition to much studied electrostatics of permanent charges, is a key parameter to consider in order to understand how enzymes work. PMID:27306204

  9. The copper active site of CBM33 polysaccharide oxygenases.

    PubMed

    Hemsworth, Glyn R; Taylor, Edward J; Kim, Robbert Q; Gregory, Rebecca C; Lewis, Sally J; Turkenburg, Johan P; Parkin, Alison; Davies, Gideon J; Walton, Paul H

    2013-04-24

    The capacity of metal-dependent fungal and bacterial polysaccharide oxygenases, termed GH61 and CBM33, respectively, to potentiate the enzymatic degradation of cellulose opens new possibilities for the conversion of recalcitrant biomass to biofuels. GH61s have already been shown to be unique metalloenzymes containing an active site with a mononuclear copper ion coordinated by two histidines, one of which is an unusual τ-N-methylated N-terminal histidine. We now report the structural and spectroscopic characterization of the corresponding copper CBM33 enzymes. CBM33 binds copper with high affinity at a mononuclear site, significantly stabilizing the enzyme. X-band EPR spectroscopy of Cu(II)-CBM33 shows a mononuclear type 2 copper site with the copper ion in a distorted axial coordination sphere, into which azide will coordinate as evidenced by the concomitant formation of a new absorption band in the UV/vis spectrum at 390 nm. The enzyme's three-dimensional structure contains copper, which has been photoreduced to Cu(I) by the incident X-rays, confirmed by X-ray absorption/fluorescence studies of both aqueous solution and intact crystals of Cu-CBM33. The single copper(I) ion is ligated in a T-shaped configuration by three nitrogen atoms from two histidine side chains and the amino terminus, similar to the endogenous copper coordination geometry found in fungal GH61. PMID:23540833

  10. The Copper Active Site of CBM33 Polysaccharide Oxygenases

    PubMed Central

    2013-01-01

    The capacity of metal-dependent fungal and bacterial polysaccharide oxygenases, termed GH61 and CBM33, respectively, to potentiate the enzymatic degradation of cellulose opens new possibilities for the conversion of recalcitrant biomass to biofuels. GH61s have already been shown to be unique metalloenzymes containing an active site with a mononuclear copper ion coordinated by two histidines, one of which is an unusual τ-N-methylated N-terminal histidine. We now report the structural and spectroscopic characterization of the corresponding copper CBM33 enzymes. CBM33 binds copper with high affinity at a mononuclear site, significantly stabilizing the enzyme. X-band EPR spectroscopy of Cu(II)-CBM33 shows a mononuclear type 2 copper site with the copper ion in a distorted axial coordination sphere, into which azide will coordinate as evidenced by the concomitant formation of a new absorption band in the UV/vis spectrum at 390 nm. The enzyme’s three-dimensional structure contains copper, which has been photoreduced to Cu(I) by the incident X-rays, confirmed by X-ray absorption/fluorescence studies of both aqueous solution and intact crystals of Cu-CBM33. The single copper(I) ion is ligated in a T-shaped configuration by three nitrogen atoms from two histidine side chains and the amino terminus, similar to the endogenous copper coordination geometry found in fungal GH61. PMID:23540833

  11. An Active Site Water Network in the Plasminogen Activator Pla from Yersinia pestis

    SciTech Connect

    Eren, Elif; Murphy, Megan; Goguen, Jon; van den Berg, Bert

    2010-08-13

    The plasminogen activator Pla from Yersinia pestis is an outer membrane protease (omptin) that is important for the virulence of plague. Here, we present the high-resolution crystal structure of wild-type, enzymatically active Pla at 1.9 {angstrom}. The structure shows a water molecule located between active site residues D84 and H208, which likely corresponds to the nucleophilic water. A number of other water molecules are present in the active site, linking residues important for enzymatic activity. The R211 sidechain in loop L4 is close to the nucleophilic water and possibly involved in the stabilization of the oxyanion intermediate. Subtle conformational changes of H208 result from the binding of lipopolysaccharide to the outside of the barrel, explaining the unusual dependence of omptins on lipopolysaccharide for activity. The Pla structure suggests a model for the interaction with plasminogen substrate and provides a more detailed understanding of the catalytic mechanism of omptin proteases.

  12. Target-classification approach applied to active UXO sites

    NASA Astrophysics Data System (ADS)

    Shubitidze, F.; Fernández, J. P.; Shamatava, Irma; Barrowes, B. E.; O'Neill, K.

    2013-06-01

    This study is designed to illustrate the discrimination performance at two UXO active sites (Oklahoma's Fort Sill and the Massachusetts Military Reservation) of a set of advanced electromagnetic induction (EMI) inversion/discrimination models which include the orthonormalized volume magnetic source (ONVMS), joint diagonalization (JD), and differential evolution (DE) approaches and whose power and flexibility greatly exceed those of the simple dipole model. The Fort Sill site is highly contaminated by a mix of the following types of munitions: 37-mm target practice tracers, 60-mm illumination mortars, 75-mm and 4.5'' projectiles, 3.5'', 2.36'', and LAAW rockets, antitank mine fuzes with and without hex nuts, practice MK2 and M67 grenades, 2.5'' ballistic windshields, M2A1-mines with/without bases, M19-14 time fuzes, and 40-mm practice grenades with/without cartridges. The site at the MMR site contains targets of yet different sizes. In this work we apply our models to EMI data collected using the MetalMapper (MM) and 2 × 2 TEMTADS sensors. The data for each anomaly are inverted to extract estimates of the extrinsic and intrinsic parameters associated with each buried target. (The latter include the total volume magnetic source or NVMS, which relates to size, shape, and material properties; the former includes location, depth, and orientation). The estimated intrinsic parameters are then used for classification performed via library matching and the use of statistical classification algorithms; this process yielded prioritized dig-lists that were submitted to the Institute for Defense Analyses (IDA) for independent scoring. The models' classification performance is illustrated and assessed based on these independent evaluations.

  13. Requirements for extravehicular activities on the lunar and Martian surfaces

    NASA Technical Reports Server (NTRS)

    Brown, Mariann F.; Schentrup, Susan M.

    1990-01-01

    Basic design reference requirements pertinent to EVA equipment on lunar and martian surfaces are provided. Environmental factors affecting surface EVA are analyzed including gravity, dust, atmospheric conditions, thermal gradients, lightning conditions, and radiation effects, and activities associated with surface EVA are outlined. Environmental and activity effects on EVA equipment are assessed, and emphasis is placed on planetary surface portable life support systems (PLSS), suit development, protection from micrometeoroids, dust, and radiation, food and water supplies, and the extravehicular mobility-unit thermal-control system. Environmental and activity impacts on PLSS design are studied, with focus on base self-sufficiency and reduction in resupply logistics.

  14. Differential Active Site Loop Conformations Mediate Promiscuous Activities in the Lactonase SsoPox

    PubMed Central

    Elias, Mikael; Chabriere, Eric

    2013-01-01

    Enzymes are proficient catalysts that enable fast rates of Michaelis-complex formation, the chemical step and products release. These different steps may require different conformational states of the active site that have distinct binding properties. Moreover, the conformational flexibility of the active site mediates alternative, promiscuous functions. Here we focused on the lactonase SsoPox from Sulfolobus solfataricus. SsoPox is a native lactonase endowed with promiscuous phosphotriesterase activity. We identified a position in the active site loop (W263) that governs its flexibility, and thereby affects the substrate specificity of the enzyme. We isolated two different sets of substitutions at position 263 that induce two distinct conformational sampling of the active loop and characterized the structural and kinetic effects of these substitutions. These sets of mutations selectively and distinctly mediate the improvement of the promiscuous phosphotriesterase and oxo-lactonase activities of SsoPox by increasing active-site loop flexibility. These observations corroborate the idea that conformational diversity governs enzymatic promiscuity and is a key feature of protein evolvability. PMID:24086491

  15. Spectroscopic Definition of the Ferroxidase Site in M Ferritin: Comparison of Binuclear Substrate vs. Cofactor Active Sites

    PubMed Central

    Schwartz, Jennifer K.; Liu, Xiaofeng S.; Tosha, Takehiko; Theil, Elizabeth C.; Solomon, Edward I.

    2008-01-01

    Maxi ferritins, 24 subunit protein nanocages, are essential in humans, plants, bacteria, and other animals for the concentration and storage of iron as hydrated ferric oxide, while minimizing free radical generation or use by pathogens. Formation of the precursors to these ferric oxides is catalyzed at a non-heme biferrous substrate site, which has some parallels with the cofactor sites in other biferrous enzymes. A combination of circular dichroism (CD), magnetic circular dichroism (MCD), and variable-temperature, variable-field MCD (VTVH MCD) has been used to probe Fe(II) binding to the substrate active site in frog M ferritin. These data determined that the active site within each subunit consists of two inequivalent five-coordinate (5C) ferrous centers that are weakly anti-ferromagnetically coupled, consistent with a μ-1,3 carboxylate bridge. The active site ligand set is unusual and likely includes a terminal water bound to each Fe(II) center. The Fe(II) ions bind to the active sites in a concerted manner, and cooperativity among the sites in each subunit is observed, potentially providing a mechanism for the control of ferritin iron loading. Differences in geometric and electronic structure – including a weak ligand field, availability of two water ligands at the biferrous substrate site, and the single carboxylate bridge in ferritin – coincide with the divergent reaction pathways observed between this substrate site and the previously studied cofactor active sites. PMID:18576633

  16. Metal active site elasticity linked to activation of homocysteine in methionine synthases

    SciTech Connect

    Koutmos, Markos; Pejchal, Robert; Bomer, Theresa M.; Matthews, Rowena G.; Smith, Janet L.; Ludwig, Martha L.

    2008-04-02

    Enzymes possessing catalytic zinc centers perform a variety of fundamental processes in nature, including methyl transfer to thiols. Cobalamin-independent (MetE) and cobalamin-dependent (MetH) methionine synthases are two such enzyme families. Although they perform the same net reaction, transfer of a methyl group from methyltetrahydrofolate to homocysteine (Hcy) to form methionine, they display markedly different catalytic strategies, modular organization, and active site zinc centers. Here we report crystal structures of zinc-replete MetE and MetH, both in the presence and absence of Hcy. Structural investigation of the catalytic zinc sites of these two methyltransferases reveals an unexpected inversion of zinc geometry upon binding of Hcy and displacement of an endogenous ligand in both enzymes. In both cases a significant movement of the zinc relative to the protein scaffold accompanies inversion. These structures provide new information on the activation of thiols by zinc-containing enzymes and have led us to propose a paradigm for the mechanism of action of the catalytic zinc sites in these and related methyltransferases. Specifically, zinc is mobile in the active sites of MetE and MetH, and its dynamic nature helps facilitate the active site conformational changes necessary for thiol activation and methyl transfer.

  17. Evidence for segmental mobility in the active site of pepsin

    SciTech Connect

    Pohl, J.; Strop, P.; Senn, H.; Foundling, S.; Kostka, V.

    1986-05-01

    The low hydrolytic activity (k/sub cat/ < 0.001 s/sup -1/) of chicken pepsin (CP) towards tri- and tetrapeptides is enhanced at least 100 times by modification of its single sulfhydryl group of Cys-115, with little effect on K/sub m/-values. Modification thus simulates the effect of secondary substrate binding on pepsin catalysis. The rate of Cys-115 modification is substantially decreased in the presence of some competitive inhibitors, suggesting its active site location. Experiments with CP alkylated at Cys-115 with Acrylodan as a fluorescent probe or with N-iodoacetyl-(4-fluoro)-aniline as a /sup 19/F-nmr probe suggest conformation change around Cys-115 to occur on substrate or substrate analog binding. The difference /sup 1/H-nmr spectra (500 MHz) of unmodified free and inhibitor-complexed CP reveal chemical shifts almost exclusively in the aromatic region. The effects of Cu/sup + +/ on /sup 19/F- and /sup 1/H-nmr spectra have been studied. Examination of a computer graphics model of CP based on E. parasitica pepsin-inhibitor complex X-ray coordinates suggests that Cys-115 is located near the S/sub 3//S/sub 5/ binding site. The results are interpreted in favor of segmental mobility of this region important for pepsin substrate binding and catalysis.

  18. Perchlorate Reductase Is Distinguished by Active Site Aromatic Gate Residues.

    PubMed

    Youngblut, Matthew D; Tsai, Chi-Lin; Clark, Iain C; Carlson, Hans K; Maglaqui, Adrian P; Gau-Pan, Phonchien S; Redford, Steven A; Wong, Alan; Tainer, John A; Coates, John D

    2016-04-22

    Perchlorate is an important ion on both Earth and Mars. Perchlorate reductase (PcrAB), a specialized member of the dimethylsulfoxide reductase superfamily, catalyzes the first step of microbial perchlorate respiration, but little is known about the biochemistry, specificity, structure, and mechanism of PcrAB. Here we characterize the biophysics and phylogeny of this enzyme and report the 1.86-Å resolution PcrAB complex crystal structure. Biochemical analysis revealed a relatively high perchlorate affinity (Km = 6 μm) and a characteristic substrate inhibition compared with the highly similar respiratory nitrate reductase NarGHI, which has a relatively much lower affinity for perchlorate (Km = 1.1 mm) and no substrate inhibition. Structural analysis of oxidized and reduced PcrAB with and without the substrate analog SeO3 (2-) bound to the active site identified key residues in the positively charged and funnel-shaped substrate access tunnel that gated substrate entrance and product release while trapping transiently produced chlorate. The structures suggest gating was associated with shifts of a Phe residue between open and closed conformations plus an Asp residue carboxylate shift between monodentate and bidentate coordination to the active site molybdenum atom. Taken together, structural and mutational analyses of gate residues suggest key roles of these gate residues for substrate entrance and product release. Our combined results provide the first detailed structural insight into the mechanism of biological perchlorate reduction, a critical component of the chlorine redox cycle on Earth. PMID:26940877

  19. Eel calcitonin binding site distribution and antinociceptive activity in rats

    SciTech Connect

    Guidobono, F.; Netti, C.; Sibilia, V.; Villa, I.; Zamboni, A.; Pecile, A.

    1986-03-01

    The distribution of binding site for (/sup 125/I)-eel-calcitonin (ECT) to rat central nervous system, studied by an autoradiographic technique, showed concentrations of binding in the diencephalon, the brain stem and the spinal cord. Large accumulations of grains were seen in the hypothalamus, the amygdala, in the fasciculus medialis prosencephali, in the fasciculus longitudinalis medialis, in the ventrolateral part of the periventricular gray matter, in the lemniscus medialis and in the raphe nuclei. The density of grains in the reticular formation and in the nucleus tractus spinalis nervi trigemini was more moderate. In the spinal cord, grains were scattered throughout the dorsal horns. Binding of the ligand was displaced equally by cold ECT and by salmon CT(sCT), indicating that both peptides bind to the same receptors. Human CT was much weaker than sCT in displacing (/sup 125/I)-ECT binding. The administration of ECT into the brain ventricles of rats dose-dependently induced a significant and long-lasting enhancement of hot-plate latencies comparable with that obtained with sCT. The antinociceptive activity induced by ECT is compatible with the topographical distribution of binding sites for the peptide and is a further indication that fish CTs are active in the mammalian brain.

  20. Low temperature adsorption and site-conversion process of CO on the Ni(111) surface

    NASA Astrophysics Data System (ADS)

    Beniya, Atsushi; Isomura, Noritake; Hirata, Hirohito; Watanabe, Yoshihide

    2012-12-01

    Low-temperature (25 K) adsorption states and the site conversion of adsorbed CO between the ontop and the hollow sites on Ni(111) were studied by means of temperature programmed desorption and infrared reflection absorption spectroscopy. The activation energy and pre-exponential factor of desorption were estimated to be 1.2 eV and 2.6 × 1013 s- 1, respectively, in the limit of zero coverage. At low coverage, CO molecules preferentially adsorbed at the hollow sites below 100 K. With increasing temperature, the ontop sites were also occupied. Using a van't Hoff plot, the enthalpy and the entropy differences between the hollow and ontop CO were estimated to be 36 meV and 0.043 meV K- 1, respectively, and the vibrational entropy difference was estimated to be 0.085 meV K- 1. The positive entropy difference was the result of the low-energy frustrated translational mode of the ontop CO, which was estimated to be 4.6 ± 0.3 meV. With the harmonic approximation, the upper limit of the activation energy of site hopping from ontop sites to hollow sites was estimated to be 61 meV. In addition, it was suggested that the activation energy of hollow-to-hollow site hopping via a bridge site was less than 37 meV.

  1. Passive and active EO sensing of small surface vessels

    NASA Astrophysics Data System (ADS)

    Steinvall, Ove; Berglund, Folke; Allard, Lars; Öhgren, Johan; Larsson, Hâkan; Amselem, Elias; Gustafsson, Frank; Repasi, Endre; Lutzmann, Peter; Göhler, Benjamin; Hammer, Marcus; McEwen, Kennedy; McEwan, Ken

    2015-10-01

    The detection and classification of small surface targets at long ranges is a growing need for naval security. This paper will present an overview of a measurement campaign which took place in the Baltic Sea in November 2014. The purpose was to test active and passive EO sensors (10 different types) for the detection, tracking and identification of small sea targets. The passive sensors were covering the visual, SWIR, MWIR and LWIR regions. Active sensors operating at 1.5 μm collected data in 1D, 2D and 3D modes. Supplementary sensors included a weather station, a scintillometer, as well as sensors for positioning and attitude determination of the boats. Three boats in the class 4-9 meters were used as targets. After registration of the boats at close range they were sent out to 5-7 km distance from the sensor site. At the different ranges the target boats were directed to have different aspect angles relative to the direction of observation. Staff from IOSB Fraunhofer in Germany and from Selex (through DSTL) in UK took part in the tests beside FOI who was arranging the trials. A summary of the trial and examples of data and imagery will be presented.

  2. Active control technology and the use of multiple control surfaces

    NASA Technical Reports Server (NTRS)

    Hart, J. E.

    1976-01-01

    Needed criteria for active control technology applications in commercial transports are lacking. Criteria for redundancy requirements, believed to be consistent with certification philosophy, are postulated to afford a discussion of the relative value of multiple control surfaces. The control power and frequency bandpass requirements of various active control technology applications are shown to be such that multiple control surfaces offer advantages in minimizing the hydraulic or auxiliary power for the control surface actuators.

  3. A study of surface and subsurface ground motions at Calico Hills, Nevada Test Site

    USGS Publications Warehouse

    King, Kenneth W.

    1982-01-01

    A study of earthquake ground motions recorded at depth in a drill hole and at the ground surface has derived the surface to subsurface transfer functions such as might be expected at a potential nuclear waste repository in a similar setting. The site under investigation has small seismic velocity contrasts in the layers of rock between the surface and the subsurface seismometer location. The subsurface seismic motions were similar in spectral characteristics to the surface motions and were lower in amplitude across the recorded band-width by a factor of 1.5.

  4. FT-IR characterization of the acidic and basic sites on a nanostructured aluminum nitride surface

    SciTech Connect

    Baraton, M.I.; Chen, X.; Gonsalves, K.E.

    1997-12-31

    A nanostructured aluminum nitride powder prepared by sol-gel type chemical synthesis is analyzed by Fourier transform infrared spectrometry. The surface acidic and basic sites are probed out by adsorption of several organic molecules. Resulting from the unavoidable presence of oxygen, the aluminum nitride surface is an oxinitride layer in fact, and its surface chemistry should present some analogies with alumina. Therefore, a thorough comparison between the acido-basicity of aluminum nitride and aluminum oxide is discussed. The remaining nitrogen atoms in the first atomic layer modify the acidity-basicity relative balance and reveals the specificity of the aluminum nitride surface.

  5. Site switch of on-surface oxygen adatoms on Rh(111) -- a DFT study

    NASA Astrophysics Data System (ADS)

    Ganduglia-Pirovano, M. V.; Scheffler, M.

    2000-03-01

    Oxygen adatoms on Rh(111) at low coverage are known to occupy fcc adsorption sites, but at higher coverages, when also oxygen occupy subsurface sites, the on-surface adatoms switch from the fcc to the hcp adsorption sites (J. Wider, T. Greber, E. Wetli, T.J. Kreutz, P. Schwaller, J. Osterwalder, Surf. Sci. 417) 301 (1998).. We report density-functional theory calculations to analyze the nature of the surface chemical bond of adsorbed oxygen and how this changes with coverage. This also yields to an understanding of the preferred sites and the site-switch. In this context we argue that the Rh_3d and O_1s core level shifts (CLSs) and the adsorption induced change of the work function provide most useful information. We compute initial- and final-state contributions to the CLSs, and compare our results (geometry as well as CLSs) to recent experimental data (A. Baraldi, S. Lizzit, G. Comelli, G. Paolucci, R. Rosei (unpublished)). The dominant factor stabilizing the fcc-site for O adatoms but the hcp-site upon subsurface O formation is found to be an increased ionic contribution to the binding compared to the less stable hollow sites.

  6. Evaluation of surface waters associated with animal feeding operations for estrogenic chemicals and activity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Estrogens and estrogenic activity (EA) were evaluated in surface waters associated with animal feeding operations. Water was sampled at 19 sites in 12 states using discrete (n=41) and POCIS (n=19) sampling methods. Estrogenic chemicals measured in unfiltered water by GC/MS2 included: estrone (E1),17...

  7. Active Sites Environmental Monitoring Program: Program plan. Revision 1

    SciTech Connect

    Ashwood, T.L.; Wickliff, D.S.; Morrissey, C.M.

    1992-02-01

    The Active Sites Environmental Monitoring Program (ASEMP), initiated in 1989, provides early detection and performance monitoring of transuranic (TRU) waste and active low-level waste (LLW) facilities at Oak Ridge National Laboratory (ORNL) in accordance with US Department of Energy (DOE) Order 5820.2A. Active LLW facilities in Solid Waste Storage Area (SWSA) 6 include Tumulus I and Tumulus II, the Interim Waste Management Facility (IWMF), LLW silos, high-range wells, asbestos silos, and fissile wells. The tumulus pads and IWMF are aboveground, high-strength concrete pads on which concrete vaults containing metal boxes of LLW are placed; the void space between the boxes and vaults is filled with grout. Eventually, these pads and vaults will be covered by an engineered multilayered cap. All other LLW facilities in SWSA 6 are below ground. In addition, this plan includes monitoring of the Hillcut Disposal Test Facility (HDTF) in SWSA 6, even though this facility was completed prior to the data of the DOE order. In SWSA 5 North, the TRU facilities include below-grade engineered caves, high-range wells, and unlined trenches. All samples from SWSA 6 are screened for alpha and beta activity, counted for gamma-emitting isotopes, and analyzed for tritium. In addition to these analytes, samples from SWSA 5 North are analyzed for specific transuranic elements.

  8. May 2012 Groundwater and Surface Water Sampling at the Rio Blanco, Colorado, Site (Data Validation Package)

    SciTech Connect

    2012-12-01

    Annual sampling was conducted at the Rio Blanco, Colorado, site for the Long-Term Hydrologic Monitoring Program May 9-10, 2012, to monitor groundwater and surface water for potential radionuclide contamination. Sampling and analyses were conducted as specified in Sampling and Analysis Plan for the U.S. Department of Energy Office of Legacy Management Sites (LMS/PRO/S04351, continually updated). A duplicate sample was collected from location Johnson Artesian WL. Samples were analyzed for gamma-emitting radionuclides by high-resolution gamma spectrometry and for tritium using the conventional and enrichment methods. Results of this monitoring at the Rio Blanco site demonstrate that groundwater and surface water outside the site boundaries have not been affected by project-related contaminants.

  9. A new temperature- and humidity-dependent surface site density approach for deposition ice nucleation

    NASA Astrophysics Data System (ADS)

    Steinke, I.; Hoose, C.; Möhler, O.; Connolly, P.; Leisner, T.

    2015-04-01

    Deposition nucleation experiments with Arizona Test Dust (ATD) as a surrogate for mineral dusts were conducted at the AIDA cloud chamber at temperatures between 220 and 250 K. The influence of the aerosol size distribution and the cooling rate on the ice nucleation efficiencies was investigated. Ice nucleation active surface site (INAS) densities were calculated to quantify the ice nucleation efficiency as a function of temperature, humidity and the aerosol surface area concentration. Additionally, a contact angle parameterization according to classical nucleation theory was fitted to the experimental data in order to relate the ice nucleation efficiencies to contact angle distributions. From this study it can be concluded that the INAS density formulation is a very useful tool to describe the temperature- and humidity-dependent ice nucleation efficiency of ATD particles. Deposition nucleation on ATD particles can be described by a temperature- and relative-humidity-dependent INAS density function ns(T, Sice) with ns(xtherm) = 1.88 ×105 · exp(0.2659 · xtherm) [m-2] , (1) where the temperature- and saturation-dependent function xtherm is defined as xtherm = -(T-273.2)+(Sice-1) ×100, (2) with the saturation ratio with respect to ice Sice >1 and within a temperature range between 226 and 250 K. For lower temperatures, xtherm deviates from a linear behavior with temperature and relative humidity over ice. Also, two different approaches for describing the time dependence of deposition nucleation initiated by ATD particles are proposed. Box model estimates suggest that the time-dependent contribution is only relevant for small cooling rates and low number fractions of ice-active particles.

  10. Simulation and preparation of surface EVA in reduced gravity at the Marseilles Bay subsea analogue sites

    NASA Astrophysics Data System (ADS)

    Weiss, P.; Gardette, B.; Chirié, B.; Collina-Girard, J.; Delauze, H. G.

    2012-12-01

    Extravehicular activity (EVA) of astronauts during space missions is simulated nowadays underwater in neutral buoyancy facilities. Certain aspects of weightlessness can be reproduced underwater by adding buoyancy to a diver-astronaut, therefore exposing the subject to the difficulties of working without gravity. Such tests were done at the COMEX' test pool in Marseilles in the 1980s to train for a French-Russian mission to the MIR station, for the development of the European HERMES shuttle and the COLUMBUS laboratory. However, space agencies are currently studying missions to other destinations than the International Space Station in orbit, such as the return to the Moon, NEO (near-Earth objects) or Mars. All these objects expose different gravities: Moon has one sixth of Earth's gravity, Mars has a third of Earth's gravity and asteroids have virtually no surface gravity; the astronaut "floats" above the ground. The preparation of such missions calls for a new concept in neutral buoyancy training, not on man-made structures, but on natural terrain, underwater, to simulate EVA operations such as sampling, locomotion or even anchoring in low gravity. Underwater sites can be used not only to simulate the reduced gravity that astronauts will experience during their field trips, also human factors like stress are more realistically reproduced in such environment. The Bay of Marseille hosts several underwater sites that can be used to simulate various geologic morphologies, such as sink-holes which can be used to simulate astronaut descends into craters, caves where explorations of lava tubes can be trained or monolithic rock structures that can be used to test anchoring devices (e.g., near Earth objects). Marseilles with its aerospace and maritime/offshore heritage hosts the necessary logistics and expertise that is needed to perform such simulations underwater in a safe manner (training of astronaut-divers in local test pools, research vessels, subsea robots and

  11. Synthesis of supported bimetallic nanoparticles with controlled size and composition distributions for active site elucidation

    SciTech Connect

    Hakim, Sikander H.; Sener, Canan; Alba Rubio, Ana C.; Gostanian, Thomas M.; O'neill, Brandon J; Ribeiro, Fabio H.; Miller, Jeffrey T.; Dumesic, James A

    2015-08-01

    Elucidation of active sites in supported bimetallic catalysts is complicated by the high level of dispersity in the nanoparticle size and composition that is inherent in conventional methods of catalyst preparation. We present a synthesis strategy that leads to highly dispersed, bimetallic nanoparticles with uniform particle size and composition by means of controlled surface reactions. We demonstrate the synthesis of three systems, RhMo, PtMo, and RhRe, consisting of a highly reducible metal with an oxophilic promoter. These catalysts are characterized by FTIR, CO chemisorption, STEM/EDS, TPR, and XAS analysis. The catalytic properties of these bimetallic nanoparticles were probed for the selective CO hydrogenolysis of (hydroxymethyl)tetrahydropyran to produce 1,6 hexanediol. Based on the characterization results and reactivity trends, the active sites in the hydrogenolysis reaction are identified to be small ensembles of the more noble metal (Rh, Pt) adjacent to highly reduced moieties of the more oxophilic metal (Mo, Re).

  12. Active Site and Laminarin Binding in Glycoside Hydrolase Family 55*

    PubMed Central

    Bianchetti, Christopher M.; Takasuka, Taichi E.; Deutsch, Sam; Udell, Hannah S.; Yik, Eric J.; Bergeman, Lai F.; Fox, Brian G.

    2015-01-01

    The Carbohydrate Active Enzyme (CAZy) database indicates that glycoside hydrolase family 55 (GH55) contains both endo- and exo-β-1,3-glucanases. The founding structure in the GH55 is PcLam55A from the white rot fungus Phanerochaete chrysosporium (Ishida, T., Fushinobu, S., Kawai, R., Kitaoka, M., Igarashi, K., and Samejima, M. (2009) Crystal structure of glycoside hydrolase family 55 β-1,3-glucanase from the basidiomycete Phanerochaete chrysosporium. J. Biol. Chem. 284, 10100–10109). Here, we present high resolution crystal structures of bacterial SacteLam55A from the highly cellulolytic Streptomyces sp. SirexAA-E with bound substrates and product. These structures, along with mutagenesis and kinetic studies, implicate Glu-502 as the catalytic acid (as proposed earlier for Glu-663 in PcLam55A) and a proton relay network of four residues in activating water as the nucleophile. Further, a set of conserved aromatic residues that define the active site apparently enforce an exo-glucanase reactivity as demonstrated by exhaustive hydrolysis reactions with purified laminarioligosaccharides. Two additional aromatic residues that line the substrate-binding channel show substrate-dependent conformational flexibility that may promote processive reactivity of the bound oligosaccharide in the bacterial enzymes. Gene synthesis carried out on ∼30% of the GH55 family gave 34 active enzymes (19% functional coverage of the nonredundant members of GH55). These active enzymes reacted with only laminarin from a panel of 10 different soluble and insoluble polysaccharides and displayed a broad range of specific activities and optima for pH and temperature. Application of this experimental method provides a new, systematic way to annotate glycoside hydrolase phylogenetic space for functional properties. PMID:25752603

  13. Active site and laminarin binding in glycoside hydrolase family 55.

    PubMed

    Bianchetti, Christopher M; Takasuka, Taichi E; Deutsch, Sam; Udell, Hannah S; Yik, Eric J; Bergeman, Lai F; Fox, Brian G

    2015-05-01

    The Carbohydrate Active Enzyme (CAZy) database indicates that glycoside hydrolase family 55 (GH55) contains both endo- and exo-β-1,3-glucanases. The founding structure in the GH55 is PcLam55A from the white rot fungus Phanerochaete chrysosporium (Ishida, T., Fushinobu, S., Kawai, R., Kitaoka, M., Igarashi, K., and Samejima, M. (2009) Crystal structure of glycoside hydrolase family 55 β-1,3-glucanase from the basidiomycete Phanerochaete chrysosporium. J. Biol. Chem. 284, 10100-10109). Here, we present high resolution crystal structures of bacterial SacteLam55A from the highly cellulolytic Streptomyces sp. SirexAA-E with bound substrates and product. These structures, along with mutagenesis and kinetic studies, implicate Glu-502 as the catalytic acid (as proposed earlier for Glu-663 in PcLam55A) and a proton relay network of four residues in activating water as the nucleophile. Further, a set of conserved aromatic residues that define the active site apparently enforce an exo-glucanase reactivity as demonstrated by exhaustive hydrolysis reactions with purified laminarioligosaccharides. Two additional aromatic residues that line the substrate-binding channel show substrate-dependent conformational flexibility that may promote processive reactivity of the bound oligosaccharide in the bacterial enzymes. Gene synthesis carried out on ∼30% of the GH55 family gave 34 active enzymes (19% functional coverage of the nonredundant members of GH55). These active enzymes reacted with only laminarin from a panel of 10 different soluble and insoluble polysaccharides and displayed a broad range of specific activities and optima for pH and temperature. Application of this experimental method provides a new, systematic way to annotate glycoside hydrolase phylogenetic space for functional properties. PMID:25752603

  14. Active Site Loop Conformation Regulates Promiscuous Activity in a Lactonase from Geobacillus kaustophilus HTA426

    PubMed Central

    Zhang, Yu; An, Jiao; Yang, Guang-Yu; Bai, Aixi; Zheng, Baisong; Lou, Zhiyong; Wu, Geng; Ye, Wei; Chen, Hai-Feng; Feng, Yan; Manco, Giuseppe

    2015-01-01

    Enzyme promiscuity is a prerequisite for fast divergent evolution of biocatalysts. A phosphotriesterase-like lactonase (PLL) from Geobacillus kaustophilus HTA426 (GkaP) exhibits main lactonase and promiscuous phosphotriesterase activities. To understand its catalytic and evolutionary mechanisms, we investigated a “hot spot” in the active site by saturation mutagenesis as well as X-ray crystallographic analyses. We found that position 99 in the active site was involved in substrate discrimination. One mutant, Y99L, exhibited 11-fold improvement over wild-type in reactivity (kcat/Km) toward the phosphotriesterase substrate ethyl-paraoxon, but showed 15-fold decrease toward the lactonase substrate δ-decanolactone, resulting in a 157-fold inversion of the substrate specificity. Structural analysis of Y99L revealed that the mutation causes a ∼6.6 Å outward shift of adjacent loop 7, which may cause increased flexibility of the active site and facilitate accommodation and/or catalysis of organophosphate substrate. This study provides for the PLL family an example of how the evolutionary route from promiscuity to specificity can derive from very few mutations, which promotes alteration in the conformational adjustment of the active site loops, in turn draws the capacity of substrate binding and activity. PMID:25706379

  15. Surface wind characteristics of some Aleutian Islands. [for selection of windpowered machine sites

    NASA Technical Reports Server (NTRS)

    Wentink, T., Jr.

    1973-01-01

    The wind power potential of Alaska is assessed in order to determine promising windpower sites for construction of wind machines and for shipment of wind derived energy. Analyses of near surface wind data from promising Aleutian sites accessible by ocean transport indicate probable velocity regimes and also present deficiencies in available data. It is shown that winds for some degree of power generation are available 77 percent of the time in the Aleutians with peak velocities depending on location.

  16. Aerosol measurements at the Southern Great Plains Site: Design and surface installation

    SciTech Connect

    Leifer, R.; Knuth, R.H.; Guggenheim, S.F.; Albert, B.

    1996-04-01

    To impropve the predictive capabilities of the Atmospheric Radiation Measurements (ARM) program radiation models, measurements of awserosol size distributions, condensation particle concentrations, aerosol scattering coefficients at a number of wavelenghts, and the aerosol absorption coefficients are needed at the Southern Great Plains (SGP) site. Alos, continuous measurements of ozone concnetrations are needed for model validation. The environmental Measuremenr Laboratory (EMK) has the responsibility to establish the surface aerosol measurements program at the SGP site. EML has designed a special sampling manifold.

  17. Spatial Variability of Surface Irradiance Measurements at the Manus ARM Site

    SciTech Connect

    Riihimaki, Laura D.; Long, Charles N.

    2014-05-16

    The location of the Atmospheric Radiation Measurement (ARM) site on Manus island in Papua New Guinea was chosen because it is very close the coast, in a geographically at, near-sea level area of the island, minimizing the impact of local island effects on the meteorology of the measurements [Ackerman et al., 1999]. In this study, we confirm that the Manus site is in deed less impacted by the island meteorology than slightly inland by comparing over a year of broadband surface irradiance and ceilometer measurements and derived quantities at the standard Manus site and a second location 7 km away as part of the AMIE-Manus campaign. The two sites show statistically similar distributions of irradiance and other derived quantities for all wind directions except easterly winds, when the inland site is down wind from the standard Manus site. Under easterly wind conditions, which occur 17% of the time, there is a higher occurrence of cloudiness at the down wind site likely do to land heating and orographic effects. This increased cloudiness is caused by shallow, broken clouds often with bases around 700 m in altitude. While the central Manus site consistently measures a frequency of occurrence of low clouds (cloud base height less than 1200 m) about 25+4% regardless of wind direction, the AMIE site has higher frequencies of low clouds (38%) when winds are from the east. This increase in low, locally produced clouds causes an additional -20 W/m2 shortwave surface cloud radiative effect at the AMIE site in easterly conditions than in other meteorological conditions that exhibit better agreement between the two sites.

  18. APOLLO 10: Training for Lunar Surface Activities

    NASA Technical Reports Server (NTRS)

    1974-01-01

    Astronauts train on a mock-up lunar surface, practicing the procedures they will follow on the real thing, and adjusting to the demands of the workload. From the film documentary 'APOLLO 10: 'Green Light for a Lunar Landing''. Part of a documentary series made in the early 70's on the APOLLO missions, and narrated by Burgess Meredith. (Actual date created is not known at this time) APOLLO 10: Manned lunar orbital flight with Thomas P Stafford, John W. Young, and Eugene A. Cernan to test all aspects of an actual manned lunar landing except the landing. Mission Duration 192hrs 3mins 23 sec

  19. Discovery and Characterization of Non-ATP Site Inhibitors of the Mitogen Activated Protein (MAP) Kinases

    SciTech Connect

    Comess, Kenneth M.; Sun, Chaohong; Abad-Zapatero, Cele; Goedken, Eric R.; Gum, Rebecca J.; Borhani, David W.; Argiriadi, Maria; Groebe, Duncan R.; Jia, Yong; Clampit, Jill E.; Haasch, Deanna L.; Smith, Harriet T.; Wang, Sanyi; Song, Danying; Coen, Michael L.; Cloutier, Timothy E.; Tang, Hua; Cheng, Xueheng; Quinn, Christopher; Liu, Bo; Xin, Zhili; Liu, Gang; Fry, Elizabeth H.; Stoll, Vincent; Ng, Teresa I.; Banach, David; Marcotte, Doug; Burns, David J.; Calderwood, David J.; Hajduk, Philip J.

    2012-03-02

    Inhibition of protein kinases has validated therapeutic utility for cancer, with at least seven kinase inhibitor drugs on the market. Protein kinase inhibition also has significant potential for a variety of other diseases, including diabetes, pain, cognition, and chronic inflammatory and immunologic diseases. However, as the vast majority of current approaches to kinase inhibition target the highly conserved ATP-binding site, the use of kinase inhibitors in treating nononcology diseases may require great selectivity for the target kinase. As protein kinases are signal transducers that are involved in binding to a variety of other proteins, targeting alternative, less conserved sites on the protein may provide an avenue for greater selectivity. Here we report an affinity-based, high-throughput screening technique that allows nonbiased interrogation of small molecule libraries for binding to all exposed sites on a protein surface. This approach was used to screen both the c-Jun N-terminal protein kinase Jnk-1 (involved in insulin signaling) and p38{alpha} (involved in the formation of TNF{alpha} and other cytokines). In addition to canonical ATP-site ligands, compounds were identified that bind to novel allosteric sites. The nature, biological relevance, and mode of binding of these ligands were extensively characterized using two-dimensional {sup 1}H/{sup 13}C NMR spectroscopy, protein X-ray crystallography, surface plasmon resonance, and direct enzymatic activity and activation cascade assays. Jnk-1 and p38{alpha} both belong to the MAP kinase family, and the allosteric ligands for both targets bind similarly on a ledge of the protein surface exposed by the MAP insertion present in the CMGC family of protein kinases and distant from the active site. Medicinal chemistry studies resulted in an improved Jnk-1 ligand able to increase adiponectin secretion in human adipocytes and increase insulin-induced protein kinase PKB phosphorylation in human hepatocytes, in

  20. Importance of surface carbide formation on the activity and selectivity of Pd surfaces in the selective hydrogenation of acetylene

    NASA Astrophysics Data System (ADS)

    Yang, Bo; Burch, Robbie; Hardacre, Christopher; Hu, P.; Hughes, Philip

    2016-04-01

    A recent experimental investigation (Kim et al. J. Catal. 306 (2013) 146-154) on the selective hydrogenation of acetylene over Pd nanoparticles with different shapes concluded that Pd(100) showed higher activity and selectivity than Pd(111) for acetylene hydrogenation. However, our recent density functional calculations (Yang et al. J. Catal. 305 (2013) 264-276) observed that the clean Pd(111) surface should result in higher activity and ethylene selectivity compared with the clean Pd(100) surface for acetylene hydrogenation. In the current work, using density functional theory calculations, we find that Pd(100) in the carbide form gives rise to higher activity and selectivity than Pd(111) carbide. These results indicate that the catalyst surface is most likely in the carbide form under the experimental reaction conditions. Furthermore, the adsorption energies of hydrogen atoms as a function of the hydrogen coverage at the surface and subsurface sites over Pd(100) are compared with those over Pd(111), and it is found that the adsorption of hydrogen atoms is always less favoured on Pd(100) over the whole coverage range. This suggests that the Pd(100) hydride surface will be less stable than the Pd(111) hydride surface, which is also in accordance with the experimental results reported.

  1. Near Surface Swimming of Salmonella Typhimurium Explains Target-Site Selection and Cooperative Invasion

    PubMed Central

    Kreibich, Saskia; Vonaesch, Pascale; Andritschke, Daniel; Rout, Samuel; Weidner, Kerstin; Sormaz, Milos; Songhet, Pascal; Horvath, Peter; Chabria, Mamta; Vogel, Viola; Spori, Doris M.; Jenny, Patrick; Hardt, Wolf-Dietrich

    2012-01-01

    Targeting of permissive entry sites is crucial for bacterial infection. The targeting mechanisms are incompletely understood. We have analyzed target-site selection by S. Typhimurium. This enteropathogenic bacterium employs adhesins (e.g. fim) and the type III secretion system 1 (TTSS-1) for host cell binding, the triggering of ruffles and invasion. Typically, S. Typhimurium invasion is focused on a subset of cells and multiple bacteria invade via the same ruffle. It has remained unclear how this is achieved. We have studied target-site selection in tissue culture by time lapse microscopy, movement pattern analysis and modeling. Flagellar motility (but not chemotaxis) was required for reaching the host cell surface in vitro. Subsequently, physical forces trapped the pathogen for ∼1.5–3 s in “near surface swimming”. This increased the local pathogen density and facilitated “scanning” of the host surface topology. We observed transient TTSS-1 and fim-independent “stopping” and irreversible TTSS-1-mediated docking, in particular at sites of prominent topology, i.e. the base of rounded-up cells and membrane ruffles. Our data indicate that target site selection and the cooperative infection of membrane ruffles are attributable to near surface swimming. This mechanism might be of general importance for understanding infection by flagellated bacteria. PMID:22911370

  2. Interaction of mining activities and aquatic environment: A review from Greek mine sites.

    NASA Astrophysics Data System (ADS)

    Vasileiou, Eleni; Kallioras, Andreas

    2016-04-01

    In Greece a significant amount of mineral and ore deposits have been recorded accompanied by large industrial interest and a long mining history. Today many active and/or abandoned mine sites are scattered within the country; while mining activities take place in different sites for exploiting various deposits (clay, limestone, slate, gypsum, kaolin, mixed sulphide ores (lead, zinc, olivine, pozzolan, quartz lignite, nickel, magnesite, aluminum, bauxite, gold, marbles etc). The most prominent recent ones are: (i) the lignite exploitation that is extended in the area of Ptolemais (Western Macedonia) and Megalopolis (Central Peloponnese); and (ii) the major bauxite deposits located in central Greece within the Parnassos-Ghiona geotectonic zone and on Euboea Island. In the latter area, significant ores of magnesite were exploited and mixed sulphide ores. Centuries of intensive mining exploitation and metallurgical treatment of lead-silver deposits in Greece, have also resulted in significant abandoned sites, such as the one in Lavrion. Mining activities in Lavrio, were initiated in ancient times and continued until the 1980s, resulting in the production of significant waste stockpiles deposited in the area, crucial for the local water resources. Ιn many mining sites, environmental pressures are also recorded after the mine closure to the aquatic environment, as the surface waters flow through waste dump areas and contaminated soils. This paper aims to the geospatial visualization of the mining activities in Greece, in connection to their negative (surface- and/or ground-water pollution; overpumping due to extensive dewatering practices) or positive (enhanced groundwater recharge; pit lakes, improvement of water budget in the catchment scale) impacts on local water resources.

  3. Crystallographic Analysis of Active Site Contributions to Regiospecificity in the Diiron Enzyme Toluene 4-Monooxygenase

    SciTech Connect

    Bailey, Lucas J.; Acheson, Justin F.; McCoy, Jason G.; Elsen, Nathaniel L.; Phillips, Jr., George N.; Fox, Brian G.

    2014-10-02

    Crystal structures of toluene 4-monooxygenase hydroxylase in complex with reaction products and effector protein reveal active site interactions leading to regiospecificity. Complexes with phenolic products yield an asymmetric {mu}-phenoxo-bridged diiron center and a shift of diiron ligand E231 into a hydrogen bonding position with conserved T201. In contrast, complexes with inhibitors p-NH{sub 2}-benzoate and p-Br-benzoate showed a {mu}-1,1 coordination of carboxylate oxygen between the iron atoms and only a partial shift in the position of E231. Among active site residues, F176 trapped the aromatic ring of products against a surface of the active site cavity formed by G103, E104 and A107, while F196 positioned the aromatic ring against this surface via a {pi}-stacking interaction. The proximity of G103 and F176 to the para substituent of the substrate aromatic ring and the structure of G103L T4moHD suggest how changes in regiospecificity arise from mutations at G103. Although effector protein binding produced significant shifts in the positions of residues along the outer portion of the active site (T201, N202, and Q228) and in some iron ligands (E231 and E197), surprisingly minor shifts (<1 {angstrom}) were produced in F176, F196, and other interior residues of the active site. Likewise, products bound to the diiron center in either the presence or absence of effector protein did not significantly shift the position of the interior residues, suggesting that positioning of the cognate substrates will not be strongly influenced by effector protein binding. Thus, changes in product distributions in the absence of the effector protein are proposed to arise from differences in rates of chemical steps of the reaction relative to motion of substrates within the active site channel of the uncomplexed, less efficient enzyme, while structural changes in diiron ligand geometry associated with cycling between diferrous and diferric states are discussed for their potential

  4. A Climatology of Surface Cloud Radiative Effects at the ARM Tropical Western Pacific Sites

    SciTech Connect

    McFarlane, Sally A.; Long, Charles N.; Flaherty, Julia E.

    2013-04-01

    Cloud radiative effects on surface downwelling fluxes are investigated using long-term datasets from the three Atmospheric Radiation Measurement (ARM) sites in the Tropical Western Pacific (TWP) region. The Nauru and Darwin sites show significant variability in sky cover, downwelling radiative fluxes, and surface cloud radiative effect (CRE) due to El Niño and the Australian monsoon, respectively, while the Manus site shows little intra-seasonal or interannual variability. Cloud radar measurement of cloud base and top heights are used to define cloud types so that the effect of cloud type on the surface CRE can be examined. Clouds with low bases contribute 71-75% of the surface shortwave (SW) CRE and 66-74% of the surface longwave (LW) CRE at the three TWP sites, while clouds with mid-level bases contribute 8-9% of the SW CRE and 12-14% of the LW CRE, and clouds with high bases contribute 16-19% of the SW CRE and 15-21% of the LW CRE.

  5. Nocturnal surface ozone enhancement and trend over urban and suburban sites in Portugal

    NASA Astrophysics Data System (ADS)

    Kulkarni, Pavan S.; Bortoli, D.; Silva, A. M.

    2013-06-01

    Long term (2000-2010) analysis of hourly surface ozone data from 6 out of 9 background air pollution monitoring sites in Portugal shows prominent secondary/nocturnal peak in monthly averaged diurnal variation during winter months (Nov-Feb). Of 9 sites: 3 are urban, 5 suburban and 1 rural. The bimodal diurnal variation of surface ozone shows a major peak around 15 h and a minor peak around 03-05 h with minima around 08 h and 20 h in the months of November-February. During winter months, more than 50% of observations in Porto and Lisbon region had nocturnal surface ozone concentrations higher than 40 μg m-3 compared to monthly averaged early morning/late evening minima (20±5 μg m-3). Analysis also shows an increasing trend in nocturnal surface ozone daily maxima over 5 urban/suburban sites and over another site (Alfragide) which exhibits the same trend but only in the last 7 years of the studied period. Also the non-parametric Mann-Kendall test confirms that the trends are statistically significant. The enhancement of nocturnal surface ozone is most likely associated with transport process and prevailing meteorological conditions since photochemical production of ozone ceases after sunset.

  6. [Field measurement of Gobi surface emissivity spectrum at Dunhuang calibration site of China].

    PubMed

    Zhang, Yong; Li, Yuan; Rong, Zhi-guo; Hu, Xiu-qing; Zhang, Li-jun; Liu, Jing-jing

    2009-05-01

    Gobi surface emissivity spectrum of Dunhuang radiometric calibration site of China is one of the key factors to calibrate the thermal infrared remote sensors using land surface. Based on the iterative spectrally smooth temperature/emissivity separation (ISSTES)algorithm, Dunhuang Gobi surface emissivity spectrum was measured using BOMEM MR154 Fourier transform spectroradiometer and Infrared Golden Board. Emissivity spectrum data were obtained at different time and locations. These spectrum data were convolved with the channel response function of CE312 radiometer and compared with the channel emissivity measured by the same instrument. The results showed that the difference between these two kinds of channel emissivity was within 0.012 and exhibited a good consistency. With these measured emissivity spectra, all of the mainstream thermal infrared remote sensors can be calibrated using Dunhuang Gobi surface at radiometric calibration site of China. PMID:19650456

  7. Ubiquitin vinyl methyl ester binding orients the misaligned active site of the ubiquitin hydrolase UCHL1 into productive conformation

    SciTech Connect

    Boudreaux, David A.; Maiti, Tushar K.; Davies, Christopher W.; Das, Chittaranjan

    2010-07-06

    Ubiquitin carboxy-terminal hydrolase L1 (UCHL1) is a Parkinson disease-associated, putative cysteine protease found abundantly and selectively expressed in neurons. The crystal structure of apo UCHL1 showed that the active-site residues are not aligned in a canonical form, with the nucleophilic cysteine being 7.7 {angstrom} from the general base histidine, an arrangement consistent with an inactive form of the enzyme. Here we report the crystal structures of the wild type and two Parkinson disease-associated variants of the enzyme, S18Y and I93M, bound to a ubiquitin-based suicide substrate, ubiquitin vinyl methyl ester. These structures reveal that ubiquitin vinyl methyl ester binds primarily at two sites on the enzyme, with its carboxy terminus at the active site and with its amino-terminal {beta}-hairpin at the distal site - a surface-exposed hydrophobic crevice 17 {angstrom} away from the active site. Binding at the distal site initiates a cascade of side-chain movements in the enzyme that starts at a highly conserved, surface-exposed phenylalanine and is relayed to the active site resulting in the reorientation and proximal placement of the general base within 4 {angstrom} of the catalytic cysteine, an arrangement found in productive cysteine proteases. Mutation of the distal-site, surface-exposed phenylalanine to alanine reduces ubiquitin binding and severely impairs the catalytic activity of the enzyme. These results suggest that the activity of UCHL1 may be regulated by its own substrate.

  8. Extensive site-directed mutagenesis reveals interconnected functional units in the alkaline phosphatase active site.

    PubMed

    Sunden, Fanny; Peck, Ariana; Salzman, Julia; Ressl, Susanne; Herschlag, Daniel

    2015-01-01

    Enzymes enable life by accelerating reaction rates to biological timescales. Conventional studies have focused on identifying the residues that have a direct involvement in an enzymatic reaction, but these so-called 'catalytic residues' are embedded in extensive interaction networks. Although fundamental to our understanding of enzyme function, evolution, and engineering, the properties of these networks have yet to be quantitatively and systematically explored. We dissected an interaction network of five residues in the active site of Escherichia coli alkaline phosphatase. Analysis of the complex catalytic interdependence of specific residues identified three energetically independent but structurally interconnected functional units with distinct modes of cooperativity. From an evolutionary perspective, this network is orders of magnitude more probable to arise than a fully cooperative network. From a functional perspective, new catalytic insights emerge. Further, such comprehensive energetic characterization will be necessary to benchmark the algorithms required to rationally engineer highly efficient enzymes. PMID:25902402

  9. DISPLAR: an accurate method for predicting DNA-binding sites on protein surfaces

    PubMed Central

    Tjong, Harianto; Zhou, Huan-Xiang

    2007-01-01

    Structural and physical properties of DNA provide important constraints on the binding sites formed on surfaces of DNA-targeting proteins. Characteristics of such binding sites may form the basis for predicting DNA-binding sites from the structures of proteins alone. Such an approach has been successfully developed for predicting protein–protein interface. Here this approach is adapted for predicting DNA-binding sites. We used a representative set of 264 protein–DNA complexes from the Protein Data Bank to analyze characteristics and to train and test a neural network predictor of DNA-binding sites. The input to the predictor consisted of PSI-blast sequence profiles and solvent accessibilities of each surface residue and 14 of its closest neighboring residues. Predicted DNA-contacting residues cover 60% of actual DNA-contacting residues and have an accuracy of 76%. This method significantly outperforms previous attempts of DNA-binding site predictions. Its application to the prion protein yielded a DNA-binding site that is consistent with recent NMR chemical shift perturbation data, suggesting that it can complement experimental techniques in characterizing protein–DNA interfaces. PMID:17284455

  10. Final report: survey and removal of radioactive surface contamination at environmental restoration sites, Sandia National Laboratories/New Mexico. Volume 1

    SciTech Connect

    Lambert, K.A.; Mitchell, M.M.; Jean, D.; Byrd, C.S.

    1997-09-01

    This report describes the survey and removal of radioactive surface contamination at Sandia`s Environmental Restoration (ER) sites. Radiological characterization was performed as a prerequisite to beginning the Resource Conservation and Recovery Act (RCRA) corrective action process. The removal of radioactive surface contamination was performed in order to reduce potential impacts to human health and the environment. The predominant radiological contaminant of concern was depleted uranium (DU). Between October 1993 and November 1996 scanning surface radiation surveys, using gamma scintillometers, were conducted at 65 sites covering approximately 908 acres. A total of 9,518 radiation anomalies were detected at 38 sites. Cleanup activities were conducted between October 1994 and November 1996. A total of 9,122 anomalies were removed and 2,072 waste drums were generated. The majority of anomalies not removed were associated with a site that has subsurface contamination beyond the scope of this project. Verification soil samples (1,008 total samples) were collected from anomalies during cleanup activities and confirm that the soil concentration achieved in the field were far below the target cleanup level of 230 pCi/g of U-238 (the primary constituent of DU) in the soil. Cleanup was completed at 21 sites and no further radiological action is required. Seventeen sites were not completed since cleanup activities wee precluded by ongoing site activity or were beyond the original project scope.

  11. Early contacts between T lymphocytes and activating surfaces

    NASA Astrophysics Data System (ADS)

    Cretel, E.; Touchard, D.; Benoliel, A. M.; Bongrand, P.; Pierres, A.

    2010-05-01

    Cells continually probe their environment to adapt their behaviour. A current challenge is to determine how they analyse nearby surfaces and how they process information to take decisions. We addressed this problem by monitoring human T lymphocyte attachment to surfaces coated with activating anti-CD3 or control anti-HLA antibodies. Interference reflection microscopy allowed us to monitor cell-to-surface apposition with a few nanometre vertical resolution during the first minutes following contact. We found that (i) when a cell fell on a surface, contact extension was preceded by a lag of several tens of seconds. (ii) During this lag, vertical membrane undulations seemed to generate transient contacts with underlying surfaces. (iii) After the lag period, the contact area started increasing linearly with a rate of about 1.5 µm2 s - 1 on activating surfaces and about 0.2 µm2 s - 1 on control surfaces. (iv) Concomitantly with lateral surface extension, the apparent distance between cell membranes and surfaces steadily decreased. These results are consistent with the hypothesis that the cell decision to spread rapidly on activating surfaces resulted from the integration of information yielded by transient contacts with these surfaces generated by membrane undulations during a period of about 1 min.

  12. Comparison of land surface temperature measurements at NOAA CRN sites with airborne and satellite observations

    NASA Astrophysics Data System (ADS)

    Krishnan, P.; Kochendorfer, J.; Baker, B.; Dumas, E.; Meyers, T. P.; Guillevic, P.; Corda, S.; Muratore, J.; Martos, B.

    2011-12-01

    Land surface temperature (LST) is a key variable for studying global or regional land surface processes and the energy and water vapor exchange at the biosphere-atmosphere interface. In an effort to better quantify the spatial variability and overall representativeness of single-point surface temperature measurement being recorded at NOAA's Climate Reference Network (CRN) sites and to improve the accuracy of satellite land surface temperature measurements, airborne flight campaigns were conducted over two vegetated sites in Tennessee, USA during 2010 to 2011. During the campaign, multiple measurements of land surface temperature were made using Infra-Red temperature sensors at micrometeorological tower sites and onboard an instrumented Piper Navajo airborne research aircraft. In addition to this, coincident Moderate Resolution Imaging Spectroradiometer (MODIS) LST observations, onboard the NASA Terra and Aqua Earth Observing System satellites were used. The aircraft-based and satellite based land surface temperature measurements were compared to in situ, tower based LST measurements. Preliminary results show good agreement between in situ, aircraft and satellite measurements.

  13. Surfaces of Fluorinated Pyridinium Block Copolymers with Enhanced Antibacterial Activity

    SciTech Connect

    Krishnan,S.; Ward, R.; Hexemer, A.; Sohn, K.; Lee, K.; Angert, E.; Fischer, D.; Kramer, E.; Ober, C.

    2006-01-01

    Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

  14. Surface diffusion activation energy determination using ion beam microtexturing

    NASA Technical Reports Server (NTRS)

    Rossnagel, S. M.; Robinson, R. S.

    1982-01-01

    The activation energy for impurity atom (adatom) surface diffusion can be determined from the temperature dependence of the spacing of sputter cones. These cones are formed on the surface during sputtering while simultaneously adding impurities. The impurities form clusters by means of surface diffusion, and these clusters in turn initiate cone formation. Values are given for the surface diffusion activation energies for various materials on polycrystalline Cu, Al, Pb, Au, and Ni. The values for different impurity species on each of these substrates are approximately independent of impurity species within the experimental uncertainty, suggesting the absence of strong chemical bonding effects on the diffusion.

  15. Metavanadate at the active site of the phosphatase VHZ.

    PubMed

    Kuznetsov, Vyacheslav I; Alexandrova, Anastassia N; Hengge, Alvan C

    2012-09-01

    Vanadate is a potent modulator of a number of biological processes and has been shown by crystal structures and NMR spectroscopy to interact with numerous enzymes. Although these effects often occur under conditions where oligomeric forms dominate, the crystal structures and NMR data suggest that the inhibitory form is usually monomeric orthovanadate, a particularly good inhibitor of phosphatases because of its ability to form stable trigonal-bipyramidal complexes. We performed a computational analysis of a 1.14 Å structure of the phosphatase VHZ in complex with an unusual metavanadate species and compared it with two classical trigonal-bipyramidal vanadate-phosphatase complexes. The results support extensive delocalized bonding to the apical ligands in the classical structures. In contrast, in the VHZ metavanadate complex, the central, planar VO(3)(-) moiety has only one apical ligand, the nucleophilic Cys95, and a gap in electron density between V and S. A computational analysis showed that the V-S interaction is primarily ionic. A mechanism is proposed to explain the formation of metavanadate in the active site from a dimeric vanadate species that previous crystallographic evidence has shown to be able to bind to the active sites of phosphatases related to VHZ. Together, the results show that the interaction of vanadate with biological systems is not solely reliant upon the prior formation of a particular inhibitory form in solution. The catalytic properties of an enzyme may act upon the oligomeric forms primarily present in solution to generate species such as the metavanadate ion observed in the VHZ structure. PMID:22876963

  16. Characterization of an Active Thermal Erosion Site, Caribou Creek, Alaska

    NASA Astrophysics Data System (ADS)

    Busey, R.; Bolton, W. R.; Cherry, J. E.; Hinzman, L. D.

    2013-12-01

    The goal of this project is to estimate volume loss of soil over time from this site, provide parameterizations on erodibility of ice rich permafrost and serve as a baseline for future landscape evolution simulations. Located in the zone of discontinuous permafrost, the interior region of Alaska (USA) is home to a large quantity of warm, unstable permafrost that is both high in ice content and has soil temperatures near the freezing point. Much of this permafrost maintains a frozen state despite the general warming air temperature trend in the region due to the presence of a thick insulating organic mat and a dense root network in the upper sub-surface of the soil column. At a rapidly evolving thermo-erosion site, located within the Caribou-Poker Creeks Research Watershed (part of the Bonanza Creek LTER) near Chatanika, Alaska (N65.140, W147.570), the protective organic layer and associated plants were disturbed by an adjacent traditional use trail and the shifting of a groundwater spring. These triggers have led to rapid geomorphological change on the landscape as the soil thaws and sediment is transported into the creek at the valley bottom. Since 2006 (approximately the time of initiation), the thermal erosion has grown to 170 meters length, 3 meters max depth, and 15 meters maximum width. This research combines several data sets: DGPS survey, imagery from an extremely low altitude pole-based remote sensing (3 to 5 meters above ground level), and imagery from an Unmanned Aerial System (UAS) at about 60m altitude.

  17. Orthogonal electrode catheter array for mapping of endocardial focal site of ventricular activation

    SciTech Connect

    Desai, J.M.; Nyo, H.; Vera, Z.; Seibert, J.A.; Vogelsang, P.J. )

    1991-04-01

    Precise location of the endocardial site of origin of ventricular tachycardia may facilitate surgical and catheter ablation of this arrhythmia. The endocardial catheter mapping technique can locate the site of ventricular tachycardia within 4-8 cm2 of the earliest site recorded by the catheter. This report describes an orthogonal electrode catheter array (OECA) for mapping and radiofrequency ablation (RFA) of endocardial focal site of origin of a plunge electrode paced model of ventricular activation in dogs. The OECA is an 8 F five pole catheter with four peripheral electrodes and one central electrode (total surface area 0.8 cm{sup 2}). In eight mongrel dogs, mapping was performed by arbitrarily dividing the left ventricle (LV) into four segments. Each segment was mapped with OECA to find the earliest segment. Bipolar and unipolar electrograms were obtained. The plunge electrode (not visible on fluoroscopy) site was identified by the earliest wave front arrival times of -30 msec or earlier at two or more electrodes (unipolar electrograms) with reference to the earliest recorded surface ECG (I, AVF, and V1). Validation of the proximity of the five electrodes of the OECA to the plunge electrode was performed by digital radiography and RFA. Pathological examination was performed to document the proximity of the OECA to the plunge electrode and also for the width, depth, and microscopic changes of the ablation. To find the segment with the earliest LV activation a total of 10 {plus minus} 3 (mean {plus minus} SD) positions were mapped. Mean arrival times at the two earlier electrodes were -39 {plus minus} 4 msec and -35 {plus minus} 3 msec. Digital radiography showed the plunge electrode to be within the area covered by all five electrodes in all eight dogs. The plunge electrode was within 1 cm2 area of the region of RFA in all eight dogs.

  18. Active nematics of flat and spherical surfaces

    NASA Astrophysics Data System (ADS)

    Dogic, Zvonimir

    2014-03-01

    The laws of equilibrium statistical mechanics impose severe constraints on the properties of conventional materials assembled from inanimate building blocks. Consequently, such materials cannot exhibit spontaneous motion or perform macroscopic work; i.e., a fluid in a beaker remains quiescent unless driven by external forces. Inspired by biological phenomena such as ciliary beating or Drosophila cytoplasmic streaming our aim is to develop a new category of materials assembled from animate, energy-consuming building blocks. Starting from a few well-characterized biochemical components we assemble and study far-from-equilibrium analogs of conventional liquid crystals. Released from the constraints of equilibrium, this internally driven polymeric material exhibits a host of highly-sought after properties including appearance of steady-state streaming flows that are accompanied by the spontaneous unbinding and annihilations of motile defects as well as appearance and subsequent self-healing of fracture lines. Active liquid crystals can serve as a platform for developing novel material applications, testing fundamental theoretical models of far-from-equilibrium active matter and potentially shedding light on self-organization in living cells.

  19. Hybrid [FeFe]-hydrogenases with modified active sites show remarkable residual enzymatic activity.

    PubMed

    Siebel, Judith F; Adamska-Venkatesh, Agnieszka; Weber, Katharina; Rumpel, Sigrun; Reijerse, Edward; Lubitz, Wolfgang

    2015-02-24

    [FeFe]-hydrogenases are to date the only enzymes for which it has been demonstrated that the native inorganic binuclear cofactor of the active site Fe2(adt)(CO)3(CN)2 (adt = azadithiolate = [S-CH2-NH-CH2-S](2-)) can be synthesized on the laboratory bench and subsequently inserted into the unmaturated enzyme to yield fully functional holo-enzyme (Berggren, G. et al. (2013) Nature 499, 66-70; Esselborn, J. et al. (2013) Nat. Chem. Biol. 9, 607-610). In the current study, we exploit this procedure to introduce non-native cofactors into the enzyme. Mimics of the binuclear subcluster with a modified bridging dithiolate ligand (thiodithiolate, N-methylazadithiolate, dimethyl-azadithiolate) and three variants containing only one CN(-) ligand were inserted into the active site of the enzyme. We investigated the activity of these variants for hydrogen oxidation as well as proton reduction and their structural accommodation within the active site was analyzed using Fourier transform infrared spectroscopy. Interestingly, the monocyanide variant with the azadithiolate bridge showed ∼50% of the native enzyme activity. This would suggest that the CN(-) ligands are not essential for catalytic activity, but rather serve to anchor the binuclear subsite inside the protein pocket through hydrogen bonding. The inserted artificial cofactors with a propanedithiolate and an N-methylazadithiolate bridge as well as their monocyanide variants also showed residual activity. However, these activities were less than 1% of the native enzyme. Our findings indicate that even small changes in the dithiolate bridge of the binuclear subsite lead to a rather strong decrease of the catalytic activity. We conclude that both the Brønsted base function and the conformational flexibility of the native azadithiolate amine moiety are essential for the high catalytic activity of the native enzyme. PMID:25633077

  20. Post-Shot Surface Damage Detected with LIDAR at the Source Physics Experiment Site (Invited)

    NASA Astrophysics Data System (ADS)

    Schultz-Fellenz, E. S.; Sussman, A. J.; Kelley, R. E.; Cooper, D. I.

    2013-12-01

    Designed to improve long-range treaty monitoring capabilities, the Source Physics Experiment series is being conducted at a location in Nevada and provides an opportunity to advance near-field monitoring and field-based investigations of suspected underground test locations. In particular, features associated with underground testing can be evaluated using Source Physics Experiment activities as analogs, linking on-site inspections with remote sensing technologies. Following a calibration shot (SPE 1), SPE 2 (10/2011) and SPE 3 (07/2012) were performed in the same emplacement hole with 1.0 ton of explosives at 150 ft depth. A fourth shot (SPE 4) is planned for August 2013 as a 220 lb (100 kg) TNT equivalent shot at a depth of 315 ft (96 m). Because one of the goals of the Source Physics Experiments is to determine damage effects on seismic wave propagation and improve modeling capabilities, a key component in the predictive component and ultimate validation of the models is a full understanding of the intervening geology between the source and instrumented bore holes. Ground-based LIDAR and fracture mapping, mechanical properties determined via laboratory testing of rock core, discontinuity analysis and optical microscopy of the core rocks were performed prior to and following each experiment. Results of the LIDAR collects from both SPE 2 and 3 indicate a permanent ground displacement of up to several centimeters aligning along the projected surface traces of two faults observed in the core and fractures mapped at the surface. Work by Los Alamos National Laboratory was sponsored by the National Nuclear Security Administration Award No. DE-AC52-06NA25946.

  1. Oxygen reduction reaction activity on Pt{111} surface alloys.

    PubMed

    Attard, Gary A; Brew, Ashley; Ye, Jin-Yu; Morgan, David; Sun, Shi-Gang

    2014-07-21

    PtM overlayers (where M=Fe, Co or Ni) supported on Pt{111} are prepared via thermal annealing in either a nitrogen/water or hydrogen ambient of dilute aqueous droplets containing M(Z+) cations directly attached to the electrode. Two different PtM phases are detected depending on the nature of the post-annealing cooling environment. The first of these consists of small (<20 nm), closely packed microcrystals comprised of a central metallic core and a shell (several monolayers thick) of mixed metal oxides/hydroxides. The second type of PtM phase is prepared by cooling in a stream of hydrogen gas. Although this second phase also consists of numerous microcrystals covering the Pt{111} electrode surface, these are both flatter than before and moreover are entirely metallic in character. A positive shift in the onset of PtM oxide formation correlates with increased activity towards the oxygen reduction reaction (ORR), which we ascribe to the greater availability of platinum metallic sites under ORR conditions. PMID:24986646

  2. May 2011 Groundwater and Surface Water Sampling at the Rio Blanco, Colorado, Site (Data Validation Package)

    SciTech Connect

    2011-12-01

    Annual sampling was conducted at the Rio Blanco, Colorado, site for the Long-Term Hydrologic Monitoring Program May 16-17, 2011, to monitor groundwater and surface water for potential radionuclide contamination. Sampling and analyses were conducted as specified in Sampling and Analysis Plan for the U.S. Department of Energy Office of Legacy Management Sites (LMS/PRO/S04351, continually updated). A duplicate sample was collected from location Johnson Artesian WL. Samples were analyzed by the U.S. Environmental Protection Agency (EPA) Radiation&Indoor Environments National Laboratory in Las Vegas, Nevada. Samples were analyzed for gamma-emitting radionuclides by high-resolution gamma spectrometry, and for tritium using the conventional method. Tritium was not measured using the enrichment method because the EPA laboratory no longer offers that service. Results of this monitoring at the Rio Blanco site demonstrate that groundwater and surface water outside the boundaries have not been affected by project-related contaminants.

  3. Site-specific PEGylation of lidamycin and its antitumor activity.

    PubMed

    Li, Liang; Shang, Boyang; Hu, Lei; Shao, Rongguang; Zhen, Yongsu

    2015-05-01

    In this study, N-terminal site-specific mono-PEGylation of the recombinant lidamycin apoprotein (rLDP) of lidamycin (LDM) was prepared using a polyethyleneglycol (PEG) derivative (M w 20 kDa) through a reactive terminal aldehyde group under weak acidic conditions (pH 5.5). The biochemical properties of mPEG-rLDP-AE, an enediyne-integrated conjugate, were analyzed by SDS-PAGE, RP-HPLC, SEC-HPLC and MALDI-TOF. Meanwhile, in vitro and in vivo antitumor activity of mPEG-rLDP-AE was evaluated by MTT assays and in xenograft model. The results indicated that mPEG-rLDP-AE showed significant antitumor activity both in vitro and in vivo. After PEGylation, mPEG-rLDP still retained the binding capability to the enediyne AE and presented the physicochemical characteristics similar to that of native LDP. It is of interest that the PEGylation did not diminish the antitumor efficacy of LDM, implying the possibility that this derivative may function as a payload to deliver novel tumor-targeted drugs. PMID:26579455

  4. Radiological impact of surface water and sediment near uranium mining sites.

    PubMed

    Ivanova, K; Stojanovska, Z; Badulin, V; Kunovska, B; Yovcheva, M

    2015-12-01

    The aim of this study is to assess the radiological impact of surface water and sediment around uranium mining sites 20 years after their closing. The areas under observations are 31 former classical underground uranium mining and exploratory sites in Bulgaria, named as objects. The extraction and processing of uranium ores in the Republic of Bulgaria were ended in 1992. To assess the radiological impact of radionuclides field expeditions were performed to sample water and bottom sediment. The migration of uranium through surface water was examined as one of the major pathways for contamination spread. The range of uranium concentration in water flowing from the mining sites was from 0.012 to 6.8 mgU l(-1) with a geometric mean of 0.192 mgU l(-1). The uranium concentrations in water downstream the mining sites were approximately 3 times higher than the background value (upstream). The concentrations of Unat, (226)Ra, (210)Pb, and (232)Th in the sediment of downstream river were higher than those upstream by 3.4, 2.6, 2, and 1.7 times, respectively. The distribution coefficient of uranium reflects its high mobility in most of the sites. In order to evaluate the impact on people as well as site prioritization for more detailed assessment and water management, screening dose assessments were done. PMID:26505204

  5. New developments for the site-specific attachment of protein to surfaces

    SciTech Connect

    Camarero, J A

    2005-05-12

    Protein immobilization on surfaces is of great importance in numerous applications in biology and biophysics. The key for the success of all these applications relies on the immobilization technique employed to attach the protein to the corresponding surface. Protein immobilization can be based on covalent or noncovalent interaction of the molecule with the surface. Noncovalent interactions include hydrophobic interactions, hydrogen bonding, van der Waals forces, electrostatic forces, or physical adsorption. However, since these interactions are weak, the molecules can get denatured or dislodged, thus causing loss of signal. They also result in random attachment of the protein to the surface. Site-specific covalent attachment of proteins onto surfaces, on the other hand, leads to molecules being arranged in a definite, orderly fashion and uses spacers and linkers to help minimize steric hindrances between the protein surface. This work reviews in detail some of the methods most commonly used as well as the latest developments for the site-specific covalent attachment of protein to solid surfaces.

  6. Preliminary Correlation Map of Geomorphic Surfaces in North-Central Frenchman Flat, Nevada Test Site

    SciTech Connect

    Bechtel Nevada

    2005-08-01

    This correlation map (scale = 1:12,000) presents the results of a mapping initiative that was part of the comprehensive site characterization required to operate the Area 5 Radioactive Waste Management Site, a low-level radioactive waste disposal facility located in northern Frenchman Flat at the Nevada Test Site. Eight primary map units are recognized for Quaternary surfaces: remnants of six alluvial fan or terrace surfaces, one unit that includes colluvial aprons associated with hill slopes, and one unit for anthropogenically disturbed surfaces. This surficial geology map provides fundamental data on natural processes for reconstruction of the Quaternary history of northern Frenchman Flat, which in turn will aid in the understanding of the natural processes that act to develop the landscape, and the time-frames involved in landscape development. The mapping was conducted using color and color-infrared aerial photographs and field verification of map unit composition and boundaries. Criteria for defining the map unit composition of geomorphic surface units are based on relative geomorphic position, landform morphology, and degree of preservation of surface morphology. The bedrock units identified on this map were derived from previous published mapping efforts and are included for completeness.

  7. Site-Specific Surface Functionalization of Gold Nanorods Using DNA Origami Clamps.

    PubMed

    Shen, Chenqi; Lan, Xiang; Lu, Xuxing; Meyer, Travis A; Ni, Weihai; Ke, Yonggang; Wang, Qiangbin

    2016-02-17

    Precise control over surface functionalities of nanomaterials offers great opportunities for fabricating complex functional nanoarchitectures but still remains challenging. In this work, we successfully developed a novel strategy to modify a gold nanorod (AuNR) with specific surface recognition sites using a DNA origami clamp. AuNRs were encapsulated by the DNA origami through hybridization of single-stranded DNA on the AuNRs and complementary capture strands inside the clamp. Another set of capture strands on the outside of the clamp create the specific recognition sites on the AuNR surface. By means of this strategy, AuNRs were site-specifically modified with gold nanoparticles at the top, middle, and bottom of the surface, respectively, to construct a series of well-defined heterostructures with controlled "chemical valence". Our study greatly expands the utility of DNA origami as a tool for building complex nanoarchitectures and represents a new approach for precise tailoring of nanomaterial surfaces. PMID:26824749

  8. Decomposition degree of chlorofluorocarbon (CFC) and CFC replacements during recovery with surface-modified activated carbon

    SciTech Connect

    Tanada, Seiki; Kawasaki, Naohito; Nakamura, Takeo; Abe, Ikuo

    1996-02-10

    The recovery efficiency of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) and three CFC replacements (1,1-dichloro-1-fluoroethane, HCFC141b; 1,3-dichloro-1,1,2,2,3-pentafluoro-propane, HCFC225cb; and 2,2,3,3,3-pentafluoro-1-propanol, 5FP) were investigated on the basis of their degree of decomposition and adsorption isotherms. The authors prepared activated carbons with various surface polarities to elucidate the recovery efficiency, the amount adsorbed, and the degree of decomposition. The amount of CFC113 adsorbed onto untreated activated carbon was the largest of all. That of HCFC225cb adsorbed onto activated carbon treated with hydrogen gas was larger than that adsorbed onto untreated activated carbon and activated carbon treated with 6 N nitric acid. The amount of 5FP and HCFC141b adsorbed on the various activated carbons was not substantial. The degree of decomposition of CFC replacements using the untreated activated carbon except for HCFC225cb was the largest of all. In the case without the activated carbon, that of CFC and the CFC replacements increased in the order 5FP, CFC113 or HCFC225cb, and HCFC141b. It is concluded that the recovery of CFC replacements was possible using the surface-modified activated carbons rather than the untreated activated carbon. The degree of decomposition of the CFC replacements during recovery using the activated carbon depends on the relationship between the adsorption site of the surface of the activated carbon and the polarity, hydrophilic site, or hydrophobic site of the CFC replacement molecule.

  9. Are methyl halides produced on all ice surfaces? Observations from snow-laden field sites

    NASA Astrophysics Data System (ADS)

    Swanson, Aaron L.; Blake, Nicola J.; Blake, Donald R.; Sherwood Rowland, F.; Dibb, Jack E.; Lefer, Barry L.; Atlas, Elliot

    We present data collected from a number of snow-covered environments including two polar locations (Summit, Greenland and the South Pole) and two mid-latitude regions (a remote site in northern Michigan, and Niwot Ridge, Colorado). At each site, concentrations of CH3I and C2H5I were enhanced within the interstitial air near the snow surface, compared to levels in boundary layer air. Fluxes of CH3Br from surface snow to the atmosphere were observed at each site except Niwot Ridge, where CH3Br appeared to have a sink. The mid-latitude sites showed significant emissions of CH3Cl, mostly originating at the ground surface and traveling up through the snow, while at the polar locations CH3Cl emissions from firn air were relatively small. In general, methyl halide mixing ratios in firn air were significantly greater at Summit than at the South Pole, with Summit showing a strong diurnal cycle in the production of alkyl halides that was well correlated with actinic radiation and firn temperature. We suggest that the most likely route to alkyl halide formation is through an acid catalyzed nucleophilic substitution of an alcohol type function by a halide, both of which should be preferentially segregated to the quasi-liquid layer at the surface of the snow grains. A series of experiments using a snow-filled quartz chamber irradiated by natural sunlight allowed estimation of emission trends that were hard to measure in the natural snowpack. These static chamber experiments confirmed significant production of the primary alkyl halides, following the order CH3Cl>CH3Br>C2H5Cl>CH3I>C2H5Br>C2H5I>1-C3H7Br>1-C3H7I. Our observations at all four locations, including polar and mid-latitude sites, imply that alkyl halide production may be associated with all surface snows.

  10. Estimations of the extent of migration of surficially applied water for various surface conditions near the potential repository perimeter; Yucca Mountain Site Characterization Project

    SciTech Connect

    Sobolik, S.R.; Fewell, M.E.

    1993-12-01

    The Yucca Mountain Site Characterization Project is studying Yucca Mountain in southwestern Nevada as a potential site for a high-level nuclear waste repository. Site characterization includes surface-based and underground testing. Analyses have been performed to support the design of site characterization activities so to have minimal impact on the ability of the site to isolate waste, and on tests performed as part of the characterization process. Two examples of site characterization activities are the construction of an Exploratory Studies Facility, which may include underground shafts, drifts, and ramps, and surface-based testing activities, which may require borehole drilling, excavation of test pits, and road watering for dust control. The information in this report pertains to two-dimensional numerical calculations modeling the movement of surficially applied water and the potential effects of that water on repository performance and underground experiments. This document contains information that has been used in preparing recommendations for two Yucca Mountain Site Characterization Project documents: Appendix I of the Exploratory Studies Facility Design Requirements document, and the Surface-Based Testing Field Requirements Document.

  11. Surface-active properties of humic and sulfochlorohumic acids

    SciTech Connect

    Ryabova, I.N.; Mustafina, G.A.; Akkulova, Z.G.; Satymbaeva, A.S.

    2009-10-15

    The surface tension of alkaline solutions of humic acids and their sulfochloroderivatives, which are synthesized by sulfonation of chlorohumic acids isolated from coal chlorinated by the electrochemical method, is investigated. It is established that humic compounds possess weak surface activity. Basic adsorption parameters are calculated.

  12. Characterization of surface active materials derived from farm products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Surface active materials obtained by chemical modification of plant protein isolates (lupin, barley, oat), corn starches (dextrin, normal, high amylose, and waxy) and soybean oil (soybean oil based polysoaps, SOPS) were investigated for their surface and interfacial properties using axisymmetric dro...

  13. Surface-Energy Dependent Contact Activation of Blood Factor XII

    PubMed Central

    Golas, Avantika; Parhi, Purnendu; Dimachkie, Ziad O.; Siedlecki, Christopher A.; Vogler, Erwin A.

    2009-01-01

    Contact activation of blood factor XII (FXII, Hageman factor) in neat-buffer solution exhibits a parabolic profile when scaled as a function of silanized-glass-particle activator surface energy (measured as advancing water adhesion tension τao=γlvocosθ in dyne/cm, where γlvo is water interfacial tension in dyne/cm and θ is the advancing contact angle). Nearly equal activation is observed at the extremes of activator water-wetting properties −36<τao<72 dyne/cm (0° ≤ θ < 120°), falling sharply through a broad minimum within the 20<τao<40 dyne/cm (55° < θ < 75°) range over which activation yield (putatively FXIIa) rises just above detection limits. Activation is very rapid upon contact with all activators tested and did not significantly vary over 30 minutes of continuous FXII-procoagulant contact. Results suggest that materials falling within the 20<τao<40 dyne/cm surface-energy range should exhibit minimal activation of blood-plasma coagulation through the intrinsic pathway. Surface chemistries falling within this range are, however, a perplexingly difficult target for surface engineering because of the critical balance that must be struck between hydrophobicity and hydrophilicity. Results are interpreted within the context of blood plasma coagulation and the role of water and proteins at procoagulant surfaces. PMID:19892397

  14. Surface activity of Acinetobacter calcoaceticus sp. 2CA2

    SciTech Connect

    Neufeld, R.J.; Zajic, J.E.

    1984-01-01

    The hydrocarbon metabolizing Acinetobacter calcoaceticus sp. 2CA2 reduces the surface tension of the culture broth during growth on liquid hydrocarbons. This activity, which is not evident during growth on soluble substrates, is associated with the whole cells. Removing the cells from the culture broth increases the surface tension of the liquid phase. The cells when resuspended in water result in a dramatic lowering of the surface tension. Acinetobacter sp. 2CA2 tends to partition between the two liquid phases during growth on hydrocarbons. Both the hydrocarbon bound and nonadhering cells are equally surface active. The whole cells are also able to form and stabilize kerosene-water emulsions. This ability is not related to the lowering of the liquid surface or interfacial tension, since both surface active and nonsurface active cells demonstrated the same emulsifying properties. An extracellular lipopeptide produced during growth on hydrocarbons is not surface active but effectively forms and stabilizes kerosene-water emulsions. The cells and extracellular lipopeptide are also effective in de-emulsifying surfactant stabilized test emulsions. The cells and extracellular lipopeptide are also effective in de-emulsifying surfactant stabilized test emulsions. The lipopeptide product reduced the half-life of a Tween-Span (TS) stabilized kerosene-water emulsion from 650 to 0.4 h at product concentrations of less than 1% (w/v).

  15. Surface activity of Corophium volutator: A role for parasites?

    NASA Astrophysics Data System (ADS)

    Damsgaard, Jacob Tørring; Mouritsen, Kim N.; Jensen, K. Thomas

    2005-08-01

    In soft-bottom intertidal habitats, the normally infaunal amphipod Corophium volutator is often found active on the sediment surface during low tide, exposed to desiccation and shorebird predation. Here we examine whether such risky behaviour is related to parasite infections. Surface-active and buried C. volutator were collected during a low tide period in the Danish Wadden Sea, and the infection patterns of the two groups were described in relation to sex and size. Surface-active males and females were more heavily infested by microphallid trematodes (four species) than buried specimens of the same sex and size class. Although the density of surfaced amphipods decreased as a function of exposure time, the mean parasite load of those that remained on the surface increased. A narrow size-specific parasite intensity threshold above which the amphipods were always surface active did not exist: heavily infected individuals were also found buried in the substrate. Although likely to be beneficial to the parasites, this suggests that the behavioural alteration is a side-effect of the infections rather than a consequence of direct parasitic manipulation. Besides the presumed mortality associated with the parasite-related surface activity in a range of size-classes, the intensity-size frequency distribution indicated that larger and hence heavily infected hosts are removed from the population. Together it demonstrates that microphallid trematodes impact the population dynamics of C. volutator.

  16. Adsorption sites on icosahedral quasicrystal surfaces: Dark stars and white flowers

    SciTech Connect

    Unal, B.; Jenks, C.J.; Thiel, P.A.

    2009-01-12

    From other work, two preferred sites have been suggested for metals and semimetals adsorbed on the fivefold surfaces of icosahedral, Al-based quasicrystals. Because of their appearance in scanning tunneling microscopy (STM) images, these sites are known as dark stars and white flowers. In this paper, we analyze four bulk structural models in physical space to determine the types, chemical decorations, and densities of the dark star - and, to a lesser extent, the white flower - adsorption sites for the fivefold planes of icosahedral Al-Pd-Mn. We find that the chemical decorations of these sites are heterogeneous, even within a single model. Both features are also structurally heterogeneous, according to STM measurements, and the structural variation is consistent with the bulk structure models. Finally, from the models, the density of dark stars in the planes correlates with the step height. This may explain previous experimental observations of different properties for different terraces.

  17. Pollution distribution of heavy metals in surface soil at an informal electronic-waste recycling site.

    PubMed

    Fujimori, Takashi; Takigami, Hidetaka

    2014-02-01

    We studied distribution of heavy metals [lead (Pb), copper (Cu) and zinc (Zn)] in surface soil at an electronic-waste (e-waste) recycling workshop near Metro Manila in the Philippines to evaluate the pollution size (spot size, small area or the entire workshop), as well as to assess heavy metal transport into the surrounding soil environment. On-site length-of-stride-scale (~70 cm) measurements were performed at each surface soil point using field-portable X-ray fluorescence (FP-XRF). The surface soil at the e-waste recycling workshop was polluted with Cu, Zn and Pb, which were distributed discretely in surface soil. The site was divided into five areas based on the distance from an entrance gate (y-axis) of the e-waste recycling workshop. The three heavy metals showed similar concentration gradients in the y-axis direction. Zn, Pb and Cu concentrations were estimated to decrease to half of their maximum concentrations at ~3, 7 and 7 m from the pollution spot, respectively, inside the informal e-waste recycling workshop. Distance from an entrance may play an important role in heavy metal transport at the soil surface. Using on-site FP-XRF, we evaluated the metal ratio to characterise pollution features of the solid surface. Variability analysis of heavy metals revealed vanishing surficial autocorrelation over metre ranges. Also, the possibility of concentration prediction at unmeasured points using geostatistical kriging was evaluated, and heavy metals had a relative "small" pollution scales and remained inside the original workshop compared with toxic organohalogen compounds. Thus, exposure to heavy metals may directly influence the health of e-waste workers at the original site rather than the surrounding habitat and environmental media. PMID:23645478

  18. Soil surface disturbances in cold deserts: Effects on nitrogenase activity in cyanobacterial-lichen soil crusts

    USGS Publications Warehouse

    Belnap, Jayne

    1996-01-01

    CyanobacteriaMichen soil crusts can be a dominant source of nitrogen for cold-desert ecosystems. Effects of surface disturbance from footprints, bike and vehicle tracks on the nitrogenase activity in these crusts was investigated. Surface disturbances reduced nitrogenase activity by 30-100%. Crusts dominated by the cyanobacterium Microcoleus vaginatus on sandy soils were the most susceptible to disruption; crusts on gypsiferous soils were the least susceptible. Crusts where the soil lichen Collema tenax was present showed less immediate effects; however, nitrogenase activity still declined over time. Levels of nitrogenase activity reduction were affected by the degree of soil disruption and whether sites were dominated by cyanobacteria with or without heterocysts. Consequently, anthropogenic surface disturbances may have serious implications for nitrogen budgets in these ecosystems.

  19. Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

    PubMed

    Kwak, Ja Hun; Dagle, Robert; Tustin, Gerald C; Zoeller, Joseph R; Allard, Lawrence F; Wang, Yong

    2014-02-01

    We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications. PMID:26276610

  20. Surface modification of active material structures in battery electrodes

    DOEpatents

    Erickson, Michael; Tikhonov, Konstantin

    2016-02-02

    Provided herein are methods of processing electrode active material structures for use in electrochemical cells or, more specifically, methods of forming surface layers on these structures. The structures are combined with a liquid to form a mixture. The mixture includes a surface reagent that chemically reacts and forms a surface layer covalently bound to the structures. The surface reagent may be a part of the initial liquid or added to the mixture after the liquid is combined with the structures. In some embodiments, the mixture may be processed to form a powder containing the structures with the surface layer thereon. Alternatively, the mixture may be deposited onto a current collecting substrate and dried to form an electrode layer. Furthermore, the liquid may be an electrolyte containing the surface reagent and a salt. The liquid soaks the previously arranged electrodes in order to contact the structures with the surface reagent.

  1. Near-surface temperatures at proposed Mars Exploration Rover land sites

    NASA Technical Reports Server (NTRS)

    Martin, T. Z.; Bridges, N. T.; Murphy, J. R.

    2003-01-01

    Minimum nighttime temperature at the Mars Exploration Rover (MER) landing sites may limit power available for science activities and thus mission lifetime. Here, 1 m air temperature at the end of the nominal 90 sol primary mission are derived for the four primary and three previously considered MER landing sites based on Mars Global Surveyor Thermal Emmision Spectrometer thermal inertia and albedo, estimated opacity, and predictions of air temperature from a one-dimensional atmospheric model.

  2. Allosteric site-mediated active site inhibition of PBP2a using Quercetin 3-O-rutinoside and its combination.

    PubMed

    Rani, Nidhi; Vijayakumar, Saravanan; P T V, Lakshmi; Arunachalam, Annamalai

    2016-08-01

    Recent crystallographic study revealed the involvement of allosteric site in active site inhibition of penicillin binding protein (PBP2a), where one molecule of Ceftaroline (Cef) binds to the allosteric site of PBP2a and paved way for the other molecule (Cef) to bind at the active site. Though Cef has the potency to inhibit the PBP2a, its adverse side effects are of major concern. Previous studies have reported the antibacterial property of Quercetin derivatives, a group of natural compounds. Hence, the present study aims to evaluate the effect of Quercetin 3-o-rutinoside (Rut) in allosteric site-mediated active site inhibition of PBP2a. The molecular docking studies between allosteric site and ligands (Rut, Que, and Cef) revealed a better binding efficiency (G-score) of Rut (-7.790318) and Cef (-6.194946) with respect to Que (-5.079284). Molecular dynamic (MD) simulation studies showed significant changes at the active site in the presence of ligands (Rut and Cef) at allosteric site. Four different combinations of Rut and Cef were docked and their G-scores ranged between -6.320 and -8.623. MD studies revealed the stability of the key residue (Ser403) with Rut being at both sites, compared to other complexes. Morphological analysis through electron microscopy confirmed that combination of Rut and Cefixime was able to disturb the bacterial cell membrane in a similar fashion to that of Rut and Cefixime alone. The results of this study indicate that the affinity of Rut at both sites were equally good, with further validations Rut could be considered as an alternative for inhibiting MRSA growth. PMID:26360629

  3. Influence of protonation on substrate and inhibitor interactions at the active site of human monoamine oxidase-A.

    PubMed

    Zapata-Torres, Gerald; Fierro, Angelica; Miranda-Rojas, Sebastian; Guajardo, Carlos; Saez-Briones, Patricio; Salgado, J Cristian; Celis-Barros, Cristian

    2012-05-25

    Although substrate conversion mediated by human monoaminooxidase (hMAO) has been associated with the deprotonated state of their amine moiety, data regarding the influence of protonation on substrate binding at the active site are scarce. Thus, in order to assess protonation influence, steered molecular dynamics (SMD) runs were carried out. These simulations revealed that the protonated form of the substrate serotonin (5-HT) exhibited stronger interactions at the protein surface compared to the neutral form. The latter displayed stronger interactions in the active site cavity. These observations support the possible role of the deprotonated form in substrate conversion. Multigrid docking studies carried out to rationalize the role of 5-HT protonation in other sites besides the active site indicated two energetically favored docking sites for the protonated form of 5-HT on the enzyme surface. These sites seem to be interconnected with the substrate/inhibitor cavity, as revealed by the tunnels observed by means of CAVER program. pK(a) calculations in the surface loci pointed to Glu³²⁷, Asp³²⁸, His⁴⁸⁸, and Asp¹³² as candidates for a possible in situ deprotonation step. Docking analysis of a group of inhibitors (structurally related to substrates) showed further interactions with the same two docking access sites. Interestingly, the protonated/deprotonated amine moiety of almost all compounds attained different docking poses in the active site, none of them oriented to the flavin moiety, thus producing a more variable and less productive orientations to act as substrates. Our results highlight the role of deprotonation in facilitating substrate conversion and also might reflect the necessity of inhibitor molecules to adopt specific orientations to achieve enzyme inhibition. PMID:22540832

  4. Active site hydrophobicity is critical to the bioluminescence activity of Vibrio harveyi luciferase.

    PubMed

    Li, Chi-Hui; Tu, Shiao-Chun

    2005-10-01

    Vibrio harveyi luciferase is an alphabeta heterodimer containing a single active site, proposed earlier to be at a cleft in the alpha subunit. In this work, six conserved phenylalanine residues at this proposed active site were subjected to site-directed mutations to investigate their possible functional roles and to delineate the makeup of luciferase active site. After initial screening of Phe --> Ala mutants, alphaF46, alphaF49, alphaF114, and alphaF117 were chosen for additional mutations to Asp, Ser, and Tyr. Comparisons of the general kinetic properties of wild-type and mutated luciferases indicated that the hydrophobic nature of alphaF46, alphaF49, alphaF114, and alphaF117 was important to luciferase V(max) and V(max)/K(m), which were reduced by 3-5 orders of magnitude for the Phe --> Asp mutants. Both alphaF46 and alphaF117 also appeared to be involved in the binding of reduced flavin substrate. Additional studies on the stability and yield of the 4a-hydroperoxyflavin intermediate II and measurements of decanal substrate oxidation by alphaF46D, alphaF49D, alphaF114D, and alphaF117D revealed that their marked reductions in the overall quantum yield (phi( degrees )) were a consequence of diminished yields of luciferase intermediates and, with the exception of alphaF114D, emission quantum yield of the excited emitter due to the replacement of the hydrophobic Phe by the anionic Asp. The locations of these four critical Phe residues in relation to other essential and/or hydrophobic residues are depicted in a refined map of the active site. Functional implications of these residues are discussed. PMID:16185065

  5. Site study plan for Exploratory shaft facilities design foundation boreholes (shaft surface facility foundation borings), Deaf Smith County Site, Texas: Surface-based geotechnical field program: Preliminary draft

    SciTech Connect

    Not Available

    1987-12-01

    This site study plan describes the Exploratory Shaft Facilities (ESF) Design Foundation Boreholes field activities to be conducted during early stages of Site Characterization at the Deaf Smith County, Texas, site. The field program has been designed to provide data useful in addressing information/data needs resulting from federal/state/local regulations, and repository program requirements. Approximately 50 foundation boreholes will be drilled within the ESP location to provide data necessary for design of the ESF and to satisfy applicable shaft permitting requirements. Soils and subsurface rock will be sampled as the foundation boreholes are advanced. Soil samples or rock core will be taken through the Blackwater Draw and Ogallala Formations and the Dockum Group. Hydrologic testing will be performed in boreholes that penetrates the water table. In-situ elastic properties will be determined from both the soil strata and rock units along the length of the boreholes. Field methods/tests are chosen that provide the best or only means of obtaining the required data. The Salt Repository Project (SRP) Networks specify the schedule under which the program will operate. Drilling will not begin until after site ground water baseline conditions have been established. The Technical Field Services Contractor is responsible for conducting the field program of drilling and testing. Samples and data will be handled and reported in accordance with established SRP procedures. A quality assurance program will be utilized to assure that activities affecting quality are performed correctly and that the appropriate documentation is maintained. 25 refs., 10 figs., 6 tabs.

  6. Urban Climate Station Site Selection Through Combined Digital Surface Model and Sun Angle Calculations

    NASA Technical Reports Server (NTRS)

    Kidd, Chris; Chapman, Lee

    2012-01-01

    Meteorological measurements within urban areas are becoming increasingly important due to the accentuating effects of climate change upon the Urban Heat Island (UHI). However, ensuring that such measurements are representative of the local area is often difficult due to the diversity of the urban environment. The evaluation of sites is important for both new sites and for the relocation of established sites to ensure that long term changes in the meteorological and climatological conditions continue to be faithfully recorded. Site selection is traditionally carried out in the field using both local knowledge and visual inspection. This paper exploits and assesses the use of lidar-derived digital surface models (DSMs) to quantitatively aid the site selection process. This is acheived by combining the DSM with a solar model, first to generate spatial maps of sky view factors and sun-hour potential and second, to generate site-specific views of the horizon. The results show that such a technique is a useful first-step approach to identify key sites that may be further evaluated for the location of meteorological stations within urban areas.

  7. Observations of Martian surface winds at the Viking Lander 1 site

    SciTech Connect

    Murphy, J.R.; Leovy, C.B.; Tillman, J.E. )

    1990-08-30

    Partial failure of the wind instrumentation on the Viking Lander 1 (VL1) in the Martian subtropics (22.5{degree}N) has limited previous analyses of meteorological data for this site. The authors describe a method for reconstructing surface winds using data from the partially failed sensor and present and analyze a time series of wind, pressure, and temperature at the site covering 350 Mars days (sols). At the beginning of the mission during early summer, winds were controlled by regional topography, but they soon underwent a transition to a regime controlled by the Hadley circulation. Diurnal and semidiurnal wind oscillations and synoptic variations have been analyzed and compared with the corresponding variations at the Viking Lander 2 middle latitude site (48{degree}N). Diurnal wind oscillations were controlled primarily by regional topography and boundary layer forcing, although a global mode may have been influencing them during two brief episodes. Semidiurnal wind oscillations were controlled by the westward propagating semidiurnal tide from sol 210 onward. Comparison of the synoptic variations at the two sites suggests that the same eastward propagating wave trains were present at both sites, at least following the first 1977 great dust storm, but discordant inferred zonal wave numbers and phase speeds at the two sites cast doubt on the zonal wave numbers deduced from analyses of combined wind and pressure data, particularly at the VL1 site where the signal to noise ratio of the dominant synoptic waves is relatively small.

  8. Surface Interrogation Scanning Electrochemical Microscopy of Ni(1-x)Fe(x)OOH (0 < x < 0.27) Oxygen Evolving Catalyst: Kinetics of the "fast" Iron Sites.

    PubMed

    Ahn, Hyun S; Bard, Allen J

    2016-01-13

    Nickel-iron mixed metal oxyhydroxides have attracted significant attention as an oxygen evolution reaction (OER) catalyst for solar fuel renewable energy applications. Here, we performed surface-selective and time-dependent redox titrations to directly measure the surface OER kinetics of Ni(IV) and Fe(IV) in NiOOH, FeOOH, and Ni(1-x)Fe(x)OOH (0 < x < 0.27) electrodes. Most importantly, two types of surface sites exhibiting "fast" and "slow" kinetics were found, where the fraction of "fast" sites in Ni(1-x)Fe(x)OOH matched the iron atom content in the film. This finding provides experimental support to the theory-proposed model of active sites in Ni(1-x)Fe(x)OOH. The OER rate constant of the "fast" site was 1.70 s(-1) per atom. PMID:26645678

  9. Evaluation of Cavity Collapse and Surface Crater Formation at the Norbo Underground Nuclear Test in U8c, Nevada Nuclear Security Site, and the Impact on Stability of the Ground Surface

    SciTech Connect

    Pawloski, G A

    2012-06-18

    Lawrence Livermore National Laboratory (LLNL) Containment Program performed a review of nuclear test-related data for the Norbo underground nuclear test in U8c to assist in evaluating this legacy site as a test bed for application technologies for use in On-Site Inspections (OSI) under the Comprehensive Nuclear Test Ban Treaty. This request is similar to one made for the Salut site in U8c (Pawloski, 2012b). Review of the Norbo site is complicated because the test first exhibited subsurface collapse, which was not unusual, but it then collapsed to the surface over one year later, which was unusual. Of particular interest is the stability of the ground surface above the Norbo detonation point. Proposed methods for on-site verification include radiological signatures, artifacts from nuclear testing activities, and imaging to identify alteration to the subsurface hydrogeology due to the nuclear detonation. Aviva Sussman from the Los Alamos National Laboratory (LANL) has also proposed work at this site. Both proposals require physical access at or near the ground surface of specific underground nuclear test locations at the Nevada Nuclear Security Site (NNSS), formerly the Nevada Test Site (NTS), and focus on possible activities such as visual observation, multispectral measurements, and shallow and deep geophysical surveys.

  10. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    SciTech Connect

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption.

  11. Land Surface Product Validation Using the DOE ARM Southern Great Plains Site

    NASA Astrophysics Data System (ADS)

    Knuteson, R.; Revercomb, H.; Tobin, D.; Osborne, B.

    2003-12-01

    The University of Wisconsin Space Science and Engineering Center (UW-SSEC) is making use of the U.S. Department of Energy Atmospheric Radiation Measurement (DOE ARM) program Southern Great Plains (SGP) site for validation of NASA EOS land surface products. The DOE ARM site covers a 250 km square region that includes most of Oklahoma and southern Kansas. The site is dominated by a mixture of vegetation and bare soil with a vegetation fraction that changes with the growing season. The land use is divided between cattle ranching (permanent pasture) and wheat farming (seasonal). The DOE ARM site provides routine state-of-the-art vertical profile measurements of the atmospheric state. Special radiosonde launches have been conducted by DOE ARM to coincide with overpasses of the NASA Aqua platform. The UW-SSEC has provided ground truth measurements of surface characteristics using a mobile research vehicle (the AERIbago) during several aircraft field campaigns. The UW-SSEC Scanning High-resolution Interferometer Sounder (S-HIS) has provided high altitude observations of the thermal infrared spectrum for comparison to satellite observations. Coincident measurements of ground-based and aircraft observations with AIRS and MODIS satellite observations have been obtained during TX-2001, TX-2002, and IHOP. Preliminary land surface products from AIRS will be compared with MODIS land products and the validation measurements obtained from aircraft and ground-based sensors.

  12. Asphaltene surface activity at oil/water interfaces

    SciTech Connect

    Sheu, E.Y.; Shields, M.B.

    1995-11-01

    Small angle neutron scattering (SANS) dynamic surface tension (DST), dynamic interfacial tension (DIFT), and zero shear viscosity were used to study the surface activity of Ratawi asphaltenes in organic solvents, in the asphaltene/water/toluene emulsions and at the toluene/aqueous solution interfaces. In organic solvents, the kinetic process of micellization and the micellar structure are characterized. Their dependence on asphaltene concentration was investigated. The emulsion droplet structure and their capability in water uptake was tested. Also, the enhancement of surface activity of asphaltenes and its potential applications are briefly discussed.

  13. Crystal structures of human tissue kallikrein 4: activity modulation by a specific zinc binding site.

    PubMed

    Debela, Mekdes; Magdolen, Viktor; Grimminger, Valerie; Sommerhoff, Christian; Messerschmidt, Albrecht; Huber, Robert; Friedrich, Rainer; Bode, Wolfram; Goettig, Peter

    2006-10-01

    Human tissue kallikrein 4 (hK4) belongs to a 15-member family of closely related serine proteinases. hK4 is predominantly expressed in prostate, activates hK3/PSA, and is up-regulated in prostate and ovarian cancer. We have identified active monomers of recombinant hK4 besides inactive oligomers in solution. hK4 crystallised in the presence of zinc, nickel, and cobalt ions in three crystal forms containing cyclic tetramers and octamers. These structures display a novel metal site between His25 and Glu77 that links the 70-80 loop with the N-terminal segment. Micromolar zinc as present in prostatic fluid inhibits the enzymatic activity of hK4 against fluorogenic substrates. In our measurements, wild-type hK4 exhibited a zinc inhibition constant (IC50) of 16 microM including a permanent residual activity, in contrast to the zinc-independent mutants H25A and E77A. Since the Ile16 N terminus of wild-type hK4 becomes more accessible for acetylating agents in the presence of zinc, we propose that zinc affects the hK4 active site via the salt-bridge formed between the N terminus and Asp194 required for a functional active site. hK4 possesses an unusual 99-loop that creates a groove-like acidic S2 subsite. These findings explain the observed specificity of hK4 for the P1 to P4 substrate residues. Moreover, hK4 shows a negatively charged surface patch, which may represent an exosite for prime-side substrate recognition. PMID:16950394

  14. Analysis of Hydrogen Tunneling in an Enzyme Active Site using von Neumann Measurements

    PubMed Central

    Sumner, Isaiah; Iyengar, Srinivasan S.

    2010-01-01

    We build on our earlier quantum wavepacket study of hydrogen transfer in the biological enzyme, soybean lipoxygenase-1, by using von Neumann quantum measurement theory to gain qualitative insights into the transfer event. We treat the enzyme active site as a measurement device which acts on the tunneling hydrogen nucleus via the potential it exerts at each configuration. A series of changing active site geometries during the tunneling process effects a sequential projection of the initial, reactant state onto the final, product state. We study this process using several different kinds of von Neumann measurements and show how a discrete sequence of such measurements not only progressively increases the projection of the hydrogen nuclear wavepacket onto the product side but also favors proton over deuteron transfer. Several qualitative features of the hydrogen tunneling problem found in wavepacket dynamics studies are also recovered here. These include the shift in the “transition state” towards the reactant as a result of nuclear quantization, greater participation of excited states in the case of deuterium, and presence of critical points along the reaction coordinate that facilitate hydrogen and deuterium transfer and coincide with surface crossings. To further “tailor” the dynamics, we construct a perturbation to the sequence of measurements, that is a perturbation to the dynamical sequence of active site geometry evolution, which leads us to insight on the existence of sensitive regions of the reaction profile where subtle changes to the dynamics of the active site can have an effect on the hydrogen and deuterium transfer process. PMID:22933858

  15. Combined Active and Passive Seismic Methods To Characterize Strongmotion Sites in Washington and Oregon, United States

    NASA Astrophysics Data System (ADS)

    Pileggi, D.; Cakir, R.; Lunedei, E.; Albarello, D.; Walsh, T. J.

    2011-12-01

    Knowledge of the shear-wave velocity profile at strongmotion station sites is important for calibrating accelerograms in terms of local site effects. Surface-wave seismic prospecting methods (both in active and passive configurations) provide an effective tool for an inexpensive and deep penetrating seismic characterization of subsoil. We used a combination of active (Multi-channel Analysis of Surface Waves, MASW) and passive (Extended Spectral AutoCorrelation, ESAC) array techniques along with the single-station ambient vibration measurements (Horizontal-to-Vertical Spectral Ratios - HVSR) to characterize strong-motion sites in Washington and Oregon. The MASW analysis was used to better constrain the shallowest part of the Vs profile, while effective dispersion curve provided by ESAC and HVSR data allow us to extend the survey downwards (up to hundred meters of depth). The combined use of these data in the frame of global-search inversion algorithms (Genetic Algorithms) allows us to manage the extreme non-linearity of the inverse problem and mitigate problems associated with the non-uniqueness of the solution. A strict synergy between geologic surveys, boreholes (when the latter was available) and seismic surveys allows a further reduction of relevant uncertainties. Preliminary results show that; i) this combined methodology is a practical, inexpensive, and fast way to characterize multiple strong motion sites; ii) local geology and/or borehole information was combined to better constrain the inversion and to reduce the uncertainty in velocity profiles; and, iii) this combined methodology gives additional information of shear-wave velocities at greater depths.

  16. Fabrication of hydrophobic polymer foams with double acid sites on surface of macropore for conversion of carbohydrate.

    PubMed

    Pan, Jianming; Mao, Yanli; Gao, Heping; Xiong, Qingang; Qiu, Fengxian; Zhang, Tao; Niu, Xiangheng

    2016-06-01

    Herein we reported a simple and novel synthetic strategy for the fabrication of two kinds of hydrophobic polymer foam catalysts (i.e. Cr(3+)-HPFs-1-H(+) and HPFs-1-H(+)) with hierarchical porous structure, inhomogeneous acidic composition and Lewis-Brønsted double acid sites distributed on the surface, which was used to one-pot conversion of carbohydrate (such as cellulose, glucose and fructose) to a key chemical platform (i.e. 5-hydroxymethylfurfural, HMF). The water-in-oil (W/O) high internal phase emulsions (HIPEs), stabilized by both Span 80 and acidic prepolymers as analogous particles offered the acidic actives, were used as the template for simultaneous polymerization of oil phase in the presence of divinylbenzene (DVB) and styrene (St). After subsequent ion-exchange process, Lewis and Brønsted acid sites derived from exchanged Cr(3+) and H(+) ion were both fixed on the surface of cell of the catalysts. The HPFs-1-H(+) and Cr(3+)-HPFs-1-H(+) had similar hierarchical porous, hydrophobic surface and acid sites (HPFs-1-H(+) with macropores ranging from 0.1 μm to 20 μm, uniform mesopores in 14.4 nm, water contact angle of 122° and 0.614 mmolg(-1) of Brønsted acid sites, as well as Cr(3+)-HPFs-1-H(+) with macropores ranging from 0.1 μm to 20 μm, uniform mesopores in 13.3 nm, water contact angle of 136° and 0.638 mmolg(-1) of Lewis-Brønsted acid sites). It was confirmed that Lewis acid sites of catalyst had a slight influence on the HMF yield of fructose came from the function of Brønsted acid sites, and Lewis acid sites were in favor of improving the HMF yield from cellulose and glucose. This work opens up a simple and novel route to synthesize multifunctional polymeric catalysts for efficient one-pot conversion of carbohydrate to HMF. PMID:27083362

  17. Lateral migration and offsite surface emission of landfill gas at City of Montreal Landfill Site.

    PubMed

    Franzidis, Jean-Pierre; Héroux, Martin; Nastev, Miroslav; Guy, Christophe

    2008-04-01

    An evaluation of lateral landfill gas migration was carried out at the Saint-Michel Environmental Complex in Montreal, City of Montreal Landfill Site, Canada, between 2003 and 2005. Biogas concentration measurements and gas-pumping tests were conducted in multilevel wells installed in the backfilled overburden beside the landfill site. A migration event recorded in autumn 2004 during the maintenance shutdown of the extraction system was simulated using TOUGH-LGM software. Eleven high-density instantaneous surface monitoring (ISM) surveys of methane were conducted on the test site. Gas fluxes were calculated by geostatistical analyses of ISM data correlated to dynamic flux chamber measurements. Variograms using normal transformed data showed good structure, and kriged estimates were much better than inverse distance weighting, due to highly skewed data. Measurement-based estimates of yearly off-site surface emissions were two orders of magnitude higher than modelled advective lateral methane flux. Nucleodensimeter measurements of the porosity were abnormally high, indicating that the backfill was poorly compacted. Kriged porosity maps correlated well with emission maps and areas with vegetation damage. Pumping tests analysis revealed that vertical permeability was higher than radial permeability. All results suggest that most of the lateral migration and consequent emissions to the atmosphere were due to the existence of preferential flow paths through macropores. In December 2006, two passively vented trenches were constructed on the test site. They were successful in countering lateral migration. PMID:18578151

  18. The abandoned surface mining sites in the Czech Republic: mapping and creating a database with a GIS web application

    NASA Astrophysics Data System (ADS)

    Pokorný, Richard; Tereza Peterková, Marie

    2016-05-01

    Based on the vectorization of the 55-volume book series the Quarry Inventories of the Czechoslovak Republic/Czechoslovak Socialist Republic, published in the years 1932-1961, a new comprehensive database was built comprising 9958 surface mining sites of raw materials, which were active in the first half of the 20th century. The mapped area covers 40.9 % of the territory of the Czech Republic. For the purposes of visualization, a map application, the Quarry Inventories Online, was created that enables the data visualization.

  19. Relating subsurface temperature changes to microbial activity at a crude oil-contaminated site.

    PubMed

    Warren, Ean; Bekins, Barbara A

    2015-11-01

    Crude oil at a spill site near Bemidji, Minnesota has been undergoing aerobic and anaerobic biodegradation for over 30 years, creating a 150-200 m plume of primary and secondary contaminants. Microbial degradation generates heat that should be measurable under the right conditions. To measure this heat, thermistors were installed in wells in the saturated zone and in water-filled monitoring tubes in the unsaturated zone. In the saturated zone, a thermal groundwater plume originates near the residual oil body with temperatures ranging from 2.9°C above background near the oil to 1.2°C down gradient. Temperatures in the unsaturated zone above the oil body were up to 2.7°C more than background temperatures. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. Enthalpy calculations and observations demonstrate that the temperature increases primarily result from aerobic methane oxidation in the unsaturated zone above the oil. Methane oxidation rates at the site independently estimated from surface CO2 efflux data are comparable to rates estimated from the observed temperature increases. The results indicate that temperature may be useful as a low-cost measure of activity but care is required to account for the correct heat-generating reactions, other heat sources and the effects of focused recharge. PMID:26409188

  20. Relating subsurface temperature changes to microbial activity at a crude oil-contaminated site

    NASA Astrophysics Data System (ADS)

    Warren, Ean; Bekins, Barbara A.

    2015-11-01

    Crude oil at a spill site near Bemidji, Minnesota has been undergoing aerobic and anaerobic biodegradation for over 30 years, creating a 150-200 m plume of primary and secondary contaminants. Microbial degradation generates heat that should be measurable under the right conditions. To measure this heat, thermistors were installed in wells in the saturated zone and in water-filled monitoring tubes in the unsaturated zone. In the saturated zone, a thermal groundwater plume originates near the residual oil body with temperatures ranging from 2.9 °C above background near the oil to 1.2 °C down gradient. Temperatures in the unsaturated zone above the oil body were up to 2.7 °C more than background temperatures. Previous work at this site has shown that methane produced from biodegradation of the oil migrates upward and is oxidized in a methanotrophic zone midway between the water table and the surface. Enthalpy calculations and observations demonstrate that the temperature increases primarily result from aerobic methane oxidation in the unsaturated zone above the oil. Methane oxidation rates at the site independently estimated from surface CO2 efflux data are comparable to rates estimated from the observed temperature increases. The results indicate that temperature may be useful as a low-cost measure of activity but care is required to account for the correct heat-generating reactions, other heat sources and the effects of focused recharge.

  1. Optimization of Sample Site Selection Imaging for OSIRIS-REx Using Asteroid Surface Analog Images

    NASA Astrophysics Data System (ADS)

    Tanquary, Hannah E.; Sahr, Eric; Habib, Namrah; Hawley, Christopher; Weber, Nathan; Boynton, William V.; Kinney-Spano, Ellyne; Lauretta, Dante

    2014-11-01

    OSIRIS-REx will return a sample of regolith from the surface of asteroid 101955 Bennu. The mission will obtain high resolution images of the asteroid in order to create detailed maps which will satisfy multiple mission objectives. To select a site, we must (i) identify hazards to the spacecraft and (ii) characterize a number of candidate sites to determine the optimal location for sampling. To further characterize the site, a long-term science campaign will be undertaken to constrain the geologic properties. To satisfy these objectives, the distribution and size of blocks at the sample site and backup sample site must be determined. This will be accomplished through the creation of rock size frequency distribution maps. The primary goal of this study is to optimize the creation of these map products by assessing techniques for counting blocks on small bodies, and assessing the methods of analysis of the resulting data. We have produced a series of simulated surfaces of Bennu which have been imaged, and the images processed to simulate Polycam images during the Reconnaissance phase. These surface analog images allow us to explore a wide range of imaging conditions, both ideal and non-ideal. The images have been “degraded”, and are displayed as thumbnails representing the limits of Polycam resolution from an altitude of 225 meters. Specifically, this study addresses the mission requirement that the rock size frequency distribution of regolith grains < 2cm in longest dimension must be determined for the sample sites during Reconnaissance. To address this requirement, we focus on the range of available lighting angles. Varying illumination and phase angles in the simulated images, we can compare the size-frequency distributions calculated from the degraded images with the known size frequency distributions of the Bennu simulant material, and thus determine the optimum lighting conditions for satisfying the 2 cm requirement.

  2. Surface and downhole shear wave seismic methods for thick soil site investigations

    USGS Publications Warehouse

    Hunter, J.A.; Benjumea, B.; Harris, J.B.; Miller, R.D.; Pullan, S.E.; Burns, R.A.; Good, R.L.

    2002-01-01

    Shear wave velocity-depth information is required for predicting the ground motion response to earthquakes in areas where significant soil cover exists over firm bedrock. Rather than estimating this critical parameter, it can be reliably measured using a suite of surface (non-invasive) and downhole (invasive) seismic methods. Shear wave velocities from surface measurements can be obtained using SH refraction techniques. Array lengths as large as 1000 m and depth of penetration to 250 m have been achieved in some areas. High resolution shear wave reflection techniques utilizing the common midpoint method can delineate the overburden-bedrock surface as well as reflecting boundaries within the overburden. Reflection data can also be used to obtain direct estimates of fundamental site periods from shear wave reflections without the requirement of measuring average shear wave velocity and total thickness of unconsolidated overburden above the bedrock surface. Accurate measurements of vertical shear wave velocities can be obtained using a seismic cone penetrometer in soft sediments, or with a well-locked geophone array in a borehole. Examples from thick soil sites in Canada demonstrate the type of shear wave velocity information that can be obtained with these geophysical techniques, and show how these data can be used to provide a first look at predicted ground motion response for thick soil sites. ?? 2002 Published by Elsevier Science Ltd.

  3. Surface activation-based nanobonding and interconnection at room temperature

    NASA Astrophysics Data System (ADS)

    Howlader, M. M. R.; Yamauchi, A.; Suga, T.

    2011-02-01

    Flip chip nanobonding and interconnect system (NBIS) equipment with high precision alignment has been developed based on the surface activated bonding method for high-density interconnection and MEMS packaging. The 3σ alignment accuracy in the IR transmission system was approximately ±0.2 µm. The performance of the NBIS has been preliminarily investigated through bonding between relatively rough surfaces of copper through silicon vias (Cu-TSVs) and gold-stud bumps (Au-SBs), and smooth surfaces of silicon wafers. The Cu-TSVs of 55 µm diameter and the Au-SBs of 35 µm diameter with ~6-10 nm surface roughness (RMS) were bonded at room temperature after surface activation using an argon fast atom beam (Ar-FAB) under 0.16 N per bump. Silicon wafers of 50 mm diameter with ~0.2 nm RMS surface roughness were bonded without heating after surface activation. Void-free interfaces both in Cu-TSV/Au-SB and silicon/silicon with bonding strength equivalent to bulk fracture of Au and silicon, respectively, were achieved. A few nm thick amorphous layers were observed across the silicon/silicon interface that was fabricated by the Ar-FAB. This study in the interconnection and bonding facilitates the required three-dimensional integration on the same surface for high-density electronic and biomedical systems.

  4. Activities affecting surface water resources: A general overview

    SciTech Connect

    Not Available

    1990-01-01

    In November 1987, P.E.I. signed a federal/provincial work-sharing arrangement on water resource management focusing on groundwater pollution, surface water degradation and estuarine eutrophication. The surface water program was designed to identify current surface water uses and users within 12 major watersheds across the Island containing 26 individual rivers, as well as problems arising due to practices that degrade the quality of surface water and restricts its value to other user groups. This report presents a general overview of the program, covering the general characteristics of the Island; operations in agriculture, fish and wildlife, forestry, recreation, fisheries, and industry; alterations of natural features of waterways; wetlands; additional watershed activities such as hydrometric stations and subdivision development; and activities affecting surface water resources such as sedimentation sources, pollution point sources and instream obstructions.

  5. Disturbance opens recruitment sites for bacterial colonization in activated sludge.

    PubMed

    Vuono, David C; Munakata-Marr, Junko; Spear, John R; Drewes, Jörg E

    2016-01-01

    Little is known about the role of immigration in shaping bacterial communities or the factors that may dictate success or failure of colonization by bacteria from regional species pools. To address these knowledge gaps, the influence of bacterial colonization into an ecosystem (activated sludge bioreactor) was measured through a disturbance gradient (successive decreases in the parameter solids retention time) relative to stable operational conditions. Through a DNA sequencing approach, we show that the most abundant bacteria within the immigrant community have a greater probability of colonizing the receiving ecosystem, but mostly as low abundance community members. Only during the disturbance do some of these bacterial populations significantly increase in abundance beyond background levels and in few cases become dominant community members post-disturbance. Two mechanisms facilitate the enhanced enrichment of immigrant populations during disturbance: (i) the availability of resources left unconsumed by established species and (ii) the increased availability of niche space for colonizers to establish and displace resident populations. Thus, as a disturbance decreases local diversity, recruitment sites become available to promote colonization. This work advances our understanding of microbial resource management and diversity maintenance in complex ecosystems. PMID:25727891

  6. Construction of DNA recognition sites active in Haemophilus transformation.

    PubMed Central

    Danner, D B; Smith, H O; Narang, S A

    1982-01-01

    Competent Haemophilus cells recognize and preferentially take up Haemophilus DNA during genetic transformation. This preferential uptake is correlated with the presence on incoming DNA of an 11-base-pair (bp) sequence, 5'-A-A-G-T-G-C-G-G-T-C-A-3'. To prove that this sequence is the recognition site that identifies Haemophilus DNA to the competent cell, we have now constructed a series of plasmids, each of which contains the 11-bp sequence. Using two different assay systems we have tested the ability of fragments from these plasmids to compete with cloned Haemophilus DNA fragments that naturally contain the 11-bp sequence. We find that the addition of the 11-bp sequence to a DNA fragment is necessary and sufficient for preferential uptake of that fragment. However, plasmid DNAs containing this sequence may vary as much as 48-fold in uptake activity, and this variation correlates with the A+T-richness of the DNA flanking the 11-mer. Images PMID:6285382

  7. Characterization of active site residues of nitroalkane oxidase.

    PubMed

    Valley, Michael P; Fenny, Nana S; Ali, Shah R; Fitzpatrick, Paul F

    2010-06-01

    The flavoenzyme nitroalkane oxidase catalyzes the oxidation of primary and secondary nitroalkanes to the corresponding aldehydes and ketones plus nitrite. The structure of the enzyme shows that Ser171 forms a hydrogen bond to the flavin N5, suggesting that it plays a role in catalysis. Cys397 and Tyr398 were previously identified by chemical modification as potential active site residues. To more directly probe the roles of these residues, the S171A, S171V, S171T, C397S, and Y398F enzymes have been characterized with nitroethane as substrate. The C397S and Y398 enzymes were less stable than the wild-type enzyme, and the C397S enzyme routinely contained a substoichiometric amount of FAD. Analysis of the steady-state kinetic parameters for the mutant enzymes, including deuterium isotope effects, establishes that all of the mutations result in decreases in the rate constants for removal of the substrate proton by approximately 5-fold and decreases in the rate constant for product release of approximately 2-fold. Only the S171V and S171T mutations alter the rate constant for flavin oxidation. These results establish that these residues are not involved in catalysis, but rather are required for maintaining the protein structure. PMID:20056514

  8. N6-Methyldeoxyadenosine Marks Active Transcription Start Sites in Chlamydomonas

    PubMed Central

    Chen, Kai; Deng, Xin; Yu, Miao; Han, Dali; Hao, Ziyang; Liu, Jianzhao; Lu, Xingyu; Dore, Louis C; Weng, Xiaocheng; Ji, Quanjiang; Mets, Laurens; He, Chuan

    2015-01-01

    SUMMARY N6-methyldeoxyadenosine (6mA or m6A) is a DNA modification preserved in prokaryotes to eukaryotes. It is widespread in bacteria, and functions in DNA mismatch repair, chromosome segregation, and virulence regulation. In contrast, the distribution and function of 6mA in eukaryotes have been unclear. Here we present a comprehensive analysis of the 6mA landscape in the genome of Chlamydomonas using new sequencing approaches. We identified the 6mA modification in 84% of genes in Chlamydomonas. We found that 6mA mainly locates at ApT dinucleotides around transcription start sites (TSS) with a bimodal distribution, and appears to mark active genes. A periodic pattern of 6mA deposition was also observed at base resolution, which is associated with nucleosome distribution near the TSS, suggesting a possible role in nucleosome positioning. The new genome-wide mapping of 6mA and its unique distribution in the Chlamydomonas genome suggest potential regulatory roles of 6mA in gene expression in eukaryotic organisms. PMID:25936837

  9. Environmental assessment of ground water compliance activities at the Uranium Mill Tailings Site, Spook, Wyoming. Revision 0

    SciTech Connect

    1996-03-01

    This document is an environmental assessment of the Spook, Wyoming, Uranium Mill Tailings Remedial Action (UMTRA) Project site. It analyzes the impacts of the U.S. Department of Energy (DOE) proposed action for ground water compliance. The proposed action is to comply with the U.S. Environmental Protection Agency (EPA) standards for the UMTRA Project sites (40 CFR Part 192) by meeting supplemental standards based on the limited use ground water at the Spook site. This proposed action would not require site activities, including ground water monitoring, characterization, or institutional controls. Ground water in the uppermost aquifer was contaminated by uranium processing activities at the Spook site, which is in Converse County, approximately 48 miles (mi) (77 kilometers [km]) northeast of Casper, Wyoming. Constituents from the site infiltrated and migrated into the uppermost aquifer, forming a plume that extends approximately 2500 feet (ft) (800 meters [m]) downgradient from the site. The principal site-related hazardous constituents in this plume are uranium, selenium, and nitrate. Background ground water in the uppermost aquifer at the site is considered limited use. It is neither a current nor a potential source of drinking water because of widespread, ambient contamination that cannot be cleaned up using treatment methods reasonably employed in public water supply systems (40 CFR {section} 192.11 (e)). Background ground water quality also is poor due to first, naturally occurring conditions (natural uranium mineralization associated with an alteration front), and second, the effects of widespread human activity not related to uranium milling operations (uranium exploration and mining activities). There are no known exposure pathways to humans, animals, or plants from the contaminated ground water in the uppermost aquifer because it does not discharge to lower aquifers, to the surface, or to surface water.

  10. May 2013 Groundwater and Surface Water Sampling at the Rio Blanco, Colorado, Site (Data Validation Package)

    SciTech Connect

    2013-10-01

    Annual sampling was conducted at the Rio Blanco, Colorado, site for the Long-Term Hydrologic Monitoring Program May 14-16, 2013, to monitor groundwater and surface water for potential radionuclide contamination. Sampling and analyses were conducted as specified in Sampling and Analysis Plan for the U.S. Department of Energy Office of Legacy Management Sites (LMS/PRO/S04351, continually updated). A duplicate sample was collected from location CER #1 Black Sulphur. Samples were analyzed for gamma-emitting radionuclides by high-resolution gamma spectrometry and for tritium using the conventional and enrichment methods.

  11. The Activity of Antimicrobial Surfaces Varies by Testing Protocol Utilized

    PubMed Central

    Campos, Matias D.; Zucchi, Paola C.; Phung, Ann; Leonard, Steven N.; Hirsch, Elizabeth B.

    2016-01-01

    Background Contaminated hospital surfaces are an important source of nosocomial infections. A major obstacle in marketing antimicrobial surfaces is a lack of efficacy data based on standardized testing protocols. Aim We compared the efficacy of multiple testing protocols against several “antimicrobial” film surfaces. Methods Four clinical isolates were used: one Escherichia coli, one Klebsiella pneumoniae, and two Staphylococcus aureus strains. Two industry methods (modified ISO 22196 and ASTM E2149), a “dried droplet”, and a “transfer” method were tested against two commercially available antimicrobial films, one film in development, an untreated control, and a positive (silver) control film. At 2 (only ISO) and 24 hours following inoculation, bacteria were collected from film surfaces and enumerated. Results Compared to untreated films in all protocols, there were no significant differences in recovery on either commercial brand at 2 or 24 hours after inoculation. The silver surface demonstrated significant microbicidal activity (mean loss 4.9 Log10 CFU/ml) in all methods and time points with the exception of 2 hours in the ISO protocol and the transfer method. Using our novel droplet method, no differences between placebo and active surfaces were detected. The surface in development demonstrated variable activity depending on method, organism, and time point. The ISO demonstrated minimal activity at 2 hours but significant activity at 24 hours (mean 4.5 Log10 CFU/ml difference versus placebo). The ASTEM protocol exhibited significant differences in recovery of staphylococci (mean 5 Log10 CFU/ml) but not Gram-negative isolates (10 fold decrease). Minimal activity was observed with this film in the transfer method. Conclusions Varying results between protocols suggested that efficacy of antimicrobial surfaces cannot be easily and reproducibly compared. Clinical use should be considered and further development of representative methods is needed. PMID

  12. The detection of intestinal spike activity on surface electroenterograms

    NASA Astrophysics Data System (ADS)

    Ye-Lin, Y.; Garcia-Casado, J.; Martinez-de-Juan, J. L.; Prats-Boluda, G.; Ponce, J. L.

    2010-02-01

    Myoelectrical recording could provide an alternative technique for assessing intestinal motility, which is a topic of great interest in gastroenterology since many gastrointestinal disorders are associated with intestinal dysmotility. The pacemaker activity (slow wave, SW) of the electroenterogram (EEnG) has been detected in abdominal surface recordings, although the activity related to bowel contractions (spike bursts, SB) has to date only been detected in experimental models with artificially favored electrical conductivity. The aim of the present work was to assess the possibility of detecting SB activity in abdominal surface recordings under physiological conditions. For this purpose, 11 recording sessions of simultaneous internal and external myolectrical signals were conducted on conscious dogs. Signal analysis was carried out in the spectral domain. The results show that in periods of intestinal contractile activity, high-frequency components of EEnG signals can be detected on the abdominal surface in addition to SW activity. The energy between 2 and 20 Hz of the surface myoelectrical recording presented good correlation with the internal intestinal motility index (0.64 ± 0.10 for channel 1 and 0.57 ± 0.11 for channel 2). This suggests that SB activity can also be detected in canine surface EEnG recording.

  13. Mapping of the Allosteric Site in Cholesterol Hydroxylase CYP46A1 for Efavirenz, a Drug That Stimulates Enzyme Activity.

    PubMed

    Anderson, Kyle W; Mast, Natalia; Hudgens, Jeffrey W; Lin, Joseph B; Turko, Illarion V; Pikuleva, Irina A

    2016-05-27

    Cytochrome P450 46A1 (CYP46A1) is a microsomal enzyme and cholesterol 24-hydroxylase that controls cholesterol elimination from the brain. This P450 is also a potential target for Alzheimer disease because it can be activated pharmacologically by some marketed drugs, as exemplified by efavirenz, the anti-HIV medication. Previously, we suggested that pharmaceuticals activate CYP46A1 allosterically through binding to a site on the cytosolic protein surface, which is different from the enzyme active site facing the membrane. Here we identified this allosteric site for efavirenz on CYP46A1 by using a combination of hydrogen-deuterium exchange coupled to MS, computational modeling, site-directed mutagenesis, and analysis of the CYP46A1 crystal structure. We also mapped the binding region for the CYP46A1 redox partner oxidoreductase and found that the allosteric and redox partner binding sites share a common border. On the basis of the data obtained, we propose the mechanism of CYP46A1 allostery and the pathway for the signal transmission from the P450 allosteric site to the active site. PMID:27056331

  14. Multiple, Ligand-Dependent Routes from the Active Site of Cytochrome P450 2C9

    SciTech Connect

    Cojocaru, Vlad; Winn, Peter J.; Wade, Rebecca C.

    2012-02-13

    The active site of liver-specific, drug-metabolizing cytochrome P450 (CYP) monooxygenases is deeply buried in the protein and is connected to the protein surface through multiple tunnels, many of which were found open in different CYP crystal structures. It has been shown that different tunnels could serve as ligand passage routes in different CYPs. However, it is not understood whether one CYP uses multiple routes for substrate access and product release and whether these routes depend on ligand properties. From 300 ns of molecular dynamics simulations of CYP2C9, the second most abundant CYP in the human liver we found four main ligand exit routes, the occurrence of each depending on the ligand type and the conformation of the F-G loop, which is likely to be affected by the CYP-membrane interaction. A non-helical F-G loop favored exit towards the putative membrane-embedded region. Important protein features that direct ligand exit include aromatic residues that divide the active site and whose motions control access to two pathways. The ligands interacted with positively charged residues on the protein surface through hydrogen bonds that appear to select for acidic substrates. The observation of multiple, ligand-dependent routes in a CYP aids understanding of how CYP mutations affect drug metabolism and provides new possibilities for CYP inhibition.

  15. Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Wang, Ziyun; Liu, Xinyi; Rooney, D. W.; Hu, P.

    2015-10-01

    The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

  16. 10 CFR 63.16 - Review of site characterization activities. 2

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses Preapplication Review § 63.16 Review of... conduct of site characterization activities at the Yucca Mountain site, DOE shall report the nature and... activities at the Yucca Mountain site, NRC staff shall be permitted to visit and inspect the locations...

  17. 10 CFR 63.16 - Review of site characterization activities. 2

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses Preapplication Review § 63.16 Review of... conduct of site characterization activities at the Yucca Mountain site, DOE shall report the nature and... activities at the Yucca Mountain site, NRC staff shall be permitted to visit and inspect the locations...

  18. 10 CFR 63.16 - Review of site characterization activities. 2

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses Preapplication Review § 63.16 Review of... conduct of site characterization activities at the Yucca Mountain site, DOE shall report the nature and... activities at the Yucca Mountain site, NRC staff shall be permitted to visit and inspect the locations...

  19. 10 CFR 63.16 - Review of site characterization activities. 2

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses Preapplication Review § 63.16 Review of... conduct of site characterization activities at the Yucca Mountain site, DOE shall report the nature and... activities at the Yucca Mountain site, NRC staff shall be permitted to visit and inspect the locations...

  20. 10 CFR 63.16 - Review of site characterization activities. 2

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... IN A GEOLOGIC REPOSITORY AT YUCCA MOUNTAIN, NEVADA Licenses Preapplication Review § 63.16 Review of... conduct of site characterization activities at the Yucca Mountain site, DOE shall report the nature and... activities at the Yucca Mountain site, NRC staff shall be permitted to visit and inspect the locations...

  1. Targeting mechanisms at sites of complement activation for imaging and therapy.

    PubMed

    Holers, V Michael

    2016-06-01

    The complement system plays a key role in many acute injury states as well as chronic autoimmune and inflammatory diseases. Localized complement activation and alternative pathway-mediated amplification on diverse target surfaces promote local recruitment of pro-inflammatory cells and elaboration of other mediators. Despite a general understanding of the architecture of the system, though, many of the mechanisms that underlie site-specific complement activation and amplification in vivo are incompletely understood. In addition, there is no capability yet to measure the level of local tissue site-specific complement activation in patients without performing biopsies to detect products using immunohistochemical techniques. Herein is reviewed emerging evidence obtained through clinical research studies of human rheumatoid arthritis along with translational studies of its disease models which demonstrate that several parallel mechanisms are involved in site-specific amplification of activation of the complement system in vivo. Among these processes are de-regulation of the alternative pathway, effector pathway-catalyzed amplification of proximal complement activation, recognition of injury-associated ligands by components of the lectin pathway, and engagement of pathogenic natural antibodies that recognize a limited set of injury-associated neoepitopes. Studies suggest that each of these inter-related processes can play key roles in amplification of complement-dependent injury on self-tissues in vivo. These findings, in addition to development of an imaging strategy described herein designed to quantitatively measure local complement C3 fixation, have relevance to therapeutic and diagnostic strategies targeting the complement system. PMID:25979851

  2. Goethite surface reactivity: III. Unifying arsenate adsorption behavior through a variable crystal face - Site density model

    NASA Astrophysics Data System (ADS)

    Salazar-Camacho, Carlos; Villalobos, Mario

    2010-04-01

    We developed a model that describes quantitatively the arsenate adsorption behavior for any goethite preparation as a function of pH and ionic strength, by using one basic surface arsenate stoichiometry, with two affinity constants. The model combines a face distribution-crystallographic site density model for goethite with tenets of the Triple Layer and CD-MUSIC surface complexation models, and is self-consistent with its adsorption behavior towards protons, electrolytes, and other ions investigated previously. Five different systems of published arsenate adsorption data were used to calibrate the model spanning a wide range of chemical conditions, which included adsorption isotherms at different pH values, and adsorption pH-edges at different As(V) loadings, both at different ionic strengths and background electrolytes. Four additional goethite-arsenate systems reported with limited characterization and adsorption data were accurately described by the model developed. The adsorption reaction proposed is: lbond2 FeOH +lbond2 SOH +AsO43-+H→lbond2 FeOAsO3[2-]…SOH+HO where lbond2 SOH is an adjacent surface site to lbond2 FeOH; with log K = 21.6 ± 0.7 when lbond2 SOH is another lbond2 FeOH, and log K = 18.75 ± 0.9, when lbond2 SOH is lbond2 Fe 2OH. An additional small contribution of a protonated complex was required to describe data at low pH and very high arsenate loadings. The model considered goethites above 80 m 2/g as ideally composed of 70% face (1 0 1) and 30% face (0 0 1), resulting in a site density for lbond2 FeOH and for lbond2 Fe 3OH of 3.125/nm 2 each. Below 80 m 2/g surface capacity increases progressively with decreasing area, which was modeled by considering a progressively increasing proportion of faces (0 1 0)/(1 0 1), because face (0 1 0) shows a much higher site density of lbond2 FeOH groups. Computation of the specific proportion of faces, and thus of the site densities for the three types of crystallographic surface groups present in

  3. Enhanced Surfactant Adsorption on Activated Carbon through Manipulation of Surface Oxygen Groups

    NASA Astrophysics Data System (ADS)

    Collins, John; Qu, Deyang; Foster, Michelle

    2012-02-01

    Passive energy storage is a necessary component for balancing the lifecycle budget with new forms of green energy. The work presented describes how surface oxygen groups (SOG) on granulated activated carbon have been manipulated using Nitric Acid in a controlled, stepwise fashion. The structure and surface functionality of the activated carbon samples were characterized using DRIFTS, Raman Spectroscopy and Porosimetry. Total surface area was found to increase proportionally with the removal of heteroatom material, exposing previously insulated active sites responsible for SOG attachment. Broad oxide peaks were deconvoluted and analyzed, allowing for absolute identification of evolving functionality at each oxidation stage. SOGs were maximized on the third oxidation cycle with the presence of conjugated aromatic, phenol, lactone, and carboxylic acid groups. FSN Zonyl nonionic was applied to all oxidized samples at various concentrations. Total adsorbed surfactant was quantified for each concentration / oxidation scheme using attenuated total reflection. The relative quantity and polarity of chemisorbed surfactant were qualitatively assessed for each equilibrium concentration.

  4. Surface Wave Investigation and Analysis Earthquake-Induced Liquefaction Sites in Asia

    NASA Astrophysics Data System (ADS)

    Kayen, R.; Tanaka, Y.; Cetin, O.; Hayashi, K.; Minasian, D.; Seed, R. B.; Suzuki, Y.; Tokimatsu, K.

    2002-12-01

    This ongoing investigation is greatly expanding the worldwide data-set of shear wave velocity characteristics at liquefaction sites, most of which are located in Asia. Doing so allows for a re-evaluation of the shear wave velocity assessment methodologies for liquefaction presented in the literature since 1992, methodologies that are data deficient in the zone of high shear wave velocity and high ground motion intensity data. To expand this data set, we are using the Spectral Analysis of Surface Waves (SASW) method, a relatively new non-invasive field approach for evaluating the shear wave velocity characteristics of potentially liquefiable ground. In our test procedure, we line-array small-lightweight sensors on the surface and gather vertical-motion vibrations produced with a small frequency-controlled electro-mechanical shaker. Real time computation of cross power spectra (CPS) between separated and precisely-spaced sensors are transformed into phase velocity-frequency dispersion space and ultimately shear wave velocity-depth space. SASW is particularly useful for lightweight reconnaissance surveys and profiling difficult materials such as gravely sand where conventional truck-based penetration methods are not practical. The dispersive nature of surface waves is the basis of the SASW method. After we have determine the dispersion characteristics of surface waves at a site, we utilize the Haskell-Thompson matrix inversion technique to estimate the shear wave velocity profile. Then, the velocity of the observed liquefied layer is used to relate the stiffness properties of the ground to an estimated intensity of the earthquake motions at the site. In Japan and Taiwan, we profiled 182 liquefaction test sites using this method, producing detailed shear wave velocity profiles in the upper 20-30 meters of the soil column. Further testing is planned for 2003. Nearly all of the post-war documented liquefaction sites in the Japan and Taiwan, evaluated with conventional

  5. Identification of the prooxidant site of human ceruloplasmin: a model for oxidative damage by copper bound to protein surfaces

    NASA Technical Reports Server (NTRS)

    Mukhopadhyay, C. K.; Mazumder, B.; Lindley, P. F.; Fox, P. L.

    1997-01-01

    Free transition metal ions oxidize lipids and lipoproteins in vitro; however, recent evidence suggests that free metal ion-independent mechanisms are more likely in vivo. We have shown previously that human ceruloplasmin (Cp), a serum protein containing seven Cu atoms, induces low density lipoprotein oxidation in vitro and that the activity depends on the presence of a single, chelatable Cu atom. We here use biochemical and molecular approaches to determine the site responsible for Cp prooxidant activity. Experiments with the His-specific reagent diethylpyrocarbonate (DEPC) showed that one or more His residues was specifically required. Quantitative [14C]DEPC binding studies indicated the importance of a single His residue because only one was exposed upon removal of the prooxidant Cu. Plasmin digestion of [14C]DEPC-treated Cp (and N-terminal sequence analysis of the fragments) showed that the critical His was in a 17-kDa region containing four His residues in the second major sequence homology domain of Cp. A full length human Cp cDNA was modified by site-directed mutagenesis to give His-to-Ala substitutions at each of the four positions and was transfected into COS-7 cells, and low density lipoprotein oxidation was measured. The prooxidant site was localized to a region containing His426 because CpH426A almost completely lacked prooxidant activity whereas the other mutants expressed normal activity. These observations support the hypothesis that Cu bound at specific sites on protein surfaces can cause oxidative damage to macromolecules in their environment. Cp may serve as a model protein for understanding mechanisms of oxidant damage by copper-containing (or -binding) proteins such as Cu, Zn superoxide dismutase, and amyloid precursor protein.

  6. Hanford Site Environmental data for Calendar Year 1990. Surface and Columbia River

    SciTech Connect

    Bisping, L.E.; Woodruff, R.K.

    1992-01-01

    Environmental monitoring at the Hanford Site, located in southeastern Washington State, is conducted by Battelle Memorial Institute, Pacific Northwest Division, as part of its contract to operate the Pacific Northwest Laboratory (PNL) for the US Department of Energy. The data collected provide a historical record of radionuclide and radiation levels attributable to natural causes, worldwide fallout, and Hanford operations. Data are also collected to monitor several chemicals. Pacific Northwest Laboratory publishes an annual environmental report for the Hanford Site each calendar year. The Hanford Site Environmental Report for Calendar Year 1990 is a summary of offsite and onsite environmental monitoring data collected during 1990 by PNL`s Environmental Monitoring Program. The data summaries included in the annual report were created from individual surface and river monitoring results. This volume contains the individual results used to create those summaries. This volume also includes additional data summaries which do not appear in the annual report.

  7. Innovative technology for expedited site remediation of extensive surface and subsurface contamination

    SciTech Connect

    Audibert, J.M.E.; Lew, L.R.

    1994-12-31

    Large scale surface and subsurface contamination resulted from numerous releases of feed stock, process streams, waste streams, and final product at a major chemical plant. Soil and groundwater was contaminated by numerous compounds including lead, tetraethyl lead, ethylene dibromide, ethylene dichloride, and toluene. The state administrative order dictated that the site be investigated fully, that remedial alternative be evaluated, and that the site be remediated within a year period. Because of the acute toxicity and extreme volatility of tetraethyl lead and other organic compounds present at the site and the short time frame ordered by the regulators, innovative approaches were needed to carry out the remediation while protecting plant workers, remediation workers, and the public.

  8. Surface Water Quality Monitoring Site Optimization for Poyang Lake, the Largest Freshwater Lake in China

    PubMed Central

    Wang, Hua; Wu, Mengan; Deng, Yanqing; Tang, Chunyan; Yang, Rui

    2014-01-01

    In this paper, we propose a coupled method to optimize the surface water quality monitoring sites for a huge freshwater lake based on field investigations, mathematical analysis, and numerical simulation tests. Poyang Lake, the largest freshwater lake in China, was selected as the research area. Based on the field investigated water quality data in the 5 years from 2008 to 2012, the water quality inter-annual variation coefficients at all the present sites and the water quality correlation coefficients between adjacent sites were calculated and analyzed to present an optimization scheme. A 2-D unsteady water quality model was established to get the corresponding water quality data at the optimized monitoring sites, which were needed for the rationality test on the optimized monitoring network. We found that: (1) the water quality of Piaoshan (No. 10) fluctuated most distinguishably and the inter-annual variation coefficient of NH3-N and TP could reach 99.77% and 73.92%, respectively. The four studied indexes were all closely related at Piaoshan (No. 10) and Tangyin (No. 11), and the correlation coefficients of COD and NH3-N could reach 0.91 and 0.94 separately. (2) It was suggested that the present site No. 10 be removed to avoid repeatability, and it was suggested that the three sites of Changling, Huzhong, and Nanjiang be added to improve the representativeness of the monitoring sites. (3) According to the rationality analysis, the 21 optimized water quality monitoring sites could scientifically replace the primary network, and the new monitoring network could better reflect the water quality of the whole lake. PMID:25407419

  9. Active-site mutagenesis of tetanus neurotoxin implicates TYR-375 and GLU-271 in metalloproteolytic activity.

    PubMed

    Rossetto, O; Caccin, P; Rigoni, M; Tonello, F; Bortoletto, N; Stevens, R C; Montecucco, C

    2001-08-01

    Tetanus neurotoxin (TeNT) blocks neurotransmitter release by cleaving VAMP/synaptobrevin, a membrane associated protein involved in synaptic vesicle fusion. Such activity is exerted by the N-terminal 50kDa domain of TeNT which is a zinc-dependent endopeptidase (TeNT-L-chain). Based on the three-dimensional structure of botulinum neurotoxin serotype A (BoNT/A) and serotype B (BoNT/B), two proteins closely related to TeNT, and on X-ray scattering studies of TeNT, we have designed mutations at two active site residues to probe their involvement in activity. The active site of metalloproteases is composed of a primary sphere of residues co-ordinating the zinc atom, and a secondary sphere of residues that determines proteolytic specificity and activity. Glu-261 and Glu-267 directly co-ordinates the zinc atom in BoNT/A and BoNT/B respectively and the corresponding residue of TeNT was replaced by Asp or by the non conservative residue Ala. Tyr-365 is 4.3A away from zinc in BoNT/A, and the corresponding residue of TeNT was replaced by Phe or by Ala. The purified mutants had CD, fluorescence and UV spectra closely similar to those of the wild-type molecule. The proteolytic activity of TeNT-Asp-271 (E271D) is similar to that of the native molecule, whereas that of TeNT-Phe-375 (Y375F) is lower than the control. Interestingly, the two Ala mutants are completely devoid of enzymatic activity. These results demonstrate that both Glu-271 and Tyr-375 are essential for the proteolytic activity of TeNT. PMID:11306125

  10. Using Surface Curvature to Control the Dimerization of a Surface-Active Protein

    NASA Astrophysics Data System (ADS)

    Kurylowicz, Martin; Giuliani, Maximiliano; Dutcher, John

    2012-02-01

    Understanding the influence of surface geometry on adsorbed proteins promises new possibilities in biophysics, such as topographical catalysis, molecular recognition of geometric cues, and modulations of oligomerization or ligand binding. We have created nano-textured hydrophobic surfaces that are stable in buffer by spin coating polystyrene (PS) nanoparticles (NPs) to form patchy NP monolayers on a PS substrate, yielding flat and highly curved areas on the same sample. Moreover, we have separated surface chemistry from texture by floating a 10 nm thick film of monodisperse PS onto the NP-functionalized surface. Using Single Molecule Force Spectroscopy we have compared in situ the distribution of detachment lengths for proteins on curved surfaces to that measured on flat surfaces. We have shown that β-Lactoglobulin (β-LG), a surface-active protein which helps to stabilize oil droplets in milk, forms dimers on both flat PS surfaces and surfaces with a radius of curvature of 100 nm, whereas β-LG monomers exist for more highly curved surfaces with radii of curvature of 25 and 40 nm. It is surprising that rather large radii of curvature have such a strong influence on proteins whose radius is only ˜2 nm. Furthermore, the transition from dimer to monomer with changes in surface curvature offers promising applications for proteins whose function can be modified by their oligomerization state.

  11. GAS HYDRATES AT TWO SITES OF AN ACTIVE CONTINENTAL MARGIN.

    USGS Publications Warehouse

    Kvenvolden, K.A.

    1985-01-01

    Sediment containing gas hydrates from two distant Deep Sea Drilling Project sites (565 and 568), located about 670 km apart on the landward flank of the Middle America Trench, was studied to determine the geochemical conditions that characterize the occurrence of gas hydrates. Site 565 was located in the Pacific Ocean offshore the Nicoya Peninsula of Costa Rica in 3,111 m of water. The depth of the hole at this site was 328 m, and gas hydrates were recovered from 285 and 319 m. Site 568 was located about 670 km to the northwest offshore Guatemala in 2,031 m of water. At this site the hole penetrated to 418 m, and gas hydrates were encountered at 404 m.

  12. Dynamically Achieved Active Site Precision in Enzyme Catalysis

    PubMed Central

    2015-01-01

    Conspectus The grand challenge in enzymology is to define and understand all of the parameters that contribute to enzymes’ enormous rate accelerations. The property of hydrogen tunneling in enzyme reactions has moved the focus of research away from an exclusive focus on transition state stabilization toward the importance of the motions of the heavy atoms of the protein, a role for reduced barrier width in catalysis, and the sampling of a protein conformational landscape to achieve a family of protein substates that optimize enzyme–substrate interactions and beyond. This Account focuses on a thermophilic alcohol dehydrogenase for which the chemical step of hydride transfer is rate determining across a wide range of experimental conditions. The properties of the chemical coordinate have been probed using kinetic isotope effects, indicating a transition in behavior below 30 °C that distinguishes nonoptimal from optimal C–H activation. Further, the introduction of single site mutants has the impact of either enhancing or eliminating the temperature dependent transition in catalysis. Biophysical probes, which include time dependent hydrogen/deuterium exchange and fluorescent lifetimes and Stokes shifts, have also been pursued. These studies allow the correlation of spatially resolved transitions in protein motions with catalysis. It is now possible to define a long-range network of protein motions in ht-ADH that extends from a dimer interface to the substrate binding domain across to the cofactor binding domain, over a distance of ca. 30 Å. The ongoing challenge to obtaining spatial and temporal resolution of catalysis-linked protein motions is discussed. PMID:25539048

  13. Downwelled longwave surface irradiance data from five sites for the FIRE/SRB Wisconsin Experiment from October 12 through November 2, 1986

    NASA Technical Reports Server (NTRS)

    Whitlock, Charles H.; Cox, Stephen K.; Lecroy, Stuart R.

    1990-01-01

    Tables are presented which show data from five sites in the First ISCCP (International Satellite Cloud Climatology Project) Regional Experiment (FIRE)/Surface Radiation Budget (SRB) Wisconsin experiment regional from October 12 through November 2, 1986. A discussion of intercomparison results is also included. The field experiment was conducted for the purposes of both intensive cirrus-cloud measurements and SRB algorithm validation activities.

  14. Direct Epoxidation of Propylene over Stabilized Cu+ Surface Sites on Ti Modified Cu2O

    SciTech Connect

    Yang, X.; Kattel, S.; Xiong, K.; Mudiyanselage, K.; Rykov, S.; Senanayake, S. D.; Rodriguez, J. A.; Liu, P.; Stacchiola, D. J.; Chen, J. G.

    2015-07-17

    Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu+ active sites in a TiCuOx mixed oxide. The TiCuOx surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

  15. An approach estimating bidirectional air-surface exchange for gaseous elemental mercury at AMNet sites

    NASA Astrophysics Data System (ADS)

    Wright, L. Paige; Zhang, Leiming

    2015-03-01

    The bidirectional air-surface exchange for gaseous elemental mercury (GEM) and existing measurements of the compensation points over a variety of canopy types are reviewed. Deposition and emission of GEM are dependent on several factors such as the type of canopy, temperature, season, atmospheric GEM concentrations, and meteorological conditions, with compensation points varying between 0.5 and 33 ng m-3. Emissions tend to increase from the spring to summer seasons, as the GEM accumulates in the foliage of the vegetation. A strong dependence on solar radiation has been observed, with higher emissions under light conditions. A bidirectional air-surface exchange flux model is proposed for estimating GEM fluxes at a two-hourly time resolution for the National Atmospheric Deposition Program's, Atmospheric Mercury Network (AMNet) sites. Compared to the unidirectional dry deposition model used in Zhang et al. (2012), two additional parameters, stomatal and soil emission potential, were needed in the bidirectional model and were chosen based on knowledge gained in the literature review and model sensitivity test results. Application of this bidirectional model to AMNet sites have produced annual net deposition fluxes comparable to those estimated in Zhang et al. (2012) at the majority of the sites. In this study, the net GEM dry deposition has been estimated separately for each dominant land use type surrounding each site, and this approach is also recommended for future calculations for easy application of the results to assessments of the mercury effects on various ecosystems.

  16. Autocatalytic Surface Hydroxylation of MgO(100) Terrace Sites Observed Under Ambient Conditions

    SciTech Connect

    Newberg, J.T.; Starr, D.; Yamamoto, S.; Kaya, S.; Kendelewicz, T.; Mysak E.R.; Porsgaard, S.; Salmeron, M.B.; Brown, Jr., G.E.; Nilsson, A.; Bluhm, H.

    2011-06-01

    We have investigated the reaction of water vapor with the MgO(100) surface using ambient pressure X-ray photoelectron spectroscopy (AP-XPS), which permits the study of the chemical composition of the MgO/water vapor interface at p(H{sub 2}O) in the Torr range. Water dissociation on thin MgO(100) films of 4-5.5 monolayers (ML) grown on Ag(100) was studied under isobaric conditions at p(H{sub 2}O) ranging from 0.005 to 0.5 Torr and temperatures from 380 to -10 C, up to a maximum relative humidity (RH) of 20%. At RH < 0.01% dissociative adsorption occurs only at defect sites (0.08 ML), while terrace sites remain unreactive toward water dissociation. In the range 0.01 < RH < 0.1% there is an abrupt onset of dissociative adsorption at terrace sites which saturates at 1 ML at 0.1% RH, and is accompanied by an increase in molecular water adsorption. At 20% RH there is 1 ML of molecularly adsorbed water interacting with a fully hydroxylated interface on MgO(100). The observed onset of hydroxylation near 0.01% RH is suggested to be due to water molecules aggregating at the surface, leading to an autocatalytic dissociation of water at MgO(100) terrace sites.

  17. DARC: Mapping Surface Topography by Ray-Casting for Effective Virtual Screening at Protein Interaction Sites.

    PubMed

    Gowthaman, Ragul; Miller, Sven A; Rogers, Steven; Khowsathit, Jittasak; Lan, Lan; Bai, Nan; Johnson, David K; Liu, Chunjing; Xu, Liang; Anbanandam, Asokan; Aubé, Jeffrey; Roy, Anuradha; Karanicolas, John

    2016-05-12

    Protein-protein interactions represent an exciting and challenging target class for therapeutic intervention using small molecules. Protein interaction sites are often devoid of the deep surface pockets presented by "traditional" drug targets, and crystal structures reveal that inhibitors typically engage these sites using very shallow binding modes. As a consequence, modern virtual screening tools developed to identify inhibitors of traditional drug targets do not perform as well when they are instead deployed at protein interaction sites. To address the need for novel inhibitors of important protein interactions, here we introduce an alternate docking strategy specifically designed for this regime. Our method, termed DARC (Docking Approach using Ray-Casting), matches the topography of a surface pocket "observed" from within the protein to the topography "observed" when viewing a potential ligand from the same vantage point. We applied DARC to carry out a virtual screen against the protein interaction site of human antiapoptotic protein Mcl-1 and found that four of the top-scoring 21 compounds showed clear inhibition in a biochemical assay. The Ki values for these compounds ranged from 1.2 to 21 μM, and each had ligand efficiency comparable to promising small-molecule inhibitors of other protein-protein interactions. These hit compounds do not resemble the natural (protein) binding partner of Mcl-1, nor do they resemble any known inhibitors of Mcl-1. Our results thus demonstrate the utility of DARC for identifying novel inhibitors of protein-protein interactions. PMID:26126123

  18. Characterization of ocean surface current properties from single site HF/VHF radar

    NASA Astrophysics Data System (ADS)

    Marmain, Julien; Forget, Philippe; Molcard, Anne

    2011-11-01

    Surface current mapping from HF/VHF coastal radars traditionally requires at least two distant sites. Vector velocities are estimated by combining the radial velocity components measured by the radars. In many circumstances (e.g., failures, interferences, logistics constraints), such a combination is not possible by lack of data from one station. Two methods are evaluated to get information on surface circulation from a single site radar: the Vectorial Reconstruction Method (VRM) for current vector mapping and the Vortex Identification Method (VIM) for detecting eddy-like structures. The VRM assumes a non-divergent horizontal surface current, and the VIM analyzes radial velocities and their radial and orthoradial gradients. These two methods are tested on modeled and measured data sets in the Northwestern Mediterranean Sea where both high-resolution ocean circulation model and radar campaigns are available. The VRM performance is strongly limited by the divergence-free hypothesis which was not satisfied in our real data. The VIM succeeded in detection of vortex in the Gulf of Lions and from an operating single site radar located on the Provence coasts in summer.

  19. Contaminants in surface water and sediments near the Tynagh silver mine site, County Galway, Ireland.

    PubMed

    O'Neill, A; Phillips, D H; Bowen, J; Sen Gupta, B

    2015-04-15

    A former silver mine in Tynagh, Co. Galway, Ireland is one of the most contaminated mine sites in Europe with maximum concentrations of Zn, As, Pb, Mn, Ni, Cu, and Cd far exceeding guideline values for water and sediment. The aims of this research were to 1) further assess the contamination, particularly metals, in surface water and sediment around the site, and 2) determine if the contamination has increased 10 years after the Environmental Protection Agency Ireland (EPAI) identified off-site contamination. Site pH is alkaline to neutral because CaCO3-rich sediment and rock material buffer the exposed acid generating sulphide-rich ore. When this study was compared to the previous EPAI study conducted 10 years earlier, it appeared that further weathering of exposed surface sediment had increased concentrations of As and other potentially toxic elements. Water samples from the tailings ponds and adjacent Barnacullia Stream had concentrations of Al, Cd, Mn, Zn and Pb above guideline values. Lead and Zn concentrations from the tailings pond sediment were 16 and 5 times higher, respectively, than concentrations reported 10 years earlier. Pb and Zn levels in most sediment samples exceeded the Expert Group (EGS) guidelines of 1000 and 5000 mg/kg, respectively. Arsenic concentrations were as high as 6238 mg/kg in the tailings ponds sediment, which is 62 and 862 times greater than the EGS and Canadian Soil Quality Guidelines (CSQG), respectively. Cadmium, Cu, Fe, Mn, Pb and Zn concentrations in water and sediment were above guideline values downstream of the site. Additionally, Fe, Mn and organic matter (OM) were strongly correlated and correlated to Zn, Pb, As, Cd, Cu and Ni in stream sediment. Therefore, the nearby Barnacullia Stream is also a significant pathway for contaminant transport to downstream areas. Further rehabilitation of the site may decrease the contamination around the area. PMID:25634731

  20. Indium phosphide negative electron affinity photocathodes: Surface cleaning and activation

    NASA Astrophysics Data System (ADS)

    Sun, Yun

    InP(100) is a very important semi-conductor for many applications. When activated by Cs and oxygen, the InP surface achieves the state of Negative Electron Affinity (NEA) making the Cs+O/InP system a very efficient electron source. Despite many years of study, the chemical cleaning and activation of InP are still not well understood. In our work, we have established an understanding of the basic physics and chemistry for the chemical cleaning and activation of the InP(100) surface. Synchrotron Radiation Photoelectron Spectroscopy is the main technique used in this study because of its high surface sensitivity and ability to identify chemical species present on the surface at each stage of our process. A clean, stoichiometric InP(100) surface is crucial for obtaining high performance of NEA photocathodes. Therefore, the first part of our study focused on the chemical cleaning of InP(100). We found that hydrogen peroxide based solutions alone, originally developed to clean GaAs(100) surfaces and widely used for InP(100), do not result in clean InP(I00) surfaces because oxide is left on the surface. A second cleaning step, which uses acid solutions like HCl or H2SO4, can remove all the oxide and leave a 0.4 ML protective layer of elemental phosphorous on the surface. The elemental phosphorous can be removed by annealing at 330°C and a clean InP(100) surface can be obtained. Cs deposition on InP(100) surface shows clear charge transfer from the Cs ad-atoms to the substrate. When the Cs/InP(100) surface is dosed with oxygen, the charge transfer from the Cs to substrate is reduced and substrate is oxidized. The activation of InP as a NEA photocathode is carried out by an alternating series of steps consisting of Cs deposition and Cs+O co-deposition. Two types of oxygen are found after activation. The first is dissociated oxygen and the other is a di-oxygen species (peroxide or superoxide). The decay of quantum-yield with time and with annealing is studied and changes in

  1. Ammonia removal using activated carbons: effect of the surface chemistry in dry and moist conditions.

    PubMed

    Gonçalves, Maraisa; Sánchez-García, Laura; Oliveira Jardim, Erika de; Silvestre-Albero, Joaquín; Rodríguez-Reinoso, Francisco

    2011-12-15

    The effect of surface chemistry (nature and amount of oxygen groups) in the removal of ammonia was studied using a modified resin-based activated carbon. NH(3) breakthrough column experiments show that the modification of the original activated carbon with nitric acid, that is, the incorporation of oxygen surface groups, highly improves the adsorption behavior at room temperature. Apparently, there is a linear relationship between the total adsorption capacity and the amount of the more acidic and less stable oxygen surface groups. Similar experiments using moist air clearly show that the effect of humidity highly depends on the surface chemistry of the carbon used. Moisture highly improves the adsorption behavior for samples with a low concentration of oxygen functionalities, probably due to the preferential adsorption of ammonia via dissolution into water. On the contrary, moisture exhibits a small effect on samples with a rich surface chemistry due to the preferential adsorption pathway via Brønsted and Lewis acid centers from the carbon surface. FTIR analyses of the exhausted oxidized samples confirm both the formation of NH(4)(+) species interacting with the Brønsted acid sites, together with the presence of NH(3) species coordinated, through the lone pair electron, to Lewis acid sites on the graphene layers. PMID:22049916

  2. Surface properties of the Mars Science Laboratory candidate landing sites: characterization from orbit and predictions

    USGS Publications Warehouse

    Fergason, R.L.; Christensen, P.R.; Golombek, M.P.; Parker, T.J.

    2012-01-01

    This work describes the interpretation of THEMIS-derived thermal inertia data at the Eberswalde, Gale, Holden, and Mawrth Vallis Mars Science Laboratory (MSL) candidate landing sites and determines how thermophysical variations correspond to morphology and, when apparent, mineralogical diversity. At Eberswalde, the proportion of likely unconsolidated material relative to exposed bedrock or highly indurated surfaces controls the thermal inertia of a given region. At Gale, the majority of the landing site region has a moderate thermal inertia (250 to 410 J m-2 K-1 s-1/2), which is likely an indurated surface mixed with unconsolidated materials. The primary difference between higher and moderate thermal inertia surfaces may be due to the amount of mantling material present. Within the mound of stratified material in Gale, layers are distinguished in the thermal inertia data; the MSL rover could be traversing through materials that are both thermophysically and compositionally diverse. The majority of the Holden ellipse has a thermal inertia of 340 to 475 J m-2 K-1 s-1/2 and consists of bed forms with some consolidated material intermixed. Mawrth Vallis has a mean thermal inertia of 310 J m-2 K-1 s-1/2 and a wide variety of materials is present contributing to the moderate thermal inertia surfaces, including a mixture of bedrock, indurated surfaces, bed forms, and unconsolidated fines. Phyllosilicates have been identified at all four candidate landing sites, and these clay-bearing units typically have a similar thermal inertia value (400 to 500 J m-2 K-1 s-1/2), suggesting physical properties that are also similar.

  3. Surface elevation change artifact at the NEEM ice core drilling site, North Greenland.

    NASA Astrophysics Data System (ADS)

    Berg Larsen, Lars; Schøtt Hvidberg, Christine; Dahl-Jensen, Dorthe; Lilja Buchardt, Susanne

    2014-05-01

    The NEEM deep drilling site (77.45°N 51.06°W) is located at the main ice divide in North Greenland. For the ice core drilling project, a number of buildings was erected and left on the snow surface during the five-year project period. The structures created snowdrifts that formed accordingly to the predominant wind direction on the lee side on the buildings and the overwintering cargo. To get access to the buildings, the snowdrifts and the accumulated snow were removed and the surface in the camp was leveled with heavy machinery each summer. In the camp a GPS reference pole was placed as a part of the NEEM strain net, 12 poles placed in three diamonds at distances of 2,5 km, 7,5 km and 25 km they were all measured with high precision GPS every year. Around the reference pole, a 1 km x 1 km grid with a spacing of 100 m was measured with differential GPS each year. In this work, we present results from the GPS surface topography measurements in and around the campsite. The mapping of the topography in and around the campsite shows how the snowdrifts evolve and are the reason for the lift of the camp site area. The accumulated snowdrifts are compared to the dominant wind directions from year to year. The annual snow accumulation at the NEEM site is 0.60 m. The reference pole in the camp indicates an additional snow accumulation of 0.50 m per year caused by collected drifting snow. The surface topography mapping shows that this artificially elevated surface extends up to several kilometers out in the terrain. This could have possible implications on other glaciological and geophysical measurements in the area i.e. pit and snow accumulation studies.

  4. Surface sites on spinel-type and corundum-type metal oxide powders

    SciTech Connect

    Busca, G.; Lorenzelli, V.; Ramis, G. |; Willey, R.J.

    1993-06-01

    The surface sites on isostructural metal oxides containing Al{sup 3+}, Fe{sup 3+}, and Cr{sup 3+} have been investigated by IR spectroscopy. The IR spectra of surface hydroxy groups and of pyridine coordinated on Lewis acidic surface cationic sites on the defective spinel-type sesquioxides {gamma}-Al{sub 2}O{sub 3}, {theta}-Al{sub 2}O{sub 3}, and {gamma}-Fe{sub 2}O{sub 3}, on the spinels MgAl{sub 2}O{sub 4}, MgFe{sub 2}O{sub 4}, MgCr{sub 2}O{sub 4}, ZnAl{sub 2}O{sub 4}, ZnFe{sub 2}O{sub 4}, and ZnCr{sub 2}O{sub 4}, as well as on the corundum-type sesquioxides {alpha}-Al{sub 2}O{sub 3}, {alpha}-Fe{sub 2}O{sub 3}, and {alpha}-Cr{sub 2}O{sub 3}, have been compared. Some Co{sup 2+} and Ni{sup 2+} spinel-type compounds have also been considered. An extension of the criteria previously proposed for the identification of the surface sites on aluminum-based materials to ferrites and chromites is suggested. The OH stretchings of surface hydroxy groups are indicative of the nature and the coordination of the cations to which they are bonded. Pyridine species bonded to tetrahedrally- and octahedrally-coordinated trivalent cations are well distinguishable on aluminates, while the distiction is more difficult for ferrites. 41 refs., 9 figs., 3 tabs.

  5. Left Ventricle Segmentation Using Model Fitting and Active Surfaces

    PubMed Central

    Tay, Peter C.; Li, Bing; Garson, Chris D.; Acton, Scott T.; Hossack, John A.

    2010-01-01

    A method to perform 4D (3D over time) segmentation of the left ventricle of a mouse heart using a set of B mode cine slices acquired in vivo from a series of short axis scans is described. We incorporate previously suggested methods such as temporal propagation, the gradient vector flow active surface, superquadric models, etc. into our proposed 4D segmentation of the left ventricle. The contributions of this paper are incorporation of a novel despeckling method and the use of locally fitted superellipsoid models to provide a better initialization for the active surface segmentation algorithm. Average distances of the improved surface segmentation to a manually segmented surface throughout the entire cardiac cycle and cross-sectional contours are provided to demonstrate the improvements produced by the proposed 4D segmentation. PMID:20300558

  6. ChemCam passive reflectance spectroscopy of surface materials at the Curiosity landing site, Mars

    NASA Astrophysics Data System (ADS)

    Johnson, Jeffrey R.; Bell, J. F.; Bender, S.; Blaney, D.; Cloutis, E.; DeFlores, L.; Ehlmann, B.; Gasnault, O.; Gondet, B.; Kinch, K.; Lemmon, M.; Le Mouélic, S.; Maurice, S.; Rice, M.; Wiens, R. C.

    2015-03-01

    The spectrometers on the Mars Science Laboratory (MSL) ChemCam instrument were used in passive mode to record visible/near-infrared (400-840 nm) radiance from the martian surface. Using the onboard ChemCam calibration targets' housing as a reflectance standard, we developed methods to collect, calibrate, and reduce radiance observations to relative reflectance. Such measurements accurately reproduce the known reflectance spectra of other calibration targets on the rover, and represent the highest spatial resolution (0.65 mrad) and spectral sampling (<1 nm) visible/near-infrared reflectance spectra from a landed platform on Mars. Relative reflectance spectra of surface rocks and soils match those from orbital observations and multispectral data from the MSL Mastcam camera. Preliminary analyses of the band depths, spectral slopes, and reflectance ratios of the more than 2000 spectra taken during the first year of MSL operations demonstrate at least six spectral classes of materials distinguished by variations in ferrous and ferric components. Initial comparisons of ChemCam spectra to laboratory spectra of minerals and Mars analog materials demonstrate similarities with palagonitic soils and indications of orthopyroxene in some dark rocks. Magnesium-rich "raised ridges" tend to exhibit distinct near-infrared slopes. The ferric absorption downturn typically found for martian materials at <600 nm is greatly subdued in brushed rocks and drill tailings, consistent with their more ferrous nature. Calcium-sulfate veins exhibit the highest relative reflectances observed, but are still relatively red owing to the effects of residual dust. Such dust is overall less prominent on rocks sampled within the "blast zone" immediately surrounding the landing site. These samples were likely affected by the landing thrusters, which partially removed the ubiquitous dust coatings. Increased dust coatings on the calibration targets during the first year of the mission were documented by

  7. Sand Dune Ridge Alignment Effects on Surface BRF over Libya-4 Calibration Site

    NASA Astrophysics Data System (ADS)

    Govaerts, Yves

    2015-12-01

    The Libya-4 desert area, located in the Great Sand Sea, is one of the most important bright desert CEOS pseudo-invariant calibration sites by its size and radiometric stability. This site is intensively used for radiometer drift monitoring, sensor intercalibration and as an absolute calibration reference based on simulated radiances traceable to the SI standard. The Libya-4 morphology is composed of oriented sand dunes shaped by dominant winds. The effects of sand dune spatial organization on the surface bidirectional reflectance factor is analyzed in this paper using Raytran, a 3D radiative transfer model. The topography is characterized with the 30 m resolution ASTER digital elevation model. Four different regions-of-interest sizes, ranging from 10 km up to 100 km, are analyzed. Results show that sand dunes generate more backscattering than forward scattering at the surface. The mean surface reflectance averaged over different viewing and illumination angles is pretty much independent of the size of the selected area, though the standard deviation differs. Sun azimuth position has an effect on the surface reflectance field, which is more pronounced for high Sun zenith angles. Such 3D azimuthal effects should be taken into account to decrease the simulated radiance uncertainty over Libya-4 below 3% for wavelengths larger than 600 nm..

  8. Sand dune ridge alignment effects on surface BRF over the Libya-4 CEOS calibration site.

    PubMed

    Govaerts, Yves M

    2015-01-01

    The Libya-4 desert area, located in the Great Sand Sea, is one of the most important bright desert CEOS pseudo-invariant calibration sites by its size and radiometric stability. This site is intensively used for radiometer drift monitoring, sensor intercalibration and as an absolute calibration reference based on simulated radiances traceable to the SI standard. The Libya-4 morphology is composed of oriented sand dunes shaped by dominant winds. The effects of sand dune spatial organization on the surface bidirectional reflectance factor is analyzed in this paper using Raytran, a 3D radiative transfer model. The topography is characterized with the 30 m resolution ASTER digital elevation model. Four different regions-of-interest sizes, ranging from 10 km up to 100 km, are analyzed. Results show that sand dunes generate more backscattering than forward scattering at the surface. The mean surface reflectance averaged over different viewing and illumination angles is pretty much independent of the size of the selected area, though the standard deviation differs. Sun azimuth position has an effect on the surface reflectance field, which is more pronounced for high Sun zenith angles. Such 3D azimuthal effects should be taken into account to decrease the simulated radiance uncertainty over Libya-4 below 3% for wavelengths larger than 600 nm. PMID:25654721

  9. Sand Dune Ridge Alignment Effects on Surface BRF over the Libya-4 CEOS Calibration Site

    PubMed Central

    Govaerts, Yves M.

    2015-01-01

    The Libya-4 desert area, located in the Great Sand Sea, is one of the most important bright desert CEOS pseudo-invariant calibration sites by its size and radiometric stability. This site is intensively used for radiometer drift monitoring, sensor intercalibration and as an absolute calibration reference based on simulated radiances traceable to the SI standard. The Libya-4 morphology is composed of oriented sand dunes shaped by dominant winds. The effects of sand dune spatial organization on the surface bidirectional reflectance factor is analyzed in this paper using Raytran, a 3D radiative transfer model. The topography is characterized with the 30 m resolution ASTER digital elevation model. Four different regions-of-interest sizes, ranging from 10 km up to 100 km, are analyzed. Results show that sand dunes generate more backscattering than forward scattering at the surface. The mean surface reflectance averaged over different viewing and illumination angles is pretty much independent of the size of the selected area, though the standard deviation differs. Sun azimuth position has an effect on the surface reflectance field, which is more pronounced for high Sun zenith angles. Such 3D azimuthal effects should be taken into account to decrease the simulated radiance uncertainty over Libya-4 below 3% for wavelengths larger than 600 nm. PMID:25654721

  10. Robotics and Automation Activities at the Savannah River Site: A Site Report for SUBWOG 39F

    SciTech Connect

    Teese, G.D.

    1995-09-28

    The Savannah River Site has successfully used robots, teleoperators, and remote video to reduce exposure to ionizing radiation, improve worker safety, and improve the quality of operations. Previous reports have described the use of mobile teleoperators in coping with a high level liquid waste spill, the removal of highly contaminated equipment, and the inspection of nuclear reactor vessels. This report will cover recent applications at the Savannah River, as well as systems which SRS has delivered to other DOE site customers.

  11. Structural Characterization of Human 8-Oxoguanine DNA Glycosylase Variants Bearing Active Site Mutations

    SciTech Connect

    Radom,C.; Banerjee, A.; Verdine, G.

    2007-01-01

    The human 8-oxoguanine DNA glycosylase (hOGG1) protein is responsible for initiating base excision DNA repair of the endogenous mutagen 8-oxoguanine. Like nearly all DNA glycosylases, hOGG1 extrudes its substrate from the DNA helix and inserts it into an extrahelical enzyme active site pocket lined with residues that participate in lesion recognition and catalysis. Structural analysis has been performed on mutant versions of hOGG1 having changes in catalytic residues but not on variants having altered 7,8-dihydro-8-oxoguanine (oxoG) contact residues. Here we report high resolution structural analysis of such recognition variants. We found that Ala substitution at residues that contact the phosphate 5 to the lesion (H270A mutation) and its Watson-Crick face (Q315A mutation) simply removed key functionality from the contact interface but otherwise had no effect on structure. Ala substitution at the only residue making an oxoG-specific contact (G42A mutation) introduced torsional stress into the DNA contact surface of hOGG1, but this was overcome by local interactions within the folded protein, indicating that this oxoG recognition motif is 'hardwired'. Introduction of a side chain intended to sterically obstruct the active site pocket (Q315F mutation) led to two different structures, one of which (Q315F{sup *149}) has the oxoG lesion in an exosite flanking the active site and the other of which (Q315F{sup *292}) has the oxoG inserted nearly completely into the lesion recognition pocket. The latter structure offers a view of the latest stage in the base extrusion pathway yet observed, and its lack of catalytic activity demonstrates that the transition state for displacement of the lesion base is geometrically demanding.

  12. Establishment of bryophytes on a reclaimed surface mine site at Goose Lake Prairie State Park, Illinois

    SciTech Connect

    Rastorfer, J.R.

    1980-01-01

    The location of the site at Goose Lake Prairie State Park provided an impetus to revegetate the reclaimed acid minesoil as a demonstration site with prairie floristic species. Because many bryophytes are pioneer plants and because baseline data were needed, surveys were made (1976-1978) to ascertain the natural establishment of mosses and liverworts on the site. Different habitats were surveyed with respect to types of fine-textured mineral soils; namely, abandoned (cultivated) field soil, old minesoil (spoil), and two reclaimed minesoils distinguished by reclamation efforts initiated in 1972 to 1973 and 1975 to 1976. Thirty moss species and one liverwort species were identified from the entire site, and two additional moss species were found in areas adjacent to the site. The role of bryophytes in the development of prairie plant communities on reclaimed minesoil is still uncertain. However, existing research data provide support for the following hypotheses: (1) bryophytes should help reduce soil erosion by binding soil particles via their rhizoidal systems, and by the relatively high water-holding capacity of their gametophytic shoots; (2) bryophytes might reduce heavy-metal toxicity to certain vascular plants at soil surfaces, because they have an ability to accumulate these elements; and (3) bryophytes may enhance nitrogen fixation through their associations with blue-green algae and possibly with nitrogen-fixing bacteria.

  13. Improving surface-subsurface water budgeting for Brownfield study sites using high resolution satellite imagery

    NASA Astrophysics Data System (ADS)

    Dujardin, J.; Boel, S.; Anibas, C.; Batelaan, O.; Canters, F.

    2009-04-01

    Countries around the world have problems with contaminated brownfield sites as resulting from a relatively anarchic economical and industrial development during the 19th and 20th centuries. Since a few decades policy makers and stakeholders have become more aware of the risk posed by these sites because some of these sites present direct public hazards. Water is often the main vector of the mobility of contaminants. In order to propose remediation measures for the contaminated sites, it is required to describe and to quantify as accurately as possible the surface and subsurface water fluxes in the polluted site. In this research a modelling approach with integrated remote sensing analysis has been developed for accurately calculating water and contaminant fluxes on the polluted sites. Groundwater pollution in urban environments is linked to patterns of land use, so to identify the sources of contamination with great accuracy in urban environments it is essential to characterize the land cover in a detailed way. The use of high resolution spatial information is required because of the complexity of the urban land use. An object-oriented classification approach applied on high resolution satellite data has been adopted. Cluster separability analysis and visual interpretation of the image objects belonging to each cluster resulted in the selection of 8 land-cover categories (water, bare soil, meadow, mixed forest, grey urban surfaces, red roofs, bright roofs and shadow).To assign the image objects to one of the 8 selected classes a multiple layer perceptron (MLP) approach was adopted, using the NeuralWorks Predict software. After a post-classification shadow removal and a rule-based classification enhancement a kappa-value of 0.86 was obtained. Once the land cover was characterized, the groundwater recharge has been simulated using the spatially distributed WetSpass model and the subsurface water flow was simulated with GMS 6.0 in order to identify and budget the

  14. Geomorphic Surface Maps of Northern Frenchman Flat, Nevada Test Site, Southern Nevada

    SciTech Connect

    Bechtel Nevada

    2005-08-01

    Large-scale (1:6000) surficial geology maps of northern Frenchman Flat were developed in 1995 as part of comprehensive site characterization required to operate a low-level radioactive waste disposal facility in that area. Seven surficial geology maps provide fundamental data on natural processes and are the platform needed to reconstruct the Quaternary history of northern Frenchman Flat. Reconstruction of the Quaternary history provides an understanding of the natural processes that act to develop the landscape, and the time-frames involved in landscape development. The mapping was conducted using color and color-infrared aerial photographs and field verification of map unit composition and boundaries. Criteria for defining the map unit composition of geomorphic surface units are based on relative geomorphic position, landform morphology, and degree of preservation of surface morphology. Seven geomorphic surfaces (Units 1 through 7) are recognized, spanning from the early Quaternary to present time.

  15. Polymeric surfaces exhibiting photocatalytic activity and controlled anisotropic wettability

    NASA Astrophysics Data System (ADS)

    Anastasiadis, Spiros H.; Frysali, Melani A.; Papoutsakis, Lampros; Kenanakis, George; Stratakis, Emmanuel; Vamvakaki, Maria; Mountrichas, Grigoris; Pispas, Stergios

    2015-03-01

    In this work we focus on surfaces, which exhibit controlled, switchable wettability in response to one or more external stimuli as well as photocatalytic activity. For this we are inspired from nature to produce surfaces with a dual-scale hierarchical roughness and combine them with the appropriate inorganic and/or polymer coating. The combination of the hierarchical surface with a ZnO coating and a pH- or temperature-responsive polymer results in efficient photo-active properties as well as reversible superhydrophobic / superhydrophilic surfaces. Furthermore, we fabricate surfaces with unidirectional wettability variation. Overall, such complex surfaces require advanced design, combining hierarchically structured surfaces with suitable polymeric materials. Acknowledgment: This research was partially supported by the European Union (European Social Fund, ESF) and Greek national funds through the ``ARISTEIA II'' Action (SMART-SURF) of the Operational Programme ``Education and Lifelong Learning,'' NSRF 2007-2013, via the General Secretariat for Research & Technology, Ministry of Education and Religious Affairs, Greece.

  16. Multi-site evaluation of the JULES land surface model using global and local data

    NASA Astrophysics Data System (ADS)

    Slevin, D.; Tett, S. F. B.; Williams, M.

    2015-02-01

    This study evaluates the ability of the JULES land surface model (LSM) to simulate photosynthesis using local and global data sets at 12 FLUXNET sites. Model parameters include site-specific (local) values for each flux tower site and the default parameters used in the Hadley Centre Global Environmental Model (HadGEM) climate model. Firstly, gross primary productivity (GPP) estimates from driving JULES with data derived from local site measurements were compared to observations from the FLUXNET network. When using local data, the model is biased with total annual GPP underestimated by 16% across all sites compared to observations. Secondly, GPP estimates from driving JULES with data derived from global parameter and atmospheric reanalysis (on scales of 100 km or so) were compared to FLUXNET observations. It was found that model performance decreases further, with total annual GPP underestimated by 30% across all sites compared to observations. When JULES was driven using local parameters and global meteorological data, it was shown that global data could be used in place of FLUXNET data with a 7% reduction in total annual simulated GPP. Thirdly, the global meteorological data sets, WFDEI and PRINCETON, were compared to local data to find that the WFDEI data set more closely matches the local meteorological measurements (FLUXNET). Finally, the JULES phenology model was tested by comparing results from simulations using the default phenology model to those forced with the remote sensing product MODIS leaf area index (LAI). Forcing the model with daily satellite LAI results in only small improvements in predicted GPP at a small number of sites, compared to using the default phenology model.

  17. Improving upon Nature: Active site remodeling produces highly efficient aldolase activity towards hydrophobic electrophilic substrates

    PubMed Central

    Cheriyan, Manoj; Toone, Eric J.; Fierke, Carol A.

    2012-01-01

    Substrate specificity of enzymes is frequently narrow and constrained by multiple interactions, limiting the use of natural enzymes in biocatalytic applications. Aldolases have important synthetic applications, but the usefulness of these enzymes is hampered by their narrow reactivity profile with unnatural substrates. To explore the determinants of substrate selectivity and alter the specificity of E. coli 2-keto-3-deoxy-6-phosphogluconate (KDPG) aldolase, we employed structure-based mutagenesis coupled with library screening of mutant enzymes localized to the bacterial periplasm. We identified two active site mutations (T161S/S184L) that work additively to enhance the substrate specificity of this aldolase to include catalysis of retro-aldol cleavage of (4S)-2-keto-4-hydroxy-4-(2′-pyridyl)butyrate (S-KHPB). These mutations improve the value of kcat/KMS-KHPB by >450-fold, resulting in a catalytic efficiency that is comparable to that of the wild-type enzyme with the natural substrate while retaining high stereoselectivity. Moreover, the value of kcatS-KHPB for this mutant enzyme, a parameter critical for biocatalytic applications, is 3-fold higher than the maximum value achieved by the natural aldolase with any substrate. This mutant also possesses high catalytic efficiency for the retro-aldol cleavage of the natural substrate, KDPG, and a >50-fold improved activity for cleavage of 2-keto-4-hydroxy-octonoate (KHO), a non-functionalized hydrophobic analog. These data suggest a substrate binding mode that illuminates the origin of facial selectivity in aldol addition reactions catalyzed by KDPG and 2-keto-3-deoxy-6-phosphogalactonate (KDPGal) aldolases. Furthermore, targeting mutations to the active site provides marked improvement in substrate selectivity, demonstrating that structure-guided active site mutagenesis combined with selection techniques can efficiently identify proteins with characteristics that compare favorably to naturally occurring enzymes. PMID

  18. Car-Parrinello study of Ziegler-Natta heterogeneous catalysis: stability and destabilization problems of the active site models

    NASA Astrophysics Data System (ADS)

    Boero, Mauro; Parrinello, Michele; Terakura, Kiyoyuki; Weiss, Horst

    Recent results on Car-Parrinello simulations of MgCl 2 /TiCl 4 Ziegler-Natta heterogeneous catalytic systems are reviewed and the stability of Ti active site configurations on the various active surfaces are discussed. In particular, the focus is on the ability of an active centre to carry out the polymerization process efficiently, achieved by monitoring geometrical changes and associated energetics during the reaction. The active site geometry is crucial in enhancing or decreasing the activation barrier, in selecting the olefin enantioface and in some cases in destabilizing the catalytic centre. A key point in the binding/destabilization interplay is the matching of Ti with the substrate, an issue that represents a fundamental difference with respect to homogeneous systems.

  19. Control surface spanwise placement in active flutter suppression systems

    NASA Technical Reports Server (NTRS)

    Nissim, E.; Burken, John J.

    1988-01-01

    A method is developed that determines the placement of an active control surface for maximum effectiveness in suppressing flutter. No specific control law is required by this method which is based on the aerodynamic energy concept. It is argued that the spanwise placement of the active controls should coincide with the locations where maximum energy per unit span is fed into the system. The method enables one to determine the distribution, over the different surfaces of the aircraft, of the energy input into the system as a result of the unstable fluttering mode. The method is illustrated using three numerical examples.

  20. Uncertainty analysis of the Operational Simplified Surface Energy Balance (SSEBop) model at multiple flux tower sites

    NASA Astrophysics Data System (ADS)

    Chen, Mingshi; Senay, Gabriel B.; Singh, Ramesh K.; Verdin, James P.

    2016-05-01

    Evapotranspiration (ET) is an important component of the water cycle - ET from the land surface returns approximately 60% of the global precipitation back to the atmosphere. ET also plays an important role in energy transport among the biosphere, atmosphere, and hydrosphere. Current regional to global and daily to annual ET estimation relies mainly on surface energy balance (SEB) ET models or statistical and empirical methods driven by remote sensing data and various climatological databases. These models have uncertainties due to inevitable input errors, poorly defined parameters, and inadequate model structures. The eddy covariance measurements on water, energy, and carbon fluxes at the AmeriFlux tower sites provide an opportunity to assess the ET modeling uncertainties. In this study, we focused on uncertainty analysis of the Operational Simplified Surface Energy Balance (SSEBop) model for ET estimation at multiple AmeriFlux tower sites with diverse land cover characteristics and climatic conditions. The 8-day composite 1-km MODerate resolution Imaging Spectroradiometer (MODIS) land surface temperature (LST) was used as input land surface temperature for the SSEBop algorithms. The other input data were taken from the AmeriFlux database. Results of statistical analysis indicated that the SSEBop model performed well in estimating ET with an R2 of 0.86 between estimated ET and eddy covariance measurements at 42 AmeriFlux tower sites during 2001-2007. It was encouraging to see that the best performance was observed for croplands, where R2 was 0.92 with a root mean square error of 13 mm/month. The uncertainties or random errors from input variables and parameters of the SSEBop model led to monthly ET estimates with relative errors less than 20% across multiple flux tower sites distributed across different biomes. This uncertainty of the SSEBop model lies within the error range of other SEB models, suggesting systematic error or bias of the SSEBop model is within the

  1. THE MECHANISM OF SURFACE DIFFUSION OF H AND D ATOMS ON AMORPHOUS SOLID WATER: EXISTENCE OF VARIOUS POTENTIAL SITES

    SciTech Connect

    Hama, Tetsuya; Kuwahata, Kazuaki; Watanabe, Naoki; Kouchi, Akira; Chigai, Takeshi; Kimura, Yuki; Pirronello, Valerio

    2012-10-01

    To understand elementary processes leading to H{sub 2} formation, and the hydrogenation and deuteration reactions of adsorbed species on dust grains in dense clouds, we experimentally investigated the diffusion of atomic hydrogen and deuterium on amorphous solid water (ASW) at temperatures of 8-15 K. The present study extended our previous study for selective detections of H and D atoms, and of H{sub 2} (J = 0 and 1) and D{sub 2} (J = 0 and 1) molecules adsorbed on ASW using both photo-stimulated desorption and resonance-enhanced multiphoton ionization, to investigate potential sites on ASW for diffusion, recombination dynamics, and the diffusion mechanism of H and D atoms. Our results demonstrate that the ASW surface contains various potential sites that can be categorized into at least three groups: very shallow, middle-, and deep-potential sites, with diffusion activation energies of {<=}18, 22 (23 meV for D atoms), and {>=}30 meV, respectively. The present study pictured the outline of H{sub 2} formation on cosmic ice dust at low temperatures: H atoms landing on the dust will diffuse rapidly at the abundant shallow and middle sites on ASW, and finally become trapped at deep sites. The H atoms that arrive next recombine with such trapped H atoms to yield H{sub 2} molecules. The small isotopic difference between the diffusion of H and D atoms on ASW indicates that the diffusion mechanism can be explained by thermal hopping, at least at middle-potential sites.

  2. Atomically-thin two-dimensional sheets for understanding active sites in catalysis.

    PubMed

    Sun, Yongfu; Gao, Shan; Lei, Fengcai; Xie, Yi

    2015-02-01

    Catalysis can speed up chemical reactions and it usually occurs on the low coordinated steps, edges, terraces, kinks and corner atoms that are often called "active sites". However, the atomic level interplay between active sites and catalytic activity is still an open question, owing to the large difference between idealized models and real catalysts. This stimulates us to pursue a suitable material model for studying the active sites-catalytic activity relationship, in which the atomically-thin two-dimensional sheets could serve as an ideal model, owing to their relatively simple type of active site and the ultrahigh fraction of active sites that are comparable to the overall atoms. In this tutorial review, we focus on the recent progress in disclosing the factors that affect the activity of reactive sites, including characterization of atomic coordination number, structural defects and disorder in ultrathin two-dimensional sheets by X-ray absorption fine structure spectroscopy, positron annihilation spectroscopy, electron spin resonance and high resolution transmission electron microscopy. Also, we overview their applications in CO catalytic oxidation, photocatalytic water splitting, electrocatalytic oxygen and hydrogen evolution reactions, and hence highlight the atomic level interplay among coordination number, structural defects/disorder, active sites and catalytic activity in the two-dimensional sheets with atomic thickness. Finally, we also present the major challenges and opportunities regarding the role of active sites in catalysis. We believe that this review provides critical insights for understanding the catalysis and hence helps to develop new catalysts with high catalytic activity. PMID:25382246

  3. (100) facets of γ-Al2O3: the active surfaces for alcohol dehydration reactions

    SciTech Connect

    Kwak, Ja Hun; Mei, Donghai; Peden, Charles HF; Rousseau, Roger J.; Szanyi, Janos

    2011-05-01

    Temperature programmed desorption (TPD) of ethanol, and methanol dehydration reaction were studied on γ-Al2O3 in order to identify the catalytic active sites for alcohol dehydration reactions. Two high temperature (> 473 K) desorption features were observed following ethanol adsorption. Samples calcined at T≤473 K displayed a desorption feature in the 523-533 K temperature range, while those calcined at T ≥ 673 K showed a single desorption feature at 498 K. The switch from the high to low temperature ethanol desorption correlated well with the dehydroxylation of the (100) facets of γ-Al2O3 that was predicted at 550 K DFT calculations. Theoretical DFT simulations of the mechanism of dehydration. on clean and hydroxylated γ-Al2O3(100) surfaces, find that a concerted elimination of ethylene from an ethanol molecule chemisorbed at an Al3+ pentacoordinated site is the rate limiting step for catalytic cycle on both surfaces. Furthermore, titration of the pentacoordinate Al3+ sites on the (100) facets of γ-Al2O3 by BaO completely turned off the methanol dehydration reaction activity. These results unambiguously demonstrate that only the (100) facets on γ-Al2O3 are the catalytic active surfaces for alcohol dehydration.

  4. Screening breeding sites of the common toad (Bufo bufo) in England and Wales for evidence of endocrine disrupting activity.

    PubMed

    Pickford, Daniel B; Jones, Alexandra; Velez-Pelez, Alejandra; Orton, Frances; Iguchi, Taisen; Mitsui, Naoko; Tooi, Osamu

    2015-07-01

    Anuran amphibians are often present in agricultural landscapes and may therefore be exposed to chemicals in surface waters used for breeding. We used passive accumulation devices (SPMD and POCIS) to sample contaminants from nine breeding sites of the Common toad (Bufo bufo) across England and Wales, measuring endocrine activity of the extracts in a recombinant yeast androgen screen (YAS) and yeast estrogen screen (YES) and an in vitro vitellogenin induction screen in primary culture of Xenopus laevis hepatocytes. We also assessed hatching, growth, survival, and development in caged larvae in situ, and sampled metamorphs for gonadal histopathology. None of the SPMD extracts exhibited estrogen receptor or androgen receptor agonist activity, while POCIS extracts from two sites in west-central England exhibited concentration-dependent androgenic activity in the YAS. Three sites exhibited significant estrogenic activity in both the YES and the Xenopus hepatocyte. Hatching rates varied widely among sites, but there was no consistent correlation between hatching rate and intensity of agricultural activity, predicted concentrations of agrochemicals, or endocrine activity measured in YES/YAS assays. While a small number of intersex individuals were observed, their incidence could not be associated with predicted pesticide exposure or endocrine activitity measured in the in vitro screens. There were no significant differences in sex ratio, as determined by gonadal histomorphology among the study sites, and no significant correlation was observed between proportion of males and predicted exposure to agrochemicals. However, a negative correlation did become apparent in later sampling periods between proportion of males and estrogenic activity of the POCIS sample, as measured in the YES. Our results suggest that larval and adult amphibians may be exposed to endocrine disrupting chemicals in breeding ponds, albeit at low concentrations, and that chemical contaminants other than

  5. Catalytic surface radical in dye-decolorizing peroxidase: a computational, spectroscopic and site-directed mutagenesis study

    PubMed Central

    Linde, Dolores; Pogni, Rebecca; Cañellas, Marina; Lucas, Fátima; Guallar, Victor; Baratto, Maria Camilla; Sinicropi, Adalgisa; Sáez-Jiménez, Verónica; Coscolín, Cristina; Romero, Antonio; Medrano, Francisco Javier; Ruiz-Dueñas, Francisco J.; Martínez, Angel T.

    2014-01-01

    Dye-decolorizing peroxidase (DyP) of Auricularia auricula-judae has been expressed in Escherichia coli as a representative of a new DyP family, and subjected to mutagenic, spectroscopic, crystallographic and computational studies. The crystal structure of DyP shows a buried haem cofactor, and surface tryptophan and tyrosine residues potentially involved in long-range electron transfer from bulky dyes. Simulations using PELE (Protein Energy Landscape Exploration) software provided several binding-energy optima for the anthraquinone-type RB19 (Reactive Blue 19) near the above aromatic residues and the haem access-channel. Subsequent QM/MM (quantum mechanics/molecular mechanics) calculations showed a higher tendency of Trp-377 than other exposed haem-neighbouring residues to harbour a catalytic protein radical, and identified the electron-transfer pathway. The existence of such a radical in H2O2-activated DyP was shown by low-temperature EPR, being identified as a mixed tryptophanyl/tyrosyl radical in multifrequency experiments. The signal was dominated by the Trp-377 neutral radical contribution, which disappeared in the W377S variant, and included a tyrosyl contribution assigned to Tyr-337 after analysing the W377S spectra. Kinetics of substrate oxidation by DyP suggests the existence of high- and low-turnover sites. The high-turnover site for oxidation of RB19 (kcat> 200 s−1) and other DyP substrates was assigned to Trp-377 since it was absent from the W377S variant. The low-turnover site/s (RB19 kcat ~20 s−1) could correspond to the haem access-channel, since activity was decreased when the haem channel was occluded by the G169L mutation. If a tyrosine residue is also involved, it will be different from Tyr-337 since all activities are largely unaffected in the Y337S variant. PMID:25495127

  6. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    NASA Astrophysics Data System (ADS)

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  7. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    PubMed Central

    Holby, Edward F.; Taylor, Christopher D.

    2015-01-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date. PMID:25788358

  8. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: role of *OH ligands.

    PubMed

    Holby, Edward F; Taylor, Christopher D

    2015-01-01

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O2 bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H2O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date. PMID:25788358

  9. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    DOE PAGESBeta

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore » structures have the highest calculated activity to date.« less

  10. Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

    SciTech Connect

    Holby, Edward F.; Taylor, Christopher D.

    2015-03-19

    We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH bound structures have the highest calculated activity to date.

  11. Integrated Cropland and Grassland Flux Tower Observation Sites over Grazinglands for Quantifying Surface-Atmosphere Exchange

    NASA Astrophysics Data System (ADS)

    Mahan, H. R.; Wagle, P.; Bajgain, R.; Zhou, Y.; Basara, J. B.; Xiao, X.; Duckles, J. M.; Steiner, J. L.; Starks, P. J.; Northup, B. K.

    2014-12-01

    Quantifying methane (CH4), carbon dioxide (CO2), and water vapor fluxes between land surface and boundary layer using the eddy covariance method have many applicable uses across several disciplines. Three eddy flux towers have been established over no-till winter wheat (Triticum aestivum L.), and native and improved pastures at the USDA ARS Grazinglands Research Laboratory, El Reno, OK. An additional tower will be established in fall 2014 over till winter wheat. Each flux site is equipped with an eddy covariance system, PhenoCam, COSMOS, and in-situ observations of soil and atmospheric state variables. The objective of this research is to measure, compare, and model the land-atmosphere exchange of CO2, water vapor, and CH4 in different land cover types and management practices (till vs no-till, grazing vs no-grazing, native vs improved pasture). Models that focus on net ecosystem CO2 exchange (NEE), gross primary production (GPP), evapotranspiration (ET), and CH4 fluxes can be improved by the cross verification of these measurements. Another application will be to link the in-situ measurements with satellite remote sensing in order to scale-up flux measurements from small spatial scales to local and regional scales. Preliminary data analysis from the native grassland site revealed that CH4 concentration was negligible (~ 0), and it increased significantly when cattle were introduced into the site. In summer 2014, daily ET magnitude was about 4-5 mm day-1 and the NEE magnitude was 4-5 g C day-1 at the native grassland site. Further analysis of data for all the sites for longer temporal periods will enhance understanding of biotic and abiotic factors that govern carbon, water, and energy exchanges between the land surface and atmosphere under different land cover and management systems. The research findings will help predict the responses of these ecosystems to management practices and global environmental change in the future.

  12. Multi-site evaluation of the JULES land surface model using global and local data

    NASA Astrophysics Data System (ADS)

    Slevin, D.; Tett, S. F. B.; Williams, M.

    2014-08-01

    Changes in atmospheric carbon dioxide and water vapour change the energy balance of the atmosphere and thus climate. One important influence on these greenhouse gases is the land surface. Land Surface Models (LSMs) represent the interaction between the atmosphere and terrestrial biosphere in Global Climate Models (GCMs). As LSMs become more advanced, there is a need to test their accuracy. Uncertainty from LSMs contributes towards uncertainty in carbon cycle simulations and thus uncertainty in future climate change. In this study, we evaluate the ability of the JULES LSM to simulate photosynthesis using local and global datasets at 12 FLUXNET sites. Model parameters include site-specific (local) values for each flux tower site and the default parameters used in the Hadley Centre Global Environmental Model (HadGEM) climate model. Firstly, we compare Gross Primary Productivity (GPP) estimates from driving JULES with data derived from local site measurements with driving JULES with data derived from global parameter and atmospheric reanalysis (on scales of 100 km or so). We find that when using local data, a negative bias is introduced into model simulations with yearly GPP underestimated by 16% on average compared to observations while when using global data, model performance decreases further with yearly GPP underestimated by 30% on average. Secondly, we drive the model using global meteorological data and local parameters and find that global data can be used in place of FLUXNET data with only a 7% reduction in total annual simulated GPP. Thirdly, we compare the global meteorological datasets, WFDEI and PRINCETON, to local data and find that the WATCH dataset more closely matches the local meteorological measurements (FLUXNET). Finally, we compare the results from forcing JULES with the remote sensing product MODIS Leaf Area Index (LAI). JULES was modified to accept MODIS LAI at daily timesteps. We show that forcing the model with daily satellite LAI results in

  13. Screening Mixtures of Small Molecules for Binding to Multiple Sites on the Surface Tetanus Toxin C Fragment by Bioaffinity NMR

    SciTech Connect

    Cosman, M; Zeller, L; Lightstone, F C; Krishnan, V V; Balhorn, R

    2002-01-01

    The clostridial neurotoxins include the closely related tetanus (TeNT) and botulinum (BoNT) toxins. Botulinum toxin is used to treat severe muscle disorders and as a cosmetic wrinkle reducer. Large quantities of botulinum toxin have also been produced by terrorists for use as a biological weapon. Because there are no known antidotes for these toxins, they thus pose a potential threat to human health whether by an accidental overdose or by a hostile deployment. Thus, the discovery of high specificity and affinity compounds that can inhibit their binding to neural cells can be used as antidotes or in the design of chemical detectors. Using the crystal structure of the C fragment of the tetanus toxin (TetC), which is the cell recognition and cell surface binding domain, and the computational program DOCK, sets of small molecules have been predicted to bind to two different sites located on the surface of this protein. While Site-1 is common to the TeNT and BoNTs, Site-2 is unique to TeNT. Pairs of these molecules from each site can then be linked together synthetically to thereby increase the specificity and affinity for this toxin. Electrospray ionization mass spectroscopy was used to experimentally screen each compound for binding. Mixtures containing binders were further screened for activity under biologically relevant conditions using nuclear magnetic resonance (NMR) methods. The screening of mixtures of compounds offers increased efficiency and throughput as compared to testing single compounds and can also evaluate how possible structural changes induced by the binding of one ligand can influence the binding of the second ligand. In addition, competitive binding experiments with mixtures containing ligands predicted to bind the same site could identify the best binder for that site. NMR transfer nuclear Overhauser effect (trNOE) confirm that TetC binds doxorubicin but that this molecule is displaced by N-acetylneuraminic acid (sialic acid) in a mixture that

  14. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface.

    PubMed

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, Lindsay R; Lammich, Lutz; Besenbacher, Flemming; Mavrikakis, Manos; Wendt, Stefan

    2015-08-25

    Within the area of surface science, one of the "holy grails" is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFT+U calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically. PMID:26027877

  15. Direct Visualization of Catalytically Active Sites at the FeO-Pt(111) Interface

    SciTech Connect

    Kudernatsch, Wilhelmine; Peng, Guowen; Zeuthen, Helene; Bai, Yunhai; Merte, L. R.; Lammich, Lutz; Besenbacher, Fleming; Mavrikakis, Manos; Wendt, Stefen

    2015-08-25

    Within the area of surface science, one of the “holy grails” is to directly visualize a chemical reaction at the atomic scale. Whereas this goal has been reached by high-resolution scanning tunneling microscopy (STM) in a number of cases for reactions occurring at flat surfaces, such a direct view is often inhibited for reaction occurring at steps and interfaces. Here we have studied the CO oxidation reaction at the interface between ultrathin FeO islands and a Pt(111) support by in situ STM and density functional theory (DFT) calculations. Time-lapsed STM imaging on this inverse model catalyst in O2 and CO environments revealed catalytic activity occurring at the FeO-Pt(111) interface and directly showed that the Fe-edges host the catalytically most active sites for the CO oxidation reaction. This is an important result since previous evidence for the catalytic activity of the FeO-Pt(111) interface is essentially based on averaging techniques in conjunction with DFT calculations. The presented STM results are in accord with DFTþU calculations, in which we compare possible CO oxidation pathways on oxidized Fe-edges and O-edges. We found that the CO oxidation reaction is more favorable on the oxidized Fe-edges, both thermodynamically and kinetically.

  16. Fluoride adsorption on goethite in relation to different types of surface sites

    SciTech Connect

    Hiemstra, T.; Van Riemsdijk, W.H.

    2000-05-01

    Metal (hydr)oxides have different types of surface groups. Fluoride ions have been used as a probe to assess the number of surface sites. The authors have studied the F{sup {minus}} adsorption on goethite by measuring the F{sup {minus}} and H{sup +} interaction and F{sup {minus}} adsorption isotherms. Fluoride ions exchange against singly coordinated surface hydroxyls at low F{sup {minus}} concentrations. At higher concentrations also the doubly coordinated OH groups are involved. The replacement of a surface OH{sup {minus}} by F{sup {minus}} suggests that all F charge ({minus}1) is located at the surface in contrast to oxyanions which have a charge distribution in the interface due to the binding structure in which the anion only partially coordinates with the surface. Analysis of their F{sup {minus}} data with the CD-MUSIC approach shows that the formation of the fluoride surface complex is accompanied by a redistribution of charge. This is supposed to be due to a net switch in the H bonding as a result of the change of the type of surface complex from donating (FeOH, FeOH{sub 2}) to proton accepting (FeF). The modeled redistribution of charge is approximately equivalent with the change of a donating H bond into an accepting H bond. At high F{sup {minus}} concentrations precipitation of F{sup {minus}}, as for instance FeF{sub 3}(s), may occur. The rate of formation is catalyzed by the presence of high electrolyte concentrations.

  17. Identification of promiscuous ene-reductase activity by mining structural databases using active site constellations

    PubMed Central

    Steinkellner, Georg; Gruber, Christian C.; Pavkov-Keller, Tea; Binter, Alexandra; Steiner, Kerstin; Winkler, Christoph; Łyskowski, Andrzej; Schwamberger, Orsolya; Oberer, Monika; Schwab, Helmut; Faber, Kurt; Macheroux, Peter; Gruber, Karl

    2014-01-01

    The exploitation of catalytic promiscuity and the application of de novo design have recently opened the access to novel, non-natural enzymatic activities. Here we describe a structural bioinformatic method for predicting catalytic activities of enzymes based on three-dimensional constellations of functional groups in active sites (‘catalophores’). As a proof-of-concept we identify two enzymes with predicted promiscuous ene-reductase activity (reduction of activated C–C double bonds) and compare them with known ene-reductases, that is, members of the Old Yellow Enzyme family. Despite completely different amino acid sequences, overall structures and protein folds, high-resolution crystal structures reveal equivalent binding modes of typical Old Yellow Enzyme substrates and ligands. Biochemical and biocatalytic data show that the two enzymes indeed possess ene-reductase activity and reveal an inverted stereopreference compared with Old Yellow Enzymes for some substrates. This method could thus be a tool for the identification of viable starting points for the development and engineering of novel biocatalysts. PMID:24954722

  18. The influence of small-mammal burrowing activity on water storage at the Hanford Site

    SciTech Connect

    Landeen, D.S.

    1994-12-31

    This paper summarizes the activities that were conducted in support of the long-term surface barrier development program by Westinghouse Hanford Company to determine the degree that small-mammal burrow systems affect the loss or retention of water in the soils at the Hanford Site in Washington state. An animal intrusion lysimeter facility was constructed, consisting of two outer boxes buried at grade, which served as receptacles for six animal intrusion lysimeters. Small burrowing animals common the Hanford Site were introduced over a 3- to 4-month period. Supplemental precipitation was added monthly to three of the lysimeters with a rainfall simulator (rainulator). Information collected from the five tests indicated that (1) during summer months, water was lost in all the lysimeters, including the supplemental precipitation added with the rainulator; and (2) during winter months, all lysimeters gained water. The data indicate little difference in the amount of water stored between control and animal lysimeters. The overall water loss was attributed to surface evaporation, a process that occurred equally in control and treatment lysimeters. Other causes of water loss are a result of (1) constant soil turnover and subsequent drying, and (2) burrow ventilation effects. This suggests that burrow systems will not contribute to any significant water storage at depth and, in fact, may enhance the removal of water from the soil.

  19. Remaining Sites Verification Package for the 100-B-1 Surface Chemical and Solid Waste Dumping Area, Waste Site Reclassification Form 2006-003

    SciTech Connect

    R. A. Carlson

    2006-04-24

    The 100-B-1 waste site was a dumping site that was divided into two areas. One area was used as a laydown area for construction materials, and the other area was used as a chemical dumping area. The 100-B-1 Surface Chemical and Solid Waste Dumping Area site meets the remedial action objectives specified in the Remaining Sites ROD. The results demonstrate that residual contaminant concentrations support future unrestricted land uses that can be represented by a rural-residential scenario. The results also demonstrate that residual contaminant concentrations are protective of groundwater and the Columbia River.

  20. TRITIUM UNCERTAINTY ANALYSIS FOR SURFACE WATER SAMPLES AT THE SAVANNAH RIVER SITE

    SciTech Connect

    Atkinson, R.

    2012-07-31

    Radiochemical analyses of surface water samples, in the framework of Environmental Monitoring, have associated uncertainties for the radioisotopic results reported. These uncertainty analyses pertain to the tritium results from surface water samples collected at five locations on the Savannah River near the U.S. Department of Energy's Savannah River Site (SRS). Uncertainties can result from the field-sampling routine, can be incurred during transport due to the physical properties of the sample, from equipment limitations, and from the measurement instrumentation used. The uncertainty reported by the SRS in their Annual Site Environmental Report currently considers only the counting uncertainty in the measurements, which is the standard reporting protocol for radioanalytical chemistry results. The focus of this work is to provide an overview of all uncertainty components associated with SRS tritium measurements, estimate the total uncertainty according to ISO 17025, and to propose additional experiments to verify some of the estimated uncertainties. The main uncertainty components discovered and investigated in this paper are tritium absorption or desorption in the sample container, HTO/H{sub 2}O isotopic effect during distillation, pipette volume, and tritium standard uncertainty. The goal is to quantify these uncertainties and to establish a combined uncertainty in order to increase the scientific depth of the SRS Annual Site Environmental Report.

  1. Predicting Ligand Binding Sites on Protein Surfaces by 3-Dimensional Probability Density Distributions of Interacting Atoms

    PubMed Central

    Jian, Jhih-Wei; Elumalai, Pavadai; Pitti, Thejkiran; Wu, Chih Yuan; Tsai, Keng-Chang; Chang, Jeng-Yih; Peng, Hung-Pin; Yang, An-Suei

    2016-01-01

    Predicting ligand binding sites (LBSs) on protein structures, which are obtained either from experimental or computational methods, is a useful first step in functional annotation or structure-based drug design for the protein structures. In this work, the structure-based machine learning algorithm ISMBLab-LIG was developed to predict LBSs on protein surfaces with input attributes derived from the three-dimensional probability density maps of interacting atoms, which were reconstructed on the query protein surfaces and were relatively insensitive to local conformational variations of the tentative ligand binding sites. The prediction accuracy of the ISMBLab-LIG predictors is comparable to that of the best LBS predictors benchmarked on several well-established testing datasets. More importantly, the ISMBLab-LIG algorithm has substantial tolerance to the prediction uncertainties of computationally derived protein structure models. As such, the method is particularly useful for predicting LBSs not only on experimental protein structures without known LBS templates in the database but also on computationally predicted model protein structures with structural uncertainties in the tentative ligand binding sites. PMID:27513851

  2. Final Clean Closure Report Site 300 Surface Impoundments Closure Lawrence Livermore National Laboratory Livermore, California

    SciTech Connect

    Haskell, K

    2006-02-14

    Lawrence Livermore National Laboratory operated two Class II surface impoundments that stored wastewater that was discharged from a number of buildings located on the Site 300 Facility (Site 300). The wastewater was the by-product of explosives processing. Reduction in the volume of water discharged from these buildings over the past several years significantly reduced the wastewater storage needs. In addition, the impoundments were constructed in 1984, and the high-density polyethylene (HDPE) geomembrane liners were nearing the end of their service life. The purpose of this project was to clean close the surface impoundments and provide new wastewater storage using above ground storage tanks at six locations. The tanks were installed and put into service prior to closure of the impoundments. This Clean Closure Report (Closure Report) complies with State Water Resources Control Board (SWRCB) Section 21400 of the California Code of Regulations Title 27 (27 CCR section 21400). As required by these regulations and guidance, this Closure Report provides the following information: (1) a brief site description; (2) the regulatory requirements relevant to clean closure of the impoundments; (3) the closure procedures; and (4) the findings and documentation of clean closure.

  3. Adsorption of naphthenic acids on high surface area activated carbons.

    PubMed

    Iranmanesh, Sobhan; Harding, Thomas; Abedi, Jalal; Seyedeyn-Azad, Fakhry; Layzell, David B

    2014-01-01

    In oil sands mining extraction, water is an essential component; however, the processed water becomes contaminated through contact with the bitumen at high temperature, and a portion of it cannot be recycled and ends up in tailing ponds. The removal of naphthenic acids (NAs) from tailing pond water is crucial, as they are corrosive and toxic and provide a substrate for microbial activity that can give rise to methane, which is a potent greenhouse gas. In this study, the conversion of sawdust into an activated carbon (AC) that could be used to remove NAs from tailings water was studied. After producing biochar from sawdust by a slow-pyrolysis process, the biochar was physically activated using carbon dioxide (CO2) over a range of temperatures or prior to producing biochar, and the sawdust was chemically activated using phosphoric acid (H3PO4). The physically activated carbon had a lower surface area per gram than the chemically activated carbon. The physically produced ACs had a lower surface area per gram than chemically produced AC. In the adsorption tests with NAs, up to 35 mg of NAs was removed from the water per gram of AC. The chemically treated ACs showed better uptake, which can be attributed to its higher surface area and increased mesopore size when compared with the physically treated AC. Both the chemically produced and physically produced AC provided better uptake than the commercially AC. PMID:24766592

  4. Evaluation of Cavity Collapse and Surface Crater Formation at the Salut Underground Nuclear Test in U20ak, Nevada National Security Site, and the Impact of Stability of the Ground Surface

    SciTech Connect

    Pawloski, G A

    2012-04-25

    At the request of Jerry Sweeney, the LLNL Containment Program performed a review of nuclear test-related data for the Salut underground nuclear test in U20ak to assist in evaluating this legacy site as a test bed for application technologies for use in On-Site Inspections (OSI) under the Comprehensive Nuclear Test Ban Treaty. Review of the Salut site is complicated because the test experienced a subsurface, rather than surface, collapse. Of particular interest is the stability of the ground surface above the Salut detonation point. Proposed methods for on-site verification include radiological signatures, artifacts from nuclear testing activities, and imaging to identify alteration to the subsurface hydrogeologogy due to the nuclear detonation. Sweeney's proposal requires physical access at or near the ground surface of specific underground nuclear test locations at the Nevada Nuclear Test Site (NNSS, formerly the Nevada Test Site), and focuses on possible activities such as visual observation, multispectral measurements, and shallow, and deep geophysical surveys.

  5. Titan's surface spectra at the Huygens landing site and Shangri-La

    NASA Astrophysics Data System (ADS)

    Rannou, P.; Toledo, D.; Lavvas, P.; D'Aversa, E.; Moriconi, M. L.; Adriani, A.; Le Mouélic, S.; Sotin, C.; Brown, R.

    2016-05-01

    Titan is an icy satellite of Saturn with a dense atmosphere and covered by a global photochemical organic haze. Ground based observations and the Huygens descent probe allowed to retrieve the main spectral signature of the water ice (Griffith, C.A. et al. [2003]. Science 300(5619), 628-630; Coustenis, A. et al. [2005]. Icarus 177, 89-105) at the surface, possibly covered by a layer of sedimented organic material (Tomasko, M.G. et al. [2005]. Nature 438(7069), 765-778). However, the spectrum of the surface is not yet understood. In this study, we find that the surface reflectivity at the Huygens Landing Site (HLS) is well modeled by a layer of water ice grains overlaid by a moist layer of weakly compacted photochemical aggregated aerosols. Moist soils have spectra shifted toward short wavelengths relatively to spectra of dry soils. Cassini observations of Shangri-La region from orbit also show a very dark surface with a reflectivity peak shifted toward short wavelengths in respect to the reflectivity peak of bright surfaces, revealing a dichotomy between terrains based to their spectra in visible.

  6. Studies on contact activation: effects of surface and inhibitors.

    PubMed

    Cameron, C L; Fisslthaler, B; Sherman, A; Reddigari, S; Silverberg, M

    1989-01-01

    Contact activation is initiated when the plasma proteins, Hageman factor (factor XII), prekallikrein and high molecular weight kininogen interact with negatively charged materials. The activation of the intrinsic pathway of blood coagulation and the production of bradykinin are among the sequelae of contact activation. The kinetics of the activation of the contact system are modified by plasma inhibitors, C1 inhibitor being quantitatively the most important. We propose that the activation of the system requires that the stimulus provided by the surface must be greater than a threshold value to overcome the effects of the inhibitors. We show in this paper that the amount of surface required for activation is much reduced in the absence of C1 inhibitor (Hereditary Angioedema) or in the cold where the inhibitor loses much of its effectiveness. Antithrombin III inhibition of activated Hageman factor is augmented by heparin which is also an activator of Hageman factor. The rate constants for inhibition remain much lower than for C1 inhibitor, however. PMID:2530427

  7. Active Flow Control Strategies Using Surface Pressure Measurements

    NASA Technical Reports Server (NTRS)

    Kumar, Vikas; Alvi, Farrukh S.

    2010-01-01

    Evaluate the efficacy of Microjets Can we eliminate/minimize flow separation? Is the flow unsteadiness reduced? Guidelines for an active control Search for an appropriate sensor. Examine for means to develop a flow model for identifying the state of flow over the surface Guidelines toward future development of a Simple and Robust control methodology

  8. Geomagnetic activity and polar surface air temperature variability

    NASA Astrophysics Data System (ADS)

    Seppälä, A.; Randall, C. E.; Clilverd, M. A.; Rozanov, E.; Rodger, C. J.

    2009-10-01

    Here we use the ERA-40 and ECMWF operational surface level air temperature data sets from 1957 to 2006 to examine polar temperature variations during years with different levels of geomagnetic activity, as defined by the A p index. Previous modeling work has suggested that NO x produced at high latitudes by energetic particle precipitation can eventually lead to detectable changes in surface air temperatures (SATs). We find that during winter months, polar SATs in years with high A p index are different than in years with low A p index; the differences are statistically significant at the 2-sigma level and range up to about ±4.5 K, depending on location. The temperature differences are larger when years with wintertime Sudden Stratospheric Warmings (SSWs) are excluded. We take into account solar irradiance variations, unlike previous analyses of geomagnetic effects in ERA-40 and operational data. Although we cannot conclusively show that the polar SAT patterns are physically linked by geomagnetic activity, we conclude that geomagnetic activity likely plays a role in modulating wintertime surface air temperatures. We tested our SAT results against variation in the Quasi Biennial Oscillation, the El Niño Southern Oscillation and the Southern Annular Mode. The results suggested that these were not driving the observed polar SAT variability. However, significant uncertainty is introduced by the Northern Annular Mode, and we cannot robustly exclude a chance linkage between sea surface temperature variability and geomagnetic activity.

  9. Delineating the pathways for the site-directed synthesis of individual nanoparticles on surfaces

    PubMed Central

    Liu, Guoliang; Eichelsdoerfer, Daniel J.; Rasin, Boris; Zhou, Yu; Brown, Keith A.; Liao, Xing; Mirkin, Chad A.

    2013-01-01

    Although nanoparticles with exquisite properties have been synthesized for a variety of applications, their incorporation into functional devices is challenging owing to the difficulty in positioning them at specified sites on surfaces. In contrast with the conventional synthesis-then-assembly paradigm, scanning probe block copolymer lithography can pattern precursor materials embedded in a polymer matrix and synthesize desired nanoparticles on site, offering great promise for incorporating nanoparticles into devices. This technique, however, is extremely limited from a materials standpoint. To develop a materials-general method for synthesizing nanoparticles on surfaces for broader applications, a mechanistic understanding of polymer-mediated nanoparticle formation is crucial. Here, we design a four-step synthetic process that enables independent study of the two most critical steps for synthesizing single nanoparticles on surfaces: phase separation of precursors and particle formation. Using this process, we elucidate the importance of the polymer matrix in the diffusion of metal precursors to form a single nanoparticle and the three pathways that the precursors undergo to form nanoparticles. Based on this mechanistic understanding, the synthetic process is generalized to create metal (Au, Ag, Pt, and Pd), metal oxide (Fe2O3, Co2O3, NiO, and CuO), and alloy (AuAg) nanoparticles. This mechanistic understanding and resulting process represent a major advance in scanning probe lithography as a tool to generate patterns of tailored nanoparticles for integration with solid-state devices. PMID:23277538

  10. Lattice site dependent cathodoluminescence behavior and surface chemical changes in a Sr5(PO4)3F host

    NASA Astrophysics Data System (ADS)

    Nagpure, I. M.; Pitale, Shreyas S.; Coetsee, E.; Ntwaeaborwa, O. M.; Terblans, J. J.; Swart, H. C.

    2012-05-01

    Eu activated Sr5(PO4)3F phosphor powders have been subjected to the electron bombardment at 2 keV (10 μA) at an oxygen pressure of 1×10-6 Torr. The synthesized Sr5(PO4)3F phosphor was identical to the hexagonal apatite structure, with the Sr present at two different sites Cs (S1) and C3 (S2) in the Sr5(PO4)3F host, as inferred from the crystallographic study. Cathodoluminescence (CL) and Auger electron spectroscopy of the phosphor excited by the same electron beam were used to monitor changes in the surface state during prolonged electron bombardment. A direct correlation between the surface reactions and the degradation of the CL brightness was observed. Both C and F were depleted from the surface during electron bombardment. The postulated mechanism for the electron stimulated chemical reactions on the phosphor surface is electron beam dissociation of molecular species to atomic species, which subsequently react with C to form volatile compounds CO2, CH4, etc. and with Sr5(PO4)3F to form a non luminescence layer of metal oxides of Sr and P.

  11. Insight into both coverage and surface structure dependent CO adsorption and activation on different Ni surfaces from DFT and atomistic thermodynamics.

    PubMed

    Hao, Xiaobin; Wang, Baojun; Wang, Qiang; Zhang, Riguang; Li, Debao

    2016-06-29

    CO adsorption and activation on Ni(100), (110) and (111) surfaces have been systematically investigated to probe the effect of coverage and surface structure on CO adsorption and activation. Herein, dispersion-corrected density functional theory calculations (DFT-D) were employed, and the related thermodynamic energies at 523 K were calculated by including the zero-point energy, thermal energy and entropic corrections; the results show that the saturated coverage of CO on the Ni(111), (100) and (110) surfaces correspond to 8/9, 9/12 and 9/9 ML, respectively. As the coverage increases, the stepwise adsorption free energies decrease on the flat (111) and (100) surfaces, whereas small changes occur on the corrugated (110) surface. CO migrates from the three-fold hollow site to the top site on the (111) surface, and from the four-fold hollow to the two-fold bridge site on the (100) surface, while all the CO molecules remain at the short-bridge site on the (110) surface. As a result, the obtained intermolecular CO-CO repulsive interactions on the flat surface are stronger than the interactions on the corrugated surface. Furthermore, the computed CO vibrational frequencies at different levels of coverage over the Ni surfaces agree well with the experimental results. On the other hand, kinetic analyses were utilized to compare the stepwise CO desorption with the dissociation at different degrees of coverage on the three Ni surfaces. CO desorption is more favorable than its dissociation at all coverage levels on the most exposed Ni(111) surface. Analogously, CO desorption becomes more favorable than its dissociation on the Ni(110) surface at higher coverage, except for coverage of 1/9 ML, in which CO desorption competes with its dissociation. However, on the Ni(100) surface, CO dissociation is more favorable than its desorption at 1/12 ML; when the coverage increases from 2/12 to 3/12 ML, equilibrium states exist between dissociation and desorption over the surface; when

  12. Structural mechanism of RuBisCO activation by carbamylation of the active site lysine

    PubMed Central

    Stec, Boguslaw

    2012-01-01

    Ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO) is a crucial enzyme in carbon fixation and the most abundant protein on earth. It has been studied extensively by biochemical and structural methods; however, the most essential activation step has not yet been described. Here, we describe the mechanistic details of Lys carbamylation that leads to RuBisCO activation by atmospheric CO2. We report two crystal structures of nitrosylated RuBisCO from the red algae Galdieria sulphuraria with O2 and CO2 bound at the active site. G. sulphuraria RuBisCO is inhibited by cysteine nitrosylation that results in trapping of these gaseous ligands. The structure with CO2 defines an elusive, preactivation complex that contains a metal cation Mg2+ surrounded by three H2O/OH molecules. Both structures suggest the mechanism for discriminating gaseous ligands by their quadrupole electric moments. We describe conformational changes that allow for intermittent binding of the metal ion required for activation. On the basis of these structures we propose the individual steps of the activation mechanism. Knowledge of all these elements is indispensable for engineering RuBisCO into a more efficient enzyme for crop enhancement or as a remedy to global warming. PMID:23112176

  13. Effects of sodium on cell surface and intracellular TH-naloxone binding sites

    SciTech Connect

    Pollack, A.E.; Wooten, G.F.

    1987-07-27

    The binding of the opiate antagonist TH-naloxone was examined in rat whole brain homogenates and in crude subcellular fractions of these homogenates (nuclear, synaptosomal, and mitochondrial fractions) using buffers that approximated intra- (low sodium concentration) and extracellular (high sodium concentration) fluids. Saturation studies showed a two-fold decrease in the dissociation constant (Kd) in all subcellular fractions examined in extracellular buffer compared to intracellular buffer. In contrast, there was no significant effect of the buffers on the Bmax. Thus, TH-naloxone did not distinguish between binding sites present on cell surface and intracellular tissues in these two buffers. These results show that the sodium effect of opiate antagonist binding is probably not a function of altered selection of intra- and extracellular binding sites. 17 references, 2 tables.

  14. Mid-Piacenzian sea surface temperature record from ODP Site 1115 in the western equatorial Pacific

    USGS Publications Warehouse

    Stoll, Danielle

    2010-01-01

    Planktic foraminifer assemblages and alkenone unsaturation ratios have been analyzed for the mid-Piacen-zian (3.3 to 2.9 Ma) section of Ocean Drilling Program (ODP) Site 1115B, located in the western equatorial Pacific off the coast of New Guinea. Cold and warm season sea surface temperature (SST) estimates were determined using a modern analog technique. ODP Site 1115 is located just south of the transition between the planktic foraminifer tropical and subtropical faunal provinces and approximates the southern boundary of the western equatorial Pacific (WEP) warm pool. Comparison of the faunal and alkenone SST estimates (presented here) with an existing nannofossil climate proxy shows similar trends. Results of this analysis show increased seasonal variability during the middle of the sampled section (3.22 to 3.10 Ma), suggesting a possible northward migration of both the subtropical faunal province and the southern boundary of the WEP warm pool.

  15. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    NASA Astrophysics Data System (ADS)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  16. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111).

    PubMed

    Xin, Hongliang; Linic, Suljo

    2016-06-21

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system. PMID:27334187

  17. Enhanced visible-light photocatalytic activity of active Al₂O₃/g-C₃N₄ heterojunctions synthesized via surface hydroxyl modification.

    PubMed

    Li, Fa-Tang; Zhao, Ye; Wang, Qing; Wang, Xiao-Jing; Hao, Ying-Juan; Liu, Rui-Hong; Zhao, Dishun

    2015-01-01

    Novel Al2O3/g-C3N4 heterojunction photocatalysts were fabricated through ultrasonic dispersion method. Al2O3, obtained via solution combustion, contained amorphous ingredient with lots of defect sites and was used as active component for transferring photo-induced electrons of g-C3N4. G-C3N4 was grafted surface hydroxyl groups in the presence of ammonia aqueous solution to combine with Al2O3 possessing positive charges via hydrogen bond. The XRD, SEM, element map, TEM, HRTEM, FT-IR, and XPS results indicate that these synthesized materials are two-phase hybrids of Al2O3 and g-C3N4 with interaction. The photocatalytic results for the degradation of rhodamine B (RhB) indicate that the most active heterojunction proportion is 60wt.% g-C3N4:40wt.% Al2O3, the visible light photocatalytic activity of which is 3.8 times that of a mechanical mixture. The enhanced performance is attributed to the high separation efficiency of photo-induced electrons from the LUMO of g-C3N4 injected into the defect sites of Al2O3, which is verified by photoluminescence spectroscopy (PL) and surface photovoltage (SPV) measurements. The electron paramagnetic resonance (EPR) signals and radical scavengers trapping experiments reveal holes (h(+)) and superoxide anion radical (O2(-)) are the main active species responsible for the degradation of RhB. PMID:25306536

  18. 78 FR 33908 - Commercial Wind Lease Issuance and Site Assessment Activities on the Atlantic Outer Continental...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-05

    ... identified Wind Energy Area (WEA) on the OCS offshore Rhode Island (RI) and Massachusetts (MA). The revised... from leasing, site characterization, and site assessment in and around the Call Area (76 FR 51391). The... Bureau of Ocean Energy Management Commercial Wind Lease Issuance and Site Assessment Activities on...

  19. 77 FR 39508 - Commercial Wind Lease Issuance and Site Assessment Activities on the Atlantic Outer Continental...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-03

    ... specific project proposals on those leases) in an identified Wind Energy Area (WEA) on the OCS offshore..., site characterization, and site assessment in and around the Call Area (76 FR 51391). The Call Area is... Bureau of Ocean Energy Management Commercial Wind Lease Issuance and Site Assessment Activities on...

  20. Active Layer and Moisture Measurements for Intensive Site 0 and 1, Barrow, Alaska

    DOE Data Explorer

    John Peterson

    2015-04-17

    These are measurements of Active Layer Thickness collected along several lines beginning in September, 2011 to the present. The data were collected at several time periods along the Site0 L2 Line, the Site1 AB Line, and an ERT Monitoring Line near Area A in Site1.

  1. Nuclear Site Security in the Event of Terrorist Activity

    SciTech Connect

    Thomson, M.L.; Sims, J.

    2008-07-01

    This paper, presented as a poster, identifies why ballistic protection should now be considered at nuclear sites to counter terrorist threats. A proven and flexible form of multi purpose protection is described in detail with identification of trial results that show its suitability for this role. (authors)

  2. Preliminary siting activities for new waste handling facilities at the Idaho National Engineering Laboratory

    SciTech Connect

    Taylor, D.D.; Hoskinson, R.L.; Kingsford, C.O.; Ball, L.W.

    1994-09-01

    The Idaho Waste Processing Facility, the Mixed and Low-Level Waste Treatment Facility, and the Mixed and Low-Level Waste Disposal Facility are new waste treatment, storage, and disposal facilities that have been proposed at the Idaho National Engineering Laboratory (INEL). A prime consideration in planning for such facilities is the selection of a site. Since spring of 1992, waste management personnel at the INEL have been involved in activities directed to this end. These activities have resulted in the (a) identification of generic siting criteria, considered applicable to either treatment or disposal facilities for the purpose of preliminary site evaluations and comparisons, (b) selection of six candidate locations for siting,and (c) site-specific characterization of candidate sites relative to selected siting criteria. This report describes the information gathered in the above three categories for the six candidate sites. However, a single, preferred site has not yet been identified. Such a determination requires an overall, composite ranking of the candidate sites, which accounts for the fact that the sites under consideration have different advantages and disadvantages, that no single site is superior to all the others in all the siting criteria, and that the criteria should be assigned different weighing factors depending on whether a site is to host a treatment or a disposal facility. Stakeholder input should now be solicited to help guide the final selection. This input will include (a) siting issues not already identified in the siting, work to date, and (b) relative importances of the individual siting criteria. Final site selection will not be completed until stakeholder input (from the State of Idaho, regulatory agencies, the public, etc.) in the above areas has been obtained and a strategy has been developed to make a composite ranking of all candidate sites that accounts for all the siting criteria.

  3. Meteorological data for four sites at surface-disruption features in Yucca Flat, Nevada Test Site, Nye County, Nevada, 1985-86

    USGS Publications Warehouse

    Carman, Rita L.

    1994-01-01

    Surface-disruption features, or craters, resulting from underground nuclear testing at the Nevada Test Site may increase the potential for ground-water recharge in an area that would normally produce little, if any, recharge. This report presents selected meteorological data resulting from a study of two surface-disruption features during May 1985 through June 1986. The data were collected at four adjacent sites in Yucca Flat, about 56 kilometers north of Mercury, Nevada. Three sites (one in each of two craters and one at an undisturbed site at the original land surface) were instrumented to collect meteorological data for calculating bare-soil evaporation. These data include (1) long-wave radiation, (2) short-wave radiation, (3) net radiation, (4) air temperae, and (5) soil surface temperature. Meteorological data also were collected at a weather station at an undisturbed site near the study craters. Data collected at this site include (1) air temperature, (2) relative humidity, (3) wind velocity, and (4) wind direction.

  4. Dynamic Kinetics of Nitrogen Cycle in Groundwater-Surface Water Interaction Zone at Hanford Site

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liu, C.; Liu, Y.; Xu, F.; Yan, A.; Shi, L.; Zachara, J. M.; Gao, Y.; Qian, W.; Nelson, W.; Fredrickson, J.; Zhong, L.; Thompson, C.

    2015-12-01

    Nitrogen cycle carried out by microbes is an important geobiological process that has global implications for carbon and nitrogen cycling and climate change. This presentation describes a study of nitrogen cycle in groundwater-surface water interaction zone (GSIZ) at the US Department of Energy's Hanford Site. Groundwater at Hanford sites has long been documented with nitrate contamination. Nearby Columbia River stage changes of up to 3 m every day because of daily discharge fluctuation from upstream Priest Rapids Dam; resulting an exchange of groundwater and surface water in a short time period. Yet, nitrogen cycle in the GSIZ at Hanford Site remains unclear. Column studies have been used to identify nitrogen metabolism pathways and investigate kinetics of nitrogen cycle in groundwater saturated zone, surface water saturated zone, and GSIZ. Functional gene and protein abundances were determined by qPCR and PRISM-SRM (high-pressure, high-resolution separations coupled with intelligent selection and multiplexing for sensitive selected reaction monitoring) to identify key enzymatic reactions and metabolic pathways of nitrogen cycle. The results showed that dissimilatory nitrate reduction to ammonium (DNRA) competed with denitrification under anaerobic conditions, reducing 30% of NO3- to NH4+, a cation strongly retained on the sediments. As dissolved oxygen intruded the anaerobic zone with river water, NH4+ was oxidized to NO3-, increasing the mobility of NO3-. Multiplicative Monod models were established to describe nitrogen cycle in columns fed with O2 depleted synthetic groundwater and O2 saturated synthetic river water, respectively. The two models were then coupled to predict the dynamic kinetics of nitrogen cycle in GSIZ.

  5. Methanol Synthesis over Cu/ZnO/Al2O3: The Active Site in Industrial Catalysis

    SciTech Connect

    Behrens, Malte

    2012-03-28

    Unlike homogeneous catalysts, heterogeneous catalysts that have been optimized through decades are typically so complex and hard to characterize that the nature of the catalytically active site is not known. This is one of the main stumbling blocks in developing rational catalyst design strategies in heterogeneous catalysis. We show here how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al{sub 2}O{sub 3} methanol synthesis catalyst. Using a combination of experimental evidence from bulk-, surface-sensitive and imaging methods collected on real high-performance catalytic systems in combination with DFT calculations. We show that the active site consists of Cu steps peppered with Zn atoms, all stabilized by a series of well defined bulk defects and surface species that need jointly to be present for the system to work.

  6. Streamlined Approach for Environmental Restoration Plan for Corrective Action Unit 484: Surface Debris, Waste Sites, and Burn Area, Tonopah Test Range, Nevada

    SciTech Connect

    Bechel Nevada

    2004-05-01

    This Streamlined Approach for Environmental Restoration plan details the activities necessary to close Corrective Action Unit (CAU) 484: Surface Debris, Waste Sites, and Burn Area (Tonopah Test Range). CAU 484 consists of sites located at the Tonopah Test Range, Nevada, and is currently listed in Appendix III of the Federal Facility Agreement and Consent Order. CAU 484 consists of the following six Corrective Action Sites: (1) CAS RG-52-007-TAML, Davis Gun Penetrator Test; (2) CAS TA-52-001-TANL, NEDS Detonation Area; (3) CAS TA-52-004-TAAL, Metal Particle Dispersion Test; (4) CAS TA-52-005-TAAL, Joint Test Assembly DU Sites; (5) CAS TA-52-006-TAPL, Depleted Uranium Site; and (6) CAS TA-54-001-TANL, Containment Tank and Steel Structure

  7. Viking landing sites, remote-sensing observations, and physical properties of Martian surface materials

    USGS Publications Warehouse

    Moore, H.J.; Jakosky, B.M.

    1989-01-01

    Important problems that confront future scientific exploration of Mars include the physical properties of Martian surface materials and the geologic processes that formed the materials. The design of landing spacecraft, roving vehicles, and sampling devices and the selection of landing sites, vehicle traverses, and sample sites will be, in part, guided by the physical properties of the materials. Four materials occur in the sample fields of the Viking landers: (1) drift, (2) crusty to cloddy, (3) blocky, and (4) rock. The first three are soillike. Drift materials is weak, loose, and porous. We estimate that it has a dielectric constant near 2.4 and a thermal inertia near 1 ?? 10-3 to 3 ?? 10-3 (cal cm-2 sec 1 2 K-1) because of its low bulk density, fine grain size, and small cohesion. Crusty to cloddy material is expected to have a dielectric constant near 2.8 and a thermal inertia near 4 ?? 10-3 to 7 ?? 10-3 because of its moderate bulk density and cementation of grains. Blocky material should have a dielectric constant near 3.3 and a thermal inertia near 7 ?? 10-3 to 9 ?? 10-3 because of its moderate bulk density and cementation. Common basaltic rocks have dielectric constans near 8 and thermal inertias near 30 ?? 10-3 to 60 ?? 10-3. Comparisons of estimated dielectric constants and thermal inertias of the materials at the landing sites with those obtained remotely by Earth-based radars and Viking Orbiter thermal sensors suggest that the materials at the landing sites are good analogs for materials elsewhere on Mars. Correlation of remotely estimated dielectric constant and thermal inertias indicates two modal values for paired values of dielectric constants and thermal inertias near (A) 2 and 2 ?? 10-3 and (B) 3 and 6 ?? 10-3, respectively. These two modes are comparable to the dielectric constants and thermal inertias for drift and crusty to cloddy material, respectively. Dielectric constants and thermal inertias for blocky material are larger but conistent

  8. Interactions of the plasma sheet with the lunar surface at the Apollo 14 site

    NASA Technical Reports Server (NTRS)

    Reiff, P. H.; Burke, W. J.

    1976-01-01

    Calculations of the magnetic shadow zones of lunar-based particle detectors are extended to include the effects of local remanent magnetic fields. At the Apollo 14 site, the local magnetic field is approximated as that of a dipole. Numerically calculated open and shadowed zones are shown to be in agreement with quiet-time plasma-sheet observations of the charged-particle lunar-environment experiment. An analysis of three storm-time observations indicates that magnetic shadowing can significantly alter the near-lunar-surface electrostatic potential distribution.

  9. Hydrocarbons in surface sediments from a Guaymas Basin hydrothermal vent site. Technical report

    SciTech Connect

    Bazylinski, D.A.; Farrington, J.W.; Jannasch, H.W.

    1988-01-01

    Petroleum-like materials found at the Guaymas Basin hydrothermal vent site (Gulf of California) are derived from pyrolysis of organic matter. Two characteristics surface sediment cores differing in temperature profiles and other parameters were collected by DSV ALVIN, sectioned, and analyzed for hydrocarbons. The quantitative and qualitative composition of alkanes, steranes, diasteranes, and triterpanes differed between these cores as well as within sections of the same core. These differences, apparent for scales of tens of centimeters, are related to interactive physical, chemical, and microbial processes as well as the influence of multiple sources for the petroleum.

  10. Blogs and Social Network Sites as Activity Systems: Exploring Adult Informal Learning Process through Activity Theory Framework

    ERIC Educational Resources Information Center

    Heo, Gyeong Mi; Lee, Romee

    2013-01-01

    This paper uses an Activity Theory framework to explore adult user activities and informal learning processes as reflected in their blogs and social network sites (SNS). Using the assumption that a web-based space is an activity system in which learning occurs, typical features of the components were investigated and each activity system then…

  11. Effective removal of field-emitting sites from metallic surfaces by dry ice cleaning

    SciTech Connect

    Dangwal, Arti; Mueller, Guenter; Reschke, Detlef; Floettmann, Klaus; Singer, Xenia

    2007-08-15

    Systematic results of the field emission properties of polycrystalline copper and niobium and single-crystal Nb are reported. Dry ice cleaning (DIC) is found to suppress enhanced field emission from metallic surfaces. The cleaning effect on the emitting sites was investigated by means of field emission scanning microscopy up to fields of 250 MV/m and high-resolution scanning electron microscopy with energy dispersive x-ray analysis. The number density of emitters at given fields was drastically reduced by dry ice cleaning. Current-voltage measurements and derived Fowler-Nordheim parameters are partially discussed with respect to the morphology and impurity content of localized emitters. No emission from grain boundaries on large-grain Nb samples was observed. The microscopy results prove the effective removal of field-emitting particulates down to 400 nm as well as the partial smoothing of surface protrusions by DIC.

  12. Active-Site Hydration and Water Diffusion in Cytochrome P450cam: A Highly Dynamic Process

    SciTech Connect

    Miao, Yinglong; Baudry, Jerome Y

    2011-01-01

    Long-timescale molecular dynamics simulations (300 ns) are performed on both the apo- (i.e., camphor-free) and camphor-bound cytochrome P450cam (CYP101). Water diffusion into and out of the protein active site is observed without biased sampling methods. During the course of the molecular dynamics simulation, an average of 6.4 water molecules is observed in the camphor-binding site of the apo form, compared to zero water molecules in the binding site of the substrate-bound form, in agreement with the number of water molecules observed in crystal structures of the same species. However, as many as 12 water molecules can be present at a given time in the camphor-binding region of the active site in the case of apo-P450cam, revealing a highly dynamic process for hydration of the protein active site, with water molecules exchanging rapidly with the bulk solvent. Water molecules are also found to exchange locations frequently inside the active site, preferentially clustering in regions surrounding the water molecules observed in the crystal structure. Potential-of-mean-force calculations identify thermodynamically favored trans-protein pathways for the diffusion of water molecules between the protein active site and the bulk solvent. Binding of camphor in the active site modifies the free-energy landscape of P450cam channels toward favoring the diffusion of water molecules out of the protein active site.

  13. Total pollen counts do not influence active surface measurements

    NASA Astrophysics Data System (ADS)

    Moshammer, Hanns; Schinko, Herwig; Neuberger, Manfred

    We investigated the temporal association of various aerosol parameters with pollen counts in the pollen season (April 2001) in Linz, Austria. We were especially interested in the relationship between active surface (or Fuchs' surface) because we had shown previously (Atmos. Environ. 37 (2003) 1737-1744) that this parameter during the same observation period was a better predictor for acute respiratory symptoms in school children (like wheezing, shortness of breath, and cough) and reduced lung function on the same day than particle mass (PM 10). While active surface is most sensitive for fine particles with a diameter of less than 100 nm it has no strict upper cut-off regarding particle size and so could eventually be influenced also by larger particles if their numbers were high. All particle mass parameters tested (TSP, PM 10, PM 1) were weakly ( r approximately 0.2) though significantly correlated with pollen counts but neither was active surface nor total particle counts (CPC). The weak association of particle mass and pollen counts was due mainly to similar diurnal variations and a linear trend over time. Only the mass of the coarse fraction (TSP minus PM 10) remained associated with pollen counts significantly after controlling for these general temporal patterns.

  14. Active nematics on the surface of a torus

    NASA Astrophysics Data System (ADS)

    Ellis, Perry; Chang, Ya-Wen; Fernandez-Nieves, Alberto

    Nematic materials on the surface of a sphere must have a net topological charge of s = + 2 . In equilibrium nematics experiments have shown that this net topological charge can be realized with four s = + 1 / 2 defects, which also corresponds to the theoretically expected ground state configuration. Surprisingly, even though active nematics are continuously driven out of equilibrium by the internal energy of the nematogens, when confined to the surface of a sphere these materials can also realize this net topological charge with four s = + 1 / 2 defects. In contrast to the spherical confinement case, the situation for toroidal confinement has not been experimentally explored despite the existence of theory and simulation work examining the structure of ordered materials on the surface of a torus. Here, we experimentally realize an extensile active nematic confined to a toroidal surface and explore how the interplay between topology, activity, and nematic elasticity affect the structure and dynamics of the material. PWE is supported by FLAMEL under Grant NSF 1258425.

  15. Noctis Landing: A Proposed Landing Site/Exploration Zone for Human Missions to the Surface of Mars

    NASA Technical Reports Server (NTRS)

    Lee, Pascal; Acedillo, Shannen; Braham, Stephen; Brown, Adrian; Elphic, Richard; Fong, Terry; Glass, Brian; Hoftun, Christopher; Johansen, Brage W.; Lorber, Kira; Mittlefehldt, David; Takagi, Yuta; Thomas, Peter; West, Michael; West, Stephen; Zolensky, Michael

    2015-01-01

    ) offer many such outcrop options. -­- Identifiable stratigraphic contacts and cross-cutting relationships from which relative ages can be determined. In place and collapsed canyon walls in NL, TC, and IC offer such opportunities. -­- Other types of ROIs include access points to surrounding plateau top areas for longer term regional exploration. A key attribute of the proposed Noctic Landing site is its strategic location to allow the shortest possible surface excusions to Tharsis and Valles Marineris (VM). VM is the feature and region on Mars that exposes the longest record of Mars' geology and evolution through time. Tharsis is the region of Mars that has experienced the longest and most extensive volcanic history, and might still be volcanically active. Some of the youngest lava flows on Mars have been identified on the western flanks of the Tharsis Bulge, i.e., within driving range of future longrange (500 - 1000 km) pressurized rover traverses. The proposed site also contains ROIs that offer the following Resources (incl. Civil Engineering) characteristics: -­- Access to raw material that exhibits the potential to (1) be used as feedstock for water-generating in situ resource utilization (ISRU) processes and (2) yield significant quantities (greater than 100 MT) of water. The raw material is likely in the form of hydrated minerals, and possibly ice/regolith mix. The top of the raw material deposit is at the surface. -­- Access to a region where infrastructure can be emplaced or constructed. This region is less than 5 km from the LS and contains flat, stable terrain. The region exhibits evidence for an abundant source of loose regolith. Several deep pits in the area combined with the availability of sand suggests that some natural terrain features can be adapted for construction purposes. -­- Access to raw material that exhibits the potential to be used as metal feedstock for ISRU and construction purposes. Iron and sulfur-rich mineral surface deposits have been

  16. Active sites and mechanisms for H2O2 decomposition over Pd catalysts.

    PubMed

    Plauck, Anthony; Stangland, Eric E; Dumesic, James A; Mavrikakis, Manos

    2016-04-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2 We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O-O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O-O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  17. Field Summary Report for Remedial Investigation of Hanford Site Releases to the Columbia River, Hanford Site, Washington, Collection of Surface Water, River Sediments, and Island Soils

    SciTech Connect

    L. C. Hulstrom

    2009-09-28

    This report has been prepared in support of the remedial investigation of Hanford Site Releases to the Columbia River and describes the 2008/2009 data collection efforts. This report documents field activities associated with collection of sediment, river water, and soil in and adjacent to the Columbia River near the Hanford Site and in nearby tributaries.

  18. Evaluating Nonpolar Surface Area and LC/MS Response: An Application for Site Occupancy Measurements for Enzyme Intermediates in Polyketide Biosynthesis

    PubMed Central

    Randall, Shan M.; Koryakina, Irina; Williams, Gavin J.; Muddiman, David C.

    2014-01-01

    RATIONALE Site occupancy measurements using LC/MS are reported throughout the literature. However, site occupancy quantification suffers from ionization bias between modified and unmodified peptides containing the active site. In this study, we explore the MS signal as a function of nonpolar surface area (NPSA) in order to better understand this bias in electrospray response. The correlation between hydrophobicity and LC/MS response was evaluated and applied to study enzyme intermediates in polyketide synthases. METHODS Site occupancy methods were developed to study acyltransferase activity. To further evaluate these methods, several standard peptides containing one cysteine residue were modified with alkylation reagents of increasing hydrophobicity to study the MS signal as a function of nonpolar surface area. RESULTS A consistent trend in MS response was observed which is dependent on the NPSA of the analyte. An optimal NPSA zone was observed for the peptides studied. CONCLUSIONS Nonpolar surface area can be used as metric to determine relative LC/MS response for peptides and evaluate site occupancy measurements. PMID:25366398

  19. Imaging Active Surface Processes in Barnacle Adhesive Interfaces.

    PubMed

    Golden, Joel P; Burden, Daniel K; Fears, Kenan P; Barlow, Daniel E; So, Christopher R; Burns, Justin; Miltenberg, Benjamin; Orihuela, Beatriz; Rittshof, Daniel; Spillmann, Christopher M; Wahl, Kathryn J; Tender, Leonard M

    2016-01-19

    Surface plasmon resonance imaging (SPRI) and voltammetry were used simultaneously to monitor Amphibalanus (=Balanus) amphitrite barnacles reattached and grown on gold-coated glass slides in artificial seawater. Upon reattachment, SPRI revealed rapid surface adsorption of material with a higher refractive index than seawater at the barnacle/gold interface. Over longer time periods, SPRI also revealed secretory activity around the perimeter of the barnacle along the seawater/gold interface extending many millimeters beyond the barnacle and varying in shape and region with time. Ex situ experiments using attenuated total reflectance infrared (ATR-IR) spectroscopy confirmed that reattachment of barnacles was accompanied by adsorption of protein to surfaces on similar time scales as those in the SPRI experiments. Barnacles were grown through multiple molting cycles. While the initial reattachment region remained largely unchanged, SPRI revealed the formation of sets of paired concentric rings having alternately darker/lighter appearance (corresponding to lower and higher refractive indices, respectively) at the barnacle/gold interface beneath the region of new growth. Ex situ experiments coupling the SPRI imaging with optical and FTIR microscopy revealed that the paired rings coincide with molt cycles, with the brighter rings associated with regions enriched in amide moieties. The brighter rings were located just beyond orifices of cement ducts, consistent with delivery of amide-rich chemistry from the ducts. The darker rings were associated with newly expanded cuticle. In situ voltammetry using the SPRI gold substrate as the working electrode revealed presence of redox active compounds (oxidation potential approx 0.2 V vs Ag/AgCl) after barnacles were reattached on surfaces. Redox activity persisted during the reattachment period. The results reveal surface adsorption processes coupled to the complex secretory and chemical activity under barnacles as they construct

  20. Active Site Structure and Peroxidase Activity of Oxidatively Modified Cytochrome c Species in Complexes with Cardiolipin.

    PubMed

    Capdevila, Daiana A; Oviedo Rouco, Santiago; Tomasina, Florencia; Tortora, Verónica; Demicheli, Verónica; Radi, Rafael; Murgida, Daniel H

    2015-12-29

    We report a resonance Raman and UV-vis characterization of the active site structure of oxidatively modified forms of cytochrome c (Cyt-c) free in solution and in complexes with cardiolipin (CL). The studied post-translational modifications of Cyt-c include methionine sulfoxidation and tyrosine nitration, which lead to altered heme axial ligation and increased peroxidase activity with respect to those of the wild-type protein. In spite of the structural and activity differences between the protein variants free in solution, binding to CL liposomes induces in all cases the formation of a spectroscopically identical bis-His axial coordination conformer that more efficiently promotes lipid peroxidation. The spectroscopic results indicate that the bis-His form is in equilibrium with small amounts of high-spin species, thus suggesting a labile distal His ligand as the basis for the CL-induced increase in enzymatic activity observed for all protein variants. For Cyt-c nitrated at Tyr74 and sulfoxidized at Met80, the measured apparent binding affinities for CL are ∼4 times larger than for wild-type Cyt-c. On the basis of these results, we propose that these post-translational modifications may amplify the pro-apoptotic signal of Cyt-c under oxidative stress conditions at CL concentrations lower than for the unmodified protein. PMID:26620444

  1. Adsorption and characterization of MCPA on DDTMA- and raw-montmorillonite: Surface sites involved.

    PubMed

    Santiago, Cintia C; Fernández, Mariela A; Torres Sánchez, Rosa M

    2016-01-01

    The 4-chloro-2-methylphenoxy acid (MCPA) is an herbicide widely used in agriculture, which generates a great concern about contamination of surface water and serious consequences for human health and the environment. In this work, the adsorption of MCPA on an Argentine montmorillonite (MMT) and its organo-montmorillonite product (OMMT) with different dodecyl trimethyl ammonium loading was investigated. MCPA adsorption on OMMT increases at least 3 times, with respect to the amount determined for MMT. X-ray diffraction and zeta potential analyses indicated the inner (interlayer) and outer surface participate as adsorption sites. Changes in surface electric charge and also interlayer expansion suggest that dimethyl amine (MCPA counterion) was also surface-adsorbed. The larger aggregates of OMMT, without and with MCPA, obtained compared to those of MMT samples, generate an improvement in the coagulation efficiency. This property, particularly after MCPA retention, allows an easier separation of the solids from the solution and enables a simple technological process application. PMID:26786275

  2. Integration of surface and upper air measurements for determining evapotranspiration at a high mountain site

    NASA Astrophysics Data System (ADS)

    Connell, Bernadette Helen

    An integrated approach using surface and upper air measurements was used to estimate evapotranspiration in a high mountain area. The first part of this work focused on identifying potential errors introduced into the results due to the characteristics of the sonde instrument and the dynamic environment it was used in. The second part of this work focused on estimating the evapotranspiration. Sources of error were reviewed for radiosonde measurements in the Atmospheric Boundary Layer and focusing on two radiosonde models manufactured by Atmospheric Instrumentation Research, Inc. Temperature and humidity lag errors and wind errors were analyzed. Errors in measurement of azimuth and elevation angles and pressure over short time intervals and at higher altitudes introduced wind vector errors greater than 5 m s-1. Mean temperature and humidity lag errors were small, but individual large lag errors occurred with dramatic changes in the environment, such as near the surface or at the top of the boundary layer. Dual sonde flights showed mean instrument error comparable to lag error. Vertical profiles of potential temperature and specific humidity measured by radiosondes within the surface boundary layer were used to estimate Bowen Ratio at a high elevation alpine site for 2 cases representing moist/windy and dry/calm conditions. The Bowen Ratio was combined with surface global radiation measurements to estimate evaporation (ET) through an energy balance approach. Weather modified vegetation characteristics and their spatial distribution reflect the large local differences in the latent (ET) and sensible heat fluxes measured a 2 surface stations close by. The sonde estimates correlated well (R2 = 0.90) with a weighted average of the surface measured ET in both an undisturbed high pressure ridge system characterized by a dry deep convective boundary layer and during the passage of a weak frontal system characterized by a shallower mechanically mixed moist boundary layer.

  3. Analysis of multi-temporal landsat satellite images for monitoring land surface temperature of municipal solid waste disposal sites.

    PubMed

    Yan, Wai Yeung; Mahendrarajah, Prathees; Shaker, Ahmed; Faisal, Kamil; Luong, Robin; Al-Ahmad, Mohamed

    2014-12-01

    This studypresents a remote sensing application of using time series Landsat satellite images for monitoring the Trail Road and Nepean municipal solid waste (MSW) disposal sites in Ottawa, Ontario, Canada. Currently, the Trail Road landfill is in operation; however, during the 1960s and 1980s, the city relied heavily on the Nepean landfill. More than 400 Landsat satellite images were acquired from the US Geological Survey (USGS) data archive between 1984 and 2011. Atmospheric correction was conducted on the Landsat images in order to derive the landfill sites' land surface temperature (LST). The findings unveil that the average LST of the landfill was always higher than the immediate surrounding vegetation and air temperature by 4 to 10 °C and 5 to 11.5 °C, respectively. During the summer, higher differences of LST between the landfill and its immediate surrounding vegetation were apparent, while minima were mostly found in fall. Furthermore, there was no significant temperature difference between the Nepean landfill (closed) and the Trail Road landfill (active) from 1984 to 2007. Nevertheless, the LST of the Trail Road landfill was much higher than the Nepean by 15 to 20 °C after 2007. This is mainly due to the construction and dumping activities (which were found to be active within the past few years) associated with the expansion of the Trail Road landfill. The study demonstrates that the use of the Landsat data archive can provide additional and viable information for the aid of MSW disposal site monitoring. PMID:25150051

  4. Microstructure and surface properties of lignocellulosic-based activated carbons

    NASA Astrophysics Data System (ADS)

    González-García, P.; Centeno, T. A.; Urones-Garrote, E.; Ávila-Brande, D.; Otero-Díaz, L. C.

    2013-01-01

    Low cost activated carbons have been produced via chemical activation, by using KOH at 700 °C, from the bamboo species Guadua Angustifolia and Bambusa Vulgaris Striata and the residues from shells of the fruits of Castanea Sativa and Juglans Regia as carbon precursors. The scanning electron microscopy micrographs show the conservation of the precursor shape in the case of the Guadua Angustifolia and Bambusa Vulgaris Striata activated carbons. Transmission electron microscopy analyses reveal that these materials consist of carbon platelet-like particles with variable length and thickness, formed by highly disordered graphene-like layers with sp2 content ≈ 95% and average mass density of 1.65 g/cm3 (25% below standard graphite). Textural parameters indicate a high porosity development with surface areas ranging from 850 to 1100 m2/g and average pore width centered in the supermicropores range (1.3-1.8 nm). The electrochemical performance of the activated carbons shows specific capacitance values at low current density (1 mA/cm2) as high as 161 F/g in the Juglans Regia activated carbon, as a result of its textural parameters and the presence of pseudocapacitance derived from surface oxygenated acidic groups (mainly quinones and ethers) identified in this activated carbon.

  5. Influence of surface charge, binding site residues and glycosylation on Thielavia terrestris cutinase biochemical characteristics.

    PubMed

    Shirke, Abhijit N; Basore, Danielle; Holton, Samantha; Su, An; Baugh, Evan; Butterfoss, Glenn L; Makhatadze, George; Bystroff, Christopher; Gross, Richard A

    2016-05-01

    Cutinases are esterases of industrial importance for applications in recycling and surface modification of polyesters. The cutinase from Thielavia terrestris (TtC) is distinct in terms of its ability to retain its stability and activity in acidic pH. Stability and activity in acidic pHs are desirable for esterases as the pH of the reaction tends to go down with the generation of acid. The pH stability and activity are governed by the charged state of the residues involved in catalysis or in substrate binding. In this study, we performed the detailed structural and biochemical characterization of TtC coupled with surface charge analysis to understand its acidic tolerance. The stability of TtC in acidic pH was rationalized by evaluating the contribution of charge interactions to the Gibbs free energy of unfolding at varying pHs. The activity of TtC was found to be limited by substrate binding affinity, which is a function of the surface charge. Additionally, the presence of glycosylation affects the biochemical characteristics of TtC owing to steric interactions with residues involved in substrate binding. PMID:26758295

  6. Environmental assessment of ground-water compliance activities at the Uranium Mill Tailings Site, Spook, Wyoming

    SciTech Connect

    1997-02-01

    This report assesses the environmental impacts of the Uranium Mill Tailings Site at Spook, Wyoming on ground water. DOE previously characterized the site and monitoring data were collected during the surface remediation. The ground water compliance strategy is to perform no further remediation at the site since the ground water in the aquifer is neither a current nor potential source of drinking water. Under the no-action alternative, certain regulatory requirements would not be met.

  7. Comparative Study of Surface-Active Properties and Antimicrobial Activities of Disaccharide Monoesters

    PubMed Central

    Zhang, Xi; Song, Fei; Taxipalati, Maierhaba; Wei, Wei; Feng, Fengqin

    2014-01-01

    The objective of this research was to determine the effect of sugar or fatty acid in sugar ester compounds on the surface-active properties and antimicrobial activities of these compounds. Disaccharides of medium-chain fatty acid monoesters were synthesized through transesterifications by immobilized lipase (Lipozyme TLIM) to yield nine monoesters for subsequent study. Their antimicrobial activities were investigated using three pathogenic microorganisms: Staphylococcus aureus, Escherichia coli O157:H7 and Candida albicans. Their surface-active properties including air–water surface tension, critical micelle concentration, and foaming and emulsion power and stability were also studied. The results showed that all of the tested monoesters were more effective against Staphylococcus aureus (Gram-positive bacterium) than against Escherichia coli O157:H7 (Gram-negative bacterium). The results demonstrated that the carbon chain length was the most important factor influencing the surface properties, whereas degree of esterification and hydrophilic groups showed little effect. PMID:25531369

  8. Comparative study of surface-active properties and antimicrobial activities of disaccharide monoesters.

    PubMed

    Zhang, Xi; Song, Fei; Taxipalati, Maierhaba; Wei, Wei; Feng, Fengqin

    2014-01-01

    The objective of this research was to determine the effect of sugar or fatty acid in sugar ester compounds on the surface-active properties and antimicrobial activities of these compounds. Disaccharides of medium-chai