Numerical analysis of one-dimensional temperature data for groundwater/surface-water exchange with 1DTempPro

NASA Astrophysics Data System (ADS)

Voytek, E. B.; Drenkelfuss, A.; Day-Lewis, F. D.; Healy, R. W.; Lane, J. W.; Werkema, D. D.

2012-12-01

Temperature is a naturally occurring tracer, which can be exploited to infer the movement of water through the vadose and saturated zones, as well as the exchange of water between aquifers and surface-water bodies, such as estuaries, lakes, and streams. One-dimensional (1D) vertical temperature profiles commonly show thermal amplitude attenuation and increasing phase lag of diurnal or seasonal temperature variations with propagation into the subsurface. This behavior is described by the heat-transport equation (i.e., the convection-conduction-dispersion equation), which can be solved analytically in 1D under certain simplifying assumptions (e.g., sinusoidal or steady-state boundary conditions and homogeneous hydraulic and thermal properties). Analysis of 1D temperature profiles using analytical models provides estimates of vertical groundwater/surface-water exchange. The utility of these estimates can be diminished when the model assumptions are violated, as is common in field applications. Alternatively, analysis of 1D temperature profiles using numerical models allows for consideration of more complex and realistic boundary conditions. However, such analyses commonly require model calibration and the development of input files for finite-difference or finite-element codes. To address the calibration and input file requirements, a new computer program, 1DTempPro, is presented that facilitates numerical analysis of vertical 1D temperature profiles. 1DTempPro is a graphical user interface (GUI) to the USGS code VS2DH, which numerically solves the flow- and heat-transport equations. Pre- and post-processor features within 1DTempPro allow the user to calibrate VS2DH models to estimate groundwater/surface-water exchange and hydraulic conductivity in cases where hydraulic head is known. This approach improves groundwater/ surface-water exchange-rate estimates for real-world data with complexities ill-suited for examination with analytical methods. Additionally, the code allows for time-varying temperature and hydraulic boundary conditions. Here, we present the approach and include examples for several datasets from stream/aquifer systems.

Distributed parameterization of complex terrain

NASA Astrophysics Data System (ADS)

Band, Lawrence E.

1991-03-01

This paper addresses the incorporation of high resolution topography, soils and vegetation information into the simulation of land surface processes in atmospheric circulation models (ACM). Recent work has concentrated on detailed representation of one-dimensional exchange processes, implicitly assuming surface homogeneity over the atmospheric grid cell. Two approaches that could be taken to incorporate heterogeneity are the integration of a surface model over distributed, discrete portions of the landscape, or over a distribution function of the model parameters. However, the computational burden and parameter intensive nature of current land surface models in ACM limits the number of independent model runs and parameterizations that are feasible to accomplish for operational purposes. Therefore, simplications in the representation of the vertical exchange processes may be necessary to incorporate the effects of landscape variability and horizontal divergence of energy and water. The strategy is then to trade off the detail and rigor of point exchange calculations for the ability to repeat those calculations over extensive, complex terrain. It is clear the parameterization process for this approach must be automated such that large spatial databases collected from remotely sensed images, digital terrain models and digital maps can be efficiently summarized and transformed into the appropriate parameter sets. Ideally, the landscape should be partitioned into surface units that maximize between unit variance while minimizing within unit variance, although it is recognized that some level of surface heterogeneity will be retained at all scales. Therefore, the geographic data processing necessary to automate the distributed parameterization should be able to estimate or predict parameter distributional information within each surface unit.

Kinetics of Interaction between ADP-ribosylation Factor-1 (Arf1) and the Sec7 Domain of Arno Guanine Nucleotide Exchange Factor, Modulation by Allosteric Factors, and the Uncompetitive Inhibitor Brefeldin A

PubMed Central

Rouhana, Jad; Padilla, André; Estaran, Sébastien; Bakari, Sana; Delbecq, Stephan; Boublik, Yvan; Chopineau, Joel; Pugnière, Martine; Chavanieu, Alain

2013-01-01

The GDP/GTP nucleotide exchange of Arf1 is catalyzed by nucleotide exchange factors (GEF), such as Arno, which act through their catalytic Sec7 domain. This exchange is a complex mechanism that undergoes conformational changes and intermediate complex species involving several allosteric partners such as nucleotides, Mg2+, and Sec7 domains. Using a surface plasmon resonance approach, we characterized the kinetic binding parameters for various intermediate complexes. We first confirmed that both GDP and GTP counteract equivalently to the free-nucleotide binary Arf1-Arno complex stability and revealed that Mg2+ potentiates by a factor of 2 the allosteric effect of GDP. Then we explored the uncompetitive inhibitory mechanism of brefeldin A (BFA) that conducts to an abortive pentameric Arf1-Mg2+-GDP-BFA-Sec7 complex. With BFA, the association rate of the abortive complex is drastically reduced by a factor of 42, and by contrast, the 15-fold decrease of the dissociation rate concurs to stabilize the pentameric complex. These specific kinetic signatures have allowed distinguishing the level and nature as well as the fate in real time of formed complexes according to experimental conditions. Thus, we showed that in the presence of GDP, the BFA-resistant Sec7 domain of Arno can also associate to form a pentameric complex, which suggests that the uncompetitive inhibition by BFA and the nucleotide allosteric effect combine to stabilize such abortive complex. PMID:23255605

Role of coordination geometry in dictating the barrier to hydride migration in d6 square-pyramidal iridium and rhodium pincer complexes.

PubMed

Findlater, Michael; Cartwright-Sykes, Alison; White, Peter S; Schauer, Cynthia K; Brookhart, Maurice

2011-08-10

Syntheses of the olefin hydride complexes [(POCOP)M(H)(olefin)][BAr(f)(4)] (6a-M, M = Ir or Rh, olefin = C(2)H(4); 6b-M, M = Ir or Rh, olefin = C(3)H(6); POCOP = 2,6-bis(di-tert-butylphosphinito)benzene; BAr(f) = tetrakis(3,5-trifluoromethylphenyl)borate) are reported. A single-crystal X-ray structure determination of 6b-Ir shows a square-pyramidal coordination geometry for Ir, with the hydride ligand occupying the apical position. Dynamic NMR techniques were used to characterize these complexes. The rates of site exchange between the hydride and the olefinic hydrogens yielded ΔG(++) = 15.6 (6a-Ir), 16.8 (6b-Ir), 12.0 (6a-Rh), and 13.7 (6b-Rh) kcal/mol. The NMR exchange data also established that hydride migration in the propylene complexes yields exclusively the primary alkyl intermediate arising from 1,2-insertion. Unexpectedly, no averaging of the top and bottom faces of the square-pyramidal complexes is observed in the NMR spectra at high temperatures, indicating that the barrier for facial equilibration is >20 kcal/mol for both the Ir and Rh complexes. A DFT computational study was used to characterize the free energy surface for the hydride migration reactions. The classical terminal hydride complexes, [M(POCOP)(olefin)H](+), are calculated to be the global minima for both Rh and Ir, in accord with experimental results. In both the Rh ethylene and propylene complexes, the transition state for hydride migration (TS1) to form the agostic species is higher on the energy surface than the transition state for in-place rotation of the coordinated C-H bond (TS2), while for Ir, TS2 is the high point on the energy surface. Therefore, only for the case of the Rh complexes is the NMR exchange rate a direct measure of the hydride migration barrier. The trends in the experimental barriers as a function of M and olefin are in good agreement with the trends in the calculated exchange barriers. The calculated barriers for the hydride migration reaction in the Rh complexes are ∼2 kcal/mol higher than for the Ir complexes, despite the fact that the energy difference between the olefin hydride ground state and the agostic alkyl structure is ∼4 kcal/mol larger for Ir than for Rh. This feature, together with the high barrier for interchange of the top and bottom faces of the complexes, is proposed to arise from the unique coordination geometry of the agostic complexes and the strong preference for a cis-divacant octahedral geometry in four-coordinate intermediates. © 2011 American Chemical Society

[Mechanistic modelling allows to assess pathways of DNA lesion interactions underlying chromosome aberration formation].

PubMed

Eĭdel'man, Iu A; Slanina, S V; Sal'nikov, I V; Andreev, S G

2012-12-01

The knowledge of radiation-induced chromosomal aberration (CA) mechanisms is required in many fields of radiation genetics, radiation biology, biodosimetry, etc. However, these mechanisms are yet to be quantitatively characterised. One of the reasons is that the relationships between primary lesions of DNA/chromatin/chromosomes and dose-response curves for CA are unknown because the pathways of lesion interactions in an interphase nucleus are currently inaccessible for direct experimental observation. This article aims for the comparative analysis of two principally different scenarios of formation of simple and complex interchromosomal exchange aberrations: by lesion interactions at chromosome territories' surface vs. in the whole space of the nucleus. The analysis was based on quantitative mechanistic modelling of different levels of structures and processes involved in CA formation: chromosome structure in an interphase nucleus, induction, repair and interactions of DNA lesions. It was shown that the restricted diffusion of chromosomal loci, predicted by computational modelling of chromosome organization, results in lesion interactions in the whole space of the nucleus being impossible. At the same time, predicted features of subchromosomal dynamics agrees well with in vivo observations and does not contradict the mechanism of CA formation at the surface of chromosome territories. On the other hand, the "surface mechanism" of CA formation, despite having certain qualities, proved to be insufficient to explain high frequency of complex exchange aberrations observed by mFISH technique. The alternative mechanism, CA formation on nuclear centres is expected to be sufficient to explain frequent complex exchanges.

Coupled land surface/hydrologic/atmospheric models

NASA Technical Reports Server (NTRS)

Pielke, Roger; Steyaert, Lou; Arritt, Ray; Lahtakia, Mercedes; Smith, Chris; Ziegler, Conrad; Soong, Su Tzai; Avissar, Roni; Wetzel, Peter; Sellers, Piers

1993-01-01

The topics covered include the following: prototype land cover characteristics data base for the conterminous United States; surface evapotranspiration effects on cumulus convection and implications for mesoscale models; the use of complex treatment of surface hydrology and thermodynamics within a mesoscale model and some related issues; initialization of soil-water content for regional-scale atmospheric prediction models; impact of surface properties on dryline and MCS evolution; a numerical simulation of heavy precipitation over the complex topography of California; representing mesoscale fluxes induced by landscape discontinuities in global climate models; emphasizing the role of subgrid-scale heterogeneity in surface-air interaction; and problems with modeling and measuring biosphere-atmosphere exchanges of energy, water, and carbon on large scales.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammond, Glenn Edward; Bao, J; Huang, M

Hyporheic exchange is a critical mechanism shaping hydrological and biogeochemical processes along a river corridor. Recent studies on quantifying the hyporheic exchange were mostly limited to local scales due to field inaccessibility, computational demand, and complexity of geomorphology and subsurface geology. Surface flow conditions and subsurface physical properties are well known factors on modulating the hyporheic exchange, but quantitative understanding of their impacts on the strength and direction of hyporheic exchanges at reach scales is absent. In this study, a high resolution computational fluid dynamics (CFD) model that couples surface and subsurface flow and transport is employed to simulate hyporheicmore » exchanges in a 7-km long reach along the main-stem of the Columbia River. Assuming that the hyporheic exchange does not affect surface water flow conditions due to its negligible magnitude compared to the volume and velocity of river water, we developed a one-way coupled surface and subsurface water flow model using the commercial CFD software STAR-CCM+. The model integrates the Reynolds-averaged Navier-Stokes (RANS) equation solver with a realizable κ-ε two-layer turbulence model, a two-layer all y + wall treatment, and the volume of fluid (VOF) method, and is used to simulate hyporheic exchanges by tracking the free water-air interface as well as flow in the river and the subsurface porous media. The model is validated against measurements from acoustic Doppler current profiler (ADCP) in the stream water and hyporheic fluxes derived from a set of temperature profilers installed across the riverbed. The validated model is then employed to systematically investigate how hyporheic exchanges are influenced by surface water fluid dynamics strongly regulated by upstream dam operations, as well as subsurface structures (e.g. thickness of riverbed and subsurface formation layers) and hydrogeological properties (e.g. permeability). The results suggest that the thickness of riverbed alluvium layer is the dominant factor for reach-scale hyporheic exchanges, followed by the alluvium permeability, the depth of the underlying impermeable layer, and the assumption of hydrostatic pressure.« less

From watershed- to stream-reach-scale: the influence of multiple spatial scales on surface water-groundwater exchange

NASA Astrophysics Data System (ADS)

Caruso, Alice; Boano, Fulvio; Ridolfi, Luca

2015-04-01

Surface water bodies continuously interact with the subsurface and it is by now widely known that the hyporheic zone plays a key role in the mixing of river water with shallow groundwater. Hyporheic exchange occurs over a very wide range of spatial and temporal scales and the exchange processes at different scales interact and determine a complex system of nested flow cells. This intricacy results from the multiplicity of spatial scale that characterize landscape and river morphology. In the last years, many processes that regulate the surface-groundwater interactions have been elucidated and a more holistic view of groundwater and surface water has been adopted. However, despite several insights on the mechanisms of hyporheic exchange have been achieved, many important aspects remain to be clarified, i.e. how surface-groundwater interactions influence solute transport, microbial activity and biogeochemical transformations at the scale of entire watersheds. To date a deep knowledge of small-scale processes has been developed but what is lacking is a unifying overview of the role of surface water-groundwater exchange for the health of the whole water system at larger scales, i.e. the scale of the entire basin. In order to better understand the complex multiscale nature of spatial patterns of surface-subsurface exchange, we aim to assess the importance of the individual scales included in the range between watershed scale to stream reach scale. Hence, we study the large-scale subsurface flow field taking into account the surface-groundwater interactions induced by landscape topography from the basin scale to smaller scales ranging from tens of kilometers to tens of meters. The aim of this research is to analyze how individual topographic scales affect the flow field and to understand which ones are the most important and should be focused on. To study the impact of various scales of landscape topography we apply an analytical model that provides an exact solution of the underlying three dimensional groundwater flow and a numerical particle tracking routine that allows to obtain streamlines and residence time distributions from the flow field. Therefore, starting from a previously published mathematical tool we set the goal of investigating the interaction between the scales and clarifying their role. We consider real basin examples and describe subsurface flow at the landscape scale, identifying inflow patterns of groundwater to the river network, in order to obtain, in the near future, results to be used for conserving, managing and restoring of a riverine ecosystem.

Consequences of gas flux model choice on the interpretation of metabolic balance across 15 lakes

USGS Publications Warehouse

Dugan, Hilary; Woolway, R. Iestyn; Santoso, Arianto; Corman, Jessica; Jaimes, Aline; Nodine, Emily; Patil, Vijay; Zwart, Jacob A.; Brentrup, Jennifer A.; Hetherington, Amy; Oliver, Samantha K.; Read, Jordan S.; Winters, Kirsten; Hanson, Paul; Read, Emily; Winslow, Luke; Weathers, Kathleen

2016-01-01

Ecosystem metabolism and the contribution of carbon dioxide from lakes to the atmosphere can be estimated from free-water gas measurements through the use of mass balance models, which rely on a gas transfer coefficient (k) to model gas exchange with the atmosphere. Theoretical and empirically based models of krange in complexity from wind-driven power functions to complex surface renewal models; however, model choice is rarely considered in most studies of lake metabolism. This study used high-frequency data from 15 lakes provided by the Global Lake Ecological Observatory Network (GLEON) to study how model choice of kinfluenced estimates of lake metabolism and gas exchange with the atmosphere. We tested 6 models of k on lakes chosen to span broad gradients in surface area and trophic states; a metabolism model was then fit to all 6 outputs of k data. We found that hourly values for k were substantially different between models and, at an annual scale, resulted in significantly different estimates of lake metabolism and gas exchange with the atmosphere.

Fabrication and characterization of magnesium and calcium trimesate complexes via ion-exchange and one-pot self-assembly reaction

NASA Astrophysics Data System (ADS)

Ozer, Demet; Oztas, Nursen Altuntas; Köse, Dursun A.; Şahin, Onur

2018-03-01

Using two different synthesis methods, two diversified magnesium and calcium complexes were successfully prepared. When the ion exchange method was used, C9H14MgO11.H2O and C18H30Ca3O24 complexes were obtained. When the one-pot self-assembly reaction was used, C18H34Mg3O26.4H2O and C9H12CaO10 complexes were produced. The structural characterizations were performed by using X-ray diffraction, FT-IR and elemental analyses. Thermal behavior of complexes were also determined via TGA method. The both complexes of magnesium and calcium trimesate have micro and mesoporosity with low porosity because of hydrogen bonds. Then hydrogen storage capacities of complexes were also determined. The differences in synthesis method result in the differences on complexes structure, morphology (shape, particle size and specific surface area) and hydrogen storage capacities.

Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

NASA Astrophysics Data System (ADS)

Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

Biofouling on polymeric heat exchanger surfaces with E. coli and native biofilms.

PubMed

Pohl, S; Madzgalla, M; Manz, W; Bart, H J

2015-01-01

The biofouling affinity of different polymeric surfaces (polypropylene, polysulfone, polyethylene terephthalate, and polyether ether ketone) in comparison to stainless steel (SS) was studied for the model bacterium Escherichia coli K12 DSM 498 and native biofilms originating from Rhine water. The biofilm mass deposited on the polymer surfaces was minimized by several magnitudes compared to SS. The cell count and the accumulated biomass of E. coli on the polymer surfaces showed an opposing linear trend. The promising low biofilm formation on the polymers is attributed to the combination of inherent surface properties (roughness, surface energy and hydrophobicity) when compared to SS. The fouling characteristics of E. coli biofilms show good conformity with the more complex native biofilms investigated. The results can be utilized for the development of new polymer heat exchangers when using untreated river water as coolant or for other processes needing antifouling materials.

Echanges, interventions et actes de langage dans la structure de la conversation (Exchanges, Turns at Talk and Speech Acts in the Structure of Conversation).

ERIC Educational Resources Information Center

Roulet, Eddy

1981-01-01

Attempts to show how the surface structure of conversation can be described by means of a few principles and simple categories, regardless of its level of complexity. Accordingly, proposes a model that emphasizes the pragmatic functions of certain connectors and markers in the context of conversation exchanges. Societe Nouvelle Didier Erudition,…

Relationship between radiation-induced aberrations in individual chromosomes and their DNA content: effects of interaction distance

NASA Technical Reports Server (NTRS)

Wu, H.; Durante, M.; Lucas, J. N.

2001-01-01

PURPOSE: To study the effect of the interaction distance on the frequency of inter- and intrachromosome exchanges in individual chromosomes with respect to their DNA content. Assumptions: Chromosome exchanges are formed by misrejoining of two DNA double-strand breaks (DSB) induced within an interaction distance, d. It is assumed that chromosomes in G(0)/G(1) phase of the cell cycle occupy a spherical domain in a cell nucleus, with no spatial overlap between individual chromosome domains. RESULTS: Formulae are derived for the probability of formation of inter-, as well as intra-, chromosome exchanges relating to the DNA content of the chromosome for a given interaction distance. For interaction distances <1 microm, the relative frequency of interchromosome exchanges predicted by the present model is similar to that by Cigarran et al. (1998) based on the assumption that the probability of interchromosome exchanges is proportional to the "surface area" of the chromosome territory. The "surface area" assumption is shown to be a limiting case of d-->0 in the present model. The present model also predicts that the probability of intrachromosome exchanges occurring in individual chromosomes is proportional to their DNA content with correction terms. CONCLUSION: When the interaction distance is small, the "surface area" distribution for chromosome participation in interchromosome exchanges has been expected. However, the present model shows that for the interaction distance as large as 1 microm, the predicted probability of interchromosome exchange formation is still close to the surface area distribution. Therefore, this distribution does not necessarily rule out the formation of complex chromosomal aberrations by long-range misrejoining of DSB.

Isotopic Exchange in Porous and Dense Magnesium Borohydride.

PubMed

Zavorotynska, Olena; Deledda, Stefano; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Hauback, Bjørn C

2015-09-01

Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of electrical imaging and distributed temperature sensing methods to characterize surface water–groundwater exchange regulating uranium transport at the Hanford 300 Area, Washington

USGS Publications Warehouse

Slater, Lee D.; Ntarlagiannis, Dimitrios; Day-Lewis, Frederick D.; Mwakanyamale, Kisa; Versteeg, Roelof J.; Ward, Andy; Strickland, Christopher; Johnson, Carole D.; Lane, John W.

2010-01-01

We explored the use of continuous waterborne electrical imaging (CWEI), in conjunction with fiber‐optic distributed temperature sensor (FO‐DTS) monitoring, to improve the conceptual model for uranium transport within the Columbia River corridor at the Hanford 300 Area, Washington. We first inverted resistivity and induced polarization CWEI data sets for distributions of electrical resistivity and polarizability, from which the spatial complexity of the primary hydrogeologic units was reconstructed. Variations in the depth to the interface between the overlying coarse‐grained, high‐permeability Hanford Formation and the underlying finer‐grained, less permeable Ringold Formation, an important contact that limits vertical migration of contaminants, were resolved along ∼3 km of the river corridor centered on the 300 Area. Polarizability images were translated into lithologic images using established relationships between polarizability and surface area normalized to pore volume (Spor). The FO‐DTS data recorded along 1.5 km of cable with a 1 m spatial resolution and 5 min sampling interval revealed subreaches showing (1) temperature anomalies (relatively warm in winter and cool in summer) and (2) a strong correlation between temperature and river stage (negative in winter and positive in summer), both indicative of reaches of enhanced surface water–groundwater exchange. The FO‐DTS data sets confirm the hydrologic significance of the variability identified in the CWEI and reveal a pattern of highly focused exchange, concentrated at springs where the Hanford Formation is thickest. Our findings illustrate how the combination of CWEI and FO‐DTS technologies can characterize surface water–groundwater exchange in a complex, coupled river‐aquifer system.

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences.

PubMed

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug-fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug-fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid.

The load and release characteristics on a strong cationic ion-exchange fiber: kinetics, thermodynamics, and influences

PubMed Central

Yuan, Jing; Gao, Yanan; Wang, Xinyu; Liu, Hongzhuo; Che, Xin; Xu, Lu; Yang, Yang; Wang, Qifang; Wang, Yan; Li, Sanming

2014-01-01

Ion-exchange fibers were different from conventional ion-exchange resins in their non-cross-linked structure. The exchange was located on the surface of the framework, and the transport resistance reduced significantly, which might mean that the exchange is controlled by an ionic reaction instead of diffusion. Therefore, this work aimed to investigate the load and release characteristics of five model drugs with the strong cationic ion-exchange fiber ZB-1. Drugs were loaded using a batch process and released in United States Pharmacopoeia (USP) dissolution apparatus 2. Opposing exchange kinetics, suitable for the special structure of the fiber, were developed for describing the exchange process with the help of thermodynamics, which illustrated that the load was controlled by an ionic reaction. The molecular weight was the most important factor to influence the drug load and release rate. Strong alkalinity and rings in the molecular structures made the affinity between the drug and fiber strong, while logP did not cause any profound differences. The drug–fiber complexes exhibited sustained release. Different kinds and concentrations of counter ions or different amounts of drug–fiber complexes in the release medium affected the release behavior, while the pH value was independent of it. The groundwork for in-depth exploration and further application of ion-exchange fibers has been laid. PMID:25114504

Combining H/D exchange mass spectroscopy and computational docking reveals extended DNA-binding surface on uracil-DNA glycosylase

PubMed Central

Roberts, Victoria A.; Pique, Michael E.; Hsu, Simon; Li, Sheng; Slupphaug, Geir; Rambo, Robert P.; Jamison, Jonathan W.; Liu, Tong; Lee, Jun H.; Tainer, John A.; Ten Eyck, Lynn F.; Woods, Virgil L.

2012-01-01

X-ray crystallography provides excellent structural data on protein–DNA interfaces, but crystallographic complexes typically contain only small fragments of large DNA molecules. We present a new approach that can use longer DNA substrates and reveal new protein–DNA interactions even in extensively studied systems. Our approach combines rigid-body computational docking with hydrogen/deuterium exchange mass spectrometry (DXMS). DXMS identifies solvent-exposed protein surfaces; docking is used to create a 3-dimensional model of the protein–DNA interaction. We investigated the enzyme uracil-DNA glycosylase (UNG), which detects and cleaves uracil from DNA. UNG was incubated with a 30 bp DNA fragment containing a single uracil, giving the complex with the abasic DNA product. Compared with free UNG, the UNG–DNA complex showed increased solvent protection at the UNG active site and at two regions outside the active site: residues 210–220 and 251–264. Computational docking also identified these two DNA-binding surfaces, but neither shows DNA contact in UNG–DNA crystallographic structures. Our results can be explained by separation of the two DNA strands on one side of the active site. These non-sequence-specific DNA-binding surfaces may aid local uracil search, contribute to binding the abasic DNA product and help present the DNA product to APE-1, the next enzyme on the DNA-repair pathway. PMID:22492624

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammond, Glenn Edward; Yang, Xiaofan; Song, Xuehang

The groundwater-surface water interaction zone (GSIZ) plays an important role in riverine and watershed ecosystems as the exchange of waters of variable composition and temperature (hydrologic exchange flows) stimulate microbial activity and associated biogeochemical reactions. Variable temporal and spatial scales of hydrologic exchange flows, heterogeneity of the subsurface environment, and complexity of biogeochemical reaction networks in the GSIZ present challenges to incorporation of fundamental process representations and model parameterization across a range of spatial scales (e.g. from pore-scale to field scale). This paper presents a novel hybrid multiscale simulation approach that couples hydrologic-biogeochemical (HBGC) processes between two distinct length scalesmore » of interest.« less

The roles of protein disulphide isomerase family A, member 3 (ERp57) and surface thiol/disulphide exchange in human spermatozoa-zona pellucida binding.

PubMed

Wong, Chi-Wai; Lam, Kevin K W; Lee, Cheuk-Lun; Yeung, William S B; Zhao, Wei E; Ho, Pak-Chung; Ou, Jian-Ping; Chiu, Philip C N

2017-04-01

Are multimeric sperm plasma membrane protein complexes, ERp57 and sperm surface thiol content involved in human spermatozoa-zona pellucida (ZP) interaction? ERp57 is a component of a multimeric spermatozoa-ZP receptor complex involved in regulation of human spermatozoa-ZP binding via up-regulation of sperm surface thiol content. A spermatozoon acquires its fertilization capacity within the female reproductive tract by capacitation. Spermatozoa-ZP receptor is suggested to be a composite structure that is assembled into a functional complex during capacitation. Sperm surface thiol content is elevated during capacitation. ERp57 is a protein disulphide isomerase that modulates the thiol-disulphide status of proteins. The binding ability and components of protein complexes in extracted membrane protein fractions of spermatozoa were studied. The roles of capacitation, thiol-disulphide reagent treatments and ERp57 on sperm functions and sperm surface thiol content were assessed. Spermatozoa were obtained from semen samples from normozoospermic men. Human oocytes were obtained from an assisted reproduction programme. Blue native polyacrylamide gel electrophoresis, western ligand blotting and mass spectrometry were used to identify the components of solubilized ZP/ZP3-binding complexes. The localization and expression of sperm surface thiol and ERp57 were studied by immunostaining and sperm surface protein biotinylation followed by western blotting. Sperm functions were assessed by standard assays. Several ZP-binding complexes were isolated from the cell membrane of capacitated spermatozoa. ERp57 was a component of one of these complexes. Capacitation significantly increased the sperm surface thiol content, acrosomal thiol distribution and ERp57 expression on sperm surface. Sperm surface thiol and ERp57 immunoreactivity were localized to the acrosomal region of spermatozoa, a region responsible for ZP-binding. Up-regulation of the surface thiol content or ERp57 surface expression in vitro stimulated ZP-binding capacity of human spermatozoa. Blocking of ERp57 function by specific antibody or inhibitors against ERp57 reduced the surface thiol content and ZP-binding capacity of human spermatozoa. N/A. The mechanisms by which up-regulation of surface thiol content stimulates spermatozoa-ZP binding have not been depicted. Thiol-disulphide exchange is a crucial event in capacitation. ERp57 modulates the event and the subsequent fertilization process. Modulation of the surface thiol content of the spermatozoa of subfertile men may help to increase fertilization rate in assisted reproduction. This work was supported by The Hong Kong Research Grant Council Grant HKU764611 and HKU764512M to P.C.N.C. The authors have no competing interests. © The Author 2017. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com

Leaching heavy metals from the surface soil of reclaimed tidal flat by alternating seawater inundation and air drying.

PubMed

Guo, Shi-Hong; Liu, Zhen-Ling; Li, Qu-Sheng; Yang, Ping; Wang, Li-Li; He, Bao-Yan; Xu, Zhi-Min; Ye, Jin-Shao; Zeng, Eddy Y

2016-08-01

Leaching experiments were conducted in a greenhouse to simulate seawater leaching combined with alternating seawater inundation and air drying. We investigated the heavy metal release of soils caused by changes associated with seawater inundation/air drying cycles in the reclaimed soils. After the treatment, the contents of all heavy metals (Cd, Pb, Cr, and Cu), except Zn, in surface soil significantly decreased (P < 0.05), with removal rates ranging from 10% to 51%. The amounts of the exchangeable, carbonate, reducible, and oxidizable fractions also significantly decreased (P < 0.05). Moreover, prolonged seawater inundation enhanced the release of heavy metals. Measurement of diffusive gradients in thin films indicated that seawater inundation significantly increased the re-mobility of heavy metals. During seawater inundation, iron oxide reduction induced the release of heavy metals in the reducible fraction. Decomposition of organic matter, and complexation with dissolved organic carbon decreased the amount of heavy metals in the oxidizable fraction. Furthermore, complexation of chloride ions and competition of cations during seawater inundation and/or leaching decreased the levels of heavy metals in the exchangeable fraction. By contrast, air drying significantly enhanced the concentration of heavy metals in the exchangeable fraction. Therefore, the removal of heavy metals in the exchangeable fraction can be enhanced during subsequent leaching with seawater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces.

PubMed

Cha, Jihoon; Cui, Mingcan; Jang, Min; Cho, Sang-Hyun; Moon, Deok Hyun; Khim, Jeehyeong

2011-01-01

This study examines the adsorption isotherms, kinetics and mechanisms of Pb²(+) sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²(+) in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²(+) with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²(+) and PO₄³⁻ concentrations during the metal sorption processes. The Pb²(+) sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb(+). The sorption isotherm results indicated that Pb²(+) sorption onto the Langmuir and Freundlich constant q(max) and K( F ) is 9.52 and 8.18 mg g⁻¹, respectively. Sorption kinetics results indicated that Pb²(+) sorption onto WCBP was pseudo-second-order rate constants K₂ was 1.12 g mg⁻¹ h⁻¹. The main mechanism is adsorption or surface complexation (≡POPb(+): 61.6%), co-precipitation or ion exchange [Ca₃(.)₉₃ Pb₁(.)₀₇ (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L⁻¹ and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²(+) removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²(+) indicates its potential as another promising way to remediate Pb²(+)-contaminated media.

Nuclear reactor cooling system decontamination reagent regeneration. [PWR; BWR

DOEpatents

Anstine, L.D.; James, D.B.; Melaika, E.A.; Peterson, J.P. Jr.

1980-06-06

An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution is described. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.

Nuclear reactor cooling system decontamination reagent regeneration

DOEpatents

Anstine, Larry D.; James, Dean B.; Melaika, Edward A.; Peterson, Jr., John P.

1985-01-01

An improved method for decontaminating the coolant system of water-cooled nuclear power reactors and for regenerating the decontamination solution. A small amount of one or more weak-acid organic complexing agents is added to the reactor coolant, and the pH is adjusted to form a decontamination solution which is circulated throughout the coolant system to dissolve metal oxides from the interior surfaces and complex the resulting metal ions and radionuclide ions. The coolant containing the complexed metal ions and radionuclide ions is passed through a strong-base anion exchange resin bed which has been presaturated with a solution containing the complexing agents in the same ratio and having the same pH as the decontamination solution. As the decontamination solution passes through the resin bed, metal-complexed anions are exchanged for the metal-ion-free anions on the bed, while metal-ion-free anions in the solution pass through the bed, thus removing the metal ions and regenerating the decontamination solution.

Surface complexation model for multisite adsorption of copper(II) onto kaolinite

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2005-08-01

We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu 2+ on ion exchangeable ≡X-H + sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH) 6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH) 2Cu(OH) 20, tridentate (≡Al 3O(OH) 2)Cu 2(OH) 30 and ≡X-Cu 2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions

Comparative adsorption of Eu(III) and Am(III) on TPD.

PubMed

Fan, Q H; Zhao, X L; Ma, X X; Yang, Y B; Wu, W S; Zheng, G D; Wang, D L

2015-09-01

Comparative adsorption behaviors of Eu(III) and Am(III) on thorium phosphate diphosphate (TPD), i.e., Th4(PO4)4P2O7, have been studied using a batch approach and surface complexation model (SCM) in this study. The results showed that Eu(III) and Am(III) adsorption increased to a large extent with the increase in TPD dose. Strong pH-dependence was observed in both Eu(III) and Am(III) adsorption processes, suggesting that inner-sphere complexes (ISCs) were possibly responsible for the adsorption of Eu(III) and Am(III). Meanwhile, the adsorption of Eu(III) and Am(III) decreased to a different extent with the increase in ion strength, which was possibly related to outer-sphere complexes and/or ion exchange. In the presence of fulvic acid (FA), the adsorption of Eu(III) and Am(III) showed high enhancement mainly due to the ternary surface complexes of TPD-FA-Eu(3+) and TPD-FA-Am(3+). The SCM showed that one ion exchange (≡S3Am/Eu) and two ISCs (≡(XO)2Am/EuNO3 and ≡(YO)2Am/EuNO3) seemed more reasonable to quantitatively describe the adsorption edges of both Eu(III) and Am(III). Our findings obviously showed that Eu(III) could be a good analogue to study actinide behaviors in practical terms. However, it should be kept in mind that there are still obvious differences between the characteristics of Eu(III) and Am(III) in some special cases, for instance, the complex ability with organic matter and adsorption affinity to a solid surface.

Global observations and modeling of atmosphere-surface exchange of elemental mercury: a critical review

NASA Astrophysics Data System (ADS)

Zhu, Wei; Lin, Che-Jen; Wang, Xun; Sommar, Jonas; Fu, Xuewu; Feng, Xinbin

2016-04-01

Reliable quantification of air-surface fluxes of elemental Hg vapor (Hg0) is crucial for understanding mercury (Hg) global biogeochemical cycles. There have been extensive measurements and modeling efforts devoted to estimating the exchange fluxes between the atmosphere and various surfaces (e.g., soil, canopies, water, snow, etc.) in the past three decades. However, large uncertainties remain due to the complexity of Hg0 bidirectional exchange, limitations of flux quantification techniques and challenges in model parameterization. In this study, we provide a critical review on the state of science in the atmosphere-surface exchange of Hg0. Specifically, the advancement of flux quantification techniques, mechanisms in driving the air-surface Hg exchange and modeling efforts are presented. Due to the semi-volatile nature of Hg0 and redox transformation of Hg in environmental media, Hg deposition and evasion are influenced by multiple environmental variables including seasonality, vegetative coverage and its life cycle, temperature, light, moisture, atmospheric turbulence and the presence of reactants (e.g., O3, radicals, etc.). However, the effects of these processes on flux have not been fundamentally and quantitatively determined, which limits the accuracy of flux modeling. We compile an up-to-date global observational flux database and discuss the implication of flux data on the global Hg budget. Mean Hg0 fluxes obtained by micrometeorological measurements do not appear to be significantly greater than the fluxes measured by dynamic flux chamber methods over unpolluted surfaces (p = 0.16, one-tailed, Mann-Whitney U test). The spatiotemporal coverage of existing Hg0 flux measurements is highly heterogeneous with large data gaps existing in multiple continents (Africa, South Asia, Middle East, South America and Australia). The magnitude of the evasion flux is strongly enhanced by human activities, particularly at contaminated sites. Hg0 flux observations in East Asia are comparatively larger in magnitude than the rest of the world, suggesting substantial re-emission of previously deposited mercury from anthropogenic sources. The Hg0 exchange over pristine surfaces (e.g., background soil and water) and vegetation needs better constraints for global analyses of the atmospheric Hg budget. The existing knowledge gap and the associated research needs for future measurements and modeling efforts for the air-surface exchange of Hg0 are discussed.

Ligand Exchange Kinetics of Environmentally Relevant Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panasci, Adele Frances

2014-07-15

The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb tomore » mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.« less

Levels of dissolved zinc and cadmium in some surface waters of western Nigeria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fatoki, O.S.

1993-12-31

Dissolved zinc and cadmium in some surface waters of Western Nigeria were separated and quantified using anion exchange of their chloro-complexes and detected by atomic absorption spectrophotometry. Concentrations of zinc and cadmium found in tested water samples ranged from 0.99 to 2.97 mg L{sup {minus}1} and 0.13 to 0.17 mg L{sup {minus}1}, respectively. 35 refs., 2 tabs.

An Experimental and Theoretical Evaluation of Multi-site Cadmium(II) Exchange in Designed Three-Stranded Coiled Coil Peptides

PubMed Central

Chakraborty, Saumen; Iranzo, Olga; Zuiderweg, Erik R.P.; Pecoraro, Vincent L.

2012-01-01

An important factor that defines the toxicity of elements such as cadmium(II), mercury(II), and lead(II) with biological macromolecules is metal ion exchange dynamics. Intriguingly, little is known about the fundamental rates and mechanisms of metal ion exchange into proteins, especially helical bundles. Herein, we investigate the exchange kinetics of cadmium(II) using de novo designed three-stranded coiled coil peptides that contain metal complexing cysteine thiolates as a model for the incorporation of this ion into trimeric, parallel helical bundles. Peptides were designed containing both single cadmium(II) binding site, GrandL12AL16C [Grand=AcG-(LKALEEK)5-GNH2], GrandL26AL30C, and GrandL26AE28QL30C, as well as GrandL12AL16CL26AL30C with two cadmium(II) binding sites. The binding of cadmium(II) to any of these sites is of high affinity (KA > 3×107 M−1). Using 113Cd NMR spectroscopy, cadmium(II) binding to these designed peptides was monitored. While the cadmium(II) binding is in extreme slow exchange without showing any chemical shift changes, incremental line broadening for the bound 113cadmium(II) signal is observed when excess 113cadmium(II) is titrated into the peptides. Most dramatically, for one site, L26AL30C, all 113cadmium(II) NMR signals disappear once a 1.7:1 ratio of cadmium(II)/(peptide)3 is reached. The observed processes are not compatible with simple “free-bound” two-site exchange kinetics at any time regime. The experimental results can, however, be simulated in detail with a multi-site binding model, which features additional cadmium(II) binding site(s) which, once occupied, perturb the primary binding site. This model is expanded into differential equations for five-site NMR chemical exchange. The numerical integration of these equations exhibits progressive loss of the primary site NMR signal without a chemical shift change and with limited line broadening, in good agreement with the observed experimental data. The mathematical model is interpreted in molecular terms as representing binding of excess cadmium(II) to surface Glu residues located at the helical interfaces. In the absence of cadmium(II), the Glu residues stabilize the three-helical structure though salt bridge interactions with surface Lys residues. We hypothesize that cadmium(II) interferes with these surface ion pairs, destabilizing the helical structure, and perturbing the primary cadmium(II) binding site. This hypothesis is supported by the observation that the cadmium(II)-excess line broadening is attenuated in GrandL26AE28QL30C where a surface Glu(28), close to the metal binding site, was changed to Gln. The external binding site may function as an entry pathway for cadmium(II) to find its internal binding site following a molecular rearrangement which may serve as a basis for our understanding of metal complexation, transport and exchange in complex native systems containing α-helical bundles. PMID:22394049

Dynamic Stabilization of Metal Oxide–Water Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBriarty, Martin E.; von Rudorff, Guido Falk; Stubbs, Joanne E.

2017-02-08

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (1102) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locationsmore » and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.« less

Sorption of Sr, Co and Zn on illite: Batch experiments and modelling including Co in-diffusion measurements on compacted samples

NASA Astrophysics Data System (ADS)

Montoya, V.; Baeyens, B.; Glaus, M. A.; Kupcik, T.; Marques Fernandes, M.; Van Laer, L.; Bruggeman, C.; Maes, N.; Schäfer, T.

2018-02-01

Experimental investigations on the uptake of divalent cations (Sr, Co and Zn) onto illite (Illite du Puy, Le-Puy-en-Velay, France) were carried out by three different international research groups (Institute for Nuclear Waste Disposal, KIT (Germany), Group Waste & Disposal, SCK-CEN, (Belgium) and Laboratory for Waste Management, PSI (Switzerland)) in the framework of the European FP7 CatClay project. The dependence of solid-liquid distribution ratios (Rd values) on pH at trace metal conditions (sorption edges) and on the metal ion concentration (sorption isotherms) was determined in dilute suspensions of homo-ionic Na-illite (Na-IdP) under controlled N2 atmosphere. The experimental results were modelled using the 2 Site Protolysis Non Electrostatic Surface Complexation and Cation Exchange (2SPNE SC/CE) sorption model. The sorption of Sr depends strongly on ionic strength, while a rather weak pH dependence is observed in a pH range between 3 and 11. The data were modelled with cation exchange reactions, taking into account competition with H, K, Ca, Mg and Al, and surface complexation on weak amphotheric edge sites at higher pH values. The sorption of Co on Na-IdP, however, is strongly pH dependent. Cation exchange on the planar sites and surface complexation on strong and weak amphoteric edge sites were used to describe the Co sorption data. Rd values for Co derived from in-diffusion measurements on compacted Na-IdP samples (bulk-dry density of 1700 kg m-3) between pH 5.0 and 9.0 are in good agreement with the batch sorption data. The equivalence of both approaches to measure sorption was thus confirmed for the present test system. In addition, the results highlight the importance of both major and minor surface species for the diffusive transport behaviour of strongly sorbing metal cations. While surface complexes at the edge sites determine largely the Rd value, the diffusive flux may be governed by those species bound to the planar sites, even at low fractional occupancies. The pH dependent sorption determined for trace Zn concentrations showed large Rd values across the entire pH range with almost no dependence on the background electrolyte concentration. Additional sorption experiments carried out at substantial fractional Zn loadings demonstrated that the selectivity for the exchange of Na+ for Zn2+ at the planar sites could not explain the large Rd values measured at low pH and trace Zn concentrations. This suggests that another mechanism is ruling Zn uptake under these conditions.

Biotic Control of Surface pH and Evidence of Light-Induced H+ Pumping and Ca2+-H+ Exchange in a Tropical Crustose Coralline Alga.

PubMed

Hofmann, Laurie C; Koch, Marguerite; de Beer, Dirk

2016-01-01

Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4' diisothiocyanatostilbene-2,2'-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA.

Biotic Control of Surface pH and Evidence of Light-Induced H+ Pumping and Ca2+-H+ Exchange in a Tropical Crustose Coralline Alga

PubMed Central

Hofmann, Laurie C.; Koch, Marguerite; de Beer, Dirk

2016-01-01

Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4′ diisothiocyanatostilbene-2,2′-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA. PMID:27459463

Defect controlled magnetism in FeP/graphene/Ni(111)

PubMed Central

Bhandary, Sumanta; Eriksson, Olle; Sanyal, Biplab

2013-01-01

Spin switching of organometallic complexes by ferromagnetic surfaces is an important topic in the area of molecular nanospintronics. Moreover, graphene has been shown as a 2D surface for physisorption of molecular magnets and strain engineering on graphene can tune the spin state of an iron porphyrin (FeP) molecule from S = 1 to S = 2. Our ab initio density functional calculations suggest that a pristine graphene layer placed between a Ni(111) surface and FeP yields an extremely weak exchange interaction between FeP and Ni whereas the introduction of defects in graphene shows a variety of ferromagnetic and antiferromagnetic exchange interactions. Moreover, these defects control the easy axes of magnetization, strengths of magnetic anisotropy energies and spin-dipolar contributions. Our study suggests a new way of manipulating molecular magnetism by defects in graphene and hence has the potential to be explored in designing spin qubits to realize logic operations in molecular nanospintronics. PMID:24296980

An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

PubMed

Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

2016-12-06

In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (E Ni(i) ), (ii) assess their corresponding kinetic constants (k (i) ), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k (i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

The Characterization of Atmospheric Boundary Layer Depth and Turbulence in a Mixed Rural and Urban Convective Environment

NASA Astrophysics Data System (ADS)

Hicks, Micheal M.

A comprehensive analysis of surface-atmosphere flux exchanges over a mixed rural and urban convective environment is conducted at Howard University Beltsville, MD Research Campus. This heterogeneous site consists of rural, suburban and industrial surface covers to its south, east and west, within a 2 km radius of a flux sensor. The eddy covariance method is utilized to estimate surface-atmosphere flux exchanges of momentum, heat and moisture. The attributes of these surface flux exchanges are contrasted to those of classical homogeneous sites and assessed for accuracy, to evaluate the following: (I) their similarity to conventional convective boundary layer (CBL) processes and (II) their representativeness of the surrounding environment's turbulent properties. Both evaluations are performed as a function of upwind surface conditions. In particular, the flux estimates' obedience to spectrum power laws and similarity theory relationships is used for performing the first evaluation, and their ability to close the surface energy balance and accurately model CBL heights is used for the latter. An algorithm that estimates atmospheric boundary layer heights from observed lidar extinction backscatter was developed, tested and applied in this study. The derived lidar based CBL heights compared well with those derived from balloon borne soundings, with an overall Pearson correlation coefficient and standard deviation of 0.85 and 223 m, respectively. This algorithm assisted in the evaluation of the response of CBL processes to surface heterogeneity, by deriving high temporal CBL heights and using them as independent references of the surrounding area averaged sensible heat fluxes. This study found that the heterogeneous site under evaluation was rougher than classical homogeneous sites, with slower dissipation rates of turbulent kinetic energy. Flux measurements downwind of the industrial complexes exhibited enhanced efficiency in surface-atmosphere momentum, heat, and moisture transport relative to their similarity theory predictions. In addition, these enhanced heat flux estimates ingested into the CBL slab model overestimated observed CBL heights. More spatial flux observations are needed to better understand the role that the industrial complexes are playing in enhancing the efficiency of turbulent processes, which may have important implications on the role humans are assuming in regional climate change.

The influences of land use and land cover on climate; an analysis of the Washington-Baltimore area that couples remote sensing with numerical simulation

USGS Publications Warehouse

Pease, R.W.; Jenner, C.B.; Lewis, J.E.

1980-01-01

The Sun drives the atmospheric heat engine by warming the terrestrial surface which in turn warms the atmosphere above. Climate, therefore, is significantly controlled by complex interaction of energy flows near and at the terrestrial surface. When man alters this delicate energy balance by his use of the land, he may alter his climatic environment as well. Land use climatology has emerged as a discipline in which these energy interactions are studied; first, by viewing the spatial distributions of their surface manifestations, and second, by analyzing the energy exchange processes involved. Two new tools for accomplishing this study are presented: one that can interpret surface energy exchange processes from space, and another that can simulate the complex of energy transfers by a numerical simulation model. Use of a satellite-borne multispectral scanner as an imaging radiometer was made feasible by devising a gray-window model that corrects measurements made in space for the effects of the atmosphere in the optical path. The simulation model is a combination of mathematical models of energy transfer processes at or near the surface. Integration of these two analytical approaches was applied to the Washington-Baltimore area to coincide with the August 5, 1973, Skylab 3 overpass which provided data for constructing maps of the energy characteristics of the Earth's surface. The use of the two techniques provides insights into the relationship of climate to land use and land cover and in predicting alterations of climate that may result from alterations of the land surface.

Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

PubMed

Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

2016-09-12

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

A Coupled THMC model of FEBEX mock-up test

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Liange; Samper, Javier

2008-09-15

FEBEX (Full-scale Engineered Barrier EXperiment) is a demonstration and research project for the engineered barrier system (EBS) of a radioactive waste repository in granite. It includes two full-scale heating and hydration tests: the in situ test performed at Grimsel (Switzerland) and a mock-up test operating at CIEMAT facilities in Madrid (Spain). The mock-up test provides valuable insight on thermal, hydrodynamic, mechanical and chemical (THMC) behavior of EBS because its hydration is controlled better than that of in situ test in which the buffer is saturated with water from the surrounding granitic rock. Here we present a coupled THMC model ofmore » the mock-up test which accounts for thermal and chemical osmosis and bentonite swelling with a state-surface approach. The THMC model reproduces measured temperature and cumulative water inflow data. It fits also relative humidity data at the outer part of the buffer, but underestimates relative humidities near the heater. Dilution due to hydration and evaporation near the heater are the main processes controlling the concentration of conservative species while surface complexation, mineral dissolution/precipitation and cation exchanges affect significantly reactive species as well. Results of sensitivity analyses to chemical processes show that pH is mostly controlled by surface complexation while dissolved cations concentrations are controlled by cation exchange reactions.« less

Processing of N-linked oligosaccharide depends on its location in the anion exchanger, AE1, membrane glycoprotein.

PubMed

Li, J; Quilty, J; Popov, M; Reithmeier, R A

2000-07-01

The human erythrocyte anion exchanger (AE)1 (Band 3) contains a single complex N-linked oligosaccharide that is attached to Asn(642) in the fourth extracellular loop of this polytopic membrane protein, while other isoforms (AE2, AE3 and trout AE1) are N-glycosylated on the preceding extracellular loop. Human AE1 expressed in transfected human embryonic kidney (HEK)-293 or COS-7 cells contained a high-mannose oligosaccharide. The lack of oligosaccharide processing was not due to retention of AE1 in the endoplasmic reticulum since biotinylation assays showed that approx. 30% of the protein was expressed at the cell surface. Moving the N-glycosylation site to the preceding extracellular loop in an AE1 glycosylation mutant (N555) resulted in processing of the oligosaccharide and production of a complex form of AE1. A double N-glycosylation mutant (N555/N642) contained both a high-mannose and a complex oligosaccharide chain. The complex form of the N555 mutant could be biotinylated showing that this form of the glycoprotein was at the cell surface. Pulse-chase experiments showed that the N555 mutant was efficiently converted from a high-mannose to a complex oligosaccharide with a half-time of approx. 4 h, which reflected the time course of trafficking of AE1 from the endoplasmic reticulum to the plasma membrane. The turnover of the complex form of the N555 mutant occurred with a half-life of approx. 15 h. The results show that the oligosaccharide attached to the endogenous site in extracellular loop 4 in human AE1 is not processed in HEK-293 or COS-7 cells, while the oligosaccharide attached to the preceding loop is converted into the complex form.

Ultrafast Multi-Dimentional Infrared Vibrational Echo Spectroscopy of Molecular Dynamics on Surfaces and in Bulk Systems

DTIC Science & Technology

2012-02-28

dimethylsulfoxide ( DMSO ). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO , both types of hydrogen bonded complexes exist. The...transition (negative) in the 2D IR spectrum. Also, line shape distortions caused by solvent background absorption and finite pulse durations do not affect...conditions as  = 7  1 ps. This is the first direct measurement of hydrogen bond exchange. b. Solute- Solvent Complex Switching Dynamics3 Hydrogen

Ultrafast Multi-Dimensional Infrared Vibrational Echo Spectroscopy of Molecular Dynamics on Surfaces and in Bulk Systems

DTIC Science & Technology

2012-02-28

dimethylsulfoxide ( DMSO ). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO , both types of hydrogen bonded complexes exist. The...transition (negative) in the 2D IR spectrum. Also, line shape distortions caused by solvent background absorption and finite pulse durations do not affect...conditions as  = 7  1 ps. This is the first direct measurement of hydrogen bond exchange. b. Solute- Solvent Complex Switching Dynamics3 Hydrogen

Turbulent water vapor exchanges and two source energy balance model estimated fluxes of heterogeneous vineyard canopies

NASA Astrophysics Data System (ADS)

Los, S.; Hipps, L.; Alfieri, J. G.; Prueger, J. H.; Kustas, W. P.

2017-12-01

Agriculture in semi-arid regions is globally facing increasing stress on water resources. Hence, knowledge of water used in irrigated crops is essential for water resource management. However, quantifying spatial and temporal distribution of evapotranspiration (ET) has proven difficult because of the inherent complexities involved. Understanding of the complex biophysical relationships that govern ET is incomplete, particularly for heterogeneous vegetation. The USDA-ARS is developing a remotely-sensed ET modeling system that utilizes a two-source energy balance (TSEB) model capable of simulating turbulent water and energy exchange from measurements of radiometric land surface temperature. The modeling system has been tested over a number of vegetated surfaces and is currently being validated for vineyard sites in the Central Valley of California through the Grape Remote sensing Atmospheric Profiling & Evapotranspiration eXperiment (GRAPEX). The highly variable, elevated canopy structure and semi-arid climatic conditions of these sites give the opportunity to gain knowledge of both turbulent exchange processes and the TSEB model's ability to simulate turbulent fluxes for heterogeneous vegetation. Analyzed are fast-response (20 Hz) 3-D velocity, temperature, and humidity measurements gathered over 4 years at two vineyard sites. These data were collected at a height of 5 m, within the surface layer but above the canopy, and at 1.5 m, below the canopy top. Power spectra and cross-spectra are used to study behavior of turbulent water vapor exchanges and coupling between the canopy layer and surface layer under various atmospheric conditions. Frequent light winds and unstable daytime conditions, combined with the complicated canopy structure, often induce intermittent and episodic turbulence transport. This resulted in a modal behavior alternating between periods of more continuous canopy venting and periods where water vapor fluxes are dominated by transient, low frequency events. Aerodynamic resistances derived by the TSEB model are examined, and modeled fluxes of water and energy are compared to measured values for various conditions. Efforts to characterize periods of intermittent behavior are presented and particular attention to model performance is given to these intermittent periods.

Microbial mutualism at a distance: The role of geometry in diffusive exchanges

NASA Astrophysics Data System (ADS)

Peaudecerf, François J.; Bunbury, Freddy; Bhardwaj, Vaibhav; Bees, Martin A.; Smith, Alison G.; Goldstein, Raymond E.; Croze, Ottavio A.

2018-02-01

The exchange of diffusive metabolites is known to control the spatial patterns formed by microbial populations, as revealed by recent studies in the laboratory. However, the matrices used, such as agarose pads, lack the structured geometry of many natural microbial habitats, including in the soil or on the surfaces of plants or animals. Here we address the important question of how such geometry may control diffusive exchanges and microbial interaction. We model mathematically mutualistic interactions within a minimal unit of structure: two growing reservoirs linked by a diffusive channel through which metabolites are exchanged. The model is applied to study a synthetic mutualism, experimentally parametrized on a model algal-bacterial co-culture. Analytical and numerical solutions of the model predict conditions for the successful establishment of remote mutualisms, and how this depends, often counterintuitively, on diffusion geometry. We connect our findings to understanding complex behavior in synthetic and naturally occurring microbial communities.

Intercalated layered clay composites and their applications

NASA Astrophysics Data System (ADS)

Phukan, Anjali

Supported inorganic reagents are rapidly emerging as new and environmentally acceptable reagents and catalysts. The smectite group of layered clay minerals, such as, Montmorillonite, provides promising character for adsorption, catalytic activity, supports etc. for their large surface area, swelling behavior and ion exchange properties. Aromatic compounds intercalated in layered clays are useful in optical molecular devices. Clay is a unique material for adsorption of heavy metals and various toxic substances. Clay surfaces are known to be catalytically active due to their surface acidity. Acid activated clays possess much improved surface areas and acidities and have higher pore volumes so that can absorb large molecules in the pores. The exchangeable cations in clay minerals play a key role in controlling surface acidity and catalytic activity. Recently, optically active metal-complex-Montmorillonite composites are reported to be active in antiracemization purposes. In view of the above, a research work, relating to the preparation of different modified clay composites and their catalytic applications were carried out. The different aspects and results of the present work have been reported in four major chapters. Chapter I: This is an introductory chapter, which contains a review of the literature regarding clay-based materials. Clay minerals are phyllosilicates with layer structure. Montmorillonite, a member of smectite group of clay, is 2:1 phyllosilicate, where a layer is composed of an octahedral sheet sandwiched by two tetrahedral sheets. Such clay shows cation exchange capacity (CEC) and is expressed in milli-equivalents per 100 gm of dry clay. Clays can be modified by interaction with metal ion, metal complexes, metal cluster and organic cations for various applications. Clays are also modified by treating with acid followed by impregnation with metal salts or ions. Montmorillonite can intercalate suitable metal complexes in excess of CEC to form double or pseudo-trilayer composites. Metal ion and metal ion metal salts intercalated on Montmorillonite are efficient catalysts for Friedel-Crafts (FC) reactions, such as benzylation of benzene, synthesis of Raspberry ketone [4-(4'-hydroxyphenyl)butan-2-one] etc. Montmorillonite clay can be used as a good support for controlled release of pesticides and medicinal drugs, adsorbent for cationic dyes, toxic substances and heavy metals effective adsorbent for radioactive and toxic industrial wastes,...

High porewater exchange in a mangrove-dominated estuary revealed from short-lived radium isotopes

NASA Astrophysics Data System (ADS)

Sadat-Noori, Mahmood; Santos, Isaac R.; Tait, Douglas R.; Reading, Michael J.; Sanders, Christian J.

2017-10-01

We hypothesise that mangroves play an important role in groundwater exchange processes in sub-tropical and tropical estuarine waters. To investigate this, multiple high resolution time series measurements of radium across a tidal estuary (Coffs Creek, NSW, Australia) were performed as well as a spatial survey in both bottom and surface layers. Results from the spatial survey revealed increasing radium concentrations in parts of the estuary surrounded by mangroves. The average radium concentration in estuary areas lined with mangroves was 2.5 times higher than the average concentration at the mouth of the estuary and 6.5-fold higher than upstream freshwater areas. Additionally, the area enriched in radium coincided with low dissolved oxygen concentrations, implying that porewater exchange may drive anoxia. A radium mass balance model based on 223Ra and 224Ra isotopes at different sections of the estuary confirmed higher porewater exchange rates from areas fringed with mangrove vegetation. Estimated porewater exchange rates were 27.8 ± 5.3 and 13.6 ± 2.1 cm d-1 (0.8 ± 0.1 and 0.4 ± 0.1 m3 s-1) based on 223Ra and 224Ra isotopes, respectively. The average saline porewater exchange was ∼ 10-fold larger than the upstream surface freshwater inputs to the estuary. We suggest that mangrove environments within subtropical estuaries are hotspots for porewater exchange due to the complex belowground structure of crab burrows and the effect of tidal pumping. Because porewater exchange releases carbon and nitrogen from coastal sediments, development and modification of mangrove areas in subtropical estuaries have a significant effect on coastal biogeochemical cycles.

Luminescence Studies of the Ligand Exchange Between Two Phenanthroline Complexes and Bovine Serum Albumin

NASA Astrophysics Data System (ADS)

Lin, H.-B.; Shen, Q.-H.

2017-03-01

The interactions between bovine serum albumin (BSA) and two Cu(II) phenanthroline complexes were studied by fluorescence and UV-visible absorption spectroscopy. The obtained results confirm that the phen ligand (phen = 1,10-phenanthroline) is dissociated from the two complexes and moves into the hydrophobic cavity of BSA and that the M-L complexes (M = Co2+, Cu2+; L = Hlact, imda; Hlact = lactic acid, H2imda = iminodiacetic acid) coordinate with the amino acids on the surface of the peptide in the solution. This mode of action significantly inhibits the denaturation of BSA. The calculated distance between the BSA and the two complexes suggests that the energy transfer from the excited state of BSA to a complex occurs with high efficiency.

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals.

PubMed

Zhou, Yun; Zhang, Zhiqiang; Zhang, Jiao; Xia, Siqing

2016-07-01

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb(2+) and Zn(2+) in aqueous single-metal solutions. A pH value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients (above 0.99 for both metal ions) and insignificant lack of fit (p=0.0838 and 0.0782 for Pb(2+) and Zn(2+), respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation (between -NH2, -CN and metal ions) and ion-exchange (between -COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions. Copyright © 2016. Published by Elsevier B.V.

Evaluating Predictive Uncertainty of Hyporheic Exchange Modelling

NASA Astrophysics Data System (ADS)

Chow, R.; Bennett, J.; Dugge, J.; Wöhling, T.; Nowak, W.

2017-12-01

Hyporheic exchange is the interaction of water between rivers and groundwater, and is difficult to predict. One of the largest contributions to predictive uncertainty for hyporheic fluxes have been attributed to the representation of heterogeneous subsurface properties. This research aims to evaluate which aspect of the subsurface representation - the spatial distribution of hydrofacies or the model for local-scale (within-facies) heterogeneity - most influences the predictive uncertainty. Also, we seek to identify data types that help reduce this uncertainty best. For this investigation, we conduct a modelling study of the Steinlach River meander, in Southwest Germany. The Steinlach River meander is an experimental site established in 2010 to monitor hyporheic exchange at the meander scale. We use HydroGeoSphere, a fully integrated surface water-groundwater model, to model hyporheic exchange and to assess the predictive uncertainty of hyporheic exchange transit times (HETT). A highly parameterized complex model is built and treated as `virtual reality', which is in turn modelled with simpler subsurface parameterization schemes (Figure). Then, we conduct Monte-Carlo simulations with these models to estimate the predictive uncertainty. Results indicate that: Uncertainty in HETT is relatively small for early times and increases with transit times. Uncertainty from local-scale heterogeneity is negligible compared to uncertainty in the hydrofacies distribution. Introducing more data to a poor model structure may reduce predictive variance, but does not reduce predictive bias. Hydraulic head observations alone cannot constrain the uncertainty of HETT, however an estimate of hyporheic exchange flux proves to be more effective at reducing this uncertainty. Figure: Approach for evaluating predictive model uncertainty. A conceptual model is first developed from the field investigations. A complex model (`virtual reality') is then developed based on that conceptual model. This complex model then serves as the basis to compare simpler model structures. Through this approach, predictive uncertainty can be quantified relative to a known reference solution.

Scaling hyporheic exchange and its influence on biogeochemical reactions in aquatic ecosystems

USGS Publications Warehouse

O'Connor, Ben L.; Harvey, Judson W.

2008-01-01

Hyporheic exchange and biogeochemical reactions are difficult to quantify because of the range in fluid‐flow and sediment conditions inherent to streams, wetlands, and nearshore marine ecosystems. Field measurements of biogeochemical reactions in aquatic systems are impeded by the difficulty of measuring hyporheic flow simultaneously with chemical gradients in sediments. Simplified models of hyporheic exchange have been developed using Darcy's law generated by flow and bed topography at the sediment‐water interface. However, many modes of transport are potentially involved (molecular diffusion, bioturbation, advection, shear, bed mobility, and turbulence) with even simple models being difficult to apply in complex natural systems characterized by variable sediment sizes and irregular bed geometries. In this study, we synthesize information from published hyporheic exchange investigations to develop a scaling relationship for estimating mass transfer in near‐surface sediments across a range in fluid‐flow and sediment conditions. Net hyporheic exchange was quantified using an effective diffusion coefficient (De) that integrates all of the various transport processes that occur simultaneously in sediments, and dimensional analysis was used to scale De to shear stress velocity, roughness height, and permeability that describe fluid‐flow and sediment characteristics. We demonstrated the value of the derived scaling relationship by using it to quantify dissolved oxygen (DO) uptake rates on the basis of DO profiles in sediments and compared them to independent flux measurements. The results support a broad application of the De scaling relationship for quantifying coupled hyporheic exchange and biogeochemical reaction rates in streams and other aquatic ecosystems characterized by complex fluid‐flow and sediment conditions.

Statistical mapping of zones of focused groundwater/surface-water exchange using fiber-optic distributed temperature sensing

USGS Publications Warehouse

Mwakanyamale, Kisa; Day-Lewis, Frederick D.; Slater, Lee D.

2013-01-01

Fiber-optic distributed temperature sensing (FO-DTS) increasingly is used to map zones of focused groundwater/surface-water exchange (GWSWE). Previous studies of GWSWE using FO-DTS involved identification of zones of focused GWSWE based on arbitrary cutoffs of FO-DTS time-series statistics (e.g., variance, cross-correlation between temperature and stage, or spectral power). New approaches are needed to extract more quantitative information from large, complex FO-DTS data sets while concurrently providing an assessment of uncertainty associated with mapping zones of focused GSWSE. Toward this end, we present a strategy combining discriminant analysis (DA) and spectral analysis (SA). We demonstrate the approach using field experimental data from a reach of the Columbia River adjacent to the Hanford 300 Area site. Results of the combined SA/DA approach are shown to be superior to previous results from qualitative interpretation of FO-DTS spectra alone.

78 FR 30357 - Self-Regulatory Organizations; BOX Options Exchange LLC; Notice of Filing and Immediate...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-22

... proposed change is designed to create an appropriate fee structure for Complex Orders on the Exchange. The... because it is designed to allow the Exchange to better compete with other exchanges for Complex Order flow... To Create a New Fee Structure for Complex Orders on the BOX Market LLC Options Facility May 16, 2013...

Cs sorption to potential host rock of low-level radioactive waste repository in Taiwan: experiments and numerical fitting study.

PubMed

Wang, Tsing-Hai; Chen, Chin-Lung; Ou, Lu-Yen; Wei, Yuan-Yaw; Chang, Fu-Lin; Teng, Shi-Ping

2011-09-15

A reliable performance assessment of radioactive waste repository depends on better knowledge of interactions between nuclides and geological substances. Numerical fitting of acquired experimental results by the surface complexation model enables us to interpret sorption behavior at molecular scale and thus to build a solid basis for simulation study. A lack of consensus on a standard set of assessment criteria (such as determination of sorption site concentration, reaction formula) during numerical fitting, on the other hand, makes lower case comparison between various studies difficult. In this study we explored the sorption of cesium to argillite by conducting experiments under different pH and solid/liquid ratio (s/l) with two specific initial Cs concentrations (100mg/L, 7.5 × 10(-4)mol/L and 0.01 mg/L, 7.5 × 10(-8)mol/L). After this, numerical fitting was performed, focusing on assessment criteria and their consequences. It was found that both ion exchange and electrostatic interactions governed Cs sorption on argillite. At higher initial Cs concentration the Cs sorption showed an increasing dependence on pH as the solid/liquid ratio was lowered. In contrast at trace Cs levels, the Cs sorption was neither s/l dependent nor pH sensitive. It is therefore proposed that ion exchange mechanism dominates Cs sorption when the concentration of surface sorption site exceeds that of Cs, whereas surface complexation is attributed to Cs uptake under alkaline environments. Numerical fitting was conducted using two different strategies to determine concentration of surface sorption sites: the clay model (based on the cation exchange capacity plus surface titration results) and the iron oxide model (where the concentration of sorption sites is proportional to the surface area of argillite). It was found that the clay model led to better fitting than the iron oxide model, which is attributed to more amenable sorption sites (two specific sorption sites along with larger site density) when using clay model. Moreover, increasing s/l ratio would produce more sorption sites, which helps to suppress the impact of heterogeneous surface on Cs sorption behavior under high pH environments. Copyright © 2011 Elsevier B.V. All rights reserved.

High fluorescence emission of carboxylic acid functionalized polystyrene/BaTiO{sub 3} nanocomposites and rare earth metal complexes: Preparation and characterization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, X. T.; Showkat, A. M.; Wang, Z.

2015-03-30

Noble fluorescence nanocomposite compound based on barium titanate nanoparticles (BTO), polystyrene (PSt), and terbium ion (Tb{sup 3+}) was synthesized by a combination of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, Friedel-Crafts alkylation reaction and coordinate chemistry. Initially, a modification of surface of BTO was conducted by an exchange process with S-benzyl S’-trimethoxysilylpropyltrithiocarbonate to create macro-initiator for polymerization of styrene. Subsequently, aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-COOH) was generated by substitution reaction between 4-(Chloromethyl) benzoic acid and PSt chains. The coordination of the nanohybrids with Tb{sup 3+} ions afforded fluorescent Tb{sup 3+} tagged aryl carboxylic acid functionalized polystyrenemore » grafted barium titanate (BTO-g-PSt-Tb{sup 3+}) complexes. Structure, morphology, and fluorescence properties of nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR and SEM analyses confirmed the formation of BTO-g-PSt-Tb{sup 3+}nanohybrids. Furthermore, TGA profiles demonstrated the grafting of aryl carboxylic acid functionalized polystyrene on BTO surface. Optical properties of BTO-g-PSt-Tb{sup 3+} complexes were investigated by fluorescence spectroscopy.« less

77 FR 58424 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-20

... Priority Customer complex orders that they send to the Exchange in these symbols. In the Select Symbols, the Exchange currently provides a base rebate of $0.34 per contract, per leg, for Priority Customer complex orders when these orders trade with non-Priority Customer complex orders in the complex order book...

Simplified correction of B1 inhomogeneity for chemical exchange saturation transfer (CEST) MRI measurement with surface transceiver coil

NASA Astrophysics Data System (ADS)

Sun, Phillip Z.; Zhou, Iris Y.; Igarashi, Takahiro; Guo, Yingkun; Xiao, Gang; Wu, Renhua

2015-03-01

Chemical exchange saturation transfer (CEST) MRI is sensitive to dilute exchangeable protons and local properties such as pH and temperate, yet its susceptibility to field inhomogeneity limits its in vivo applications. Particularly, CEST measurement varies with RF irradiation power, the dependence of which is complex due to concomitant direct RF saturation (RF spillover) effect. Because the volume transmitters provide relatively homogeneous RF field, they have been conventionally used for CEST imaging despite of their elevated specific absorption rate (SAR) and relatively low sensitivity than surface coils. To address this limitation, we developed an efficient B1 inhomogeneity correction algorithm that enables CEST MRI using surface transceiver coils. This is built on recent work that showed the inverse CEST asymmetry analysis (CESTRind) is not susceptible to confounding RF spillover effect. We here postulated that the linear relationship between RF power level and CESTRind can be extended for correcting B1 inhomogeneity induced CEST MRI artifacts. Briefly, we prepared a tissue-like Creatine gel pH phantom and collected multiparametric MRI including relaxation, field map and CEST MRI under multiple RF power levels, using a conventional surface transceiver coil. The raw CEST images showed substantial heterogeneity due to B1 inhomogeneity, with pH contrast to noise ratio (CNR) being 8.8. In comparison, pH MRI CNR of the fieldinhomogeneity corrected CEST MRI was found to be 17.2, substantially higher than that without correction. To summarize, our study validated an efficient field inhomogeneity correction that enables sensitive CEST MRI with surface transceiver, promising for in vivo translation.

Sorption of Metal Ions on Clay Minerals.

PubMed

Schlegel; Charlet; Manceau

1999-12-15

The mechanism of Co uptake from aqueous solution onto hectorite (a magnesian smectite) and its impact on the stability of this clay mineral were investigated as a function of Co concentration (TotCo = 20 to 200 µM, 0.3 M NaNO(3)) and ionic strength (0.3 and 0.01 M NaNO(3), TotCo = 100 µM) by combining kinetics measurements and Co K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The morphology of the sorbent phase was characterized by atomic force microscopy (AFM) and consists of lath-type particles bounded by large basal planes and layer edges. At low ionic strength (0.01 M NaNO(3)), important Co uptake occurred within the first 5 min of reaction, consistent with Co adsorption on exchange sites of hectorite basal planes. Thereafter, the sorption rate dramatically decreased. In contrast, at high ionic strength (0.3 M NaNO(3)), Co uptake rate was much slower within the first 5 min and afterward higher than at 0.01 M NaNO(3), consistent with Co adsorption on specific surface sites located on the edges of hectorite. Time-dependent isotherms for Co uptake at high ionic strength indicated the existence of several sorption mechanisms having distinct equilibration times. The dissolution of hectorite was monitored before and after Co addition. A congruent dissolution regime was observed prior to Co addition. Just after Co addition, an excess release of Mg relatively to congruent dissolution rates occurred at both high and low ionic strengths. At high ionic strength, this excess release nearly equaled the amount of sorbed Co. The dissolution rate of hectorite then decreased at longer Co sorption times. EXAFS spectra of hectorite reacted with Co at high and low ionic strengths and for reaction times longer than 6 h, exhibited similar features, suggesting that the local structural environments of Co atoms are similar. Spectral simulations revealed the occurrence of approximately 2 Mg and approximately 2 Si neighboring cations at interatomic distances characteristic of edge-sharing linkages between Co and Mg octahedra and corner-sharing linkages between Co octahedra and Si tetrahedra, respectively. This local structure is characteristic of inner sphere mononuclear surface complexes at layer edges of hectorite platelets. The occurrence of these complexes even at low ionic strength apparently conflicts with kinetics results, as exchangeable divalent cations are known to form outer sphere surface complexes. To clarify this issue, the amount of Co adsorbed on exchange sites was calculated from the solute Co concentration, assuming that cation exchange was always at equilibrium. These calculations showed that sorbed Co was transferred within 48 h from exchange sites to edge sorption sites. Copyright 1999 Academic Press.

Dissecting Arabidopsis Gβ Signal Transduction on the Protein Surface1[W][OA

PubMed Central

Jiang, Kun; Frick-Cheng, Arwen; Trusov, Yuri; Delgado-Cerezo, Magdalena; Rosenthal, David M.; Lorek, Justine; Panstruga, Ralph; Booker, Fitzgerald L.; Botella, José Ramón; Molina, Antonio; Ort, Donald R.; Jones, Alan M.

2012-01-01

The heterotrimeric G-protein complex provides signal amplification and target specificity. The Arabidopsis (Arabidopsis thaliana) Gβ-subunit of this complex (AGB1) interacts with and modulates the activity of target cytoplasmic proteins. This specificity resides in the structure of the interface between AGB1 and its targets. Important surface residues of AGB1, which were deduced from a comparative evolutionary approach, were mutated to dissect AGB1-dependent physiological functions. Analysis of the capacity of these mutants to complement well-established phenotypes of Gβ-null mutants revealed AGB1 residues critical for specific AGB1-mediated biological processes, including growth architecture, pathogen resistance, stomata-mediated leaf-air gas exchange, and possibly photosynthesis. These findings provide promising new avenues to direct the finely tuned engineering of crop yield and traits. PMID:22570469

The Phosphatidylinositol (3,4,5)-Trisphosphate-dependent Rac Exchanger 1·Ras-related C3 Botulinum Toxin Substrate 1 (P-Rex1·Rac1) Complex Reveals the Basis of Rac1 Activation in Breast Cancer Cells.

PubMed

Lucato, Christina M; Halls, Michelle L; Ooms, Lisa M; Liu, Heng-Jia; Mitchell, Christina A; Whisstock, James C; Ellisdon, Andrew M

2015-08-21

The P-Rex (phosphatidylinositol (3,4,5)-trisphosphate (PIP3)-dependent Rac exchanger) family (P-Rex1 and P-Rex2) of the Rho guanine nucleotide exchange factors (Rho GEFs) activate Rac GTPases to regulate cell migration, invasion, and metastasis in several human cancers. The family is unique among Rho GEFs, as their activity is regulated by the synergistic binding of PIP3 and Gβγ at the plasma membrane. However, the molecular mechanism of this family of multi-domain proteins remains unclear. We report the 1.95 Å crystal structure of the catalytic P-Rex1 DH-PH tandem domain in complex with its cognate GTPase, Rac1 (Ras-related C3 botulinum toxin substrate-1). Mutations in the P-Rex1·Rac1 interface revealed a critical role for this complex in signaling downstream of receptor tyrosine kinases and G protein-coupled receptors. The structural data indicated that the PIP3/Gβγ binding sites are on the opposite surface and markedly removed from the Rac1 interface, supporting a model whereby P-Rex1 binding to PIP3 and/or Gβγ releases inhibitory C-terminal domains to expose the Rac1 binding site. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Interaction between like-charged polyelectrolyte-colloid complexes in electrolyte solutions: a Monte Carlo simulation study in the Debye-Hückel approximation.

PubMed

Truzzolillo, D; Bordi, F; Sciortino, F; Sennato, S

2010-07-14

We study the effective interaction between differently charged polyelectrolyte-colloid complexes in electrolyte solutions via Monte Carlo simulations. These complexes are formed when short and flexible polyelectrolyte chains adsorb onto oppositely charged colloidal spheres, dispersed in an electrolyte solution. In our simulations the bending energy between adjacent monomers is small compared to the electrostatic energy, and the chains, once adsorbed, do not exchange with the solution, although they rearrange on the particles surface to accommodate further adsorbing chains or due to the electrostatic interaction with neighbor complexes. Rather unexpectedly, when two interacting particles approach each other, the rearrangement of the surface charge distribution invariably produces antiparallel dipolar doublets that invert their orientation at the isoelectric point. These findings clearly rule out a contribution of dipole-dipole interactions to the observed attractive interaction between the complexes, pointing out that such suspensions cannot be considered dipolar fluids. On varying the ionic strength of the electrolyte, we find that a screening length kappa(-1), short compared with the size of the colloidal particles, is required in order to observe the attraction between like-charged complexes due to the nonuniform distribution of the electric charge on their surface ("patch attraction"). On the other hand, by changing the polyelectrolyte/particle charge ratio xi(s), the interaction between like-charged polyelectrolyte-decorated particles, at short separations, evolves from purely repulsive to strongly attractive. Hence, the effective interaction between the complexes is characterized by a potential barrier, whose height depends on the net charge and on the nonuniformity of their surface charge distribution.

Multisite adsorption of cadmium on goethite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Venema, P.; Hiemstra, T.; Riemsdijk, W.H. van

1996-11-10

Recently a new general ion adsorption model has been developed for ion binding to mineral surfaces (Hiemstra and van Riemsdijk, 1996). The model uses the Pauling concept of charge distribution (CD) and is an extension of the multi-site complexation (MUSIC) approach. In the CD-MUSIC model the charge of an adsorbing ion that forms an inner sphere complex is distributed over its ligands, which are present in two different electrostatic planes. In this paper the authors have applied the CD-MUSIC model to the adsorption of metal cations, using an extended data set for cadmium adsorbing on goethite. The adsorption of cadmiummore » and the cadmium-proton exchange ratio were measured as function of metal ion concentration, pH, and ionic strength. The data could be described well, taking into account the surface heterogeneity resulting from the presence of two different crystal planes (the dominant 110 face and the minor 021 face). The surface species used in the model are consistent with recent EXAFS data. In accordance with the EXAFS results, high-affinity complexes at the 021 face were used in the model.« less

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?

DOE PAGES

Tomkiewicz, Alex C.; Tamimi, Mazin A.; Huq, Ashfia; ...

2015-03-02

There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of threemore » Ruddlesden-Popper phases, general form A n-1A 2'BnO 3n+1, A n-1A 2'BnX 3n+1; LaSrCo 0.5Fe 0.5O 4-δ (n = 1), La 0.3Sr 2.7CoFeO 7-δ (n = 2) and LaSr 3Co 1.5Fe 1.5O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.« less

Simulation of within-canopy radiation exchange

USDA-ARS?s Scientific Manuscript database

Radiation exchange at the surface plays a critical role in the surface energy balance, plant microclimate, and plant growth. The ability to simulate the surface energy balance and the microclimate within the plant canopy is contingent upon simulation of the surface radiation exchange. A validation a...

Enrofloxacin sorption on smectite clays: effects of pH, cations, and humic acid.

PubMed

Yan, Wei; Hu, Shan; Jing, Chuanyong

2012-04-15

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR-FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs

Interactions of bluff-body obstacles with turbulent airflows affecting evaporative fluxes from porous surfaces

NASA Astrophysics Data System (ADS)

Haghighi, Erfan; Or, Dani

2015-11-01

Bluff-body obstacles interacting with turbulent airflows are common in many natural and engineering applications (from desert pavement and shrubs over natural surfaces to cylindrical elements in compact heat exchangers). Even with obstacles of simple geometry, their interactions within turbulent airflows result in a complex and unsteady flow field that affects surface drag partitioning and transport of scalars from adjacent evaporating surfaces. Observations of spatio-temporal thermal patterns on evaporating porous surfaces adjacent to bluff-body obstacles depict well-defined and persistent zonation of evaporation rates that were used to construct a simple mechanistic model for surface-turbulence interactions. Results from evaporative drying of sand surfaces with isolated cylindrical elements (bluff bodies) subjected to constant turbulent airflows were in good agreement with model predictions for localized exchange rates. Experimental and theoretical results show persistent enhancement of evaporative fluxes from bluff-rough surfaces relative to smooth flat surfaces under similar conditions. The enhancement is attributed to formation of vortices that induce a thinner boundary layer over part of the interacting surface footprint. For a practical range of air velocities (0.5-4.0 m/s), low-aspect ratio cylindrical bluff elements placed on evaporating sand surfaces enhanced evaporative mass losses (relative to a flat surface) by up to 300% for high density of elements and high wind velocity, similar to observations reported in the literature. Concepts from drag partitioning were used to generalize the model and upscale predictions to evaporation from surfaces with multiple obstacles for potential applications to natural bluff-rough surfaces.

Surface temperatures in New York City: Geospatial data enables the accurate prediction of radiative heat transfer.

PubMed

Ghandehari, Masoud; Emig, Thorsten; Aghamohamadnia, Milad

2018-02-02

Despite decades of research seeking to derive the urban energy budget, the dynamics of thermal exchange in the densely constructed environment is not yet well understood. Using New York City as a study site, we present a novel hybrid experimental-computational approach for a better understanding of the radiative heat transfer in complex urban environments. The aim of this work is to contribute to the calculation of the urban energy budget, particularly the stored energy. We will focus our attention on surface thermal radiation. Improved understanding of urban thermodynamics incorporating the interaction of various bodies, particularly in high rise cities, will have implications on energy conservation at the building scale, and for human health and comfort at the urban scale. The platform presented is based on longwave hyperspectral imaging of nearly 100 blocks of Manhattan, in addition to a geospatial radiosity model that describes the collective radiative heat exchange between multiple buildings. Despite assumptions in surface emissivity and thermal conductivity of buildings walls, the close comparison of temperatures derived from measurements and computations is promising. Results imply that the presented geospatial thermodynamic model of urban structures can enable accurate and high resolution analysis of instantaneous urban surface temperatures.

Blueprint for a coupled model of sedimentology, hydrology, and hydrogeology in streambeds

NASA Astrophysics Data System (ADS)

Partington, Daniel; Therrien, Rene; Simmons, Craig T.; Brunner, Philip

2017-06-01

The streambed constitutes the physical interface between the surface and the subsurface of a stream. Across all spatial scales, the physical properties of the streambed control surface water-groundwater interactions. Continuous alteration of streambed properties such as topography or hydraulic conductivity occurs through erosion and sedimentation processes. Recent studies from the fields of ecology, hydrogeology, and sedimentology provide field evidence that sedimentological processes themselves can be heavily influenced by surface water-groundwater interactions, giving rise to complex feedback mechanisms between sedimentology, hydrology, and hydrogeology. More explicitly, surface water-groundwater exchanges play a significant role in the deposition of fine sediments, which in turn modify the hydraulic properties of the streambed. We explore these feedback mechanisms and critically review the extent of current interaction between the different disciplines. We identify opportunities to improve current modeling practices. For example, hydrogeological models treat the streambed as a static rather than a dynamic entity, while sedimentological models do not account for critical catchment processes such as surface water-groundwater exchange. We propose a blueprint for a new modeling framework that bridges the conceptual gaps between sedimentology, hydrogeology, and hydrology. Specifically, this blueprint (1) fully integrates surface-subsurface flows with erosion, transport, and deposition of sediments and (2) accounts for the dynamic changes in surface elevation and hydraulic conductivity of the streambed. Finally, we discuss the opportunities for new research within the coupled framework.

Using Ion Exchange Chromatography to Separate and Quantify Complex Ions

ERIC Educational Resources Information Center

Johnson, Brian J.

2014-01-01

Ion exchange chromatography is an important technique in the separation of charged species, particularly in biological, inorganic, and environmental samples. In this experiment, students are supplied with a mixture of two substitution-inert complex ions. They separate the complexes by ion exchange chromatography using a "flash"…

Acetone and Water on TiO₂(110): H/D Exchange

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A.

2005-04-12

Isotopic H/D exchange between coadsorbed acetone and water on the TiO?(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (oxidation and reduction). Coadsorbed acetone and water interact repulsively on reduced TiO?(110) based on results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 ML of a 1 ML d6-acetone on the reduced surface exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in themore » high temperature region of the d?-acetone TPD spectrum at {approx}340 K. The effect was confirmed with combinations of d?-acetone and D?O. The extent of exchange decreased on the reduced surface with water coverages above {approx}0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when the surface was pre-oxidized prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d?- or d?-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at {approx}390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation. The H/D exchange mechanism likely involves an enolate or propenol surface intermediate formed transiently during the desorption of oxygen-stabilized acetone molecules.« less

Surface defect chemistry and oxygen exchange kinetics in La2-xCaxNiO4+δ

NASA Astrophysics Data System (ADS)

Tropin, E. S.; Ananyev, M. V.; Farlenkov, A. S.; Khodimchuk, A. V.; Berenov, A. V.; Fetisov, A. V.; Eremin, V. A.; Kolchugin, A. A.

2018-06-01

Surface oxygen exchange kinetics and diffusion in La2-xCaxNiO4+δ (x = 0; 0.1; 0.3) have been studied by the isotope exchange method with gas phase equilibration in the temperature range of 600-800 °C and oxygen pressure range 0.13-2.5 kPa. Despite an enhanced electrical conductivity of La2-xCaxNiO4+δ theirs oxygen surface exchange (k*) and oxygen tracer diffusion (D*) coefficients were significantly lower in comparison with La2NiO4+δ. The rates of the elementary stages of oxygen exchange have been calculated. Upon Ca doping the change of the rate-determining stage was observed. The surface of the oxides was found to be inhomogeneous towards oxygen exchange process according to the recently developed model. The reasons of such inhomogeneity are discussed as well as Ca influence on the surface defect chemistry and oxygen surface exchange and diffusivity.

Effects of a flood pulse on exchange flows along a sinuous stream

NASA Astrophysics Data System (ADS)

Käser, D.; Brunner, P.; Renard, P.; Perrochet, P.; Schirmer, M.; Hunkeler, D.

2012-04-01

Flood pulses are important events for river ecosystems: they create hydrological interactions at the terrestrial/aquatic interface that fuel biological productivity and shape the hyporheic-riparian habitats. For example, floods promote faunal activity and decomposition by increasing the supply of oxygenated water in downwelling areas, while the following recession periods tend to provide stable thermal conditions favoured by fish or insects in areas of groundwater upwelling. This 3-D modelling study investigates the effect of stream stage transience (with events characterised by their intensity and duration) on hydrological exchanges between the surface and the near-stream subsurface. It evaluates, in particular, its effect on streams of varying sinuosity by quantifying the dynamic response of: (1) subsurface flow paths, (2) the exchange pattern at the sediment-water interface, and (3) integrative measures such as total exchange flux and total storage. Understanding geomorphological controls on groundwater/surface water interactions is attractive because topography is generally better constrained than subsurface parameters, and can be used in data-poor situations. The numerical model represents a hypothetical alluvial plain limited by impervious bedrock on all four sides, and in which the channel meanders according to the sine-generated curve of Langbein and Leopold (1966). As the model (HydroGeoSphere) couples surface and subsurface flow, the stream stage transience is imposed by a fluctuating head at the channel inlet. Preliminary results show that a simple rectangular flood pulse in an idealised sinuous stream without additional complexity can generate multiple flow direction reversals at a single point in the channel. The initial conditions of the groundwater table, the channel sinuosity and the time characteristics of the flood pulse all control exchange flow features in different ways. Results are also compared with 'bank storage' analytical solutions that typically assume a straight channel. The discussion covers an evaluation of this work with respect to previous studies that considered the influence of sinuosity on interfacial exchange flows. It addresses the issue of steady vs. transient exchanges, which is of uppermost importance at the operational scale of river restoration schemes. Langbein WB, Leopold LB. 1966. River meanders - theory of minimum variance. U.S. Geol. Surv. Prof. Pap. 422-H: 15 p.

Theoretical study of the acid-base properties of the montmorillonite/electrolyte interface: influence of the surface heterogeneity and ionic strength on the potentiometric titration curves.

PubMed

Zarzycki, Piotr; Thomas, Fabien

2006-10-15

The parallel shape of the potentiometric titration curves for montmorillonite suspension is explained using the surface complexation model and taking into account the surface heterogeneity. The homogeneous models give accurate predictions only if they assume unphysically large values of the equilibrium constants for the exchange process occurring on the basal plane. However, the assumption that the basal plane is energetically heterogeneous allows to fit the experimental data (reported by Avena and De Pauli [M. Avena, C.P. De Pauli, J. Colloid Interface Sci. 202 (1998) 195-204]) for reasonable values of exchange equilibrium constant equal to 1.26 (suggested by Fletcher and Sposito [P. Fletcher, G. Sposito, Clay Miner. 24 (1989) 375-391]). Moreover, we observed the typical behavior of point of zero net proton charge (pznpc) as a function of logarithm of the electrolyte concentration (log[C]). We showed that the slope of the linear dependence, pznpc=f(log[C]), is proportional to the number of isomorphic substitutions in the crystal phase, which was also observed in the experimental studies.

CentNet—A deployable 100-station network for surface exchange research

NASA Astrophysics Data System (ADS)

Oncley, S.; Horst, T. W.; Semmer, S.; Militzer, J.; Maclean, G.; Knudson, K.

2014-12-01

Climate, air quality, atmospheric composition, surface hydrology, and ecological processes are directly affected by the Earth's surface. Complexity of this surface exists at multiple spatial scales, which complicates the understanding of these processes. NCAR/EOL currently provides a facility to the research community to make direct eddy-covariance flux observations to quantify surface-atmosphere interactions. However, just as model resolution has continued to increase, there is a need to increase the spatial density of flux measurements to capture the wide variety of scales that contribute to exchange processes close to the surface. NCAR/EOL now has developed the CentNet facility, that is envisioned to have on the order of 100 surface flux stations deployable for periods of months to years. Each station would measure standard meteorological variables, all components of the surface energy balance (including turbulence fluxes and radiation), atmospheric composition, and other quantities to characterize the surface. Thus, CentNet can support observational research in the biogeosciences, hydrology, urban meteorology, basic meteorology, and turbulence. CentNet has been designed to be adaptable to a wide variety of research problems while keeping operations manageable. Tower infrastructure has been designed to be lightweight, easily deployed, and with a minimal set-up footprint. CentNet uses sensor networks to increase spatial sampling at each station. The data system saves every sample on site to retain flexibility in data analysis. We welcome guidance on development and funding priorities as we build CentNet.

Insights into the role of wettability in cathode catalyst layer of proton exchange membrane fuel cell; pore scale immiscible flow and transport processes

NASA Astrophysics Data System (ADS)

Fathi, H.; Raoof, A.; Mansouri, S. H.

2017-05-01

The production of liquid water in cathode catalyst layer, CCL, is a significant barrier to increase the efficiency of proton exchange membrane fuel cell. Here we present, for the first time, a direct three-dimensional pore-scale modelling to look at the complex immiscible two-phase flow in CCL. After production of the liquid water at the surface of CCL agglomerates due to the electrochemical reactions, water spatial distribution affects transport of oxygen through the CCL as well as the rate of reaction at the agglomerate surfaces. To explore the wettability effects, we apply hydrophilic and hydrophobic properties using different surface contact angles. Effective diffusivity is calculated under several water saturation levels. Results indicate larger diffusive transport values for hydrophilic domain compared to the hydrophobic media where the liquid water preferentially floods the larger pores. However, hydrophobic domain showed more available surface area and higher oxygen consumption rate at the reaction sites under various saturation levels, which is explained by the effect of wettability on pore-scale distribution of water. Hydrophobic domain, with a contact angle of 150, reveals efficient water removal where only 28% of the pore space stays saturated. This condition contributes to the enhanced available reaction surface area and oxygen diffusivity.

Monomers of cutin biopolymer: sorption and esterification on montmorillonite surfaces

NASA Astrophysics Data System (ADS)

Olshansky, Yaniv; Polubesova, Tamara; Chefetz, Benny

2013-04-01

One of the important precursors for soil organic matter is plant cuticle, a thin layer of predominantly lipids that cover all primary aerial surfaces of vascular plants. In most plant species cutin biopolymer is the major component of the cuticle (30-85% weight). Therefore cutin is the third most abundant plant biopolymer (after lignin and cellulose). Cutin is an insoluble, high molecular weight bio-polyester, which is constructed of inter-esterified cross linked hydroxy-fatty acids and hydroxyepoxy-fatty acids. The most common building blocks of the cutin are derivatives of palmitic acid, among them 9(10),16 dihydroxy palmitic acid (diHPA) is the main component. These fatty acids and their esters are commonly found in major organo-mineral soil fraction-humin. Hence, the complexes of cutin monomers with minerals may serve as model of humin. Both cutin and humin act as adsorption efficient domains for organic contaminants. However, only scarce information is available about the interactions of cutin with soil mineral surfaces, in particular with common soil mineral montmorillonite. The main hypothesize of the study is that adsorbed cutin monomers will be reconstituted on montmorillonite surface due to esterification and oligomerization, and that interactions of cutin monomers with montmorillonite will be affected by the type of exchangeable cation. Cutin monomers were obtained from the fruits of tomato (Lycopersicon esculentum). Adsorption of monomers was measured for crude Wyoming montmorillonites and montmorillonites saturated with Fe3+ and Ca2+. To understand the mechanism of monomer-clay interactions and to evaluate esterification on the clay surface, XRD and FTIR analyses of the montmorillonite-monomers complexes were performed. Our results demonstrated that the interactions of cutin monomers with montmorillonite are affected by the type of exchangeable cation. Isotherms of adsorption of cutin monomers on montmorillonites were fitted by a dual mode model of sorption, which combines site specific adsorption mechanism (Langmuir) and partitioning mechanism. Adsorption of monomers by Fe3+-montmorillonite was higher than for Ca2+ and crude -montmorillonites. XRD measurements showed expansion of d-spacing of montmorillonite samples with the increase in diHPA loading from 12.32, 12.66 and 12.17 Å for Fe3+- Ca2+- and crude-montmorillonite up to 16.84, 16.62 and 16.79 Å for organo-clay complexes of Fe3+-, Ca2+- and crude-montmorillonites respectively. This significant expansion of d-spacing suggests interlayer, and probably, multilayer diHPA adsorption by montmorillonite. Based on FTIR data we suggest that diHPA forms inner-sphere complexes with Fe3+-montmorillonite surface but not with Ca2+ and crude-montmorillonites. However all montmorillonite samples induce esterification and oligomerization of the monomers, which was demonstrated by FTIR spectra of the organo-montmorillonite complexes and by LC-MS analysis of the organic material extracted from organo-clay complexes. These results confirmed our hypothesis about oligomerization of cuticular monomers on mineral surfaces. We assume that esterification and oligomerization of monomers on montmorillonite surfaces simulate similar soil processes, which result in the formation of soil organo-mineral complexes and humin.

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Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.

Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

Post-Self-Assembly Cross-Linking to Integrate Molecular Nanofibers with Copolymers in Oscillatory Hydrogels

DTIC Science & Technology

2013-05-09

The BZ reaction provides a model system to mimic a variety of complex processes, such as biological morphogenesis, in monodisperse microemulsions .15...surfaces, ion-exchange resins, membranes, and microemulsions . For example, in addition to minimizing the hydrodynamic effects and formation of bubbles...Reaction-Diffusion Microemulsions Reveals Three-Dimensional Tu- ring Patterns. Science (Washington, DC, U.S.) 2011, 331, 1309−1312. (16) Agladze, K. I

Development and Verification of Enclosure Radiation Capabilities in the CHarring Ablator Response (CHAR) Code

NASA Technical Reports Server (NTRS)

Salazar, Giovanni; Droba, Justin C.; Oliver, Brandon; Amar, Adam J.

2016-01-01

With the recent development of multi-dimensional thermal protection system (TPS) material response codes, the capability to account for surface-to-surface radiation exchange in complex geometries is critical. This paper presents recent efforts to implement such capabilities in the CHarring Ablator Response (CHAR) code developed at NASA's Johnson Space Center. This work also describes the different numerical methods implemented in the code to compute geometric view factors for radiation problems involving multiple surfaces. Verification of the code's radiation capabilities and results of a code-to-code comparison are presented. Finally, a demonstration case of a two-dimensional ablating cavity with enclosure radiation accounting for a changing geometry is shown.

Scales and Patterns of Nitrate Transport and Transformation in the Hyporheic Zone of a Lowland River

NASA Astrophysics Data System (ADS)

Naden, E.; Krause, S.; Tecklenburg, C.; Munz, M.

2009-04-01

The Hyporheic Zone (HZ) represents the spatially and temporally variable part of the streambed that is affected by the mixture of groundwater and surface water and often characterised by strong redox gradients and high turnover rates of redox reactive substances. The HZ has often been understood as a complex bioreactor with a high potential to affect groundwater-surface water exchange as well control the chemical signature of waters along the hyporheic passage. Currently, 73% of groundwater and 28% of UK rivers sampled exhibit either high nitrate levels or rising trends (Defra, 2008) Because of the high metabolic rates that have often be observed, the HZ is by many expected to potentially ameliorate groundwater nitrate fluxes and thus to reduce nitrate pollution and benefit freshwater ecosystems. The objective of this pilot study was to set up a monitoring program on a typical lowland river within glacio-fluvial deposits and well connected to the shallow groundwater aquifer. This study aims to derive a conceptual model of hyporheic exchange and nutrient metabolism in an agriculturally used lowland system including the development of upscaling strategies that allow for the assessment of hyporheic uptake or contribution on a subcatchment scale. The research area covers a 250 metre stream reach of the River Tern (Shropshire, UK), a lowland groundwater dependent surface water body at risk of failing to achieve ‘good water' status under the WFD, primarily due to diffuse agricultural pollution. In two horizontal arrays 42 multi piezometers have been installed in the river bed offering sampling from between three and eight sampling points ranging from 5 cm to 200 cm depth. These allow the sampling of streambed porewater from more than 150 locations. Additionally, ten shallow groundwater boreholes (up to 3m depth) have been installed within the riparian floodplain. From June to September 2008 head measurements were taken at the streambed piezometers, riparian groundwater boreholes and the river in order to determine the groundwater flowfield and exchange with the surface water. At the same time interval streambed pore water and riparian groundwater were sampled from piezometers and boreholes alongside surface water samples from the river. The samples were analysed for dissolved oxygen and major anion concentrations. Initial results confirm indicate that the water sources mixing in the HZ are statistically distinctive. In contrast to the many observed head water streams the exchange between groundwater and surface water is not just determined by gradually changing hydraulic conductivities of the sediment material but strongly controlled by the spatial pattern of a discontinuous impermeable regional peat layer located in 50 cm depth on average. The peat layer is separating the fluxes within the streambed into two (partially connected) flow systems, with semi-confined conditions underneath and pattern of surface water mixing above the peat. Areas where the peat layer is disrupted are characterised by strong connection of both flow systems. Dependent on flow paths and residence times redox conditions and nitrate concentrations are showing substantial changes along the hyporheic flow path. The spatial very heterogeneous patterns of nitrate concentrations in the streambed were found controlled by complex flow processes at multiple scales covering small scale hyporheic exchange in pools, riffles and sand bars as well as large scale pattern of groundwater - surface water connectivity and riparian influences.

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Application of surface analytical methods in thin film analysis

NASA Astrophysics Data System (ADS)

Wen, Xingu

Self-assembly and the sol-gel process are two promising methods for the preparation of novel materials and thin films. In this research, these two methods were utilized to prepare two types of thin films: self-assembled monolayers of peptides on gold and SiO2 sol-gel thin films modified with Ru(II) complexes. The properties of the resulting thin films were investigated by several analytical techniques in order to explore their potential applications in biomaterials, chemical sensors, nonlinear optics and catalysis. Among the analytical techniques employed in the study, surface analytical techniques, such as X-ray photoelectron spectroscopy (XPS) and grazing angle reflection absorption Fourier transform infrared spectroscopy (RA-FTIR), are particularly useful in providing information regarding the compositions and structures of the thin films. In the preparation of peptide thin films, monodisperse peptides were self-assembled on gold substrate via the N-terminus-coupled lipoic acid. The film compositions were investigated by XPS and agreed well with the theoretical values. XPS results also revealed that the surface coverage of the self-assembled films was significantly larger than that of the physisorbed films and that the chemisorption between the peptides and gold surface was stable in solvent. Studies by angle dependent XPS (ADXPS) and grazing angle RA-FTIR indicated that the peptides were on average oriented at a small angle from the surface normal. By using a model of orientation distribution function, both the peptide tilt angle and film thickness can be well calculated. Ru(II) complex doped SiO2 sol-gel thin films were prepared by low temperature sol-gel process. The ability of XPS coupled with Ar + ion sputtering to provide both chemical and compositional depth profile information of these sol-gel films was evaluated. This technique, together with UV-VIS and electrochemical measurements, was used to investigate the stability of Ru complexes in the composite films. The stability of Ru complexes with respect to dopant leaching was dependent on the film microstructures. Three methods aiming to improve the dopant stability were also explored. In addition, the ion exchange properties of the composite films, upon exposure to various ions in aqueous solutions, were investigated by XPS, and the ion exchange mechanism was elucidated.

Complex magnetic structure of clusters and chains of Ni and Fe on Pt(111)

PubMed Central

Bezerra-Neto, Manoel M.; Ribeiro, Marcelo S.; Sanyal, Biplab; Bergman, Anders; Muniz, Roberto B.; Eriksson, Olle; Klautau, Angela B.

2013-01-01

We present an approach to control the magnetic structure of adatoms adsorbed on a substrate having a high magnetic susceptibility. Using finite Ni-Pt and Fe-Pt nanowires and nanostructures on Pt(111) surfaces, our ab initio results show that it is possible to tune the exchange interaction and magnetic configuration of magnetic adatoms (Fe or Ni) by introducing different numbers of Pt atoms to link them, or by including edge effects. The exchange interaction between Ni (or Fe) adatoms on Pt(111) can be considerably increased by introducing Pt chains to link them. The magnetic ordering can be regulated allowing for ferromagnetic or antiferromagnetic configurations. Noncollinear magnetic alignments can also be stabilized by changing the number of Pt-mediated atoms. An Fe-Pt triangularly-shaped nanostructure adsorbed on Pt(111) shows the most complex magnetic structure of the systems considered here: a spin-spiral type of magnetic order that changes its propagation direction at the triangle vertices. PMID:24165828

Surface-Tension Replica-Exchange Molecular Dynamics Method for Enhanced Sampling of Biological Membrane Systems.

PubMed

Mori, Takaharu; Jung, Jaewoon; Sugita, Yuji

2013-12-10

Conformational sampling is fundamentally important for simulating complex biomolecular systems. The generalized-ensemble algorithm, especially the temperature replica-exchange molecular dynamics method (T-REMD), is one of the most powerful methods to explore structures of biomolecules such as proteins, nucleic acids, carbohydrates, and also of lipid membranes. T-REMD simulations have focused on soluble proteins rather than membrane proteins or lipid bilayers, because explicit membranes do not keep their structural integrity at high temperature. Here, we propose a new generalized-ensemble algorithm for membrane systems, which we call the surface-tension REMD method. Each replica is simulated in the NPγT ensemble, and surface tensions in a pair of replicas are exchanged at certain intervals to enhance conformational sampling of the target membrane system. We test the method on two biological membrane systems: a fully hydrated DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine) lipid bilayer and a WALP23-POPC (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine) membrane system. During these simulations, a random walk in surface tension space is realized. Large-scale lateral deformation (shrinking and stretching) of the membranes takes place in all of the replicas without collapse of the lipid bilayer structure. There is accelerated lateral diffusion of DPPC lipid molecules compared with conventional MD simulation, and a much wider range of tilt angle of the WALP23 peptide is sampled due to large deformation of the POPC lipid bilayer and through peptide-lipid interactions. Our method could be applicable to a wide variety of biological membrane systems.

A comparative study of chelating and cationic ion exchange resins for the removal of palladium(II) complexes from acidic chloride media.

PubMed

Hubicki, Zbigniew; Wołowicz, Anna

2009-05-30

The increasing demand for palladium for technological application requires the development of ion exchange chromatography. Recently ion exchange chromatography has developed largely as a result of new types of ion exchangers available on the market of which two types are widely applied. One of them are selective (chelating) and modified ion exchangers and the other one are liquid exchangers. Two types of ion exchange resins such as chelating (Lewatit TP 214, Purolite S 920) and cationic (Chelite S, Duolite GT 73) ion exchangers are used for the recovery of palladium(II) complexes from chloride media (0.1-2.0M HCl-1.0M NaCl-0.0011 M Pd(II); 0.1-2.0M HCl-2.0M NaCl-0.0011M Pd(II)). The influence of concentration of hydrochloric acid, sodium chloride as well as the phase contact time on the degree of recovery of palladium(II) complexes was studied. Moreover, the amount of palladium(II) chlorocomplexes sorbed onto ion exchangers, the working ion exchange capacities and the weight and bed distribution coefficients were calculated in order to judge which of two types of resins possesses the best performance towards palladium(II) complexes.

Sensitivity of the acid-base properties of clays to the methods of preparation and measurement. 1. Literature review.

PubMed

Duc, Myriam; Gaboriaud, Fabien; Thomas, Fabien

2005-09-01

Measuring and modeling the surface charge of clays, and more especially smectites, has become an important issue in the use of bentonites as a waste confinement material aimed at retarding migration of water and solutes. Therefore, many studies of the acid-base properties of montmorillonite have appeared recently in the literature, following older studies principally devoted to cation exchange. It is striking that beyond the consensus about the complex nature of the surface charge of clays, there are many discrepancies, especially concerning the dissociable charge, that prevents intercomparison among the published data. However, a general trend is observed regarding the absence of common intersection point on raw titration curves at different ionic strengths. Analysis of the literature shows that these discrepancies originate from the experimental procedures for the preparation of the clays and for the quantification of their surface charge. The present work is an attempt to understand how these procedures can impact the final results. Three critical operations can be identified as having significant effects on the surface properties of the studied clays. The first one is the preparation of purified clay from the raw material: the use of acid or chelation treatments, and the repeated washings in deionized water result in partial dissolution of the clays. Then storage of the purified clay in dry or wet conditions strongly influences the equilibria in the subsequent experiments respectively by precipitation or enhanced dissolution. The third critical operation is the quantification of the surface charge by potentiometric titration, which requires the use of strong acids and bases. As a consequence, besides dissociation of surface sites, many secondary titrant consuming reactions were described in the literature, such as cation exchange, dissolution, hydrolysis, or precipitation. The cumulated effects make it difficult to derive proper dissociation constants, and to build adequate models. The inadequation of the classical surface complexation models to describe the acid-base behavior of clays is illustrated by the electrokinetic behavior of smectites, which is independent from the pH and the ionic strength. Therefore, there is still a need on one hand for accurate data recorded in controlled conditions, and on the other hand for new models taking into account the complex nature of the charge of clays.

Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

PubMed

Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

2017-07-01

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

A Method to Access Absolute fIPAR fo Vegetation in Spatially Complex Ecosystems

NASA Technical Reports Server (NTRS)

Wessman, Carol A.; Nel, Elizabeth M.; Bateson, C. Ann; Asner, Gregory P.

1998-01-01

Arid and semi-arid lands compose a large fraction of the earth's terrestrial vegetation, and thereby contribute significantly to global atmospheric-biospheric interactions. The thorny shrubs and small trees in these semi-arid shrub lands have counterparts throughout much of the world's tropical and subtropical zones and have captured substantial areas of the world's former grasslands. The objective of our field and remotely sensed measurements in the semi-arid shrublands of Texas is to monitor interannual variability and directional change in landscape structure, ecosystem processes and atmosphere-biosphere exchanges. To understand the role ecosystems play in controlling the composition of the atmosphere, it is necessary to quantify processes such as photosynthesis and primary production, decomposition and soil carbon storage, and trace gas exchanges. Photosynthesis is the link whereby surface-atmosphere exchanges such as the radiation balance and exchange of heat, moisture, and gas can be inferred. It also describes the efficiency of carbon dioxide exchange and is directly related to the primary production of vegetation. Our efforts in this paper focus on the indirect, quantification of photosynthesis, and thereby carbon flux and net primary production, via remote sensing and direct measurements of intercepted photosynthetically active radiation (IPAR).

Identification of protein–protein interfaces by decreased amide proton solvent accessibility

PubMed Central

Mandell, Jeffrey G.; Falick, Arnold M.; Komives, Elizabeth A.

1998-01-01

Matrix-assisted laser desorption ionization–time-of-flight mass spectrometry was used to identify peptic fragments from protein complexes that retained deuterium under hydrogen exchange conditions due to decreased solvent accessibility at the interface of the complex. Short deuteration times allowed preferential labeling of rapidly exchanging surface amides so that primarily solvent accessibility changes and not conformational changes were detected. A single mass spectrum of the peptic digest mixture was analyzed to determine the deuterium content of all proteolytic fragments of the protein. The protein–protein interface was reliably indicated by those peptides that retained more deuterons in the complex compared with control experiments in which only one protein was present. The method was used to identify the kinase inhibitor [PKI(5–24)] and ATP-binding sites in the cyclic-AMP-dependent protein kinase. Three overlapping peptides identified the ATP-binding site, three overlapping peptides identified the glycine-rich loop, and two peptides identified the PKI(5–24)-binding site. A complex of unknown structure also was analyzed, human α-thrombin bound to an 83-aa fragment of human thrombomodulin [TMEGF(4–5)]. Five peptides from thrombin showed significantly decreased solvent accessibility in the complex. Three peptides identified the anion-binding exosite I, confirming ligand competition experiments. Two peptides identified a new region of thrombin near the active site providing a potential mechanism of how thrombomodulin alters thrombin substrate specificity. PMID:9843953

First-order exchange coefficient coupling for simulating surface water-groundwater interactions: Parameter sensitivity and consistency with a physics-based approach

USGS Publications Warehouse

Ebel, B.A.; Mirus, B.B.; Heppner, C.S.; VanderKwaak, J.E.; Loague, K.

2009-01-01

Distributed hydrologic models capable of simulating fully-coupled surface water and groundwater flow are increasingly used to examine problems in the hydrologic sciences. Several techniques are currently available to couple the surface and subsurface; the two most frequently employed approaches are first-order exchange coefficients (a.k.a., the surface conductance method) and enforced continuity of pressure and flux at the surface-subsurface boundary condition. The effort reported here examines the parameter sensitivity of simulated hydrologic response for the first-order exchange coefficients at a well-characterized field site using the fully coupled Integrated Hydrology Model (InHM). This investigation demonstrates that the first-order exchange coefficients can be selected such that the simulated hydrologic response is insensitive to the parameter choice, while simulation time is considerably reduced. Alternatively, the ability to choose a first-order exchange coefficient that intentionally decouples the surface and subsurface facilitates concept-development simulations to examine real-world situations where the surface-subsurface exchange is impaired. While the parameters comprising the first-order exchange coefficient cannot be directly estimated or measured, the insensitivity of the simulated flow system to these parameters (when chosen appropriately) combined with the ability to mimic actual physical processes suggests that the first-order exchange coefficient approach can be consistent with a physics-based framework. Copyright ?? 2009 John Wiley & Sons, Ltd.

Oxygen exchange at gas/oxide interfaces: how the apparent activation energy of the surface exchange coefficient depends on the kinetic regime.

PubMed

Fielitz, Peter; Borchardt, Günter

2016-08-10

In the dedicated literature the oxygen surface exchange coefficient KO and the equilibrium oxygen exchange rate [Fraktur R] are considered to be directly proportional to each other regardless of the experimental circumstances. Recent experimental observations, however, contradict the consequences of this assumption. Most surprising is the finding that the apparent activation energy of KO depends dramatically on the kinetic regime in which it has been determined, i.e. surface exchange controlled vs. mixed or diffusion controlled. This work demonstrates how the diffusion boundary condition at the gas/solid interface inevitably entails a correlation between the oxygen surface exchange coefficient KO and the oxygen self-diffusion coefficient DO in the bulk ("on top" of the correlation between KO and [Fraktur R] for the pure surface exchange regime). The model can thus quantitatively explain the range of apparent activation energies measured in the different regimes: in the surface exchange regime the apparent activation energy only contains the contribution of the equilibrium exchange rate, whereas in the mixed or in the diffusion controlled regime the contribution of the oxygen self-diffusivity has also to be taken into account, which may yield significantly higher apparent activation energies and simultaneously quantifies the correlation KO ∝ DO(1/2) observed for a large number of oxides in the mixed or diffusion controlled regime, respectively.

76 FR 31385 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing of...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-05-31

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The effect of organic contaminants on the spectral induced polarization response of porous media - mechanistic approach

NASA Astrophysics Data System (ADS)

Schwartz, N.; Huisman, J. A.; Furman, A.

2012-12-01

In recent years, there is a growing interest in using geophysical methods in general and spectral induced polarization (SIP) in particular as a tool to detect and monitor organic contaminants within the subsurface. The general idea of the SIP method is to inject alternating current through a soil volume and to measure the resultant potential in order to obtain the relevant soil electrical properties (e.g. complex impedance, complex conductivity/resistivity). Currently, a complete mechanistic understanding of the effect of organic contaminants on the SIP response of soil is still absent. In this work, we combine laboratory experiments with modeling to reveal the main processes affecting the SIP signature of soil contaminated with organic pollutant. In a first set of experiments, we investigate the effect of non-aqueous phase liquids (NAPL) on the complex conductivity of unsaturated porous media. Our results show that addition of NAPL to the porous media increases the real component of the soil electrical conductivity and decreases the polarization of the soil (imaginary component of the complex conductivity). Furthermore, addition of NAPL to the soil resulted in an increase of the electrical conductivity of the soil solution. Based on these results, we suggest that adsorption of NAPL to the soil surface, and exchange process between polar organic compounds in the NAPL and inorganic ions in the soil are the main processes affecting the SIP signature of the contaminated soil. To further support our hypothesis, the temporal change of the SIP signature of a soil as function of a single organic cation concentration was measured. In addition to the measurements of the soil electrical properties, we also measured the effect of the organic cation on the chemical composition of both the bulk and the surface of the soil. The results of those experiments again showed that the electrical conductivity of the soil increased with increasing contaminant concentration. In addition, direct evidence showed that the organic cation was adsorbed on the soil surface and exchanged with inorganic ions that usually exist in soil. This experiment confirmed that adsorption to the soil surface and the associated release of inorganic ions is the main mechanism affecting the complex conductivity of the contaminated porous media. Furthermore, our results show that adsorption of organic ions to the soil surface resulted in a decrease of the soil polarization. Using a chemical complexation model of the soil surface and a model for the polarization of the Stern layer, we were able to show that the decrease in the polarization of the soil can be related to the decrease in the surface site density of inorganic ions, and that the contribution of the soil-organic complexes to the polarization of the soil is negligible. We attribute this to the strong interaction between polar organic compounds and soil which results in a significant decrease in the mobility of the organic compounds in the Stern layer. The results of this work are essential to better interpret SIP signatures of soil contaminated with organic contaminants.

Copepod communities from surface and ground waters in the everglades, south Florida

USGS Publications Warehouse

Bruno, M.C.; Cunningham, K.J.; Perry, S.A.

2003-01-01

We studied species composition and individual abundance of copepods in the surficial aquifer northeast of Everglades National Park. We identified the spatial distribution of subsurface habitats by assessing the depth of the high porosity layers in the limestone along a canal system, and we used copepods to assess the exchange between surface water and ground water along canal banks, at levels in the wells where high porosity connections to the canals exist. Surface- and ground-water taxa were defined, and species composition was related to areal position, sampling depth, and time. Subsurface copepod communities were dominated by surface copepods that disperse into the aquifer following the groundwater seepage along canal L-31N. The similarities in species composition between wells along canal reaches, suggest that copepods mainly enter ground water horizontally along canals via active and passive dispersal. Thus, the copepod populations indicate continuous connections between surface- and ground waters. The most abundant species were Orthocyclops modestus, Arctodiaptomus floridanus, Mesocyclops edax, and Thermocyclops parvus, all known in literature from surface habitats; however, these species have been collected in ground water in ENP. Only two stygophiles were collected: Diacylcops nearcticus and Diacyclops crassicaudis brachycercus. Restoration of the Everglades ecosystem requires a mosaic of data to reveal a complete picture of this complex system. The use of copepods as indicators of seepage could be a tool in helping to assess the direction and the duration of surface and ground water exchange.

Capture and dissociation in the complex-forming CH + H2 → CH2 + H, CH + H2 reactions.

PubMed

González, Miguel; Saracibar, Amaia; Garcia, Ernesto

2011-02-28

The rate coefficients for the capture process CH + H(2)→ CH(3) and the reactions CH + H(2)→ CH(2) + H (abstraction), CH + H(2) (exchange) have been calculated in the 200-800 K temperature range, using the quasiclassical trajectory (QCT) method and the most recent global potential energy surface. The reactions, which are of interest in combustion and in astrochemistry, proceed via the formation of long-lived CH(3) collision complexes, and the three H atoms become equivalent. QCT rate coefficients for capture are in quite good agreement with experiments. However, an important zero point energy (ZPE) leakage problem occurs in the QCT calculations for the abstraction, exchange and inelastic exit channels. To account for this issue, a pragmatic but accurate approach has been applied, leading to a good agreement with experimental abstraction rate coefficients. Exchange rate coefficients have also been calculated using this approach. Finally, calculations employing QCT capture/phase space theory (PST) models have been carried out, leading to similar values for the abstraction rate coefficients as the QCT and previous quantum mechanical capture/PST methods. This suggests that QCT capture/PST models are a good alternative to the QCT method for this and similar systems.

Adsorptive Desulfurization of Model Gasoline by Using Different Zn Sources Exchanged NaY Zeolites.

PubMed

Rui, Jingwei; Liu, Fei; Wang, Rijie; Lu, Yanfei; Yang, Xiaoxia

2017-02-17

A series of Zn-modified NaY zeolites were prepared by the liquid-phase ion-exchange method with different Zn sources, including Zn(NO₃)₂, Zn(Ac)₂ and ZnSO₄. The samples were tested as adsorbents for removing an organic sulfur compound from a model gasoline fuel containing 1000 ppmw sulfur. Zn(Ac)₂-Y exhibited the best performance for the desulfurization of gasoline at ambient conditions. Combined with the adsorbents' characterization results, the higher adsorption capacity of Zn(Ac)₂-Y is associated with a higher ion-exchange degree. Further, the results demonstrated that the addition of 5 wt % toluene or 1-hexene to the diluted thiophene (TP) solution in cyclohexane caused a large decrease in the removal of TP from the model gasoline fuel. This provides evidence about the competition through the π-complexation between TP and toluene for adsorption on the active sites. The acid-catalyzed alkylation by 1-hexene of TP and the generated complex mixture of bulky alkylthiophenes would adsorb on the surface active sites of the adsorbent and block the pores. The regenerated Zn(Ac)₂-Y adsorbent afforded 84.42% and 66.10% of the initial adsorption capacity after the first two regeneration cycles.

Pressure dependence of carbonate exchange with [NpO 2(CO 3) 3] 4– in aqueous solutions

DOE PAGES

Pilgrim, Corey D.; Zavarin, Mavrik; Casey, William H.

2016-12-13

Here, the rates of ligand exchange into the geochemically important [NpO 2(CO 3) 3] 4– aqueous complex are measured as a function of pressure in order to complement existing data on the isostructural [UO 2(CO 3) 3] 4– complex. Experiments are conducted at pH conditions where the rate of exchange is independent of the proton concentration. Unexpectedly, the experiments show a distinct difference in the pressure dependencies of rates of exchange for the uranyl and neptunyl complexes.

Catalytic biofilms on structured packing for the production of glycolic acid.

PubMed

Li, Xuan Zhong; Hauer, Bernhard; Rosche, Bettina

2013-02-01

While structured packing modules are known to be efficient for surface wetting and gas-liquid exchange in abiotic surface catalysis, this model study explores structured packing as a growth surface for catalytic biofilms. Microbial biofilms have been proposed as self-immobilized and self-regenerating catalysts for the production of chemicals. A concern is that the complex and dynamic nature of biofilms may cause fluctuations in their catalytic performance over time or may affect process reproducibility. An aerated continuous trickle-bed biofilm reactor system was designed with a 3 L structured packing, liquid recycling and pH control. Pseudomonas diminuta established a biofilm on the stainless steel structured packing with a specific surface area of 500 m2 m-3 and catalyzed the oxidation of ethylene glycol to glycolic acid for over two months of continuous operation. A steady-state productivity of up to 1.6 gl-1h-1 was achieved at a dilution rate of 0.33 h-1. Process reproducibility between three independent runs was excellent, despite process interruptions and activity variations in cultures grown from biofilm effluent cells. The results demonstrate the robustness of a catalytic biofilm on structured packing, despite its dynamic nature. Implementation is recommended for whole-cell processes that require efficient gas-liquid exchange, catalyst retention for continuous operation, or improved catalyst stability.

77 FR 35723 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-06-14

.../taker fees and rebates, which are designed to attract complex orders to the Exchange, and has a specific... per contract applicable to customers that transact in complex orders, i.e., customer complex orders that interact with complex orders residing on the complex order book thereby taking liquidity from the...

Multi-Scale Observation and Modelling of Energy and Matter Exchange in the Atmospheric Boundary-Layer (ScaleX Campaigns)

NASA Astrophysics Data System (ADS)

Zeeman, M. J.; Wolz, K.; Adler, B.; Brenner, C.; De Roo, F.; Emeis, S.; Kalthoff, N.; Mauder, M.; Schäfer, K.; Wohlfahrt, G.; Zhao, P.

2016-12-01

We investigated biosphere-atmosphere exchange processes in relation to the atmospheric boundary-layer (ABL) flow in a shallow valley. Land-use heterogeneity and topography can force local atmospheric flow patterns, including local circulations. Such flow patterns can impair current techniques for the quantification and source attribution of surface-exchange fluxes due to flux-divergence, advection and decoupling. Wind field, temperature and humidity structures in the ABL were observed in high resolution with spatially distributed observations in a 1 km3 experimental domain. Remote-sensing observations of wind, temperature and particles in the ABL (Raman-lidar; RASS; ceilometer; microwave radiometer; 3D Doppler-lidar) were combined with a high-resolution network of in-situ observations that included vertical and horizontal profiles of wind, temperature, carbon dioxide, methane and water vapor concentrations. The experiments were co-located with the long-term eddy covariance (EC) observatory Fendt (DE-Fen; ICOS, TERENO) and were part of international cooperative efforts in 2015 and 2016 (the ScaleX campaigns). The gathered experimental data offers a scale-transcending insight in local flow patterns in mountainous terrain and their influence on surface-exchange fluxes of energy and matter as observed by EC and flux-gradient methodology. In addition, the data is used for validation of Large-Eddy Simulations in complex terrain using PALM-LES. Within this modelling framework, virtual measurements are conducted to further assess the importance of three-dimensional advective and horizontal turbulent transport terms.

Structural complexity and land-surface energy exchange along a gradient from arctic tundra to boreal forest

USGS Publications Warehouse

Thompson, C.; Beringer, J.; Chapin, F. S.; McGuire, A.D.

2004-01-01

Question: Current climate changes in the Alaskan Arctic, which are characterized by increases in temperature and length of growing season, could alter vegetation structure, especially through increases in shrub cover or the movement of treeline. These changes in vegetation structure have consequences for the climate system. What is the relationship between structural complexity and partitioning of surface energy along a gradient from tundra through shrub tundra to closed canopy forest? Location: Arctic tundra-boreal forest transition in the Alaskan Arctic. Methods: Along this gradient of increasing canopy complexity, we measured key vegetation characteristics, including community composition, biomass, cover, height, leaf area index and stem area index. We relate these vegetation characteristics to albedo and the partitioning of net radiation into ground, latent, and sensible heating fluxes. Results: Canopy complexity increased along the sequence from tundra to forest due to the addition of new plant functional types. This led to non-linear changes in biomass, cover, and height in the understory. The increased canopy complexity resulted in reduced ground heat fluxes, relatively conserved latent heat fluxes and increased sensible heat fluxes. The localized warming associated with increased sensible heating over more complex canopies may amplify regional warming, causing further vegetation change in the Alaskan Arctic.

Fabrication of High-Temperature Heat Exchangers by Plasma Spraying Exterior Skins on Nickel Foams

NASA Astrophysics Data System (ADS)

Hafeez, P.; Yugeswaran, S.; Chandra, S.; Mostaghimi, J.; Coyle, T. W.

2016-06-01

Thermal-sprayed heat exchangers were tested at high temperatures (750 °C), and their performances were compared to the foam heat exchangers made by brazing Inconel sheets to their surface. Nickel foil was brazed to the exterior surface of 10-mm-thick layers of 10 and 40 PPI nickel foam. A plasma torch was used to spray an Inconel coating on the surface of the foil. A burner test rig was built to produce hot combustion gases that flowed over exposed face of the heat exchanger. Cooling air flowed through the foam heat exchanger at rates of up to 200 SLPM. Surface temperature and air inlet/exit temperature were measured. Heat transfer to air flowing through the foam was significantly higher for the thermally sprayed heat exchangers than for the brazed heat exchangers. On an average, thermally sprayed heat exchangers show 36% higher heat transfer than conventionally brazed foam heat exchangers. At low flow rates, the convective resistance is large (~4 × 10-2 m2 K/W), and the effect of thermal contact resistance is negligible. At higher flow rates, the convective resistance decreases (~2 × 10-3 m2 K/W), and the lower contact resistance of the thermally sprayed heat exchanger provides better performance than the brazed heat exchangers.

Modeling of protein-anion exchange resin interaction for the human growth hormone charge variants.

PubMed

Lapelosa, Mauro; Patapoff, Thomas W; Zarraga, Isidro E

2015-12-01

Modeling ion exchange chromatography (IEC) behavior has generated significant interest because of the wide use of IEC as an analytical technique as well as a preparative protein purification process; indeed there is a need for better understanding of what drives the unique behavior of protein charge variants. We hypothesize that a complex protein molecule, which contains both hydrophobic and charged moieties, would interact strongly with an in silico designed resin through charged electrostatic patches on the surface of the protein. In the present work, variants of recombinant human growth hormone that mimic naturally-occurring deamidation products were produced and characterized in silico. The study included these four variants: rhGH, N149D, N152D, and N149D/N152D. Poisson-Boltzmann calculations were used to determine surface electrostatic potential. Metropolis Monte Carlo simulations were carried out with the resulting variants to simulate IEC systems, examining the free energy of the interaction of the protein with an in silico anion exchange column represented by polylysine polypeptide. The results show that the charge variants have different average binding energies and the free energy of interaction can be used to predict the retention time for the different variants. Copyright © 2015 Elsevier B.V. All rights reserved.

Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes

NASA Astrophysics Data System (ADS)

Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna

2017-04-01

Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

A study of mesoscale surface heat and moisture budgets and their relationship to airmass cumulus clouds observed in LANDSAT imagery. [Manhatten, Kansas and Fargo, North Dakota

NASA Technical Reports Server (NTRS)

Merritt, E. S. (Principal Investigator); Sabatini, R. R.; Heitkemper, L.; Hart, W. D.; Hlavka, D. L.

1976-01-01

The author has identified the following significant results. The three budget analyses show a weak correspondence between LANDSAT cloud patterns and elements of the energy and moisture budgets. It was found that a little more energy is contributed by the ground to heat the air in cloudy areas. Improvements are warranted in the budget models and data coverage necessary to describe the environment. These models can serve as a basis for more complex models of surface air heat and moisture exchanges which would utilize readily available meteorological data on a mesoscale.

Improvement of drug loading onto ion exchange resin by cyclodextrin inclusion complex.

PubMed

Samprasit, Wipada; Rojanarata, Theerasak; Akkaramongkolporn, Prasert; Ngawhirunpat, Tanasait; Sila-on, Warisada; Opanasopit, Praneet

2013-11-01

Ion exchange resins have ability to exchange their counter ions for ionized drug in the surrounding medium, yielding "drug resin complex." Cyclodextrin can be applied for enhancement of drug solubility and stability. Cyclodextrin inclusion complex of poorly water-soluble NSAIDs, i.e. meloxicam and piroxicam, was characterized and its novel application for improving drug loading onto an anionic exchange resin, i.e. Dowex® 1×2, was investigated. β-Cyclodextrin (β-CD) and hydroxypropyl β-cyclodextrin (HP-β-CD) were used for the preparation of inclusion complex with drugs in solution state at various pH. The inclusion complex was characterized by phase solubility, continuous variation, spectroscopic and electrochemistry methods. Then, the drug with and without cyclodextrin were equilibrated with resin at 1:1 and 1:2 weight ratio of drug and resin. Solubility of the drugs was found to increase with increasing cyclodextrin concentration and pH. The increased solubility was explained predominantly due to the formation of inclusion complex at low pH and the increased ionization of drug at high pH. According to characterization studies, the inclusion complex was successfully formed with a 1:1 stoichiometry. The presence of cyclodextrin in the loading solution resulted in the improvement of drug loading onto resin. Enhancing drug loading onto ion-exchange resin via the formation of cyclodextrin inclusion complex is usable in the development of ion-exchange based drug delivery systems, which will beneficially reduce the use of harmful acidic or basic and organic chemicals.

Complex chromosomal rearrangements induced in vivo by heavy ions.

PubMed

Durante, M; Ando, K; Furusawa, Y; Obe, G; George, K; Cucinotta, F A

2004-01-01

It has been suggested that the ratio complex/simple exchanges can be used as a biomarker of exposure to high-LET radiation. We tested this hypothesis in vivo, by considering data from several studies that measured complex exchanges in peripheral blood from humans exposed to mixed fields of low- and high-LET radiation. In particular, we studied data from astronauts involved in long-term missions in low-Earth-orbit, and uterus cancer patients treated with accelerated carbon ions. Data from two studies of chromosomal aberrations in astronauts used blood samples obtained before and after space flight, and a third study used blood samples from patients before and after radiotherapy course. Similar methods were used in each study, where lymphocytes were stimulated to grow in vitro, and collected after incubation in either colcemid or calyculin A. Slides were painted with whole-chromosome DNA fluorescent probes (FISH), and complex and simple chromosome exchanges in the painted genome were classified separately. Complex-type exchanges were observed at low frequencies in control subjects, and in our test subjects before the treatment. No statistically significant increase in the yield of complex-type exchanges was induced by the space flight. Radiation therapy induced a high fraction of complex exchanges, but no significant differences could be detected between patients treated with accelerated carbon ions or X-rays. Complex chromosomal rearrangements do not represent a practical biomarker of radiation quality in our test subjects. Copyright 2003 S. Karger AG, Basel

Complex Chromosomal Rearrangements Induced in Vivo by Heavy Ions

NASA Technical Reports Server (NTRS)

Durante, M.; Ando, K.; Furusawa, G.; Obe, G.; George, K.; Cucinotta, F. A.

2004-01-01

It has been suggested that the ratio complex/simple exchanges can be used as a biomarker of exposure to high-LET radiation. We tested this hypothesis in vivo, by considering data from several studies that measured complex exchanges in peripheral blood from humans exposed to mixed fields of low- and high-LET radiation. In particular, we studied data from astronauts involved in long-term missions in low-Earth-orbit, and uterus cancer patients treated with accelerated carbon ions. Data from two studies of chromosomal aberrations in astronauts used blood samples obtained before and after space flight, and a third study used blood samples from patients before and after radiotherapy course. Similar methods were used in each study, where lymphocytes were stimulated to grow in vitro, and collected after incubation in either colcemid or calyculin A. Slides were painted with whole-chromosome DNA fluorescent probes (FISH), and complex and simple chromosome exchanges in the painted genome were classified separately. Complex-type exchanges were observed at low frequencies in control subjects, and in our test subjects before the treatment. No statistically significant increase in the yield of complex-type exchanges was induced by the space flight. Radiation therapy induced a high fraction of complex exchanges, but no significant differences could be detected between patients treated with accelerated carbon ions or X-rays. Complex chromosomal rearrangements do not represent a practical biomarker of radiation quality in our test subjects. Copyright 2003 S. Karger AG, Basel.

Explicit modeling of groundwater-surface water interactions using a simple bucket-type model

NASA Astrophysics Data System (ADS)

Staudinger, Maria; Carlier, Claire; Brunner, Philip; Seibert, Jan

2017-04-01

Longer dry spells can become critical for water supply and groundwater dependent ecosystems. During these dry spells groundwater is often the most relevant source for streams. Hence, the hydrological behavior of a catchment is often dominated by groundwater surface water interactions, which can vary considerably in space and time. While classical hydrological approaches hardly consider this spatial dependence, quantitative, hydrogeological modeling approaches can couple surface runoff processes and groundwater processes. Hydrogeological modeling can help to gain an improved understanding of catchment processes during low flow. However, due to their complex parametrization and large computational requirements, such hydrogeological models are difficult to employ at catchment scale, particularly for a larger set of catchments. Then bucket-type hydrological models remain a practical alternative. In this study we combine the strengths of both the hydrogeological and bucket-type hydrological models to better understand low flow processes and ultimately to use this knowledge for low flow projections. Bucket-type hydrological models have traditionally not been developed with focus on the simulation of low flow. One consequence is that interactions between surface and groundwater are not explicitly considered. Water fluxes in bucket-type hydrological models are commonly simulated only in one direction, namely from the groundwater to the stream but not from the stream to the groundwater. This latter flux, however, can become more important during low flow situations. We therefore further developed the bucket-type hydrological model HBV to simulate low flow situations by allowing for exchange in both directions i.e. also from the stream to the groundwater. The additional HBV exchange box is developed by using a variety of synthetic hydrogeological models as training set that were generated using a fully coupled, physically based hydrogeological model. In this way processes that occur in different spatial settings within the catchment are translated to functional relationships and effective parameter values for the conceptual exchange box can be extracted. Here, we show the development and evaluation of the HBV exchange box. We further show a first application in real catchments and evaluate the model performance by comparing the simulations to benchmark models that do not consider groundwater surface water interaction.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

PubMed

Xu, Weinan; Ledin, Petr A; Shevchenko, Valery V; Tsukruk, Vladimir V

2015-06-17

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

Space shuttle main engine computed tomography applications

NASA Technical Reports Server (NTRS)

Sporny, Richard F.

1990-01-01

For the past two years the potential applications of computed tomography to the fabrication and overhaul of the Space Shuttle Main Engine were evaluated. Application tests were performed at various government and manufacturer facilities with equipment produced by four different manufacturers. The hardware scanned varied in size and complexity from a small temperature sensor and turbine blades to an assembled heat exchanger and main injector oxidizer inlet manifold. The evaluation of capabilities included the ability to identify and locate internal flaws, measure the depth of surface cracks, measure wall thickness, compare manifold design contours to actual part contours, perform automatic dimensional inspections, generate 3D computer models of actual parts, and image the relationship of the details in a complex assembly. The capabilities evaluated, with the exception of measuring the depth of surface flaws, demonstrated the existing and potential ability to perform many beneficial Space Shuttle Main Engine applications.

Seasonal patterns and controls on net ecosystem CO2 exchange in a boreal peatland complex

NASA Astrophysics Data System (ADS)

Bubier, Jill L.; Crill, Patrick M.; Moore, Tim R.; Savage, Kathleen; Varner, Ruth K.

1998-12-01

We measured seasonal patterns of net ecosystem exchange (NEE) of CO2 in a diverse peatland complex underlain by discontinuous permafrost in northern Manitoba, Canada, as part of the Boreal Ecosystems Atmosphere Study (BOREAS). Study sites spanned the full range of peatland trophic and moisture gradients found in boreal environments from bog (pH 3.9) to rich fen (pH 7.2). During midseason (July-August, 1996), highest rates of NEE and respiration followed the trophic sequence of bog (5.4 to -3.9 μmol CO2 m-2 s-1) < poor fen (6.3 to -6.5 μmol CO2 m-2 s-1) < intermediate fen (10.5 to -7.8 μmol CO2 m-2 s-1) < rich fen (14.9 to -8.7 μmol CO2m-2 s-1). The sequence changed during spring (May-June) and fall (September-October) when ericaceous shrub (e.g., Chamaedaphne calyculata) bogs and sedge (Carex spp.) communities in poor to intermediate fens had higher maximum CO2 fixation rates than deciduous shrub-dominated (Salix spp. and Betula spp.) rich fens. Timing of snowmelt and differential rates of peat surface thaw in microtopographic hummocks and hollows controlled the onset of carbon uptake in spring. Maximum photosynthesis and respiration were closely correlated throughout the growing season with a ratio of approximately 1/3 ecosystem respiration to maximum carbon uptake at all sites across the trophic gradient. Soil temperatures above the water table and timing of surface thaw and freeze-up in the spring and fall were more important to net CO2 exchange than deep soil warming. This close coupling of maximum CO2 uptake and respiration to easily measurable variables, such as trophic status, peat temperature, and water table, will improve models of wetland carbon exchange. Although trophic status, aboveground net primary productivity, and surface temperatures were more important than water level in predicting respiration on a daily basis, the mean position of the water table was a good predictor (r2 = 0.63) of mean respiration rates across the range of plant community and moisture gradients. Q10 values ranged from 3.0 to 4.1 from bog to rich fen, but when normalized by above ground vascular plant biomass, the Q10 for all sites was 3.3.

77 FR 42029 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-17

... to market participants that add or remove liquidity in the complex order book (``maker/taker fees and... quotations for complex order strategies in the complex order book.\\8\\ Given this enhancement to the complex... Customer orders, the Exchange has adopted maker fees that apply to transactions in the complex order book...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Guoping; Luo, Wensui; Brooks, Scott C

We conducted batch and recirculating column titration tests with contaminated acidic sediments with controlled CO2 in the headspace, and extended the geochemical model by Gu et al. (2003, GCA) to better understand and quantify the reactions governing trace metal fate in the subsurface. The sediment titration curve showed slow pH increase due to strong buffering by Al precipitation and CO2 uptake. Assuming precipitation of basaluminite at low saturation index (SI=-4), and decreasing cation exchange selectivity coefficient (kNa\\Al=0.3), the predictions are close to the observed pH and Al; and the model explains 1) the observed Ca, Mg, and Mn concentration decreasemore » by cation exchange with sorbed Al, and 2) the decrease of U by surface complexation with Fe hydroxides at low pH, and precipitation as liebigite (Ca2UO2(CO3)3:10H2O) at pH>5.5. Without further adjustment geochemical parameters, the model describes reasonably well previous sediment and column titration tests without CO2 in the headspace, as well as the new large column test. The apparent inhibition of U and Ni decrease in the large column can be explained by formation of aqueous carbonate complexes and/or competition with carbonate for surface sites. These results indicated that ignoring labile solid phase Al would underestimate base requirement in titration of acidic aquifers.« less

Flo11p-Independent Control of “Mat” Formation by Hsp70 Molecular Chaperones and Nucleotide Exchange Factors in Yeast

PubMed Central

Martineau, Céline N.; Beckerich, Jean-Marie; Kabani, Mehdi

2007-01-01

The yeast Saccharomyces cerevisiae has been used as a model for fungal biofilm formation due to its ability to adhere to plastic surfaces and to form mats on low-density agar petri plates. Mats are complex multicellular structures composed of a network of cables that form a central hub from which emanate multiple radial spokes. This reproducible and elaborate pattern is indicative of a highly regulated developmental program that depends on specific transcriptional programming, environmental cues, and possibly cell–cell communication systems. While biofilm formation and sliding motility were shown to be strictly dependent on the cell-surface adhesin Flo11p, little is known about the cellular machinery that controls mat formation. Here we show that Hsp70 molecular chaperones play key roles in this process with the assistance of the nucleotide exchange factors Fes1p and Sse1p and the Hsp40 family member Ydj1p. The disruption of these cofactors completely abolished mat formation. Furthermore, complex interactions among SSA genes were observed: mat formation depended mostly on SSA1 while minor defects were observed upon loss of SSA2; additional mutations in SSA3 or SSA4 further enhanced these phenotypes. Importantly, these mutations did not compromise invasive growth or Flo11p expression, suggesting that Flo11p-independent pathways are necessary to form mats. PMID:17947402

Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

PubMed

Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

2017-05-17

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pilgrim, Corey D.; Zavarin, Mavrik; Casey, William H.

Here, the rates of ligand exchange into the geochemically important [NpO 2(CO 3) 3] 4– aqueous complex are measured as a function of pressure in order to complement existing data on the isostructural [UO 2(CO 3) 3] 4– complex. Experiments are conducted at pH conditions where the rate of exchange is independent of the proton concentration. Unexpectedly, the experiments show a distinct difference in the pressure dependencies of rates of exchange for the uranyl and neptunyl complexes.

Sample displacement chromatography as a method for purification of proteins and peptides from complex mixtures

PubMed Central

Gajdosik, Martina Srajer; Clifton, James; Josic, Djuro

2012-01-01

Sample displacement chromatography (SDC) in reversed-phase and ion-exchange modes was introduced approximately twenty years ago. This method takes advantage of relative binding affinities of components in a sample mixture. During loading, there is a competition among different sample components for the sorption on the surface of the stationary phase. SDC was first used for the preparative purification of proteins. Later, it was demonstrated that this kind of chromatography can also be performed in ion-exchange, affinity and hydrophobic-interaction mode. It has also been shown that SDC can be performed on monoliths and membrane-based supports in both analytical and preparative scale. Recently, SDC in ion-exchange and hydrophobic interaction mode was also employed successfully for the removal of trace proteins from monoclonal antibody preparations and for the enrichment of low abundance proteins from human plasma. In this review, the principals of SDC are introduced, and the potential for separation of proteins and peptides in micro-analytical, analytical and preparative scale is discussed. PMID:22520159

Infectious polymorphic toxins delivered by outer membrane exchange discriminate kin in myxobacteria.

PubMed

Vassallo, Christopher N; Cao, Pengbo; Conklin, Austin; Finkelstein, Hayley; Hayes, Christopher S; Wall, Daniel

2017-08-18

Myxobacteria are known for complex social behaviors including outer membrane exchange (OME), in which cells exchange large amounts of outer membrane lipids and proteins upon contact. The TraA cell surface receptor selects OME partners based on a variable domain. However, traA polymorphism alone is not sufficient to precisely discriminate kin. Here, we report a novel family of OME-delivered toxins that promote kin discrimination of OME partners. These SitA lipoprotein toxins are polymorphic and widespread in myxobacteria. Each sitA is associated with a cognate sitI immunity gene, and in some cases a sitB accessory gene. Remarkably, we show that SitA is transferred serially between target cells, allowing the toxins to move cell-to-cell like an infectious agent. Consequently, SitA toxins define strong identity barriers between strains and likely contribute to population structure, maintenance of cooperation, and strain diversification. Moreover, these results highlight the diversity of systems evolved to deliver toxins between bacteria.

Imino proton exchange and base-pair kinetics in the AMP-RNA aptamer complex.

PubMed

Nonin, S; Jiang, F; Patel, D J

1997-05-02

We report on the dynamics of base-pair opening in the ATP-binding asymmetric internal loop and flanking base-pairs of the AMP-RNA aptamer complex by monitoring the exchange characteristics of the extremely well resolved imino protons in the NMR spectrum of the complex. The kinetics of imino proton exchange as a function of basic pH or added ammonia catalyst are used to measure the apparent base-pair dissociation constants and lifetimes of Watson-Crick and mismatched base-pairs, as well as the solvent accessibility of the unpaired imino protons in the complex. The exchange characteristics of the imino protons identify the existence of four additional hydrogen bonds stabilizing the conformation of the asymmetric ATP-binding internal loop that were not detected by NOEs and coupling constants alone, but are readily accommodated in the previously reported solution structure of the AMP-RNA aptamer complex published from our laboratory. The hydrogen exchange kinetics of the non-Watson-Crick pairs in the asymmetric internal loop of the AMP-RNA aptamer complex have been characterized and yield apparent dissociation constants (alphaKd) that range from 10(-2) to 10(-7). Surprisingly, three of these alphaKd values are amongst the lowest measured for all base-pairs in the AMP-RNA aptamer complex. Comparative studies of hydrogen exchange of the imino protons in the free RNA aptamer and the AMP-RNA aptamer complex establish that complexation stabilizes not only the bases within the ATP-binding asymmetric internal loop, but also the flanking stem base-pairs (two pairs on either side) of the binding site. We also outline some preliminary results related to the exchange properties of a sugar 2'-hydroxyl proton of a guanosine residue involved in a novel hydrogen bond that has been shown to contribute to the immobilization of the bound AMP by the RNA aptamer, and whose resonance is narrow and downfield shifted in the spectrum.

Electrochemical evidences and consequences of significant differences in ions diffusion rate in polyacrylate-based ion-selective membranes.

PubMed

Woźnica, Emilia; Mieczkowski, Józef; Michalska, Agata

2011-11-21

The origin and effect of surface accumulation of primary ions within the ion-selective poly(n-butyl acrylate)-based membrane, obtained by thermal polymerization, is discussed. Using a new method, based on the relation between the shape of a potentiometric plot and preconditioning time, the diffusion of copper ions in the membrane was found to be slow (the diffusion coefficient estimated to be close to 10(-11) cm(2) s(-1)), especially when compared to ion-exchanger counter ions--sodium cations diffusion (a diffusion coefficient above 10(-9) cm(2) s(-1)). The higher mobility of sodium ions than those of the copper-ionophore complex results in exposed ion-exchanger role leading to undesirably exposed sensitivity to sodium or potassium ions.

Carbohydrate and alditol analysis by high-performance anion-exchange chromatography coupled with electrochemical detection at a cobalt-modified electrode.

PubMed

Casella, Innocenzo G; Contursi, Michela

2003-07-01

A cobalt oxyhydroxide film dispersed on a carbon electrode surface was characterized and proposed as an amperometric sensor for determination of alditols and carbohydrates in flowing streams. Complex mixtures of carbohydrates were separated by anion-exchange chromatography using a moderately alkaline solution as mobile phase. The cobalt modified electrode (GC-Co) was employed under a constant applied potential of 0.5 V (vs Ag/AgCl). Under these experimental conditions the detection limits (S/N=3) for all analyzed electroactive molecules ranged between 0.3 micromol L(-1) and 1.5 micromol L(-1) and the dynamic linear ranges spanned generally three orders of magnitude above the relevant detection limits. Analytical determinations of carbohydrates and alditols in red and white wines, are reported.

Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

PubMed

Fernandes, M Marques; Scheinost, A C; Baeyens, B

2016-08-01

The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one or two carbonate groups pointing away from the surface into the solution phase. Within the spectroscopically observable concentration range these complexes could only be identified on the weak sites, in line with the small strong site capacity suggested by the refined sorption model. When the solubility of carbonates was exceeded, formation of an Am carbonate hydroxide could be identified. The excellent agreement between the thermodynamic model parameters obtained by fitting the macroscopic data, and the spectroscopically identified mechanisms, demonstrates the mature state of the 2SPNE SC/CE model for predicting and quantifying the retention of Ln/An(III) elements by montmorillonite-rich clay rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tensiometry and dilational rheology of mixed β-lactoglobulin/ionic surfactant adsorption layers at water/air and water/hexane interfaces.

PubMed

Dan, Abhijit; Gochev, Georgi; Miller, Reinhard

2015-07-01

Oscillating drop tensiometry was applied to study adsorbed interfacial layers at water/air and water/hexane interfaces formed from mixed solutions of β-lactoglobulin (BLG, 1 μM in 10 mM buffer, pH 7 - negative net charge) and the anionic surfactant SDS or the cationic DoTAB. The interfacial pressure Π and the dilational viscoelasticity modulus |E| of the mixed layers were measured for mixtures of varying surfactant concentrations. The double capillary technique was employed which enables exchange of the protein solution in the drop bulk by surfactant solution (sequential adsorption) or by pure buffer (washing out). The first protocol allows probing the influence of the surfactant on a pre-adsorbed protein layer thus studying the protein/surfactant interactions at the interface. The second protocol gives access to the residual values of Π and |E| measured after the washing out procedure thus bringing information about the process of protein desorption. The DoTAB/BLG complexes exhibit higher surface activity and higher resistance to desorption in comparison with those for the SDS/BLG complexes due to hydrophobization via electrostatic binding of surfactant molecules. The neutral DoTAB/BLG complexes achieve maximum elastic response of the mixed layer. Mixed BLG/surfactant layers at the water/oil interface are found to reach higher surface pressure and lower maximum dilational elasticity than those at the water/air surface. The sequential adsorption mode experiments and the desorption study reveal that binding of DoTAB to pre-adsorbed BLG globules is somehow restricted at the water/air surface in comparison with the case of complex formation in the solution bulk and subsequently adsorbed at the water/air surface. Maximum elasticity is achieved with washed out layers obtained after simultaneous adsorption, i.e. isolation of the most surface active DoTAB/BLG complex. These specific effects are much less pronounced at the W/H interface. Copyright © 2015 Elsevier Inc. All rights reserved.

Hydrogen exchange mass spectrometry of functional membrane-bound chemotaxis receptor complexes.

PubMed

Koshy, Seena S; Eyles, Stephen J; Weis, Robert M; Thompson, Lynmarie K

2013-12-10

The transmembrane signaling mechanism of bacterial chemotaxis receptors is thought to involve changes in receptor conformation and dynamics. The receptors function in ternary complexes with two other proteins, CheA and CheW, that form extended membrane-bound arrays. Previous studies have shown that attractant binding induces a small (∼2 Å) piston displacement of one helix of the periplasmic and transmembrane domains toward the cytoplasm, but it is not clear how this signal propagates through the cytoplasmic domain to control the kinase activity of the CheA bound at the membrane-distal tip, nearly 200 Å away. The cytoplasmic domain has been shown to be highly dynamic, which raises the question of how a small piston motion could propagate through a dynamic domain to control CheA kinase activity. To address this, we have developed a method for measuring dynamics of the receptor cytoplasmic fragment (CF) in functional complexes with CheA and CheW. Hydrogen-deuterium exchange mass spectrometry (HDX-MS) measurements of global exchange of the CF demonstrate that the CF exhibits significantly slower exchange in functional complexes than in solution. Because the exchange rates in functional complexes are comparable to those of other proteins with similar structures, the CF appears to be a well-structured protein within these complexes, which is compatible with its role in propagating a signal that appears to be a tiny conformational change in the periplasmic and transmembrane domains of the receptor. We also demonstrate the feasibility of this protocol for local exchange measurements by incorporating a pepsin digest step to produce peptides with 87% sequence coverage and only 20% back exchange. This method extends HDX-MS to membrane-bound functional complexes without detergents that may perturb the stability or structure of the system.

Hydrogen Exchange Mass Spectrometry of Functional Membrane-bound Chemotaxis Receptor Complexes

PubMed Central

Koshy, Seena S.; Eyles, Stephen J.; Weis, Robert M.; Thompson, Lynmarie K.

2014-01-01

The transmembrane signaling mechanism of bacterial chemotaxis receptors is thought to involve changes in receptor conformation and dynamics. The receptors function in ternary complexes with two other proteins, CheA and CheW, that form extended membrane-bound arrays. Previous studies have shown that attractant binding induces a small (~2 Å) piston displacement of one helix of the periplasmic and transmembrane domains towards the cytoplasm, but it is not clear how this signal propagates through the cytoplasmic domain to control the kinase activity of the CheA bound at the membrane-distal tip, nearly 200 Å away. The cytoplasmic domain has been shown to be highly dynamic, which raises the question of how a small piston motion could propagate through a dynamic domain to control CheA kinase activity. To address this, we have developed a method for measuring dynamics of the receptor cytoplasmic fragment (CF) in functional complexes with CheA and CheW. Hydrogen exchange mass spectrometry (HDX-MS) measurements of global exchange of CF demonstrate that CF exhibits significantly slower exchange in functional complexes than in solution. Since the exchange rates in functional complexes are comparable to that of other proteins of similar structure, the CF appears to be a well-structured protein within these complexes, which is compatible with its role in propagating a signal that appears to be a tiny conformational change in the periplasmic and transmembrane domains of the receptor. We also demonstrate the feasibility of this protocol for local exchange measurements, by incorporating a pepsin digest step to produce peptides with 87% sequence coverage and only 20% back exchange. This method extends HDX-MS to membrane-bound functional complexes without detergents that may perturb the stability or structure of the system. PMID:24274333

Analysis of complex-type chromosome exchanges in astronauts' lymphocytes after space flight as a biomarker of high-LET exposure

NASA Technical Reports Server (NTRS)

George, Kerry; Wu, Honglu; Willingham, Veronica; Cucinotta, Francis A.

2002-01-01

High-LET radiation is more efficient in producing complex-type chromosome exchanges than sparsely ionizing radiation, and this can potentially be used as a biomarker of radiation quality. To investigate if complex chromosome exchanges are induced by the high-LET component of space radiation exposure, damage was assessed in astronauts' blood lymphocytes before and after long duration missions of 3-4 months. The frequency of simple translocations increased significantly for most of the crewmembers studied. However, there were few complex exchanges detected and only one crewmember had a significant increase after flight. It has been suggested that the yield of complex chromosome damage could be underestimated when analyzing metaphase cells collected at one time point after irradiation, and analysis of chemically-induced PCC may be more accurate since problems with complicated cell-cycle delays are avoided. However, in this case the yields of chromosome damage were similar for metaphase and PCC analysis of astronauts' lymphocytes. It appears that the use of complex-type exchanges as biomarker of radiation quality in vivo after low-dose chronic exposure in mixed radiation fields is hampered by statistical uncertainties.

76 FR 57793 - Self-Regulatory Organizations; NYSE Amex LLC; Notice of Filing and Immediate Effectiveness of...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-16

...). The Exchange had been informed by several Order Flow Providers that the absence of marketing charges for Customer executions in the complex order book was hindering their ability to route complex order flow to the Exchange, particularly since competing exchanges do allow for the collection of marketing...

Eddy covariance measurement of the spatial heterogeneity of surface energy exchanges over Heron Reef, Great Barrier Reef, Australia

NASA Astrophysics Data System (ADS)

MacKellar, M.; McGowan, H. A.; Phinn, S. R.

2011-12-01

Coral reefs cover 2.8 to 6.0 x 105 km2 of the Earth's surface and are warm, shallow regions that are believed to contribute enhanced sensible and latent heat to the atmosphere, relative to the surrounding ocean. To predict the impact of climate variability on coral reefs and their weather and climate including cloud, winds, rainfall patterns and cyclone genesis, accurate parameterisation of air-sea energy exchanges over coral reefs is essential. This is also important for the parameterisation and validation of regional to global scale forecast models to improve prediction of tropical and sub-tropical marine and coastal weather. Eddy covariance measurements of air-sea fluxes over coral reefs are rare due to the complexities of installing instrumentation over shallow, tidal water. Consequently, measurements of radiation and turbulent flux data for coral reefs have been captured remotely (satellite data) or via single measurement sites downwind of coral reefs (e.g. terrestrial or shipboard instrumentation). The resolution of such measurements and those that have been made at single locations on reefs may not capture the spatial heterogeneity of surface-atmosphere energy exchanges due to the different geomorphic and biological zones on coral reefs. Accordingly, the heterogeneity of coral reefs with regard to substrate, benthic communities and hydrodynamic processes are not considered in the characterization of the surface radiation energy flux transfers across the water-atmosphere interface. In this paper we present a unique dataset of concurrent in situ eddy covariance measurements made on instrumented pontoons of the surface energy balance over different geomorphic zones of a coral reef (shallow reef flat, shallow and deep lagoons). Significant differences in radiation transfers and air-sea turbulent flux exchanges over the reef were highlighted, with higher Bowen ratios over the shallow reef flat. Increasing wind speed was shown to increase flux divergence between sites to the extent that under unstable, south-easterly Trade Winds the net flux of heat was positive and negative over different geomorphic zones. The surface drag coefficient ranged from 1 to 2.5 x 10-3, with no significant difference between sites. Results highlight the spatial variation of air-sea energetics across a lagoonal platform reef in response to local meteorology, hydrodynamics and benthic/substrate cover.

Growth of carbon structured over Pd, Pt and Ni: A comparative DFT study

NASA Astrophysics Data System (ADS)

Quiroga, Matías Abel

2013-03-01

To elucidate the graphene-like structures mechanisms growth over the M(1 1 1) surface (M = Pd, Pt and Ni) we performed ab initio calculus in the frame of density functional theory with the exchange-correlation functional treated according to the Generalized Gradient Approximation (GGA). In order to avoid the problem that represent the complex interaction between the well formed graphene layer and the metallic surface, we recreate the carbon rings formation initial steps, by adding one by one carbon atoms over M(1 1 1) surface. With this strategy, the chemical bonding is always present until the graphene layer is well formed, in which case the GGA neglects van der Waals dispersive forces. We investigate the electronic properties by studying the band structure and the density of states.

78 FR 37870 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-06-24

... Market Maker Risk Parameters and Complex Orders June 18, 2013. Pursuant to Section 19(b)(1) of the... makers to enter values in the Exchange-provided risk parameters and by limiting the types of complex... complex instruments on the complex order book. Market makers establish a time frame during which the...

78 FR 22926 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing of...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-04-17

... System (a) Definition: No change. (b) Types of Complex Orders: No change. (c) Complex Order Book (i)-(iii..., the System will evaluate the COB when a complex order enters the COB, when the Exchange BBO changes... System may generate leg orders for the remaining size of the complex order in accordance with...

Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange : an RPSCB Peer Exchange

DOT National Transportation Integrated Search

2014-08-01

This report summarizes the Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange, held in Birmingham, Alabama, sponsored by the Federal Highway Administration (FHWA) Office of Safetys Roadway Safety Professi...

Impact of soil properties on selected pharmaceuticals adsorption in soils

NASA Astrophysics Data System (ADS)

Kodesova, Radka; Kocarek, Martin; Klement, Ales; Fer, Miroslav; Golovko, Oksana; Grabic, Roman; Jaksik, Ondrej

2014-05-01

The presence of human and veterinary pharmaceuticals in the environment has been recognized as a potential threat. Pharmaceuticals may contaminate soils and consequently surface and groundwater. Study was therefore focused on the evaluation of selected pharmaceuticals adsorption in soils, as one of the parameters, which are necessary to know when assessing contaminant transport in soils. The goals of this study were: (1) to select representative soils of the Czech Republic and to measure soil physical and chemical properties; (2) to measure adsorption isotherms of selected pharmaceuticals; (3) to evaluate impact of soil properties on pharmaceutical adsorptions and to propose pedotransfer rules for estimating adsorption coefficients from the measured soil properties. Batch sorption tests were performed for 6 selected pharmaceuticals (beta blockers Atenolol and Metoprolol, anticonvulsant Carbamazepin, and antibiotics Clarithromycin, Trimetoprim and Sulfamethoxazol) and 13 representative soils (soil samples from surface horizons of 11 different soil types and 2 substrates). The Freundlich equations were used to describe adsorption isotherms. The simple correlations between measured physical and chemical soil properties (soil particle density, soil texture, oxidable organic carbon content, CaCO3 content, pH_H2O, pH_KCl, exchangeable acidity, cation exchange capacity, hydrolytic acidity, basic cation saturation, sorption complex saturation, salinity), and the Freundlich adsorption coefficients were assessed using Pearson correlation coefficient. Then multiple-linear regressions were applied to predict the Freundlich adsorption coefficients from measured soil properties. The largest adsorption was measured for Clarithromycin (average value of 227.1) and decreased as follows: Trimetoprim (22.5), Metoprolol (9.0), Atenolol (6.6), Carbamazepin (2.7), Sulfamethoxazol (1.9). Absorption coefficients for Atenolol and Metoprolol closely correlated (R=0.85), and both were also related to absorption coefficients of Carbamazepin (R=0.67 and 0.68). Positive correlation was found between Trimetoprim absorption coefficients and Atenolol, Metoprolol or Carbamazepin absorption coefficients. The negative relationship was found between absorption coefficients of Sulfomethoxazol and Clarithromycin (R=-0.80). Sulfamethoxazol absorption coefficient was negatively related to pH_H2O, pH_KCL or sorption complex saturation and positively to the hydrolytic acidity or exchangeable acidity. Trimetoprim absorption coefficient was positively related to the oxidable organic carbon content, cation exchange capacity, basic cation saturation or silt content and negatively to particle density or sand content. Clarithromycin absorption coefficient was positively related to pH_H2O, pH_KCL, CaCO3 content, basic cation saturation or sorption complex saturation and negatively to hydrolytic acidity or exchangeable acidity. Atenolol and Metoprolol absorption coefficients were positively related to the oxidable organic carbon content, cation exchange capacity, basic cation saturation, salinity, clay content or silt content, and negatively to the particle density or sand content. Finally Carbamazepin absorption coefficient was positively related to the oxidable organic carbon content, cation exchange capacity or basic cation saturation, and negatively to the particle density or sand content. Evaluated pedotransfer rules for different pharmaceuticals included different sets of soil properties. Absorption coefficients could be predicted from: the hydrolytic acidity (Sulfamethoxazol), the oxidable organic carbon content (Trimetoprim and Carbamazepin), the oxidable organic carbon content, hydrolytic acidity and cation exchange capacity (Clarithromycin), the basic cation saturation (Atenolol and Metoprolol). Acknowledgement: Authors acknowledge the financial support of the Czech Science Foundation (Project No. 13-12477S).

The long-term carbon cycle, fossil fuels and atmospheric composition.

PubMed

Berner, Robert A

2003-11-20

The long-term carbon cycle operates over millions of years and involves the exchange of carbon between rocks and the Earth's surface. There are many complex feedback pathways between carbon burial, nutrient cycling, atmospheric carbon dioxide and oxygen, and climate. New calculations of carbon fluxes during the Phanerozoic eon (the past 550 million years) illustrate how the long-term carbon cycle has affected the burial of organic matter and fossil-fuel formation, as well as the evolution of atmospheric composition.

pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

PubMed

Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

2008-09-21

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

Mapping the contact surfaces in the Lamin A:AIMP3 complex by hydrogen/deuterium exchange FT-ICR mass spectrometry.

PubMed

Tao, Yeqing; Fang, Pengfei; Kim, Sunghoon; Guo, Min; Young, Nicolas L; Marshall, Alan G

2017-01-01

Aminoacyl-tRNA synthetases-interacting multifunctional protein3 (AIMP3/p18) is involved in the macromolecular tRNA synthetase complex via its interaction with several aminoacyl-tRNA synthetases. Recent reports reveal a novel function of AIMP3 as a tumor suppressor by accelerating cellular senescence and causing defects in nuclear morphology. AIMP3 specifically mediates degradation of mature Lamin A (LmnA), a major component of the nuclear envelope matrix; however, the mechanism of how AIMP3 interacts with LmnA is unclear. Here we report solution-phase hydrogen/deuterium exchange (HDX) for AIMP3, LmnA, and AIMP3 in association with the LmnA C-terminus. Reversed-phase LC coupled with LTQ 14.5 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results in high mass accuracy and resolving power for comparing the D-uptake profiles for AIMP3, LmnA, and their complex. The results show that the AIMP3-LmnA interaction involves one of the two putative binding sites and an adjacent novel interface on AIMP3. LmnA binds AIMP3 via its extreme C-terminus. Together these findings provide a structural insight for understanding the interaction between AIMP3 and LmnA in AIMP3 degradation.

SERENA: A suite of four instruments (ELENA, STROFIO, PICAM and MIPA) on board BepiColombo-MPO for particle detection in the Hermean environment

NASA Astrophysics Data System (ADS)

Orsini, S.; Livi, S.; Torkar, K.; Barabash, S.; Milillo, A.; Wurz, P.; di Lellis, A. M.; Kallio, E.; The Serena Team

2010-01-01

'Search for Exospheric Refilling and Emitted Natural Abundances' (SERENA) is an instrument package that will fly on board the BepiColombo/Mercury Planetary Orbiter (MPO). It will investigate Mercury's complex particle environment that is composed of thermal and directional neutral atoms (exosphere) caused by surface release and charge-exchange processes, and of ionized particles caused by photo-ionization of neutrals as well by charge exchange and surface release processes. In order to investigate the structure and dynamics of the environment, an in-situ analysis of the key neutral and charged components is necessary, and for this purpose the SERENA instrument shall include four units: two neutral particle analyzers (Emitted Low Energy Neutral Atoms (ELENA) sensor and Start from a Rotating FIeld mass spectrometer (STROFIO)) and two ion spectrometers (Miniature Ion Precipitation Analyzer (MIPA) and Planetary Ion Camera (PICAM)). The scientific merits of SERENA are presented, and the basic characteristics of the four units are described, with a focus on novel technological aspects.

High-Efficiency Photovoltaic Devices using Trap-Controlled Quantum-Dot Ink prepared via Phase-Transfer Exchange.

PubMed

Aqoma, Havid; Al Mubarok, Muhibullah; Hadmojo, Wisnu Tantyo; Lee, Eun-Hye; Kim, Tae-Wook; Ahn, Tae Kyu; Oh, Seung-Hwan; Jang, Sung-Yeon

2017-05-01

Colloidal-quantum-dot (CQD) photovoltaic devices are promising candidates for low-cost power sources owing to their low-temperature solution processability and bandgap tunability. A power conversion efficiency (PCE) of >10% is achieved for these devices; however, there are several remaining obstacles to their commercialization, including their high energy loss due to surface trap states and the complexity of the multiple-step CQD-layer-deposition process. Herein, high-efficiency photovoltaic devices prepared with CQD-ink using a phase-transfer-exchange (PTE) method are reported. Using CQD-ink, the fabrication of active layers by single-step coating and the suppression of surface trap states are achieved simultaneously. The CQD-ink photovoltaic devices achieve much higher PCEs (10.15% with a certified PCE of 9.61%) than the control devices (7.85%) owing to improved charge drift and diffusion. Notably, the CQD-ink devices show much lower energy loss than other reported high-efficiency CQD devices. This result reveals that the PTE method is an effective strategy for controlling trap states in CQDs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface nanobubble nucleation dynamics during water-ethanol exchange

NASA Astrophysics Data System (ADS)

Chan, Chon U.; Ohl, Claus-Dieter

2015-11-01

Water-ethanol exchange has been a promising nucleation method for surface attached nanobubbles since their discovery. In this process, water and ethanol displace each other sequentially on a substrate. As the gas solubility is 36 times higher in ethanol than water, it was suggested that the exchange process leads to transient supersaturation and is responsible for the nanobubble nucleation. In this work, we visualize the nucleation dynamics by controllably mixing water and ethanol. It depicts the temporal evolution of the conventional exchange in a single field of view, detailing the conditions for surface nanobubble nucleation and the flow field that influences their spatial organization. This technique can also pattern surface nanobubbles with variable size distribution.

Investigation of protein selectivity in multimodal chromatography using in silico designed Fab fragment variants.

PubMed

Karkov, Hanne Sophie; Krogh, Berit Olsen; Woo, James; Parimal, Siddharth; Ahmadian, Haleh; Cramer, Steven M

2015-11-01

In this study, a unique set of antibody Fab fragments was designed in silico and produced to examine the relationship between protein surface properties and selectivity in multimodal chromatographic systems. We hypothesized that multimodal ligands containing both hydrophobic and charged moieties would interact strongly with protein surface regions where charged groups and hydrophobic patches were in close spatial proximity. Protein surface property characterization tools were employed to identify the potential multimodal ligand binding regions on the Fab fragment of a humanized antibody and to evaluate the impact of mutations on surface charge and hydrophobicity. Twenty Fab variants were generated by site-directed mutagenesis, recombinant expression, and affinity purification. Column gradient experiments were carried out with the Fab variants in multimodal, cation-exchange, and hydrophobic interaction chromatographic systems. The results clearly indicated that selectivity in the multimodal system was different from the other chromatographic modes examined. Column retention data for the reduced charge Fab variants identified a binding site comprising light chain CDR1 as the main electrostatic interaction site for the multimodal and cation-exchange ligands. Furthermore, the multimodal ligand binding was enhanced by additional hydrophobic contributions as evident from the results obtained with hydrophobic Fab variants. The use of in silico protein surface property analyses combined with molecular biology techniques, protein expression, and chromatographic evaluations represents a previously undescribed and powerful approach for investigating multimodal selectivity with complex biomolecules. © 2015 Wiley Periodicals, Inc.

Quantizing the electromagnetic field near two-sided semitransparent mirrors

NASA Astrophysics Data System (ADS)

Furtak-Wells, Nicholas; Clark, Lewis A.; Purdy, Robert; Beige, Almut

2018-04-01

This paper models light scattering through flat surfaces with finite transmission, reflection, and absorption rates, with wave packets approaching the mirror from both sides. While using the same notion of photons as in free space, our model also accounts for the presence of mirror images and the possible exchange of energy between the electromagnetic field and the mirror surface. To test our model, we derive the spontaneous decay rate and the level shift of an atom in front of a semitransparent mirror as a function of its transmission and reflection rates. When considering limiting cases and using standard approximations, our approach reproduces well-known results but it also paves the way for the modeling of more complex scenarios.

Characterization of Colloidal Quantum Dot Ligand Exchange by X-ray Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Atewologun, Ayomide; Ge, Wangyao; Stiff-Roberts, Adrienne D.

2013-05-01

Colloidal quantum dots (CQDs) are chemically synthesized semiconductor nanoparticles with size-dependent wavelength tunability. Chemical synthesis of CQDs involves the attachment of long organic surface ligands to prevent aggregation; however, these ligands also impede charge transport. Therefore, it is beneficial to exchange longer surface ligands for shorter ones for optoelectronic devices. Typical characterization techniques used to analyze surface ligand exchange include Fourier-transform infrared spectroscopy, x-ray diffraction, transmission electron microscopy, and nuclear magnetic resonance spectroscopy, yet these techniques do not provide a simultaneously direct, quantitative, and sensitive method for evaluating surface ligands on CQDs. In contrast, x-ray photoelectron spectroscopy (XPS) can provide nanoscale sensitivity for quantitative analysis of CQD surface ligand exchange. A unique aspect of this work is that a fingerprint is identified for shorter surface ligands by resolving the regional XPS spectrum corresponding to different types of carbon bonds. In addition, a deposition technique known as resonant infrared matrix-assisted pulsed laser evaporation is used to improve the CQD film uniformity such that stronger XPS signals are obtained, enabling more accurate analysis of the ligand exchange process.

Nanosilver particle formation on a high surface area titanate.

PubMed

Shi, Meng; Lin, Christopher C H; Wu, Lan; Holt, Christopher M B; Mitlin, David; Kuznicki, Steven M

2010-12-01

Titanium based molecular sieves, such as ETS-10, have the ability to exchange silver ions and subsequently support self assembly of stable silver nanoparticles when heated. We report that a high surface area sodium titanate (resembling ETS-2) displays a similar ability to self template silver nanoparticles on its surface. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show high concentrations of silver nanoparticles on the surface of this sodium titanate, formed by thermal reduction of exchanged silver cations. The nanoparticles range in size from 4 to 12 nm, centered at around 6 nm. In addition to SEM and TEM, XRD and surface area analysis were used to characterize the material. The results indicate that this sodium titanate has a high surface area (>263 m2/g), and high ion exchange capacity for silver (30+ wt%) making it an excellent substrate for the exchange and generation of uniform, high-density silver nanoparticles.

78 FR 9959 - Self-Regulatory Organizations; C2 Options Exchange, Incorporated; Notice of Filing and Immediate...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-12

... Change Related to the Opening of the Complex Order Book February 6, 2013. Pursuant to Section 19(b)(1) of... complex orders are currently processed through the Exchange's complex order book (``COB'') when the COB... individual orders and quotes in the electronic book or other complex orders in the COB, execute or cancel if...

Integrated Heat Exchange For Recuperation In Gas Turbine Engines

DTIC Science & Technology

2016-12-01

exchange system within the engine using existing blade surfaces to extract and insert heat. Due to the highly turbulent and transient flow, heat...transfer coefficients in turbomachinery are extremely high, making this possible. Heat transfer between the turbine and compressor blade surfaces could be...exchange system within the engine using existing blade surfaces to extract and insert heat. Due to the highly turbulent and transient flow, heat transfer

The energy balance of an urban area: Examining temporal and spatial variability through measurements, remote sensing and modeling

NASA Astrophysics Data System (ADS)

Offerle, Brian

Urban environmental problems related to air quality, thermal stress, issues of water demand and quality, all of which are linked directly or indirectly to urban climate, are emerging as major environmental concerns at the start of the 21st century. Thus there are compelling social, political and economic, and scientific reasons that make the study and understanding of the fundamental causes of urban climates critically important. This research addresses these topics through an intensive study of the surface energy balance of Lodz, Poland. The research examines the temporal variability in long-term measurements of urban surface-atmosphere exchange at a downtown location and the spatial variability of this exchange over distinctly different neighborhoods using shorter-term observations. These observations provide the basis for an evaluation of surface energy balance models. Monthly patterns in energy exchange are consistent from year-to-year with variability determined by net radiation and the timing and amount of precipitation. Spatial variability can be determined from plan area fractions of vegetation and impervious surface, though heat storage exerts a strong control on shorter term variability of energy exchange, within and between locations in an urban area. Anthropogenic heat fluxes provide most of the energy driving surface-atmosphere exchange in winter, From a modeling perspective, sensible heat fluxes can be reliably determined from radiometrically sensed surface temperatures and spatially representative surface-atmosphere exchange in an urban area can be determined from satellite remote sensing products. Models of the urban surface energy balance showed good agreement with mean values of energy exchange and under most conditions represented the temporal variability due to synoptic and shorter time scale forcing well.

Quantum impurity models for magnetic adsorbates on superconductor surfaces

NASA Astrophysics Data System (ADS)

Žitko, Rok

2018-05-01

Magnetic atoms adsorbed on surfaces have a quenched orbital moment while their ground-state spin multiplet is partially split as a consequence of the spin-orbit coupling which, even if intrinsically weak, has a large effect due to the abrupt change of the potential at the surface. Such metal adsorbates should be modelled using quantum impurity models that include the relevant internal degrees of freedom and the interaction terms, in particular the magnetic anisotropy and the Kondo exchange coupling. When adsorbed on superconducting surfaces, these impurities have complex spectra of sub-gap excitations due to magnetic anisotropy splitting and Kondo screening. Both anisotropy splitting and Zeeman splitting due to the external magnetic field are significantly renormalized by the coupling to the substrate electrons. In this work I discuss the quantum-to-classical crossover and the applicability of classical static-local-spin picture for discussing magnetic nanostructures on superconductors.

Effect of grinding and fluoride-gel exposure on strength of ion-exchanged porcelain.

PubMed

Anusavice, K J; Hojjatie, B; Chang, T C

1994-08-01

Strengthening of dental porcelain through a diffusion heat treatment at 450 degrees C of a potassium-enriched, ion-exchange surface coating has been demonstrated in several recent studies. However, little attention has been focused on the potential strength reduction of these materials when the treated surfaces are ground or etched under clinically simulated conditions. The objective of this study was to test the hypothesis that partial removal of the surface layers of ion-exchanged porcelains by grinding or exposure to acidulated fluoride gel will significantly reduce their flexure strength. Nine groups of body porcelain disks were ion-exchanged at 450 degrees C for 30 min. One of these groups was subjected to ion exchange and no further surface treatment. Eight specimen groups were subjected to the following procedures after ion exchange: grinding to depths of 50 microns, 100 microns, 150 microns, 200 microns, and 250 microns, and exposure to acidulated fluoride for 30 min, 60 min, and 300 min. A tenth group (FC) was fired at 960 degrees C and fast-cooled in air, but the disks were not subjected to the ion-exchange treatment. Surface stress was calculated from measured values of cracks induced in the treated surfaces. Fluoride exposure for up to 60 min resulted in a significant decrease in surface compression (P < or = 0.05), although this treatment had no effect on strength. Grinding to a depth of from 100 microns to 250 microns caused a significant decrease in strength, while removal of a 50-microns layer caused no significant change (P > 0.05).

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Influence of pH, layer charge location and crystal thickness distribution on U(VI) sorption onto heterogeneous dioctahedral smectite.

PubMed

Guimarães, Vanessa; Rodríguez-Castellón, Enrique; Algarra, Manuel; Rocha, Fernando; Bobos, Iuliu

2016-11-05

The UO2(2+) adsorption on smectite (samples BA1, PS2 and PS3) with a heterogeneous structure was investigated at pH 4 (I=0.02M) and pH 6 (I=0.2M) in batch experiments, with the aim to evaluate the influence of pH, layer charge location and crystal thickness distribution. Mean crystal thickness distribution of smectite crystallite used in sorption experiments range from 4.8nm (sample PS2), to 5.1nm (sample PS3) and, to 7.4nm (sample BA1). Smaller crystallites have higher total surface area and sorption capacity. Octahedral charge location favor higher sorption capacity. The sorption isotherms of Freundlich, Langmuir and SIPS were used to model the sorption experiments. The surface complexation and cation exchange reactions were modeled using PHREEQC-code to describe the UO2(2+) sorption on smectite. The amount of UO2(2+) adsorbed on smectite samples decreased significantly at pH 6 and higher ionic strength, where the sorption mechanism was restricted to the edge sites of smectite. Two binding energy components at 380.8±0.3 and 382.2±0.3eV, assigned to hydrated UO2(2+) adsorbed by cation exchange and by inner-sphere complexation on the external sites at pH 4, were identified after the U4f7/2 peak deconvolution by X-photoelectron spectroscopy. Also, two new binding energy components at 380.3±0.3 and 381.8±0.3eV assigned to AlOUO2(+) and SiOUO2(+) surface species were observed at pH 6. Copyright © 2016 Elsevier B.V. All rights reserved.

Preparation of hydrophilic interaction/ion-exchange mixed-mode chromatographic stationary phase with adjustable selectivity by controlling different ratios of the co-monomers.

PubMed

Bo, Chunmiao; Wang, Xiaomeng; Wang, Chaozhan; Wei, Yinmao

2017-03-03

Development of mixed-mode chromatography (MMC) stationary phase with adjustable selectivity is beneficial to meet the needs of complex samples. In this work, surface-initiated atom transfer radical polymerization (SI-ATRP) using the mixture of two functional monomers was proposed as a new preparation strategy for MMC stationary phase with adjustable selectivity. The mixture of sodium 4-styrenesulfonate (NASS) and dimethylaminoethyl methacrylate (DMAEMA) underwent SI-ATRP to bond poly(NASS-co-DMAEMA) on the surface of silica to prepare hydrophilic interaction/ion-exchange mixed-mode stationary phase. Various analytes (neutral, acidic, basic analytes and strong polar nucleosides) were employed to investigate the retention behaviors. The influences of water content and pH of the mobile phase on the retention validated the mixed-mode retention mechanisms of HILIC and ion-exchange. The charge and polarity of stationary phase as well as the separation selectivity were conveniently manipulated by the ratio of NASS to DMAEMA monomer, and the use of DMAEMA in the mixture additionally endowed the column with the temperature-responsive characteristics. Moreover, the application of the developed column was demonstrated by the successful separation of nucleosides, β-agonists and safflower injection. In a word, the proposed strategy can be potentially applied in the controllable preparation of MMC stationary phase with adjustable selectivity. Copyright © 2017 Elsevier B.V. All rights reserved.

Fluctuation Dynamics of Exchange Rates on Indian Financial Market

NASA Astrophysics Data System (ADS)

Sarkar, A.; Barat, P.

Here we investigate the scaling behavior and the complexity of the average daily exchange rate returns of the Indian Rupee against four foreign currencies namely US Dollar, Euro, Great Britain Pound and Japanese Yen. Our analysis revealed that the average daily exchange rate return of the Indian Rupee against the US Dollar exhibits a persistent scaling behavior and follow Levy stable distribution. On the contrary the average daily exchange rate returns of the other three foreign currencies show randomness and follow Gaussian distribution. Moreover, it is seen that the complexity of the average daily exchange rate return of the Indian Rupee against US Dollar is less than the other three exchange rate returns.

Making Mn substitutional impurities in InAs using a scanning tunneling microscope.

PubMed

Song, Young Jae; Erwin, Steven C; Rutter, Gregory M; First, Phillip N; Zhitenev, Nikolai B; Stroscio, Joseph A

2009-12-01

We describe in detail an atom-by-atom exchange manipulation technique using a scanning tunneling microscope probe. As-deposited Mn adatoms (Mn(ad)) are exchanged one-by-one with surface In atoms (In(su)) to create a Mn surface-substitutional (Mn(In)) and an exchanged In adatom (In(ad)) by an electron tunneling induced reaction Mn(ad) + In(su) --> Mn(In) + In(ad) on the InAs(110) surface. In combination with density-functional theory and high resolution scanning tunneling microscopy imaging, we have identified the reaction pathway for the Mn and In atom exchange.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy.

PubMed

Niu, Shuqiang; Huang, Dao-Ling; Dau, Phuong D; Liu, Hong-Tao; Wang, Lai-Sheng; Ichiye, Toshiko

2014-03-11

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH 3 ) 2 ] 1-/0 , [Cu(NCS) 2 ] 1-/0 , [FeCl 4 ] 1-/0 , and [Fe(SCH 3 ) 4 ] 1-/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree-Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC- ω PBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy

PubMed Central

2015-01-01

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH3)2]1–/0, [Cu(NCS)2]1–/0, [FeCl4]1–/0, and [Fe(SCH3)4]1–/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree–Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC-ωPBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes. PMID:24803858

Ion-exchange sorption of silver(I) chloride complexes from aqueous HCl solutions

NASA Astrophysics Data System (ADS)

Kononova, O. N.; Duba, E. V.; Medovikov, D. V.; Efimova, A. S.; Ivanov, A. I.; Krylov, A. S.

2017-12-01

The ion-exchange sorption of silver(I) chloride complexes from 1-4 M aqueous solutions of HCl on a series of Purolite anionites with various functional groups was studied. The ion-exchange equilibria in the systems were found to be anomalous according to Raman spectroscopy, which does not significantly affect the sorption properties of the ionites.

Dynamic NMR of Intramolecular Exchange Processes in EDTA Complexes of Sc[superscript 3+], Y[superscript 3+], and La[superscript 3+

ERIC Educational Resources Information Center

Ba, Yong; Han, Steven; Ni, Lily; Su, Tony; Garcia, Andres

2006-01-01

Dynamic NMR makes use of the effect of chemical exchanges on NMR spectra to study kinetics and thermodynamics. An advanced physical chemistry lab experiment was developed to study the intramolecular exchange processes of EDTA (the disodium salt of ethylenediaminetetraacetic acid) metal complexes. EDTA is an important chelating agent, used in…

Determination of association constants at moderately fast chemical exchange: complexation of camphor enantiomers by alpha-cyclodextrin.

PubMed

Bernatowicz, Piotr; Nowakowski, Michał; Dodziuk, Helena; Ejchart, Andrzej

2006-08-01

Association constants in weak molecular complexes can be determined by analysis of chemical shifts variations resulting from changes of guest to host concentration ratio. In the regime of very fast exchange, i.e., when exchange rate is several orders of magnitude larger than the Larmor angular frequency difference of the observed resonance in free and complexed molecule, the apparent position of averaged resonance is a population-weighted mean of resonances of particular forms involved in the equilibrium. The assumption of very fast exchange is often, however, tacitly admitted in literature even in cases where the process of interest is much slower than required. We show that such an unjustified simplification may, under certain circumstances, lead to significant underestimation of association constant and, in consequence, to non-negligible errors in Gibbs free energy under determination. We present a general method, based on iterative numerical NMR line shape analysis, which allows one for the compensation of chemical exchange effects, and delivers both the correct association constants and the exchange rates. The latter are not delivered by the other mentioned method. Practical application of our algorithm is illustrated by the case of camphor-alpha-cyclodextrin complexes.

Ion Exchange Formation via Sulfonated Bicomponent Nonwovens

NASA Astrophysics Data System (ADS)

Stoughton, Hannah L.

For many years ion exchange resins were used to: remove heavy metals from water, recover materials from wastewater, and eliminate harmful gases from the air. While use of these resin beads dominates the ion exchange industry, the beads have limitations that should be considered when decisions are made to employ them. For instance, officials must balance the inherent zero sum surface area and porosity of the materials. This series of studies investigates the use of bicomponent nonwovens as a base substrate for producing high surface area ion exchange materials for the removal of heavy metal ions. Functionalized materials were produced in a two-step process: (1) PET/PE spunbond bicomponent fibers were fractured completely, producing the high surface area nonwoven to be used as the base ion exchange material, and (2) the conditions for functionalizing the PET fibers of the nonwoven webs were investigated where an epoxy containing monomer was grafted to the surface followed by sulfonation of the monomer. The functionalization reactions of the PET fibers were monitored based on: weight gain, FTIR, TOF-SIMS, and SEM. Ion exchange properties were evaluated using titration and copper ion removal capacity from test solutions. The relationship between web structure and removal efficiency of the metal ions was defined through a comparison of the bicomponent and homocomponent nonwovens for copper ion removal efficiency. The investigation revealed that utilizing the high surface area, fractured bicomponent nonwoven ion exchange materials with capacities comparable to commercially available ion exchange resins could be produced.

Minimum wear tube support hole design

DOEpatents

Glatthorn, Raymond H.

1986-01-01

A minimum-wear through-bore (16) is defined within a heat exchanger tube support plate (14) so as to have an hourglass configuration as determined by means of a constant radiused surface curvature (18) as defined by means of an external radius (R3), wherein the surface (18) extends between the upper surface (20) and lower surface (22) of the tube support plate (14). When a heat exchange tube (12) is disposed within the tube support plate (14) so as to pass through the through-bore (16), the heat exchange tube (12) is always in contact with a smoothly curved or radiused portion of the through-bore surface (16) whereby unacceptably excessive wear upon the heat exchange tube (12), as normally developed by means of sharp edges, lands, ridges, or the like conventionally part of the tube support plates, is eliminated or substantially reduced.

Unifying Exchange Sensitivity in Transition-Metal Spin-State Ordering and Catalysis through Bond Valence Metrics.

PubMed

Gani, Terry Z H; Kulik, Heather J

2017-11-14

Accurate predictions of spin-state ordering, reaction energetics, and barrier heights are critical for the computational discovery of open-shell transition-metal (TM) catalysts. Semilocal approximations in density functional theory, such as the generalized gradient approximation (GGA), suffer from delocalization error that causes them to overstabilize strongly bonded states. Descriptions of energetics and bonding are often improved by introducing a fraction of exact exchange (e.g., erroneous low-spin GGA ground states are instead correctly predicted as high-spin with a hybrid functional). The degree of spin-splitting sensitivity to exchange can be understood based on the chemical composition of the complex, but the effect of exchange on reaction energetics within a single spin state is less well-established. Across a number of model iron complexes, we observe strong exchange sensitivities of reaction barriers and energies that are of the same magnitude as those for spin splitting energies. We rationalize trends in both reaction and spin energetics by introducing a measure of delocalization, the bond valence of the metal-ligand bonds in each complex. The bond valence thus represents a simple-to-compute property that unifies understanding of exchange sensitivity for catalytic properties and spin-state ordering in TM complexes. Close agreement of the resulting per-metal-organic-bond sensitivity estimates, together with failure of alternative descriptors demonstrates the utility of the bond valence as a robust descriptor of how differences in metal-ligand delocalization produce differing relative energetics with exchange tuning. Our unified description explains the overall effect of exact exchange tuning on the paradigmatic two-state FeO + /CH 4 reaction that combines challenges of spin-state and reactivity predictions. This new descriptor-sensitivity relationship provides a path to quantifying how predictions in transition-metal complex screening are sensitive to the method used.

Evaluation of direct-exchange areas for a cylindrical enclosure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sika, J.

1991-11-01

This paper reports on a method for calculating the radiative heat transfer direct-exchange areas for surface-to-surface, volume-to-surface, and volume-to-volume pairs of zones in axisymmetric cylindrical geometries. With this method the calculation of the direct-exchange areas can be transformed from the original four-, five-, and sixfold integrals in the defining relations to just single and/or double integrals. Gray gas with absorption coefficient K is assumed.

Energy exchanges in a Central Business District - Interpretation of Eddy Covariance and radiation flux measurements (London UK)

NASA Astrophysics Data System (ADS)

Kotthaus, S.; Grimmond, S.

2013-12-01

Global urbanisation brings increasingly dense and complex urban structures. To manage cities sustainably and smartly, currently and into the future under changing climates, urban climate research needs to advance in areas such as Central Business Districts (CBD) where human interactions with the environment are particularly concentrated. Measurement and modelling approaches may be pushed to their limits in dense urban settings, but if urban climate research is to contribute to the challenges of real cities those limits have to be addressed. The climate of cities is strongly governed by surface-atmosphere exchanges of energy, moisture and momentum. Observations of the relevant fluxes provide important information for improvement and evaluation of modelling approaches. Due to the CBD's heterogeneity, a very careful analysis of observations is required to understand the relevant processes. Current approaches used to interpret observations and set them in a wider context may need to be adapted for use in these more complex areas. Here, we present long-term observations of the radiation balance components and turbulent fluxes of latent heat, sensible heat and momentum in the city centre of London. This is one of the first measurement studies in a CBD covering multiple years with analysis at temporal scales from days to seasons. Data gathered at two sites in close vicinity, but with different measurement heights, are analysed to investigate the influence of source area characteristics on long-term radiation and turbulent fluxes. Challenges of source area modelling and the critical aspect of siting in such a complex environment are considered. Outgoing long- and short-wave radiation are impacted by the anisotropic nature of the urban surface and the high reflectance materials increasingly being used as building materials. Results highlight the need to consider the source area of radiometers in terms of diffuse and direct irradiance. Sensible heat fluxes (QH) are positive all year round, even at night. QH systematically exceeds input from net all-wave radiation (Q*), probably sustained by a both storage and anthropogenic heat fluxes (QF). Model estimates suggest QF can exceed the Q* nearly all year round. The positive QH inhibits stable conditions, but the stability classification is determined predominantly by the pattern of friction velocity over the rough urban surface. Turbulent latent heat flux variations are controlled (beyond the available energy) by rainfall due to the small vegetation cover. The Bowen ratio is mostly larger than one. Analysis of the eddy covariance footprint surface controls for the different land cover types by flow patterns for measurements at the two heights suggests the spatial variations of the sensible heat flux observed are partly related to changes in surface roughness, even at the local scale. Where the source areas are most homogeneous, flow conditions are vertically consistent - even if initial morphometric parameters suggested the measurements may be below the blending height. Turbulence statistics and momentum flux patterns prove useful for the interpretation of turbulent heat exchanges observed.

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How important is getting the land surface energy exchange correct in WRF for wind energy forecasting?

NASA Astrophysics Data System (ADS)

Wharton, S.; Simpson, M.; Osuna, J. L.; Newman, J. F.; Biraud, S.

2013-12-01

Wind power forecasting is plagued with difficulties in accurately predicting the occurrence and intensity of atmospheric conditions at the heights spanned by industrial-scale turbines (~ 40 to 200 m above ground level). Better simulation of the relevant physics would enable operational practices such as integration of large fractions of wind power into power grids, scheduling maintenance on wind energy facilities, and deciding design criteria based on complex loads for next-generation turbines and siting. Accurately simulating the surface energy processes in numerical models may be critically important for wind energy forecasting as energy exchange at the surface strongly drives atmospheric mixing (i.e., stability) in the lower layers of the planetary boundary layer (PBL), which in turn largely determines wind shear and turbulence at heights found in the turbine rotor-disk. We hypothesize that simulating accurate a surface-atmosphere energy coupling should lead to more accurate predictions of wind speed and turbulence at heights within the turbine rotor-disk. Here, we tested 10 different land surface model configurations in the Weather Research and Forecasting (WRF) model including Noah, Noah-MP, SSiB, Pleim-Xiu, RUC, and others to evaluate (1) the accuracy of simulated surface energy fluxes to flux tower measurements, (2) the accuracy of forecasted wind speeds to observations at rotor-disk heights, and (3) the sensitivity of forecasting hub-height rotor disk wind speed to the choice of land surface model. WRF was run for four, two-week periods covering both summer and winter periods over the Southern Great Plains ARM site in Oklahoma. Continuous measurements of surface energy fluxes and lidar-based wind speed, direction and turbulence were also available. The SGP ARM site provided an ideal location for this evaluation as it centrally located in the wind-rich Great Plains and multi-MW wind farms are rapidly expanding in the area. We found significant differences in simulated wind speeds at rotor-disk heights from WRF which indicated, in part, the sensitivity of lower PBL winds to surface energy exchange. We also found significant differences in energy partitioning between sensible heat and latent energy depending on choice of land surface model. Overall, the most consistent, accurate model results were produced using Noah-MP. Noah-MP was most accurate at simulating energy fluxes and wind shear. Hub-height wind speed, however, was predicted with most accuracy with Pleim-Xiu. This suggests that simulating wind shear in the surface layer is consistent with accurately simulating surface energy exchange while the exact magnitudes of wind speed may be more strongly influenced by the PBL dynamics. As the nation is working towards a 20% wind energy goal by 2030, increasing the accuracy of wind forecasting at rotor-disk heights becomes more important considering that utilities require wind farms to estimate their power generation 24 to 36 hours ahead and face penalties for inaccuracies in those forecasts.

The effects of tether placement on antibody stability on surfaces

NASA Astrophysics Data System (ADS)

Grawe, Rebecca W.; Knotts, Thomas A.

2017-06-01

Despite their potential benefits, antibody microarrays have fallen short of performing reliably and have not found widespread use outside of the research setting. Experimental techniques have been unable to determine what is occurring on the surface of an atomic level, so molecular simulation has emerged as the primary method of investigating protein/surface interactions. Simulations of small proteins have indicated that the stability of the protein is a function of the residue on the protein where a tether is placed. The purpose of this research is to see whether these findings also apply to antibodies, with their greater size and complexity. To determine this, 24 tethering locations were selected on the antibody Protein Data Bank (PDB) ID: 1IGT. Replica exchange simulations were run on two different surfaces, one hydrophobic and one hydrophilic, to determine the degree to which these tethering sites stabilize or destabilize the antibody. Results showed that antibodies tethered to hydrophobic surfaces were in general less stable than antibodies tethered to hydrophilic surfaces. Moreover, the stability of the antibody was a function of the tether location on hydrophobic surfaces but not hydrophilic surfaces.

Surface Modification and Surface - Subsurface Exchange Processes on Europa

NASA Astrophysics Data System (ADS)

Phillips, Cynthia B.; Molaro, Jamie; Hand, Kevin P.

2017-10-01

The surface of Jupiter’s moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa’s leading-trailing hemisphere brightness asymmetry.Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted “chaos-type” terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features.In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa’s surface area.Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age (~50myr) of Europa. Quantifying the timescale and volume of transported material will yield insight on whether such a process may provide fuel to sustain a biosphere in Europa’s subsurface ocean, which is relevant to searches for life by a future mission such as a potential Europa Lander.

Surface Modification and Surface - Subsurface Exchange Processes on Europa

NASA Astrophysics Data System (ADS)

Phillips, C. B.; Molaro, J.; Hand, K. P.

2017-12-01

The surface of Jupiter's moon Europa is modified by exogenic processes such as sputtering, gardening, radiolysis, sulfur ion implantation, and thermal processing, as well as endogenic processes including tidal shaking, mass wasting, and the effects of subsurface tectonic and perhaps cryovolcanic activity. New materials are created or deposited on the surface (radiolysis, micrometeorite impacts, sulfur ion implantation, cryovolcanic plume deposits), modified in place (thermal segregation, sintering), transported either vertically or horizontally (sputtering, gardening, mass wasting, tectonic and cryovolcanic activity), or lost from Europa completely (sputtering, plumes, larger impacts). Some of these processes vary spatially, as visible in Europa's leading-trailing hemisphere brightness asymmetry. Endogenic geologic processes also vary spatially, depending on terrain type. The surface can be classified into general landform categories that include tectonic features (ridges, bands, cracks); disrupted "chaos-type" terrain (chaos blocks, matrix, domes, pits, spots); and impact craters (simple, complex, multi-ring). The spatial distribution of these terrain types is relatively random, with some differences in apex-antiapex cratering rates and latitudinal variation in chaos vs. tectonic features. In this work, we extrapolate surface processes and rates from the top meter of the surface in conjunction with global estimates of transport and resurfacing rates. We combine near-surface modification with an estimate of surface-subsurface (and vice versa) transport rates for various geologic terrains based on an average of proposed formation mechanisms, and a spatial distribution of each landform type over Europa's surface area. Understanding the rates and mass balance for each of these processes, as well as their spatial and temporal variability, allows us to estimate surface - subsurface exchange rates over the average surface age ( 50myr) of Europa. Quantifying the timescale and volume of transported material will yield insight on whether such a process may provide fuel to sustain a biosphere in Europa's subsurface ocean, which is relevant to searches for life by a future mission such as a potential Europa Lander.

Behavioral Consequences of Embeddedness: Effects of the Underlying Forms of Exchange

ERIC Educational Resources Information Center

Molm, Linda D.; Melamed, David; Whitham, Monica M.

2013-01-01

Network structures have strong effects on the frequency and terms of negotiated exchanges, shaping who exchanges with whom and who fares better or worse. In this study we ask how exchange patterns of commitment and inequality are affected when negotiated exchanges are combined with reciprocal exchanges in more complex relationships of…

Impact of the surface roughness of AISI 316L stainless steel on biofilm adhesion in a seawater-cooled tubular heat exchanger-condenser.

PubMed

García, Sergio; Trueba, Alfredo; Vega, Luis M; Madariaga, Ernesto

2016-11-01

The present study evaluated biofilm growth in AISI 316L stainless steel tubes for seawater-cooled exchanger-condensers that had four different arithmetic mean surface roughness values ranging from 0.14 μm to 1.2 μm. The results of fluid frictional resistance and heat transfer resistance regarding biofilm formation in the roughest surface showed increases of 28.2% and 19.1% respectively, compared with the smoothest surface. The biofilm thickness taken at the end of the experiment showed variations of up to 74% between the smoothest and roughest surfaces. The thermal efficiency of the heat transfer process in the tube with the roughest surface was 17.4% greater than that in the tube with the smoothest surface. The results suggest that the finish of the inner surfaces of the tubes in heat exchanger-condensers is critical for improving energy efficiency and avoiding biofilm adhesion. This may be utilised to reduce biofilm adhesion and growth in the design of heat exchanger-condensers.

An electron transfer driven magnetic switch: ferromagnetic exchange and spin delocalization in iron verdazyl complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brook, David J. R.; Fleming, Connor; Chung, Dorothy

A single electron reduction of an iron bis(verdazyl) complex results in a large change in spin multiplicity resulting from a combination of spin crossover and exceptionally strong ferromagnetic exchange.

An electron transfer driven magnetic switch: ferromagnetic exchange and spin delocalization in iron verdazyl complexes

DOE PAGES

Brook, David J. R.; Fleming, Connor; Chung, Dorothy; ...

2018-01-01

A single electron reduction of an iron bis(verdazyl) complex results in a large change in spin multiplicity resulting from a combination of spin crossover and exceptionally strong ferromagnetic exchange.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

On the dynamics of water molecules at the protein solute interfaces.

PubMed

Bernini, A; Spiga, O; Ciutti, A; Chiellini, S; Menciassi, N; Venditti, V; Niccolai, N

2004-10-01

Proteins, with the large variety of chemical groups they present at their molecular surface, are a class of molecules which can be very informative on most of the possible solute-solvent interactions. Hen egg white lysozyme has been used as a probe to investigate the complex solvent dynamics occurring at the protein surface, by analysing the results obtained from Nuclear Magnetic Resonance, X-ray diffractometry and Molecular Dynamics simulations. A consistent overall picture for the dynamics of water molecules close to the protein is obtained, suggesting that a rapid exchange occurs, in a picosecond timescale, among all the possible hydration surface sites both in solution and the solid state, excluding the possibility that solvent molecules can form liquid-crystal-like supramolecular adducts, which have been proposed as a molecular basis of 'memory of water'.

Induced polarization of volcanic rocks - 1. Surface versus quadrature conductivity

NASA Astrophysics Data System (ADS)

Revil, A.; Le Breton, M.; Niu, Q.; Wallin, E.; Haskins, E.; Thomas, D. M.

2017-02-01

We performed complex conductivity measurements on 28 core samples from the hole drilled for the Humu'ula Groundwater Research Project (Hawai'i Island, HI, USA). The complex conductivity measurements were performed at 4 different pore water conductivities (0.07, 0.5, 1.0 or 2.0, and 10 S m-1 prepared with NaCl) over the frequency range 1 mHz to 45 kHz at 22 ± 1 °C. The in-phase conductivity data are plotted against the pore water conductivity to determine, sample by sample, the intrinsic formation factor and the surface conductivity. The intrinsic formation factor is related to porosity by Archie's law with an average value of the cementation exponent m of 2.45, indicating that only a small fraction of the connected pore space controls the transport properties. Both the surface and quadrature conductivities are found to be linearly related to the cation exchange capacity of the material, which was measured with the cobalt hexamine chloride method. Surface and quadrature conductivities are found to be proportional to each other like for sedimentary siliclastic rocks. A Stern layer polarization model is used to explain these experimental results. Despite the fact that the samples contain some magnetite (up to 5 per cent wt.), we were not able to identify the effect of this mineral on the complex conductivity spectra. These results are very encouraging in showing that galvanometric induced polarization measurements can be used in volcanic areas to separate the bulk from the surface conductivity and therefore to define some alteration attributes. Such a goal cannot be achieved with resistivity alone.

Asymptotic behavior of the Kohn-Sham exchange potential at a metal surface

NASA Astrophysics Data System (ADS)

Qian, Zhixin

2012-03-01

The asymptotic structure of the Kohn-Sham exchange potential vx(r) in the classically forbidden region of a metal surface is investigated, together with that of the Slater exchange potential VxS(r) and those of the approximate Krieger-Li-Iafrate VxKLI(r) and Harbola-Sahni Wx(r) exchange potentials. Particularly, the former is shown to have the form of vx(z→∞)=-αx/z with αx a constant dependent only of bulk electron density. The same result in previous work is thus confirmed; in the meanwhile, a controversy raised recently gets resolved. The structure of the exchange hole ρx(r,r') is examined, and the delocalization of it in the metal bulk when the electron is at large distance from the metal surface is demonstrated with analytical expressions. The asymptotic structures of vx(r), VxS(r), VxKLI(r), and Wx(r) at a slab metal surface are also investigated. Particularly, vx(z→∞)=-1/z in the slab case. The distinction, in this respect, between the semi-infinite and the slab metal surfaces is elucidated.

Kinetics of oxygen surface exchange on epitaxial Ruddlesden–Popper phases and correlations to first-principles descriptors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Yueh -Lin; Wang, Xiao Renshaw; Lee, Ho Nyung

2015-12-17

Through alignment of theoretical modeling with experimental measurements of oxygen surface-exchange kinetics on (001)-oriented La 2–xSr xMO 4+δ (M = Co, Ni, Cu) thin films, we demonstrate here the capability of the theoretical bulk O 2p-band centers to correlate with oxygen surface-exchange kinetics of the Ruddlesden–Popper oxide (RP 214) (001)-oriented thin films. In addition, we demonstrate that the bulk O 2p-band centers can also correlate with the experimental activation energies for bulk oxygen transport and oxygen surface exchange of both the RP 214 and the perovskite polycrystalline materials reported in the literature, indicating the effectiveness of the bulk O 2p-bandmore » centers in describing the associated energetics and kinetics. Here, we propose that the opposite slopes of the bulk O 2p-band center correlations between the RP 214 and the perovskite materials are due to the intrinsic mechanistic differences of their oxygen surface-exchange kinetics bulk anionic transport.« less

Tautomerism, acid-base equilibria, and H-bonding of the six histidines in subtilisin BPN′ by NMR

PubMed Central

Day, Regina M.; Thalhauser, Craig J.; Sudmeier, James L.; Vincent, Matthew P.; Torchilin, Ekaterina V.; Sanford, David G.; Bachovchin, Christopher W.; Bachovchin, William W.

2003-01-01

We have determined by 15N, 1H, and 13C NMR, the chemical behavior of the six histidines in subtilisin BPN′ and their PMSF and peptide boronic acid complexes in aqueous solution as a function of pH in the range of from 5 to 11, and have assigned every 15N, 1H, Cɛ1, and Cδ2 resonance of all His side chains in resting enzyme. Four of the six histidine residues (17, 39, 67, and 226) are neutrally charged and do not titrate. One histidine (238), located on the protein surface, titrates with pKa = 7.30 ± 0.03 at 25°C, having rapid proton exchange, but restricted mobility. The active site histidine (64) in mutant N155A titrates with a pKa value of 7.9 ± 0.3 and sluggish proton exchange behavior, as shown by two-site exchange computer lineshape simulation. His 64 in resting enzyme contains an extremely high Cɛ1-H proton chemical shift of 9.30 parts per million (ppm) owing to a conserved Cɛ1-H. . .O=C H-bond from the active site imidazole to a backbone carbonyl group, which is found in all known serine proteases representing all four superfamilies. Only His 226, and His 64 at high pH, exist as the rare Nδ1-H tautomer, exhibiting 13Cδ1 chemical shifts ~9 ppm higher than those for Nɛ2-H tautomers. His 64 in the PMSF complex, unlike that in the resting enzyme, is highly mobile in its low pH form, as shown by 15N-1H NOE effects, and titrates with rapid proton exchange kinetics linked to a pKa value of 7.47 ± 0.02. PMID:12649438

Structures and mechanisms in clay nanopore trapping of structurally-different fluoroquinolone antimicrobials.

PubMed

Okaikue-Woodi, Fanny E K; Kelch, Sabrina E; Schmidt, Michael P; Enid Martinez, Carmen; Youngman, Randall E; Aristilde, Ludmilla

2018-03-01

Smectite clay nanoparticles are implicated in the retention of antimicrobials within soils and sediments; these clays are also inspected as drug carriers in physiological systems. Cation exchange is considered the primary adsorption mechanism of antimicrobials within smectite nanopores. However, a dual role of acid-base chemistry and adsorptive structures is speculated by recent studies. Using the prototypical smectite clay montmorillonite, we employed a combination of X-ray diffraction (XRD), nuclear magnetic resonance, attenuated total reflectance-Fourier transform infrared spectroscopy, and molecular dynamics simulations to investigate the interlayer nanopore trapping of two structurally-different fluoroquinolone (FQ) antimicrobials with similar acid-base chemistry: ciprofloxacin (a first-generation FQ) and moxifloxacin (a third-generation FQ). Greater sorption at pH 5.0 than at pH 7.0 for both FQs was consistent with cation-exchange of positively-charged species. However, the clay exhibited a near twofold higher sorption capacity for moxifloxacin than for ciprofloxacin. This difference was shown by the XRD data to be accompanied by enhanced trapping of moxifloxacin within the clay interlayers. Using the XRD-determined nanopore sizes, we performed molecular dynamics simulations of thermodynamically-favorable model adsorbates, which revealed that ciprofloxacin was adsorbed parallel to the clay surface but moxifloxacin adopted a tilted conformation across the nanopore. These conformations resulted in more slowly-exchanged than quickly-exchanged Na complexes with ciprofloxacin compared with moxifloxacin. These different Na populations were also captured by 23 Na nuclear magnetic resonance. Furthermore, the simulated adsorbates uncovered different complexation interactions that were corroborated by infrared spectroscopy. Therefore, beyond acid-base chemistry, our findings imply that distinct adsorbate structures control antimicrobial trapping within clay nanopores, which can promote persistence in environmental matrices and stable delivery in biological systems. Copyright © 2017 Elsevier Inc. All rights reserved.

ION-EXCHANGE METHOD FOR SEPARATING RADIUM FROM RADIUM-BARIUM MIXTURES

DOEpatents

Fuentevilla, M.E.

1959-06-30

An improved process is presented for separating radium from an aqueous feed solution containing radium and barium values and a complexing agent for these metals. In this process a feed solutlon containing radium and barium ions and a complexing agent for said ions ls cycled through an exchange zone in resins. The radiumenriched resin is then stripped of radium values to form a regeneration liquid, a portion of which is collected as an enriched product, the remaining portion being recycled to the exchange zone to further enrich the ion exchange resin in radium.

Major World Ecosystem Complexes Ranked by Carbon in Live Vegetation: A Database (NDP-017) (2001 version of original 1985 data)

DOE Data Explorer

Olsen, Jerry S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Watts, Julia A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Allison, Linda J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2001-01-01

In 1980, this data base and the corresponding map were completed after more than 20 years of field investigations, consultations, and analyses of published literature. They characterize the use and vegetative cover of the Earth's land surface with a 0.5° × 0.5° grid. This world-ecosystem-complex data set and the accompanying map provide a current reference base for interpreting the role of vegetation in the global cycling of CO2 and other gases and a basis for improved estimates of vegetation and soil carbon, of natural exchanges of CO2, and of net historic shifts of carbon between the biosphere and the atmosphere.

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Quantifying Surface Water, Porewater, and Groundwater Interactions Using Tracers: Tracer Fluxes, Water Fluxes, and End-member Concentrations

NASA Astrophysics Data System (ADS)

Cook, Peter G.; Rodellas, Valentí; Stieglitz, Thomas C.

2018-03-01

Tracer approaches to estimate both porewater exchange (the cycling of water between surface water and sediments, with zero net water flux) and groundwater inflow (the net flow of terrestrially derived groundwater into surface water) are commonly based on solute mass balances. However, this requires appropriate characterization of tracer end-member concentrations in exchanging or discharging water. Where either porewater exchange or groundwater inflow to surface water occur in isolation, then the water flux is easily estimated from the net tracer flux if the end-member is appropriately chosen. However, in most natural systems porewater exchange and groundwater inflow will occur concurrently. Our analysis shows that if groundwater inflow (Qg) and porewater exchange (Qp) mix completely before discharging to surface water, then the combined water flux (Qg + Qp) can be approximated by dividing the combined tracer flux by the difference between the porewater and surface water concentrations, (cp - c). If Qg and Qp do not mix prior to discharge, then (Qg + Qp) can only be constrained by minimum and maximum values. The minimum value is obtained by dividing the net tracer flux by the groundwater concentration, and the maximum is obtained by dividing by (cp - c). Dividing by the groundwater concentration gives a maximum value for Qg. If porewater exchange and groundwater outflow occur concurrently, then dividing the net tracer flux by (cp - c) will provide a minimum value for Qp. Use of multiple tracers, and spatial and temporal replication should provide a more complete picture of exchange processes and the extent of subsurface mixing.

Complex conductivity of oil-contaminated clayey soils

NASA Astrophysics Data System (ADS)

Deng, Y.; Revil, A.; Shi, X.

2017-12-01

Non-intrusive hydrogeophysical techniques have been wildly applied to detect organic contaminants because of the difference of electrical properties for contaminated soil. Among them, spectral induced polarization (SIP) has emerged as a promising tool for the identification of contamination due to its sensitivity to the chemistry of pore water, solid-fluid interfaces and fluid content. Previous works have investigated the influences of oil on the electrical signatures of porous media, which demonstrated the potentials of SIP in the detection of hydrocarbon contamination. However, few works have done on the SIP response of oil in clayey soils. In this study, we perform a set of SIP measurements on the clayey samples under different water saturations. These clayey soils are characterized by relatively high cation exchange capacity. The objective in this work is to test the empirical relationships between the three exponents, including the cementation exponent (m), the saturation exponent (n) and the quadrature conductivity exponent (p), which is expected to reduce the model parameters needed in geophysical and hydraulic properties predictions. Our results show that the complex conductivity are saturation dependent. The magnitude of both in-phase and quadrature conductivities generally decrease with decreasing water saturation. The shape of quadrature conductivity spectra slightly changes when water saturation decreases in some cases. The saturation exponent slightly increases with cation exchange capacity, specific surface area and clay content, with an average value around 2.05. Compared to saturation exponent, the quadrature conductivity exponent apparently increases with cation exchange capacity and specific surface area while has little to do with the clay content. Further, the results indicate that the quadrature conductivity exponent p does not strictly obey to p=n-1 as proposed by Vinegar and Waxman (1984). Instead, it mostly ranges between p=n-1.5 and p=n-0.5. The relationship between the saturation exponent n and the cementation exponent m is comprised between m=n and m=n-0.5.

Hydrogen exchange differences between chemoreceptor signaling complexes localize to functionally important subdomains.

PubMed

Koshy, Seena S; Li, Xuni; Eyles, Stephen J; Weis, Robert M; Thompson, Lynmarie K

2014-12-16

The goal of understanding mechanisms of transmembrane signaling, one of many key life processes mediated by membrane proteins, has motivated numerous studies of bacterial chemotaxis receptors. Ligand binding to the receptor causes a piston motion of an α helix in the periplasmic and transmembrane domains, but it is unclear how the signal is then propagated through the cytoplasmic domain to control the activity of the associated kinase CheA. Recent proposals suggest that signaling in the cytoplasmic domain involves opposing changes in dynamics in different subdomains. However, it has been difficult to measure dynamics within the functional system, consisting of extended arrays of receptor complexes with two other proteins, CheA and CheW. We have combined hydrogen exchange mass spectrometry with vesicle template assembly of functional complexes of the receptor cytoplasmic domain to reveal that there are significant signaling-associated changes in exchange, and these changes localize to key regions of the receptor involved in the excitation and adaptation responses. The methylation subdomain exhibits complex changes that include slower hydrogen exchange in complexes in a kinase-activating state, which may be partially consistent with proposals that this subdomain is stabilized in this state. The signaling subdomain exhibits significant protection from hydrogen exchange in complexes in a kinase-activating state, suggesting a tighter and/or larger interaction interface with CheA and CheW in this state. These first measurements of the stability of protein subdomains within functional signaling complexes demonstrate the promise of this approach for measuring functionally important protein dynamics within the various physiologically relevant states of multiprotein complexes.

Hydrogen Exchange Differences between Chemoreceptor Signaling Complexes Localize to Functionally Important Subdomains

PubMed Central

2015-01-01

The goal of understanding mechanisms of transmembrane signaling, one of many key life processes mediated by membrane proteins, has motivated numerous studies of bacterial chemotaxis receptors. Ligand binding to the receptor causes a piston motion of an α helix in the periplasmic and transmembrane domains, but it is unclear how the signal is then propagated through the cytoplasmic domain to control the activity of the associated kinase CheA. Recent proposals suggest that signaling in the cytoplasmic domain involves opposing changes in dynamics in different subdomains. However, it has been difficult to measure dynamics within the functional system, consisting of extended arrays of receptor complexes with two other proteins, CheA and CheW. We have combined hydrogen exchange mass spectrometry with vesicle template assembly of functional complexes of the receptor cytoplasmic domain to reveal that there are significant signaling-associated changes in exchange, and these changes localize to key regions of the receptor involved in the excitation and adaptation responses. The methylation subdomain exhibits complex changes that include slower hydrogen exchange in complexes in a kinase-activating state, which may be partially consistent with proposals that this subdomain is stabilized in this state. The signaling subdomain exhibits significant protection from hydrogen exchange in complexes in a kinase-activating state, suggesting a tighter and/or larger interaction interface with CheA and CheW in this state. These first measurements of the stability of protein subdomains within functional signaling complexes demonstrate the promise of this approach for measuring functionally important protein dynamics within the various physiologically relevant states of multiprotein complexes. PMID:25420045

Cooling field and ion-beam bombardment effects on exchange bias behavior in NiFe/(Ni,Fe)O bilayers.

PubMed

Lin, K W; Wei, M R; Guo, J Y

2009-03-01

The dependence of the cooling field and the ion-beam bombardment on the exchange bias effects in NiFe/(Ni,Fe)O bilayers were investigated. The positive exchange bias was found in the zero-field-cooled (ZFC) process whereas a negative exchange bias occurred in the FC process. The increased exchange field, H(ex) with increasing (Ni,Fe)O thicknesses indicates the thicker the AF (Ni,Fe)O, the stronger the exchange coupling between the NiFe layer and the (Ni,Fe)O layer. In addition, the dependence of the H(ex) (ZFC vs. FC) on the (Ni,Fe)O thicknesses reflects the competition between the applied magnetic field and the (Ni,Fe)O surface layer exchange coupled to the NiFe layer. Further, an unusual oscillating exchange bias was observed in NiFe/(Ni,Fe)O bilayers that results from the surface of the (Ni,Fe)O layer being bombarded with different Ar-ion energies using End-Hall deposition voltages (V(EH)) from 0 to 150 V. The behavior of the H(ex) and the H(c) with the V(EH) is attributed to the surface spin reorientation that is due to moderate ion-beam bombardment effects on the surface of the (Ni,Fe)O layer. Whether the (Ni,Fe)O antiferromagnetic spins are coupled to the NiFe moments antiferromagnetically or ferromagnetically changes the sign of the exchange bias.

Ligand exchange in quaternary alloyed nanocrystals--a spectroscopic study.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Giedyk, Kamila; Kotwica, Kamil; Ostrowski, Andrzej; Malinowska, Karolina; Lisowski, Wojciech; Sobczak, Janusz W; Pron, Adam

2014-11-14

Exchange of initial, predominantly stearate ligands for pyridine in the first step and butylamine (BA) or 11-mercaptoundecanoic acid (MUA) in the second one was studied for alloyed quaternary Cu-In-Zn-S nanocrystals. The NMR results enabled us to demonstrate, for the first time, direct binding of the pyridine labile ligand to the nanocrystal surface as evidenced by paramagnetic shifts of the three signals attributed to its protons to 7.58, 7.95 and 8.75 ppm. XPS investigations indicated, in turn, a significant change in the composition of the nanocrystal surface upon the exchange of initial ligands for pyridine, which being enriched in indium in the 'as prepared' form became enriched in zinc after pyridine binding. This finding indicated that the first step of ligand exchange had to involve the removal of the surface layer enriched in indium with simultaneous exposure of a new, zinc-enriched layer. In the second ligand exchange step (replacement of pyridine with BA or MUA) the changes in the nanocrystal surface compositions were much less significant. The presence of zinc in the nanocrystal surface layer turned out necessary for effective binding of pyridine as shown by a comparative study of ligand exchange in Cu-In-Zn-S, Ag-In-Zn-S and CuInS2, carried out by complementary XPS and NMR investigations.

Research on Heat Exchange Process in Aircraft Air Conditioning System

NASA Astrophysics Data System (ADS)

Chichindaev, A. V.

2017-11-01

Using of heat-exchanger-condenser in the air conditioning system of the airplane Tu-204 (Boeing, Airbus, Superjet 100, MS-21, etc.) for cooling the compressed air by the cold air with negative temperature exiting the turbine results in a number of operational problems. Mainly it’s frosting of the heat exchange surface, which is the cause of live-section channels frosting, resistance increasing and airflow in the system decreasing. The purpose of this work is to analyse the known freeze-up-fighting methods for heat-exchanger-condenser, description of the features of anti-icing protection and offering solutions to this problem. For the problem of optimizing the design of heat exchangers in this work used generalized criterion that describes the ratio of thermal resistances of cold and hot sections, which include: the ratio of the initial values of heat transfer agents flow state; heat exchange surface finning coefficients; factors which describes the ratio of operating parameters and finning area. By controlling the ratio of the thermal resistances can be obtained the desired temperature of the heat exchange surface, which would prevent freezing. The work presents the results of a numerical study of the effect of different combinations of regime and geometrical factors changes on reduction of the heat-exchanger-condenser freezing surface area, including using of variable ratio of thermal resistances.

A Mass Computation Model for Lightweight Brayton Cycle Regenerator Heat Exchangers

NASA Technical Reports Server (NTRS)

Juhasz, Albert J.

2010-01-01

Based on a theoretical analysis of convective heat transfer across large internal surface areas, this paper discusses the design implications for generating lightweight gas-gas heat exchanger designs by packaging such areas into compact three-dimensional shapes. Allowances are made for hot and cold inlet and outlet headers for assembly of completed regenerator (or recuperator) heat exchanger units into closed cycle gas turbine flow ducting. Surface area and resulting volume and mass requirements are computed for a range of heat exchanger effectiveness values and internal heat transfer coefficients. Benefit cost curves show the effect of increasing heat exchanger effectiveness on Brayton cycle thermodynamic efficiency on the plus side, while also illustrating the cost in heat exchanger required surface area, volume, and mass requirements as effectiveness is increased. The equations derived for counterflow and crossflow configurations show that as effectiveness values approach unity, or 100 percent, the required surface area, and hence heat exchanger volume and mass tend toward infinity, since the implication is that heat is transferred at a zero temperature difference. To verify the dimensional accuracy of the regenerator mass computational procedure, calculation of a regenerator specific mass, that is, heat exchanger weight per unit working fluid mass flow, is performed in both English and SI units. Identical numerical values for the specific mass parameter, whether expressed in lb/(lb/sec) or kg/(kg/sec), show the dimensional consistency of overall results.

A Mass Computation Model for Lightweight Brayton Cycle Regenerator Heat Exchangers

NASA Technical Reports Server (NTRS)

Juhasz, Albert J.

2010-01-01

Based on a theoretical analysis of convective heat transfer across large internal surface areas, this paper discusses the design implications for generating lightweight gas-gas heat exchanger designs by packaging such areas into compact three-dimensional shapes. Allowances are made for hot and cold inlet and outlet headers for assembly of completed regenerator (or recuperator) heat exchanger units into closed cycle gas turbine flow ducting. Surface area and resulting volume and mass requirements are computed for a range of heat exchanger effectiveness values and internal heat transfer coefficients. Benefit cost curves show the effect of increasing heat exchanger effectiveness on Brayton cycle thermodynamic efficiency on the plus side, while also illustrating the cost in heat exchanger required surface area, volume, and mass requirements as effectiveness is increased. The equations derived for counterflow and crossflow configurations show that as effectiveness values approach unity, or 100 percent, the required surface area, and hence heat exchanger volume and mass tend toward infinity, since the implication is that heat is transferred at a zero temperature difference. To verify the dimensional accuracy of the regenerator mass computational procedure, calculation of a regenerator specific mass, that is, heat exchanger weight per unit working fluid mass flow, is performed in both English and SI units. Identical numerical values for the specific mass parameter, whether expressed in lb/(lb/sec) or kg/ (kg/sec), show the dimensional consistency of overall results.

Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities

USGS Publications Warehouse

Lee, Jiunn-Fwu; Mortland, Max M.; Chiou, Cary T.; Kite, Daniel E.; Boyd, Stephen A.

1990-01-01

A high-charge smectite from Arizona [cation-exchange capacity (CEC) = 120 meq/100 g] and a low-charge smectite from Wyoming (CEC = 90 meq/100 g) were used to prepare homoionic tetramethylammonium (TMA)-clay complexes. The adsorption of benzene, toluene, and o-xylene as vapors by the dry TMA-clays and as solutes from water by the wet TMA-clays was studied. The adsorption of the organic vapors by the dry TMA-smectite samples was strong and apparently consisted of interactions with both the aluminosilicate mineral surfaces and the TMA exchange ions in the interlayers. In the adsorption of organic vapors, the closer packing of TMA ions in the dry high-charge TMA-smectite, compared with the dry low-charge TMA-smectite, resulted in a somewhat higher degree of shape-selective adsorption of benzene, toluene, and xylene. In the presence of water, the adsorption capacities of both samples for the aromatic compounds were significantly reduced, although the uptake of benzene from water by the low-charge TMA-smectite was still substantial. This lower sorption capacity was accompanied by increased shape-selectivity for the aromatic compounds. The reduction in uptake and increased selectivity was much more pronounced for the water-saturated, high-charge TMA-smectite than for the low-charge TMA-smectite. Hydration of the TMA exchange ions and/or the mineral surfaces apparently reduced the accessibility of the aromatic molecules to interlamellar regions. The resulting water-induced sieving effect was greater for the high-charge TMA-smectite due to the higher density of exchanged TMA-ions. The low-charge Wyoming TMA-smectite was a highly effective adsorbent for removing benzene from water and may be useful for purifying benzene-contaminated water.

Influence of genome and bio-ecology on the prevalence of genome exchange in unisexuals of the Ambystoma complex.

PubMed

Beauregard, France; Angers, Bernard

2018-05-31

Unisexuals of the blue-spotted salamander complex are thought to reproduce by kleptogenesis. Genome exchanges associated with this sperm-dependent mode of reproduction are expected to result in a higher genetic variation and multiple ploidy levels compared to clonality. However, the existence of some populations exclusively formed of genetically identical individuals suggests that factors could prevent genome exchanges. This study aimed at assessing the prevalence of genome exchange among unisexuals of the Ambystoma laterale-jeffersonianum complex from 10 sites in the northern part of their distribution. A total of 235 individuals, including 207 unisexuals, were genotyped using microsatellite loci and AFLP. Unisexual individuals could be sorted in five genetically distinct groups, likely derived from the same paternal A. jeffersonianum haplome. One of these groups exclusively reproduced clonally, even when found in sympatry with lineages presenting signature of genome exchange. Genome exchange was site-dependent for another group. Genome exchange was detected at all sites for the three remaining groups. Prevalence of genome exchange appears to be associated with ecological conditions such as availability of effective sperm donors. Intrinsic genomic factors may also affect this process, since different lineages in sympatry present highly variable rate of genome exchange. The coexistence of clonal and genetically diversified lineages opens the door to further research on alternatives to genetic variation.

Spectral radiation analyses of the GOES solar illuminated hexagonal cell scan mirror back

NASA Technical Reports Server (NTRS)

Fantano, Louis G.

1993-01-01

A ray tracing analytical tool has been developed for the simulation of spectral radiation exchange in complex systems. Algorithms are used to account for heat source spectral energy, surface directional radiation properties, and surface spectral absorptivity properties. This tool has been used to calculate the effective solar absorptivity of the geostationary operational environmental satellites (GOES) scan mirror in the calibration position. The development and design of Sounder and Imager instruments on board GOES is reviewed and the problem of calculating the effective solar absorptivity associated with the GOES hexagonal cell configuration is presented. The analytical methodology based on the Monte Carlo ray tracing technique is described and results are presented and verified by experimental measurements for selected solar incidence angles.

Potential for Small Unmanned Aircraft Systems applications for identifying groundwater-surface water exchange in a meandering river reach

USGS Publications Warehouse

Pai, H.; Malenda, H.; Briggs, Martin A.; Singha, K.; González-Pinzón, R.; Gooseff, M.; Tyler, S.W.; ,

2017-01-01

The exchange of groundwater and surface water (GW-SW), including dissolved constituents and energy, represents a critical yet challenging characterization problem for hydrogeologists and stream ecologists. Here, we describe the use of a suite of high spatial-resolution remote-sensing techniques, collected using a small unmanned aircraft system (sUAS), to provide novel and complementary data to analyze GW-SW exchange. sUAS provided centimeter-scale resolution topography and water surface elevations, which are often drivers of exchange along the river corridor. Additionally, sUAS-based vegetation imagery, vegetation-top elevation, and normalized difference vegetation index (NDVI) mapping indicated GW-SW exchange patterns that are difficult to characterize from the land surface and may not be resolved from coarser satellite-based imagery. We combined these data with estimates of sediment hydraulic conductivity to provide a direct estimate of GW “shortcutting” through meander necks, which was corroborated by temperature data at the riverbed interface.

Potential for Small Unmanned Aircraft Systems Applications for Identifying Groundwater-Surface Water Exchange in a Meandering River Reach

NASA Astrophysics Data System (ADS)

Pai, H.; Malenda, H. F.; Briggs, M. A.; Singha, K.; González-Pinzón, R.; Gooseff, M. N.; Tyler, S. W.

2017-12-01

The exchange of groundwater and surface water (GW-SW), including dissolved constituents and energy, represents a critical yet challenging characterization problem for hydrogeologists and stream ecologists. Here we describe the use of a suite of high spatial resolution remote sensing techniques, collected using a small unmanned aircraft system (sUAS), to provide novel and complementary data to analyze GW-SW exchange. sUAS provided centimeter-scale resolution topography and water surface elevations, which are often drivers of exchange along the river corridor. Additionally, sUAS-based vegetation imagery, vegetation-top elevation, and normalized difference vegetation index mapping indicated GW-SW exchange patterns that are difficult to characterize from the land surface and may not be resolved from coarser satellite-based imagery. We combined these data with estimates of sediment hydraulic conductivity to provide a direct estimate of GW "shortcutting" through meander necks, which was corroborated by temperature data at the riverbed interface.

A multiscale model of placental oxygen exchange: The effect of villous tree structure on exchange efficiency.

PubMed

Lin, Mabelle; Mauroy, Benjamin; James, Joanna L; Tawhai, Merryn H; Clark, Alys R

2016-11-07

The placenta is critical to fetal health during pregnancy as it supplies oxygen and nutrients to maintain life. It has a complex structure, and alterations to this structure across spatial scales are associated with several pregnancy complications, including intrauterine growth restriction (IUGR). The relationship between placental structure and its efficiency as an oxygen exchanger is not well understood in normal or pathological pregnancies. Here we present a computational framework that predicts oxygen transport in the placenta which accounts for blood and oxygen transport in the space around a placental functional unit (the villous tree). The model includes the well-defined branching structure of the largest villous tree branches, as well as a smoothed representation of the small terminal villi that comprise the placenta's gas exchange interfaces. The model demonstrates that oxygen exchange is sensitive to villous tree geometry, including the villous branch length and volume, which are seen to change in IUGR. This is because, to be an efficient exchanger, the architecture of the villous tree must provide a balance between maximising the surface area available for exchange, and the opposing condition of allowing sufficient maternal blood flow to penetrate into the space surrounding the tree. The model also predicts an optimum oxygen exchange when the branch angle is 24 °, as villous branches and TBs are spread out sufficiently to channel maternal blood flow deep into the placental tissue for oxygen exchange without being shunted directly into the DVs. Without concurrent change in the branch length and angles, the model predicts that the number of branching generations has a small influence on oxygen exchange. The modelling framework is presented in 2D for simplicity but is extendible to 3D or to incorporate the high-resolution imaging data that is currently evolving to better quantify placental structure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

PubMed

Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

2017-08-22

Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

Simulating adsorption of U(VI) under transient groundwater flow and hydrochemistry: Physical versus chemical nonequilibrium model

USGS Publications Warehouse

Greskowiak, J.; Hay, M.B.; Prommer, H.; Liu, C.; Post, V.E.A.; Ma, R.; Davis, J.A.; Zheng, C.; Zachara, J.M.

2011-01-01

Coupled intragrain diffusional mass transfer and nonlinear surface complexation processes play an important role in the transport behavior of U(VI) in contaminated aquifers. Two alternative model approaches for simulating these coupled processes were analyzed and compared: (1) the physical nonequilibrium approach that explicitly accounts for aqueous speciation and instantaneous surface complexation reactions in the intragrain regions and approximates the diffusive mass exchange between the immobile intragrain pore water and the advective pore water as multirate first-order mass transfer and (2) the chemical nonequilibrium approach that approximates the diffusion-limited intragrain surface complexation reactions by a set of multiple first-order surface complexation reaction kinetics, thereby eliminating the explicit treatment of aqueous speciation in the intragrain pore water. A model comparison has been carried out for column and field scale scenarios, representing the highly transient hydrological and geochemical conditions in the U(VI)-contaminated aquifer at the Hanford 300A site, Washington, USA. It was found that the response of U(VI) mass transfer behavior to hydrogeochemically induced changes in U(VI) adsorption strength was more pronounced in the physical than in the chemical nonequilibrium model. The magnitude of the differences in model behavior depended particularly on the degree of disequilibrium between the advective and immobile phase U(VI) concentrations. While a clear difference in U(VI) transport behavior between the two models was noticeable for the column-scale scenarios, only minor differences were found for the Hanford 300A field scale scenarios, where the model-generated disequilibrium conditions were less pronounced as a result of frequent groundwater flow reversals. Copyright 2011 by the American Geophysical Union.

Validation of a new device to quantify groundwater-surface water exchange

NASA Astrophysics Data System (ADS)

Cremeans, Mackenzie M.; Devlin, J. F.

2017-11-01

Distributions of flow across the groundwater-surface water interface should be expected to be as complex as the geologic deposits associated with stream or lake beds and their underlying aquifers. In these environments, the conventional Darcy-based method of characterizing flow systems (near streams) has significant limitations, including reliance on parameters with high uncertainties (e.g., hydraulic conductivity), the common use of drilled wells in the case of streambank investigations, and potentially lengthy measurement times for aquifer characterization and water level measurements. Less logistically demanding tools for quantifying exchanges across streambeds have been developed and include drive-point mini-piezometers, seepage meters, and temperature profiling tools. This project adds to that toolbox by introducing the Streambed Point Velocity Probe (SBPVP), a reusable tool designed to quantify groundwater-surface water interactions (GWSWI) at the interface with high density sampling, which can effectively, rapidly, and accurately complement conventional methods. The SBPVP is a direct push device that measures in situ water velocities at the GWSWI with a small-scale tracer test on the probe surface. Tracer tests do not rely on hydraulic conductivity or gradient information, nor do they require long equilibration times. Laboratory testing indicated that the SBPVP has an average accuracy of ± 3% and an average precision of ± 2%. Preliminary field testing, conducted in the Grindsted Å in Jutland, Denmark, yielded promising agreement between groundwater fluxes determined by conventional methods and those estimated from the SBPVP tests executed at similar scales. These results suggest the SBPVP is a viable tool to quantify groundwater-surface water interactions in high definition in sandy streambeds.

Organic matter composition of soil macropore surfaces under different agricultural management practices

NASA Astrophysics Data System (ADS)

Glæsner, Nadia; Leue, Marin; Magid, Jacob; Gerke, Horst H.

2016-04-01

Understanding the heterogeneous nature of soil, i.e. properties and processes occurring specifically at local scales is essential for best managing our soil resources for agricultural production. Examination of intact soil structures in order to obtain an increased understanding of how soil systems operate from small to large scale represents a large gap within soil science research. Dissolved chemicals, nutrients and particles are transported through the disturbed plow layer of agricultural soil, where after flow through the lower soil layers occur by preferential flow via macropores. Rapid movement of water through macropores limit the contact between the preferentially moving water and the surrounding soil matrix, therefore contact and exchange of solutes in the water is largely restricted to the surface area of the macropores. Organomineral complex coated surfaces control sorption and exchange properties of solutes, as well as availability of essential nutrients to plant roots and to the preferentially flowing water. DRIFT (Diffuse Reflectance infrared Fourier Transform) Mapping has been developed to examine composition of organic matter coated macropores. In this study macropore surfaces structures will be determined for organic matter composition using DRIFT from a long-term field experiment on waste application to agricultural soil (CRUCIAL, close to Copenhagen, Denmark). Parcels with 5 treatments; accelerated household waste, accelerated sewage sludge, accelerated cattle manure, NPK and unfertilized, will be examined in order to study whether agricultural management have an impact on the organic matter composition of intact structures.

78 FR 9953 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-02-12

... Effectiveness of Proposed Rule Change Related to the Opening of the Complex Order Book February 6, 2013... Exchange's complex order book (``COB'') when the COB opens for trading. Currently the rule does not include... individual orders and quotes in the electronic book or other complex orders in the COB, execute or route for...

Affinity of Smectite and Divalent Metal Ions (Mg(2+), Ca(2+), Cu(2+)) with L-leucine: An Experimental and Theoretical Approach Relevant to Astrobiology.

PubMed

Pandey, Pramod; Pant, Chandra Kala; Gururani, Kavita; Arora, Priyanka; Pandey, Neetu; Bhatt, Preeti; Sharma, Yogesh; Negi, Jagmohan Singh; Mehata, Mohan Singh

2015-12-01

Earth is the only known planet bestowed with life. Several attempts have been made to explore the pathways of the origin of life on planet Earth. The search for the chemistry which gave rise to life has given answers related to the formation of biomonomers, and their adsorption on solid surfaces has gained much attention for the catalysis and stabilization processes related to the abiotic chemical evolution of the complex molecules of life. In this communication, surface interactions of L-leucine (Leu) on smectite (SMT) group of clay (viz. bentonite and montmorillonite) and their divalent metal ion (Mg(2+), Ca(2+) and Cu(2+)) incorporated on SMT has been studied to find the optimal conditions of time, pH, and concentration at ambient temperature (298 K). The progress of adsorption was followed spectrophotometrically and further characterized by FTIR, SEM/EDS and XRD. Leu, a neutral/non polar amino acid, was found to have more affinity in its zwitterionic form towards Cu(2+)- exchanged SMT and minimal affinity for Mg(2+)- exchanged SMT. The vibrational frequency shifts of -NH3 (+) and -COO(-) favor Van der Waal's forces during the course of surface interaction. Quantum calculations using density functional theory (DFT) have been applied to investigate the absolute value of metal ion affinities of Leu (Leu-M(2+) complex, M = Mg(2+), Ca(2+), Cu(2+)) with the help of their physico-chemical parameters. The hydration effect on the relative stability and geometry of the individual species of Leu-M(2+) × (H2O)n, (n =2 and 4) has also been evaluated within the supermolecule approach. Evidence gathered from investigations of surface interactions, divalent metal ions affinities and hydration effects with biomolecules may be important for better understanding of chemical evolution, the stabilization of biomolecules on solid surfaces and biomolecular-metal interactions. These results may have implications for understanding the origin of life and the preservation of biomarkers.

Year-round CH4 and CO2 flux dynamics in two contrasting freshwater ecosystems of the subarctic

NASA Astrophysics Data System (ADS)

Jammet, Mathilde; Dengel, Sigrid; Kettner, Ernesto; Parmentier, Frans-Jan W.; Wik, Martin; Crill, Patrick; Friborg, Thomas

2017-11-01

Lakes and wetlands, common ecosystems of the high northern latitudes, exchange large amounts of the climate-forcing gases methane (CH4) and carbon dioxide (CO2) with the atmosphere. The magnitudes of these fluxes and the processes driving them are still uncertain, particularly for subarctic and Arctic lakes where direct measurements of CH4 and CO2 emissions are often of low temporal resolution and are rarely sustained throughout the entire year. Using the eddy covariance method, we measured surface-atmosphere exchange of CH4 and CO2 during 2.5 years in a thawed fen and a shallow lake of a subarctic peatland complex. Gas exchange at the fen exhibited the expected seasonality of a subarctic wetland with maximum CH4 emissions and CO2 uptake in summer, as well as low but continuous emissions of CH4 and CO2 throughout the snow-covered winter. The seasonality of lake fluxes differed, with maximum CO2 and CH4 flux rates recorded at spring thaw. During the ice-free seasons, we could identify surface CH4 emissions as mostly ebullition events with a seasonal trend in the magnitude of the release, while a net CO2 flux indicated photosynthetic activity. We found correlations between surface CH4 emissions and surface sediment temperature, as well as between diel CO2 uptake and diel solar input. During spring, the breakdown of thermal stratification following ice thaw triggered the degassing of both CH4 and CO2. This spring burst was observed in 2 consecutive years for both gases, with a large inter-annual variability in the magnitude of the CH4 degassing. On the annual scale, spring emissions converted the lake from a small CO2 sink to a CO2 source: 80 % of total annual carbon emissions from the lake were emitted as CO2. The annual total carbon exchange per unit area was highest at the fen, which was an annual sink of carbon with respect to the atmosphere. Continuous respiration during the winter partly counteracted the fen summer sink by accounting for, as both CH4 and CO2, 33 % of annual carbon exchange. Our study shows (1) the importance of overturn periods (spring or fall) for the annual CH4 and CO2 emissions of northern lakes, (2) the significance of lakes as atmospheric carbon sources in subarctic landscapes while fens can be a strong carbon sink, and (3) the potential for ecosystem-scale eddy covariance measurements to improve the understanding of short-term processes driving lake-atmosphere exchange of CH4 and CO2.

Heat and mass exchanger

DOEpatents

Lowenstein, Andrew; Sibilia, Marc J.; Miller, Jeffrey A.; Tonon, Thomas

2007-09-18

A mass and heat exchanger includes at least one first substrate with a surface for supporting a continuous flow of a liquid thereon that either absorbs, desorbs, evaporates or condenses one or more gaseous species from or to a surrounding gas; and at least one second substrate operatively associated with the first substrate. The second substrate includes a surface for supporting the continuous flow of the liquid thereon and is adapted to carry a heat exchange fluid therethrough, wherein heat transfer occurs between the liquid and the heat exchange fluid.

Heat and mass exchanger

DOEpatents

Lowenstein, Andrew [Princeton, NJ; Sibilia, Marc J [Princeton, NJ; Miller, Jeffrey A [Hopewell, NJ; Tonon, Thomas [Princeton, NJ

2011-06-28

A mass and heat exchanger includes at least one first substrate with a surface for supporting a continuous flow of a liquid thereon that either absorbs, desorbs, evaporates or condenses one or more gaseous species from or to a surrounding gas; and at least one second substrate operatively associated with the first substrate. The second substrate includes a surface for supporting the continuous flow of the liquid thereon and is adapted to carry a heat exchange fluid therethrough, wherein heat transfer occurs between the liquid and the heat exchange fluid.

The (FHCl)- molecular anion - Structural aspects, global surface, and vibrational eigenspectrum

NASA Technical Reports Server (NTRS)

Klepeis, Neil E.; East, Allan L. L.; Csaszar, Attila G.; Allen, Wesley D.; Lee, Timothy J.; Schwenke, David W.

1993-01-01

State of the art ab initio electronic structure methods have been used to investigate the (FHCl)- molecular anion. It is proposed that the geometric structure and binding energies of the complex are r(e)(H-F) = 0.963 +/- 0.003 A, R(e)(H-Cl) = 1.925 +/- 0.015 A, and D0(HF + Cl(-)) = 21.8 +/- 0.4 kcal/mol. A Morokuma decomposition of the ion-molecular bonding give the following electrostatic, polarization, exchange repulsion, dispersion, and charge-transfer plus higher-order mixing components of the vibrationless complexation energy: -27.3, -5.2, +18.3, -4.5, and -5.0 kcal/mol, respectively. A couples cluster single and doubles global surface is constructed from 208 and 228 energy points for linear and bent configurations, respectively, these being fit to rms errors of only 3.9 and 9.3/cm, respectively, below 8000/cm. Converged J = 0 and J = 1 variational eigenstates of the (FHCl)- surface to near the HF + Cl(-) dissociation threshold are determined. The fundamental vibrational frequencies are found to be nu1 = 247/cm, nu2 = 876/cm, and nu3 = 2884/cm. The complete vibrational eigenspectrum is analyzed.

Functional Synergy between Rab5 Effector Rabaptin-5 and Exchange Factor Rabex-5 When Physically Associated in a Complex

PubMed Central

Lippé, Roger; Miaczynska, Marta; Rybin, Vladimir; Runge, Anja; Zerial, Marino

2001-01-01

Rab GTPases are central elements of the vesicular transport machinery. An emerging view is that downstream effectors of these GTPases are multiprotein complexes that include nucleotide exchange factors to ensure coupling between GTPase activation and effector function. We have previously shown that Rab5, which regulates various steps of transport along the early endocytic pathway, is activated by a complex consisting of Rabex-5, a Rab5 nucleotide exchange factor, and the effector Rabaptin-5. We postulated that the physical association of these two proteins is necessary for their activity in Rab5-dependent endocytic membrane transport. To evaluate the functional implications of such complex formation, we have reconstituted it with the use of recombinant proteins and characterized its properties. First, we show that Rabaptin-5 increases the exchange activity of Rabex-5 on Rab5. Second, Rab5-dependent recruitment of Rabaptin-5 to early endosomes is completely dependent on its physical association with Rabex-5. Third, complex formation between Rabaptin-5 and Rabex-5 is essential for early endosome homotypic fusion. These results reveal a functional synergy between Rabaptin-5 and Rabex-5 in the complex and have implications for the function of analogous complexes for Rab and Rho GTPases. PMID:11452015

An Analysis of the Effect of Surface Heat Exchange on the Thermal Behavior of an Idealized Aquifer Thermal Energy Storage System

NASA Astrophysics Data System (ADS)

Güven, O.; Melville, J. G.; Molz, F. J.

1983-06-01

Analytical expressions are derived for the temperature distribution and the mean temperature of an idealized aquifer thermal energy storage (ATES) system, taking into account the heat exchange at the ground surface and the finite thickness of the overlying layer above the storage aquifer. The analytical expressions for the mean temperature may be used to obtain rough estimates of first-cycle recovery factors for preliminary evaluations of shallow confined or unconfined ATES systems. The results, which are presented in nondimensional plots, indicate that surface heat exchange may have a significant influence on the thermal behavior of shallow ATES systems. Thus it is suggested that the effects of surface heat exchange should be considered carefully and included in the detailed analyses of such ATES systems.

Cation Exchange in the Presence of Oil in Porous Media

PubMed Central

2017-01-01

Cation exchange is an interfacial process during which cations on a clay surface are replaced by other cations. This study investigates the effect of oil type and composition on cation exchange on rock surfaces, relevant for a variety of oil-recovery processes. We perform experiments in which brine with a different composition than that of the in situ brine is injected into cores with and without remaining oil saturation. The cation-exchange capacity (CEC) of the rocks was calculated using PHREEQC software (coupled to a multipurpose transport simulator) with the ionic composition of the effluent histories as input parameters. We observe that in the presence of crude oil, ion exchange is a kinetically controlled process and its rate depends on residence time of the oil in the pore, the temperature, and kinetic rate of adsorption of the polar groups on the rock surface. The cation-exchange process occurs in two stages during two phase flow in porous media. Initially, the charged sites of the internal surface of the clays establish a new equilibrium by exchanging cations with the aqueous phase. At later stages, the components of the aqueous and oleic phases compete for the charged sites on the external surface or edges of the clays. When there is sufficient time for crude oil to interact with the rock (i.e., when the core is aged with crude oil), a fraction of the charged sites are neutralized by the charged components stemming from crude oil. Moreover, the positively charged calcite and dolomite surfaces (at the prevailing pH environment of our experiments) are covered with the negatively charged components of the crude oil and therefore less mineral dissolution takes place when oil is present in porous media. PMID:28580442

The effect of post-synthesis aging on the ligand exchange activity of iron oxide nanoparticles.

PubMed

Davis, Kathleen; Vidmar, Michael; Khasanov, Airat; Cole, Brian; Ghelardini, Melanie; Mayer, Justin; Kitchens, Christopher; Nath, Amar; Powell, Brian A; Mefford, O Thompson

2018-02-01

Ligand exchange is a widely-used method of controlling the surface chemistry of nanomaterials. Exchange is dependent on many factors including the age of the core particle being modified. Aging of the particles can impact surface structure and composition, which in turn can affect ligand binding. To quantify the effects of aging on ligand exchange, we employed a technique to track the exchange of radiolabeled 14 C-oleic acid with unlabeled, oleic acid bound to iron oxide nanoparticles. Liquid scintillation counting (LSC) was used to determine the amount of 14 C-oleic acid adsorbing to the particles throughout the duration of the exchange for particles aged for 2days, 7days, and 30days. Results revealed an increase in the total amount of ligands exchanged with aging up to 30days. Kinetic analysis of these results revealed a significant decrease in the overall rate of ligand exchange between 2 and 30days. The change in extent of adsorption with age could suggest increased availability of free binding sites. A follow-up study comparing exchange with oxidized and unoxidized particles suggested this increase in ligand adsorption may be due to changes in the Fe 2+ /Fe 3+ ratio on the surface as the particles aged. Copyright © 2017 Elsevier Inc. All rights reserved.

Predicting Organic Cation Sorption Coefficients: Accounting for Competition from Sorbed Inorganic Cations Using a Simple Probe Molecule.

PubMed

Jolin, William C; Goyetche, Reaha; Carter, Katherine; Medina, John; Vasudevan, Dharni; MacKay, Allison A

2017-06-06

With the increasing number of emerging contaminants that are cationic at environmentally relevant pH values, there is a need for robust predictive models of organic cation sorption coefficients (K d ). Current predictive models fail to account for the differences in the identity, abundance, and affinity of surface-associated inorganic exchange ions naturally present at negatively charged receptor sites on environmental solids. To better understand how organic cation sorption is influenced by surface-associated inorganic exchange ions, sorption coefficients of 10 organic cations (including eight pharmaceuticals and two simple probe organic amines) were determined for six homoionic forms of the aluminosilicate mineral, montmorillonite. Organic cation sorption coefficients exhibited consistent trends for all compounds across the various homoionic clays with sorption coefficients (K d ) decreasing as follows: K d Na + > K d NH 4 + ≥ K d K + > K d Ca 2+ ≥ K d Mg 2+ > K d Al 3+ . This trend for competition between organic cations and exchangeable inorganic cations is consistent with the inorganic cation selectivity sequence, determined for exchange between inorganic ions. Such consistent trends in competition between organic and inorganic cations suggested that a simple probe cation, such as phenyltrimethylammonium or benzylamine, could capture soil-to-soil variations in native inorganic cation identity and abundance for the prediction of organic cation sorption to soils and soil minerals. Indeed, sorption of two pharmaceutical compounds to 30 soils was better described by phenyltrimethylammonium sorption than by measures of benzylamine sorption, effective cation exchange capacity alone, or a model from the literature (Droge, S., and Goss, K. Environ. Sci. Technol. 2013, 47, 14224). A hybrid approach integrating structural scaling factors derived from this literature model of organic cation sorption, along with phenyltrimethylammonium K d values, allowed for estimation of K d values for more structurally complex organic cations to homoionic montmorillonites and to heteroionic soils (mean absolute error of 0.27 log unit). Accordingly, we concluded that the use of phenyltrimethylammonium as a probe compound was a promising means to account for the identity, affinity, and abundance of natural exchange ions in the prediction of organic cation sorption coefficients for environmental solids.

Influence of dose rate on the induction of simple and complex chromosome exchanges by gamma rays.

PubMed

Loucas, Bradford D; Eberle, Richard; Bailey, Susan M; Cornforth, Michael N

2004-10-01

Single-color painting of whole chromosomes, or protocols in which only a few chromosomes are distinctively painted, will always fail to detect a proportion of complex exchanges because they frequently produce pseudosimple painting patterns that are indistinguishable from those produced by bona fide simple exchanges. When 24-color multi-fluor FISH (mFISH) was employed for the purpose of distinguishing (truly) simple from pseudosimple exchanges, it was confirmed that the acute low-LET radiation dose-response relationship for simple exchanges lacked significant upward curvature. This result has been interpreted to indicate that the formation of simple exchanges requires only one chromosome locus be damaged (e.g. broken) by radiation to initiate an exchange-not two, as classical cytogenetic theory maintains. Because a one-lesion mechanism implies single-track action, it follows that the production of simple exchanges should not be influenced by changes in dose rate. To examine this prediction, we irradiated noncycling primary human fibroblasts with graded doses of (137)Cs gamma rays at an acute dose rate of 1.10 Gy/min and compared, using mFISH, the yield of simple exchanges to that observed after exposure to the same radiation delivered at a chronic dose rate of 0.08 cGy/min. The shape of the dose response was found to be quasi-linear for both dose rates, but, counter to providing support for a one-lesion mechanism, the yield of simple aberrations was greatly reduced by protracted exposure. Although chronic doses were delivered at rates low enough to produce damage exclusively by single-track action, this did not altogether eliminate the formation of complex aberrations, an analysis of which leads to the conclusion that a single track of low-LET radiation is capable of inducing complex exchanges requiring up to four proximate breaks for their formation. For acute exposures, the ratio of simple reciprocal translocations to simple dicentrics was near unity.

Advances in understanding, models and parameterisations of biosphere-atmosphere ammonia exchange

NASA Astrophysics Data System (ADS)

Flechard, C. R.; Massad, R.-S.; Loubet, B.; Personne, E.; Simpson, D.; Bash, J. O.; Cooter, E. J.; Nemitz, E.; Sutton, M. A.

2013-03-01

Atmospheric ammonia (NH3) dominates global emissions of total reactive nitrogen (Nr), while emissions from agricultural production systems contribute about two thirds of global NH3 emissions; the remaining third emanates from oceans, natural vegetation, humans, wild animals and biomass burning. On land, NH3 emitted from the various sources eventually returns to the biosphere by dry deposition to sink areas, predominantly semi-natural vegetation, and by wet and dry deposition as ammonium (NH4+) to all surfaces. However, the land/atmosphere exchange of gaseous NH3 is in fact bi-directional over unfertilized as well as fertilized ecosystems, with periods and areas of emission and deposition alternating in time (diurnal, seasonal) and space (patchwork landscapes). The exchange is controlled by a range of environmental factors, including meteorology, surface layer turbulence, thermodynamics, air and surface heterogeneous-phase chemistry, canopy geometry, plant development stage, leaf age, organic matter decomposition, soil microbial turnover, and, in agricultural systems, by fertilizer application rate, fertilizer type, soil type, crop type, and agricultural management practices. We review the range of processes controlling NH3 emission and uptake in the different parts of the soil-canopy-atmosphere continuum, with NH3 emission potentials defined at the substrate and leaf levels by different [NH4+] / [H+] ratios (Γ). Surface/atmosphere exchange models for NH3 are necessary to compute the temporal and spatial patterns of emissions and deposition at the soil, plant, field, landscape, regional and global scales, in order to assess the multiple environmental impacts of air-borne and deposited NH3 and NH4+. Models of soil/vegetation/atmosphereem NH3 exchange are reviewed from the substrate and leaf scales to the global scale. They range from simple steady-state, "big leaf" canopy resistance models, to dynamic, multi-layer, multi-process, multi-chemical species schemes. Their level of complexity depends on their purpose, the spatial scale at which they are applied, the current level of parameterisation, and the availability of the input data they require. State-of-the-art solutions for determining the emission/sink Γ potentials through the soil/canopy system include coupled, interactive chemical transport models (CTM) and soil/ecosystem modelling at the regional scale. However, it remains a matter for debate to what extent realistic options for future regional and global models should be based on process-based mechanistic versus empirical and regression-type models. Further discussion is needed on the extent and timescale by which new approaches can be used, such as integration with ecosystem models and satellite observations.

Advances in understanding, models and parameterizations of biosphere-atmosphere ammonia exchange

NASA Astrophysics Data System (ADS)

Flechard, C. R.; Massad, R.-S.; Loubet, B.; Personne, E.; Simpson, D.; Bash, J. O.; Cooter, E. J.; Nemitz, E.; Sutton, M. A.

2013-07-01

Atmospheric ammonia (NH3) dominates global emissions of total reactive nitrogen (Nr), while emissions from agricultural production systems contribute about two-thirds of global NH3 emissions; the remaining third emanates from oceans, natural vegetation, humans, wild animals and biomass burning. On land, NH3 emitted from the various sources eventually returns to the biosphere by dry deposition to sink areas, predominantly semi-natural vegetation, and by wet and dry deposition as ammonium (NH4+) to all surfaces. However, the land/atmosphere exchange of gaseous NH3 is in fact bi-directional over unfertilized as well as fertilized ecosystems, with periods and areas of emission and deposition alternating in time (diurnal, seasonal) and space (patchwork landscapes). The exchange is controlled by a range of environmental factors, including meteorology, surface layer turbulence, thermodynamics, air and surface heterogeneous-phase chemistry, canopy geometry, plant development stage, leaf age, organic matter decomposition, soil microbial turnover, and, in agricultural systems, by fertilizer application rate, fertilizer type, soil type, crop type, and agricultural management practices. We review the range of processes controlling NH3 emission and uptake in the different parts of the soil-canopy-atmosphere continuum, with NH3 emission potentials defined at the substrate and leaf levels by different [NH4+] / [H+] ratios (Γ). Surface/atmosphere exchange models for NH3 are necessary to compute the temporal and spatial patterns of emissions and deposition at the soil, plant, field, landscape, regional and global scales, in order to assess the multiple environmental impacts of airborne and deposited NH3 and NH4+. Models of soil/vegetation/atmosphere NH3 exchange are reviewed from the substrate and leaf scales to the global scale. They range from simple steady-state, "big leaf" canopy resistance models, to dynamic, multi-layer, multi-process, multi-chemical species schemes. Their level of complexity depends on their purpose, the spatial scale at which they are applied, the current level of parameterization, and the availability of the input data they require. State-of-the-art solutions for determining the emission/sink Γ potentials through the soil/canopy system include coupled, interactive chemical transport models (CTM) and soil/ecosystem modelling at the regional scale. However, it remains a matter for debate to what extent realistic options for future regional and global models should be based on process-based mechanistic versus empirical and regression-type models. Further discussion is needed on the extent and timescale by which new approaches can be used, such as integration with ecosystem models and satellite observations.

Bacterial interactions in dental biofilm development.

PubMed

Hojo, K; Nagaoka, S; Ohshima, T; Maeda, N

2009-11-01

Recent analyses with ribosomal RNA-based technologies have revealed the diversity of bacterial populations within dental biofilms, and have highlighted their important contributions to oral health and disease. Dental biofilms are exceedingly complex and multispecies ecosystems, where oral bacteria interact cooperatively or competitively with other members. Bacterial interactions that influence dental biofilm communities include various different mechanisms. During the early stage of biofilm formation, it is known that planktonic bacterial cells directly attach to surfaces of the oral cavity or indirectly bind to other bacterial cells that have already colonized. Adherence through co-aggregation may be critical for the temporary retention of bacteria on dental surfaces, and may facilitate eventual bacterial colonization. It is likely that metabolic communication, genetic exchange, production of inhibitory factors (e.g., bacteriocins, hydrogen peroxide, etc.), and quorum-sensing are pivotal regulatory factors that determine the bacterial composition and/or metabolism. Since each bacterium can easily access a neighboring bacterial cell and its metabolites, genetic exchanges and metabolic communication may occur frequently in dental biofilms. Quorum-sensing is defined as gene regulation in response to cell density, which influences various functions, e.g., virulence and bacteriocin production. In this review, we discuss these important interactions among oral bacteria within the dental biofilm communities.

Rab14 and Its Exchange Factor FAM116 Link Endocytic Recycling and Adherens Junction Stability in Migrating Cells

PubMed Central

Linford, Andrea; Yoshimura, Shin-ichiro; Bastos, Ricardo Nunes; Langemeyer, Lars; Gerondopoulos, Andreas; Rigden, Daniel J.; Barr, Francis A.

2012-01-01

Summary Rab GTPases define the vesicle trafficking pathways underpinning cell polarization and migration. Here, we find that Rab4, Rab11, and Rab14 and the candidate Rab GDP-GTP exchange factors (GEFs) FAM116A and AVL9 are required for cell migration. Rab14 and its GEF FAM116A localize to and act on an intermediate compartment of the transferrin-recycling pathway prior to Rab11 and after Rab5 and Rab4. This Rab14 intermediate recycling compartment has specific functions in migrating cells discrete from early and recycling endosomes. Rab14-depleted cells show increased N-cadherin levels at junctional complexes and cannot resolve cell-cell junctions. This is due to decreased shedding of cell-surface N-cadherin by the ADAM family protease ADAM10/Kuzbanian. In FAM116A- and Rab14-depleted cells, ADAM10 accumulates in a transferrin-positive endocytic compartment, and the cell-surface level of ADAM10 is correspondingly reduced. FAM116 and Rab14 therefore define an endocytic recycling pathway needed for ADAM protease trafficking and regulation of cell-cell junctions. PMID:22595670

Hafnium radioisotope recovery from irradiated tantalum

DOEpatents

Taylor, Wayne A.; Jamriska, David J.

2001-01-01

Hafnium is recovered from irradiated tantalum by: (a) contacting the irradiated tantalum with at least one acid to obtain a solution of dissolved tantalum; (b) combining an aqueous solution of a calcium compound with the solution of dissolved tantalum to obtain a third combined solution; (c) precipitating hafnium, lanthanide, and insoluble calcium complexes from the third combined solution to obtain a first precipitate; (d) contacting the first precipitate of hafnium, lanthanide and calcium complexes with at least one fluoride ion complexing agent to form a fourth solution; (e) selectively adsorbing lanthanides and calcium from the fourth solution by cationic exchange; (f) separating fluoride ion complexing agent product from hafnium in the fourth solution by adding an aqueous solution of ferric chloride to obtain a second precipitate containing the hafnium and iron; (g) dissolving the second precipitate containing the hafnium and iron in acid to obtain an acid solution of hafnium and iron; (h) selectively adsorbing the iron from the acid solution of hafnium and iron by anionic exchange; (i) drying the ion exchanged hafnium solution to obtain hafnium isotopes. Additionally, if needed to remove residue remaining after the product is dried, dissolution in acid followed by cation exchange, then anion exchange, is performed.

Physical characteristics of lanthanide complexes that act as magnetization transfer (MT) contrast agents

NASA Astrophysics Data System (ADS)

Zhang, Shanrong; Sherry, A. Dean

2003-02-01

Rapid water exchange is normally considered a prerequisite for efficient Gd3+-based MRI contrast agents. Yet recent measures of exchange rates in some Gd3+ complexes have shown that water exchange can become limiting when such complexes are attached to larger macromolecular structures. A new class of lanthanide complexes that display unusually slow water exchange (bound water lifetimes (τM298) > 10 μs) has recently been reported. This apparent disadvantage may be taken advantage of by switching the metal ion from gadolinium(III) to a lanthanide that shifts the bound water resonance substantially away from bulk water. Given appropriate water exchange kinetics, one can then alter the intensity of the bulk water signal by selective presaturation of this highly shifted, Ln3+-bound water resonance. This provides the basis of a new method to alter MR image contrast in tissue. We have synthesized a variety of DOTA-tetra(amide) ligands to evaluate as potential magnetization transfer (MT) contrast agents and found that the bound water lifetimes in these complexes are sensitive to both ligand structure (a series of Eu3+ complexes have τM298 values that range from 1 to 1300 μs) and the identity of the paramagnetic Ln3+ cation (from 3 to 800 μs for a single ligand). This demonstrates that it may be possible either to fine-tune the ligand structure or to select proper lanthanide cation to create an optimal MT agent for any clinical imaging field.

The effect of monomolecular surface films on the microwave brightness temperature of the sea surface

NASA Technical Reports Server (NTRS)

Alpers, W.; Blume, H.-J. C.; Garrett, W. D.; Huehnerfuss, H.

1982-01-01

It is pointed out that monomolecular surface films of biological origin are often encountered on the ocean surface, especially in coastal regions. The thicknesses of the monomolecular films are of the order of 3 x 10 to the -9th m. Huehnerfuss et al. (1978, 1981) have shown that monomolecular surface films damp surface waves quite strongly in the centimeter to decimeter wavelength regime. Other effects caused by films are related to the reduction of the gas exchange at the air-sea interface and the decrease of the wind stress. The present investigation is concerned with experiments which reveal an unexpectedly large response of the microwave brightness temperature to a monomolecular oleyl alcohol slick at 1.43 GHz. Brightness temperature is a function of the complex dielectric constant of thy upper layer of the ocean. During six overflights over an ocean area covered with an artificial monomolecular alcohol film, a large decrease of the brightness temperature at the L-band was measured, while at the S-band almost no decrease was observed.

Tensile Lattice Strain Accelerates Oxygen Surface Exchange and Diffusion in La1–xSrxCoO3−δ Thin Films

PubMed Central

2013-01-01

The influence of lattice strain on the oxygen exchange kinetics and diffusion in oxides was investigated on (100) epitaxial La1–xSrxCoO3−δ (LSC) thin films grown by pulsed laser deposition. Planar tensile and compressively strained LSC films were obtained on single-crystalline SrTiO3 and LaAlO3. 18O isotope exchange depth profiling with ToF-SIMS was employed to simultaneously measure the tracer surface exchange coefficient k* and the tracer diffusion coefficient D* in the temperature range 280–475 °C. In accordance with recent theoretical findings, much faster surface exchange (∼4 times) and diffusion (∼10 times) were observed for the tensile strained films compared to the compressively strained films in the entire temperature range. The same strain effect—tensile strain leading to higher k* and D*—was found for different LSC compositions (x = 0.2 and x = 0.4) and for surface-etched films. The temperature dependence of k* and D* is discussed with respect to the contributions of strain states, formation enthalpy of oxygen vacancies, and vacancy mobility at different temperatures. Our findings point toward the control of oxygen surface exchange and diffusion kinetics by means of lattice strain in existing mixed conducting oxides for energy conversion applications. PMID:23527691

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Federal Register 2010, 2011, 2012, 2013, 2014

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New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

PubMed

Ferreira-Aparicio, Paloma

2009-09-01

The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

Fluid to fluid contact heat exchanger

NASA Technical Reports Server (NTRS)

Clark, W. E.

1986-01-01

Heat transfer and pressure drop test results for a fluid to fluid contact heat exchanger are reported. The heat exchanger, fabricated and tested to demonstrate one method of transferring heat between structures in space, had a total contact area of 0.18 sq m. It utilized contact surfaces which were flexible and conformed to the mating contact surfaces upon pressurization of the fluid circulating within the heat exchanger. During proof-of-concept performance tests, the heat exchanger was operated in a typical earth environment. It demonstrated a contact conductance of 3.8 kW/sq m C at contact pressures in the 15 to 70 kPa range.

A highly stable gadolinium complex with a fast, associative mechanism of water exchange.

PubMed

Thompson, Marlon K; Botta, Mauro; Nicolle, Gaëlle; Helm, Lothar; Aime, Silvio; Merbach, André E; Raymond, Kenneth N

2003-11-26

The stability and water exchange dynamics of gadolinium (GdIII) complexes are critical characteristics that determine their effectiveness as contrast agents for magnetic resonance imaging (MRI). A new heteropodal GdIII chelate, [Gd-TREN-bis(6-Me-HOPO)-(TAM-TRI)(H2O)2] (Gd-2), is presented which is based on a hydroxypyridinate (HOPO)-terephthalamide (TAM) ligand design. Thermodynamic equilibrium constants for the acid-base properties and the GdIII complexation strength of TREN-bis(6-Me-HOPO)-(TAM-TRI) (2) were measured by potentiometric and spectrophotometric titration techniques, respectively. The pGd of 2 is 20.6 (pH 7.4, 25 degrees C, I = 0.1 M), indicating that Gd-2 is of more than sufficient thermodynamic stability for in vivo MRI applications. The water exchange rate of Gd-2 (kex = 5.3(+/-0.6) x 107 s-1) was determined by variable temperature 17O NMR and is in the fast exchange regime - ideal for MRI. Variable pressure 17O NMR was used to determine the volume of activation (DeltaV) of Gd-2. DeltaV for Gd-2 is -5 cm3 mol-1, indicative of an interchange associative (Ia) water exchange mechanism. The results reported herein are important as they provide insight into the factors influencing high stability and fast water exchange in the HOPO series of complexes, potentially future clinical contrast agents.

Effect of impeller design and spacing on gas exchange in a percutaneous respiratory assist catheter.

PubMed

Jeffries, R Garrett; Frankowski, Brian J; Burgreen, Greg W; Federspiel, William J

2014-12-01

Providing partial respiratory assistance by removing carbon dioxide (CO2 ) can improve clinical outcomes in patients suffering from acute exacerbations of chronic obstructive pulmonary disease and acute respiratory distress syndrome. An intravenous respiratory assist device with a small (25 Fr) insertion diameter eliminates the complexity and potential complications associated with external blood circuitry and can be inserted by nonspecialized surgeons. The impeller percutaneous respiratory assist catheter (IPRAC) is a highly efficient CO2 removal device for percutaneous insertion to the vena cava via the right jugular or right femoral vein that utilizes an array of impellers rotating within a hollow-fiber membrane bundle to enhance gas exchange. The objective of this study was to evaluate the effects of new impeller designs and impeller spacing on gas exchange in the IPRAC using computational fluid dynamics (CFD) and in vitro deionized water gas exchange testing. A CFD gas exchange and flow model was developed to guide a progressive impeller design process. Six impeller blade geometries were designed and tested in vitro in an IPRAC device with 2- or 10-mm axial spacing and varying numbers of blades (2-5). The maximum CO2 removal efficiency (exchange per unit surface area) achieved was 573 ± 8 mL/min/m(2) (40.1 mL/min absolute). The gas exchange rate was found to be largely independent of blade design and number of blades for the impellers tested but increased significantly (5-10%) with reduced axial spacing allowing for additional shaft impellers (23 vs. 14). CFD gas exchange predictions were within 2-13% of experimental values and accurately predicted the relative improvement with impellers at 2- versus 10-mm axial spacing. The ability of CFD simulation to accurately forecast the effects of influential design parameters suggests it can be used to identify impeller traits that profoundly affect facilitated gas exchange. Copyright © 2014 International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

DNA Strand Exchange and RecA Homologs in Meiosis

PubMed Central

Brown, M. Scott; Bishop, Douglas K.

2015-01-01

Homology search and DNA strand–exchange reactions are central to homologous recombination in meiosis. During meiosis, these processes are regulated such that the probability of choosing a homolog chromatid as recombination partner is enhanced relative to that of choosing a sister chromatid. This regulatory process occurs as homologous chromosomes pair in preparation for assembly of the synaptonemal complex. Two strand–exchange proteins, Rad51 and Dmc1, cooperate in regulated homology search and strand exchange in most organisms. Here, we summarize studies on the properties of these two proteins and their accessory factors. In addition, we review current models for the assembly of meiotic strand–exchange complexes and the possible mechanisms through which the interhomolog bias of recombination partner choice is achieved. PMID:25475089

NASA geometry data exchange specification for computational fluid dynamics (NASA IGES)

NASA Technical Reports Server (NTRS)

Blake, Matthew W.; Kerr, Patricia A.; Thorp, Scott A.; Jou, Jin J.

1994-01-01

This document specifies a subset of an existing product data exchange specification that is widely used in industry and government. The existing document is called the Initial Graphics Exchange Specification. This document, a subset of IGES, is intended for engineers analyzing product performance using tools such as computational fluid dynamics (CFD) software. This document specifies how to define mathematically and exchange the geometric model of an object. The geometry is represented utilizing nonuniform rational B-splines (NURBS) curves and surfaces. Only surface models are represented; no solid model representation is included. This specification does not include most of the other types of product information available in IGES (e.g., no material properties or surface finish properties) and does not provide all the specific file format details of IGES. The data exchange protocol specified in this document is fully conforming to the American National Standard (ANSI) IGES 5.2.

Liquid cooled plate heat exchanger for battery cooling of an electric vehicle (EV)

NASA Astrophysics Data System (ADS)

Rahman, M. M.; Rahman, H. Y.; Mahlia, T. M. I.; Sheng, J. L. Y.

2016-03-01

A liquid cooled plate heat exchanger was designed to improve the battery life of an electric vehicle which suffers from premature aging or degradation due to the heat generation during discharging and charging period. Computational fluid dynamics (CFD) was used as a tool to analyse the temperature distribution when a constant surface heat flux was set at the bottom surface of the battery. Several initial and boundary conditions were set based on the past studies on the plate heat exchanger in the simulation software. The design of the plate heat exchanger was based on the Nissan Leaf battery pack to analyse the temperature patterns. Water at different mass flow rates was used as heat transfer fluid. The analysis revealed the designed plate heat exchanger could maintain the surface temperature within the range of 20 to 40°C which is within the safe operating temperature of the battery.

All-inorganic Germanium nanocrystal films by cationic ligand exchange

DOE PAGES

Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; ...

2016-01-21

In this study, we introduce a new paradigm for group IV nanocrystal surface chemistry based on room temperature surface activation that enables ionic ligand exchange. Germanium nanocrystals synthesized in a gas-phase plasma reactor are functionalized with labile, cationic alkylammonium ligands rather than with traditional covalently bound groups. We employ Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies to demonstrate the alkylammonium ligands are freely exchanged on the germanium nanocrystal surface with a variety of cationic ligands, including short inorganic ligands such as ammonium and alkali metal cations. This ionic ligand exchange chemistry is used to demonstrate enhanced transport inmore » germanium nanocrystal films following ligand exchange as well as the first photovoltaic device based on an all-inorganic germanium nanocrystal absorber layer cast from solution. This new ligand chemistry should accelerate progress in utilizing germanium and other group IV nanocrystals for optoelectronic applications.« less

[Characteristics of mercury exchange flux between soil and atmosphere under the snow retention and snow melting control].

PubMed

Zhang, Gang; Wang, Ning; Ai, Jian-Chao; Zhang, Lei; Yang, Jing; Liu, Zi-Qi

2013-02-01

Jiapigou gold mine, located in the upper Songhua River, was once the largest mine in China due to gold output, where gold extraction with algamation was widely applied to extract gold resulting in severe mercury pollution to ambient environmental medium. In order to study the characteristics of mercury exchange flux between soil (snow) and atmosphere under the snow retention and snow melting control, sampling sites were selected in equal distances along the slope which is situated in the typical hill-valley terrain unit. Mercury exchange flux between soil (snow) and atmosphere was determined with the method of dynamic flux chamber and in all sampling sites the atmosphere concentration from 0 to 150 cm near to the earth in the vertical direction was measured. Furthermore, the impact factors including synchronous meteorology, the surface characteristics under the snow retention and snow melting control and the mercury concentration in vertical direction were also investigated. The results are as follows: During the period of snow retention and melting the air mercury tends to gather towards valley bottom along the slope and an obvious deposit tendency process was found from air to the earth's surface under the control of thermal inversion due to the underlying surface of cold source (snow surface). However, during the period of snow melting, mercury exchange flux between the soil and atmosphere on the surface of the earth with the snow being melted demonstrates alternative deposit and release processes. As for the earth with snow covered, the deposit level of mercury exchange flux between soil and atmosphere is lower than that during the period of snow retention. The relationship between mercury exchange flux and impact factors shows that in snow retention there is a remarkable negative linear correlation between mercury exchange flux and air mercury concentration as well as between the former and the air temperature. In addition, in snow melting mercury exchange flux is remarkably negatively linearly correlated to air mercury concentration and positively linearly correlated to air temperature. Furthermore, there is a general positive linear correlation between mercury exchange flux and soil temperature on the surface of earth after snow melting.

Truly Incomplete and Complex Chromosomal Exchanges in Human Fibroblast Cells Exposed In Situ to Energetic Heavy Ions

NASA Technical Reports Server (NTRS)

Wu, Honglu; Durante, marco; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis A.

2003-01-01

Confluent human fibroblast cells (AG 1522) were irradiated with gamma rays, 490 MeV/nucleon Si, or with Fe ions at either 200 or 500 MeV/nucleon. The cells were allowed to repair at 37 C for 24 hours after exposure, and a chemically induced premature chromosome condensation (PCC) technique was used to condense chromosomes in the G2 phase of the cell cycle. Incomplete and complex exchanges were analyzed in the irradiated samples. In order to verify that chromosomal breaks were truly unrejoined, chromosome aberrations were analyzed using a combination of whole chromosome specific probes and probes specific for the telomere region of the chromosome. Results showed that the frequency of unrejoined chromosome breaks was higher after high-LET radiation, and consequently, the ratio of incomplete to complete exchanges increased steadily with LET up to 440 keV/micron, the highest LET value in the present study. For samples exposed to 200 MeV/nucleon Fe ions, chromosome aberrations were analyzed using the multicolor FISH (mFISH) technique that allow identification of both complex and truly incomplete exchanges. Results of the mFISH study showed that 0.7 and 3 Gy dose of the Fe ions produced similar ratios of complex to simple exchanges and incomplete to complete exchanges, values for which were higher than those obtained after a 6 Gy gamma exposure. After 0.7 Gy of Fe ions, most complex aberrations were found to involve three or four chromosomes, which is a likely indication of the maximum number of chromosome domains traversed by a single Fe ion track.

The impact of 90 years of drainage works on some chemical properties of raised peat bog organic soils - case study from valley of the Upper San river in Polish Bieszczady Mts. (Eastern Carpathians).

NASA Astrophysics Data System (ADS)

Stolarczyk, Mateusz

2016-04-01

Wetland ecosystems, including raised peat bogs are characterized by a specific water conditions and unique vegetation, which makes peatland highly important habitats due to protection of biodiversity. Transformation of peat bog areas is particularly related to changes in the environment e.g. according to reclamation works. Drainage of peatlands is directly associated to the decrease of groundwater levels and lead to a number of changes in the chemical and physical properties of peat material, included contents of exchangeable cations in the surface layers of peat soils in the decession phase of peat development and release above compounds from the soil to ground or surface waters. The aim of the research was to determine the impact of extended drainage works on chemical composition of sorption complex of raised peat bog organic soils and identification the potential environmental effects of alkaline cations leaching to the surface waters. Research was carried out on the peat bogs located in the Upper San valley in Polish Bieszczady Mts. (Eastern Carpathians). Soil samples used in this study were collected from 3 soil profiles in 10 or 20 cm intervals to the approximately 130 cm depth. Laboratory analyses included determination of basic properties of organic material such as the degree of peat decomposition, ash content, soil pH and carbon, hydrogen, nitrogen concentrations. Additionally the amount of alkaline cations, exchangeable and extractable acidity was determined. Furthermore, the degree of saturation of the sorption complex with alkaline cations (V) and cation exchange capacity (CEC) are calculated. In order to evaluate the impact of the examined peat bog to the environment, also water samples were collected and ions composition was measured. The obtained results show that studied organic soils are oligotrophic and strongly acidic. In the case of organic material related to decession phase of peat development, as a result of the lengthy drainage works, increased pH values, changes in the morphology of the peat, high nitrogen contents and lower values of C/N ratios are noticed. The increased contents of calcium, occurred in soil layers comprised of moorsh forming process are probably the effect of peat mineralization process or changes in the chemistry and fluctuations of groundwater levels. As a result of above factors, increased calcium and magnesium concentrations in surface waters in the immediate vicinity of investigated bogs are observed.

Bismuth generator method

DOEpatents

Bray, Lane Allan; DesChane, Jaquetta R.

1998-01-01

A method for separating .sup.213 Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon .sup.213 Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as .sup.225 Ra, .sup.225 Ac, and .sup.221 Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The .sup.213 Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the .sup.213 Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the .sup.213 Bi. A preferred stripping solution for purification of .sup.213 Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc, to receive the .sup.213 Bi as it is being released from the anion exchange resin.

Bismuth generator method

DOEpatents

Bray, L.A.; DesChane, J.R.

1998-05-05

A method is described for separating {sup 213}Bi from a solution of radionuclides wherein the solution contains a concentration of the chloride ions and hydrogen ions adjusted to allow the formation of a chloride complex. The solution is then brought into contact with an anion exchange resin, whereupon {sup 213}Bi is absorbed from the solution and adhered onto the anion exchange resin in the chloride complex. Other non-absorbing radionuclides such as {sup 225}Ra, {sup 225}Ac, and {sup 221}Fr, along with HCl are removed from the anion exchange resin with a scrub solution. The {sup 213}Bi is removed from the anion exchange resin by washing the anion exchange resin with a stripping solution free of chloride ions and with a reduced hydrogen ion concentration which breaks the chloride anionic complex, releasing the {sup 213}Bi as a cation. In a preferred embodiment of the present invention, the anion exchange resin is provided as a thin membrane, allowing for extremely rapid adherence and stripping of the {sup 213}Bi. A preferred stripping solution for purification of {sup 213}Bi for use in medical applications includes sodium acetate, pH 5.5. A protein conjugated with bifunctional chelating agents in vivo with the NaOAc receives the {sup 213}Bi as it is being released from the anion exchange resin. 10 figs.

Graphene/Ionic Liquid Composite Films and Ion Exchange

PubMed Central

Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

2014-01-01

Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

Additional hydrogen bonds and base-pair kinetics in the symmetrical AMP-DNA aptamer complex.

PubMed Central

Nonin-Lecomte, S; Lin, C H; Patel, D J

2001-01-01

The solution structure of an adenosine monophosphate (AMP)-DNA aptamer complex has been determined previously [Lin, C. H., and Patel, D. J. (1997) Chem. Biol. 4:817-832]. On a symmetrical aptamer complex containing the same binding loop, but with better resolved spectra, we have identified two additional hydrogen bond-mediated associations in the binding loop. One of these involves a rapidly exchanging G imino proton. The phosphate group of the AMP ligand was identified as the acceptor by comparison with other aptamer complexes. Imino proton exchange measurements also yielded the dissociation constants of the stem and binding loop base pairs. This study shows that nuclear magnetic resonance-based imino proton exchange is a good probe for detection of weak hydrogen-bond associations. PMID:11721004

Lung Structure and the Intrinsic Challenges of Gas Exchange

PubMed Central

Hsia, Connie C.W.; Hyde, Dallas M.; Weibel, Ewald R.

2016-01-01

Structural and functional complexities of the mammalian lung evolved to meet a unique set of challenges, namely, the provision of efficient delivery of inspired air to all lung units within a confined thoracic space, to build a large gas exchange surface associated with minimal barrier thickness and a microvascular network to accommodate the entire right ventricular cardiac output while withstanding cyclic mechanical stresses that increase several folds from rest to exercise. Intricate regulatory mechanisms at every level ensure that the dynamic capacities of ventilation, perfusion, diffusion, and chemical binding to hemoglobin are commensurate with usual metabolic demands and periodic extreme needs for activity and survival. This article reviews the structural design of mammalian and human lung, its functional challenges, limitations, and potential for adaptation. We discuss (i) the evolutionary origin of alveolar lungs and its advantages and compromises, (ii) structural determinants of alveolar gas exchange, including architecture of conducting bronchovascular trees that converge in gas exchange units, (iii) the challenges of matching ventilation, perfusion, and diffusion and tissue-erythrocyte and thoracopulmonary interactions. The notion of erythrocytes as an integral component of the gas exchanger is emphasized. We further discuss the signals, sources, and limits of structural plasticity of the lung in alveolar hypoxia and following a loss of lung units, and the promise and caveats of interventions aimed at augmenting endogenous adaptive responses. Our objective is to understand how individual components are matched at multiple levels to optimize organ function in the face of physiological demands or pathological constraints. PMID:27065169

76 FR 40758 - Self-Regulatory Organizations; International Securities Exchange, LLC; Order Approving a Proposed...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-07-11

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-64805; File No. SR-ISE-2011-30] Self-Regulatory Organizations; International Securities Exchange, LLC; Order Approving a Proposed Rule Change Relating to Complex Orders July 5, 2011. I. Introduction On May 23, 2011, the International Securities Exchange, LLC...

76 FR 64980 - Self-Regulatory Organizations; International Securities Exchange, LLC; Order Approving a Proposed...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-19

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-65548; File No. SR-ISE-2011-39] Self-Regulatory Organizations; International Securities Exchange, LLC; Order Approving a Proposed Rule Change Relating to Complex Orders October 13, 2011. I. Introduction On July 1, 2011, the International Securities Exchange...

Spin crossover in Fe(phen)2(NCS)2 complexes on metallic surfaces

NASA Astrophysics Data System (ADS)

Gruber, Manuel; Miyamachi, Toshio; Davesne, Vincent; Bowen, Martin; Boukari, Samy; Wulfhekel, Wulf; Alouani, Mebarek; Beaurepaire, Eric

2017-03-01

In this review, we give an overview on the spin crossover of Fe(phen)2(NCS)2 complexes adsorbed on Cu(100), Cu2N/Cu(100), Cu(111), Co/Cu(111), Co(100), Au(100), and Au(111) surfaces. Depending on the strength of the interaction of the molecules with the substrates, the spin crossover behavior can be drastically changed. Molecules in direct contact with non-magnetic metallic surfaces coexist in both the high- and low-spin states but cannot be switched between the two. Our analysis shows that this is due to a strong interaction with the substrate in the form of a chemisorption that dictates the spin state of the molecules through its adsorption geometry. Upon reducing the interaction to the surface either by adding a second molecular layer or inserting an insulating thin film of Cu2N, the spin crossover behavior is restored and molecules can be switched between the two states with the help of scanning tunneling microscopy. Especially on Cu2N, the two states of single molecules are stable at low temperature and thus allow the realization of a molecular memory. Similarly, the molecules decoupled from metallic substrates in the second or higher layers display thermally driven spin crossover as has been revealed by X-ray absorption spectroscopy. Finally, we discuss the situation when the complex is brought into contact with a ferromagnetic substrate. This leads to a strong exchange coupling between the Fe spin in the high-spin state and the magnetization of the substrate as deduced from spin-polarized scanning tunneling spectroscopy and ab initio calculation.

Self-optimizing charge-transfer energy phenomena in metallosupramolecular complexes by dynamic constitutional self-sorting.

PubMed

Legrand, Yves-Marie; van der Lee, Arie; Barboiu, Mihail

2007-11-12

In this paper we report an extended series of 2,6-(iminoarene)pyridine-type ZnII complexes [(Lii)2Zn]II, which were surveyed for their ability to self-exchange both their ligands and their aromatic arms and to form different homoduplex and heteroduplex complexes in solution. The self-sorting of heteroduplex complexes is likely to be the result of geometric constraints. Whereas the imine-exchange process occurs quantitatively in 1:1 mixtures of [(Lii)2Zn]II complexes, the octahedral coordination process around the metal ion defines spatial-frustrated exchanges that involve the selective formation of heterocomplexes of two, by two different substituents; the bulkiest ones (pyrene in principle) specifically interact with the pseudoterpyridine core, sterically hindering the least bulky ones, which are intermolecularly stacked with similar ligands of neighboring molecules. Such a self-sorting process defined by the specific self-constitution of the ligands exchanging their aromatic substituents is self-optimized by a specific control over their spatial orientation around a metal center within the complex. They ultimately show an improved charge-transfer energy function by virtue of the dynamic amplification of self-optimized heteroduplex architectures. These systems therefore illustrate the convergence of the combinatorial self-sorting of the dynamic combinatorial libraries (DCLs) strategy and the constitutional self-optimized function.

Surface treatment of nanocrystal quantum dots after film deposition

DOEpatents

Sykora, Milan; Koposov, Alexey; Fuke, Nobuhiro

2015-02-03

Provided are methods of surface treatment of nanocrystal quantum dots after film deposition so as to exchange the native ligands of the quantum dots for exchange ligands that result in improvement in charge extraction from the nanocrystals.

Exchange coupling in the complex magnetic multilayers

NASA Astrophysics Data System (ADS)

Uzdin, V. M.; Adamowicz, L.; Kocinski, P.

1996-06-01

Exchange coupling in the complex magnetic sandwich structures containing nonmagnetic (NM) and ferromagnetic (FM) layers composed of two different ferromagnetic metals has been studied within the framework of the quantum wells model. The strength of the exchange coupling in the multilayer structure with thin layers of a second ferromagnetic material inserted at the interface of FM/NM/FM sandwich was calculated at various physical situations. In one case the exponential dependence of the exchange coupling on the thickness of the interface ferromagnetic layer has been obtained in striking resemblance to the Parkin experimental results for magnetoresistance (S. S. P. Parkin, Phys. Rev. Lett., 71 (1993) 1641).

Natural Underwater Adhesives

PubMed Central

Stewart, Russell J.; Ransom, Todd C.; Hlady, Vladimir

2011-01-01

The general topic of this review is protein-based underwater adhesives produced by aquatic organisms. The focus is on mechanisms of interfacial adhesion to native surfaces and controlled underwater solidification of natural water-borne adhesives. Four genera that exemplify the broad range of function, general mechanistic features, and unique adaptations are discussed in detail: blue mussels, acorn barnacles, sandcastle worms, and freshwater caddisfly larva. Aquatic surfaces in nature are charged and in equilibrium with their environment, populated by an electrical double layer of ions as well as adsorbed natural polyelectrolytes and microbial biofilms. Surface adsorption of underwater bioadhesives likely occurs by exchange of surface bound ligands by amino acid sidechains, driven primarily by relative affinities and effective concentrations of polymeric functional groups. Most aquatic organisms exploit modified amino acid sidechains, in particular phosphorylated serines and hydroxylated tyrosines (dopa), with high-surface affinity that form coordinative surface complexes. After delivery to the surfaces as a fluid, permanent natural adhesives solidify to bear sustained loads. Mussel plaques are assembled in a manner superficially reminiscent of in vitro layer-by-layer strategies, with sequentially delivered layers associated through Fe(dopa)3 coordination bonds. The adhesives of sandcastle worms, caddisfly larva, and barnacles may be delivered in a form somewhat similar to in vitro complex coacervation. Marine adhesives are secreted, or excreted, into seawater that has a significantly higher pH and ionic strength than the internal environment. Empirical evidence suggests these environment triggers could provide minimalistic, fail-safe timing mechanisms to prevent premature solidification (insolubilization) of the glue within the secretory system, yet allow rapid solidification after secretion. Underwater bioadhesives are further strengthened by secondary covalent curing. PMID:21643511

Carbonation of wollastonite(001) competing hydration: microscopic insights from ion spectroscopy and density functional theory.

PubMed

Longo, Roberto C; Cho, Kyeongjae; Brüner, Philipp; Welle, Alexander; Gerdes, Andreas; Thissen, Peter

2015-03-04

In this paper, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as a model surface of cement and concrete. Total energy calculations based on density functional theory combined with kinetic barrier predictions based on nudge elastic band method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO3(2-)) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (also called early stage hydration) and Ca(2+) ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca(2+) reacts again with CO2 and forms carbonate complexes, ending in a delocalized layer. By means of high-resolution time-of-flight secondary-ion mass spectrometry images, we confirm that hydration can lead to a partially delocalization of Ca(2+) ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by the meaning of low-energy ion-scattering spectroscopy combined with careful discussion about the competing reactions of carbonation vs hydration.

Investigation of Liquid Metal Heat Exchanger Designs for Fission Surface Power

NASA Technical Reports Server (NTRS)

Dyson, Rodger W.; Penswick, Barry; Robbie, Malcolm; Geng, Steven M.

2009-01-01

Fission surface power is an option for future Moon and Mars surface missions. High power nuclear reactor heated Stirling convertors are an option to provide reliable power for long duration outpost operations. This report investigates various design approaches for the liquid metal to acceptor heat exchange and clarifies the details used in the analysis.

Impact of aerodynamic resistance formulations used in two-source modeling of energy exchange from the soil and vegetation using land surface temperature

USDA-ARS?s Scientific Manuscript database

Application of the Two-Source Energy Balance (TSEB) Model using land surface temperature (LST) requires aerodynamic resistance parameterizations for the flux exchange above the canopy layer, within the canopy air space and at the soil/substrate surface. There are a number of aerodynamic resistance f...

Exchange interactions in a dinuclear manganese (II) complex with cyanopyridine-N-oxide bridging ligands

NASA Astrophysics Data System (ADS)

Markosyan, A. S.; Gaidukova, I. Yu.; Ruchkin, A. V.; Anokhin, A. O.; Irkhin, V. Yu.; Ryazanov, M. V.; Kuz'mina, N. P.; Nikiforov, V. N.

2014-01-01

The magnetic properties of dinuclear manganese(II) complex [Mn(hfa)2cpo]2 (where hfa is hexafluoroacetylacetonate anion and cpo is 4-cyanopyridine-N-oxide) are presented. The non-monotonous dependence of magnetic susceptibility is explained in terms of the hierarchy of exchange parameters by using exact diagonalization. The thermodynamic behavior of pure cpo and [Mn(hfa)2(cpo)]2 is simulated numerically by an extrapolation to spin S=5/2. The Mn-Mn exchange integral is evaluated.

CATALYTIC PROMOTION OF THE ADSORPTION OF VANADIUM ON AN ANIONIC EXCHANGE RESIN

DOEpatents

Bailes, R.H.; Ellis, D.A.

1958-08-26

An improvement in the process for the recovery of vanadium from acidic phosphatic solutions is presented. In this process the vanadium is first oxidized to the pentavaleat state, and is then separated by contacting such solutions with an anion exchange resin whereby adsorption of the complexed pentavalent vanadium is effected. The improvement lies in the fact that adsorp tion of the vanadium complex by the anion exchange resin is promoted and improved by providing fiuoride ions in solution to be contacted.

A Water Balance Model for Hill reservoir - Aquifer Exchange Water Flux Quantification and Uncertainty Analysis - Application to the Kamech catchment, Tunisia

NASA Astrophysics Data System (ADS)

Bouteffeha, Maroua; Dagès, Cécile; Bouhlila, Rachida; Raclot, Damien; Molénat, Jérôme

2013-04-01

In Mediterranean regions, food and water demand increase with population growth leading to considerable changes of the land use and agricultural practices. In North Africa, particularly in the Mediterranean zones, hill reservoirs are water harvesting infrastructures that have been increasingly adopted to mobilize runoff and create alternative water resource that can be used to develop agriculture. Hill reservoirs are also used to prevent from silting of downstream dams. Management of water resources collected in these infrastructures requires a good knowledge of their hydrological functioning. In particular, the rate of water exchanges between the reservoir and the underlying aquifer, called surface-subsurface exchange hereafter, is still an open question. The main purpose of the study is to better know the hydrological functioning of hill reservoirs in quantifying at the annual and intra-annual time scales the flux of surface-subsurface exchange and the uncertainty associated to the flux. The approach is based on the hydrological water balance of the hill reservoir. It was applied to the hill reservoir of the 2.6 km² Kamech catchment (Tunisia), which belongs to the long term Mediterranean hydrological observatory OMERE (Voltz and Albergel, 2002). The dense monitoring of the observation catchment allowed quantifying the fluxes of all hydrological processes governing the reservoir hydrology, and their associated uncertainties. The water balance was established by considering water inputs (direct rainfall, waddy and hillslope runoff, surface-subsurface exchange), water outputs (evaporation, spillway discharge) and hill reservoir water volume changes. The surface-subsurface exchange component was deduced as the default closure term in the water balance. The results first demonstrate the ability of the proposed approach to estimate the net surface-subsurface exchange flux and its uncertainty at various time scales. Its application on the Kamech catchment for two hydrological years (09/2009-08/2010 and 09/2010-08/2011) shows that the net surface-subsurface exchange flux is positive, i.e. the infiltration from the hill reservoir to the aquifer predominates the discharge from the aquifer to the reservoir. Moreover the surface-subsurface exchange constitutes the main output component in the water balance. The annual surface-subsurface exchange flux appeared almost constant from one year to the other one whatever the hydrological conditions variability over the catchment. Moreover, the analysis of the intra-annual variability shows that the flux was nearly constant within every year. Reference: Voltz , M. and Albergel , J., 2002. OMERE : Observatoire Méditerranéen de l'Environnement Rural et de l'Eau - Impact des actions anthropiques sur les transferts de masse dans les hydrosystèmes méditerranéens ruraux. Proposition d'Observatoire de Recherche en Environnement, Ministère de la Recherche.

Enhancing Europa surface characterization with ice penetrating radar: A Comparative study in Antarctica

NASA Astrophysics Data System (ADS)

Curra, C.; Arnold, E.; Karwoski, B.; Grima, C.; Schroeder, D. M.; Young, D. A.; Blankenship, D. D.

2013-12-01

The shape and composition of the surface of Europa result from multiple processes, most of them involving direct and indirect interactions between the liquid and solid phases of its outer water layer. The surface ice composition is likely to reflect the material exchanged with the sub-glacial ocean and potentially holds signatures of organic compounds that could demonstrate the ability of the icy moon to sustain life. Therefore, the most likely targets for in-situ landing missions are primarily located in complex terrains disrupted by exchange mechanisms with the ocean/lenses of sub-glacial liquid water. Any landing site selection process to ensure a safe delivery of a future lander, will then have to confidently characterize its surface roughness. We evaluate the capability of an ice-penetrating radar to characterize the roughness using a statistical method applied to the surface echoes. Our approach is to compare radar-derived data with nadir-imagery and laser altimetry simultaneously acquired on an airborne platform over Marie Byrd Land, West Antarctica, during the 2012-13 GIMBLE survey. The radar is the High-Capability Radar Sounder 2 (HiCARS 2, 60 MHz) system operated by the University of Texas Institute for Geophysics (UTIG), with specifications similar to the Ice Penetrating Radar (IPR) of the Europa Clipper project. Surface textures as seen by simultaneously collected nadir imagery are manually classified, allowing individual contrast stretching for better identification. We identified crevasse fields, blue ice patches, and families of wind-blown patterns. Homogeneity/heterogeneity of the textures has also been an important classification criterion. The various textures are geolocated and compared to the evolution and amplitude of laser-derived and radar-derived roughness. Similarities and discrepancies between these three datasets are illustrated and analyzed to qualitatively constrain radar sensitivity to the surface textures. The result allows for a first insight and discussion into how to interpret statistically-inverted radar data from an icy planetary surface.

U-folds as K3 fibrations

NASA Astrophysics Data System (ADS)

Braun, Andreas P.; Fucito, Francesco; Morales, Jose Francisco

2013-10-01

We study four-dimensional flux vacua describing intrinsic non- perturbative systems of 3 and 7 branes in type IIB string theory. The solutions are described as compactifications of a G(ravity) theory on a Calabi Yau threefold which consists of a fibration of an auxiliary K3 surface over an S 2 base. In the spirit of F-theory, the complex structure of the K3 surface varying over the base codifies the details of the fluxes, the dilaton and the warp factors in type IIB string theory. We discuss in detail some simple examples of geometric and non-geometric solutions where the precise flux/geometry dictionary can be explicitly worked out. In particular, we describe non-geometric T-fold solutions exhibiting non-trivial T-duality monodromies exchanging 3- and 7-branes.

Ligand exchange and MIP-based paraoxon memories onto QCM sensor

NASA Astrophysics Data System (ADS)

Birlik Özkütük, Ebru; Emir Diltemiz, Sibel; Özalp, Elif; Uzun, Lokman; Ersöz, Arzu

2015-04-01

In this study, we have aimed to prepare quartz crystal microbalance (QCM) sensor using paraoxon-imprinted particles. Firstly, methacryloyl antipyrine (MAAP)-based metal-chelate-coordinated pre-complex has been prepared and used for paraoxon templation. Then, paraoxon-imprinted nanofilms were formed on QCM sensor after modification of the gold surfaces with allyl mercaptan. By this way, specific and selective memories, which depend on metal-chelate interactions between Eu(III) ions and template, for paraoxon molecules have been obtained on the electrode surface. QCM sensor has characterized using AFM and ellipsometer. The detection limit and the affinity constant have found to be 0.09 μM and 5.71 × 103 M-1 for MAAP-Eu paraoxon-based nanofilm, respectively. The specificity of the QCM sensor has shown using parathion as a competitor molecule.

Suppressing breakers with polar oil films: Using an epic sea rescue to model wave energy budgets

NASA Astrophysics Data System (ADS)

Cox, Charles S.; Zhang, Xin; Duda, Timothy F.

2017-02-01

Oil has been used to still stormy seas for centuries, but the mechanisms are poorly understood. Here we examine the processes by using quantitative information from a remarkable 1883 sea rescue where oil was used to reduce large breakers during a storm. Modeling of the oil film's extent and waves under the film suggests that large breakers were suppressed by a reduction of wind energy input. Modification of surface roughness by the film is hypothesized to alter the wind profile above the sea and the energy flow. The results are central to understanding air-sea momentum exchange, including its role in such processes as cyclone growth and storm surge, although they address only one aspect of the complex problem of wind interaction with the ocean surface.

Giant exchange interaction in mixed lanthanides

PubMed Central

Vieru, Veacheslav; Iwahara, Naoya; Ungur, Liviu; Chibotaru, Liviu F.

2016-01-01

Combining strong magnetic anisotropy with strong exchange interaction is a long standing goal in the design of quantum magnets. The lanthanide complexes, while exhibiting a very strong ionic anisotropy, usually display a weak exchange coupling, amounting to only a few wavenumbers. Recently, an isostructural series of mixed (Ln = Gd, Tb, Dy, Ho, Er) have been reported, in which the exchange splitting is estimated to reach hundreds wavenumbers. The microscopic mechanism governing the unusual exchange interaction in these compounds is revealed here by combining detailed modeling with density-functional theory and ab initio calculations. We find it to be basically kinetic and highly complex, involving non-negligible contributions up to seventh power of total angular momentum of each lanthanide site. The performed analysis also elucidates the origin of magnetization blocking in these compounds. Contrary to general expectations the latter is not always favored by strong exchange interaction. PMID:27087470

Structural and functional characterization of the PNKP–XRCC4–LigIV DNA repair complex

DOE PAGES

Aceytuno, R.  Daniel; Piett, Cortt G.; Havali-Shahriari, Zahra; ...

2017-04-27

Non-homologous end joining (NHEJ) repairs DNA double strand breaks in non-cycling eukaryotic cells. NHEJ relies on polynucleotide kinase/phosphatase (PNKP), which generates 5'-phosphate/3'-hydroxyl DNA termini that are critical for ligation by the NHEJ DNA ligase, LigIV. PNKP and LigIV require the NHEJ scaffolding protein, XRCC4. The PNKP FHA domain binds to the CK2-phosphorylated XRCC4 C-terminal tail, while LigIV uses its tandem BRCT repeats to bind the XRCC4 coiled-coil. Yet, the assembled PNKP-XRCC4-LigIV complex remains uncharacterized. Here, we report purification and characterization of a recombinant PNKP-XRCC4-LigIV complex. We show that the stable binding of PNKP in this complex requires XRCC4 phosphorylation andmore » that only one PNKP protomer binds per XRCC4 dimer. Small angle X-ray scattering (SAXS) reveals a flexiblemultistate complex that suggests that both the PNKP FHA and catalytic domains contact the XRCC4 coiled-coil and LigIV BRCT repeats. Hydrogen-deuterium exchange indicates protection of a surface on the PNKP phosphatase domain that may contact XRCC4-LigIV. Amutation on this surface (E326K) causes the hereditary neuro-developmental disorder, MCSZ. This mutation impairs PNKP recruitment to damaged DNA in human cells and provides a possible disease mechanism. Together, this work unveils multipoint contacts between PNKP and XRCC4-LigIV that regulate PNKP recruitment and activity within NHEJ.« less

Structural and functional characterization of the PNKP–XRCC4–LigIV DNA repair complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aceytuno, R.  Daniel; Piett, Cortt G.; Havali-Shahriari, Zahra

Non-homologous end joining (NHEJ) repairs DNA double strand breaks in non-cycling eukaryotic cells. NHEJ relies on polynucleotide kinase/phosphatase (PNKP), which generates 5'-phosphate/3'-hydroxyl DNA termini that are critical for ligation by the NHEJ DNA ligase, LigIV. PNKP and LigIV require the NHEJ scaffolding protein, XRCC4. The PNKP FHA domain binds to the CK2-phosphorylated XRCC4 C-terminal tail, while LigIV uses its tandem BRCT repeats to bind the XRCC4 coiled-coil. Yet, the assembled PNKP-XRCC4-LigIV complex remains uncharacterized. Here, we report purification and characterization of a recombinant PNKP-XRCC4-LigIV complex. We show that the stable binding of PNKP in this complex requires XRCC4 phosphorylation andmore » that only one PNKP protomer binds per XRCC4 dimer. Small angle X-ray scattering (SAXS) reveals a flexiblemultistate complex that suggests that both the PNKP FHA and catalytic domains contact the XRCC4 coiled-coil and LigIV BRCT repeats. Hydrogen-deuterium exchange indicates protection of a surface on the PNKP phosphatase domain that may contact XRCC4-LigIV. Amutation on this surface (E326K) causes the hereditary neuro-developmental disorder, MCSZ. This mutation impairs PNKP recruitment to damaged DNA in human cells and provides a possible disease mechanism. Together, this work unveils multipoint contacts between PNKP and XRCC4-LigIV that regulate PNKP recruitment and activity within NHEJ.« less

State insurance exchanges face challenges in offering standardized choices alongside innovative value-based insurance.

PubMed

Corlette, Sabrina; Downs, David; Monahan, Christine H; Yondorf, Barbara

2013-02-01

Value-based insurance is a relatively new approach to health insurance in which financial barriers, such as copayments, are lowered for clinical services that are considered high value, while consumer cost sharing may be increased for services considered to be of uncertain value. Such plans are complex and do not easily fit into the simplified, consumer-friendly comparison tools that many state health insurance exchanges are formulating for use in 2014. Nevertheless some states and plans are attempting to strike the right balance between a streamlined health exchange shopping experience and innovative, albeit complex, benefit design that promotes value. For example, agencies administering exchanges in Vermont and Oregon are contemplating offering value-based insurance plans as an option in addition to a set of standardized plans. In the postreform environment, policy makers must find ways to present complex value-based insurance plans in a way that consumers and employers can more readily understand.

Fundamental characteristics study of anion-exchange PVDF-SiO(2) membranes.

PubMed

Zuo, Xingtao; Shi, Wenxin; Yu, Shuili; He, Jiajie

2012-01-01

A new type of poly(vinylidene fluoride)(PVDF)-SiO(2) hybrid anion-exchange membrane was prepared by blending method. The anion-exchange groups were introduced by the reaction of epoxy groups with trimethylamine (TMA). Contact angle between water and the membrane surface was measured to characterize the hydrophilicity change of the membrane surface. The effects of nano-sized SiO(2) particles in the membrane-forming materials on the membrane mechanical properties and conductivity were also investigated. The experimental results indicated that PVDF-SiO(2) anion-exchange membranes exhibited better water content, ion-exchange capacity, conductivity and mechanic properties, and so may find potential applications in alkaline membrane fuel cells and water treatment processes.

A new synthesis route for Os-complex modified redox polymers for potential biofuel cell applications.

PubMed

Pöller, Sascha; Beyl, Yvonne; Vivekananthan, Jeevanthi; Guschin, Dmitrii A; Schuhmann, Wolfgang

2012-10-01

A new synthesis route for Os-complex modified redox polymers was developed. Instead of ligand exchange reactions for coordinative binding of suitable precursor Os-complexes at the polymer, Os-complexes already exhibiting the final ligand shell containing a suitable functional group were bound to the polymer via an epoxide opening reaction. By separation of the polymer synthesis from the ligand exchange reaction at the Os-complex, the modification of the same polymer backbone with different Os-complexes or the binding of the same Os-complex to a number of different polymer backbones becomes feasible. In addition, the Os-complex can be purified and characterized prior to its binding to the polymer. In order to further understand and optimize suitable enzyme/redox polymer systems concerning their potential application in biosensors or biofuel cells, a series of redox polymers was synthesized and used as immobilization matrix for Trametes hirsuta laccase. The properties of the obtained biofuel cell cathodes were compared with similar biocatalytic interfaces derived from redox polymers obtained via ligand exchange reaction of the parent Os-complex with a ligand integrated into the polymer backbone during the polymer synthesis. Copyright © 2011 Elsevier B.V. All rights reserved.

A DFT based ligand field model for magnetic exchange coupling in transition metal dimer complexes:. (ii) application to magnetic systems with more than one unpaired electron per site

NASA Astrophysics Data System (ADS)

Atanasov, M.; Daul, C. A.

2003-11-01

The DFT based ligand field model for magnetic exchange coupling proposed recently, has been extended to systems containing more than one unpaired electron per site. The guidelines for this extension are described using a model example - the complex (NH 3) 3Cr III(OH) 3Cr III (NH 3) 33+. The exchange Hamiltonian, H ex=-J 12S1S2 has been simplified using symmetry principles, i.e. utilizing the D 3h(C 3v) Cr III - dimer(site) symmetry. Both antiferro- and ferromagnetic exchange coupling constants are found to yield important contributions to the value of the (negative, antiferromagnetic) exchange coupling constant in good agreement with experiment.

Recordkeeping alters economic history by promoting reciprocity

PubMed Central

Basu, Sudipta; Dickhaut, John; Hecht, Gary; Towry, Kristy; Waymire, Gregory

2009-01-01

We experimentally demonstrate a causal link between recordkeeping and reciprocal exchange. Recordkeeping improves memory of past interactions in a complex exchange environment, which promotes reputation formation and decision coordination. Economies with recordkeeping exhibit a beneficially altered economic history where the risks of exchanging with strangers are substantially lessened. Our findings are consistent with prior assertions that complex and extensive reciprocity requires sophisticated memory to store information on past transactions. We offer insights on this research by scientifically demonstrating that reciprocity can be facilitated by information storage external to the brain. This is consistent with the archaeological record, which suggests that prehistoric transaction records and the invention of writing for recordkeeping were linked to increased complexity in human interaction. PMID:19147843

A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals.

PubMed

Dong, Angang; Ye, Xingchen; Chen, Jun; Kang, Yijin; Gordon, Thomas; Kikkawa, James M; Murray, Christopher B

2011-02-02

The ability to engineer surface properties of nanocrystals (NCs) is important for various applications, as many of the physical and chemical properties of nanoscale materials are strongly affected by the surface chemistry. Here, we report a facile ligand-exchange approach, which enables sequential surface functionalization and phase transfer of colloidal NCs while preserving the NC size and shape. Nitrosonium tetrafluoroborate (NOBF4) is used to replace the original organic ligands attached to the NC surface, stabilizing the NCs in various polar, hydrophilic media such as N,N-dimethylformamide for years, with no observed aggregation or precipitation. This approach is applicable to various NCs (metal oxides, metals, semiconductors, and dielectrics) of different sizes and shapes. The hydrophilic NCs obtained can subsequently be further functionalized using a variety of capping molecules, imparting different surface functionalization to NCs depending on the molecules employed. Our work provides a versatile ligand-exchange strategy for NC surface functionalization and represents an important step toward controllably engineering the surface properties of NCs.

Spin exchange effects on the physicochemical properties of tetraoxolene-bridged bimetallic complexes.

PubMed

Guo, Dong; McCusker, James K

2007-04-16

The synthesis, physical, and spectroscopic properties of a series of metal complexes bridged by the redox-active chloranilate ligand are described. Compounds containing the (CAcat,cat)4- ligand, where (CAcat,cat)4- represents the fully reduced aromatic form of chloranilate, have been prepared by two different routes from H2CA and H4CA starting materials; the corresponding (CAsq,cat)3- analogue was obtained by one-electron oxidation with decamethylferrocenium tetrafluoroborate. Homo- and heterobimetallic complexes containing CrIII and GaIII with chloranilate have been prepared, yielding the following six complexes: [Ga2(tren)2(CAcat,cat)](BPh4)2 (1), [Ga2(tren)2(CAsq,cat)](BPh4)2(BF4) (2), [GaCr(tren)2(CAcat,cat)](BPh4)2 (3), [GaCr(tren)2(CAsq,cat)](BPh4)2(BF4) (4), [Cr2(tren)2(CAcat,cat)] (BPh4)2 (5), and [Cr2(tren)2(CAsq,cat)](BPh4)2(BF4) (6) (where tren is tris(2-aminoethyl)amine). Single-crystal X-ray structures have been obtained for complexes 1, 3, and 5; nearly identical C-C bond distances within the quinoidal ligand confirm the aromatic character of the bridge in each case. Complex 2 exhibits a temperature-independent magnetic moment of microeff = 1.64 +/- 0.04 microB in the solid state between 4 and 350 K, consistent with the CAsq,cat formulation of the ligand and an S = 1/2 ground state for complex 2. Complex 3 exhibits a value of microeff = 3.44 +/- 0.09 microB that is also temperature-independent, indicating an S = 3/2 ground state. Complexes 4-6 are all influenced by Heisenberg spin exchange. The temperature-independent behavior of complexes 4 and 6 indicate the presence of strong antiferromagnetic exchange between the CrIII and the (sq,cat) bridging radical yielding well-isolated ground states of S = 1 and 5/2 for 4 and 6, respectively. In contrast, complex 5 exhibits a weak intramolecular antiferromagnetic exchange interaction between the two CrIII centers (J = -2 cm-1 for H = -2Jŝ1.ŝ2) via superexchange through the diamagnetic CAcat,cat bridge. The absorption spectra of the CAsq,cat-containing complexes exhibit a number of sharp, relatively intense features in fluid solution. Group theoretical arguments coupled with a qualitative ligand-field analysis including the effects of Heisenberg spin exchange suggest that several of the observed transitions are a consequence of exchange interactions in both the ground- and excited-state manifolds of the compounds.

Crocodiles count on it: Regulation of discharge to Lake St Lucia Estuary by a South African peatland

NASA Astrophysics Data System (ADS)

Price, J. S.; Grundling, P.; Grootjans, A.

2010-12-01

The Mfabeni mire is located within the iSimangaliso Wetland Park in north-eastern KwaZulu-Natal Province on the Indian Ocean sea-board of South Africa. This mire complex includes open peatland with occurrences of sedge communities, Sphagnum (rare in South Africa), and swamp forest which is common in the region (but rare in South Africa). It is one of the largest (1650 ha), thickest (10.8 m of peat) and the oldest (~45,000 years Before Present) known peatlands in South Africa. The mire is almost pristine, with very few disturbances. In the past the surrounding area supported pine plantations but these alien trees were recently removed, with conservation and tourism the primary designated activities. Surface and groundwater exchanges to and within the mire and its surrounding coastal dune landscape were studied. Profiles of electrical conductivity and major cations and anions, as well as natural isotopes (δ2H and δ18O) in water samples of ground and surface water were also analysed to develop a conceptual model of the system’s hydrological function. Water efflux from an inland dune complex provides substantial recharge towards Mfabeni, while coastward hydraulic gradients from the dune complex through the wetland are evident. Consequently, the linkages between the dune system and Mfabeni, and the peatland’s water regulation function, dictate the nature and magnitude of the local freshwater discharge to the estuary, and internal water exchanges that control peatland ecological function. The hydrograph from the stream outlet indicate an initial rapid response in increased flows after major rainfall events but with a delayed drawdown over time reflecting the contribution of the relatively large size of the mire (comprising 38% of the catchment) in attenuating flood events and ensuring sustained flow to the estuary. Freshwater discharge from the Mfabeni mire to the St. Lucia estuary, which has provided refuge for aquatic species during periods of drought, may become crucial under a more erratic climate.

Development of a Direct Contact Heat Exchanger, Phase 1 Study Report

NASA Technical Reports Server (NTRS)

Manvi, R.

1978-01-01

Electric power generation from geothermal brine requires, first, bringing the hot brine to the surface and then converting the heat to electric power. Binary conversion schemes were proposed, with the heat transfer between the brine and the working organic fluid taking place in a conventional tube and shell heat exchanger. If the brine is heavily laden with dissolved solids, however, solids buildup on the heat exchanger surfaces leads to a considerable degree of fouling and an accompanying drop in performance is experienced. A possible solution to this problem is the use of a direct contact exchanger with the secondary fluid power cycle. The proposed concept involves the formation of fluid sheets and bells as heat angles. Results of a study concerning the fluid mechanics of such surfaces are given.

The impact of changing the land surface scheme in ACCESS(v1.0/1.1) on the surface climatology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kowalczyk, Eva A.; Stevens, Lauren E.; Law, Rachel M.

The Community Atmosphere Biosphere Land Exchange (CABLE) model has been coupled to the UK Met Office Unified Model (UM) within the existing framework of the Australian Community Climate and Earth System Simulator (ACCESS), replacing the Met Office Surface Exchange Scheme (MOSES). Here we investigate how features of the CABLE model impact on present-day surface climate using ACCESS atmosphere-only simulations. The main differences attributed to CABLE include a warmer winter and a cooler summer in the Northern Hemisphere (NH), earlier NH spring runoff from snowmelt, and smaller seasonal and diurnal temperature ranges. The cooler NH summer temperatures in canopy-covered regions aremore » more consistent with observations and are attributed to two factors. Firstly, CABLE accounts for aerodynamic and radiative interactions between the canopy and the ground below; this placement of the canopy above the ground eliminates the need for a separate bare ground tile in canopy-covered areas. Secondly, CABLE simulates larger evapotranspiration fluxes and a slightly larger daytime cloud cover fraction. Warmer NH winter temperatures result from the parameterization of cold climate processes in CABLE in snow-covered areas. In particular, prognostic snow density increases through the winter and lowers the diurnally resolved snow albedo; variable snow thermal conductivity prevents early winter heat loss but allows more heat to enter the ground as the snow season progresses; liquid precipitation freezing within the snowpack delays the building of the snowpack in autumn and accelerates snow melting in spring. Altogether we find that the ACCESS simulation of surface air temperature benefits from the specific representation of the turbulent transport within and just above the canopy in the roughness sublayer as well as the more complex snow scheme in CABLE relative to MOSES.« less

The impact of changing the land surface scheme in ACCESS(v1.0/1.1) on the surface climatology

DOE PAGES

Kowalczyk, Eva A.; Stevens, Lauren E.; Law, Rachel M.; ...

2016-08-23

The Community Atmosphere Biosphere Land Exchange (CABLE) model has been coupled to the UK Met Office Unified Model (UM) within the existing framework of the Australian Community Climate and Earth System Simulator (ACCESS), replacing the Met Office Surface Exchange Scheme (MOSES). Here we investigate how features of the CABLE model impact on present-day surface climate using ACCESS atmosphere-only simulations. The main differences attributed to CABLE include a warmer winter and a cooler summer in the Northern Hemisphere (NH), earlier NH spring runoff from snowmelt, and smaller seasonal and diurnal temperature ranges. The cooler NH summer temperatures in canopy-covered regions aremore » more consistent with observations and are attributed to two factors. Firstly, CABLE accounts for aerodynamic and radiative interactions between the canopy and the ground below; this placement of the canopy above the ground eliminates the need for a separate bare ground tile in canopy-covered areas. Secondly, CABLE simulates larger evapotranspiration fluxes and a slightly larger daytime cloud cover fraction. Warmer NH winter temperatures result from the parameterization of cold climate processes in CABLE in snow-covered areas. In particular, prognostic snow density increases through the winter and lowers the diurnally resolved snow albedo; variable snow thermal conductivity prevents early winter heat loss but allows more heat to enter the ground as the snow season progresses; liquid precipitation freezing within the snowpack delays the building of the snowpack in autumn and accelerates snow melting in spring. Altogether we find that the ACCESS simulation of surface air temperature benefits from the specific representation of the turbulent transport within and just above the canopy in the roughness sublayer as well as the more complex snow scheme in CABLE relative to MOSES.« less

NCHRP peer exchange 2008.

DOT National Transportation Integrated Search

2008-09-01

Peer exchanges for state department of transportation (DOT) research programs originated with : the Intermodal Surface Transportation Efficiency Act of 1991 (ISTEA). That federal legislation : required the states to conduct periodic peer exchanges to...

77 FR 10016 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-21

... attractive to members and their customers. The Exchange believes that adopting maker/taker fees and rebates... Exchange believes it remains an attractive venue for market participants to trade complex orders as its... proposed fee change, the Exchange believes it remains an attractive venue for market participants to trade...

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

USGS Publications Warehouse

Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

2004-01-01

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the pKa2 and ?? values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER. ?? 2003 Elsevier Ltd. All rights reserved.

Radon (222Rn) in ground water of fractured rocks: A diffusion/ion exchange model

USGS Publications Warehouse

Wood, W.W.; Kraemer, T.F.; Shapiro, A.

2004-01-01

Ground waters from fractured igneous and high-grade sialic metamorphic rocks frequently have elevated activity of dissolved radon (222Rn). A chemically based model is proposed whereby radium (226Ra) from the decay of uranium (238U) diffuses through the primary porosity of the rock to the water-transmitting fracture where it is sorbed on weathering products. Sorption of 226Ra on the fracture surface maintains an activity gradient in the rock matrix, ensuring a continuous supply of 226Ra to fracture surfaces. As a result of the relatively long half-life of 226Ra (1601 years), significant activity can accumulate on fracture surfaces. The proximity of this sorbed 226Ra to the active ground water flow system allows its decay progeny 222Rn to enter directly into the water. Laboratory analyses of primary porosity and diffusion coefficients of the rock matrix, radon emanation, and ion exchange at fracture surfaces are consistent with the requirements of a diffusion/ion- exchange model. A dipole-brine injection/withdrawal experiment conducted between bedrock boreholes in the high-grade metamorphic and granite rocks at the Hubbard Brook Experimental Forest, Grafton County, New Hampshire, United States (42??56???N, 71??43???W) shows a large activity of 226Ra exchanged from fracture surfaces by a magnesium brine. The 226Ra activity removed by the exchange process is 34 times greater than that of 238U activity. These observations are consistent with the diffusion/ion-exchange model. Elutriate isotopic ratios of 223Ra/226Ra and 238U/226Ra are also consistent with the proposed chemically based diffusion/ion-exchange model.

Investigation and optimization of the depth of flue gas heat recovery in surface heat exchangers

NASA Astrophysics Data System (ADS)

Bespalov, V. V.; Bespalov, V. I.; Melnikov, D. V.

2017-09-01

Economic issues associated with designing deep flue gas heat recovery units for natural gas-fired boilers are examined. The governing parameter affecting the performance and cost of surface-type condensing heat recovery heat exchangers is the heat transfer surface area. When firing natural gas, the heat recovery depth depends on the flue gas temperature at the condenser outlet and determines the amount of condensed water vapor. The effect of the outlet flue gas temperature in a heat recovery heat exchanger on the additionally recovered heat power is studied. A correlation has been derived enabling one to determine the best heat recovery depth (or the final cooling temperature) maximizing the anticipated reduced annual profit of a power enterprise from implementation of energy-saving measures. Results of optimization are presented for a surface-type condensing gas-air plate heat recovery heat exchanger for the climatic conditions and the economic situation in Tomsk. The predictions demonstrate that it is economically feasible to design similar heat recovery heat exchangers for a flue gas outlet temperature of 10°C. In this case, the payback period for the investment in the heat recovery heat exchanger will be 1.5 years. The effect of various factors on the optimal outlet flue gas temperature was analyzed. Most climatic, economical, or technological factors have a minor effect on the best outlet temperature, which remains between 5 and 20°C when varying the affecting factors. The derived correlation enables us to preliminary estimate the outlet (final) flue gas temperature that should be used in designing the heat transfer surface of a heat recovery heat exchanger for a gas-fired boiler as applied to the specific climatic conditions.

Adsorption-desorption mechanism of phosphate by immobilized nano-sized magnetite layer: interface and bulk interactions.

PubMed

Zach-Maor, Adva; Semiat, Raphael; Shemer, Hilla

2011-11-15

Phosphate adsorption mechanism by a homogenous porous layer of nano-sized magnetite particles immobilized onto granular activated carbon (nFe-GAC) was studied for both interface and bulk structures. X-ray Photoelectron Spectroscopy (XPS) analysis revealed phosphate bonding to the nFe-GAC predominantly through bidentate surface complexes. It was established that phosphate was adsorbed to the magnetite surface mainly via ligand exchange mechanism. Initially, phosphate was adsorbed by the active sites on the magnetite surface, after which it diffused into the interior of the nano-magnetite layer, as indicated by intraparticle diffusion model. This diffusion process continues regardless of interface interactions, revealing some of the outer magnetite binding sites for further phosphate uptake. Desorption, using NaOH solution, was found to be predominantly a surface reaction, at which hydroxyl ions replace the adsorbed phosphate ions only at the surface outer biding sites. Five successive fix-bed adsorption/regeneration cycles were successfully applied, without significant reduction in the nFe-GAC adsorption capacity and at high regeneration efficiency. Copyright © 2011 Elsevier Inc. All rights reserved.

Magnetic Exchange Couplings from Semilocal Functionals Evaluated Nonself-Consistently on Hybrid Densities: Insights on Relative Importance of Exchange, Correlation, and Delocalization.

PubMed

Phillips, Jordan J; Peralta, Juan E

2012-09-11

Semilocal functionals generally yield poor magnetic exchange couplings for transition-metal complexes, typically overpredicting in magnitude the experimental values. Here we show that semilocal functionals evaluated nonself-consistently on densities from hybrid functionals can yield magnetic exchange couplings that are greatly improved with respect to their self-consistent semilocal values. Furthermore, when semilocal functionals are evaluated nonself-consistently on densities from a "half-and-half" hybrid, their errors with respect to experimental values can actually be lower than those from self-consistent calculations with standard hybrid functionals such as PBEh or TPSSh. This illustrates that despite their notoriously poor performance for exchange couplings, for many systems semilocal functionals are capable of delivering accurate relative energies for magnetic states provided that their electron delocalization error is corrected. However, while self-consistent calculations with hybrids uniformly improve results for all complexes, evaluating nonself-consistently with semilocal functionals does not give a balanced improvement for both ferro- and antiferromagnetically coupled complexes, indicating that there is more at play with the overestimation problem than simply the delocalization error. Additionally, we show that for some systems the conventional wisdom of choice of exchange functional mattering more than correlation does not hold. This combined with results from the nonself-consistent calculations provide insight on clarifying the relative roles of exchange, correlation, and delocalization in calculating magnetic exchange coupling parameters in Kohn-Sham Density Functional Theory.

In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

NASA Astrophysics Data System (ADS)

Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

2017-04-01

Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ. In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage.

Synthesis and structural characterization of betaine- and imidazoline-based organoclays

NASA Astrophysics Data System (ADS)

Lazorenko, Georgy; Kasprzhitskii, Anton; Yavna, Victor

2018-01-01

The samples of organic-modified clays based on a Wyoming SWy-2 sodium montmorillonite (Na+-Mt) with the cationic surfactant hydroxyethylalkyl imidazoline (HEAI) and the amphoteric surfactant oleylamidopropyl betaine (OAPB) were synthesized via a cation exchange process. The obtained materials were characterized using XRD analysis, ATR-FTIR spectroscopy, SEM, BET and Water contact angle measurements. The potential sites of binding of OAPB and HEAI to the mineral surface were determined by the DFT calculations. For the variants of the structure of the complex, DFT calculations is performed and the interaction energy of the surfactant and clay mineral is estimated.

Preservation of NOM-metal complexes in a modern hyperalkaline stalagmite: Implications for speleothem trace element geochemistry

NASA Astrophysics Data System (ADS)

Hartland, Adam; Fairchild, Ian J.; Müller, Wolfgang; Dominguez-Villar, David

2014-03-01

We report the first quantitative study of the capture of colloidal natural organic matter (NOM) and NOM-complexed trace metals (V, Co, Cu, Ni) in speleothems. This study combines published NOM-metal dripwater speciation measurements with high-resolution laser ablation ICPMS (LA-ICPMS) and sub-annual stable isotope ratio (δ18O and δ13C), fluorescence and total organic carbon (TOC) analyses of a fast-growing hyperalkaline stalagmite (pH ˜11) from Poole’s Cavern, Derbyshire UK, which formed between 1997 and 2008 AD. We suggest that the findings reported here elucidate trace element variations arising from colloidal transport and calcite precipitation rate changes observed in multiple, natural speleothems deposited at ca. pH 7-8. We find that NOM-metal(aq) complexes on the boundary between colloidal and dissolved (˜1 nm diameter) show an annual cyclicity which is inversely correlated with the alkaline earth metals and is explained by calcite precipitation rate changes (as recorded by kinetically-fractionated stable isotopes). This relates to the strength of the NOM-metal complexation reaction, resulting in very strongly bound metals (Co in this system) essentially recording NOM co-precipitation (ternary complexation). More specifically, empirical partition coefficient (Kd) values between surface-reactive metals (V, Co, Cu, Ni) [expressed as ratio of trace element to Ca ratios in calcite and in solution] arise from variations in the ‘free’ fraction of total metal in aqueous solution (fm). Hence, differences in the preservation of each metal in calcite can be explained quantitatively by their complexation behaviour with aqueous NOM. Differences between inorganic Kd values and field measurements for metal partitioning into calcite occur where [free metal] ≪ [total metal] due to complexation reactions between metals and organic ligands (and potentially inorganic colloids). It follows that where fm ≈ 0, apparent inorganic Kd app values are also ≈0, but the true partition coefficient (Kd actual) is significantly higher. Importantly, the Kd of NOM-metal complexes [organic carbon-metal ratio) approaches 1 for the most stable aqueous complexes, as is shown here for Co, but has values of 24-150 for V, Ni and Cu. This implies that ternary surface complexation (metal-ligand co-adsorption) can occur (as for NOM-Co), but is the exception rather than the rule. We also demonstrate the potential for trace metals to record information on NOM composition as expressed through changing NOM-metal complexation patterns in dripwaters. Therefore, a suite of trace metals in stalagmites show variations clearly attributable to changes in organic ligand concentration and composition, and which potentially reflect the state of overlying surface ecosystems. The heterogeneous speciation and size distribution of aqueous NOM and metals (Lead and Wilkinson, 2006; Aiken et al., 2011). The variability in NOM-metal transport in caves that arises from the interaction between infiltration, flow routing, and the hydrodynamic properties of the fine colloids and particulates (Hartland et al., 2012). Variable dissociation kinetics through time as a function of (a) (Hartland et al., 2011). The surface charge of calcite and the availability of CaCO3 lattice sites as well as increased incidence of crystallographic defects with implications for incorporation of a range of trace species (Fairchild and Treble, 2009; Fairchild and Hartland, 2010). Thus, incorporation in speleothem calcite with consistent surface site properties will be determined by: The size and composition (i.e. hydrophilicity/hydrophobicity) of the NOM ligand, affecting adsorption and stability at the calcite surface. The lability (i.e. exchangeability) of the complexed metal and its binding affinity for the calcite surface. The concentration of aqueous complexes. Given the complexities, a partitioning approach to the problem is appropriate as a first approximation rather than a precise description. This study seeks to make the first quantitative connection between the organic and inorganic compositions of speleothems and thus determine the potential for speleothems to encode fluctuations in colloid-facilitated trace metal transport in karst aquifers. Recent findings of direct relevance to the present studyThe conjugate dripwater (PE1) to the stalagmite studied here (PC-08-1) was characterised in June 2009 using an array of complementary techniques, in which the size, speciation and lability of NOM-metal complexes was characterised (Hartland et al., 2011), where lability is defined as the capacity for complexes to dissociate in the context of the on-going interfacial process at the stalagmite surface. In PE1 dripwater, the most stable aqueous complexes were formed between Co and the finest, low molecular weight component of the NOM spectrum (Hartland et al., 2011). Speciation experiments demonstrated that Co was essentially non-exchangeable (free metal (fm) = <0.05), being retained in aqueous complexes, whilst Cu, Ni and V were all predominantly bound by NOM (fm = 0.2-0.3).In contrast, Sr and Ba were freely exchangeable between the solution and solid phase (Hartland et al., 2011) and Mg was absent, presumably due to the poor solubility of Mg(OH)2 at hyperalkaline pH (Ksp = 1.5 × 10-11): Mg2+(aq)+2OH-(aq)↔Mg( On the other hand, the transition metals were not lost as insoluble hydroxides (Hartland et al., 2012), despite having lower solubility than Mg (e.g. Cu(OH)2Ksp = 2.2 × 10-20); and this is consistent with the dominant role of NOM in solubilising and transporting the transition metals in this system (Hartland et al., 2011).The transport of metals by complexes with NOM in PE1 dripwater through the hydrological year was studied by Hartland et al. (2012). This study had two findings of direct relevance to the study of trace metal variations in the conjugate PC-08-1 stalagmite: Complexes between metals and the smallest, low-molecular weight fraction of NOM showed an attenuated delivery in dripwaters consistent with the non-conservative behaviour of analogous tracers in fractured-rock studies due to diffusion into micro-fractures. This mode of transport was termed ‘low-flux’ and was the dominant mode of transport for Co and V. Complexes between metals and coarse colloids (>100 nm) and particulates (>1000 nm) showed a rapid responsiveness to infiltration events. This was termed the ‘high-flux’ mode of NOM-metal transport and was interpreted as being dominantly fracture-fed. This mode of transport was dominated by Cu, Zn and Ni. The ‘high-flux’ vs ‘low-flux’ interplay of trace metal transport is summarised in Fig. 1.The PC-08-1 stalagmite studied here was deposited following the removal of stalagmite PC-97-1 studied by Baker et al. (1999b) and which grew under the PE1 drip point between 1927 and 1997. Both the PC-97-1 stalagmite and its regrowth (PC-08-1) are characterised by annual lamina couplets consisting of a porous pale layer and a dense fluorescent layer. Fluorescence in the PC-97-1 stalagmite displayed a marked sinusoidal pattern with 10% of laminae exhibiting a double band structure (Baker et al., 1999b).

Sorption properties of Th(IV) on the raw diatomite--effects of contact time, pH, ionic strength and temperature.

PubMed

Sheng, Guodong; Hu, Jun; Wang, Xiangke

2008-10-01

Diatomite has a number of unique physicochemical properties and has diversified industrial uses. Natural diatomite has been tested as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that sorption of Th(IV) is strongly dependent on ionic strength at pH<3, and is independent of ionic strength at pH>3. Outer-sphere complexation or ion exchange may be the main sorption mechanism of Th(IV) to diatomite at low pH values, whereas the sorption of Th(IV) at pH>3 is mainly dominated by inner-sphere complexation or precipitation. The competition for Th(IV) between aqueous or surface adsorbed anions (e.g., herein ClO(4)(-), NO(3)(-) and Cl(-)) and surface functional groups of diatomite is important for Th(IV) sorption. The thermodynamic data (DeltaH(0), DeltaS(0), DeltaG(0)) are calculated from the temperature-dependent sorption isotherms. The results suggest that sorption process of Th(IV) on diatomite is spontaneous and endothermic.

Truly incomplete and complex exchanges in prematurely condensed chromosomes of human fibroblasts exposed in vitro to energetic heavy ions

NASA Technical Reports Server (NTRS)

Wu, Honglu; Durante, Marco; Furusawa, Yoshiya; George, Kerry; Kawata, Tetsuya; Cucinotta, Francis A.

2003-01-01

Confluent human fibroblast cells (AG1522) were irradiated with gamma rays, 490 MeV/nucleon silicon ions, or iron ions at either 200 or 500 MeV/nucleon. The cells were allowed to repair at 37 degrees C for 24 h after exposure, and a chemically induced premature chromosome condensation (PCC) technique was used to condense chromosomes in the G2 phase of the cell cycle. Incomplete and complex exchanges were analyzed in the irradiated samples. To verify that chromosomal breaks were truly unrejoined, chromosome aberrations were analyzed using a combination of whole-chromosome specific probes and probes specific for the telomere region of the chromosome. Results showed that the frequency of unrejoined chromosome breaks was higher after irradiation with the heavy ions of high LET, and consequently the ratio of incomplete to complete exchanges increased steadily with LET up to 440 keV/microm, the highest LET included in the present study. For samples exposed to 200 MeV/nucleon iron ions, chromosome aberrations were analyzed using the multicolor FISH (mFISH) technique, which allows identification of both complex and truly incomplete exchanges. Results of the mFISH study showed that 0.7 and 3 Gy iron ions produced similar ratios of complex to simple exchanges and incomplete to complete exchanges; these ratios were higher than those obtained after exposure to 6 Gy gamma rays. After 0.7 Gy of iron ions, most complex aberrations were found to involve three or four chromosomes, which is a likely indication of the maximum number of chromosome domains traversed by a single iron-ion track.

Evaluate the Relative Importance of Subsurface Lateral Energy Exchange to Ground Heat Flux and Energy Balance over the Heterogeneous Surface of a Sub-tropical Wetland

NASA Astrophysics Data System (ADS)

CUI, W.; Chui, T. F. M.

2016-12-01

Subsurface lateral water and energy exchanges are often ignored in methods involving a surface energy balance under the homogeneity assumption, which may affect the estimation of evapotranspiration over a heterogeneous surface. Wetlands, however, are heterogeneous with vegetated areas and open water, making it difficult to accurately measure and estimate evapotranspiration. This study estimated the subsurface lateral energy exchange between the reed bed and shallow open water of a wetland within Mai Po Nature Reserve in Hong Kong, and further discussed its relative importance to the ground heat flux and energy balance over the wetland surface. An array of water level and temperature sensors were installed in the reed bed and the adjacent water, together with an eddy covariance system. The results suggested that the lateral energy exchange was over 30% of ground heat flux for half of the monitoring period, and should therefore be accounted for during the measurement of ground heat flux. However, the lateral energy exchange could not explain the energy balance disclosure at the site, as the variation was in phase with the residual of energy budget during the summer but was out of phase during the winter. Furthermore, this study developed a convolution model to estimate the lateral energy exchange based on air temperature which is readily available at many sites worldwide. This study overall enhanced our understanding of the subsurface lateral energy exchange, and possibly our estimation of evapotranspiration in heterogeneous environment.

Testing complex networks of interaction at the onset of the Near Eastern Neolithic using modelling of obsidian exchange

PubMed Central

Ibáñez, Juan José; Ortega, David; Campos, Daniel; Khalidi, Lamya; Méndez, Vicenç

2015-01-01

In this paper, we explore the conditions that led to the origins and development of the Near Eastern Neolithic using mathematical modelling of obsidian exchange. The analysis presented expands on previous research, which established that the down-the-line model could not explain long-distance obsidian distribution across the Near East during this period. Drawing from outcomes of new simulations and their comparison with archaeological data, we provide results that illuminate the presence of complex networks of interaction among the earliest farming societies. We explore a network prototype of obsidian exchange with distant links which replicates the long-distance movement of ideas, goods and people during the Early Neolithic. Our results support the idea that during the first (Pre-Pottery Neolithic A) and second (Pre-Pottery Neolithic B) phases of the Early Neolithic, the complexity of obsidian exchange networks gradually increased. We propose then a refined model (the optimized distant link model) whereby long-distance exchange was largely operated by certain interconnected villages, resulting in the appearance of a relatively homogeneous Neolithic cultural sphere. We hypothesize that the appearance of complex interaction and exchange networks reduced risks of isolation caused by restricted mobility as groups settled and argue that these networks partially triggered and were crucial for the success of the Neolithic Revolution. Communities became highly dynamic through the sharing of experiences and objects, while the networks that developed acted as a repository of innovations, limiting the risk of involution. PMID:25948614

78 FR 66980 - Self-Regulatory Organizations; BOX Options Exchange LLC; Notice of Designation of Longer Period...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-11-07

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-70797; File No. SR-BOX-2013-43] Self-Regulatory... Proposed Rule Change To Permit Complex Orders To Participate in Price Improvement Periods November 1, 2013... to permit Complex Orders to participate in Price Improvement Periods (the ``COPIP'') and to make...

Cyclometalated products of [(COE)(2)RhCl](2) and 1,3-(RSCH(2))(2)C(6)H(4) (R = (t)Bu, (i)Pr) Are Dimeric. Synthesis, molecular structures, and solution dynamics of [mu-ClRh(H)(RSCH(2))(2)C(6)H(3)-2,6](2).

PubMed

Evans, Daniel R; Huang, Mingsheng; Seganish, W Michael; Chege, Esther W; Lam, Yiu-Fai; Fettinger, James C; Williams, Tracie L

2002-05-20

Two tridentate thioether pincer ligands, 1,3-(RSCH(2))(2)C(6)H(4) (R = (t)()Bu, 1a; R = (i)()Pr, 1b) underwent cyclometalation using [(COE)(2)RhCl](2) in air/moisture-free benzene at room temperature. The resultant complexes, [mu-ClRh(H)(RSCH(2))(2)C(6)H(3)-2,6](2) (R = (t)Bu, 2a; R = (i)Pr, 2b) are dimeric both in the solid state and in solution. A battery of variable-temperature one- and two-dimensional (1)H NMR experiments showed conclusively that both complexes undergo dynamic exchange in solution. Exchange between two dimeric diastereomers of 2a in solution occurred via rotation about the Rh-C(ipso) bond. The dynamic exchange of 2b was significantly more complex as an additional exchange mechanism, sulfur inversion, occurred, which resulted in the exchange between several diastereomers in solution.

Concomitant Zn-Cd and Pb retention in a carbonated fluvio-glacial deposit under both static and dynamic conditions.

PubMed

Lassabatere, Laurent; Spadini, Lorenzo; Delolme, Cécile; Février, Laureline; Galvez Cloutier, Rosa; Winiarski, Thierry

2007-11-01

The chemical and physical processes involved in the retention of 10(-2)M Zn, Pb and Cd in a calcareous medium were studied under saturated dynamic (column) and static (batch) conditions. Retention in columns decreased in order: Pb>Cd approximately Zn. In the batch experiments, the same order was observed for a contact time of less than 40h and over, Pb>Cd>Zn. Stronger Pb retention is in accordance with the lower solubility of Pb carbonates. However, the equality of retained Zn and Cd does not fit the solubility constants of carbonated solids. SEM analysis revealed that heavy metals and calcareous particles are associated. Pb precipitated as individualized Zn-Cd-Ca- free carbonated crystallites. All the heavy metals were also found to be associated with calcareous particles, without any change in their porosity, pointing to a surface/lattice diffusion-controlled substitution process. Zn and Cd were always found in concomitancy, though Pb fixed separately at the particle circumferences. The Phreeqc 2.12 interactive code was used to model experimental data on the following basis: flow fractionation in the columns, precipitation of Pb as cerrusite linked to kinetically controlled calcite dissolution, and heavy metal sorption onto proton exchanging sites (presumably surface complexation onto a calcite surface). This model simulates exchanges of metals with surface protons, pH buffering and the prevention of early Zn and Cd precipitation. Both modeling and SEM analysis show a probable significant decrease of calcite dissolution along with its contamination with metals.

Local Heat Transfer for Finned-Tube Heat Exchangers using Oval Tubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

O'Brien, James Edward; Sohal, Manohar Singh

2000-08-01

This paper presents the results of an experimental study of forced convection heat transfer in a narrow rectangular duct fitted with either a circular tube or an elliptical tube in crossflow. The duct was designed to simulate a single passage in a fin-tube heat exchanger. Heat transfer measurements were obtained using a transient technique in which a heated airflow is suddenly introduced to the test section. High-resolution local fin-surface temperature distributions were obtained at several times after initiation of the transient using an imaging infrared camera. Corresponding local fin-surface heat transfer coefficient distributions were then calculated from a locally appliedmore » one-dimensional semi-infinite inverse heat conduction model. Heat transfer results were obtained over an airflow rate ranging from 1.56 x 10-3 to 15.6 x 10-3 kg/s. These flow rates correspond to a duct-height Reynolds number range of 630 – 6300 with a duct height of 1.106 cm and a duct width-toheight ratio, W/H, of 11.25. The test cylinder was sized such that the diameter-to-duct height ratio, D/H is 5. The elliptical tube had an aspect ratio of 3:1 and a/H equal to 4.33. Results presented in this paper reveal visual and quantitative details of local fin-surface heat transfer distributions in the vicinity of circular and oval tubes and their relationship to the complex horseshoe vortex system that forms in the flow stagnation region. Fin surface stagnation-region Nusselt numbers are shown to be proportional to the square-root of Reynolds number.« less

Microbiological investigation of an industrial ultra pure supply water plant using cultivation-based and cultivation-independent methods.

PubMed

Bohus, Veronika; Tóth, Erika M; Székely, Anna J; Makk, Judit; Baranyi, Krisztián; Patek, Gábor; Schunk, János; Márialigeti, Károly

2010-12-01

Ultra pure waters (UPW), characterized by extremely low salt and nutrient concentrations, can suffer from microbial contamination which causes biofouling and biocorrosion, possibly leading to reduced lifetime and increased operational costs. Samples were taken from an ultra pure supply water producing plant of a power plant. Scanning electron microscopic examination was carried out on the biofilms formed in the system. Biofilm, ion exchange resin, and water samples were characterized by culture-based methods and molecular fingerprinting (terminal restriction fragment length polymorphism [T-RFLP] analysis and molecular cloning). Identification of bacteria was based on 16S rDNA sequence comparison. A complex microbial community structure was revealed. Nearly 46% of the clones were related to as yet uncultured bacteria. The community profiles of the water samples were the most diverse and most of bacteria were recruited from bacterial communities of tube surface and ion exchange resin biofilms. Microbiota of different layers of the mixed bed ion exchange resin showed the highest similarity. Most of the identified taxa (dominated by β-Proteobacteria) could take part in microbially influenced corrosion. Copyright © 2010 Elsevier Ltd. All rights reserved.

The Cdc42 guanine nucleotide exchange factor FGD6 coordinates cell polarity and endosomal membrane recycling in osteoclasts.

PubMed

Steenblock, Charlotte; Heckel, Tobias; Czupalla, Cornelia; Espírito Santo, Ana Isabel; Niehage, Christian; Sztacho, Martin; Hoflack, Bernard

2014-06-27

The initial step of bone digestion is the adhesion of osteoclasts onto bone surfaces and the assembly of podosomal belts that segregate the bone-facing ruffled membrane from other membrane domains. During bone digestion, membrane components of the ruffled border also need to be recycled after macropinocytosis of digested bone materials. How osteoclast polarity and membrane recycling are coordinated remains unknown. Here, we show that the Cdc42-guanine nucleotide exchange factor FGD6 coordinates these events through its Src-dependent interaction with different actin-based protein networks. At the plasma membrane, FGD6 couples cell adhesion and actin dynamics by regulating podosome formation through the assembly of complexes comprising the Cdc42-interactor IQGAP1, the Rho GTPase-activating protein ARHGAP10, and the integrin interactors Talin-1/2 or Filamin A. On endosomes and transcytotic vesicles, FGD6 regulates retromer-dependent membrane recycling through its interaction with the actin nucleation-promoting factor WASH. These results provide a mechanism by which a single Cdc42-exchange factor controlling different actin-based processes coordinates cell adhesion, cell polarity, and membrane recycling during bone degradation. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Spin-wave resonance frequency in ferromagnetic thin film with interlayer exchange coupling and surface anisotropy

NASA Astrophysics Data System (ADS)

Zhang, Shuhui; Rong, Jianhong; Wang, Huan; Wang, Dong; Zhang, Lei

2018-01-01

We have investigated the dependence of spin-wave resonance(SWR) frequency on the surface anisotropy, the interlayer exchange coupling, the ferromagnetic layer thickness, the mode number and the external magnetic field in a ferromagnetic superlattice film by means of the linear spin-wave approximation and Green's function technique. The SWR frequency of the ferromagnetic thin film is shifted to higher values corresponding to those of above factors, respectively. It is found that the linear behavior of SWR frequency curves of all modes in the system is observed as the external magnetic field is increasing, however, SWR frequency curves are nonlinear with the lower and the higher modes for different surface anisotropy and interlayer exchange coupling in the system. In addition, the SWR frequency of the lowest (highest) mode is shifted to higher (lower) values when the film thickness is thinner. The interlayer exchange coupling is more important for the energetically higher modes than for the energetically lower modes. The surface anisotropy has a little effect on the SWR frequency of the highest mode, when the surface anisotropy field is further increased.

Wireless majorana fermions: from magnetic tunability to braiding (Conference Presentation)

NASA Astrophysics Data System (ADS)

Fatin, Geoffrey L.; Matos-Abiague, Alex; Scharf, Benedikt; Zutic, Igor

2016-10-01

In condensed-matter systems Majorana bound states (MBSs) are emergent quasiparticles with non-Abelian statistics and particle-antiparticle symmetry. While realizing the non-Abelian braiding statistics under exchange would provide both an ultimate proof for MBS existence and the key element for fault-tolerant topological quantum computing, even theoretical schemes imply a significant complexity to implement such braiding. Frequently examined 1D superconductor/semiconductor wires provide a prototypical example of how to produce MBSs, however braiding statistics are ill-defined in 1D and complex wire networks must be used. By placing an array of magnetic tunnel junctions (MTJs) above a 2D electron gas formed in a semiconductor quantum well grown on the surface of an s-wave superconductor, we have predicted the existence of highly tunable zero-energy MBSs and have proposed a novel scheme by which MBSs could be exchanged [1]. This scheme may then be used to demonstrate the states' non-Abelian statistics through braiding. The underlying magnetic textures produced by MTJ array provides a pseudo-helical texture which allows for highly-controllable topological phase transitions. By defining a local condition for topological nontriviality which takes into account the local rotation of magnetic texture, effective wire geometries support MBS formation and permit their controlled movement in 2D by altering the shape and orientation of such wires. This scheme then overcomes the requirement for a network of physical wires in order to exchange MBSs, allowing easier manipulation of such states. [1] G. L. Fatin, A. Matos-Abiague, B. Scharf, and I. Zutic, arXiv:1510.08182, preprint.

Exploring the potential energy surface for the interaction of sterically hindered trichloro(diethylenetriamine)gold(III) complexes with water.

PubMed

Dos Santos, Hélio F; Paschoal, Diego; Burda, Jaroslav V

2012-11-15

The reactivity of gold(III) complexes is analyzed for a series of derivatives of 3-azapentane-1,5-diamine (dien) tridentate ligand that can contain some bulky substituents. Two distinct series of compounds are considered where the dien ligand is either deprotonated (R-dien-H) or protonated (R-dien) at the secondary amine where R = ethyl (Et) or methyl (Me). While the deprotonated species will occur in neutral and basic solutions, the protonated forms are likely to be present in acidic environment. Hydration reaction (water/Cl(-) ligand exchange) of 14 complexes is modeled with quantum chemical calculations. Our calculations predict that the reactivity decreases with the increase in the molecular volume of the substituted dien ligand, and the calculated rate constants are in satisfactory agreement with experimental results. In addition, quantitative structure/reactivity models are proposed where the angle between the entering and leaving groups in the transition state structure (the reactivity angle) is used as a molecular descriptor. These models explain the trend of the relative reactivity of these complexes and can be used to design new ligands for gold(III) complexes aiming to adjust the reactivity of the complex.

Uncoupled surface spin induced exchange bias in α-MnO2 nanowires

PubMed Central

Li, Wenxian; Zeng, Rong; Sun, Ziqi; Tian, Dongliang; Dou, Shixue

2014-01-01

We have studied the microstructure, surface states, valence fluctuations, magnetic properties, and exchange bias effect in MnO2 nanowires. High purity α-MnO2 rectangular nanowires were synthesized by a facile hydrothermal method with microwave-assisted procedures. The microstructure analysis indicates that the nanowires grow in the [0 0 1] direction with the (2 1 0) plane as the surface. Mn3+ and Mn2+ ions are not found in the system by X-ray photoelectron spectroscopy. The effective magnetic moment of the manganese ions fits in with the theoretical and experimental values of Mn4+ very well. The uncoupled spins in 3d3 orbitals of the Mn4+ ions in MnO6 octahedra on the rough surface are responsible for the net magnetic moment. Spin glass behavior is observed through magnetic measurements. Furthermore, the exchange bias effect is observed for the first time in pure α-MnO2 phase due to the coupling of the surface spin glass with the antiferromagnetic α-MnO2 matrix. These α-MnO2 nanowires, with a spin-glass-like behavior and with an exchange bias effect excited by the uncoupled surface spins, should therefore inspire further study concerning the origin, theory, and applicability of surface structure induced magnetism in nanostructures. PMID:25319531

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

PubMed

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

2017-09-28

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

Laser Processed Condensing Heat Exchanger Technology Development

NASA Technical Reports Server (NTRS)

Hansen, Scott; Wright, Sarah; Wallace, Sarah; Hamilton, Tanner; Dennis, Alexander; Zuhlke, Craig; Roth, Nick; Sanders, John

2017-01-01

The reliance on non-permanent coatings in Condensing Heat Exchanger (CHX) designs is a significant technical issue to be solved before long-duration spaceflight can occur. Therefore, high reliability CHXs have been identified by the Evolvable Mars Campaign (EMC) as critical technologies needed to move beyond low earth orbit. The Laser Processed Condensing Heat Exchanger project aims to solve these problems through the use of femtosecond laser processed surfaces, which have unique wetting properties and potentially exhibit anti-microbial growth properties. These surfaces were investigated to identify if they would be suitable candidates for a replacement CHX surface. Among the areas researched in this project include microbial growth testing, siloxane flow testing in which laser processed surfaces were exposed to siloxanes in an air stream, and manufacturability.

Adaptive Biasing Combined with Hamiltonian Replica Exchange to Improve Umbrella Sampling Free Energy Simulations.

PubMed

Zeller, Fabian; Zacharias, Martin

2014-02-11

The accurate calculation of potentials of mean force for ligand-receptor binding is one of the most important applications of molecular simulation techniques. Typically, the separation distance between ligand and receptor is chosen as a reaction coordinate along which a PMF can be calculated with the aid of umbrella sampling (US) techniques. In addition, restraints can be applied on the relative position and orientation of the partner molecules to reduce accessible phase space. An approach combining such phase space reduction with flattening of the free energy landscape and configurational exchanges has been developed, which significantly improves the convergence of PMF calculations in comparison with standard umbrella sampling. The free energy surface along the reaction coordinate is smoothened by iteratively adapting biasing potentials corresponding to previously calculated PMFs. Configurations are allowed to exchange between the umbrella simulation windows via the Hamiltonian replica exchange method. The application to a DNA molecule in complex with a minor groove binding ligand indicates significantly improved convergence and complete reversibility of the sampling along the pathway. The calculated binding free energy is in excellent agreement with experimental results. In contrast, the application of standard US resulted in large differences between PMFs calculated for association and dissociation pathways. The approach could be a useful alternative to standard US for computational studies on biomolecular recognition processes.

A Geophysical Characterization & Monitoring Strategy for Determining Hydrologic Processes in the Hyporheic Corridor at the Hanford 300-Area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Slater, Lee; Day-Lewis, Frederick; Lane, John

2011-08-31

The primary objective of this research was to advance the prediction of solute transport between the Uranium contaminated Hanford aquifer and the Columbia River at the Hanford 300 Area by improving understanding of how fluctuations in river stage, combined with subsurface heterogeneity, impart spatiotemporal complexity to solute exchange along the Columbia River corridor. Our work explored the use of continuous waterborne electrical imaging (CWEI), in conjunction with fiber-optic distributed temperature sensor (FO-DTS) and time-lapse resistivity monitoring, to improve the conceptual model for how groundwater/surface water exchange regulates uranium transport. We also investigated how resistivity and induced polarization can be usedmore » to generate spatially rich estimates of the variation in depth to the Hanford-Ringold (H-R) contact between the river and the 300 Area Integrated Field Research Challenge (IFRC) site. Inversion of the CWEI datasets (a data rich survey containing {approx}60,000 measurements) provided predictions of the distributions of electrical resistivity and polarizability, from which the spatial complexity of the primary hydrogeologic units along the river corridor was reconstructed. Variation in the depth to the interface between the overlying coarse-grained, high permeability Hanford Formation and the underlying finer-grained, less permeable Ringold Formation, an important contact that limits vertical migration of contaminants, has been resolved along {approx}3 km of the river corridor centered on the IFRC site in the Hanford 300 Area. Spatial variability in the thickness of the Hanford Formation captured in the CWEI datasets indicates that previous studies based on borehole projections and drive-point and multi-level sampling likely overestimate the contributing area for uranium exchange within the Columbia River at the Hanford 300 Area. Resistivity and induced polarization imaging between the river and the 300 Area IFRC further imaged spatial variability in the depth to the Hanford-Ringold inland over a critical region where borehole information is absent, identifying evidence for a continuous depression in the H-R contact between the IFRC and the river corridor. Strong natural contrasts in temperature and specific conductance of river water compared to groundwater at this site, along with periodic river stage fluctuations driven by dam operations, were exploited to yield new insights into the dynamics of groundwater-surface water interaction. Whereas FO-DTS datasets have provided meter-scale measurements of focused groundwater discharge at the riverbed along the corridor, continuous resistivity monitoring has non-invasively imaged spatiotemporal variation in the resistivity inland driven by river stage fluctuations. Time series and time-frequency analysis of FO-DTS and 3D resistivity datasets has provided insights into the role of forcing variables, primarily daily dam operations, in regulating the occurrence of focused exchange at the riverbed and its extension inland. High amplitudes in the DTS and 3D resistivity signals for long periods that dominate the stage time series identify regions along the corridor where stage-driven exchange is preferentially focused. Our work has demonstrated how time-series analysis of both time-lapse resistivity and DTS datasets, in conjunction with resistivity/IP imaging of lithology, can improve understanding of groundwater-surface water exchange along river corridors, offering unique opportunities to connect stage-driven groundwater discharge observed with DTS on the riverbed to stage-driven groundwater and solute fluctuations captured with resistivity inland.« less

FINAL PROJECT REPORT: A Geophysical Characterization & Monitoring Strategy for Determining Hydrologic Processes in the Hyporheic Corridor at the Hanford 300-Area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee Slater

2011-08-15

The primary objective of this research was to advance the prediction of solute transport between the Uranium contaminated Hanford aquifer and the Columbia River at the Hanford 300 Area by improving understanding of how fluctuations in river stage, combined with subsurface heterogeneity, impart spatiotemporal complexity to solute exchange along the Columbia River corridor. Our work explored the use of continuous waterborne electrical imaging (CWEI), in conjunction with fiber-optic distributed temperature sensor (FO-DTS) and time-lapse resistivity monitoring, to improve the conceptual model for how groundwater/surface water exchange regulates uranium transport. We also investigated how resistivity and induced polarization can be usedmore » to generate spatially rich estimates of the variation in depth to the Hanford-Ringold (H-R) contact between the river and the 300 Area Integrated Field Research Challenge (IFRC) site. Inversion of the CWEI datasets (a data rich survey containing ~60,000 measurements) provided predictions of the distributions of electrical resistivity and polarizability, from which the spatial complexity of the primary hydrogeologic units along the river corridor was reconstructed. Variation in the depth to the interface between the overlying coarse-grained, high permeability Hanford Formation and the underlying finer-grained, less permeable Ringold Formation, an important contact that limits vertical migration of contaminants, has been resolved along ~3 km of the river corridor centered on the IFRC site in the Hanford 300 Area. Spatial variability in the thickness of the Hanford Formation captured in the CWEI datasets indicates that previous studies based on borehole projections and drive-point and multi-level sampling likely overestimate the contributing area for uranium exchange within the Columbia River at the Hanford 300 Area. Resistivity and induced polarization imaging between the river and the 300 Area IFRC further imaged spatial variability in the depth to the Hanford-Ringold inland over a critical region where borehole information is absent, identifying evidence for a continuous depression in the H-R contact between the IFRC and the river corridor. Strong natural contrasts in temperature and specific conductance of river water compared to groundwater at this site, along with periodic river stage fluctuations driven by dam operations, were exploited to yield new insights into the dynamics of groundwater-surface water interaction. Whereas FO-DTS datasets have provided meter-scale measurements of focused groundwater discharge at the riverbed along the corridor, continuous resistivity monitoring has non-invasively imaged spatiotemporal variation in the resistivity inland driven by river stage fluctuations. Time series and time-frequency analysis of FO-DTS and 3D resistivity datasets has provided insights into the role of forcing variables, primarily daily dam operations, in regulating the occurrence of focused exchange at the riverbed and its extension inland. High amplitudes in the DTS and 3D resistivity signals for long periods that dominate the stage time series identify regions along the corridor where stage-driven exchange is preferentially focused. Our work has demonstrated how time-series analysis of both time-lapse resistivity and DTS datasets, in conjunction with resistivity/IP imaging of lithology, can improve understanding of groundwater-surface water exchange along river corridors, offering unique opportunities to connect stage-driven groundwater discharge observed with DTS on the riverbed to stage-driven groundwater and solute fluctuations captured with resistivity inland.« less

Heat transfer to and from vegetated surfaces - An analytical method for the bulk exchange coefficients

NASA Technical Reports Server (NTRS)

Massman, William J.

1987-01-01

The semianalytical model outlined in a previous study (Massman, 1987) to describe momentum exchange between the atmosphere and vegetated surfaces is extended to include the exchange of heat. The methods employed are based on one-dimensional turbulent diffusivities, and use analytical solutions to the steady-state diffusion equation. The model is used to assess the influence that the canopy foliage structure and density, the wind profile structure within the canopy, and the shelter factor can have upon the inverse surface Stanton number (kB exp -1), as well as to explore the consequences of introducing a scalar displacement height which can be different from the momentum displacement height. In general, the triangular foliage area density function gives results which agree more closely with observations than that for constant foliage area density. The intended application of this work is for parameterizing the bulk aerodynamic resistances for heat and momentum exchange for use within large-scale models of plant-atmosphere exchanges.

Organic and inorganic molecules as probes of mineral surfaces (Invited)

NASA Astrophysics Data System (ADS)

Sverjensky, D. A.

2010-12-01

Although the multi-site nature of mineral surfaces is to be expected based on the underlying crystal structure, definitive evidence of the need to use more than one site in modelling proton surface charge or adsorption of a single adsorbate at the mineral-water interface is lacking. Instead, a single-site approach affords a practical way of averaging over all possible crystal planes and sites in a powdered mineral sample. Extensive analysis of published proton surface charge and adsorption of metals on oxide mineral surfaces can be undertaken with a single site density for each mineral based on tritium exchange or estimation from averages of the site densities of likely exposed surfaces. Even in systems with competing metals (e.g. Cu and Pb on hematite), the same site density as used for proton surface charge can be employed depending on the reaction stoichiometry. All of this indicates that protons and metals can bind to a great variety of sites with the same overall site density. However, simple oxyanions such as carbonate, sulfate, selenate, arsenate and arsenite require a much lower site density for a given mineral. For example, on goethite these oxyanions utilize a site density that correlates with the BET surface area of the goethite. In this way, the oxyanions can be thought of as selectively probing the available sites on the mineral. The correlation probably arises because goethites with different BET surface areas have different proportions of singly and multiply-bonded oxygens, and only the singly-bonded oxygens are useful for inner-sphere surface complexation by the ligand exchange mechanism. Small organic molecules behave in a remarkably similar way. For example, adsorption of oxalate on goethite, and aspartate, glutamate, dihydroxyphenylalanine, lysine and arginine on rutile are all consistent with a much smaller site density than those required for metals such as calcium or neodymium. Overall, these results suggest that both inorganic oxyanions and organic molecules containing carboxylate functional groups serve as much more sensitive probes of the surface structures of minerals than do protons or metals.

Binding characteristics of copper and cadmium by cyanobacterium Spirulina platensis.

PubMed

Fang, Linchuan; Zhou, Chen; Cai, Peng; Chen, Wenli; Rong, Xingmin; Dai, Ke; Liang, Wei; Gu, Ji-Dong; Huang, Qiaoyun

2011-06-15

Cyanobacteria are promising biosorbent for heavy metals in bioremediation. Although sequestration of metals by cyanobacteria is known, the actual mechanisms and ligands involved are not very well understood. The binding characteristics of Cu(II) and Cd(II) by the cyanobacterium Spirulina platensis were investigated using a combination of chemical modifications, batch adsorption experiments, Fourier transform infrared (FTIR) spectroscopy and X-ray absorption fine structure (XAFS) spectroscopy. A significant increase in Cu(II) and Cd(II) binding was observed in the range of pH 3.5-5.0. Dramatical decrease in adsorption of Cu(II) and Cd(II) was observed after methanol esterification of the nonliving cells demonstrating that carboxyl functional groups play an important role in the binding of metals by S. platensis. The desorption rate of Cu(II) and Cd(II) from S. platensis surface was 72.7-80.7% and 53.7-58.0% by EDTA and NH(4)NO(3), respectively, indicating that ion exchange and complexation are the dominating mechanisms for Cu(II) and Cd(II) adsorption. XAFS analysis provided further evidence on the inner-sphere complexation of Cu by carboxyl ligands and showed that Cu is complexed by two 5-membered chelate rings on S. platensis surface. Copyright © 2011 Elsevier B.V. All rights reserved.

Theoretical Modeling of the Magnetic Behavior of Thiacalix[4]arene Tetranuclear Mn(II)2Gd(III)2 and Co(II)2Eu(III)2 Complexes.

PubMed

Aldoshin, Sergey M; Sanina, Nataliya A; Palii, Andrew V; Tsukerblat, Boris S

2016-04-04

In view of a wide perspective of 3d-4f complexes in single-molecule magnetism, here we propose an explanation of the magnetic behavior of the two thiacalix[4]arene tetranuclear heterometallic complexes Mn(II)2Gd(III)2 and Co(II)2Eu(III)2. The energy pattern of the Mn(II)2Gd(III)2 complex evaluated in the framework of the isotropic exchange model exhibits a rotational band of the low-lying spin excitations within which the Landé intervals are affected by the biquadratic spin-spin interactions. The nonmonotonic temperature dependence of the χT product observed for the Mn(II)2Gd(III)2 complex is attributed to the competitive influence of the ferromagnetic Mn-Gd and antiferromagnetic Mn-Mn exchange interactions, the latter being stronger (J(Mn, Mn) = -1.6 cm(-1), Js(Mn, Gd) = 0.8 cm(-1), g = 1.97). The model for the Co(II)2Eu(III)2 complex includes uniaxial anisotropy of the seven-coordinate Co(II) ions and an isotropic exchange interaction in the Co(II)2 pair, while the Eu(III) ions are diamagnetic in their ground states. Best-fit analysis of χT versus T showed that the anisotropic contribution (arising from a large zero-field splitting in Co(II) ions) dominates (weak-exchange limit) in the Co(II)2Eu(III)2 complex (D = 20.5 cm(-1), J = -0.4 cm(-1), gCo = 2.22). This complex is concluded to exhibit an easy plane of magnetization (arising from the Co(II) pair). It is shown that the low-lying part of the spectrum can be described by a highly anisotropic effective spin-(1)/2 Hamiltonian that is deduced for the Co(II)2 pair in the weak-exchange limit.

Impact of debris dams on hyporheic interaction along a semi-arid stream

NASA Astrophysics Data System (ADS)

Lautz, Laura K.; Siegel, Donald I.; Bauer, Robert L.

2006-01-01

Hyporheic exchange increases the potential for solute retention in streams by slowing downstream transport and increasing solute contact with the substrate. Hyporheic exchange may be a major mechanism to remove nutrients in semi-arid watersheds, where livestock have damaged stream riparian zones and contributed nutrients to stream channels. Debris dams, such as beaver dams and anthropogenic log dams, may increase hyporheic interactions by slowing stream water velocity, increasing flow complexity and diverting water to the subsurface.Here, we report the results of chloride tracer injection experiments done to evaluate hyporheic interaction along a 320 m reach of Red Canyon Creek, a second order stream in the semi-arid Wind River Range of Wyoming. The study site is part of a rangeland watershed managed by The Nature Conservancy of Wyoming, and used as a hydrologic field site by the University of Missouri Branson Geologic Field Station. The creek reach we investigated has debris dams and tight meanders that hypothetically should enhance hyporheic interaction. Breakthrough curves of chloride measured during the field experiment were modelled with OTIS-P, a one-dimensional, surface-water, solute-transport model from which we extracted the storage exchange rate and cross-sectional area of the storage zone As for hyporheic exchange. Along gaining reaches of the stream reach, short-term hyporheic interactions associated with debris dams were comparable to those associated with severe meanders. In contrast, along the non-gaining reach, stream water was diverted to the subsurface by debris dams and captured by large-scale near-stream flow paths. Overall, hyporheic exchange rates along Red Canyon Creek during snowmelt recession equal or exceed exchange rates observed during baseflow at other streams.

Processes of Ammonia Air-Surface Exchange in a Fertilized Zea Mays Canopy

EPA Science Inventory

Recent incorporation of coupled soil biogeochemical and bi-directional NH3 air-surface exchange algorithms into regional air quality models holds promise for further reducing uncertainty in estimates of NH3 emissions from fertilized soils. While this advancement represents a sig...

Sorption of Cm(III) and Eu(III) onto clay minerals under saline conditions: Batch adsorption, laser-fluorescence spectroscopy and modeling

NASA Astrophysics Data System (ADS)

Schnurr, Andreas; Marsac, Rémi; Rabung, Thomas; Lützenkirchen, Johannes; Geckeis, Horst

2015-02-01

The present work reports experimental data for trivalent metal cation (Cm/Eu) sorption onto illite (Illite du Puy) and montmorillonite (Na-SWy-2) in NaCl solutions up to 4.37 molal (m) in the absence of carbonate. Batch sorption experiments were carried out for a given ionic strength at fixed metal concentration (mEu = 2 × 10-7 m, labeled with 152Eu for γ-counting) and at a constant solid to liquid ratio (S:L = 2 g/L) for 3 < pHm < 12 (pHm = -log mH+). The amount of clay sorbed Eu approaches almost 100% (with log KD > 5) for pHm > 8, irrespective of the NaCl concentration. Variations in Eu uptake are minor at elevated NaCl concentrations. Time-resolved laser fluorescence spectroscopy (TRLFS) studies on Cm sorption covering a wide range of NaCl concentrations reveal nearly identical fluorescence emission spectra after peak deconvolution, i.e. no significant variation of Cm surface speciation with salinity. Beyond the three surface complexes already found in previous studies an additional inner-sphere surface species with a fluorescence peak maximum at higher wavelength (λ ∼ 610 nm) could be resolved. This new surface species appears in the high pH range and is assumed to correspond to a clay/curium/silicate complex as already postulated in the literature for kaolinite. The 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model (2SPNE SC/CE) was applied to describe Eu sorption data by involving the Pitzer and SIT (specific ion interaction) formalism in the calculation of the activities of dissolved aqueous species. Good agreement of model and experiment is achieved for sorption data at pHm < 6 without the need of adjusting surface complexation constants. For pHm > 6 in case of illite and pHm > 8 in case of montmorillonite calculated sorption data systematically fall below experimental data with increasing ionic strength. Under those conditions sorption is almost quantitative and deviations must be discussed considering uncertainties of measured Eu concentrations in the range of analytical detection limits.

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Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-19

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Federal Register 2010, 2011, 2012, 2013, 2014

2012-01-09

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Advanced Heat/Mass Exchanger Technology for Geothermal and Solar Renewable Energy Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greiner, Miles; Childress, Amy; Hiibel, Sage

2014-12-16

Northern Nevada has abundant geothermal and solar energy resources, and these renewable energy sources provide an ample opportunity to produce economically viable power. Heat/mass exchangers are essential components to any energy conversion system. Improvements in the heat/mass exchange process will lead to smaller, less costly (more efficient) systems. There is an emerging heat transfer technology, based on micro/nano/molecular-scale surface science that can be applied to heat/mass exchanger design. The objective is to develop and characterize unique coating materials, surface configurations and membranes capable of accommodating a 10-fold increase in heat/mass exchanger performance via phase change processes (boiling, condensation, etc.) andmore » single phase convective heat/mass transfer.« less

Brazilian exchange rate complexity: Financial crisis effects

NASA Astrophysics Data System (ADS)

Piqueira, José Roberto C.; Mortoza, Letícia Pelluci D.

2012-04-01

With the financial market globalization, foreign investments became vital for the economies, mainly in emerging countries. In the last decades, Brazilian exchange rates appeared as a good indicator to measure either investors' confidence or risk aversion. Here, some events of global or national financial crisis are analyzed, trying to understand how they influenced the "dollar-real" rate evolution. The theoretical tool to be used is the López-Mancini-Calbet (LMC) complexity measure that, applied to real exchange rate data, has shown good fitness between critical events and measured patterns.

Three-Dimensional Modeling of Flow and Thermochemical Behavior in a Blast Furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Guo, Baoyu; Chew, Sheng; Austin, Peter; Yu, Aibing

2015-02-01

An ironmaking blast furnace (BF) is a complex high-temperature moving bed reactor involving counter-, co- and cross-current flows of gas, liquid and solid, coupled with heat and mass exchange and chemical reactions. Two-dimensional (2D) models were widely used for understanding its internal state in the past. In this paper, a three-dimensional (3D) CFX-based mathematical model is developed for describing the internal state of a BF in terms of multiphase flow and the related thermochemical behavior, as well as process indicators. This model considers the intense interactions between gas, solid and liquid phases, and also their competition for the space. The model is applied to a BF covering from the burden surface at the top to the liquid surface in the hearth, where the raceway cavity is considered explicitly. The results show that the key in-furnace phenomena such as flow/temperature patterns and component distributions of solid, gas and liquid phases can be described and characterized in different regions inside the BF, including the gas and liquids flow circumferentially over the 3D raceway surface. The in-furnace distributions of key performance indicators such as reduction degree and gas utilization can also be predicted. This model offers a cost-effective tool to understand and control the complex BF flow and performance.

NMR Investigation of Chloromethane Complexes of Cryptophane-A and Its Analogue with Butoxy Groups

PubMed Central

2014-01-01

Host–guest complexes between cryptophane-A as host and dichloromethane and chloroform as guests are investigated using 1H and 13C NMR spectroscopy. Moreover, a related cryptophane, with the methoxy groups replaced by butoxy units (cryptophane-But), and its complexes with the same guests were also studied. Variable temperature spectra showed effects of chemical exchange between the free and bound guests, as well as of conformational exchange of the host. The guest exchange was studied quantitatively by exchange spectroscopy or line shape analysis. Extraction of kinetic and thermodynamic parameters led to the characterization of the affinity between guests and hosts. On the other hand, the host exchange was investigated by means of 13C Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion which aims at the determination of the transverse relaxation rate R2, the inverse of the transverse relaxation time T2, as a function of the repetition of the π pulses in a CPMG train. The variation of the measured transverse relaxation rate with the repetition rate νCPMG indicated conformational exchange occurring on the microsecond–millisecond time scale. Structural information was obtained through measurements of cross-relaxation rates, both within the host and between the host and the guest protons. The NMR results were supported by DFT calculations. PMID:24472055

The study of RMB exchange rate complex networks based on fluctuation mode

NASA Astrophysics Data System (ADS)

Yao, Can-Zhong; Lin, Ji-Nan; Zheng, Xu-Zhou; Liu, Xiao-Feng

2015-10-01

In the paper, we research on the characteristics of RMB exchange rate time series fluctuation with methods of symbolization and coarse gaining. First, based on fluctuation features of RMB exchange rate, we define the first type of fluctuation mode as one specific foreign currency against RMB in four days' fluctuating situations, and the second type as four different foreign currencies against RMB in one day's fluctuating situation. With the transforming method, we construct the unique-currency and multi-currency complex networks. Further, through analyzing the topological features including out-degree, betweenness centrality and clustering coefficient of fluctuation-mode complex networks, we find that the out-degree distribution of both types of fluctuation mode basically follows power-law distributions with exponents between 1 and 2. The further analysis reveals that the out-degree and the clustering coefficient generally obey the approximated negative correlation. With this result, we confirm previous observations showing that the RMB exchange rate exhibits a characteristic of long-range memory. Finally, we analyze the most probable transmission route of fluctuation modes, and provide probability prediction matrix. The transmission route for RMB exchange rate fluctuation modes exhibits the characteristics of partially closed loop, repeat and reversibility, which lays a solid foundation for predicting RMB exchange rate fluctuation patterns with large volume of data.

A multi-species exchange model for fully fluctuating polymer field theory simulations.

PubMed

Düchs, Dominik; Delaney, Kris T; Fredrickson, Glenn H

2014-11-07

Field-theoretic models have been used extensively to study the phase behavior of inhomogeneous polymer melts and solutions, both in self-consistent mean-field calculations and in numerical simulations of the full theory capturing composition fluctuations. The models commonly used can be grouped into two categories, namely, species models and exchange models. Species models involve integrations of functionals that explicitly depend on fields originating both from species density operators and their conjugate chemical potential fields. In contrast, exchange models retain only linear combinations of the chemical potential fields. In the two-component case, development of exchange models has been instrumental in enabling stable complex Langevin (CL) simulations of the full complex-valued theory. No comparable stable CL approach has yet been established for field theories of the species type. Here, we introduce an extension of the exchange model to an arbitrary number of components, namely, the multi-species exchange (MSE) model, which greatly expands the classes of soft material systems that can be accessed by the complex Langevin simulation technique. We demonstrate the stability and accuracy of the MSE-CL sampling approach using numerical simulations of triblock and tetrablock terpolymer melts, and tetrablock quaterpolymer melts. This method should enable studies of a wide range of fluctuation phenomena in multiblock/multi-species polymer blends and composites.

PARACEST Properties of a Dinuclear Neodymium(III) Complex Bound to DNA or Carbonate

PubMed Central

Nwe, Kido; Andolina, Christopher M.; Huang, Ching-Hui; Morrow, Janet R.

2009-01-01

A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s−1) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln2(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethylphosphate and DNA. The CEST amide peak of Nd2(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu2(1) show that double-stranded and hairpin loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu2(1) carbonate complex (Kd = 15 µM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds. PMID:19555071

PARACEST properties of a dinuclear neodymium(III) complex bound to DNA or carbonate.

PubMed

Nwe, Kido; Andolina, Christopher M; Huang, Ching-Hui; Morrow, Janet R

2009-07-01

A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane, 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications, because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s(-1)) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln(2)(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethyl phosphate, and DNA. The CEST amide peak of Nd(2)(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu(2)(1) show that double-stranded and hairpin-loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu(2)(1) carbonate complex (K(d) = 15 microM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds.

Corrosive resistant heat exchanger

DOEpatents

Richlen, Scott L.

1989-01-01

A corrosive and errosive resistant heat exchanger which recovers heat from a contaminated heat stream. The heat exchanger utilizes a boundary layer of innocuous gas, which is continuously replenished, to protect the heat exchanger surface from the hot contaminated gas. The innocuous gas is conveyed through ducts or perforations in the heat exchanger wall. Heat from the heat stream is transferred by radiation to the heat exchanger wall. Heat is removed from the outer heat exchanger wall by a heat recovery medium.

Heat exchanger with transpired, highly porous fins

DOEpatents

Kutscher, Charles F.; Gawlik, Keith

2002-01-01

The heat exchanger includes a fin and tube assembly with increased heat transfer surface area positioned within a hollow chamber of a housing to provide effective heat transfer between a gas flowing within the hollow chamber and a fluid flowing in the fin and tube assembly. A fan is included to force a gas, such as air, to flow through the hollow chamber and through the fin and tube assembly. The fin and tube assembly comprises fluid conduits to direct the fluid through the heat exchanger, to prevent mixing with the gas, and to provide a heat transfer surface or pathway between the fluid and the gas. A heat transfer element is provided in the fin and tube assembly to provide extended heat transfer surfaces for the fluid conduits. The heat transfer element is corrugated to form fins between alternating ridges and grooves that define flow channels for directing the gas flow. The fins are fabricated from a thin, heat conductive material containing numerous orifices or pores for transpiring the gas out of the flow channel. The grooves are closed or only partially open so that all or substantially all of the gas is transpired through the fins so that heat is exchanged on the front and back surfaces of the fins and also within the interior of the orifices, thereby significantly increasing the available the heat transfer surface of the heat exchanger. The transpired fins also increase heat transfer effectiveness of the heat exchanger by increasing the heat transfer coefficient by disrupting boundary layer development on the fins and by establishing other beneficial gas flow patterns, all at desirable pressure drops.

Interpenetrating polymer network ion exchange membranes and method for preparing same

DOEpatents

Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

1989-01-01

Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

Substrate water exchange in photosystem II depends on the peripheral proteins.

PubMed

Hillier, W; Hendry, G; Burnap, R L; Wydrzynski, T

2001-12-14

The (18)O exchange rates for the substrate water bound in the S(3) state were determined in different photosystem II sample types using time-resolved mass spectrometry. The samples included thylakoid membranes, salt-washed Triton X-100-prepared membrane fragments, and purified core complexes from spinach and cyanobacteria. For each sample type, two kinetically distinct isotopic exchange rates could be resolved, indicating that the biphasic exchange behavior for the substrate water is inherent to the O(2)-evolving catalytic site in the S(3) state. However, the fast phase of exchange became somewhat slower (by a factor of approximately 2) in NaCl-washed membrane fragments and core complexes from spinach in which the 16- and 23-kDa extrinsic proteins have been removed, compared with the corresponding rate for the intact samples. For CaCl(2)-washed membrane fragments in which the 33-kDa manganese stabilizing protein (MSP) has also been removed, the fast phase of exchange slowed down even further (by a factor of approximately 3). Interestingly, the slow phase of exchange was little affected in the samples from spinach. For core complexes prepared from Synechocystis PCC 6803 and Synechococcus elongatus, the fast and slow exchange rates were variously affected. Nevertheless, within the experimental error, nearly the same exchange rates were measured for thylakoid samples made from wild type and an MSP-lacking mutant of Synechocystis PCC 6803. This result could indicate that the MSP has a slightly different function in eukaryotic organisms compared with prokaryotic organisms. In all samples, however, the differences in the exchange rates are relatively small. Such small differences are unlikely to arise from major changes in the metal-ligand structure at the catalytic site. Rather, the observed differences may reflect subtle long range effects in which the exchange reaction coordinates become slightly altered. We discuss the results in terms of solvent penetration into photosystem II and the regional dielectric around the catalytic site.

Surface Chemistry of La0.99Sr0.01NbO4-d and Its Implication for Proton Conduction.

PubMed

Li, Cheng; Pramana, Stevin S; Ni, Na; Kilner, John; Skinner, Stephen J

2017-09-06

Acceptor-doped LaNbO 4 is a promising electrolyte material for proton-conducting fuel cell (PCFC) applications. As charge transfer processes govern device performance, the outermost surface of acceptor-doped LaNbO 4 will play an important role in determining the overall cell performance. However, the surface composition is poorly characterized, and the understanding of its impact on the proton exchange process is rudimentary. In this work, the surface chemistry of 1 atom % Sr-doped LaNbO 4 (La 0.99 Sr 0.01 NbO 4-d , denoted as LSNO) proton conductor is characterized using LEIS and SIMS. The implication of a surface layer on proton transport is studied using the isotopic exchange technique. It has shown that a Sr-enriched but La-deficient surface layer of about 6-7 nm thick forms after annealing the sample under static air at 1000 °C for 10 h. The onset of segregation is found to be between 600 and 800 °C, and an equilibrium surface layer forms after 10 h annealing. A phase separation mechanism, due to the low solubility of Sr in LaNbO 4 , has been proposed to explain the observed segregation behavior. The surface layer was concluded to impede the water incorporation process, leading to a reduced isotopic fraction after the D 2 16 O wet exchange process, highlighting the impact of surface chemistry on the proton exchange process.

Capacity and mechanisms of ammonium and cadmium sorption on different wetland-plant derived biochars.

PubMed

Cui, Xiaoqiang; Hao, Hulin; Zhang, Changkuan; He, Zhenli; Yang, Xiaoe

2016-01-01

The objective of this study was to investigate the relationship between Cd(2+)/NH4(+) sorption and physicochemical properties of biochars produced from different wetland plants. Biochars from six species of wetland plants (i.e., Canna indica, Pennisetum purpureum Schum, Thalia dealbata, Zizania caduciflora, Phragmites australis and Vetiveria zizanioides) were obtained at 500°C and characterized, and their sorption for ammonium and cadmium was determined. There were significant differences in elemental composition, functional groups and specific surface area among the biochars derived from different wetland plant species. Sorption of ammonium and cadmium on the biochars could be described by a pseudo second order kinetic model, and the simple Langmuir model fits the isotherm data better than the Freundlich or Temkin model. The C. indica derived biochar had the largest sorption capacity for NH4(+) and Cd(2+), with a maximum sorption of 13.35 and 125.8mgg(-1), respectively. P. purpureum Schum derived biochar had a similar maximum sorption (119.3mgg(-1)) for Cd(2+). Ammonium sorption was mainly controlled by cation exchange, surface complexation with oxygen-containing functional groups and the formation of magnesium ammonium phosphate compounds, whereas for Cd(2+) sorption, the formation of cadmium phosphate precipitates, cation exchange and binding to oxygen-containing groups were the major possible mechanisms. In addition, the sorption of ammonium and cadmium was not affected by surface area and microporosity of the biochars. Copyright © 2015 Elsevier B.V. All rights reserved.

Sea surface microlayers: A unified physicochemical and biological perspective of the air-ocean interface

NASA Astrophysics Data System (ADS)

Cunliffe, Michael; Engel, Anja; Frka, Sanja; Gašparović, Blaženka; Guitart, Carlos; Murrell, J. Colin; Salter, Matthew; Stolle, Christian; Upstill-Goddard, Robert; Wurl, Oliver

2013-02-01

The sea surface microlayer (SML) covers more than 70% of the Earth's surface and is the boundary layer interface between the ocean and the atmosphere. This important biogeochemical and ecological system is critical to a diverse range of Earth system processes, including the synthesis, transformation and cycling of organic material, and the air-sea exchange of gases, particles and aerosols. In this review we discuss the SML paradigm, taking into account physicochemical and biological characteristics that define SML structure and function. These include enrichments in biogenic molecules such as carbohydrates, lipids and proteinaceous material that contribute to organic carbon cycling, distinct microbial assemblages that participate in air-sea gas exchange, the generation of climate-active aerosols and the accumulation of anthropogenic pollutants with potentially serious implications for the health of the ocean. Characteristically large physical, chemical and biological gradients thus separate the SML from the underlying water and the available evidence implies that the SML retains its integrity over wide ranging environmental conditions. In support of this we present previously unpublished time series data on bacterioneuston composition and SML surfactant activity immediately following physical SML disruption; these imply timescales of the order of minutes for the reestablishment of the SML following disruption. A progressive approach to understanding the SML and hence its role in global biogeochemistry can only be achieved by considering as an integrated whole, all the key components of this complex environment.

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

DOE PAGES

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.; ...

2018-05-11

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

Surfactant titration of nanoparticle-protein corona.

PubMed

Maiolo, Daniele; Bergese, Paolo; Mahon, Eugene; Dawson, Kenneth A; Monopoli, Marco P

2014-12-16

Nanoparticles (NP), when exposed to biological fluids, are coated by specific proteins that form the so-called protein corona. While some adsorbing proteins exchange with the surroundings on a short time scale, described as a "dynamic" corona, others with higher affinity and long-lived interaction with the NP surface form a "hard" corona (HC), which is believed to mediate NP interaction with cellular machineries. In-depth NP protein corona characterization is therefore a necessary step in understanding the relationship between surface layer structure and biological outcomes. In the present work, we evaluate the protein composition and stability over time and we systematically challenge the formed complexes with surfactants. Each challenge is characterized through different physicochemical measurements (dynamic light scattering, ζ-potential, and differential centrifugal sedimentation) alongside proteomic evaluation in titration type experiments (surfactant titration). 100 nm silicon oxide (Si) and 100 nm carboxylated polystyrene (PS-COOH) NPs cloaked by human plasma HC were titrated with 3-[(3-Cholamidopropyl) dimethylammonio]-1-propanesulfonate (CHAPS, zwitterionic), Triton X-100 (nonionic), sodium dodecyl sulfate (SDS, anionic), and dodecyltrimethylammonium bromide (DTAB, cationic) surfactants. Composition and density of HC together with size and ζ-potential of NP-HC complexes were tracked at each step after surfactant titration. Results on Si NP-HC complexes showed that SDS removes most of the HC, while DTAB induces NP agglomeration. Analogous results were obtained for PS NP-HC complexes. Interestingly, CHAPS and Triton X-100, thanks to similar surface binding preferences, enable selective extraction of apolipoprotein AI (ApoAI) from Si NP hard coronas, leaving unaltered the dispersion physicochemical properties. These findings indicate that surfactant titration can enable the study of NP-HC stability through surfactant variation and also selective separation of certain proteins from the HC. This approach thus has an immediate analytical value as well as potential applications in HC engineering.

Water Vapor Exchange in a Costa Rican Lower Montane Tropical Forest

NASA Astrophysics Data System (ADS)

Andrews, R.; Miller, G. R.; Cahill, A. T.; Moore, G. W.; Aparecido, L. M. T.

2015-12-01

Because of high canopy interception in tropical forests, evaporation from wet canopy surfaces makes up a sizeable portion of the total water vapor flux. The modeling complexities presented by changing canopy wetness, along with a scarcity of land-atmosphere flux exchange data from tropical forests, means evapotranspiration (ET) processes have been poorly represented in the tropics in land-surface modeling schemes. To better understand tropical forest ET, we will evaluate the influence of canopy wetness and various micrometeorological data on ET partitioning and total ET flux. We have collected flux data from a lower montane forest in Costa Rica at a newly established AmeriFlux site, which notably has the highest mean annual precipitation of any site in the network. The site features a 39-m canopy tower, equipped with two eddy covariance systems (LI-7200, LI-COR), a CO2/H2O atmospheric profile system (AP200, Campbell Scientific), leaf wetness sensors (LWS, Decagon Devices), sap flow sensors, and a soil respiration chamber (LI-8100A, LI-COR) as well as an array of other micrometeorological sensors. At the site, total ET is driven primarily by available energy, and to a lesser extent, by vapor pressure deficit. Average daily latent energy fluxes peak at values of 160, 75, and 35 W m-2 for dry, partially wet, and wet canopy conditions respectively. Correlations between latent energy flux and all other variables are strongest for drier canopy conditions. Complex relationships between canopy wetness and tropical forest ET cause the environmental controls on these fluxes to be significantly different from those in other biomes. As a result, a new modeling paradigm is needed to more accurately model ET differences between tropical forests and other vegetation types.

The Nubian Complex of Dhofar, Oman: an African middle stone age industry in Southern Arabia.

PubMed

Rose, Jeffrey I; Usik, Vitaly I; Marks, Anthony E; Hilbert, Yamandu H; Galletti, Christopher S; Parton, Ash; Geiling, Jean Marie; Cerný, Viktor; Morley, Mike W; Roberts, Richard G

2011-01-01

Despite the numerous studies proposing early human population expansions from Africa into Arabia during the Late Pleistocene, no archaeological sites have yet been discovered in Arabia that resemble a specific African industry, which would indicate demographic exchange across the Red Sea. Here we report the discovery of a buried site and more than 100 new surface scatters in the Dhofar region of Oman belonging to a regionally-specific African lithic industry--the late Nubian Complex--known previously only from the northeast and Horn of Africa during Marine Isotope Stage 5, ∼128,000 to 74,000 years ago. Two optically stimulated luminescence age estimates from the open-air site of Aybut Al Auwal in Oman place the Arabian Nubian Complex at ∼106,000 years ago, providing archaeological evidence for the presence of a distinct northeast African Middle Stone Age technocomplex in southern Arabia sometime in the first half of Marine Isotope Stage 5.

Microalgal-biochar immobilized complex: A novel efficient biosorbent for cadmium removal from aqueous solution.

PubMed

Shen, Ying; Li, Huan; Zhu, Wenzhe; Ho, Shih-Hsin; Yuan, Wenqiao; Chen, Jianfeng; Xie, Youping

2017-11-01

The feasibility of the bioremediation of cadmium (Cd) using microalgal-biochar immobilized complex (MBIC) was investigated. Major operating parameters (e.g., pH, biosorbent dosage, initial Cd(II) concentration and microalgal-biochar ratio) were varied to compare the treatability of viable algae (Chlorella sp.), biochar and MBIC. The biosorption isotherms obtained by using algae or biochar were found to have satisfactory Langmuir predictions, while the best fitting adsorption isotherm model for MBIC was the Sips model. The maximum Cd(II) adsorption capacity of MBIC with a Chlorella sp.: biochar ratio of 2:3 (217.41mgg -1 ) was higher than that of Chlorella sp. (169.92mgg -1 ) or biochar (95.82mgg -1 ) alone. The pseudo-second-order model fitted the biosorption process of MBIC well (R 2 >0.999). Moreover, zeta potential, SEM and FTIR studies revealed that electrostatic attraction, ion exchange and surface complexation were the main mechanisms responsible for Cd removal when using MBIC. Copyright © 2017 Elsevier Ltd. All rights reserved.

The Nubian Complex of Dhofar, Oman: An African Middle Stone Age Industry in Southern Arabia

PubMed Central

Rose, Jeffrey I.; Usik, Vitaly I.; Marks, Anthony E.; Hilbert, Yamandu H.; Galletti, Christopher S.; Parton, Ash; Geiling, Jean Marie; Černý, Viktor; Morley, Mike W.; Roberts, Richard G.

2011-01-01

Despite the numerous studies proposing early human population expansions from Africa into Arabia during the Late Pleistocene, no archaeological sites have yet been discovered in Arabia that resemble a specific African industry, which would indicate demographic exchange across the Red Sea. Here we report the discovery of a buried site and more than 100 new surface scatters in the Dhofar region of Oman belonging to a regionally-specific African lithic industry - the late Nubian Complex - known previously only from the northeast and Horn of Africa during Marine Isotope Stage 5, ∼128,000 to 74,000 years ago. Two optically stimulated luminescence age estimates from the open-air site of Aybut Al Auwal in Oman place the Arabian Nubian Complex at ∼106,000 years ago, providing archaeological evidence for the presence of a distinct northeast African Middle Stone Age technocomplex in southern Arabia sometime in the first half of Marine Isotope Stage 5. PMID:22140561

Depalmitoylated Ras traffics to and from the Golgi complex via a nonvesicular pathway

PubMed Central

Goodwin, J. Shawn; Drake, Kimberly R.; Rogers, Carl; Wright, Latasha; Lippincott-Schwartz, Jennifer; Philips, Mark R.; Kenworthy, Anne K.

2005-01-01

Palmitoylation is postulated to regulate Ras signaling by modulating its intracellular trafficking and membrane microenvironment. The mechanisms by which palmitoylation contributes to these events are poorly understood. Here, we show that dynamic turnover of palmitate regulates the intracellular trafficking of HRas and NRas to and from the Golgi complex by shifting the protein between vesicular and nonvesicular modes of transport. A combination of time-lapse microscopy and photobleaching techniques reveal that in the absence of palmitoylation, GFP-tagged HRas and NRas undergo rapid exchange between the cytosol and ER/Golgi membranes, and that wild-type GFP-HRas and GFP-NRas are recycled to the Golgi complex by a nonvesicular mechanism. Our findings support a model where palmitoylation kinetically traps Ras on membranes, enabling the protein to undergo vesicular transport. We propose that a cycle of depalmitoylation and repalmitoylation regulates the time course and sites of Ras signaling by allowing the protein to be released from the cell surface and rapidly redistributed to intracellular membranes. PMID:16027222

Photoactivation of Diiodido-Pt(IV) Complexes Coupled to Upconverting Nanoparticles.

PubMed

Perfahl, Stefanie; Natile, Marta M; Mohamad, Heba S; Helm, Christiane A; Schulzke, Carola; Natile, Giovanni; Bednarski, Patrick J

2016-07-05

The preparation, characterization, and surface modification of upconverting lanthanide-doped hexagonal NaGdF4 nanocrystals attached to light sensitive diiodido-Pt(IV) complexes is presented. The evaluation for photoactivation and cytotoxicity of the novel carboxylated diiodido-Pt(IV) cytotoxic prodrugs by near-infrared (NIR) light (λ = 980 nm) is also reported. We attempted two different strategies for attachment of light-sensitive diiodido-Pt(IV) complexes to Yb,Er- and Yb,Tm-doped β-NaGdF4 upconverting nanoparticles (UCNPs) in order to provide nanohybrids, which offer unique opportunities for selective drug activation within the tumor cells and subsequent spatiotemporal controlled drug release by NIR-to-visible light-upconversion: (A) covalent attachment of the Pt(IV) complex via amide bond formation and (B) carboxylate exchange of oleate on the surface of the UCNPs with diiodido-Pt(IV) carboxylato complexes. Initial feasibility studies showed that NIR applied by a 980 nm laser had only a slight effect on the stability of the various diiodido-Pt(IV) complexes, but when UCNPs were present more rapid loss of the ligand-metal-charge transfer (LMCT) bands of the diiodido-Pt(IV) complexes was observed. Furthermore, Pt released from the Pt(IV) complexes platinated calf-thymus DNA (ct-DNA) more rapidly when NIR was applied compared to dark controls. Of the two attachment strategies, method A with the covalently attached diiodido-Pt(IV) carboxylates via amide bond formation proved to be the most effective method for generating UCNPs that release Pt when irradiated with NIR; the released Pt was also able to bind irreversibly to calf thymus DNA. Nonetheless, only ca. 20% of the Pt on the surface of the UCNPs was in the Pt(IV) oxidation state, the rest was Pt(II), indicating chemical reduction of the diiodido-Pt(IV) prodrug by the UCNPs. Cytotoxicity studies with the various UCNP-Pt conjugates and constructs, tested on human leukemia HL60 cells in culture, indicated a substantial increase in cytotoxicity when modified UCNPs were combined with five rounds of 30 min irradiation with NIR compared to dark controls, but NIR alone also had a significant cytotoxic effect at this duration.

Lung Structure and the Intrinsic Challenges of Gas Exchange.

PubMed

Hsia, Connie C W; Hyde, Dallas M; Weibel, Ewald R

2016-03-15

Structural and functional complexities of the mammalian lung evolved to meet a unique set of challenges, namely, the provision of efficient delivery of inspired air to all lung units within a confined thoracic space, to build a large gas exchange surface associated with minimal barrier thickness and a microvascular network to accommodate the entire right ventricular cardiac output while withstanding cyclic mechanical stresses that increase several folds from rest to exercise. Intricate regulatory mechanisms at every level ensure that the dynamic capacities of ventilation, perfusion, diffusion, and chemical binding to hemoglobin are commensurate with usual metabolic demands and periodic extreme needs for activity and survival. This article reviews the structural design of mammalian and human lung, its functional challenges, limitations, and potential for adaptation. We discuss (i) the evolutionary origin of alveolar lungs and its advantages and compromises, (ii) structural determinants of alveolar gas exchange, including architecture of conducting bronchovascular trees that converge in gas exchange units, (iii) the challenges of matching ventilation, perfusion, and diffusion and tissue-erythrocyte and thoracopulmonary interactions. The notion of erythrocytes as an integral component of the gas exchanger is emphasized. We further discuss the signals, sources, and limits of structural plasticity of the lung in alveolar hypoxia and following a loss of lung units, and the promise and caveats of interventions aimed at augmenting endogenous adaptive responses. Our objective is to understand how individual components are matched at multiple levels to optimize organ function in the face of physiological demands or pathological constraints. Copyright © 2016 John Wiley & Sons, Inc.

Plasma particle simulation of electrostatic ion thrusters

NASA Technical Reports Server (NTRS)

Peng, Xiaohang; Keefer, Dennis; Ruyten, Wilhelmus

1990-01-01

Charge exchange collisons between beam ions and neutral propellant gas can result in erosion of the accelerator grid surfaces of an ion engine. A particle in cell (PIC) is developed along with a Monte Carlo method to simulate the ion dynamics and charge exchange processes in the grid region of an ion thruster. The simulation is two-dimensional axisymmetric and uses three velocity components (2d3v) to investigate the influence of charge exchange collisions on the ion sputtering of the accelerator grid surfaces. An example calculation has been performed for an ion thruster operated on xenon propellant. The simulation shows that the greatest sputtering occurs on the downstream surface of the grid, but some sputtering can also occur on the upstream surface as well as on the interior of the grid aperture.

Radiant exchange in partially specular architectural environments

NASA Astrophysics Data System (ADS)

Beamer, C. Walter; Muehleisen, Ralph T.

2003-10-01

The radiant exchange method, also known as radiosity, was originally developed for thermal radiative heat transfer applications. Later it was used to model architectural lighting systems, and more recently it has been extended to model acoustic systems. While there are subtle differences in these applications, the basic method is based on solving a system of energy balance equations, and it is best applied to spaces with mainly diffuse reflecting surfaces. The obvious drawback to this method is that it is based around the assumption that all surfaces in the system are diffuse reflectors. Because almost all architectural systems have at least some partially specular reflecting surfaces in the system it is important to extend the radiant exchange method to deal with this type of surface reflection. [Work supported by NSF.

Anisotropic microporous supports impregnated with polymeric ion-exchange materials

DOEpatents

Friesen, Dwayne; Babcock, Walter C.; Tuttle, Mark

1985-05-07

Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets.

Testing complex networks of interaction at the onset of the Near Eastern Neolithic using modelling of obsidian exchange.

PubMed

Ibáñez, Juan José; Ortega, David; Campos, Daniel; Khalidi, Lamya; Méndez, Vicenç

2015-06-06

In this paper, we explore the conditions that led to the origins and development of the Near Eastern Neolithic using mathematical modelling of obsidian exchange. The analysis presented expands on previous research, which established that the down-the-line model could not explain long-distance obsidian distribution across the Near East during this period. Drawing from outcomes of new simulations and their comparison with archaeological data, we provide results that illuminate the presence of complex networks of interaction among the earliest farming societies. We explore a network prototype of obsidian exchange with distant links which replicates the long-distance movement of ideas, goods and people during the Early Neolithic. Our results support the idea that during the first (Pre-Pottery Neolithic A) and second (Pre-Pottery Neolithic B) phases of the Early Neolithic, the complexity of obsidian exchange networks gradually increased. We propose then a refined model (the optimized distant link model) whereby long-distance exchange was largely operated by certain interconnected villages, resulting in the appearance of a relatively homogeneous Neolithic cultural sphere. We hypothesize that the appearance of complex interaction and exchange networks reduced risks of isolation caused by restricted mobility as groups settled and argue that these networks partially triggered and were crucial for the success of the Neolithic Revolution. Communities became highly dynamic through the sharing of experiences and objects, while the networks that developed acted as a repository of innovations, limiting the risk of involution. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Relative abundance of chemical forms of Cu(II) and Cd(II) on soybean roots as influenced by pH, cations and organic acids

PubMed Central

Zhou, Qin; Liu, Zhao-dong; Liu, Yuan; Jiang, Jun; Xu, Ren-kou

2016-01-01

Little information is available on chemical forms of heavy metals on integrate plant roots. KNO3 (1 M), 0.05M EDTA at pH6 and 0.01 M HCl were used sequentially to extract the exchangeable, complexed and precipitated forms of Cu(II) and Cd(II) from soybean roots and then to investigate chemical form distribution of Cu(II) and Cd(II) on soybean roots. Cu(II) and Cd(II) adsorbed on soybean roots were mainly exchangeable form, followed by complexed form, while their precipitated forms were very low under acidic conditions. Soybean roots had a higher adsorption affinity to Cu(II) than Cd(II), leading to higher toxic of Cu(II) than Cd(II). An increase in solution pH increased negative charge on soybean and thus increased exchangeable Cu(II) and Cd(II) on the roots. Ca2+, Mg2+ and NH4+ reduced exchangeable Cu(II) and Cd(II) levels on soybean roots and these cations showed greater effects on Cd(II) than Cu(II) due to greater adsorption affinity of the roots to Cu(II) than Cd(II). L-malic and citric acids decreased exchangeable and complexed Cu(II) on soybean roots. In conclusion, Cu(II) and Cd(II) mainly existed as exchangeable and complexed forms on soybean roots. Ca2+ and Mg2+ cations and citric and L-malic acids can potentially alleviate Cu(II) and Cd(II) toxicity to plants. PMID:27805020

Aqueous turbulence structure immediately adjacent to the air - water interface and interfacial gas exchange

NASA Astrophysics Data System (ADS)

Wang, Binbin

Air-sea interaction and the interfacial exchange of gas across the air-water interface are of great importance in coupled atmospheric-oceanic environmental systems. Aqueous turbulence structure immediately adjacent to the air-water interface is the combined result of wind, surface waves, currents and other environmental forces and plays a key role in energy budgets, gas fluxes and hence the global climate system. However, the quantification of turbulence structure sufficiently close to the air-water interface is extremely difficult. The physical relationship between interfacial gas exchange and near surface turbulence remains insufficiently investigated. This dissertation aims to measure turbulence in situ in a complex environmental forcing system on Lake Michigan and to reveal the relationship between turbulent statistics and the CO2 flux across the air-water interface. The major objective of this dissertation is to investigate the physical control of the interfacial gas exchange and to provide a universal parameterization of gas transfer velocity from environmental factors, as well as to propose a mechanistic model for the global CO2 flux that can be applied in three dimensional climate-ocean models. Firstly, this dissertation presents an advanced measurement instrument, an in situ free floating Particle Image Velocimetry (FPIV) system, designed and developed to investigate the small scale turbulence structure immediately below the air-water interface. Description of hardware components, design of the system, measurement theory, data analysis procedure and estimation of measurement error were provided. Secondly, with the FPIV system, statistics of small scale turbulence immediately below the air-water interface were investigated under a variety of environmental conditions. One dimensional wave-number spectrum and structure function sufficiently close to the water surface were examined. The vertical profiles of turbulent dissipation rate were intensively studied. Comparison between the turbulence structures measured during the wind wave initiation period and those obtained during the growing period was presented. Significant wave effects on near surface turbulence were found. A universal scaling law was proposed to parameterize turbulent dissipation rate immediately below the air-water interface with friction velocity, significant wave height and wave age. Finally, the gas transfer velocity was measured with a floating chamber (FC) system, along with simultaneously FPIV measurements. Turbulent dissipation rate both at the interface and at a short distance away from the interface (~ 10 cm) were analyzed and used to examine the small scale eddy model. The model coefficient was found to be dependent on the level of turbulence, instead of being a constant. An empirical relationship between the model coefficient and turbulent dissipation rate was provided, which improved the accuracy of the gas transfer velocity estimation by more than 100% for data acquired. Other data from the literature also supported this empirical relation. Furthermore, the relationship between model coefficient and turbulent Reynolds number was also investigated. In addition to physical control of gas exchange, the disturbance on near surface hydrodynamics by the FC was also discussed. Turbulent dissipation rates are enhanced at the short distance away from the interface, while the surface dissipation rates do not change significantly.

Synthesis and SMM behaviour of trinuclear versus dinuclear 3d-5f uranyl(v)-cobalt(ii) cation-cation complexes.

PubMed

Chatelain, Lucile; Tuna, Floriana; Pécaut, Jacques; Mazzanti, Marinella

2017-05-02

Trinuclear versus dinuclear heterodimetallic U V O 2 + Co 2+ complexes were selectively assembled via a cation-cation interaction by tuning the ligand. The trimeric complex 2, with a linear [Co-O[double bond, length as m-dash]U[double bond, length as m-dash]O-Co] core, exhibits magnetic exchange and slow relaxation with a reversal barrier of 30.5 ± 0.9 K providing the first example of a U-Co exchange-coupled SMM.

Transition of surface energy budget in the Gobi Desert between spring and summer seasons

NASA Technical Reports Server (NTRS)

Smith, Eric A.; Reiter, Elmar R.; Gao, Youxi

1986-01-01

The surface energetics of the southwest Gobi Desert, including the temporal variations and diurnally averaged properties of the surface energy budget components, was investigated. The field program was conducted during the spring and summer of 1984, with the measurement system designed to monitor radiative exchange, heat/moisture storage in the soil, and sensible and latent heat exhange between the ground and the atmosphere. Results of the analysis reveal a seasonal transition feature not expected of a midlatitude desert. Namely, the differences in both surface radiation exchange and the distibution of sensible and latent heat transfer arise within a radiatively forced environment that barely deviates from spring to summer in terms of available solar energy at the surface. Both similarities and differences in the spring and summer surface energy budgets arise from differences imparted to the system by an increase in the summertime atmospheric moisture content. Changes in the near-surface mixing ratio are shown to alter the effectiveness of the desert surface in absorbing radiative energy and redistibuting it to the lower atmosphere through sensible and latent heat exchange.

Modeling of Radiative Heat Transfer in an Electric Arc Furnace

NASA Astrophysics Data System (ADS)

Opitz, Florian; Treffinger, Peter; Wöllenstein, Jürgen

2017-12-01

Radiation is an important means of heat transfer inside an electric arc furnace (EAF). To gain insight into the complex processes of heat transfer inside the EAF vessel, not only radiation from the surfaces but also emission and absorption of the gas phase and the dust cloud need to be considered. Furthermore, the radiative heat exchange depends on the geometrical configuration which is continuously changing throughout the process. The present paper introduces a system model of the EAF which takes into account the radiative heat transfer between the surfaces and the participating medium. This is attained by the development of a simplified geometrical model, the use of a weighted-sum-of-gray-gases model, and a simplified consideration of dust radiation. The simulation results were compared with the data of real EAF plants available in literature.

A corrosive resistant heat exchanger

DOEpatents

Richlen, S.L.

1987-08-10

A corrosive and erosive resistant heat exchanger which recovers heat from a contaminated heat stream. The heat exchanger utilizes a boundary layer of innocuous gas, which is continuously replenished, to protect the heat exchanger surface from the hot contaminated gas. The innocuous gas is pumped through ducts or perforations in the heat exchanger wall. Heat from the heat stream is transferred by radiation to the heat exchanger wall. Heat is removed from the outer heat exchanger wall by a heat recovery medium. 3 figs., 3 tabs.

Using a Spectral Method to Evaluate Hyporheic Exchange and its Effect on Reach Scale Nitrate Removal.

NASA Astrophysics Data System (ADS)

Moren, I.; Worman, A. L. E.; Riml, J.

2017-12-01

Previous studies have shown that hyporheic exchange processes can be of great importance for the transport, retention and mass removal of nutrients in streams. Specifically, the flow of surface water through the hyporheic zone enhances redox-sensitive reactions such as coupled nitrification-denitrification. This self-cleaning capacity of streams can be utilized in stream restoration projects aiming to improve water quality by reconstructing the geomorphology of the streams. To optimize the effect of restoration actions we need quantitative understanding of the linkage between stream geomorphology, hyporheic exchange processes and the desired water quality targets. Here we propose an analytical, spectral methodology to evaluate how different stream geomorphologies induce hyporheic exchange on a wide range of spatial and temporal scales. Measurements of streambed topographies and surface water profiles from agricultural streams were used to calculate the average hyporheic exchange velocity and residence times and the result was compared with in-stream tracer test. Furthermore, the hyporheic exchange induced by steps in the surface water profile was derived as a comparison of the theoretical capacity of the system. Based on differences in hyporheic exchange, the mass removal of nitrate could be derived for the different geomorphologies. The maximum nitrate mass removal was found to be related to a specific Damkhöler number, which reflects that the mass removal can be either reaction or transport controlled. Therefore, although hyporheic exchange induced by steps in the surface water profile was generally larger than the hyporheic exchange in the observed natural reaches, this would not necessarily lead a larger nitrate mass removal provided that the hyporheic residence times are not long enough to facilitate denitrification processes. The study illustrates the importance to investigate a stream thoroughly before any remediation actions are implemented, specifically to evaluate if the mass removal is reaction or transport controlled.

Copper-Exchanged Zeolite L Traps Oxygen

NASA Technical Reports Server (NTRS)

Sharma, Pramod K.; Seshan, Panchalam K.

1991-01-01

Brief series of simple chemical treatments found to enhance ability of zeolite to remove oxygen from mixture of gases. Thermally stable up to 700 degrees C and has high specific surface area which provides high capacity for adsorption of gases. To increase ability to adsorb oxygen selectively, copper added by ion exchange, and copper-exchanged zeolite reduced with hydrogen. As result, copper dispersed atomically on inner surfaces of zeolite, making it highly reactive to oxygen, even at room temperature. Reactivity to oxygen even greater at higher temperatures.

76 FR 77878 - Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Proposed...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-12-14

... SECURITIES AND EXCHANGE COMMISSION [Release No. 34-65914; File No. SR-CBOE-2011-114] Self-Regulatory Organizations; Chicago Board Options Exchange, Incorporated; Notice of Proposed Rule Change Related to Complex Order Processing in Hybrid 3.0 Classes December 8, 2011. Pursuant to Section 19(b)(1) of the Securities Exchange Act of 1934 (the ``Act...

Exchange biased Co3O4 nanowires: A new insight into its magnetic core-shell nature

NASA Astrophysics Data System (ADS)

Thomas, S.; Jose, A.; Thanveer, T.; Anantharaman, M. R.

2017-06-01

We investigated interfacial exchange coupling effect in nano casted Co3O4 nanowires. Magnetometry measurements indicated that the magnetic response of the wires has two contributions. First one from the core of the wire which has characteristics of a 2D-DAFF(two-dimensional diluted antiferromagnet in a field). The second one is from uncompensated surface spins which get magnetically ordered towards the field direction once field cooled below 25 K. Below 25 K, the net magnetization of the core of the wire gets exchange coupled with the uncompensated surface spins giving rise to exchange bias effect. The unique 2D-DAFF/spin-glass core/shell heterostructure showed a pronounced training effect in the first field cycling itself. The magnitude of exchange bias field showed a maximum at intermediate cooling fields and for the higher cooling field, exchange bias got reduced.

Intermixing enables strong exchange coupling in nanocomposites: Magnetism through the interfacial ferrite in γ -Fe2O3/NiO

NASA Astrophysics Data System (ADS)

Skoropata, E.; Su, T. T.; Ouyang, H.; Freeland, J. W.; van Lierop, J.

2017-07-01

γ -Fe2O3 particles, surface modified with NiO crystallites, form a unique nanocomposite that points to how to tune strong interfacial exchange coupling. We find that Ni2 + migrates into the octahedral sites of the γ -Fe2O3 nanoparticle surface, and this NiFe2O4 -like layer permits effective magnetic coupling of Ni and Fe sites that strengthens the interface exchange. A large increase in coercivity coinciding with a loss of exchange bias is achieved by this strong interfacial coupling that results in a Ni2 + moment reversal in the NiO with the γ -Fe2O3 . This work reveals the importance of intermixing in, and possibility to use, such an exchange coupling regime to alter substantially the coercivity and hence control an important property of exchange-coupled nanocomposite magnets.

Iron(II)-Catalyzed Iron Atom Exchange and Mineralogical Changes in Iron-rich Organic Freshwater Flocs: An Iron Isotope Tracer Study.

PubMed

ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben

2017-06-20

In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short-term Fe(III)-reducing conditions facilitating the fast attainment of solid-solution equilibria (e.g., in stagnant waters), Fe-rich freshwater flocs are expected to remain an effective sink for trace elements.

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

PubMed Central

Perry, Nicola H.; Ishihara, Tatsumi

2016-01-01

Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

Dominant controls of transpiration along a hillslope transect inferred from ecohydrological measurements and thermodynamic limits

NASA Astrophysics Data System (ADS)

Renner, Maik; Hassler, Sibylle K.; Blume, Theresa; Weiler, Markus; Hildebrandt, Anke; Guderle, Marcus; Schymanski, Stanislaus J.; Kleidon, Axel

2016-05-01

We combine ecohydrological observations of sap flow and soil moisture with thermodynamically constrained estimates of atmospheric evaporative demand to infer the dominant controls of forest transpiration in complex terrain. We hypothesize that daily variations in transpiration are dominated by variations in atmospheric demand, while site-specific controls, including limiting soil moisture, act on longer timescales. We test these hypotheses with data of a measurement setup consisting of five sites along a valley cross section in Luxembourg. Both hillslopes are covered by forest dominated by European beech (Fagus sylvatica L.). Two independent measurements are used to estimate stand transpiration: (i) sap flow and (ii) diurnal variations in soil moisture, which were used to estimate the daily root water uptake. Atmospheric evaporative demand is estimated through thermodynamically constrained evaporation, which only requires absorbed solar radiation and temperature as input data without any empirical parameters. Both transpiration estimates are strongly correlated to atmospheric demand at the daily timescale. We find that neither vapor pressure deficit nor wind speed add to the explained variance, supporting the idea that they are dependent variables on land-atmosphere exchange and the surface energy budget. Estimated stand transpiration was in a similar range at the north-facing and the south-facing hillslopes despite the different aspect and the largely different stand composition. We identified an inverse relationship between sap flux density and the site-average sapwood area per tree as estimated by the site forest inventories. This suggests that tree hydraulic adaptation can compensate for heterogeneous conditions. However, during dry summer periods differences in topographic factors and stand structure can cause spatially variable transpiration rates. We conclude that absorption of solar radiation at the surface forms a dominant control for turbulent heat and mass exchange and that vegetation across the hillslope adjusts to this constraint at the tree and stand level. These findings should help to improve the description of land-surface-atmosphere exchange at regional scales.

A series of tetraazalene radical-bridged M2 (M = CrIII, MnII, FeII, CoII) complexes with strong magnetic exchange coupling.

PubMed

DeGayner, Jordan A; Jeon, Ie-Rang; Harris, T David

2015-11-13

The ability of tetraazalene radical bridging ligands to mediate exceptionally strong magnetic exchange coupling across a range of transition metal complexes is demonstrated. The redox-active bridging ligand N , N ', N '', N '''-tetra(2-methylphenyl)-2,5-diamino-1,4-diiminobenzoquinone ( NMePh LH 2 ) was metalated to give the series of dinuclear complexes [(TPyA) 2 M 2 ( NMePh L 2- )] 2+ (TPyA = tris(2-pyridylmethyl)amine, M = Mn II , Fe II , Co II ). Variable-temperature dc magnetic susceptibility data for these complexes reveal the presence of weak superexchange interactions between metal centers, and fits to the data provide coupling constants of J = -1.64(1) and -2.16(2) cm -1 for M = Mn II and Fe II , respectively. One-electron reduction of the complexes affords the reduced analogues [(TPyA) 2 M 2 ( NMePh L 3- ˙)] + . Following a slightly different synthetic procedure, the related complex [(TPyA) 2 CrIII2( NMePh L 3- ˙)] 3+ was obtained. X-ray diffraction, cyclic voltammetry, and Mössbauer spectroscopy indicate the presence of radical NMePh L 3- ˙ bridging ligands in these complexes. Variable-temperature dc magnetic susceptibility data of the radical-bridged species reveal the presence of strong magnetic interactions between metal centers and ligand radicals, with simulations to data providing exchange constants of J = -626(7), -157(7), -307(9), and -396(16) cm -1 for M = Cr III , Mn II , Fe II , and Co II , respectively. Moreover, the strength of magnetic exchange in the radical-bridged complexes increases linearly with decreasing M-L bond distance in the oxidized analogues. Finally, ac magnetic susceptibility measurements reveal that [(TPyA) 2 Fe 2 ( NMePh L 3- ˙)] + behaves as a single-molecule magnet with a relaxation barrier of U eff = 52(1) cm -1 . These results highlight the ability of redox-active tetraazalene bridging ligands to enable dramatic enhancement of magnetic exchange coupling upon redox chemistry and provide a rare opportunity to examine metal-radical coupling trends across a transmetallic series of complexes.

Strain control of oxygen kinetics in the Ruddlesden-Popper oxide La 1.85Sr 0.15CuO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Tricia L.; Jacobs, Ryan; Lee, Dongkyu

Oxygen defect control has long been considered an important route to functionalizing complex oxide films. However, the nature of oxygen defects in thin films is often not investigated beyond basic redox chemistry. One of the model examples for oxygen-defect studies is the layered Ruddlesden–Popper phase La 2-xSr x CuO 4-δ (LSCO), in which the superconducting transition temperature is highly sensitive to epitaxial strain. However, previous observations of strain-superconductivity coupling in LSCO thin films were mainly understood in terms of elastic contributions to mechanical buckling, with minimal consideration of kinetic or thermodynamic factors. Here, we report that the oxygen nonstoichiometry commonlymore » reported for strained cuprates is mediated by the strain-modified surface exchange kinetics, rather than reduced thermodynamic oxygen formation energies. Remarkably, tensile-strained LSCO shows nearly an order of magnitude faster oxygen exchange rate than a compressively strained film, providing a strategy for developing high-performance energy materials.« less

Toward a universal mass-momentum transfer relationship for predicting nutrient uptake and metabolite exchange in benthic reef communities

NASA Astrophysics Data System (ADS)

Falter, James L.; Lowe, Ryan J.; Zhang, Zhenlin

2016-09-01

Here we synthesize data from previous field and laboratory studies describing how rates of nutrient uptake and metabolite exchange (mass transfer) are related to form drag and bottom stresses (momentum transfer). Reanalysis of this data shows that rates of mass transfer are highly correlated (r2 ≥ 0.9) with the root of the bottom stress (τbot0.4) under both waves and currents and only slightly higher under waves (~10%). The amount of mass transfer that can occur per unit bottom stress (or form drag) is influenced by morphological features ranging anywhere from millimeters to meters in scale; however, surface-scale roughness (millimeters) appears to have little effect on actual nutrient uptake by living reef communities. Although field measurements of nutrient uptake by natural reef communities agree reasonably well with predictions based on existing mass-momentum transfer relationships, more work is needed to better constrain these relationships for more rugose and morphologically complex communities.

Strain control of oxygen kinetics in the Ruddlesden-Popper oxide La 1.85Sr 0.15CuO 4

DOE PAGES

Meyer, Tricia L.; Jacobs, Ryan; Lee, Dongkyu; ...

2018-01-08

Oxygen defect control has long been considered an important route to functionalizing complex oxide films. However, the nature of oxygen defects in thin films is often not investigated beyond basic redox chemistry. One of the model examples for oxygen-defect studies is the layered Ruddlesden–Popper phase La 2-xSr x CuO 4-δ (LSCO), in which the superconducting transition temperature is highly sensitive to epitaxial strain. However, previous observations of strain-superconductivity coupling in LSCO thin films were mainly understood in terms of elastic contributions to mechanical buckling, with minimal consideration of kinetic or thermodynamic factors. Here, we report that the oxygen nonstoichiometry commonlymore » reported for strained cuprates is mediated by the strain-modified surface exchange kinetics, rather than reduced thermodynamic oxygen formation energies. Remarkably, tensile-strained LSCO shows nearly an order of magnitude faster oxygen exchange rate than a compressively strained film, providing a strategy for developing high-performance energy materials.« less

77 FR 21615 - Self-Regulatory Organizations; International Securities Exchange, LLC; Notice of Filing and...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-10

... by ISE. The first note relates to Non-ISE Market Maker fees, which apply to regular and complex orders, and how those fees are applied to execution of complex orders on the Exchange.\\3\\ Non-ISE Market Maker fees were adopted by ISE in 2006.\\4\\ Prior to this fee change, Non-ISE Market Makers were subject...

The solution of private problems for optimization heat exchangers parameters

NASA Astrophysics Data System (ADS)

Melekhin, A.

2017-11-01

The relevance of the topic due to the decision of problems of the economy of resources in heating systems of buildings. To solve this problem we have developed an integrated method of research which allows solving tasks on optimization of parameters of heat exchangers. This method decides multicriteria optimization problem with the program nonlinear optimization on the basis of software with the introduction of an array of temperatures obtained using thermography. The author have developed a mathematical model of process of heat exchange in heat exchange surfaces of apparatuses with the solution of multicriteria optimization problem and check its adequacy to the experimental stand in the visualization of thermal fields, an optimal range of managed parameters influencing the process of heat exchange with minimal metal consumption and the maximum heat output fin heat exchanger, the regularities of heat exchange process with getting generalizing dependencies distribution of temperature on the heat-release surface of the heat exchanger vehicles, defined convergence of the results of research in the calculation on the basis of theoretical dependencies and solving mathematical model.

A comprehensive review of milk fouling on heated surfaces.

PubMed

Sadeghinezhad, E; Kazi, S N; Dahari, M; Safaei, Mohammad Reza; Sadri, Rad; Badarudin, A

2015-01-01

Heat exchanger performance degrades rapidly during operation due to formation of deposits on heat transfer surfaces which ultimately reduces service life of the equipment. Due to scaling, product deteriorates which causes lack of proper heating. Chemistry of milk scaling is qualitatively understood and the mathematical models for fouling at low temperatures have been produced but the behavior of systems at ultra high temperature processing has to be studied further to understand in depth. In diversified field, the effect of whey protein fouling along with pressure drop in heat exchangers were conducted by many researchers. Adding additives, treatment of heat exchanger surfaces and changing of heat exchanger configurations are notable areas of investigation in milk fouling. The present review highlighted information about previous work on fouling, influencing parameters of fouling and its mitigation approach and ends up with recommendations for retardation of milk fouling and necessary measures to perform the task.

Theoretical study of the magnetic exchange coupling behavior substituting Cr(III) with Mo(III) in cyano-bridged transition metal complexes

NASA Astrophysics Data System (ADS)

Zhang, Yi-Quan; Luo, Cheng-Lin

Molecular magnetism in a series of cyano-bridged first and second transition metal complexes has been investigated using density functional theory (DFT) combined with the broken-symmetry (BS) approach. Several exchange-correlation (XC) functionals in the ADF package were used to investigate complexes I [-(Me3tacn)2(cyclam)NiMo2(CN)6]2+, II [-(Me3tacn)2(cyclam)Ni-Cr2(CN)6]2+, III [(Me3tacn)6MnMo6(CN)18]2+, and IV [(Me3tacn)6MnCr6(CN)18]2+ (Me3tacn = N,N?,N‴-trimethyl-1,4,7-triazacyclononane). For models A (the molded structure of complex I) and B (the modeled structure of complex II), all the XCs given qualitatively reasonable results and predict ferromagnetic coupling character between M (M = MoIII for A or CrIII for B) and NiII in coincidence with the experimental results (see Tables and ). The calculated using Operdew, OPBE, O3LYP, and B3LYP functionals and experimental J values show that substituting CrIII with MoIII will enhance the ferromagnetic exchange coupling interactions. But VWN, PW91, PBE, VSXC, and tau-HCTH functionals have no way to differentiate the relative strength of the intramolecular magnetic exchange coupling interactions of A and B correctly. For models C (the modeled structure of complex III) and D (the modeled structure of complex IV), all the XCs in ADF and B3LYP in Gaussian 03 with several basis sets show that substituting CrIII with MoIII will enhance the antiferromagnetic exchange coupling interactions. From the above calculations, the substitution of CrIII by MoIII will enhance the magnetic coupling interactions, whether the magnetic coupling interactions are ferro- or antiferromagnetic. Moreover, Kahn's model was applied to investigate the above facts.

A Scale Model of Cation Exchange for Classroom Demonstration.

ERIC Educational Resources Information Center

Guertal, E. A.; Hattey, J. A.

1996-01-01

Describes a project that developed a scale model of cation exchange that can be used for a classroom demonstration. The model uses kaolinite clay, nails, plywood, and foam balls to enable students to gain a better understanding of the exchange complex of soil clays. (DDR)

Anisotropic microporous supports impregnated with polymeric ion-exchange materials

DOEpatents

Friesen, D.; Babcock, W.C.; Tuttle, M.

1985-05-07

Novel ion-exchange media are disclosed, the media comprising polymeric anisotropic microporous supports containing polymeric ion-exchange or ion-complexing materials. The supports are anisotropic, having small exterior pores and larger interior pores, and are preferably in the form of beads, fibers and sheets. 5 figs.

76 FR 49832 - Notice of Market Assessment and Public Meeting for Digital Transportation Exchange

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-11

... Market Assessment and Public Meeting for Digital Transportation Exchange AGENCY: Office of the Secretary...--creating a thriving marketplace for digital transportation solutions. The Digital Transportation Exchange... best digital products and services for the transportation industry--from very simple to very complex...

Chapter 5: Thermal Indices and Their Applications for Livestock Environments

USDA-ARS?s Scientific Manuscript database

Heat exchanges with the environment are a crucial process for maintaining homeothermy by humans and other animals. These exchanges involve heat production, conservation and dissipation, and are dependent on both biological and physical factors. The complexity of these exchanges has led to many attem...

Ion Exchange Chromatography and Spectrophotometry: An Introductory Undergraduate Laboratory Experiment.

ERIC Educational Resources Information Center

Foster, N.; And Others

1985-01-01

Describes an experiment in which students use ion exchange chromatography to separate a mixture of chloro complexes of transition metal ions and then use spectrophotometry to define qualitatively the efficiency of the ion exchange columns. Background information, materials needed, and procedures used are included. (JN)

HEAT TRANSFER MEANS

DOEpatents

Fraas, A.P.; Wislicenus, G.F.

1961-07-11

A heat exchanger is adapted to unifomly cool a spherical surface. Equations for the design of a spherical heat exchanger hav~g tubes with a uniform center-to-center spining are given. The heat exchanger is illustrated in connection with a liquid-fueled reactor.

p47phox Molecular Activation for Assembly of the Neutrophil NADPH Oxidase Complex*

PubMed Central

Marcoux, Julien; Man, Petr; Petit-Haertlein, Isabelle; Vivès, Corinne; Forest, Eric; Fieschi, Franck

2010-01-01

The p47phox cytosolic factor from neutrophilic NADPH oxidase has always been resistant to crystallogenesis trials due to its modular organization leading to relative flexibility. Hydrogen/deuterium exchange coupled to mass spectrometry was used to obtain structural information on the conformational mechanism that underlies p47phox activation. We confirmed a relative opening of the protein with exposure of the SH3 Src loops that are known to bind p22phox upon activation. A new surface was shown to be unmasked after activation, representing a potential autoinhibitory surface that may block the interaction of the PX domain with the membrane in the resting state. Within this surface, we identified 2 residues involved in the interaction with the PX domain. The double mutant R162A/D166A showed a higher affinity for specific phospholipids but none for the C-terminal part of p22phox, reflecting an intermediate conformation between the autoinhibited and activated forms. PMID:20592030

Reflections and meditations upon complex chromosomal exchanges.

PubMed

Savage, John R K

2002-12-01

The application of FISH chromosome painting techniques, especially the recent mFISH (and its equivalents) where all 23 human chromosome pairs can be distinguished, has demonstrated that many chromosome-type structural exchanges are much more complicated (involving more "break-rejoins" and arms) than has hitherto been assumed. It is clear that we have been greatly under-estimating the damage produced in chromatin by such agents as ionising radiation. This article gives a brief historical summary of observations leading up to this conclusion, and after outlining some of the problems surrounding the formation of complex chromosomes exchanges, speculates about possible solutions currently being proposed.

Air- ice-snow interaction in the Northern Hemisphere under different stability conditions

NASA Astrophysics Data System (ADS)

Repina, Irina; Chechin, Dmitry; Artamonov, Arseny

2013-04-01

The traditional parameterizations of the atmospheric boundary layer are based on similarity theory and the coefficients of turbulent transfer, describing the atmospheric-surface interaction and the diffusion of impurities in the operational models of air pollution, weather forecasting and climate change. Major drawbacks of these parameterizations is that they are not applicable for the extreme conditions of stratification and currents over complex surfaces (such as sea ice, marginal ice zone or stormy sea). These problem could not be overcome within the framework of classical theory, i.e, by rectifying similarity functions or through the introduction of amendments to the traditional turbulent closure schemes. Lack of knowledge on the structure of the surface air layer and the exchange of momentum, heat and moisture between the rippling water surface and the atmosphere at different atmospheric stratifications is at present the major obstacle which impede proper functioning of the operational global and regional weather prediction models and expert models of climate and climate change. This is especially important for the polar regions, where in winter time the development of strong stable boundary layer in the presence of polynyas and leads usually occur. Experimental studies of atmosphere-ice-snow interaction under different stability conditions are presented. Strong stable and unstable conditions are discussed. Parametrizations of turbulent heat and gas exchange at the atmosphere ocean interface are developed. The dependence of the exchange coefficients and aerodynamic roughness on the atmospheric stratification over the snow and ice surface is experimentally confirmed. The drag coefficient is reduced with increasing stability. The behavior of the roughness parameter is simple. This result was obtained in the Arctic from the measurements over hummocked surface. The value of the roughness in the Arctic is much less than that observed over the snow in the middle and even high latitudes of the Northern Hemisphere because the stable conditions above Arctic ice field dominate. Under such conditions the air flow over the uneven surface behaves in the way it does over the even one. This happens because depressions between ridges are filled with heavier air up to the height of irreguralities. As a result, the air moves at the level of ridges without entering depressions. Increased heat and mass transfer over polynyas and leads through self-organization of turbulent convection is found. The work was sponsored by RFBR grants and funded by the Government of the Russian Federation grants.

Estimating gas exchange of CO2 and CH4 between headwater systems and the atmosphere in Southwest Sweden

NASA Astrophysics Data System (ADS)

Somlai, Celia; Natchimuthu, Sivakiruthika; Bastviken, David; Lorke, Andreas

2015-04-01

Quantifying the role of inland water systems in terms of carbon sinks and sources and their connection to the terrestrial ecosystems and landscapes is fundamental for improving the balance approach of regional and global carbon budgets. Recent research showed that freshwater bodies emit significant amounts of CO2 and CH4 into the atmosphere. The extent of the emissions from small streams and headwaters, however, remains uncertain due to a limited availability of data. Studies have shown that headwater systems receive most of the terrestrial organic carbon, have the highest dissolved CO2 concentration and the highest gas exchange velocities and cover the largest fractional surface area within fluvial networks. The gas exchange between inland waters and the atmosphere is controlled by two factors: the difference between the dissolved gas concentration and its atmospheric equilibrium concentration, and the gas exchange velocity. The direct measurement of the dissolved gas concentration of greenhouse gases can be measured straightforwardly, for example, by gas chromatography from headspace extraction of water sample. In contrast, direct measurement of gas exchange velocity is more complex and time consuming, as simultaneous measurements with a volatile and nonvolatile inert tracer gas are needed. Here we analyze measurements of gas exchange velocities, concentrations and fluxes of dissolved CO2 and CH4, as well as loads of total organic and inorganic carbon in 10 reaches in headwater streams in Southwest Sweden. We compare the gas exchange velocities measured directly through tracer injections with those estimated through various empirical approaches, which are based on modelled and measured current velocity, stream depth and slope. Furthermore, we estimate the resulting uncertainties of the flux estimates. We also present different time series of dissolved CO2, CH4 and O2 concentration, water temperature, barometric pressure, electro conductivity, and pH values measured during the period of tracer injection.

Integrated hydrologic and hydrodynamic modeling to assess water exchange in a data-scarce reservoir

NASA Astrophysics Data System (ADS)

Wu, Binbin; Wang, Guoqiang; Wang, Zhonggen; Liu, Changming; Ma, Jianming

2017-12-01

Integrated hydrologic and hydrodynamic modeling is useful in evaluating hydrodynamic characteristics (e.g. water exchange processes) in data-scarce water bodies, however, most studies lack verification of the hydrologic model. Here, water exchange (represented by water age) was investigated through integrated hydrologic and hydrodynamic modeling of the Hongfeng Reservoir, a poorly gauged reservoir in southwest China. The performance of the hydrologic model and parameter replacement among sub-basins with hydrological similarity was verified by historical data. Results showed that hydrological similarity based on the hierarchical cluster analysis and topographic index probability density distribution was reliable with satisfactory performance of parameter replacement. The hydrodynamic model was verified using daily water levels and water temperatures from 2009 and 2010. The water exchange processes in the Hongfeng Reservoir are very complex with temporal, vertical, and spatial variations. The temporal water age was primarily controlled by the variable inflow and outflow, and the maximum and minimum ages for the site near the dam were 406.10 d (15th June) and 90.74 d (3rd August), respectively, in 2010. Distinct vertical differences in water age showed that surface flow, interflow, and underflow appeared alternately, depending on the season and water depth. The worst water exchange situation was found in the central areas of the North Lake with the highest water ages in the bottom on both 15th June and 3rd August, in 2010. Comparison of the spatial water ages revealed that the more favorable hydraulic conditions on 3rd August mainly improved the water exchange in the dam areas and most areas of the South Lake, but had little effect on the bottom layers of the other deepest areas in the South and North Lakes. The presented framework can be applied in other data-scarce waterbodies worldwide to provide better understanding of water exchange processes.

Surface-Cross-Linked Micelles as Multifunctionalized Organic Nanoparticles for Controlled Release, Light Harvesting, and Catalysis

PubMed Central

2016-01-01

Surfactant micelles are dynamic entities with a rapid exchange of monomers. By “clicking” tripropargylammonium-containing surfactants with diazide cross-linkers, we obtained surface-cross-linked micelles (SCMs) that could be multifunctionalized for different applications. They triggered membrane fusion through tunable electrostatic interactions with lipid bilayers. Antenna chromophores could be installed on them to create artificial light-harvesting complexes with efficient energy migration among tens to hundreds of chromophores. When cleavable cross-linkers were used, the SCMs could break apart in response to redox or pH signals, ejecting entrapped contents quickly as a result of built-in electrostatic stress. They served as caged surfactants whose surface activity was turned on by environmental stimuli. They crossed cell membranes readily. Encapsulated fluorophores showed enhanced photophysical properties including improved quantum yields and greatly expanded Stokes shifts. Catalytic groups could be installed on the surface or in the interior, covalently attached or physically entrapped. As enzyme mimics, the SCMs enabled rational engineering of the microenvironment around the catalysts to afford activity and selectivity not possible with conventional catalysts. PMID:27181610

Pu Anion Exchange Process Intensification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor-Pashow, Kathryn M. L.

This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through themore » large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.« less

Tropical Ocean and Global Atmosphere (TOGA) heat exchange project: A summary report

NASA Technical Reports Server (NTRS)

Liu, W. T.; Niiler, P. P.

1985-01-01

A pilot data center to compute ocean atmosphere heat exchange over the tropical ocean is prposed at the Jet Propulsion Laboratory (JPL) in response to the scientific needs of the Tropical Ocean and Global Atmosphere (TOGA) Program. Optimal methods will be used to estimate sea surface temperature (SET), surface wind speed, and humidity from spaceborne observations. A monthly summary of these parameters will be used to compute ocean atmosphere latent heat exchanges. Monthly fields of surface heat flux over tropical oceans will be constructed using estimations of latent heat exchanges and short wave radiation from satellite data. Verification of all satellite data sets with in situ measurements at a few locations will be provided. The data center will be an experimental active archive where the quality and quantity of data required for TOGA flux computation are managed. The center is essential to facilitate the construction of composite data sets from global measurements taken from different sensors on various satellites. It will provide efficient utilization and easy access to the large volume of satellite data available for studies of ocean atmosphere energy exchanges.

Complex conductivity of organic-rich shales

NASA Astrophysics Data System (ADS)

Woodruff, W. F.; Revil, A.; Torres-Verdin, C.

2013-12-01

We can accurately determine the intrinsic anisotropy and material properties in the laboratory, providing empirical evidence of transverse isotropy and the polarization of the organic and metallic fractions in saturated and unsaturated shales. We develop two distinct approaches to obtain the complex conductivity tensor from spectral induced polarization (SIP) measurements. Experimental results indicate clear anisotropy, and characterize the effects of thermal maturation, TOC, and pyrite, aiding in the calibration and interpretation of geophysical data. SIP is a non-intrusive measurement, sensitive to the surface conductance of mineral grains, frequency-dependent polarization of the electrical double layer, and bulk conductivity of the pore water. The in-phase and quadrature components depend upon parameters of principal importance in unconventional shale formation evaluation (e.g., the distribution of pore throat sizes, formation factor, permeability, salinity and cation exchange capacity (CEC), fluid saturation and wettability). In addition to the contribution of the electrical double layer of non-conducting minerals to surface conductivity, we have observed a clear relaxation associated with kerogen pyrolysis, pyrite distribution, and evidence that the CEC of the kerogen fraction may also contribute, depending on thermal maturation history. We utilize a recent model for anisotropic complex conductivity, and rigorous experimental protocols to quantify the role of kerogen and pyrolysis on surface and quadrature conductivity in mudrocks. The complex conductivity tensor σ* describes the directional dependence of electrical conduction in a porous medium, and accounts for both conduction and polarization. The complex-valued tensor components are given as σ*ij , where σ'ij represents in-phase and σ"ij denotes quadrature conductivities. The directional dependence of the complex conductivity tensor is relegated to the textural properties of the material. The components of the formation factor and connectivity (tortuosity) tensors Fij and Tij (affecting the bulk and surface conductivity, respectively) are correlated as Fij=TijΦ. Both conductivity and connectivity tensors share the same eigenvectors; the anisotropy ratio is equivalent in TI media. At high pore water salinity, surface and quadrature conductivity share the same bulk tortuosity; when surface conductivity dominates (low salinity), conductivity is controlled by the surface conductance, and the tortuosity of electrical current along mineral surfaces usually higher than that of the pore water. We developed two distinct SIP measurement protocols to obtain the tensor: (1) azimuthal sampling and inversion of phasor potentials through the full-field solution of the Laplace equation; (2) direct measurement of complex conductivity eigenvalues by polarized, single-component stimulus current. Experiments also include unsaturated and saturated measurements with three brines of known salinity and pH, at log-distributed frequencies ranging 1 mHz to 45 kHz. Both azimuthal spectra and eigenvalue spectra validate the theoretical model and illustrate the effectiveness of the protocols themselves. We obtain the textural tensors and invert key parameters including Archie exponents and CEC, and characterize the relaxation phenomena associated with kerogen content and maturity for multiphase fluid systems.

Dynamics of Cross-Shore Thermal Exchange Over Nonuniform Bathymetry

NASA Astrophysics Data System (ADS)

Safaie, A.; Davis, K. A.; Pawlak, G. R.

2016-02-01

The hydrodynamics of cross-shelf circulation on the inner shelf influence coastal ecosystems through the transport of heat, salt, nutrients, and planktonic organisms. While cross-shelf exchange on wide continental shelves has received a fair amount of attention in literature, the mechanisms for cross-shelf exchange on narrow shelves with steep, rough, and highly irregular bathymetry, characteristic of coral reef shorelines, is not well understood. Previous observational studies from reefs at Eilat, Israel and Oahu, Hawaii, have demonstrated the importance of surface heat flux in driving cross-shore transport. While both sites experienced offshore surface flow during daytime warming periods and offshore flow near the bed during nighttime cooling, the phase differences between the surface heat fluxes and thermal responses at the two sites indicate different dynamic flow regimes based on momentum and thermal balances. This study examines the dynamical structure of thermally driven flows using numerical modeling to investigate the hypothesis that thermally driven baroclinic exchange is important to cross-shore circulation for tropical coastlines. We use the open-source Regional Ocean Modeling System (ROMS), a free-surface, three-dimensional circulation model, considering a simple wedge case with uniform bathymetry in the alongshore direction, and heat flux applied uniformly to the surface. We examine different flow regimes using scaling of the momentum and thermal balance equations. We also explore the parameter space for the momentum balance describing cross-shore thermal exchange, and thoroughly characterize the exchange structure by investigating the dominant forcing regimes, the mechanisms responsible for modulating thermal circulation, and the effects of temporal variations in vertical mixing and heating/cooling buoyancy flux. Results are compared against existing data sets to evaluate the ability of the model to represent these flows.

Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

PubMed

Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

2018-04-25

The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

Oxidovanadium(IV) complexes involving dehydroacetic acid and β-diketones of bioinorganic and medicinal relevance: Their synthesis, characterization, thermal behavior and DFT aspects

NASA Astrophysics Data System (ADS)

Maurya, R. C.; Malik, B. A.; Mir, J. M.; Vishwakarma, P. K.

2015-03-01

Six new mixed-ligand complexes of oxidovanadium(IV) of the general composition [VO(dha)(L)(H2O)], where dhaH = dehydroacetic acid, LH = β-diketones, viz., acetoacetanilide (aaaH), o-acetoacetotoluidide (o-aatdH), o-acetoacetanisidide (o-aansH), acetylacetone (acacH), methyl acetoacetate (macacH) or ethyl acetoacetate (eacacH) have been synthesized by the reaction of VOSO4ṡ5H2O and the ligands given above in aqueous-ethanol medium. The resulting complexes have been characterized on the basis of elemental analyses, vanadium determination, molar conductance and magnetic measurements, mass spectrometry, thermogravimetric analysis, infrared and electron spin resonance spectral studies. The thermal decomposition processes of two representative complexes are discussed and the order of reaction (n) and the activation energy (Ea) for the particular decomposition steps have been calculated from thermogravimetric (TG) curve. Geometry optimizations were performed with the Gaussian 09 software package by using density functional theory (DFT) methods with Becke-3-Lee-Yang-Parr (B3LYP) hybrid exchange-correlation functional and the standard LANL2 MB basis set for dhaH and its complex [VO(dha)(acac)(H2O)]. Molecular surface electrostatic potentials (MSEP), vibrational frequency calculations, bond lengths, bond angles, dihedral angles, natural population analysis and calculations of molecular energies, HOMO and LUMO were made. No imaginary frequency was found in the optimized model compounds and hence ensures that the molecule is in the lowest point of the potential energy surface, that is, a energy minimum. Finally calculated results were applied to simulated Infrared spectra of the title compound which show good agreement with observed spectra. Based on experimental and theoretical data, suitable trans-octahedral structures have been proposed for these complexes.

48 CFR 315.201 - Exchanges with industry before receipt of proposals.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 48 Federal Acquisition Regulations System 4 2010-10-01 2010-10-01 false Exchanges with industry... Receipt of Proposals and Information 315.201 Exchanges with industry before receipt of proposals. (e)(1... complex projects involving R & D, IT, construction, and other highly technical requirements. An RFI may...

The Effects of a Virtual Exchange on Language Skills and Intercultural Competence

ERIC Educational Resources Information Center

Schenker, Theresa

2012-01-01

This dissertation explores the effects of a cross-cultural, cross-lingual virtual exchange on students' foreign language skills and intercultural competence. Specifically, the dissertation investigates the effects of students' participation in a twelve-week telecollaborative exchange on their use of syntactic complexity in foreign language writing…

GROUNDWATER-SURFACE WATER EXCHANGE AND IMPLICATIONS FOR LARGE RIVER RESTORATION

EPA Science Inventory

Movement of river water into and out of high-porosity alluvial deposits can have an important influence on surface water quality and aquatic habitat. In our study of a 60-km reach of the Willamette River in Oregon, USA, we: 1) used tracers to estimate the rate of exchange betw...

Impacts of differing aerodynamic resistance formulae on modeled energy exchange at the above-canopy/within-canopy/soil interface

USDA-ARS?s Scientific Manuscript database

Application of the Two-Source Energy Balance (TSEB) Model using land surface temperature (LST) requires aerodynamic resistance parameterizations for the flux exchange above the canopy layer, within the canopy air space and at the soil/substrate surface. There are a number of aerodynamic resistance f...

Carbon speciation at the air-sea interface during rain

NASA Astrophysics Data System (ADS)

McGillis, Wade; Hsueh, Diana; Takeshita, Yui; Donham, Emily; Markowitz, Michele; Turk, Daniela; Martz, Todd; Price, Nicole; Langdon, Chris; Najjar, Raymond; Herrmann, Maria; Sutton, Adrienne; Loose, Brice; Paine, Julia; Zappa, Christopher

2015-04-01

This investigation demonstrates the surface ocean dilution during rain events on the ocean and quantifies the lowering of surface pCO2 affecting the air-sea exchange of carbon dioxide. Surface salinity was measured during rain events in Puerto Rico, the Florida Keys, East Coast USA, Panama, and the Palmyra Atoll. End-member analysis is used to determine the subsequent surface ocean carbonate speciation. Surface ocean carbonate chemistry was measured during rain events to verify any approximations made. The physical processes during rain (cold, fresh water intrusion and buoyancy, surface waves and shear, microscale mixing) are described. The role of rain on surface mixing, biogeochemistry, and air-sea gas exchange will be discussed.

A primer on trace metal-sediment chemistry

USGS Publications Warehouse

Horowitz, Arthur J.

1985-01-01

In most aquatic systems, concentrations of trace metals in suspended sediment and the top few centimeters of bottom sediment are far greater than concentrations of trace metals dissolved in the water column. Consequently, the distribution, transport, and availability of these constituents can not be intelligently evaluated, nor can their environmental impact be determined or predicted solely through the sampling and analysis of dissolved phases. This Primer is designed to acquaint the reader with the basic principles that govern the concentration and distribution of trace metals associated with bottom and suspended sediments. The sampling and analysis of suspended and bottom sediments are very important for monitoring studies, not only because trace metal concentrations associated with them are orders of magnitude higher than in the dissolved phase, but also because of several other factors. Riverine transport of trace metals is dominated by sediment. In addition, bottom sediments serve as a source for suspended sediment and can provide a historical record of chemical conditions. This record will help establish area baseline metal levels against which existing conditions can be compared. Many physical and chemical factors affect a sediment's capacity to collect and concentrate trace metals. The physical factors include grain size, surface area, surface charge, cation exchange capacity, composition, and so forth. Increases in metal concentrations are strongly correlated with decreasing grain size and increasing surface area, surface charge, cation exchange capacity, and increasing concentrations of iron and manganese oxides, organic matter, and clay minerals. Chemical factors are equally important, especially for differentiating between samples having similar bulk chemistries and for inferring or predicting environmental availability. Chemical factors entail phase associations (with such sedimentary components as interstitial water, sulfides, carbonates, and organic matter) and ways in which the metals are entrained by the sediments (such as adsorption, complexation, and within mineral lattices).

Heat Exchangers for Utilization of the Heat of High-Temperature Geothermal Brines

NASA Astrophysics Data System (ADS)

Alkhasov, A. B.; Alkhasova, D. A.

2018-03-01

The basic component of two-circuit geothermal systems is the heat exchanger. When used in geothermal power systems, conventional shell-and-tube and plate heat exchangers cause problems related to the cleaning of the latter from salt-deposition and corrosion products. Their lifetime does not exceed, as a rule, 1 year. To utilize the heat of high-temperature geothermal brines, a heat exchanger of the "tube-in-tube" type is proposed. A heat exchanger of this design has been operated for several years in Ternair geothermal steam field; in this heat exchanger, the thermal potential of the saline thermal water is transferred to the fresh water of the secondary circuit of the heating system for apartment houses. The reduction in the weight and size characteristics of the heat exchangers is a topical problem that can be solved with the help of heat transfer enhancers. To enhance the heat transfer process in the heat exchanger, longitudinal ribbing of the heat exchange surface is proposed. The increase in the heat exchange surface from the heat carrier side by ribbing results in an increase in the amount of the heat transferred from the heating agent. The heat exchanger is easy to manufacture and is assembled out of components comprised of two concentrically positioned tubes of a definite length, 3-6 m, serially connected with each other. The method for calculation of the impact of the number and the size of the longitudinal ribs on the heat transfer in the well heat exchanger is presented and a criterion for the selection of the optimal number and design parameters of the ribs is formulated. To prevent the corrosion and salt deposition in the heat exchanger, the use of an effective OEDFK (oxyethylidenediphosphonic acid) agent is proposed. This agent has a long-lasting corrosion-inhibiting and antiscaling effect, which is explained by the formation of a strongly adhesive chelate layer difficult to wash off the surface. The passivating OEDFK layer is restored by periodical pulsed introduction of the agent solution into the brine at the heat exchanger inlet.

Cationic Exchanger with Activated Clay. Part I. Characteristics of the Materials and Preparation of the Cationic Exchanger. Part II. Chemical Separation. Part III. Effect of Thermal Treatment and Gamma Irradiation on the Internal Surface and Capacity of Acidic Montmorillonite; SCAMBIO CATIONICO CON ARGILLE ATTIVATE. PARTE I. CARATTERISTICHE DEI MATERIALI E PREPARAZIONE DELLO SCAMBIATORE CATIONICO. PARTE II. SEPARAZIONI CHIMICHE. PARTE III. EFFETTO DEL TRATTAMENTO TERMICO E DELLA IRRADIAZIONE GAMMA SULLA SUPERFICIE INTERNA E SULLA CAPACITA DELLE MONTMORILLONITI ACIDE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cerrai, E.; Ronchetti, C.; Triulzi, C.

1963-05-01

The preparation of an acidic cationic exchanger from a calcium bentonite is described. The behavior and properties of acidic montmorillonite and activated clay are given as well as the effect of thermal treatment and gamma irradiation on cationic exchange capacity and internal surface area. (auth)

Lanthanide ion (III) complexes of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate (DOTA-4AmP8−) for dual biosensing of pH with CEST (chemical exchange saturation transfer) and BIRDS (biosensor imaging of redundant deviation in shifts)

PubMed Central

Huang, Yuegao; Coman, Daniel; Ali, Meser M.; Hyder, Fahmeed

2014-01-01

Relaxivity based magnetic resonance of phosphonated ligands chelated with gadolinium (Gd3+) shows promise for pH imaging. However instead of monitoring the paramagnetic effect of lanthanide complexes on the relaxivity of water protons, biosensor (or molecular) imaging with magnetic resonance is also possible by detecting either the non-exchangeable or the exchangeable protons on the lanthanide complexes themselves. The non-exchangeable protons (e.g., –CHx, where 3≥x≥1) are detected using a three-dimensional chemical shift imaging method called Biosensor Imaging of Redundant Deviation in Shifts (BIRDS), whereas the exchangeable protons (e.g., –OH or –NHy, where 2≥y≥1) are measured with Chemical Exchange Saturation Transfer (CEST) contrast. Here we tested the feasibility of BIRDS and CEST for pH imaging of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraaminophosphonate (DOTA-4AmP8−) chelated with thulium (Tm3+) and ytterbium (Yb3+). BIRDS and CEST experiments show that both complexes are responsive to pH and temperature changes. Higher pH and temperature sensitivities are obtained with BIRDS for either complex when using the chemical shift difference between two proton resonances vs. using the chemical shift of a single proton resonance, thereby eliminating the need to use water resonance as reference. While CEST contrast for both agents is linearly dependent on pH within a relatively large range (i.e., 6.3-7.9), much stronger CEST contrast is obtained with YbDOTA-4AmP5− than with TmDOTA-4AmP5−. In addition, we demonstrate the prospect of using BIRDS to calibrate CEST as new platform for quantitative pH imaging. PMID:24801742

Oxygen surface exchange kinetics measurement by simultaneous optical transmission relaxation and impedance spectroscopy: Sr(Ti,Fe)O3-x thin film case study.

PubMed

Perry, Nicola H; Kim, Jae Jin; Tuller, Harry L

2018-01-01

We compare approaches to measure oxygen surface exchange kinetics, by simultaneous optical transmission relaxation (OTR) and AC-impedance spectroscopy (AC-IS), on the same mixed conducting SrTi 0.65 Fe 0.35 O 3-x film. Surface exchange coefficients were evaluated as a function of oxygen activity in the film, controlled by gas partial pressure and/or DC bias applied across the ionically conducting yttria-stabilized zirconia substrate. Changes in measured light transmission through the film over time (relaxations) resulted from optical absorption changes in the film corresponding to changes in its oxygen and oxidized Fe (~Fe 4+ ) concentrations; such relaxation profiles were successfully described by the equation for surface exchange-limited kinetics appropriate for the film geometry. The k chem values obtained by OTR were significantly lower than the AC-IS derived k chem values and k q values multiplied by the thermodynamic factor (bulk or thin film), suggesting a possible enhancement in k by the metal current collectors (Pt, Au). Long-term degradation in k chem and k q values obtained by AC-IS was also attributed to deterioration of the porous Pt current collector, while no significant degradation was observed in the optically derived k chem values. The results suggest that, while the current collector might influence measurements by AC-IS, the OTR method offers a continuous, in situ , and contact-free method to measure oxygen exchange kinetics at the native surfaces of thin films.

Oxygen surface exchange kinetics measurement by simultaneous optical transmission relaxation and impedance spectroscopy: Sr(Ti,Fe)O3-x thin film case study

PubMed Central

Perry, Nicola H.; Kim, Jae Jin; Tuller, Harry L.

2018-01-01

Abstract We compare approaches to measure oxygen surface exchange kinetics, by simultaneous optical transmission relaxation (OTR) and AC-impedance spectroscopy (AC-IS), on the same mixed conducting SrTi0.65Fe0.35O3-x film. Surface exchange coefficients were evaluated as a function of oxygen activity in the film, controlled by gas partial pressure and/or DC bias applied across the ionically conducting yttria-stabilized zirconia substrate. Changes in measured light transmission through the film over time (relaxations) resulted from optical absorption changes in the film corresponding to changes in its oxygen and oxidized Fe (~Fe4+) concentrations; such relaxation profiles were successfully described by the equation for surface exchange-limited kinetics appropriate for the film geometry. The kchem values obtained by OTR were significantly lower than the AC-IS derived kchem values and kq values multiplied by the thermodynamic factor (bulk or thin film), suggesting a possible enhancement in k by the metal current collectors (Pt, Au). Long-term degradation in kchem and kq values obtained by AC-IS was also attributed to deterioration of the porous Pt current collector, while no significant degradation was observed in the optically derived kchem values. The results suggest that, while the current collector might influence measurements by AC-IS, the OTR method offers a continuous, in situ, and contact-free method to measure oxygen exchange kinetics at the native surfaces of thin films. PMID:29511391

Calcium distribution in Amoeba proteus

PubMed Central

1979-01-01

A preliminary investigation of the distribution of cellular calcium in Amoeba proteus was undertaken. Total cellular calcium under control conditions was found to be 4.59 mmol/kg of cells. When the external Ca++ concentration is increased from the control level of 0.03 to 20 mM, a net Ca++ influx results with a new steady-state cellular calcium level being achieved in integral of 3 h. At steady state the amount of calcium per unit weight of cells is higher than the amount of calcium per unit weight of external solution when the external concentration of Ca++ is below 10 mM. At external Ca++ concentrations above this level, total cellular calcium approaches the medium level of Ca++. Steady- state calcium exchange in Amoeba proteus was determined with 45Ca. There is an immediate and rapid exchange of integral of 0.84 mmol/kg of cells or 18% of the total cellular calcium with the labelled Ca++. Following this initial exchange, there was very little if any further exchange observed. Most of this exchanged calcium could be eliminated from the cell with 1 mM La+++, suggesting that the exchanged calcium is associated with the surface of the cell. Increase in either the external Ca++ concentration of pH raise the amount of exchangeable calcium associated with the cell. Calcium may be associated with the cell surface as a co-ion in the diffuse double layer or bound to fixed negative sites on the surface of the cell. If Ca++-binding sites do exist on the cell surface, there may be more than one type and they may have different dissociation constants. The cytoplasmic Ca++ ion activity is probably maintained at very low levels. PMID:512628

The effects of intramolecular H-bond formation on the stability constant and water exchange rate of the Gd(III)-diethylenetriamine-N'-(3-amino-1,1-propylenephosphonic)-N, N,N'',N''-tetraacetate complex.

PubMed

Baranyai, Zsolt; Gianolio, Eliana; Ramalingam, Kondareddiar; Swenson, Rolf; Ranganathan, Ramachandran; Brücher, E; Aime, Silvio

2007-01-01

The binding interaction of metal chelates to biological macromolecules, though driven by properly devoted recognition synthons, may cause dramatic changes in some property associated with the coordination cage such as the thermodynamic stability or the exchange rate of the metal coordinated water. Such changes are due to electrostatic and H-bonding interactions involving atoms of the coordination cage and atoms of the biological molecule at the binding site. To mimic this type of H-bonding interactions, lanthanide(III) complexes with a DTPA-monophosphonate ligand bearing a propylamino moiety (H6NP-DTPA) were synthesized. Their thermodynamic stabilities and the exchange lifetime of the coordinated water molecule (for the Gd-complex) were compared with those of the analog complexes with DTPA and the parent DTPA-monophosphonate derivative (H6P-DTPA). It was found that the intramolecular H-bond between the epsilon-amino group and the phosphonate moiety in NP-DTPA complexes causes displacements of electric charges in their coordination cage that are markedly pH dependent. In turn, this affects the characteristic properties of the coordination cage. In particular it results in a marked elongation of the exchange lifetime of the coordinated water molecule. (c) 2007 John Wiley & Sons, Ltd.

Controlled drug delivery for glaucoma therapy using montmorillonite/Eudragit microspheres as an ion-exchange carrier

PubMed Central

Tian, Shuangyan; Li, Juan; Tao, Qi; Zhao, Yawen; Lv, Zhufen; Yang, Fan; Duan, Haoyun; Chen, Yanzhong; Zhou, Qingjun; Hou, Dongzhi

2018-01-01

Background Glaucoma is a serious eye disease that can lead to loss of vision. Unfortunately, effective treatments are limited by poor bioavailability of antiglaucoma medicine due to short residence time on the preocular surface. Materials and methods To solve this, we successfully prepared novel controlled-release ion-exchange microparticles to deliver betaxolol hydrochloride (BH). Montmorillonite/BH complex (Mt-BH) was prepared by acidification-intercalation, and this complex was encapsulated in microspheres (Mt-BH encapsulated microspheres [BMEMs]) by oil-in-oil emulsion–solvent evaporation method. The BH loaded into ion-exchange Mt was 47.45%±0.54%. After the encapsulation of Mt-BH into Eudragit microspheres, the encapsulation efficiency of BH into Eudragit microspheres was 94.35%±1.01% and BH loaded into Eudragit microspheres was 14.31%±0.47%. Results Both Fourier transform infrared spectra and X-ray diffraction patterns indicated that BH was successfully intercalated into acid-Mt to form Mt-BH and then Mt-BH was encapsulated into Eudragit microspheres to obtain BMEMs. Interestingly, in vitro release duration of the prepared BMEMs was extended to 12 hours, which is longer than both of the BH solution (2.5 hours) and the conventional BH microspheres (5 hours). Moreover, BMEM exhibited lower toxicity than that of BH solution as shown by the results of cytotoxicity tests, chorioallantoic membrane-trypan blue staining, and Draize rabbit eye test. In addition, both in vivo and in vitro preocular retention capacity study of BMEMs showed a prolonged retention time. The pharmacodynamics showed that BMEMs could extend the drug duration of action. Conclusion The developed BMEMs have the potential to be further applied as ocular drug delivery systems for the treatment of glaucoma. PMID:29391798

Controlled drug delivery for glaucoma therapy using montmorillonite/Eudragit microspheres as an ion-exchange carrier.

PubMed

Tian, Shuangyan; Li, Juan; Tao, Qi; Zhao, Yawen; Lv, Zhufen; Yang, Fan; Duan, Haoyun; Chen, Yanzhong; Zhou, Qingjun; Hou, Dongzhi

2018-01-01

Glaucoma is a serious eye disease that can lead to loss of vision. Unfortunately, effective treatments are limited by poor bioavailability of antiglaucoma medicine due to short residence time on the preocular surface. To solve this, we successfully prepared novel controlled-release ion-exchange microparticles to deliver betaxolol hydrochloride (BH). Montmorillonite/BH complex (Mt-BH) was prepared by acidification-intercalation, and this complex was encapsulated in microspheres (Mt-BH encapsulated microspheres [BMEMs]) by oil-in-oil emulsion-solvent evaporation method. The BH loaded into ion-exchange Mt was 47.45%±0.54%. After the encapsulation of Mt-BH into Eudragit microspheres, the encapsulation efficiency of BH into Eudragit microspheres was 94.35%±1.01% and BH loaded into Eudragit microspheres was 14.31%±0.47%. Both Fourier transform infrared spectra and X-ray diffraction patterns indicated that BH was successfully intercalated into acid-Mt to form Mt-BH and then Mt-BH was encapsulated into Eudragit microspheres to obtain BMEMs. Interestingly, in vitro release duration of the prepared BMEMs was extended to 12 hours, which is longer than both of the BH solution (2.5 hours) and the conventional BH microspheres (5 hours). Moreover, BMEM exhibited lower toxicity than that of BH solution as shown by the results of cytotoxicity tests, chorioallantoic membrane-trypan blue staining, and Draize rabbit eye test. In addition, both in vivo and in vitro preocular retention capacity study of BMEMs showed a prolonged retention time. The pharmacodynamics showed that BMEMs could extend the drug duration of action. The developed BMEMs have the potential to be further applied as ocular drug delivery systems for the treatment of glaucoma.

Calculation of the rate constant for state-selected recombination of H+O2(v) as a function of temperature and pressure

NASA Astrophysics Data System (ADS)

Teitelbaum, Heshel; Caridade, Pedro J. S. B.; Varandas, António J. C.

2004-06-01

Classical trajectory calculations using the MERCURY/VENUS code have been carried out on the H+O2 reactive system using the DMBE-IV potential energy surface. The vibrational quantum number and the temperature were selected over the ranges v=0 to 15, and T=300 to 10 000 K, respectively. All other variables were averaged. Rate constants were determined for the energy transfer process, H+O2(v)-->H+O2(v''), for the bimolecular exchange process, H+O2(v)-->OH(v')+O, and for the dissociative process, H+O2(v)-->H+O+O. The dissociative process appears to be a mere extension of the process of transferring large amounts of energy. State-to-state rate constants are given for the exchange reaction, and they are in reasonable agreement with previous results, while the energy transfer and dissociative rate constants have never been reported previously. The lifetime distributions of the HO2 complex, calculated as a function of v and temperature, were used as a basis for determining the relative contributions of various vibrational states of O2 to the thermal rate coefficients for recombination at various pressures. This novel approach, based on the complex's ability to survive until it collides in a secondary process with an inert gas, is used here for the first time. Complete falloff curves for the recombination of H+O2 are also calculated over a wide range of temperatures and pressures. The combination of the two separate studies results in pressure- and temperature-dependent rate constants for H+O2(v)(+Ar)⇄HO2(+Ar). It is found that, unlike the exchange reaction, vibrational and rotational-translational energy are liabilities in promoting recombination.

Responses of Surface Ozone Air Quality to Anthropogenic Nitrogen Deposition

NASA Astrophysics Data System (ADS)

Zhang, L.; Zhao, Y.; Tai, A. P. K.; Chen, Y.; Pan, Y.

2017-12-01

Human activities have substantially increased atmospheric deposition of reactive nitrogen to the Earth's surface, inducing unintentional effects on ecosystems with complex environmental and climate consequences. One consequence remaining unexplored is how surface air quality might respond to the enhanced nitrogen deposition through surface-atmosphere exchange. We combine a chemical transport model (GEOS-Chem) and a global land model (Community Land Model) to address this issue with a focus on ozone pollution in the Northern Hemisphere. We consider three processes that are important for surface ozone and can be perturbed by addition of atmospheric deposited nitrogen: emissions of biogenic volatile organic compounds (VOCs), ozone dry deposition, and soil nitrogen oxide (NOx) emissions. We find that present-day anthropogenic nitrogen deposition (65 Tg N a-1 to the land), through enhancing plant growth (represented as increases in vegetation leaf area index (LAI) in the model), could increase surface ozone from increased biogenic VOC emissions, but could also decrease ozone due to higher ozone dry deposition velocities. Meanwhile, deposited anthropogenic nitrogen to soil enhances soil NOx emissions. The overall effect on summer mean surface ozone concentrations show general increases over the globe (up to 1.5-2.3 ppbv over the western US and South Asia), except for some regions with high anthropogenic NOx emissions (0.5-1.0 ppbv decreases over the eastern US, Western Europe, and North China). We compare the surface ozone changes with those driven by the past 20-year climate and historical land use changes. We find that the impacts from anthropogenic nitrogen deposition can be comparable to the climate and land use driven surface ozone changes at regional scales, and partly offset the surface ozone reductions due to land use changes reported in previous studies. Our study emphasizes the complexity of biosphere-atmosphere interactions, which can have important implications for future air quality prediction.

Application of the π-accepting ability parameter of N-heterocyclic carbene ligands in iridium complexes for signal amplification by reversible exchange (SABRE).

PubMed

van Weerdenburg, Bram J A; Eshuis, Nan; Tessari, Marco; Rutjes, Floris P J T; Feiters, Martin C

2015-09-21

The new π-accepting ability parameter (PAAP) appears to be the best tool to analyse the electronic properties of NHC ligands in [Ir(H)2(NHC)(Py)3](+) complexes for SABRE. Together with the buried volume, the efficiency of hyperpolarisation transfer in SABRE, depending on the exchange rate of pyridine, can be described.

Photosynthetic adaptation strategy of Ulva prolifera floating on the sea surface to environmental changes.

PubMed

Zhao, Xinyu; Tang, Xuexi; Zhang, Huanxin; Qu, Tongfei; Wang, Ying

2016-10-01

For 8 consecutive years, a green tide has originated in the southern Yellow Sea and spread to the Qingdao offshore area. The causative species, Ulva prolifera, always forms a very thick thallus mat that is capable of drifting long distances over long periods. During this process, although the thalli face disturbance by complex environmental factors, they maintain high biomass and proliferation. We hypothesized that some form of photosynthetic adaptation strategy must exist to protect the thalli. Therefore, we studied the different photosynthetic response characteristics of the surface and lower layers of the floating thallus mats, and investigated the physiological and molecular-level adaptation mechanisms. The results showed that: (1) U. prolifera has strong photosynthetic capability that ensures it can gain sufficient energy to increase its biomass and adapt to long-distance migration. (2) Surface layer thalli adapt to the complex environment by dissipating excess energy via photosynthetic quantum control (energy quenching and energy redistribution between PSII/PSI) to avoid irreversible damage to the photosynthetic system. (3) Lower layer thalli increase their contents of Chlorophyll a (Chl a) and Chlorophyll b (Chl b) and decrease their Chl a/Chl b ratio to improve their ability to use light energy. (4) U. prolifera has strong photosynthetic plasticity and can adapt to frequent exchange between the surface and lower layer environments because of wave disturbance. Pigment component changes, energy quenching, and energy redistribution between PSII/PSI contribute to this photosynthetic plasticity. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Quantum model of a solid-state spin qubit: Ni cluster on a silicon surface by the generalized spin Hamiltonian and X-ray absorption spectroscopy investigations

NASA Astrophysics Data System (ADS)

Farberovich, Oleg V.; Mazalova, Victoria L.; Soldatov, Alexander V.

2015-11-01

We present here the quantum model of a Ni solid-state electron spin qubit on a silicon surface with the use of a density-functional scheme for the calculation of the exchange integrals in the non-collinear spin configurations in the generalized spin Hamiltonian (GSH) with the anisotropic exchange coupling parameters linking the nickel ions with a silicon substrate. In this model the interaction of a spin qubit with substrate is considered in GSH at the calculation of exchange integrals Jij of the nanosystem Ni7-Si in the one-electron approach taking into account chemical bonds of all Si-atoms of a substrate (environment) with atoms of the Ni7-cluster. The energy pattern was found from the effective GSH Hamiltonian acting in the restricted spin space of the Ni ions by the application of the irreducible tensor operators (ITO) technique. In this paper we offer the model of the quantum solid-state N-spin qubit based on the studying of the spin structure and the spin-dynamics simulations of the 3d-metal Ni clusters on the silicon surface. The solution of the problem of the entanglement between spin states in the N-spin systems is becoming more interesting when considering clusters or molecules with a spectral gap in their density of states. For quantifying the distribution of the entanglement between the individual spin eigenvalues (modes) in the spin structure of the N-spin system we use the density of entanglement (DOE). In this study we have developed and used the advanced high-precision numerical techniques to accurately assess the details of the decoherence process governing the dynamics of the N-spin qubits interacting with a silicon surface. We have studied the Rabi oscillations to evaluate the N-spin qubits system as a function of the time and the magnetic field. We have observed the stabilized Rabi oscillations and have stabilized the quantum dynamical qubit state and Rabi driving after a fixed time (0.327 μs). The comparison of the energy pattern with the anisotropic exchange models conventionally used for the analysis of this system and, with the results of the experimental XANES spectra, shows that our complex investigations provide a good description of the pattern of the spin levels and the spin structures of the nanomagnetic Ni7 qubit. The results are discussed in the view of the general problem of the solid-state spin qubits and the spin structure of the Ni cluster.

The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

PubMed Central

Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

2017-01-01

Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II) adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

Theoretical study of the magnetic behavior of hexanuclear Cu(II) and Ni(II) polysiloxanolato complexes.

PubMed

Ruiz, Eliseo; Cano, Joan; Alvarez, Santiago; Caneschi, Andrea; Gatteschi, Dante

2003-06-04

A theoretical density functional study of the exchange coupling in hexanuclear polysiloxanolato-bridged complexes of Cu(II) and Ni(II) is presented. By calculating the energies of three different spin configurations, we can obtain estimates of the first-, second-, and third-neighbor exchange coupling constants. The study has been carried out for the complete structures of the Cu pristine cluster and of the chloroenclathrated Ni complex as well as for the hypotethical pristine Ni compound and for magnetically dinuclear analogues M(2)Zn(4) (M = Cu, Ni).

KSC-2011-1962

NASA Image and Video Library

2011-03-01

VANDENBERG AIR FORCE BASE, Calif. -- The first stage of the Delta II rocket that will carry NASA's Aquarius satellite into low Earth orbit arrives to the launch pad at Vandenberg Air Force Base's Space Launch Complex-2 (SLC-2) in California. While the Delta II rocket is stacked on SLC-2, teams for NASA's Glory spacecraft and Orbital Sciences Taurus XL rocket are in launch preparation mode at Vandenberg's nearby Space Launch Complex 576-E. Scheduled to launch in June, Aquarius' mission will be to provide monthly maps of global changes in sea surface salinity. By measuring ocean salinity from space, Aquarius will provide new insights into how the massive natural exchange of freshwater between the ocean, atmosphere and sea ice influences ocean circulation, weather and climate. Also going up with the satellite are optical and thermal cameras, a microwave radiometer and the SAC-D spacecraft, which were developed with the help of institutions in Italy, France, Canada and Argentina. Photo credit: NASA/VAFB

KSC-2011-1963

NASA Image and Video Library

2011-03-01

VANDENBERG AIR FORCE BASE, Calif. -- The first stage of the Delta II rocket that will carry NASA's Aquarius satellite into low Earth orbit arrives to the launch pad at Vandenberg Air Force Base's Space Launch Complex-2 (SLC-2) in California. While the Delta II rocket is stacked on SLC-2, teams for NASA's Glory spacecraft and Orbital Sciences Taurus XL rocket are in launch preparation mode at Vandenberg's nearby Space Launch Complex 576-E. Scheduled to launch in June, Aquarius' mission will be to provide monthly maps of global changes in sea surface salinity. By measuring ocean salinity from space, Aquarius will provide new insights into how the massive natural exchange of freshwater between the ocean, atmosphere and sea ice influences ocean circulation, weather and climate. Also going up with the satellite are optical and thermal cameras, a microwave radiometer and the SAC-D spacecraft, which were developed with the help of institutions in Italy, France, Canada and Argentina. Photo credit: NASA/VAFB

Biosorption: current perspectives on concept, definition and application.

PubMed

Fomina, Marina; Gadd, Geoffrey Michael

2014-05-01

Biosorption is a physico-chemical and metabolically-independent process based on a variety of mechanisms including absorption, adsorption, ion exchange, surface complexation and precipitation. Biosorption processes are highly important in the environment and conventional biotreatment processes. As a branch of biotechnology, biosorption has been aimed at the removal or recovery of organic and inorganic substances from solution by biological material which can include living or dead microorganisms and their components, seaweeds, plant materials, industrial and agricultural wastes and natural residues. For decades biosorption has been heralded as a promising cost-effective clean-up biotechnology. Despite significant progress in our understanding of this complex phenomenon and a dramatic increase in publications in this research area, commercialization of biosorption technologies has been limited so far. This article summarizes existing knowledge on various aspects of the fundamentals and applications of biosorption and critically reviews the obstacles to commercial success and future perspectives. Copyright © 2014 Elsevier Ltd. All rights reserved.

Description and hydrogeologic implications of cored sedimentary material from the 1975 drilling program at the radioactive waste management complex, Idaho

USGS Publications Warehouse

Rightmire, C.T.

1984-01-01

Samples of sedimentary material from interbeds between basalt flows and from fractures in the flows, taken from two drill cores at the Radioactive Waste Management Complex at the Idaho National Engineering Laboratory were analyzed for (1) particle-size dribution, (2) bulk mineralogy, (3) clay mineralogy, (4) cation-exchange capacity, and (5) carbonate content. Thin sections of selected sediment material were made for petrographic examination. Preliminary interpretations indicate that (1) it may be possible to distinguish the various sediment interbeds on the basis of their mineralogy, (2) the presence of carbonate horizons in sedimentary interbeds may be utilized to approximate the time of exposure and the climate while the surface was exposed (which affected the hydrogeologic character of the sediment), and the type and orientation of fracture-filling material may be utilized to determine the mechanism by which fractures were filled. (USGS)

Optical Absorbance Enhancement in PbS QD/Cinnamate Ligand Complexes.

PubMed

Kroupa, Daniel M; Vörös, Márton; Brawand, Nicholas P; Bronstein, Noah; McNichols, Brett W; Castaneda, Chloe V; Nozik, Arthur J; Sellinger, Alan; Galli, Giulia; Beard, Matthew C

2018-06-08

We studied the optical absorption enhancement in colloidal suspensions of PbS quantum dots (QD) upon ligand exchange from oleate to a series of cinnamate ligands. By combining experiments and ab initio simulations, we elucidate physical parameters that govern the optical absorption enhancement. We find that, within the cinnamate/PbS QD system, the optical absorption enhancement scales linearly with the electronic gap of the ligand, indicating that the ligand/QD coupling occurs equally efficient between the QD and ligand HOMO and their respective LUMO levels. Disruption of the conjugation that connects the aromatic ring and its substituents to the QD core causes a reduction of the electronic coupling. Our results further support the notion that the ligand/QD complex should be considered as a distinct chemical system with emergent behavior rather than a QD core with ligands whose sole purpose is to passivate surface dangling bonds and prevent agglomeration.

Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment

NASA Astrophysics Data System (ADS)

Fernández-Ramos, Antonio; Smedarchina, Zorka; Rodríguez-Otero, Jesús

2001-01-01

To test the approximate instanton approach to intermolecular proton-transfer dynamics, we report multidimensional ab initio bimolecular rate constants of HH, HD, and DD exchange in the complex of acetic acid with methanol in tetrahydrofuran-d8, and compare them with the NMR (nuclear magnetic resonance) experiments of Gerritzen and Limbach. The bimolecular rate constants are evaluated as products of the exchange rates and the equilibrium rate constants of complex formation in solution. The two molecules form hydrogen-bond bridges and the exchange occurs via concerted transfer of two protons. The dynamics of this transfer is evaluated in the complete space of 36 vibrational degrees of freedom. The geometries of the two isolated molecules, the complex, and the transition states corresponding to double proton transfer are fully optimized at QCISD (quadratic configuration interaction including single and double substitutions) level of theory, and the normal-mode frequencies are calculated at MP2 (Møller-Plesset perturbation theory of second order) level with the 6-31G (d,p) basis set. The presence of the solvent is taken into account via single-point calculations over the gas phase geometries with the PCM (polarized continuum model). The proton exchange rate constants, calculated with the instanton method, show the effect of the structure and strength of the hydrogen bonds, reflected in the coupling between the tunneling motion and the other vibrations of the complex. Comparison with experiment, which shows substantial kinetic isotopic effects (KIE), indicates that tunneling prevails over classic exchange for the whole temperature range of observation. The unusual behavior of the experimental KIE upon single and double deuterium substitution is well reproduced and is related to the synchronicity of two-atom tunneling.

Surface characteristics of clinically used dental implant screws

NASA Astrophysics Data System (ADS)

Han, Myung-Ju; Choe, Han-Cheol; Chung, Chae-Heon

2005-12-01

Surface alteration of implant screws after function may be associated with mechanicalffailure. This type of metal fatigue appears to be the most common cause of structural failure. The purpose of this study was to evaluate surface alteration of implant screws after function through an examination of used and unused implant screws via scanning electron microscopy (SEM). In this study, abutment screws (Steri-oss, 3i, USA), gold retaining screws (3i, USA), and titanium retaining screws (3i, USA) were retrieved from patients, New, unused abutment, and retaining screws were prepared for a control group. Each of the old, used screws was retrieved with a screwdriver. The retrieved implant complex of a Steri-oss system was also prepared for this study. SEM investigation and energy dispersive spectroscopy (EDS) analysis of the abutment and retaining screws were then performed, as well as SEM investigation of a cross-sectioned sample of the retrieved implant complex in the case of new, unused implant screws, as-manufactured circumferential grooves were regularly examined and screw threads were sharply maintained. Before ultrasonic cleansing of old, used implant screws, there was a large amount of debris accumulation and corrosion products. After ultrasonic cleansing of old, used implant screws, circumferential grooves were examined were found to be randomly deepened and scratching increased. Also, dull screw fhreads were observed. More surface alterations after function were observed in titanium screws than in gold screws. Furthermore, more surface alteration was observed when the screws were retrieved with a driver than without a driver. These surface alterations after function may result in screw instability. Regular cleansing and exchange of screws is therefore recommended. We also recommend the use of gold screws over titanium screws, and careful manipulation of the driver.

Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment.

PubMed

Appelo, C A J; Vinsot, A; Mettler, S; Wechner, S

2008-10-23

A borehole in the Callovo-Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.

Spume Drops: Their Potential Role in Air-Sea Gas Exchange

NASA Astrophysics Data System (ADS)

Monahan, Edward C.; Staniec, Allison; Vlahos, Penny

2017-12-01

After summarizing the time scales defining the change of the physical properties of spume and other droplets cast up from the sea surface, the time scales governing drop-atmosphere gas exchange are compared. Following a broad review of the spume drop production functions described in the literature, a subset of these functions is selected via objective criteria, to represent typical, upper bound, and lower bound production functions. Three complementary mechanisms driving spume-atmosphere gas exchange are described, and one is then used to estimate the relative importance, over a broad range of wind speeds, of this spume drop mechanism compared to the conventional, diffusional, sea surface mechanism in air-sea gas exchange. While remaining uncertainties in the wind dependence of the spume drop production flux, and in the immediate sea surface gas flux, preclude a definitive conclusion, the findings of this study strongly suggest that, at high wind speeds (>20 m s-1 for dimethyl sulfide and >30 m s-1 for gases such a carbon dioxide), spume drops do make a significant contribution to air-sea gas exchange.