Spectroscopic identification of binary and ternary surface complexes of Np(V) on gibbsite.

PubMed

Gückel, Katharina; Rossberg, André; Müller, Katharina; Brendler, Vinzenz; Bernhard, Gert; Foerstendorf, Harald

2013-12-17

For the first time, detailed molecular information on the Np(V) sorption species on amorphous Al(OH)3 and crystalline gibbsite was obtained by in situ time-resolved Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The results consistently demonstrate the formation of mononuclear inner sphere complexes of the NpO2(+) ion irrespective of the prevailing atmospheric condition. The impact of the presence of atmospheric equivalent added carbonate on the speciation in solution and on the surfaces becomes evident from vibrational data. While the 1:1 aqueous carbonato species (NpO2CO3(-)) was found to become predominant in the circumneutral pH range, it is most likely that this species is sorbed onto the gibbsite surface as a ternary inner sphere surface complex where the NpO2(+) moiety is directly coordinated to the functional groups of the gibbsite's surface. These findings are corroborated by results obtained from EXAFS spectroscopy providing further evidence for a bidentate coordination of the Np(V) ion on amorphous Al(OH)3. The identification of the Np(V) surface species on gibbsite constitutes a basic finding for a comprehensive description of the dissemination of neptunium in groundwater systems.

On the anomalous adsorption of [Pd(edta)]2- at the water/Goethite interface: spectroscopic evidence for two types of surface complexes.

PubMed

Kaplun, Marina; Nordin, Agneta; Persson, Per

2008-01-15

The structure of palladium(II) ethylenediaminetetraacetate (edta) in aqueous solutions and its adsorption on the surface of goethite (alpha-FeOOH) were studied using extended X-ray absorption fine structure spectroscopy and attenuated total reflection Fourier transform infrared spectroscopy. The obtained results show that in aqueous solutions, Pd-edta exists as a 1:1 complex, [Pd(edta)]2-, with edta acting as a quadridentate ligand. On the surface of goethite, [Pd(edta)]2- forms two different types of complexes over a pH range of 3.40-8.12. At pH < 5, [Pd(edta)]2- adsorbs as an outer-sphere species with possible hydrogen bonding. At higher pH values, the formation of inner-sphere complexes of the cation-type sets in after a cleavage of one glycinate ring and the formation of an (edta)Pd-O-Fe linkage.

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.

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

Interaction of NaOH solutions with silica surfaces

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

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Interaction of NaOH solutions with silica surfaces

DOE PAGES

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

2018-01-16

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

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

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments.

PubMed

Brechbühl, Yves; Christl, Iso; Elzinga, Evert J; Kretzschmar, Ruben

2012-07-01

The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures. Copyright © 2012 Elsevier Inc. All rights reserved.

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

NASA Astrophysics Data System (ADS)

Filius, Jeroen D.; Meeussen, Johannes C. L.; Lumsdon, David G.; Hiemstra, Tjisse; van Riemsdijk, Willem H.

2003-04-01

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.

Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

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

Ilgen, Anastasia G.; Kruichak, Jessica N.; Artyushkova, Kateryna

Adsorption and redox transformations on clay mineral surfaces are prevalent in surface environments. We examined the redox reactivity of iron Fe(II)/Fe(III) associated with natural and synthetic ferric nontronites. Specifically, we assessed how Fe(II) residing in the octahedral sheets, or Fe(II) adsorbed at the edge sites alters redox activity of nontronites. To probe the redox activity we used arsenic (As) and selenium (Se). Activation of both synthetic and natural ferric nontronites was. observed following the introduction of Fe(II) into predominantly-Fe(III) octahedral sheets or through the adsorption of Fe(II) onto the mineral surface. The oxidation of As(III) to As(V) was observed viamore » catalytic (oxic conditions) and, to a lesser degree, via direct (anoxic conditions) pathways. We provide experimental evidence for electron transfer from As(III) to Fe(111) at the natural and synthetic nontronite surfaces, and illustrate that only a fraction of structural Fe(III) is accessible for redox transformations. We show that As adsorbed onto natural and synthetic nontronites forms identical adsorption complexes, namely inner-sphere binuclear bidentate. In conclusion, we show that the formation of an inner-sphere adsorption complex may be a necessary step for the redox transformation via catalytic or direct oxidation pathways.« less

Redox Transformations of As and Se at the Surfaces of Natural and Synthetic Ferric Nontronites: Role of Structural and Adsorbed Fe(II)

DOE PAGES

Ilgen, Anastasia G.; Kruichak, Jessica N.; Artyushkova, Kateryna; ...

2017-08-29

Adsorption and redox transformations on clay mineral surfaces are prevalent in surface environments. We examined the redox reactivity of iron Fe(II)/Fe(III) associated with natural and synthetic ferric nontronites. Specifically, we assessed how Fe(II) residing in the octahedral sheets, or Fe(II) adsorbed at the edge sites alters redox activity of nontronites. To probe the redox activity we used arsenic (As) and selenium (Se). Activation of both synthetic and natural ferric nontronites was. observed following the introduction of Fe(II) into predominantly-Fe(III) octahedral sheets or through the adsorption of Fe(II) onto the mineral surface. The oxidation of As(III) to As(V) was observed viamore » catalytic (oxic conditions) and, to a lesser degree, via direct (anoxic conditions) pathways. We provide experimental evidence for electron transfer from As(III) to Fe(111) at the natural and synthetic nontronite surfaces, and illustrate that only a fraction of structural Fe(III) is accessible for redox transformations. We show that As adsorbed onto natural and synthetic nontronites forms identical adsorption complexes, namely inner-sphere binuclear bidentate. In conclusion, we show that the formation of an inner-sphere adsorption complex may be a necessary step for the redox transformation via catalytic or direct oxidation pathways.« less

Steric hindrance and the enhanced stability of light rare-earth elements in hydrothermal fluids

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2009-01-01

A series of X-ray absorption spectroscopy (XAS) experiments were made to determine the structure and stability of aqueous REE (La, Nd, Gd, and Yb) chloride complexes to 500 ??C and 520 MPa. The REE3+ ions exhibit inner-sphere chloroaqua complexation with a steady increase of chloride coordination with increasing temperature in the 150 to 500 ??C range. Furthermore, the degree of chloride coordination of REE3+ inner-sphere chloroaqua complexes decreases significantly from light to heavy REE. These results indicate that steric hindrance drives the reduction of chloride coordination of REE3+ inner-sphere chloroaqua complexes from light to heavy REE. This results in greater stability and preferential transport of light REE3+ over heavy REE3+ ions in saline hydrothermal fluids. Accordingly, the preferential mobility of light REE directly influences the relative abundance of REE in rocks and minerals and thus needs to be considered in geochemical modeling of petrogenetic and ore-forming processes affected by chloride-bearing hydrothermal fluids.

Multiple conformational states of the hammerhead ribozyme, broad time range of relaxation and topology of dynamics

PubMed Central

Menger, Marcus; Eckstein, Fritz; Porschke, Dietmar

2000-01-01

The dynamics of a hammerhead ribozyme was analyzed by measurements of fluorescence-detected temperature jump relaxation. The ribozyme was substituted at different positions by 2-aminopurine (2-AP) as fluorescence indicator; these substitutions do not inhibit catalysis. The general shape of relaxation curves reported from different positions of the ribozyme is very similar: a fast decrease of fluorescence, mainly due to physical quenching, is followed by a slower increase of fluorescence due to conformational relaxation. In most cases at least three relaxation time constants in the time range from a few microseconds to ~200 ms are required for fitting. Although the relaxation at different positions of the ribozyme is similar in general, suggesting a global type of ribozyme dynamics, a close examination reveals differences, indicating an individual local response. For example, 2-AP in a tetraloop reports mainly the local loop dynamics known from isolated loops, whereas 2-AP located at the core, e.g. at the cleavage site or its vicinity, also reports relatively large amplitudes of slower components of the ribozyme dynamics. A variant with an A→G substitution in domain II, resulting in an inactive form, leads to the appearance of a particularly slow relaxation process (τ ≈200 ms). Addition of Mg2+ ions induces a reduction of amplitudes and in most cases a general increase of time constants. Differences between the hammerhead variants are clearly demonstrated by subtraction of relaxation curves recorded under corresponding conditions. The changes induced in the relaxation response by Mg2+ are very similar to those induced by Ca2+. The relaxation data do not provide any evidence for formation of Mg2+-inner sphere complexes in hammerhead ribozymes, because a Mg2+-specific relaxation effect was not visible. However, a Mg2+-specific effect was found for a dodeca-riboadenylate substituted with 2-AP, showing that the fluorescence of 2-AP is able to indicate inner sphere complexation. Amplitudes and time constants show that the equilibrium constant of inner sphere complexation is 1.2, corresponding to 55% inner sphere state of the Mg2+ complexes; the rate constant 6.6 × 103 s–1 for inner sphere complexation is relatively low and shows the existence of some barrier(s) on the way to inner sphere complexes. PMID:11071929

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

USGS Publications Warehouse

Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

2005-01-01

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

Macroscopic and molecular-scale assessment of soil lead contamination impacted by seasonal dove hunting activities

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

Arai, Y.; Tappero, R.; Rick, A.R.

Environmental contamination of lead (Pb) in soils and sediments poses serious threats to human and ecological health. The objective of this study is to investigate the effect of seasonal dove sports hunting activities on Pb contamination in acid forest soils. A grid sampling method was used to investigate the spatial distribution of Pb contamination in surface soils. Soils were analyzed for total metal(loid) concentration and characterized for physicochemical properties and mineralogy. Adsorption isotherm experiments were also conducted to understand the reactivity and retention capacity of Pb(II) in soils. Finally, synchrotron-based X-ray microprobe and X-ray absorption spectroscopy were used to understandmore » the chemical speciation of Pb that controls the retention/release mechanisms of Pb in soils. There was no excessive accumulation of Pb at the site. However, the concentration of Pb in surface soils was greater than the background level (<16 mg kg{sup -1}). The contamination level of Pb was as high as 67 mg kg{sup -1} near a patch of corn field where lime was frequently applied. A microfocused X-ray microprobe analysis showed the presence of Pb pellet fragments that predominantly contain oxidized Pb(II), suggesting that oxidative dissolution was occurring in soils. Dissolved Pb(II) can be readily retained in soils up to {approx}3,600 mg kg{sup -1} via inner-sphere and outer-sphere surface complexation on carbon and aluminol functional groups of soil components, suggesting that partitioning reactions control the concentration of Pb in soil solution. The fate of Pb is likely to be controlled by (1) oxidative dissolution process of Pb(0) pellets and (2) the release of outer-sphere and/or inner-sphere Pb surface complexes in humic substances and aluminosilicate/Al oxyhydroxides. Although no remedial actions are immediately required, the long-term accumulation of Pb in soils should be carefully monitored in protecting ecosystem and water quality at the dove hunting field.« less

Simulations of the kinematic dynamo onset of spherical Couette flows with smooth and rough boundaries.

PubMed

Finke, K; Tilgner, A

2012-07-01

We study numerically the dynamo transition of an incompressible electrically conducting fluid filling the gap between two concentric spheres. In a first series of simulations, the fluid is driven by the rotation of a smooth inner sphere through no-slip boundary conditions, whereas the outer sphere is stationary. In a second series a volume force intended to simulate a rough surface drives the fluid next to the inner sphere within a layer of thickness one-tenth of the gap width. We investigate the effect of the boundary layer thickness on the dynamo threshold in the turbulent regime. The simulations show that the boundary forcing simulating the rough surface lowers the necessary rotation rate, which may help to improve spherical dynamo experiments.

Red mud carbonation using carbon dioxide: Effects of carbonate and calcium ions on goethite surface properties and settling.

PubMed

Liang, Gaojie; Chen, Wenmi; Nguyen, Anh V; Nguyen, Tuan A H

2018-05-01

Carbonation using CO 2 appears as an attractive solution for disposing of red mud suspensions, an aluminum industry hazardous waste since it also offers an option for CO 2 sequestration. Here we report the novel findings that CO 3 2- together with Ca 2+ can significantly affect the surface properties and settling of goethite, a major component of red mud. Specifically, their effects on the goethite surface chemistry, colloidal interaction forces and settling in alkaline solutions are investigated. The surface potential becomes more negative by the formation of carbonate inner-sphere complexes on goethite surface. It is consistent with the strong repulsion, decreased particle size and settling velocity with increased carbonate concentrations as measured by atomic force microscopy, particle size analysis, and particle settling. Adding Ca 2+ that forms outer-sphere complexes with pre-adsorbed carbonate changes goethite surface charge negligibly. Changing repulsion to the attraction between goethite surfaces by increasing calcium dosage indicates the surface bridging, in accordance with the increased settling velocity. The adverse effect of carbonate on goethite flocculation is probably due to its specific chemisorption and competition with flocculants. By forming outer-sphere complexes together with the flocculant-calcium bridging effect, calcium ions can eliminate the negative influence of carbonate and improve the flocculation of goethite particles. These findings contribute to a better understanding of goethite particle interaction with salt ions and flocculants in controlling the particle behavior in the handling processes, including the red mud carbonation. Copyright © 2018 Elsevier Inc. All rights reserved.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Background electrolytes and pH effects on selenate adsorption using iron-impregnated granular activated carbon and surface binding mechanisms.

PubMed

Zhang, Ning; Gang, Daniel Dianchen; McDonald, Louis; Lin, Lian-Shin

2018-03-01

Iron-impregnated granular activated carbon (Fe-GAC) has been shown effective for selenite adsorptive removal from aqueous solutions, but similar effectiveness was not observed with selenate. This study examined the effects of background electrolytes and pH on selenate adsorption on to Fe-GAC, and surface bindings to elucidate the selenate adsorption mechanisms. The decrease magnitude of selenate adsorption capacity under three background electrolytes followed the order: LiCl > NaCl > KCl, as ionic strength increased from 0.01 to 0.1 M. Larger adsorption capacity differences among the three electrolytes were observed under the higher ionic strengths (0.05 and 0.1 M) than those under 0.01 M. Multiplet peak fittings of high resolution X-ray photoelectron spectra for O1s and Fe2p 3/2 indicated the presence of iron (III) on adsorbent surface. pH variations during the adsorbent preparation within 3-8 in NaCl solutions did not cause appreciable changes in the iron redox state and composition. Raman spectra showed the formation of both monodentate and bidentate inner sphere complexes under pHs <7 and a mixture of outer sphere and inner sphere complexes at pH 8. These results explained the lower selenate adsorption under alkaline conditions. Mechanisms for monodentate and bidentate formations and a stable six-member ring structure were proposed. Two strategies were recommended for modifying Fe-GAC preparation procedure to enhance the selenate adsorption: (1) mixed-metal oxide coatings to increase the point of zero charge (pH zpc ); and (2) ferrous iron coating to initially reduce selenate followed by selenite adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of humic acid preloading on phosphate adsorption onto zirconium-modified zeolite.

PubMed

Lin, Jianwei; Zhang, Zhe; Zhan, Yanhui

2017-05-01

A zirconium-modified zeolite (ZrMZ) was prepared, and then, humic acid (HA) was immobilized on the ZrMZ surface to prepare HA-loaded ZrMZ (HA-ZrMZ). The obtained ZrMZ and HA-ZrMZ were characterized by energy dispersive X-ray spectroscopy, elemental analyzer, N 2 adsorption/desorption isotherms, pH at the point of zero charge, and X-ray photoelectron spectroscopy. The adsorption characteristics of phosphate on ZrMZ and HA-ZrMZ were comparatively investigated in batch mode. The adsorption mechanism of phosphate on ZrMZ and HA-ZrMZ was investigated by ionic strength effect and 31 P nuclear magnetic resonance. The mechanism for phosphate adsorption onto ZrMZ was the formation of inner-sphere phosphate complexes at the solid/solution interface. The preloading of HA on ZrMZ reduced the phosphate adsorption capacity, and the more the HA loading amount, the lower the phosphate adsorption capacity. However, the preloading of HA on ZrMZ did not change the phosphate adsorption mechanism; i.e., the formation of inner-sphere phosphate surface complexes was still responsible for the adsorption of phosphate on HA-ZrMZ. The decreased phosphate adsorption capacity for ZrMZ after HA coating could be attributed to the fact that the coating of HA on ZrMZ reduced the amount of binding active sites available for phosphate adsorption, changed the adsorbent surface charges, and reduced the specific surface areas and pore volumes of ZrMZ.

Use of high temperature insulation for ceramic matrix composites in gas turbines

DOEpatents

Morrison, Jay Alan; Merrill, Gary Brian; Ludeman, Evan McNeil; Lane, Jay Edgar

2001-01-01

A ceramic composition for insulating components, made of ceramic matrix composites, of gas turbines is provided. The composition comprises a plurality of hollow oxide-based spheres of various dimensions, a phosphate binder, and at least one oxide filler powder, whereby the phosphate binder partially fills gaps between the spheres and the filler powders. The spheres are situated in the phosphate binder and the filler powders such that each sphere is in contact with at least one other sphere and the arrangement of spheres is such that the composition is dimensionally stable and chemically stable at a temperature of approximately 1600.degree. C. A stationary vane of a gas turbine comprising the composition of the present invention bonded to the outer surface of the vane is provided. A combustor comprising the composition bonded to the inner surface of the combustor is provided. A transition duct comprising the insulating coating bonded to the inner surface of the transition is provided. Because of abradable properties of the composition, a gas turbine blade tip seal comprising the composition also is provided. The composition is bonded to the inside surface of a shroud so that a blade tip carves grooves in the composition so as to create a customized seal for the turbine blade tip.

Synthesis, crystal structures and Hirshfeld surface analyses of two new Salen type nickel/sodium heteronuclear complexes

NASA Astrophysics Data System (ADS)

Mahlooji, Niloofar; Behzad, Mahdi; Tarahhomi, Atekeh; Maroney, Michael; Rudbari, Hadi Amiri; Bruno, Giuseppe; Ghanbari, Bahram

2016-04-01

Two new heteronuclear Nickel(II)/Sodium(I) complexes of a side-off compartmental Schiff base ligand were synthesized and characterized by spectroscopic methods. Crystal structures of both of the complexes were also obtained. The Schiff base ligand was synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with 2-hydroxy-3-methoxybenzaldehyde. In both of the complexes the Ni(II) ion is coordinated to the inner N2O2 coordination sphere with square-planar geometry and the Na(I) ion is coordinated to the outer O2 O2‧ coordination sphere. In Complex (1) with general formula [Ni(L)Na(CH3OH)(ClO4)] the sodium ion is seven coordinated while in (2) with general formula [{Ni(L)Na(OH2)}2(μ-Ni(CN)4)] the sodium ion is six coordinated. Intermolecular interactions in two studied complexes were analyzed using 3D Hirshfeld surfaces and corresponding 2D fingerprint plots. This analysis showed that the H … H and C … H/H … C contacts for both structures (altogether 67.5% of total Hirshfeld surface area for (1) and 77.6% for (2)) and the O … H/H … O (24.2%) for (1) and the N … H/H … N (8.1%) contacts for (2) were the characteristic intermolecular contacts in the related crystal structures.

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes.

PubMed

Yan, Jinlong; Jiang, Tao; Yao, Ying; Lu, Song; Wang, Qilei; Wei, Shiqiang

2016-04-01

Iron oxide (FeO) coated by natural organic matter (NOM) is ubiquitous. The associations of minerals with organic matter (OM) significantly changes their surface properties and reactivity, and thus affect the environmental fate of pollutants, including nutrients (e.g., phosphorus (P)). In this study, ferrihydrite/goethite-humic acid (FH/GE-HA) complexes were prepared and their adsorption characteristics on P at various pH and ionic strength were investigated. The results indicated that the FeO-OM complexes showed a decreased P adsorption capacity in comparison with bare FeO. The maximum adsorption capacity (Qmax) decreased in the order of FH (22.17 mg/g)>FH-HA (5.43 mg/g)>GE (4.67 mg/g)>GE-HA (3.27 mg/g). After coating with HA, the amorphous FH-HA complex still showed higher P adsorption than the crystalline GE-HA complex. The decreased P adsorption observed might be attributed to changes of the FeO surface charges caused by OM association. The dependence of P adsorption on the specific surface area of adsorbents suggests that the FeO component in the complexes is still the main contributor for the adsorption surfaces. The P adsorptions on FeO-HA complexes decreased with increasing initial pH or decreasing initial ionic strength. A strong dependence of P adsorption on ionic strength and pH may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the FeO component and P. Therefore, previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils, especially in humic-rich areas. Copyright © 2015. Published by Elsevier B.V.

Simultaneous and continuous stabilization of As and Pb in contaminated solution and soil by a ferrihydrite-gypsum sorbent.

PubMed

Kameda, Kentaro; Hashimoto, Yohey; Wang, Shan-Li; Hirai, Yasumasa; Miyahara, Hidetaka

2017-04-05

For the increasing need of stabilization both cationic and anionic metal(loid)s simultaneously, we newly developed a metal sorbent (FIXALL), consisting mainly of ferrihydrite and gypsum. The objectives of this study were to determine the molecular mechanisms of Pb and As stabilization in an aqueous system and to examine a simultaneous and long-term (up to 754days) effect on Pb and As stabilization in an anthropogenically contaminated soil using the FIXALL sorbent. When the solution contained a low concentration of Pb (5mgL -1 ), the mechanisms of Pb removal by FIXALL were based chiefly on the formation of inner-sphere surface complex with ferrihydrite. In the highly concentrated Pb solution (1200mgL -1 ), contrarily, the removal of Pb by FIXALL was the direct consequence of the dissolution of gypsum and subsequent precipitation of PbSO 4 , which strengthens the drawback of low capability of ferrihydrite for Pb removal. Regardless of initial concentrations, the primary mechanism of FIXALL for As stabilization is attributed to the formation of inner-sphere surface complex with ferrihydrite. A contaminated soil study demonstrated that FIXALL could decrease the concentration of water soluble As and Pb simultaneously and continuously for 754days without notable changes in their chemical species and soil pH. Copyright © 2016 Elsevier B.V. All rights reserved.

X-ray absorption spectroscopy as a tool investigating arsenic(III) and arsenic(V) sorption by an aluminum-based drinking-water treatment residual.

PubMed

Makris, Konstantinos C; Sarkar, Dibyendu; Parsons, Jason G; Datta, Rupali; Gardea-Torresdey, Jorge L

2009-11-15

Historic applications of arsenical pesticides to agricultural land have resulted in accumulation of residual arsenic (As) in such soils. In situ immobilization represents a cost-effective and least ecological disrupting treatment technology for soil As. Earlier work in our laboratory showed that drinking-water treatment residuals (WTRs), a low-cost, waste by-product of the drinking-water treatment process exhibit a high affinity for As. Wet chemical experiments (sorption kinetics and desorption) were coupled with X-ray absorption spectroscopy measurements to elucidate the bonding strength and type of As(V) and As(III) sorption by an aluminum-based WTR. A fast (1h), followed by a slower sorption stage resulted in As(V) and As(III) sorption capacities of 96% and 77%, respectively. Arsenic desorption with a 5mM oxalate from the WTR was minimal, being always <4%. X-ray absorption spectroscopy data showed inner-sphere complexation between As and surface hydroxyls. Reaction time (up to 48h) had no effect on the initial As oxidation state for sorbed As(V) and As(III). A combination of inner-sphere bonding types occurred between As and Al on the WTR surface because mixed surface geometries and interatomic distances were observed.

Deconvolution of Raman spectroscopic signals for electrostatic, H-bonding, and inner-sphere interactions between ions and dimethyl phosphate in solution

PubMed Central

Christian, Eric L; Anderson, Vernon E.; Harris, Michael E

2011-01-01

Quantitative analysis of metal ion-phosphodiester interactions is a significant experimental challenge due to the complexities introduced by inner-sphere, outer-sphere (H-bonding with coordinated water), and electrostatic interactions that are difficult to isolate in solution studies. Here, we provide evidence that inner-sphere, H-bonding and electrostatic interactions between ions and dimethyl phosphate can be deconvoluted through peak fitting in the region of the Raman spectrum for the symmetric stretch of non-bridging phosphate oxygens (νsPO 2-). An approximation of the change in vibrational spectra due to different interaction modes is achieved using ions capable of all or a subset of the three forms of metal ion interaction. Contribution of electrostatic interactions to ion-induced changes to the Raman νsPO2- signal could be modeled by monitoring attenuation of νsPO2- in the presence of tetramethylammonium, while contribution of H-bonding and inner-sphere coordination could be approximated from the intensities of altered νsPO2- vibrational modes created by an interaction with ammonia, monovalent or divalent ions. A model is proposed in which discrete spectroscopic signals for inner-sphere, H-bonding, and electrostatic interactions are sufficient to account for the total observed change in νsPO2- signal due to interaction with a specific ion capable of all three modes of interaction. Importantly, the quantitative results are consistent with relative levels of coordination predicted from absolute electronegativity and absolute hardness of alkali and alkaline earth metals. PMID:21334281

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

Competitive adsorption of copper(II), cadmium(II), lead(II) and zinc(II) onto basic oxygen furnace slag.

PubMed

Xue, Yongjie; Hou, Haobo; Zhu, Shujing

2009-02-15

Polluted and contaminated water can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a solution system will be affected by the presence of other metals. In this study, we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto basic oxygen furnace slag (BOF slag) in single- and multi-element solution systems as a function of pH and concentration, in a background solution of 0.01M NaNO(3). In adsorption edge experiments, the pH was varied from 2.0 to 13.0 with total metal concentration 0.84mM in the single element system and 0.21mM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH(50) (the pH at which 50% adsorption occurs) was found to follow the sequence Zn>Cu>Pb>Cd in single-element systems, but Pb>Cu>Zn>Cd in the multi-element system. Adsorption isotherms at pH 6.0 in the multi-element systems showed that there is competition among various metals for adsorption sites on BOF slag. The adsorption and potentiometric titrations data for various slag-metal systems were modeled using an extended constant-capacitance surface complexation model that assumed an ion-exchange process below pH 6.5 and the formation of inner-sphere surface complexes at higher pH. Inner-sphere complexation was more dominant for the Cu(II), Pb(II) and Zn(II) systems.

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.

Reaction of Hydroquinone with Hematite I. Study of Adsorption by Electrochemical-Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy

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

Stack, Andrew G; Eggleston, Carrick M; Engelhard, Mark H

2004-06-15

The reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate ofreductive dissolution, especially by iron-reducing bacteria. Here, the electrochemical and physical properties of hydroquinone adsorbed on hematite surfaces at pH 2.5–3 were investigated with cyclic voltammetry (CV), electrochemical-scanning tunneling microscopy (EC-STM), and X-ray photoelectron spectroscopy (XPS). An oxidation peak for hydroquinone was observed in the CV experiments, as well as (photo)reduction of iron and decomposition of the solvent. The EC-STM results indicate that hydroquinone sometimes forms an ordered monolayer with ~1.1 H₂/nm², but can be fairly disordered (especiallymore » when viewed at larger scales). XPS results indicate that hydroquinone and benzoquinone are retained at the interface in increasing amounts as the reaction proceeds, but reduced iron is not observed. These results suggest that quinones do not adsorb by an inner-sphere complex where adsorbate–surface interactions determine the adsorbate surface structure, but rather in an outer-sphere complex where interactions among the adsorbate molecules dominate.« less

Reaction of hydroquinone with hematite I. Study of asdsorption by electrochemical-scanning tunneling microscopy and X-ray photoelectron spectroscopy.

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

Stack, Andrew G; Eggleston, Carrick M; Engelhard, Mark H

2003-12-01

The reaction of hematite with quinones and the quinone moieties of larger molecules may be an important factor in limiting the rate of reductive dissolution, especially by iron-reducing bacteria. Here, the electrochemical and physical properties of hydroquinone adsorbed on hematite surfaces at pH 2.5-3 were investigated with cyclic voltammetry (CV), electrochemical-scanning tunneling microscopy (EC-STM), and X-ray photoelectron spectroscopy (XPS). An oxidation peak for hydroquinone was observed in the CV experiments, as well as (photo)reduction of iron and decomposition of the solvent. The EC-STM results indicate that hydroquinone sometimes forms an ordered monolayer with {approx}1.1 QH{sub 2}/nm{sup 2}, but can bemore » fairly disordered (especially when viewed at larger scales). XPS results indicate that hydroquinone and benzoquinone are retained at the interface in increasing amounts as the reaction proceeds, but reduced iron is not observed. These results suggest that quinones do not adsorb by an inner-sphere complex where adsorbate-surface interactions determine the adsorbate surface structure, but rather in an outer-sphere complex where interactions among the adsorbate molecules dominate.« less

Self-assembled clusters of spheres related to spherical codes.

PubMed

Phillips, Carolyn L; Jankowski, Eric; Marval, Michelle; Glotzer, Sharon C

2012-10-01

We consider the thermodynamically driven self-assembly of spheres onto the surface of a central sphere. This assembly process forms self-limiting, or terminal, anisotropic clusters (N-clusters) with well-defined structures. We use Brownian dynamics to model the assembly of N-clusters varying in size from two to twelve outer spheres and free energy calculations to predict the expected cluster sizes and shapes as a function of temperature and inner particle diameter. We show that the arrangements of outer spheres at finite temperatures are related to spherical codes, an ideal mathematical sequence of points corresponding to the densest possible sphere packings. We demonstrate that temperature and the ratio of the diameters of the inner and outer spheres dictate cluster morphology. We present a surprising result for the equilibrium structure of a 5-cluster, for which the square pyramid arrangement is preferred over a more symmetric structure. We show this result using Brownian dynamics, a Monte Carlo simulation, and a free energy approximation. Our results suggest a promising way to assemble anisotropic building blocks from constituent colloidal spheres.

Interaction of ribonucleotides with oxide and silicate minerals under varying environmental conditions

NASA Astrophysics Data System (ADS)

Feuillie, C.; Sverjensky, D. A.; Hazen, R. M.

2013-12-01

Large quantities of nucleic acids are found in natural environments, released after the death of an organism and subsequent cell lysis [1]. Nucleic acids are known to adsorb on mineral surfaces [2, 3, 4], which protect them from degradation, whether enzymatic [5, 6] or UV-mediated [7]. It may then contribute to the extracellular genetic pool available in soils to microorganisms for horizontal gene transfers [8]. In order to better understand the behaviour of extracellular nucleic acids in soils, we have investigated the interactions between nucleotides, 5'-GMP, 5'-CMP, 5'-AMP and 5'-UMP, and α-alumina as a model compound for Al in six-fold coordination in soil minerals. We carried out batch adsorption experiments over a wide range of pH, ionic strength and surface loading. Alumina adsorbs high amounts of nucleotides > 2 μmol/m2. In similar environmental conditions, swelling clays such as nontronite and montmorillonite adsorb less than 0.1 μmol/m2 if the total surface area is taken under consideration. However, if only the edges of clay particles are considered, the amount of nucleotides adsorbed reaches values between 1.2 and 2 μmol/m2 [9], similar to the alumina and consistent with ';oxide-like' surface sites on the edges of the clay particles. Surface complexation modeling enabled us to predict the speciation of the surface species on the alumina, as well as the stoichiometry and thermodynamic equilibrium constants for the adsorption of nucleotides. We used the extended triple-layer model (ETLM), that takes into account the electrical work linked to the desorption of chemisorbed water molecules during the formation of inner-sphere complexes. Two surface species are thought to form on the surface of corundum: a monodentate inner-sphere complex, dominant at pH < 7.5, and a bidentate outer-sphere complex, dominant at higher pH. Both complexes involve interactions between the negatively charged phosphate group and the positively charged surface of alumina. Our results provide a better understanding of how nucleic acids attach to mineral surfaces under varying environmental conditions in soil environments. Moreover, the predicted configuration of nucleotide surface species, bound via the phosphate group, could have implications for the abiotic formation and concentration of nucleic acids in the context of the origin of life. References : [1] Lorenz and Wackernagel (1987), Applied and environmental microbial., 2948-2952 [2] Ferris (2005), Reviews in mineralogy & geochemistry 59, 187-210 [3] Cleaves H.J. et al. (2011), Chemosphere 83, 1560-1567 [4] Arora & Kamaluddin (2009), Astrobiology 9, 165-171 [5] Cai et al. (2006), Environ. Sci. Technol. 40 (9), 2971-2976 [6] Franchi and Gallori (2005),Gene 346, 205-214 [7] Scappini et al. (2004), International Journal of Astrobiology 3(1), 17-19 [8] Levy-Booth et al. (2007), Soil Biol. Biochem. 39, 2977-2991. [9] Feuillie et al. (2013), Geochimica et Cosmochimica Acta (in press)

Microcalorimetric and potentiometric titration studies on the adsorption of copper by P. putida and B. thuringiensis and their composites with minerals.

PubMed

Fang, Linchuan; Cai, Peng; Li, Pengxiang; Wu, Huayong; Liang, Wei; Rong, Xingmin; Chen, Wenli; Huang, Qiaoyun

2010-09-15

In order to have a better understanding of the interactions of heavy metals with bacteria and minerals in soil and associated environments, isothermal titration calorimetry (ITC), potentiometric titration and equilibrium sorption experiments were conducted to investigate the adsorption behavior of Cu(II) by Bacillus thuringiensis, Pseudomonas putida and their composites with minerals. The interaction of montmorillonite with bacteria increased the reactive sites and resulted in greater adsorption for Cu(II) on their composites, while decreased adsorption sites and capacities for Cu(II) were observed on goethite-bacteria composites. A gram-positive bacterium B. thuringiensis played a more important role than a gram-negative bacterium P. putida in determining the properties of the bacteria-minerals interfaces. The enthalpy changes (DeltaH(ads)) from endothermic (6.14 kJ mol(-1)) to slightly exothermic (-0.78 kJ mol(-1)) suggested that Cu(II) is complexed with the anionic oxygen ligands on the surface of bacteria-mineral composites. Large entropies (32.96-58.89 J mol(-1) K(-1)) of Cu(II) adsorption onto bacteria-mineral composites demonstrated the formation of inner-sphere complexes in the presence of bacteria. The thermodynamic data implied that Cu(II) mainly bound to the carboxyl and phosphoryl groups as inner-sphere complexes on bacteria and mineral-bacteria composites. Copyright 2010 Elsevier B.V. All rights reserved.

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

USGS Publications Warehouse

Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

1994-01-01

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate.

PubMed

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-02-04

In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. The results have shown that the reaction is first order with respect to both [IO4(-)] and the complex concentration, and the rate increases over the pH range 2.62 - 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 x 10(-3) s(-1)), is greater than the value of k1 (1.22 x 10(-3) s(-1)) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0 degrees C and I = 0.20 mol dm(-3). It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4(-) to chromium(III). The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between DeltaH* and DeltaS* values for these reactions.

Inner-sphere oxidation of ternary iminodiacetatochromium(III) complexes involving DL-valine and L-arginine as secondary ligands. Isokinetic relationship for the oxidation of ternary iminodiacetato-chromium(III) complexes by periodate

PubMed Central

Ewais, Hassan A; Dahman, Faris D; Abdel-Khalek, Ahmed A

2009-01-01

Background In this paper, the kinetics of oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ (HIDA = iminodiacetic acid, Val = DL-valine and Arg = L-arginine) were studied. The choice of ternary complexes was attributed to two considerations. Firstly, in order to study the effect of the secondary ligands DL-valine and L-arginine on the stability of binary complex [CrIII(HIDA)(IDA)(H2O)] towards oxidation. Secondly, transition metal ternary complexes have received particular focus and have been employed in mapping protein surfaces as probes for biological redox centers and in protein capture for both purification and study. Results The results have shown that the reaction is first order with respect to both [IO4-] and the complex concentration, and the rate increases over the pH range 2.62 – 3.68 in both cases. The experimental rate law is consistent with a mechanism in which both the deprotonated forms of the complexes [CrIII(IDA)(Val)(H2O)2] and [CrIII(IDA)(Arg)(H2O)2] are significantly more reactive than the conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3 (1.82 × 10-3 s-1), is greater than the value of k1 (1.22 × 10-3 s-1) for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+ at 45.0°C and I = 0.20 mol dm-3. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of IO4- to chromium(III). Conclusion The oxidation of [CrIII(HIDA)(Val)(H2O)2]+ and [CrIII(HIDA)(Arg)(H2O)2]+ by periodate may proceed through an inner-sphere mechanism via two electron transfer giving chromium(VI). The value of the intramolecular electron transfer rate constant for the oxidation of [CrIII(HIDA)(Arg)(H2O)2]+, k3, is greater than the value of k1 for the oxidation of [CrIII(HIDA)(Val)(H2O)2]+. A common mechanism for the oxidation of ternary iminodiacetatochromium(III) complexes by periodate is proposed, and this is supported by an excellent isokinetic relationship between ΔH* and ΔS* values for these reactions. PMID:19193241

Surface-complexation synthesis of silica-supported high-loading well-dispersed reducible nano-Co3O4 catalysts using CoIII ammine hydroxo complexes

NASA Astrophysics Data System (ADS)

Zhang, Weidong; Pan, Feng; Li, Jinjun; Wang, Zhen; Ding, Wei; Qin, Yi; Wu, Feng

2018-06-01

Silica-supported highly dispersed cobalt oxides prepared by adsorption are likely to be poorly reducible Co-phyllosilicates or CoO species. Here we report the synthesis of silica-supported monodispersed spinel nano-Co3O4 catalysts by inner-sphere complexation using CoIII ammine hydroxo complexes as precursors. The precursors were facilely prepared by stirring ammoniacal CoII solutions exposed to air. The cobalt loadings (up to 188 mg/g) and particle sizes (3-10 nm) were tailored by successive complexation-calcination cycles. Such catalysts showed significantly superior reducibility and catalytic activity in complete propane oxidation in comparison to supported Co-phyllosilicates and CoO. A further development of this synthesis process may provide a variety of cobalt-based catalysts for important catalytic applications.

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.

Preservation of organic matter in marine sediments by inner-sphere interactions with reactive iron

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

Barber, Andrew; Brandes, Jay; Leri, Alessandra

Interactions between organic matter and mineral matrices are critical to the preservation of soil and sediment organic matter. In addition to clay minerals, Fe(III) oxides particles have recently been shown to be responsible for the protection and burial of a large fraction of sedimentary organic carbon (OC). Through a combination of synchrotron X-ray techniques and high-resolution images of intact sediment particles, we assessed the mechanism of interaction between OC and iron, as well as the composition of organic matter co-localized with ferric iron. We present scanning transmission x-ray microscopy images at the Fe L 3 and C K1 edges showingmore » that the organic matter co-localized with Fe(III) consists primarily of C=C, C=O and C-OH functional groups. Coupling the co-localization results to iron K-edge X-ray absorption spectroscopy fitting results allowed to quantify the relative contribution of OC-complexed Fe to the total sediment iron and reactive iron pools, showing that 25–62% of total reactive iron is directly associated to OC through inner-sphere complexation in coastal sediments, as much as four times more than in low OC deep sea sediments. Direct inner-sphere complexation between OC and iron oxides (Fe-O-C) is responsible for transferring a large quantity of reduced OC to the sedimentary sink, which could otherwise be oxidized back to CO 2.« less

Six-coordinate manganese(3+) in catalysis by yeast manganese superoxide dismutase

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

Sheng, Yuewei; Gralla, Edith Butler; Schumacher, Mikhail

Reduction of superoxide (O{sub 2}{sup -}) by manganese-containing superoxide dismutase occurs through either a 'prompt protonation' pathway, or an 'inner-sphere' pathway, with the latter leading to formation of an observable Mn-peroxo complex. We recently reported that wild-type (WT) manganese superoxide dismutases (MnSODs) from Saccharomyces cerevisiae and Candida albicans are more gated toward the 'prompt protonation' pathway than human and bacterial MnSODs and suggested that this could result from small structural changes in the second coordination sphere of manganese. We report here that substitution of a second-sphere residue, Tyr34, by phenylalanine (Y34F) causes the MnSOD from S. cerevisiae to react exclusivelymore » through the 'inner-sphere' pathway. At neutral pH, we have a surprising observation that protonation of the Mn-peroxo complex in the mutant yeast enzyme occurs through a fast pathway, leading to a putative six-coordinate Mn3+ species, which actively oxidizes O{sub 2}{sup -} in the catalytic cycle. Upon increasing pH, the fast pathway is gradually replaced by a slow proton-transfer pathway, leading to the well-characterized five-coordinate Mn{sup 3+}. We here propose and compare two hypothetical mechanisms for the mutant yeast enzyme, diffeeing in the structure of the Mn-peroxo complex yet both involving formation of the active six-coordinate Mn{sup 3+} and proton transfer from a second-sphere water molecule, which has substituted for the -OH of Tyr34, to the Mn-peroxo complex. Because WT and the mutant yeast MnSOD both rest in the 2+ state and become six-coordinate when oxidized up from Mn{sup 2+}, six-coordinate Mn{sup 3+} species could also actively function in the mechanism of WT yeast MnSODs.« less

Copper(II) adsorption on the kaolinite(001) surface: Insights from first-principles calculations and molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Kong, Xiang-Ping; Wang, Juan

2016-12-01

The adsorption behavior of Cu(II) on the basal hydroxylated kaolinite(001) surface in aqueous environment was investigated by first-principles calculations and molecular dynamics simulations. Structures of possible monodentate and bidentate inner-sphere adsorption complexes of Cu(II) were examined, and the charge transfer and bonding mechanism were analyzed. Combining the binding energy of complex, the radial distribution function of Cu(II) with oxygen and the extended X-ray absorption fine structure data, monodentate complex on site of surface oxygen with ;upright; hydrogen and bidentate complex on site of two oxygens (one with ;upright; hydrogen and one with ;lying; hydrogen) of single Al center have been found to be the major adsorption species of Cu(II). Both adsorption species are four-coordinated with a square planar geometry. The distribution of surface hydroxyls with ;lying; hydrogen around Cu(II) plays a key role in the structure and stability of adsorption complex. Upon the Mulliken population analysis and partial density of states, charge transfer occurs with Cu(II) accepting some electrons from both surface oxygens and aqua oxygens, and the bonding Cu 3d-O 2p state filling is primarily responsible for the strong covalent interaction of Cu(II) with surface oxygen.

In Situ Real-Time Radiographic Study of Thin Film Formation Inside Rotating Hollow Spheres

DOE PAGES

Braun, Tom; Walton, Christopher C.; Dawedeit, Christoph; ...

2016-02-03

The hollow spheres with uniform coatings on the inner surface have applications in optical devices, time- or site-controlled drug release, heat storage devices, and target fabrication for inertial confinement fusion experiments. The fabrication of uniform coatings, which is often critical for the application performance, requires precise understanding and control over the coating process and its parameters. We report on in situ real-time radiography experiments that provide critical spatiotemporal information about the distribution of fluids inside hollow spheres during uniaxial rotation. Furthermore, image analysis and computer fluid dynamics simulations were used to explore the effect of liquid viscosity and rotational velocitymore » on the film uniformity. The data were then used to demonstrate the fabrication of uniform sol–gel chemistry derived porous polymer films inside 2 mm inner diameter diamond shells.« less

In Situ Real-Time Radiographic Study of Thin Film Formation Inside Rotating Hollow Spheres

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

Braun, Tom; Walton, Christopher C.; Dawedeit, Christoph

2016-02-03

Hollow spheres with uniform coatings on the inner surface have applications in optical devices, time- or site controlled drug release, heat storage devices, and target fabrication for inertial confinement fusion experiments. The fabrication of uniform coatings, which is often critical for the application performance, requires precise understanding and control over the coating process and its parameters. Here, we report on in-situ real-time radiography experiments that provide critical spatio-temporal information about the distribution of fluids inside hollow spheres during uniaxial rotation. Image analysis and computer fluid dynamics simulations were used to explore the effect of liquid viscosity and rotational velocity onmore » the film uniformity. The data were then used to demonstrate the fabrication of uniform sol-gel chemistry derived porous polymer films inside 2mm inner diameter diamond shells.« less

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

PubMed Central

Gao, Xiaodong; Root, Robert A.; Farrell, James; Ela, Wendell; Chorover, Jon

2014-01-01

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 – 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92–2.94 and 3.41–3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms. PMID:25382933

Mutual effects of copper and phosphate on their interaction with γ-Al2O3: combined batch macroscopic experiments with DFT calculations.

PubMed

Ren, Xuemei; Yang, Shitong; Tan, Xiaoli; Chen, Changlun; Sheng, Guodong; Wang, Xiangke

2012-10-30

The mutual effects of Cu(II) and phosphate on their interaction with γ-Al(2)O(3) are investigated by using batch experiments combined with density functional theory (DFT) calculations. The results of batch experiments show that coexisting phosphate promotes the retention of Cu(II) on γ-Al(2)O(3), whereas phosphate retention is not affected by coexisting Cu(II) at low initial phosphate concentrations (≤ 3.6 mg P/L). Cu-phosphate aqueous complexes control Cu(II) retention through the formation of type B ternary surface complexes (where phosphate bridges γ-Al(2)O(3) and Cu(II)) at pH 5.5. This deduction is further supported by the results of DFT calculations. More specifically, the DFT calculation results indicate that the type B ternary surface complexes prefer to form outer-sphere or monodentate inner-sphere binding mode under our experimental conditions. The enhancement of phosphate retention on γ-Al(2)O(3) in the presence of Cu(II) at high initial phosphate concentrations (>3.6 mg P/L) may be attributed to the formation of 1:2 Cu(II)-phosphate species and/or surface precipitates. Understanding the mutual effects of phosphate and Cu(II) on their mobility and transport in mineral/water environments is more realistic to design effective remediation strategies for reducing their negative impacts on aquatic/terrestrial environments. Copyright © 2012 Elsevier B.V. All rights reserved.

Process for making hollow carbon spheres

DOEpatents

Luhrs, Claudia C.; Phillips, Jonathan; Richard, Monique N.; Knapp, Angela Michelle

2013-04-16

A hollow carbon sphere having a carbon shell and an inner core is disclosed. The hollow carbon sphere has a total volume that is equal to a volume of the carbon shell plus an inner free volume within the carbon shell. The inner free volume is at least 25% of the total volume. In some instances, a nominal diameter of the hollow carbon sphere is between 10 and 180 nanometers.

Surface reactions of iron - enriched smectites: adsorption and transformation of hydroxy fatty acids and phenolic acids

NASA Astrophysics Data System (ADS)

Polubesova, Tamara; Olshansky, Yaniv; Eldad, Shay; Chefetz, Benny

2014-05-01

Iron-enriched smectites play an important role in adsorption and transformation of soil organic components. Soil organo-clay complexes, and in particular humin contain hydroxy fatty acids, which are derived from plant biopolymer cutin. Phenolic acids belong to another major group of organic acids detected in soil. They participate in various soil processes, and are of concern due to their allelopathic activity. We studied the reactivity of iron-enriched smectites (Fe(III)-montmorillonite and nontronite) toward both groups of acids. We used fatty acids- 9(10),16-dihydroxypalmitic acid (diHPA), isolated from curtin, and 9,10,16-trihydroxypalmitic acid (triHPA); the following phenolic acids were used: ferulic, p-coumaric, syringic, and vanillic. Adsorption of both groups of acids was measured. The FTIR spectra of fatty acid-mineral complexes indicated inner-sphere complexation of fatty acids with iron-enriched smectites (versus outer-sphere complexation with Ca(II)-montmorillonite). The LC-MS results demonstrated enhanced esterification of fatty acids on the iron-enriched smectite surfaces (as compared to Ca(II)-montmorillonite). This study suggests that fatty acids can be esterified on the iron-enriched smectite surfaces, which results in the formation of stable organo-mineral complexes. These complexes may serve as a model for the study of natural soil organo-clay complexes and humin. The reaction of phenolic acids with Fe(III)-montmorillonite demonstrated their oxidative transformation by the mineral surfaces, which was affected by molecular structure of acids. The following order of their transformation was obtained: ferulic >syringic >p-coumaric >vanillic. The LC-MS analysis demonstrated the presence of dimers, trimers, and tetramers of ferulic acid on the surface of Fe(III)-montmorillonite. Oxidation and transformation of ferulic acid were more intense on the surface of Fe(III)-montmorillonite as compared to Fe(III) in solution due to stronger complexation on the Fe(III)-motnomrillonite surface. Our study demonstrate the importance of iron-enriched minerals for the abiotic formation of humic materials and for the transformation of aromatic (phenolic) pollutants.

Isolation of sphere-forming stem cells from the mouse inner ear.

PubMed

Oshima, Kazuo; Senn, Pascal; Heller, Stefan

2009-01-01

The mammalian inner ear has very limited ability to regenerate lost sensory hair cells. This deficiency becomes apparent when hair cell loss leads to hearing loss as a result of either ototoxic insult or the aging process. Coincidently, with this inability to regenerate lost hair cells, the adult cochlea does not appear to harbor cells with a proliferative capacity that could serve as progenitor cells for lost cells. In contrast, adult mammalian vestibular sensory epithelia display a limited ability for hair cell regeneration, and sphere-forming cells with stem cell features can be isolated from the adult murine vestibular system. The neonatal inner ear, however, does harbor sphere-forming stem cells residing in cochlear and vestibular tissues. Here, we provide protocols to isolate sphere-forming stem cells from neonatal vestibular and cochlear sensory epithelia as well as from the spiral ganglion. We further describe procedures for sphere propagation, cell differentiation, and characterization of inner ear cell types derived from spheres. Sphere-forming stem cells from the mouse inner ear are an important tool for the development of cellular replacement strategies of damaged inner ears and are a bona fide progenitor cell source for transplantation studies.

Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

DOE PAGES

Greathouse, Jeffery A.; Hart, David; Bowers, Geoffrey M.; ...

2015-07-20

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water andmore » ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.« less

Speciation of aqueous Ni(II)-carboxylate and Ni(II)-fulvic acid solutions: Combined ATR-FTIR and XAFS analysis

NASA Astrophysics Data System (ADS)

Strathmann, Timothy J.; Myneni, Satish C. B.

2004-09-01

Aqueous solutions containing Ni(II) and a series of structurally related carboxylic acids were analyzed using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Ni K-edge X-ray absorption fine structure spectroscopy (XAFS). XAFS spectra were also collected for solutions containing Ni 2+ and chelating ligands (ethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA)) as well as soil fulvic acid. Limited spectral changes are observed for aqueous Ni(II) complexes with monocarboxylates (formate, acetate) and long-chain polycarboxylates (succinate, tricarballylate), where individual donor groups are separated by multiple bridging methylene groups. These spectral changes indicate weak interactions between Ni(II) and carboxylates, and the trends are similar to some earlier reports for crystalline Ni(II)-acetate solids, for which X-ray crystallography studies have indicated monodentate Ni(II)-carboxylate coordination. Nonetheless, electrostatic or outer-sphere coordination cannot be ruled out for these complexes. However, spectral changes observed for short-chain dicarboxylates (oxalate, malonate) and carboxylates that contain an alcohol donor group adjacent to one of the carboxylate groups (lactate, malate, citrate) demonstrate inner-sphere metal coordination by multiple donor groups. XAFS spectral fits of Ni(II) solutions containing soil fulvic acid are consistent with inner-sphere Ni(II) coordination by one or more carboxylate groups, but spectra are noisy and outer-sphere modes of coordination cannot be ruled out. These molecular studies refine our understanding of the interactions between carboxylates and weakly complexing divalent transition metals, such as Ni(II).

Enhanced adsorption of Eu(III) on mesoporous Al2O3/expanded graphite composites investigated by macroscopic and microscopic techniques.

PubMed

Sun, Yubing; Chen, Changlun; Tan, Xiaoli; Shao, Dadong; Li, Jiaxing; Zhao, Guixia; Yang, Shubin; Wang, Qi; Wang, Xiangke

2012-11-21

Mesoporous Al(2)O(3) was intercalated into an expanded graphite (EG) interlayer to prepare mesoporous Al(2)O(3)/EG composites. The basal spacing of mesoporous Al(2)O(3)/EG composites was enlarged as compared to raw graphite from the X-ray diffraction analysis. The massive surface functional groups and wedge-shaped pores were observed in terms of potentiometric acid-base titration analysis and scanning electron microscope, respectively. The pH-dependent adsorption of Eu(III) on mesoporous Al(2)O(3)/EG composites was evidently independent of ionic strength. The maximum adsorption capacity of Eu(III) on mesoporous Al(2)O(3)/EG composites at pH 6.0 and T = 293 K was calculated to be 5.14 mg g(-1). Desorption kinetics and cyclic operation results showed that mesoporous Al(2)O(3)/EG composites presented high hydrothermal stability in aqueous solution. The thermodynamic parameters suggested that Eu(III) adsorption on mesoporous Al(2)O(3)/EG composites is an endothermic and a spontaneous process. The decrease of Eu-O bond distance with the increasing pH demonstrated that the adsorption mechanism between Eu(III) and mesoporous Al(2)O(3)/EG composites would shift from outer-sphere surface complexation to inner-sphere surface complexation in terms of extended X-ray absorption fine structure spectroscopy analysis.

Amorphous silica as a versatile supermolecular ligand for Ni(II) amine complexes: toward interfacial molecular recognition.

PubMed

Boujday, Souhir; Lambert, Jean-François; Che, Michel

2004-07-19

Selective adsorption of Ni(II) amine complexes used as precursors for supported catalysts was studied on amorphous silica surfaces. The nature of the adsorption sites was probed by [Ni(en)(dien) (H2O)]2+, [Ni(en)2(H2O)2]2+, and [Ni(dien)(H2O)3]2+ (en = ethylenediamine, dien = diethylenetriamine), which respectively contain one, two, and three labile aqua ligands. The silica surface acts as a mono- or polydentate ligand that can substitute the aqua ligands of the Ni(II) complexes in an inner-sphere adsorption mechanism. Room-temperature adsorption isotherms indicate that each nickel complex selects a limited number of adsorption sites; different sites are recognised by the three complexes, even though they have the same charge and comparable sizes. Several spectroscopic techniques (UV/Vis/NIR, EXAFS, and 29Si NMR) were used to confirm the selective character of the interaction of Ni(II) amine complexes with the silica surface. The specific sites include both silanol/silanolate groups in the same number as the original labile ligands and other surface groups that probably act as hydrogen-bond acceptors. These two types of groups cooperate to result in interfacial molecular-recognition phenomena with interactional complementarity.

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

Electromagnetic studies of redox systems for energy storage

NASA Technical Reports Server (NTRS)

Wu, C. D.; Scherson, D.; Yeager, E.

1981-01-01

Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.

Rb + adsorption at the quartz(101)-aqueous interface: comparison of resonant anomalous x-ray reflectivity with ab initio calculations

DOE PAGES

Bellucci, Francesco; Lee, Sang Soo; Kubicki, James D.; ...

2015-01-29

We study adsorption of Rb + to the quartz(101)–aqueous interface at room temperature with specular X-ray reflectivity, resonant anomalous X-ray reflectivity, and density functional theory. The interfacial water structures observed in deionized water and 10 mM RbCl solution at pH 9.8 were similar, having a first water layer at height of 1.7 ± 0.1 Å above the quartz surface and a second layer at 4.8 ± 0.1 Å and 3.9 ± 0.8 Å for the water and RbCl solutions, respectively. The adsorbed Rb + distribution is broad and consists of presumed inner-sphere (IS) and outer-sphere (OS) complexes at heights ofmore » 1.8 ± 0.1 and 6.4 ± 1.0 Å, respectively. Projector-augmented planewave density functional theory (DFT) calculations of potential configurations for neutral and negatively charged quartz(101) surfaces at pH 7 and 12, respectively, reveal a water structure in agreement with experimental results. These DFT calculations also show differences in adsorbed speciation of Rb + between these two conditions. At pH 7, the lowest energy structure shows that Rb + adsorbs dominantly as an IS complex, whereas at pH 12 IS and OS complexes have equivalent energies. The DFT results at pH 12 are generally consistent with the two site Rb distribution observed from the X-ray data at pH 9.8, albeit with some differences that are discussed. In conclusion, surface charge estimated on the basis of the measured total Rb + coverage was -0.11 C/m 2, in good agreement with the range of the surface charge magnitudes reported in the literature.« less

Surface speciation of phosphate on goethite as seen by InfraRed Surface Titrations (IRST)

NASA Astrophysics Data System (ADS)

Arroyave, Jeison Manuel; Puccia, Virginia; Zanini, Graciela P.; Avena, Marcelo J.

2018-06-01

Phosphate adsorption at the metal oxide-water interface has been intensely studied, and the system phosphate-goethite in aqueous media is normally used as a model system with abundant information regarding adsorption-desorption under very different conditions. In spite of this, there is still discussion on whether the main inner-sphere surface complexes that phosphate forms on goethite are monodentate or bidentate. A new spectroscopic technique, InfraRed Surface Titration (IRST), is presented here and used to systematically explore the surface speciation of phosphate on goethite in the pH range 4.5-9.5 at different surface coverages. IRST enabled to construct distribution curves of surface species and distribution curves of dissolved phosphate species. In combination with the CD-MUSIC surface complexation model it was possible to conclude that surface complexes are monodentate. Very accurate distribution curves were obtained, showing a crossing point at pH 5.5 at a surface coverage of 2.0 μmol m-2, with a mononuclear monoprotonated species predominating at pH > 5.5 and a mononuclear diprotonated species prevailing at pH < 5.5. On the contrary, at the low surface coverage of 0.7 μmol m-2 there is no crossing point, with the mononuclear monoprotonated species prevailing at all pH. IRST can become a powerful technique to investigate structure, properties and reactions of any IR-active surface complex at the solid-water interface.

Parametric study of power absorption from electromagnetic waves by small ferrite spheres

NASA Technical Reports Server (NTRS)

Englert, Gerald W.

1989-01-01

Algebraic expressions in terms of elementary mathematical functions are derived for power absorption and dissipation by eddy currents and magnetic hysteresis in ferrite spheres. Skin depth is determined by using a variable inner radius in descriptive integral equations. Numerical results are presented for sphere diameters less than one wavelength. A generalized power absorption parameter for both eddy currents and hysteresis is expressed in terms of the independent parameters involving wave frequency, sphere radius, resistivity, and complex permeability. In general, the hysteresis phenomenon has a greater sensitivity to these independent parameters than do eddy currents over the ranges of independent parameters studied herein. Working curves are presented for obtaining power losses from input to the independent parameters.

Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

PubMed Central

Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

2011-01-01

Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

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

Zhang, Hailin; Li, Ping; Wang, Zheming

Boehmite (γ-AlOOH) was synthesized to selectively adsorb V(V) from K 2CrO 4-KVO 3-H 2O solutions with highly concentrated Cr(VI) and low concentration V(V). The synthesized γ-AlOOH has a BET surface area of 433.2 m 2/g and an average pore size of 3.5 nm. It possesses a maximum adsorption capacity of V(V) of 1.53 mmol/g from K 2CrO 4-KVO 3-H 2O solutions. The adsorption of V(V) onto γ-AlOOH follows the Langmuir isotherm model and pseudo-second-order kinetics equation by forming innersphere complexes while the Cr(VI) adsorption forms both inner-sphere and outer-sphere chromate complexes depending on solution pH. The γ-AlOOH was further synthesizedmore » in situ by adding HNO 3 into the K 2CrO 4-KAlO 2- KVO 3-H 2O solutions and then used for synchronous adsorption of V(V) and Cr(VI), resulting in increased adsorption capacity of V(V) of 2.88 mmol/g and decreased adsorption capacity of Cr(VI) to 0.073 mmol/g, respectively. In the latter process, adsorption pH values were adjustable, and adsorption reached equilibrium instantaneously, supporting a novel in situ synthesis and adsorption integration strategy with adjustable surface charge of adsorbent and disappearance of diffusion effect.« less

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

Effects of pH and anions on the sorption of selenium ions onto magnetite.

PubMed

Kim, Seung Soo; Min, Je Ho; Lee, Jae Kwang; Baik, Min Hoon; Choi, Jong-Won; Shin, Hyung Seon

2012-02-01

This study analyzes the influence of carbonate and silicate, which are generally abundant in granitic groundwater, on the sorption of selenium ions onto magnetite in order to understand the behaviors of selenium in a radioactive waste repository. Selenite was sorbed onto magnetite very well below pH 10, but silicate and carbonate hindered the sorption of selenite onto magnetite. On the other hand, little selenate was sorbed onto magnetite in neutral and weak alkaline solutions of 0.02 M NaNO(3) or NaClO(4), matching the ionic strength in a granitic groundwater, even though silicate or carbonate was not contained in the solutions. The surface complexation constants between selenite and magnetite were obtained by using a geochemical program, FITEQL 4.0, from the experimental data, and the formation of an inner-sphere surface complex such as =FeOSeO(2)(-) was suggested for the sorption of selenite onto magnetite from the diffuse double layer model calculation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Insight into the adsorption of tetracycline onto amino and amino-Fe3+ gunctionalized mesoporous silica: Effect of functionalized groups.

PubMed

Zhang, Ziyang; Li, Haiyan; Liu, Huijuan

2018-03-01

In order to study the influences of functionalized groups onto the adsorption of tetracycline, we prepared a series of amino and amino-Fe 3+ complex mesoporous silica adsorbents with diverse content of amino and Fe 3+ groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR) and N 2 adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe 3+ groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe 3+ increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe 3+ content increased from 3.93% to 8.26%, the Q max of the adsorbents increased from 102 to 188mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications. Copyright © 2017. Published by Elsevier B.V.

Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

PubMed Central

Kubicki, James D; Halada, Gary P; Jha, Prashant; Phillips, Brian L

2009-01-01

Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids. PMID:19689800

Sorption mechanisms of metals to graphene oxide

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

Showalter, Allison R.; Duster, Thomas A.; Szymanowski, Jennifer E. S.

2016-05-01

Environmental toxic metal contamination remediation and prevention is an ongoing issue. Graphene oxide is highly sorptive for many heavy metals over a wide pH range under different ionic strength conditions. We present x-ray absorption fine structure (XAFS) spectroscopy results investigating the binding environment of Pb(II), Cd(II) and U(VI) ions onto multi-layered graphene oxide (MLGO). Analysis indicates that the dominant sorption mechanism of Pb to MLGO changes as a function of pH, with increasing inner sphere contribution as pH increases. In contrast, the sorption mechanism of Cd to MLGO remains constant under the studied pH range. This adsorption mechanism is anmore » electrostatic attraction between the hydrated Cd+2 ion and the MLGO surface. The U(VI), present as the uranyl ion, changes only subtly as a function of pH and is bound to the surface via an inner sphere bond. Knowledge of the binding mechanism for each metal is necessary to help in optimizing environmental remediation or prevention in filtration systems.« less

The adsorption behavior of U(VI) on granite.

PubMed

Fan, Q H; Hao, L M; Wang, C L; Zheng, Z; Liu, C L; Wu, W S

2014-03-01

The effects of pH, counter ions and temperature on the adsorption of U(VI) on Beishan granite (BsG) were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The adsorption edge of U(VI) on BsG suggested that U(VI) adsorption was mainly controlled by ion exchange and outer-sphere complexation at low pH, whereas inner-sphere complex was the dominant adsorption species in the pH range of 4.0-9.0. Above pH 9.0, Na2U2O7 might play an important role in the rise of U(VI) adsorption again. Counter ions such as Cl(-), SO4(2-) and PO4(3-) can provoke U(VI) adsorption on BsG to some extent, which was directly correlated to the complexing ability of U(VI)-ligand. More noticeably, the large enhancement of U(VI) adsorption in the presence of phosphate can be attributed to the ternary complex formation (BsG-PO4-UO2), precipitation ((UO2)3(PO4)2(s)) and secondary phase (Na-autunite). Both FA and HA can slightly increase U(VI) adsorption at low pH, whereas they strongly inhibited U(VI) adsorption at high pH range. Artificial synthesized granite (AsG) prepared in the laboratory is impossible to use as an analogue of natural granite because of the large difference in the adsorption and surface properties.

Eu(III) sorption to TiO2 (anatase and rutile): batch, XPS, and EXAFS studies.

PubMed

Tan, Xiaoli; Fan, Qiaohui; Wang, Xiangke; Grambow, Bernd

2009-05-01

The sorption of Eu(III) on anatase and rutile was studied as a function of ionic strength, humic acid (HA, 7.5 mg/L), and electrolyte anions over a large range of pH (2-12). The presence of HA significantly affected Eu(III) sorption to anatase and rutile. The sorption of Eu(III) on anatase and rutile was independent of ionic strength. Results of an X-ray photoelectron spectroscopy (XPS) analysis showed that Eu(III) was chemically present within the near-surface of TiO2 due to the formation of triple bond SOEu and triple bond SOHAEu complexes. An extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the local structural environment of the adsorbed Eu(III), and the results indicated that Eu(III) was bound to about seven or eight O atoms at a distance of about 2.40 A. The functional groups of surface-bound HA were expected to be involved in the sorption process. The measured Eu-Ti distance confirmed the formation of inner-sphere sorption complexes on a TiO2 surface.

Surface structural ion adsorption modeling of competitive binding of oxyanions by metal (hydr)oxides

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

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

1999-02-01

An important challenge in surface complexation models (SCM) is to connect the molecular microscopic reality to macroscopic adsorption phenomena. This study elucidates the primary factor controlling the adsorption process by analyzing the adsorption and competition of PO{sub 4}, AsO{sub 4}, and SeO{sub 3}. The authors show that the structure of the surface-complex acting in the dominant electrostatic field can be ascertained as the primary controlling adsorption factor. The surface species of arsenate are identical with those of phosphate and the adsorption behavior is very similar. On the basis of the selenite adsorption, The authors show that the commonly used 1pKmore » models are incapable to incorporate in the adsorption modeling the correct bidentate binding mechanism found by spectroscopy. The use of the bidentate mechanism leads to a proton-oxyanion ratio and corresponding pH dependence that are too large. The inappropriate intrinsic charge attribution to the primary surface groups and the condensation of the inner sphere surface complex to a point charge are responsible for this behavior of commonly used 2pK models. Both key factors are differently defined in the charge distributed multi-site complexation (CD-MUSIC) model and are based in this model on a surface structural approach. The CD-MUSIC model can successfully describe the macroscopic adsorption phenomena using the surface speciation and binding mechanisms as found by spectroscopy. The model is also able to predict the anion competition well. The charge distribution in the interface is in agreement with the observed structure of surface complexes.« less

Multishell inertial confinement fusion target

DOEpatents

Holland, James R.; Del Vecchio, Robert M.

1984-01-01

A method of fabricating multishell fuel targets for inertial confinement fusion usage. Sacrificial hemispherical molds encapsulate a concentric fuel pellet which is positioned by fiber nets stretched tautly across each hemispherical mold section. The fiber ends of the net protrude outwardly beyond the mold surfaces. The joint between the sacrificial hemispheres is smoothed. A ceramic or glass cover is then deposited about the finished mold surfaces to produce an inner spherical surface having continuously smooth surface configuration. The sacrificial mold is removed by gaseous reaction accomplished through the porous ceramic cover prior to enclosing of the outer sphere by addition of an outer coating. The multishell target comprises the inner fuel pellet concentrically arranged within a surrounding coated cover or shell by fiber nets imbedded within the cover material.

Multishell inertial confinement fusion target

DOEpatents

Holland, James R.; Del Vecchio, Robert M.

1987-01-01

A method of fabricating multishell fuel targets for inertial confinement fusion usage. Sacrificial hemispherical molds encapsulate a concentric fuel pellet which is positioned by fiber nets stretched tautly across each hemispherical mold section. The fiber ends of the net protrude outwardly beyond the mold surfaces. The joint between the sacrificial hemispheres is smoothed. A ceramic or glass cover is then deposited about the finished mold surfaces to produce an inner spherical surface having continuously smooth surface configuration. The sacrificial mold is removed by gaseous reactions accomplished through the porous ceramic cover prior to enclosing of the outer sphere by addition of an outer coating. The multishell target comprises the inner fuel pellet concentrically arranged within a surrounding coated cover or shell by fiber nets imbedded within the cover material.

Relaxometry, luminescence measurements, electrophoresis, and animal biodistribution of lanthanide(III) complexes of some polyaza macrocyclic acetates containing pyridine

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

Kim, W.D.; Sherry, A.D.; Kiefer, G.E.

Four Gd{sup 3+} complexes [Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}] with polyazamacrocyclic ligands that contain a pyridine moiety were prepared and examined for possible use as MRI contrast enhancement agents. The authors estimated the number of inner sphere water molecules (q{sub Gd}) for the Gd{sup 3+} complexes from the values of q found for the Tb{sup 3+} and/or Eu{sup 3+} complexes by luminescence lifetime measurements. It was estimated that q{sub Gd} = 3.5, 3.3, 2.4, and 0.2 for Gd(BP2A){sup +}, Gd(PC2A){sup +}, Gd(PCTA){sup 0}, and Gd(BPO4A){sup {minus}}, respectively. The inner sphere relaxivities (r{sub 1,inner}) of these tetraazamore » macrocyclic complexes were higher than that of Gd(DOTA){sup {minus}} [i.e. 6.79 for Gd(BP2A){sup +}, 6.21 for Gd(PC2A){sup +}, and 4.60 for Gd(PCTA){sup 0} mM{sup {minus}1}s{sup {minus}1} at 40 MHz and 25{degrees}C], but the normalized relaxivities per q{sub Gd} (1.94, 1.88, and 1.92 mM{sup {minus}1}s{sup {minus}1}, respectively) were comparable to that of Gd(DOTA){sup {minus}}. A quantitative treatment of the NMRD profiles based on Solomon-Bloembergen-Morgan theory, using the NMRD profile of Gd(BPO4A){sup {minus}} to correct for an outer sphere contribution, showed that the complexes exhibit characteristics similar to that of Gd(DOTA){sup {minus}} but with shorter electronic relaxation times. Tissue biodistribution results using radioactive {sup 153}Sm and {sup 159}Gd complexes in rats indicate that the cationic [{sup 153}Sm-(BP2A){sup +} and {sup 153}Sm(PC2A){sup +}] complexes accumulate preferably in the bone tissue while the neutral [{sup 153}Sm-(PCTA){sup 0}] and anionic [{sup 153}Sm(BPO4A){sup {minus}}] complexes appear to have renal clearances similar to those of other low molecular weight contrast agents [i.e. Gd(DTPA){sup 2{minus}} and Gd(DOTA){sup {minus}}].« less

Equatorial symmetry of Boussinesq convective solutions in a rotating spherical shell allowing rotation of the inner and outer spheres

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

Kimura, Keiji; Takehiro, Shin-ichi; Yamada, Michio

2014-08-15

We investigate properties of convective solutions of the Boussinesq thermal convection in a moderately rotating spherical shell allowing the respective rotation of the inner and outer spheres due to the viscous torque of the fluid. The ratio of the inner and outer radii of the spheres, the Prandtl number, and the Taylor number are fixed to 0.4, 1, and 500{sup 2}, respectively. The Rayleigh number is varied from 2.6 × 10{sup 4} to 3.4 × 10{sup 4}. In this parameter range, the behaviours of obtained asymptotic convective solutions are almost similar to those in the system whose inner and outermore » spheres are restricted to rotate with the same constant angular velocity, although the difference is found in the transition process to chaotic solutions. The convective solution changes from an equatorially symmetric quasi-periodic one to an equatorially symmetric chaotic one, and further to an equatorially asymmetric chaotic one, as the Rayleigh number is increased. This is in contrast to the transition in the system whose inner and outer spheres are assumed to rotate with the same constant angular velocity, where the convective solution changes from an equatorially symmetric quasi-periodic one, to an equatorially asymmetric quasi-periodic one, and to equatorially asymmetric chaotic one. The inner sphere rotates in the retrograde direction on average in the parameter range; however, it sometimes undergoes the prograde rotation when the convective solution becomes chaotic.« less

Strong and weak adsorptions of polyelectrolyte chains onto oppositely charged spheres

NASA Astrophysics Data System (ADS)

Cherstvy, A. G.; Winkler, R. G.

2006-08-01

We investigate the complexation of long thin polyelectrolyte (PE) chains with oppositely charged spheres. In the limit of strong adsorption, when strongly charged PE chains adapt a definite wrapped conformation on the sphere surface, we analytically solve the linear Poisson-Boltzmann equation and calculate the electrostatic potential and the energy of the complex. We discuss some biological applications of the obtained results. For weak adsorption, when a flexible weakly charged PE chain is localized next to the sphere in solution, we solve the Edwards equation for PE conformations in the Hulthén potential, which is used as an approximation for the screened Debye-Hückel potential of the sphere. We predict the critical conditions for PE adsorption. We find that the critical sphere charge density exhibits a distinctively different dependence on the Debye screening length than for PE adsorption onto a flat surface. We compare our findings with experimental measurements on complexation of various PEs with oppositely charged colloidal particles. We also present some numerical results of the coupled Poisson-Boltzmann and self-consistent field equation for PE adsorption in an assembly of oppositely charged spheres.

Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

2000-01-01

We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes

DOE PAGES

Carter, Tyler J.; Wilson, Richard E.

2015-09-10

Here, the synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et 4N] 4[Pu IV(NCS) 8], [Et 4N] 4[Th IV(NCS) 8], and [Et 4N] 4[Ce III(NCS) 7(H 2O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu III in acidic solutions (pH<1) in the presence of NCS –. The optical spectrum of [Et 4N][SCN] containing Pu III solution was indistinguishable from that of aquated Pu III suggesting that inner-sphere complexation with [Et 4N][SCN] does not occur in water. However, upon concentration, the homoleptic thiocyanate complex [Et 4N] 4[Pu IV(NCS) 8] was crystallized when amore » large excess of [Et 4N][NCS] was present. This compound, along with its U IV analogue, maintains inner-sphere thiocyanate coordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An IV–NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.« less

Creatine supports propagation and promotes neuronal differentiation of inner ear progenitor cells.

PubMed

Di Santo, Stefano; Mina, Amir; Ducray, Angélique; Widmer, Hans R; Senn, Pascal

2014-05-07

Long-term propagation of inner ear-derived progenitor/stem cells beyond the third generation and differentiation into inner ear cell types has been shown to be feasible, but challenging. We investigated whether the known neuroprotective guanidine compound creatine (Cr) promotes propagation of inner ear progenitor/stem cells as mitogen-expanded neurosphere cultures judged from the formation of spheres over passages. In addition, we studied whether Cr alone or in combination with brain-derived neurotrophic factor (BDNF) promotes neuronal differentiation of inner ear progenitors. For this purpose, early postnatal rat spiral ganglia, utricle, and organ of Corti-derived progenitors were grown as floating spheres in the absence (controls) or presence of Cr (5 mM) from passage 3 onward. Similarly, dissociated sphere-derived cultures were differentiated for 14 days in the presence or absence of Cr (5 mM) and spiral ganglia sphere-derived cultures in a combination of Cr with the neurotrophin BDNF (50 ng/ml). We found that the cumulative total number of spheres over all passages was significantly higher after Cr supplementation as compared with controls in all the three inner ear cultures. In contrast, sphere sizes were not affected by the administration of Cr. Administration of Cr during differentiation of spiral ganglia cells resulted in a significantly higher density of β-III-tubulin-positive cells compared with controls, whereas densities of myosin VIIa-positive cells in cultures of utricle and organ of Corti were not affected by the treatment. Importantly, a combination of Cr with the neurotrophin BDNF resulted in further significantly increased densities of β-III-tubulin-positive cells in cultures of spiral ganglia cells as compared with single treatments. In sum, Cr promoted continuing propagation of rat inner ear-derived progenitor cells and supported specifically in combination with BDNF the differentiation of neuronal cell types from spiral ganglion-derived spheres.

Electrohydrodynamics of a compound vesicle under an AC electric field

NASA Astrophysics Data System (ADS)

Priti Sinha, Kumari; Thaokar, Rochish M.

2017-07-01

Compound vesicles are relevant as simplified models for biological cells as well as in technological applications such as drug delivery. Characterization of these compound vesicles, especially the inner vesicle, remains a challenge. Similarly their response to electric field assumes importance in light of biomedical applications such as electroporation. Fields lower than that required for electroporation cause electrodeformation in vesicles and can be used to characterize their mechanical and electrical properties. A theoretical analysis of the electrohydrodynamics of a compound vesicle with outer vesicle of radius R o and an inner vesicle of radius λ {{R}o} , is presented. A phase diagram for the compound vesicle is presented and elucidated using detailed plots of electric fields, free charges and electric stresses. The electrohydrodynamics of the outer vesicle in a compound vesicle shows a prolate-sphere and prolate-oblate-sphere shape transitions when the conductivity of the annular fluid is greater than the outer fluid, and vice-versa respectively, akin to single vesicle electrohydrodynamics reported in the literature. The inner vesicle in contrast shows sphere-prolate-sphere and sphere-prolate-oblate-sphere transitions when the inner fluid conductivity is greater and smaller than the annular fluid, respectively. Equations and methodology are provided to determine the bending modulus and capacitance of the outer as well as the inner membrane, thereby providing an easy way to characterize compound vesicles and possibly biological cells.

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

Wu, Chunya; Skelton, Adam A.; Chen, Mingjun

Here the binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg 2+, Ca 2+, or Sr 2+) or monovalent (Na +, K +, or Rb +) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na + > K + >more » Rb + shows a “reverse” lyotropic trend, while the divalent cations on the same surface exhibit a “regular” lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr 2+ > Ca 2+ > Mg 2+). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO – group and the rutile, helping to “trap” the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO– group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.« less

Mechanisms of boron removal from hydraulic fracturing wastewater by aluminum electrocoagulation.

PubMed

Sari, Mutiara Ayu; Chellam, Shankararaman

2015-11-15

Boron uptake from highly saline hydraulic fracturing wastewater by freshly precipitated amorphous Al(OH)3 precipitates is due to ligand exchange and complexation with surface hydroxyl groups. Consequently, aluminum electrocoagulation can be a feasible approach to remove boron from flowback/produced water. Actual hydraulic fracturing wastewater containing ∼120mg/L boron from the Eagle Ford shale play was employed. Electrocoagulation was performed over a range of aluminum dosages (0-1350mg/L), pH 6.4 and 8, and high current densities (20-80mA/cm(2)) using a cylindrical aluminum anode encompassed by a porous cylindrical 316-stainless steel cathode. Direct measurements of boron uptake along with its chemical state and coordination were made using Attenuated Total Reflection-Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-Ray Photoelectron Spectroscopy. Boron removal increased monotonically with aluminum dosage and was higher at pH 8, but remained relatively constant at ⩾20mA/cm(2). Chloride ions induced anodic pitting and super-Faradaic (131% efficiency) aluminum dissolution and their electrooxidation produced free chlorine. ATR-FTIR suggested outer-sphere and inner-sphere complexation of trigonal B(OH)3 with Al(OH)3, which was confirmed by the BO bond shifting toward lower binding energies in XPS. Severe AlO interferences precluded evidence for tetrahedral B(OH)4(-) complexation. No evidence for co-precipitation was obtained. Copyright © 2015 Elsevier Inc. All rights reserved.

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

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

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Self-templated formation of uniform NiCo2O4 hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors.

PubMed

Shen, Laifa; Yu, Le; Yu, Xin-Yao; Zhang, Xiaogang; Lou, Xiong Wen David

2015-02-02

Despite the significant advancement in preparing metal oxide hollow structures, most approaches rely on template-based multistep procedures for tailoring the interior structure. In this work, we develop a new generally applicable strategy toward the synthesis of mixed-metal-oxide complex hollow spheres. Starting with metal glycerate solid spheres, we show that subsequent thermal annealing in air leads to the formation of complex hollow spheres of the resulting metal oxide. We demonstrate the concept by synthesizing highly uniform NiCo2O4 hollow spheres with a complex interior structure. With the small primary building nanoparticles, high structural integrity, complex interior architectures, and enlarged surface area, these unique NiCo2O4 hollow spheres exhibit superior electrochemical performances as advanced electrode materials for both lithium-ion batteries and supercapacitors. This approach can be an efficient self-templated strategy for the preparation of mixed-metal-oxide hollow spheres with complex interior structures and functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nano-micro carbon spheres anchored on porous carbon derived from dual-biomass as high rate performance supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Liu, Shaobo; Zhao, Yang; Zhang, Baihui; Xia, Hui; Zhou, Jianfei; Xie, Wenke; Li, Hongjian

2018-03-01

Hierarchical nano-micro carbon spheres@rice straw-derived porous carbon composites are successfully synthesized by the in situ decoration of the porous carbon with carbon spheres from glucose under the assistance of cetyltrimethyl ammonium bromide micelles and further activated by KOH. The scanning electron microscope images clearly show the carbon spheres disperse homogeneously and orderly onto the surface and in the inner macropores of the porous carbon. The diameter of the carbon spheres varies from 475 nm to 1.6 μm, which can be easily controlled by introducing extra inducing agent. The optimal composites exhibit a large specific surface area (1122 m2 g-1), rich content of oxygen (14.2 wt %), and tunable hierarchical porous structure. When used as supercapacitor electrodes, the novel composites with abundant fruits present a high specific capacitance of 337 F g-1 at 1 A g-1, excellent rate retention of 83% from 1 to 20 A g-1 and a good cycling stability with 96% capacitance retention after 10000 cycles. In this strategy, the thought of shared ion-buffering reservoirs is proposed and the mutual promotion effects between the carbon spheres and porous carbon in the composites are also practically demonstrated to contribute the enhanced electrochemical performances.

Molecular insight into the nanoconfined calcite–solution interface

PubMed Central

Diao, Yijue; Espinosa-Marzal, Rosa M.

2016-01-01

Little is known about the influence of nanoconfinement on calcium carbonate mineralization. Here, colloidal probe atomic force microscopy is used to confine the calcite–solution interface with a silica microsphere and to measure Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO forces as a function of the calcium concentration, also after charge reversal of both surfaces occurs. Through the statistical analysis of the oscillatory component of a strong hydration force, the subnanometer interfacial structure of the confined atomically flat calcite is resolved in aqueous solution. By applying a mechanical work, both water and hydrated counterions are squeezed out from the nanoconfined solution, leaving the calcite surface more negatively charged than the analogous unconfined surfaces. Layer size and applied work allow a distinction between the hydration states of the counterions in the Stern layer; we propose counterions to be inner- and outer-sphere calcium ions, with a population of inner-sphere calcium ions larger than on unconfined calcite surfaces. It is also shown that the composition of the nanoconfined solution can be tuned by varying calcium concentration. This is a fundamental study of DLVO and hydration forces, and of their connection, on atomically flat calcite. More broadly, our work scrutinizes the greatly unexplored relation between surface science and confined mineralization, with implications for diverse areas of inquiry, such as nanoconfined biomineralization, CO2 sequestration in porous aquifers, and pressure solution and crystallization in confined hydrosystems. PMID:27790988

Surface speciation of yttrium and neodymium sorbed on rutile: Interpretations using the change distribution model.

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

Ridley, Mora K.; Hiemstra, T; Machesky, Michael L.

2012-01-01

The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3 11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Sternmore » layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (110) rutile surface (Zhang et al., 2004b). TheMDsimulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs) should aid in elucidating a fundamental understating of ion-adsorption reactions.« less

Surface speciation of yttrium and neodymium sorbed on rutile: Interpretations using the charge distribution model

NASA Astrophysics Data System (ADS)

Ridley, Moira K.; Hiemstra, Tjisse; Machesky, Michael L.; Wesolowski, David J.; van Riemsdijk, Willem H.

2012-10-01

The adsorption of Y3+ and Nd3+ onto rutile has been evaluated over a wide range of pH (3-11) and surface loading conditions, as well as at two ionic strengths (0.03 and 0.3 m), and temperatures (25 and 50 °C). The experimental results reveal the same adsorption behavior for the two trivalent ions onto the rutile surface, with Nd3+ first adsorbing at slightly lower pH values. The adsorption of both Y3+ and Nd3+ commences at pH values below the pHznpc of rutile. The experimental results were evaluated using a charge distribution (CD) and multisite complexation (MUSIC) model, and Basic Stern layer description of the electric double layer (EDL). The coordination geometry of possible surface complexes were constrained by molecular-level information obtained from X-ray standing wave measurements and molecular dynamic (MD) simulation studies. X-ray standing wave measurements showed an inner-sphere tetradentate complex for Y3+ adsorption onto the (1 1 0) rutile surface (Zhang et al., 2004b). The MD simulation studies suggest additional bidentate complexes may form. The CD values for all surface species were calculated based on a bond valence interpretation of the surface complexes identified by X-ray and MD. The calculated CD values were corrected for the effect of dipole orientation of interfacial water. At low pH, the tetradentate complex provided excellent fits to the Y3+ and Nd3+ experimental data. The experimental and surface complexation modeling results show a strong pH dependence, and suggest that the tetradentate surface species hydrolyze with increasing pH. Furthermore, with increased surface loading of Y3+ on rutile the tetradentate binding mode was augmented by a hydrolyzed-bidentate Y3+ surface complex. Collectively, the experimental and surface complexation modeling results demonstrate that solution chemistry and surface loading impacts Y3+ surface speciation. The approach taken of incorporating molecular-scale information into surface complexation models (SCMs) should aid in elucidating a fundamental understating of ion-adsorption reactions.

Neutron dose equivalent meter

DOEpatents

Olsher, Richard H.; Hsu, Hsiao-Hua; Casson, William H.; Vasilik, Dennis G.; Kleck, Jeffrey H.; Beverding, Anthony

1996-01-01

A neutron dose equivalent detector for measuring neutron dose capable of accurately responding to neutron energies according to published fluence to dose curves. The neutron dose equivalent meter has an inner sphere of polyethylene, with a middle shell overlying the inner sphere, the middle shell comprising RTV.RTM. silicone (organosiloxane) loaded with boron. An outer shell overlies the middle shell and comprises polyethylene loaded with tungsten. The neutron dose equivalent meter defines a channel through the outer shell, the middle shell, and the inner sphere for accepting a neutron counter tube. The outer shell is loaded with tungsten to provide neutron generation, increasing the neutron dose equivalent meter's response sensitivity above 8 MeV.

Adenosine/guanosine-3',5'-bis-phosphates as biocompatible and selective Zn2+-ion chelators. Characterization and comparison with adenosine/guanosine-5'-di-phosphate.

PubMed

Sayer, Alon Haim; Blum, Eliav; Major, Dan Thomas; Vardi-Kilshtain, Alexandra; Levi Hevroni, Bosmat; Fischer, Bilha

2015-04-28

Although involved in various physiological functions, nucleoside bis-phosphate analogues and their metal-ion complexes have been scarcely studied. Hence, here, we explored the solution conformation of 2′-deoxyadenosine- and 2′-deoxyguanosine-3′,5′-bisphosphates, 3 and 4, d(pNp), as well as their Zn(2+)/Mg(2+) binding sites and binding-modes (i.e. inner- vs. outer-sphere coordination), acidity constants, stability constants of their Zn(2+)/Mg(2+) complexes, and their species distribution. Analogues 3 and 4, in solution, adopted a predominant Southern ribose conformer (ca. 84%), gg conformation around C4'-C5' and C5'-O5' bonds, and glycosidic angle in the anti-region (213-270°). (1)H- and (31)P-NMR experiments indicated that Zn(2+)/Mg(2+) ions coordinated to P5' and P3' groups of 3 and 4 but not to N7 nitrogen atom. Analogues 3 and 4 formed ca. 100-fold more stable complexes with Zn(2+)vs. Mg(2+)-ions. Complexes of 3 and 4 with Mg(2+) at physiological pH were formed in minute amounts (11% and 8%, respectively) vs. Zn(2+) complexes (46% and 44%). Stability constants of Zn(2+)/Mg(2+) complexes of analogues 3 and 4 (log KML(M) = 4.65-4.75/2.63-2.79, respectively) were similar to those of the corresponding complexes of ADP and GDP (log KML(M) = 4.72-5.10/2.95-3.16, respectively). Based on the above findings, we hypothesized that the unexpectedly low log K values of Zn(2+)-d(pNp) as compared to Zn(2+)-NDP complexes, are possibly due to formation of outer-sphere coordination in the Zn(2+)-d(pNp) complex vs. inner-sphere in the NDP-Zn(2+) complex, in addition to loss of chelation to N7 nitrogen atom in Zn(2+)-d(pNp). Indeed, explicit solvent molecular dynamics simulations of 1 and 3 for 100 ns supported this hypothesis.

Mechanisms of antimony adsorption onto soybean stover-derived biochar in aqueous solutions.

PubMed

Vithanage, Meththika; Rajapaksha, Anushka Upamali; Ahmad, Mahtab; Uchimiya, Minori; Dou, Xiaomin; Alessi, Daniel S; Ok, Yong Sik

2015-03-15

Limited mechanistic knowledge is available on the interaction of biochar with trace elements (Sb and As) that exist predominantly as oxoanions. Soybean stover biochars were produced at 300 °C (SBC300) and 700 °C (SBC700), and characterized by BET, Boehm titration, FT-IR, NMR and Raman spectroscopy. Bound protons were quantified by potentiometric titration, and two acidic sites were used to model biochar by the surface complexation modeling based on Boehm titration and NMR observations. The zero point of charge was observed at pH 7.20 and 7.75 for SBC300 and SBC700, respectively. Neither antimonate (Sb(V)) nor antimonite (Sb(III)) showed ionic strength dependency (0.1, 0.01 and 0.001 M NaNO3), indicating inner sphere complexation. Greater adsorption of Sb(III) and Sb(V) was observed for SBC300 having higher -OH content than SBC700. Sb(III) removal (85%) was greater than Sb(V) removal (68%). Maximum adsorption density for Sb(III) was calculated as 1.88 × 10(-6) mol m(-2). The Triple Layer Model (TLM) successfully described surface complexation of Sb onto soybean stover-derived biochar at pH 4-9, and suggested the formation of monodentate mononuclear and binuclear complexes. Spectroscopic investigations by Raman, FT-IR and XPS further confirmed strong chemisorptive binding of Sb to biochar surfaces. Copyright © 2014 Elsevier Ltd. All rights reserved.

Adsorption of MCPA on goethite and humic acid-coated goethite.

PubMed

Iglesias, A; López, R; Gondar, D; Antelo, J; Fiol, S; Arce, F

2010-03-01

Anionic pesticides are adsorbed on the mineral oxide fraction of the soil surface but considerably less on the organic fraction, so that the presence of organic matter causes a decrease in the amount of pesticide adsorbed, and may affect the mechanism of adsorption. In the present study we investigated the adsorption of the weak acid pesticide MCPA on the surface of goethite and of humic acid-coated goethite, selected as models of the mineral oxide fraction and organic components present in soil systems. Adsorption of the anionic form of the pesticide on goethite fitted an S-type isotherm and the amount adsorbed increased as the ionic strength decreased and the pH of the medium decreased. Application of the charge distribution multi site complexation model (CD-MUSIC model) enabled interpretation of the results, which suggested the formation of inner and outer sphere complexes between the pesticide and the singly-coordinated surface sites of goethite. Less pesticide was adsorbed on the humic acid-coated goethite than on the bare goethite and the pattern fitted an L-type isotherm, which indicates a change in the mechanism of adsorption. Simplified calculations with the CD-MUSIC model enabled interpretation of the results, which suggested that the pesticide molecules form the same type of surface complexes as in the previous case. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

USGS Publications Warehouse

Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

2001-01-01

Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

Distribution pattern of rare earth ions between water and montmorillonite and its relation to the sorbed species of the ions.

PubMed

Takahashi, Yoshio; Tada, Akisa; Shimizu, Hiroshi

2004-09-01

REE (rare earth element) distribution coefficients (Kd) between the aqueous phase and montmorillonite surface were obtained to investigate the relation between the REE distribution patterns and the species of REE sorbed on the solid-water interface. It was shown that the features in the REE patterns, such as the slope of the REE patterns, the tetrad effect, and the Y/Ho ratio, were closely related to the REE species at the montmorillonite-water interface. In a binary system (REE-montmorillonite) below pH 5, three features (a larger Kd value for a lighter REE, the absence of the tetrad effect, and the Y/Ho ratio being unchanged from its initial value) suggest that hydrated REE are directly sorbed as an outer-sphere complex at the montmorillonite-water interface. Above pH 5.5, the features in the REE patterns, the larger Kd value for heavier REE, the M-type tetrad effect, and the reduced Y/Ho ratio, showed the formation of an inner-sphere complex of REE with -OH group at the montmorillonite surface. In addition, the REE patterns in the presence of humic acid at pH 5.9 were also studied, where the REE patterns became flat, suggesting that the humate complex is dominant as both dissolved and sorbed species of REE in the ternary system. All of these results were consistent with the spectroscopic data (laser-induced fluorescence spectroscopy) showing the local structure of Eu(III) conducted in the same experimental system. The present results suggest that the features in the REE distribution patterns include information on the REE species at the solid-water interface.

High-order central ENO finite-volume scheme for hyperbolic conservation laws on three-dimensional cubed-sphere grids

NASA Astrophysics Data System (ADS)

Ivan, L.; De Sterck, H.; Susanto, A.; Groth, C. P. T.

2015-02-01

A fourth-order accurate finite-volume scheme for hyperbolic conservation laws on three-dimensional (3D) cubed-sphere grids is described. The approach is based on a central essentially non-oscillatory (CENO) finite-volume method that was recently introduced for two-dimensional compressible flows and is extended to 3D geometries with structured hexahedral grids. Cubed-sphere grids feature hexahedral cells with nonplanar cell surfaces, which are handled with high-order accuracy using trilinear geometry representations in the proposed approach. Varying stencil sizes and slope discontinuities in grid lines occur at the boundaries and corners of the six sectors of the cubed-sphere grid where the grid topology is unstructured, and these difficulties are handled naturally with high-order accuracy by the multidimensional least-squares based 3D CENO reconstruction with overdetermined stencils. A rotation-based mechanism is introduced to automatically select appropriate smaller stencils at degenerate block boundaries, where fewer ghost cells are available and the grid topology changes, requiring stencils to be modified. Combining these building blocks results in a finite-volume discretization for conservation laws on 3D cubed-sphere grids that is uniformly high-order accurate in all three grid directions. While solution-adaptivity is natural in the multi-block setting of our code, high-order accurate adaptive refinement on cubed-sphere grids is not pursued in this paper. The 3D CENO scheme is an accurate and robust solution method for hyperbolic conservation laws on general hexahedral grids that is attractive because it is inherently multidimensional by employing a K-exact overdetermined reconstruction scheme, and it avoids the complexity of considering multiple non-central stencil configurations that characterizes traditional ENO schemes. Extensive numerical tests demonstrate fourth-order convergence for stationary and time-dependent Euler and magnetohydrodynamic flows on cubed-sphere grids, and robustness against spurious oscillations at 3D shocks. Performance tests illustrate efficiency gains that can be potentially achieved using fourth-order schemes as compared to second-order methods for the same error level. Applications on extended cubed-sphere grids incorporating a seventh root block that discretizes the interior of the inner sphere demonstrate the versatility of the spatial discretization method.

Development of a Self-Consistent Model of Plutonium Sorption: Quantification of Sorption Enthalpy and Ligand-Promoted Dissolution

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

Powell, Brian; Kaplan, Daniel I; Arai, Yuji

2016-12-29

This university lead SBR project is a collaboration lead by Dr. Brian Powell (Clemson University) with co-principal investigators Dan Kaplan (Savannah River National Laboratory), Yuji Arai (presently at the University of Illinois), Udo Becker (U of Michigan) and Rod Ewing (presently at Stanford University). Hypothesis: The underlying hypothesis of this work is that strong interactions of plutonium with mineral surfaces are due to formation of inner sphere complexes with a limited number of high-energy surface sites, which results in sorption hysteresis where Pu(IV) is the predominant sorbed oxidation state. The energetic favorability of the Pu(IV) surface complex is strongly influencedmore » by positive sorption entropies, which are mechanistically driven by displacement of solvating water molecules from the actinide and mineral surface during sorption. Objectives: The overarching objective of this work is to examine Pu(IV) and Pu(V) sorption to pure metal (oxyhydr)oxide minerals and sediments using variable temperature batch sorption, X-ray absorption spectroscopy, electron microscopy, and quantum-mechanical and empirical-potential calculations. The data will be compiled into a self-consistent surface complexation model. The novelty of this effort lies largely in the manner the information from these measurements and calculations will be combined into a model that will be used to evaluate the thermodynamics of plutonium sorption reactions as well as predict sorption of plutonium to sediments from DOE sites using a component additivity approach.« less

Characterization of diatomite and its application for the retention of radiocobalt: role of environmental parameters.

PubMed

Sheng, Guodong; Dong, Huaping; Li, Yimin

2012-11-01

Clay minerals have been extensively studied because of their strong sorption and complexation ability. In this work, diatomite was characterized by using acid-base titration. Retention of radionuclide (60)Co(II) from aqueous solution by sorption onto diatomite was investigated by using batch technique under various environmental conditions such as pH, ionic strength, humic acid (HA), fulvic acid (FA), and temperature. The results indicated that the sorption of Co(II) onto diatomite was strongly dependent on pH. At low pH value, the sorption of Co(II) was dominated by outer-sphere surface complexation and ion exchange with Na(+)/H(+) on diatomite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH value. The D-R model fitted the sorption isotherms better than the Langmuir and Freundlich models. The thermodynamic parameters (ΔH(0), ΔS(0) and ΔG(0)) calculated from the temperature-dependent sorption isotherms suggested that the sorption of Co(II) was an endothermic and spontaneous process. In addition, diatomite showed higher sorption capacity than that of lots of the sorbents reported in the literatures we surveyed. From the results of Co(II) removal by diatomite, the optimum reaction conditions can be obtained for the maximum removal of Co(II) from water. It is clear that the best pH values of the system to remove Co(II) from solution by using diatomite are 7-8. Considering the low cost and effective disposal of Co(II)-contaminated wastewaters, the best condition for Co(II) removal is at room temperature and solid content of 0.5 g/L. The results might be important for assessing the potential of practical application of diatomite in Co(II) and related radionuclide pollution management. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sorption of Eu(III) on humic acid or fulvic acid bound to hydrous alumina studied by SEM-EDS, XPS, TRLFS, and batch techniques.

PubMed

Tan, X L; Wang, X K; Geckeis, H; Rabung, Th

2008-09-01

To identify the effect of humic acid (HA) and fulvic acid (FA) on the sorption mechanism of Eu(III) on organic--inorganic colloids in the environment at a molecular level, surface adsorbed/ complexed Eu(III) on hydrous alumina, HA-, and FA-hydrous alumina hybrids were characterized by using X-ray photoelectron spectroscopy (XPS) and time-resolved laser fluorescence spectroscopy (TRLFS). The experiments were performed in 0.1 mol/L KNO3 or 0.1 mol/L NaClO4 under ambient conditions. The pH values were varied between 2 and 11 at a fixed Eu(III) concentration of 6.0 x 10(-7) mol/L and 4.3 x 10(-5) mol/L. The different Eu(III)/FA(HA)/hydrous alumina complexes were characterized by their fluorescence emission spectra ((5D0-F1)/ (5D0 --> 7F2)) and binding energy of Eu(III). Inner-sphere surface complexation may contribute mainly to Eu(III) sorption on hydrous alumina, and a ternary surface complex is formed at the HA/ FA-hydrous alumina hybrid surfaces. The sorption and species of Eu(III) in ternary Eu-HA/FA-hydrous alumina systems are not dominated by either HA/FA or hydrous alumina, but are dominated by both HA/FA and hydrous alumina. The results are important for understanding the sorption mechanisms and the nature of surface adsorbed Eu(III) species and trivalent chemical homologues of Eu(III) in the natural environment.

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

PubMed

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water oxygen density near the pyrophyllite surface is similar to the other cases, but the hydrogen density profile indicates reduced hydrogen bonding between adsorbed water molecules and the surface.

Porous Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, Fred

2005-01-01

This document is a slide presentation that examines the use of a simple templating process to produce hollow ceramic spheres with a pore size of 1 to 10 microns. Using ion exchange process it was determined that the method produces porous ceramic spheres with a unique structure: (i.e., inner sphere surrounded by an outer sphere.)

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Peacock, Caroline L.; Sherman, David M.

2004-06-01

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe 2O 3) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO 4H n) n-6 and binuclear (Cu 2O 6H n) n-8 complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH) 6 polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe 2(OH) 2(H 2O) 8Cu(OH) 4and Fe 3(OH) 4(H 2O) 10Cu 2(OH) 6 clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO 4H n) n-6 and Fe(O,OH) 6 polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH) 2. Having identified the bidentate (FeOH) 2Cu(OH) 20 and tridentate (Fe 3O(OH) 2)Cu 2(OH) 30 surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions 3( FeOH)+2 Cu2++3 H2O=( Fe3O( OH) 2) Cu2( OH) 30+4 H+ and 2( FeOH)+ Cu2++2 H2O=( FeOH) 2Cu( OH) 20+2 H+. The two stability constants are similar for the three iron (hydr)oxide phases investigated.

Effect of Coexisting Ions on Adsorption of Arsenic by Metal Oxides

NASA Astrophysics Data System (ADS)

Meng, Xiaoguang; Shi, Qiantao; Christodoulatos, Christos

2017-04-01

Iron hydroxides and nano TiO2 are commonly used adsorbents for removal of arsenic in water. Iron hydroxides also play an important role in controlling the fate and transport of arsenic in groundwater. Co-existing anions, such as phosphate, silicate, and bicarbonate could significantly affect the adsorption capacity of the adsorbents for arsenate and arsenite and increase their mobility in groundwater aquifers. Arsenate and arsenite interactions at the solid-water interface were investigated using electrophoretic mobility (EM) measurements, Fourier transform infrared (FTIR) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Electrochemical scanning tunneling microscopy (ECSTM) and in-situ flow cell ATR-FTIR were applied to investigate the interactions between As(III), As(V) and carbonate in water and at the solid-water interface. The experimental results suggested that arsenate and arsenite formed inner-sphere complexes with the hydroxide groups on the adsorbents. Arsenite and carbonate could form ternary surface complexes with the hydroxyl groups on iron hydroxide.

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

Versino, Daniele; Brock, Jerry Steven

In this manuscript we describe test cases for the dynamic sphere problem in presence of finite deformations. The spherical shell in exam is made of a homogeneous, isotropic or transverse isotropic material and elastic and elastic-plastic material behaviors are considered. Twenty cases, (a) to (t), are thus defined combining material types and boundary conditions. The inner surface radius, the outer surface radius and the material's density are kept constant for all the considered test cases and their values are r i = 10mm, r o = 20mm and p = 1000Kg/m 3 respectively.

Molecular-Scale Study of Aspartate Adsorption on Goethite and Competition with Phosphate.

PubMed

Yang, Yanli; Wang, Shengrui; Xu, Yisheng; Zheng, Binghui; Liu, Jingyang

2016-03-15

Knowledge of the interfacial interactions between aspartate and minerals, especially its competition with phosphate, is critical to understanding the fate and transport of amino acids in the environment. Adsorption reactions play important roles in the mobility, bioavailability, and degradation of aspartate and phosphate. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements and density functional theory (DFT) calculations were used to investigate the interfacial structures and their relative contributions in single-adsorbate and competition systems. Our results suggest three dominant mechanisms for aspartate: bidentate inner-sphere coordination involving both α- and γ-COO(-), outer-sphere complexation via electrostatic attraction and H-bonding between aspartate NH2 and goethite surface hydroxyls. The interfacial aspartate is mainly governed by pH and is less sensitive to changes of ionic strength and aspartate concentration. The phosphate competition significantly reduces the adsorption capacity of aspartate on goethite. Whereas phosphate adsorption is less affected by the presence of aspartate, including the relative contributions of diprotonated monodentate, monoprotonated bidentate, and nonprotonated bidentate structures. The adsorption process facilitates the removal of bioavailable aspartate and phosphate from the soil solution as well as from the sediment pore water and the overlying water.

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.

Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF 3SO 3 Media to 250 °C

DOE PAGES

Machesky, Michael L.; Předota, Milan; Ridley, Moira K.; ...

2015-06-01

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF 3SO 3 –) electrolyte media from 25 to 250 °C. Rb + primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m 2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitancemore » values and intrinsic Rb + binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na + results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb + and Na + reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.« less

Constrained Surface Complexation Modeling: Rutile in RbCl, NaCl, and NaCF 3SO 3 Media to 250 °C

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

Machesky, Michael L.; Předota, Milan; Ridley, Moira K.

In this paper, a comprehensive set of molecular-level results, primarily from classical molecular dynamics (CMD) simulations, are used to constrain CD-MUSIC surface complexation model (SCM) parameters describing rutile powder titrations conducted in RbCl, NaCl, and NaTr (Tr = triflate, CF 3SO 3 –) electrolyte media from 25 to 250 °C. Rb + primarily occupies the innermost tetradentate binding site on the rutile (110) surface at all temperatures (25, 150, 250 °C) and negative charge conditions (-0.1 and -0.2 C/m 2) probed via CMD simulations, reflecting the small hydration energy of this large, monovalent cation. Consequently, variable SCM parameters (Stern-layer capacitancemore » values and intrinsic Rb + binding constants) were adjusted relatively easily to satisfactorily match the CMD and titration data. The larger hydration energy of Na + results in a more complex inner-sphere distribution, which shifts from bidentate to tetradentate binding with increasing negative charge and temperature, and this distribution was not matched well for both negative charge conditions, which may reflect limitations in the CMD and/or SCM approaches. Finally, in particular, the CMD axial density profiles for Rb + and Na + reveal that peak binding distances shift toward the surface with increasing negative charge, suggesting that the CD-MUSIC framework may be improved by incorporating CD or Stern-layer capacitance values that vary with charge.« less

High Relaxivity Gadolinium Hydroxypyridonate-Viral Capsid Conjugates: Nano-sized MRI Contrast Agents

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

Meux, Susan C.; Datta, Ankona; Hooker, Jacob M.

2007-08-29

High relaxivity macromolecular contrast agents based on the conjugation of gadolinium chelates to the interior and exterior surfaces of MS2 viral capsids are assessed. The proton nuclear magnetic relaxation dispersion (NMRD) profiles of the conjugates show up to a five-fold increase in relaxivity, leading to a peak relaxivity (per Gd{sup 3+} ion) of 41.6 mM{sup -1}s{sup -1} at 30 MHz for the internally modified capsids. Modification of the exterior was achieved through conjugation to flexible lysines, while internal modification was accomplished by conjugation to relatively rigid tyrosines. Higher relaxivities were obtained for the internally modified capsids, showing that (1) theremore » is facile diffusion of water to the interior of capsids and (2) the rigidity of the linker attaching the complex to the macromolecule is important for obtaining high relaxivity enhancements. The viral capsid conjugated gadolinium hydroxypyridonate complexes appear to possess two inner-sphere water molecules (q = 2) and the NMRD fittings highlight the differences in the local motion for the internal ({tau}{sub RI} = 440 ps) and external ({tau}{sub RI} = 310 ps) conjugates. These results indicate that there are significant advantages of using the internal surface of the capsids for contrast agent attachment, leaving the exterior surface available for the installation of tissue targeting groups.« less

Preparation of Geophysical Fluid Flow Experiments With The Rotating Spherical Gap Flow Model In Space

NASA Astrophysics Data System (ADS)

Egbers, C.

The'GeoFlow' is an ESA experiment planned for the Fluid Science Laboratory on ISS under the scientific coordination (PI) of the Department of Aerodynamics and Fluid Mechanics (LAS) at the Brandenburg Technical University (BTU) of Cottbus, Germany. The objective of the experiment is to study thermal convection in the gap between two concentric rotating (full) spheres. A central symmetric force field simi- lar to the gravity field acting on planets can be produced by applying a high voltage between inner and outer sphere using the dielectrophoretic effect (rotating capacitor). To counter the unidirectional gravity under terrestrial conditions, this experiment re- quires a microgravity environment. The parameters of the experiment are chosen in analogy to the thermal convective motions in the outer core of the Earth. In analogy to geophysical motions in the Earth`s liquid core the experiment can rotate as solid body as well as differential (inner to outer). Thermal convection is produced by heat- ing the inner sphere and cooling the outer ones. Furtheron, the variation of radius ratio between inner and outer sphere is foreseen as a parameter variation. The flows to be investigated will strongly depend on the gap width and on the Prandtl number.

Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms for organometallic complexes

NASA Astrophysics Data System (ADS)

Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO(exp 2+) transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

Theoretical Elastic Stress Distributions Arising from Discontinuities and Edge Loads in Several Shell-Type Structures

NASA Technical Reports Server (NTRS)

Johns, Robert H.; Orange, Thomas W.

1961-01-01

The deformation and complete stress distribution are determined for each of the following edge loaded thin shells of revolution: (1) a right circular cylinder, (2) a frustum of a right circular cone, and (3) a portion of a sphere. The locations of the maximum circumferential and meridional stresses on both the inner and outer surfaces are also found. The basic equations for the above were selected from the published literature on the subject and expanded to produce to resultant-stress equations in closed from where practicable to do so. Equations are also developed for the discontinuity shear force and bending moment at each of the following junction: (1) axial change of thickness in a circular cylinder, (2) axial change of thickness in a cone, (3) change of thickness in a portion of a sphere, (4) a cylinder and a cone, (5) a cylinder and a portion of a sphere(6) a cylinder and a flat head, and (7) a cone and a portion of a sphere.

Surface Complexation of Neodymium at the Rutile-Water Interface: A Potentiometric and Modeling Study in NaCl Media to 250°C

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

Ridley, Mora K.; Machesky, Michael L.; Wesolowski, David J

2005-01-01

The adsorption of Nd{sup 3+} onto rutile surfaces was examined by potentiometric titration from 25 to 250 C, in 0.03 and 0.30m NaCl background electrolyte. Experimental results show that Nd{sup 3+} sorbs strongly, even at low temperature, with adsorption commencing below the pHznpc of rutile. In addition, there is a systematic increase in Nd{sup 3+} adsorption with increasing temperature. The experimental results were rationalized and described using surface oxygen proton affinities computed from the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three-layer description of the oxide/water interface. Moreover, molecular-scale information was incorporated successfully into the surface complexationmore » model, providing a unique geometry for the adsorption of Nd{sup 3+} on rutile. The primary mode of Nd{sup 3+} adsorption was assumed to be the tetradentate configuration found for Y{sup 3+} adsorption on the rutile (110) surface from previously described in situ X-ray standing wave experiments, wherein the sorbing cations bond directly with two adjacent ''terminal'' and two adjacent ''bridging'' surface oxygen atoms. Similarly, the adsorption of Na{sup +} counterions was also assumed to be tetradentate, as supported by MD simulations of Na{sup +} interactions with the rutile (110) surface, and by analogous X-ray standing wave results for Rb{sup +} adsorption on rutile. Fitting parameters for Nd{sup 3+} adsorption included binding constants for the tetradentate adsorption complex and capacitance values for the inner-sphere binding plane. In addition, hydrolysis of the tetradentate adsorption complex was permitted and resulted in significantly improved model fits at higher temperature and pH values. The modeling results indicate that the Stern-based MUSIC surface-complexation model adequately accommodates molecular-scale information to uniquely rationalize and describe multivalent ion adsorption systematically into the hydrothermal regime.« less

Molecular binding mechanisms of aqueous cadmium and lead to siderophores, bacteria and mineral surfaces

NASA Astrophysics Data System (ADS)

Mishra, Bhoopesh

Recent studies have shown that diverse groups of bacteria adsorb metals to similar extents and uptake can be modeled using a universal adsorption model. In this study, XAFS has been used to resolve whether binding sites determined for single species systems are responsible for adsorption in more complex natural bacterial assemblages. Results obtained from a series of XAFS experiments on pure Gram positive and Gram negative bacterial strains and consortia of bacteria as a function of pH and Cd loading suggests that every bacterial strain has a complex physiology and they are all slightly different from each other. Nevertheless from the metal adsorption chemistry point of view, the main difference between them lies in the site ratio of three fundamental sites only - carboxyl, phosphoryl and sulfide. Two completely different consortia of bacteria (obtained from natural river water, and soil system with severe organic contamination) were successfully modeled in the pH range 3.4--7.8 using the EXAFS models developed for single species systems. Results thus obtained can potentially have very high impact on the modeling of the complex bacterial systems in realistic geological settings, leading to further refinement and development of robust remediation strategies for metal contamination at macroscopic level. In another study, solution speciation of Pb and Cd with DFO-B has been examined using a combination of techniques (ICP, TOC, thermodynamic modeling and XAFS). Results indicate that Pb does not complex with DFO-B at all until about pH 3.5, but forms a totally caged structure at pH 7.5. At intermediate pH conditions, mixture of species (one and two hydroxamate groups complexed) is formed. Cd on the other hand, does not complex until pH 5, forms intermediate complexes at pH 8 and is totally chelated at pH 9. Further studies were conducted for Pb sorption to mineral surface kaolinite with and without DFO-B. In the absence of DFO-B, results suggest outer sphere and inner sphere sorption of Pb on kaolinite surface at acidic and circumneutral pH conditions respectively. In the presence of DFO-B, bulk sorption studies indicated that Pb sorption is enhanced in the presence of DFO-B around pH 6 and inhibited above pH 6.5. This was confirmed by x-ray fluorescence measurements. Extended XAFS study clearly indicated unwrapping of DFO-B molecule at the surface. Our study has unambiguously recognized it as a "Type A" ternary complex ("Type A" complex means surface-metal-ligand type of interaction). Taken together, bulk adsorption measurements and XAFS experiments represent a powerful approach for determining and modeling metal speciation and adsorption.

Selenium adsorption to aluminum-based water treatment residuals

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

Ippolito, James A.; Scheckel, Kirk G.; Barbarick, Ken A.

2009-09-02

Aluminum-based water treatment residuals (WTR) can adsorb water- and soil-borne P, As(V), As(III), and perchlorate, and may be able to adsorb excess environmental selenium. WTR, clay minerals, and amorphous aluminum hydroxide were shaken for 24 h in selenate or selenite solutions at pH values of 5-9, and then analyzed for selenium content. Selenate and selenite adsorption edges were unaffected across the pH range studied. Selenate adsorbed on to WTR, reference mineral phases, and amorphous aluminum hydroxide occurred as outer sphere complexes (relatively loosely bound), while selenite adsorption was identified as inner-sphere complexation (relatively tightly bound). Selenite sorption to WTR inmore » an anoxic environment reduced Se(IV) to Se(0), and oxidation of Se(0) or Se(IV) appeared irreversible once sorbed to WTR. Al-based WTR could play a favorable role in sequestering excess Se in affected water sources.« less

Lanthanide chelates of (bis)-hydroxymethyl-substituted DTTA with potential application as contrast agents in magnetic resonance imaging.

PubMed

Silvério, Sara; Torres, Susana; Martins, André F; Martins, José A; André, João P; Helm, Lothar; Prata, M Isabel M; Santos, Ana C; Geraldes, Carlos F G C

2009-06-28

A novel bis-hydroxymethyl-substituted DTTA chelator N'-Bz-C(4,4')-(CH(2)OH)(2)-DTTA () and its DTPA analogue C(4,4')-(CH(2)OH)(2)-DTPA () were synthesized and characterized. A variable-temperature (1)H NMR spectroscopy study of the solution dynamics of their diamagnetic (La) and paramagnetic (Sm, Eu) Ln(3+) complexes showed them to be rigid when compared with analogous Ln(3+)-DTTA and Ln(3+)-DTPA complexes, as a result of their C(4,4')-(CH(2)OH)(2) ligand backbone substitution. The parameters that govern the water (1)H relaxivity of the [Gd()(H(2)O)(2)](-) and [Gd()(H(2)O)](2-) complexes were obtained by (17)O and (1)H NMR relaxometry. While the relaxometric behaviour of the [Gd()(H(2)O)](2-) complex is very similar to the parent [Gd(DTPA)(H(2)O)](2-) system, the [Gd()(H(2)O)(2)](-) complex displays higher relaxivity, due to the presence of two inner sphere water molecules and an accelerated, near optimal water exchange rate. The [Gd()(H(2)O)(2)](-) complex interacts weakly with human serum albumin (HSA), and its fully bound relaxivity is limited by slow water exchange, as monitored by (1)H NMR relaxometry. This complex interacts weakly with phosphate, but does not form ternary complexes with bidentate bicarbonate and l-lactate anions, indicating that the two inner-sphere water molecules of the [Gd()(H(2)O)(2)](-) complex are not located in adjacent positions in the coordination sphere of the Gd(3+) ion. The transmetallation reaction rate of [Gd()(H(2)O)(2)](-) with Zn(2+) in phosphate buffer solution (pH 7.0) was measured to be similar to that of the backbone unsubstituted [Gd(DTTA-Me)(H(2)O)(2)](-), but twice faster than for [Gd(DTPA-BMA)(H(2)O)]. The in vivo biodistribution studies of the (153)Sm(3+)-labelled ligand () in Wistar rats reveal slow blood elimination and short term fixation in various organs, indicating some dissociation. The bis-hydroxymethyl-substituted DTTA skeleton can be seen as a new lead for the synthesis of high relaxivity contrast agents, although its low thermodynamic and kinetic stability will limit its use to in vitro and animal studies.

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

NASA Astrophysics Data System (ADS)

Pokrovsky, O. S.; Viers, J.; Emnova, E. E.; Kompantseva, E. I.; Freydier, R.

2008-04-01

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric ( Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic ( Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine ( Skeletonema costatum) and freshwater ( Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ 65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria ( Rhodobacter sp.), cyanobacteria ( Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria ( P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ 65Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ 65Cu (solid-solution) = -1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ 65Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively. Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu 2+ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution. Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.

Effect of grain-coating mineralogy on nitrate and sulfate storage in the unsaturated zone

USGS Publications Warehouse

Reilly, T.J.; Fishman, N.S.; Baehr, A.L.

2009-01-01

Unsaturated-zone sediments and the chemistry of shallow groundwater underlying a small (???8-km2) watershed were studied to identify the mechanisms responsible for anion storage within the Miocene Bridgeton Formation and weathered Coastal Plain deposits in southern New Jersey. Lower unsaturated-zone sediments and shallow groundwater samples were collected and concentrations of selected ions (including NO3- and SO42-) from 11 locations were determined. Grain size, sorting, and color of the lower unsaturated-zone sediments were determined and the mineralogy of these grains and the composition of coatings were analyzed by petrographic examination, scanning electron microscopy and energy dispersive analysis of x-rays, and quantitative whole-rock x-ray diffraction. The sediment grains, largely quartz and chert (80-94% w/w), are coated with a very fine-grained (<20 ??m), complex mixture of kaolinite, halloysite, goethite, and possibly gibbsite and lepidocrocite. The mineral coatings are present as an open fabric, resulting in a large surface area in contact with pore water. Significant correlations between the amount of goethite in the grain coatings and the concentration of sediment-bound SO42- were observed, indicative of anion sorption. Other mineral-chemical relations indicate that negatively charged surfaces and competition with SO 42- results in exclusion of NO3- from inner sphere exchange sites. The observed NO3- storage may be a result of matrix forces within the grain coatings and outer sphere complexation. The results of this study indicate that the mineralogy of grain coatings can have demonstrable effects on the storage of NO 3- and SO42- in the unsaturated zone. ?? Soil Science Society of America. All rights reserved.

Torsional Alfvén Waves in a Dipolar Magnetic Field

NASA Astrophysics Data System (ADS)

Nataf, H. C.; Tigrine, Z.; Cardin, P.; Schaeffer, N.

2017-12-01

The discovery of torsional Alfvén waves in the Earth's core (Gillet et al, 2010) is a strong motivation for investigating the properties of these waves. Here, we report on the first experimental study of such waves. Alfvén waves are difficult to excite and observe in liquid metals because of their high magnetic diffusivity. Nevertheless, we obtained clear signatures of such diffusive waves in our DTS experiment. In this setup, some 40 liters of liquid sodium are contained between a ro = 210 mm-radius stainless steel outer shell, and a ri = 74 mm-radius copper inner sphere. Both spherical boundaries can rotate independently around a common vertical axis. The inner sphere shells a strong permanent magnet, which produces a nearly dipolar magnetic field whose intensity falls from 175 mT at ri to 8 mT at ro in the equatorial plane. We excite Alfvén waves in the liquid sodium by applying a sudden jerk of the inner sphere. To study the effect of global rotation, which leads to the formation of geostrophic torsional Alfvén waves, we spin the experiment at rotation rates fo = fi up to 15 Hz. The Alfvén wave produces a clear azimuthal magnetic signal on magnetometers installed in a sleeve inside the fluid. We also probe the associated azimuthal velocity field using ultrasound Doppler velocimetry. Electric potentials at the surface of the outer sphere turn out to be very revealing as well. In parallel, we use the XSHELLS magnetohydrodynamics spherical code to model torsional Alfvén waves in the experimental conditions, and beyond. We explore both linear and non-linear regimes. We observe a strong excitation of inertial waves in the equatorial plane, where the wave transits from a region of strong magnetic field to a region dominated by rotation (see figure of meridian map of azimuthal velocity). These novel observations should help deciphering the dynamics of Alfvén waves in planetary cores.

Results of a hubble space telescope search for natural satellites of dwarf planet 1 ceres

NASA Astrophysics Data System (ADS)

DeMario, Benjamin E.; Schmidt, Britney E.; Mutchler, Max J.; Li, Jian-Yang; McFadden, Lucy A.; McLean, Brian J.; Russell, Christopher T.

2016-12-01

In order to prepare for the arrival of the Dawn spacecraft at Ceres, a search for satellites was undertaken by the Hubble Space Telescope (HST) to enhance the mission science return and to ensure spacecraft safety. Previous satellite searches from ground-based telescopes have detected no satellites within Ceres' Hill sphere down to a size of 3 km (Gehrels et al. 1987) and early HST investigations searched to a limit of 1-2 km (Bieryla et al. 2011). The Wide Field Camera 3 (WFC3) on board the HST was used to image Ceres between 14 April-28 April 2014. These images cover approximately the inner third of Ceres' Hill sphere, where the Hill sphere is the region surrounding Ceres where stable satellite orbits are possible. We performed a deep search for possible companions orbiting Ceres. No natural companions were located down to a diameter of 48 m, over most of the Hill sphere to a distance of 205,000 km (434 Ceres radii) from the surface of Ceres. It was impossible to search all the way to the surface of Ceres because of scattered light, but at a distance of 2865 km (five Ceres radii), the search limit was determined to be 925 m.

Hyperfine coupling constants on inner-sphere water molecules of a triazacyclononane-based Mn(II) complex and related systems relevant as MRI contrast agents.

PubMed

Patinec, Véronique; Rolla, Gabriele A; Botta, Mauro; Tripier, Raphaël; Esteban-Gómez, David; Platas-Iglesias, Carlos

2013-10-07

We report the synthesis of the ligand H2MeNO2A (1,4-bis(carboxymethyl)-7-methyl-1,4,7-triazacyclononane) and a detailed experimental and computational study of the hyperfine coupling constants (HFCCs) on the inner-sphere water molecules of [Mn(MeNO2A)] and related Mn(2+) complexes relevant as potential contrast agents in magnetic resonance imaging (MRI). Nuclear magnetic relaxation dispersion (NMRD) profiles, (17)O NMR chemical shifts, and transverse relaxation rates of aqueous solutions of [Mn(MeNO2A)] were recorded to determine the parameters governing the relaxivity in this complex and the (17)O and (1)H HFCCs. DFT calculations (TPSSh model) performed in aqueous solution (PCM model) on the [Mn(MeNO2A)(H2O)]·xH2O and [Mn(EDTA)(H2O)](2-)·xH2O (x = 0-4) systems were used to determine theoretically the (17)O and (1)H HFCCs responsible for the (17)O NMR chemical shifts and the scalar contributions to (17)O and (1)H NMR relaxation rates. The use of a mixed cluster/continuum approach with the explicit inclusion of a few second-sphere water molecules is critical for an accurate calculation of HFCCs of coordinated water molecules. The impact of complex dynamics on the calculated HFCCs was evaluated with the use of molecular dynamics simulations within the atom-centered density matrix propagation (ADMP) approach. The (17)O and (1)H HFCCs calculated for these complexes and related systems show an excellent agreement with the experimental data. Both the (1)H and (17)O HFCCs (A(iso) values) are dominated by the spin delocalization mechanism. The A(iso) values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the Mn(2+) ion, as well as by the orientation of the water molecule plane with respect to the Mn-O vector.

Interaction of Tl +3 with mononucleotides: metal ion binding and sugar conformation

NASA Astrophysics Data System (ADS)

Nafisi, Sh.; Mohajerani, N.; Hadjiakhoondi, A.; Monajemi, M.; Garib, F.

2001-05-01

The interaction of Tl 3+ with sodium salts of adenosine-5'-monophosphate (5'-AMP), guanosine-5'-monophosphate (5'-GMP), cytidine-5'-monophosphate (5'-CMP), thymidine 5'-monophosphate (5'-dTMP) in ratios 1 and 2 have been studied in neutral pH. The solid complexes were isolated and characterized by Fourier transform infrared (FTIR) and 1H NMR spectroscopy. In the Tl 2(AMP) 3, Tl 3+ binds directly to N-7 and indirectly to the N-1 position of the pyrimidine ring and phosphate group with sugar moiety in C2'-endoanti. The crystalline salt of Tl 2(GMP) 3 show direct Tl-N-7 and Tl-PO 3(inner-sphere) binding. The conformation of ribose moiety in Tl 2(GMP) 3 is C3'-endoanti. In the Tl 2(CMP) 3, Tl 3+ bind directly to N-3 and PO32- (inner-sphere). The conformation of ribose moiety in Tl 2(CMP) 3 is C2'-endoanti. In the Tl 2(dTMP) 3, Tl 3+ bind indirectly to carbonyl group. The sugar moiety in Tl 2(dTMP) 3 is C3'-endoanti.

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.

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants

NASA Technical Reports Server (NTRS)

Quinn, R. C.; Zent, A. P.

1999-01-01

Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Interaction between Eu(III) and graphene oxide nanosheets investigated by batch and extended X-ray absorption fine structure spectroscopy and by modeling techniques.

PubMed

Sun, Yubing; Wang, Qi; Chen, Changlun; Tan, Xiaoli; Wang, Xiangke

2012-06-05

The interaction mechanism between Eu(III) and graphene oxide nanosheets (GONS) was investigated by batch and extended X-ray absorption fine structure (EXAFS) spectroscopy and by modeling techniques. The effects of pH, ionic strength, and temperature on Eu(III) adsorption on GONS were evaluated. The results indicated that ionic strength had no effect on Eu(III) adsorption on GONS. The maximum adsorption capacity of Eu(III) on GONS at pH 6.0 and T = 298 K was calculated to be 175.44 mg·g(-1), much higher than any currently reported. The thermodynamic parameters calculated from temperature-dependent adsorption isotherms suggested that Eu(III) adsorption on GONS was an endothermic and spontaneous process. Results of EXAFS spectral analysis indicated that Eu(III) was bound to ∼6-7 O atoms at a bond distance of ∼2.44 Å in the first coordination shell. The value of Eu-C bond distance confirmed the formation of inner-sphere surface complexes on GONS. Surface complexation modeling gave an excellent fit with the predominant mononuclear monodentate >SOEu(2+) and binuclear bidentate (>SO)(2)Eu(2)(OH)(2)(2+) complexes. This paper highlights the application of GONS as a suitable material for the preconcentration and removal of trivalent lanthanides and actinides from aqueous solutions in environmental pollution management.

New Synthesis of nZVI/C Composites as an Efficient Adsorbent for the Uptake of U(VI) from Aqueous Solutions.

PubMed

Liu, Haibo; Li, Mengxue; Chen, Tianhu; Chen, Changlun; Alharbi, Njud S; Hayat, Tasawar; Chen, Dong; Zhang, Qiang; Sun, Yubing

2017-08-15

New nanoscale zerovalent iron/carbon (nZVI/C) composites were successfully prepared via heating natural hematite and pine sawdust at 800 °C under nitrogen conditions. Characterization by SEM, XRD, FTIR, and XPS analyses indicated that the as-prepared nZVI/C composites contained a large number of reactive sites. The lack of influence of the ionic strength revealed inner-sphere complexation dominated U(VI) uptake by the nZVI/C composites. Simultaneous adsorption and reduction were involved in the uptake process of U(VI) according to the results of XPS and XANES analyses. The presence of U-C/U-U shells demonstrated that innersphere complexation and surface coprecipitation dominated the U(VI) uptake at low and high pH conditions, respectively. The uptake behaviors of U(VI) by the nZVI/C composites were fitted well by surface complexation modeling with two weak and two strong sites. The maximum uptake capacity of U(VI) by the nZVI/C composites was 186.92 mg/g at pH 4.0 and 328 K. Additionally, the nZVI/C composites presented good recyclability and recoverability for U(VI) uptake in regeneration experiments. These observations indicated that the nZVI/C composites can be considered as potential adsorbents to remove radionuclides for environmental remediation.

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

Dynamic domains of the Derviche Tourneur sodium experiment: Simulations of a spherical magnetized Couette flow

NASA Astrophysics Data System (ADS)

Kaplan, E. J.; Nataf, H.-C.; Schaeffer, N.

2018-03-01

The Derviche Tourneur sodium experiment, a spherical Couette magnetohydrodynamics experiment with liquid sodium as the medium and a dipole magnetic field imposed from the inner sphere, recently underwent upgrades to its diagnostics to better characterize the flow and induced magnetic fields with global rotation. In tandem with the upgrades, a set of direct numerical simulations were run to give a more complete view of the fluid and magnetic dynamics at various rotation rates of the inner and outer spheres. These simulations reveal several dynamic regimes, determined by the Rossby number. At positive differential rotation there is a regime of quasigeostrophic flow, with low levels of fluctuations near the outer sphere. Negative differential rotation shows a regime of what appear to be saturated hydrodynamic instabilities at low negative differential rotation, followed by a regime where filamentary structures develop at low latitudes and persist over five to ten differential rotation periods as they drift poleward. We emphasize that all these coherent structures emerge from turbulent flows. At least some of them seem to be related to linear instabilities of the mean flow. The simulated flows can produce the same measurements as those that the physical experiment can take, with signatures akin to those found in the experiment. This paper discusses the relation between the internal velocity structures of the flow and their magnetic signatures at the surface.

Effect of soil humic and fulvic acids, pH and ionic strength on Th(IV) sorption to TiO2 nanoparticles.

PubMed

Tan, Xiaoli; Wang, Xiangke; Chen, Changlun; Sun, Aihua

2007-04-01

Thorium is considered as a chemical analog of other tetravalent actinides. Herein, the sorption of Th(IV) on TiO(2) in the presence or absence of soil fulvic acid (FA)/humic acid (HA) as a function of pH, ionic strength and FA/HA concentration has been studied by a batch method. The morphology was characterized by scanning electron microscopy (SEM). The results indicate that sorption of Th(IV) on TiO(2) increases from 0% to approximately 94% at pH 1 approximately 4, and then maintains level with increasing pH values. Both FA and HA have a positive effect on Th(IV) sorption at low pH values and the contribution of FA on Th(IV) sorption is rather higher than that of HA at pH<4. The sorption is weakly dependent on the concentration of KNO(3) in solution, but the cations K(+), Na(+) and Li(+) influence Th(IV) sorption more obviously. The batch results indicate that the inner sphere complex formation is formed at bare surfaces or FA/HA-bound TiO(2) particle surfaces. Results of SEM analysis show that the particle sizes of TiO(2), Th-TiO(2) and Th-HA-TiO(2) colloids are quite different. Surface complexation may be considered as the main sorption mechanism.

Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

2014-02-05

Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO 2 2+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO 2Cl 2 ,more » 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si 4Al 2 rings near aluminum substitution sites.« less

A Bridge to Coordination Isomer Selection in Lanthanide(III) DOTA-tetraamide Complexes

PubMed Central

Vipond, Jeff; Woods, Mark; Zhao, Piyu; Tircso, Gyula; Ren, Jimin; Bott, Simon G.; Ogrin, Doug; Kiefer, Garry E.; Kovacs, Zoltan; Sherry, A.Dean

2008-01-01

Interest in macrocyclic lanthanide complexes such as DOTA is driven largely through interest in their use as contrast agents for MRI. The lanthanide tetraamide derivatives of DOTA have shown considerable promise as PARACEST agents, taking advantage of the slow water exchange kinetics of this class of complex. We postulated that water exchange in these tetraamide complexes could be slowed even further by introducing a group to sterically encumber the space above the water coordination site, thereby hindering the departure and approach of water molecules to the complex. The ligand 8O2-bridged-DOTAM was synthesized in a 34% yield from cyclen. It was found that the lanthanide complexes of this ligand did not possess a water molecule in the inner coordination sphere of the bound lanthanide. The crystal structure of the ytterbium complex revealed that distortions to the coordination sphere were induced by the steric constraints imposed on the complex by the bridging unit. The extent of the distortion was found to increase with increasing ionic radius of the lanthanide ion, eventually resulting in a complete loss of symmetry in the complex. Because this ligand system is bicyclic, the conformation of each ring in the system is constrained by that of the other, in consequence inclusion of the bridging unit in the complexes means only a twisted square antiprismatic coordination geometry is observed for complexes of 8O2-bridged-DOTAM. PMID:17295475

Preparation of Geophysical Fluid Flow Experiments ( GeoFlow ) in the Fluid Science Laboratory on ISS

NASA Astrophysics Data System (ADS)

Egbers, C.

The ,,GeoFlow" is an ESA experiment planned for the Fluid Science Laboratory on ISS under the scientific coordination (PI) of the Department of Aerodynamics and Fluidmechanics (LAS) at the Brandenburg Technical University (BTU) of Cottbus, Germany. The objective of the experiment is to study thermal convection in the gap between two concentric rotating (full) spheres. A central symmetric force field similar to the gravity field acting on planets can be produced by applying a high voltage between inner and outer sphere using the dielectrophoretic effect (rotating capacitor). To counter the unidirectional gravity under terrestrial conditions, this experiment requires a microgravity environment. The parameters of the experiment are chosen in analogy to the thermal convective motions in the outer core of the Earth. In analogy to geophysical motions in the Earth's liquid core the exp eriment can rotate as solid body as well as differential (inner to outer). Thermal convection is produced by heating the inner sphere and cooling the outer ones. Furtheron, the variation of radius ratio between inner and outer sphere is foreseen as a parameter variation. The flows to be investigated will strongly depend on the gap width and on the Prandtl number. Results of preparatory experiments and numerical simulation of the space experiment will be presented. Funding from DLR under grant 50 WM 0122 is greatfully ackwnoledged.

Localization switching of a large object in a crowded cavity: A rigid/soft object prefers surface/inner positioning.

PubMed

Shew, Chwen-Yang; Oda, Soutaro; Yoshikawa, Kenichi

2017-11-28

For living cells in the real world, a large organelle is commonly positioned in the inner region away from membranes, such as the nucleus of eukaryotic cells, the nucleolus of nuclei, mitochondria, chloroplast, Golgi body, etc. It contradicts the expectation by the current depletion-force theory in that the larger particle should be excluded from the inner cell space onto cell boundaries in a crowding media. Here we simply model a sizable organelle as a soft-boundary large particle allowing crowders, which are smaller hard spheres in the model, to intrude across its boundary. The results of Monte Carlo simulation indicate that the preferential location of the larger particle switches from the periphery into the inner region of the cavity by increasing its softness. An integral equation theory is further developed to account for the structural features of the model, and the theoretical predictions are found consistent with our simulation results.

Localization switching of a large object in a crowded cavity: A rigid/soft object prefers surface/inner positioning

NASA Astrophysics Data System (ADS)

Shew, Chwen-Yang; Oda, Soutaro; Yoshikawa, Kenichi

2017-11-01

For living cells in the real world, a large organelle is commonly positioned in the inner region away from membranes, such as the nucleus of eukaryotic cells, the nucleolus of nuclei, mitochondria, chloroplast, Golgi body, etc. It contradicts the expectation by the current depletion-force theory in that the larger particle should be excluded from the inner cell space onto cell boundaries in a crowding media. Here we simply model a sizable organelle as a soft-boundary large particle allowing crowders, which are smaller hard spheres in the model, to intrude across its boundary. The results of Monte Carlo simulation indicate that the preferential location of the larger particle switches from the periphery into the inner region of the cavity by increasing its softness. An integral equation theory is further developed to account for the structural features of the model, and the theoretical predictions are found consistent with our simulation results.

Adsorption of Eu(III) onto TiO2: effect of pH, concentration, ionic strength and soil fulvic acid.

PubMed

Tan, Xiaoli; Fang, Ming; Li, Jiaxing; Lu, Yi; Wang, Xiangke

2009-08-30

The effects of pH, initial Eu(III) concentration, ionic strength and fulvic acid (FA) on the adsorption of Eu(III) on TiO(2) are investigated by using batch techniques. The results indicate that the presence of FA strongly enhances the adsorption of Eu(III) on TiO(2) at low pH values. Besides, the adsorption of Eu(III) on TiO(2) is significantly dependent on pH values and independent of ionic strength. The adsorption of Eu(III) on TiO(2) is attributed to inner-sphere surface complexation. The diffuse layer model (DLM) is applied to simulate the adsorption data, and fits the experimental data well with the aid of FITEQL 3.2. X-ray photoelectron spectroscopy (XPS) is performed to study the species of Eu(III) adsorbed on the surfaces of TiO(2)/FA-TiO(2) hybrids at a molecular level, which suggest that FA act as "bridge" between Eu(III) and TiO(2) particles to enhance the ability to adsorb Eu(III) in solution.

Recovery of phosphate from aqueous solution by magnesium oxide decorated magnetic biochar and its potential as phosphate-based fertilizer substitute.

PubMed

Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Lahori, Altaf Hussain; Mahar, Amanullah

2016-09-01

The present study deals with the preparation of a novel MgO-impregnated magnetic biochar (MMSB) for phosphate recovery from aqueous solution. The MMSB was evaluated against sugarcane harvest residue biochar (SB) and magnetic biochar without Mg (MSB). The results showed that increasing Mg content in MMSB greatly improved the phosphate adsorption compared to SB and MSB, with 20% Mg-impregnated MMSB (20MMSB) recovering more than 99.5% phosphate from aqueous solution. Phosphate adsorption capacity of 20MMSB was 121.25mgP/g at pH 4 and only 37.53% of recovered phosphate was desorbed by 0.01mol/L HCl solutions. XRD and FTIR analysis showed that phosphate sorption mechanisms involved predominately with surface electrostatic attraction and precipitation with impregnated MgO and surface inner-sphere complexation with Fe oxide. The 20MMSB exhibited both maximum phosphate sorption and strong magnetic separation ability. Overall, phosphate-loaded 20MMSB significantly enhanced plant growth and could be used as a potential substitute for phosphate-based fertilizer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Study on competitive adsorption mechanism among oxyacid-type heavy metals in co-existing system: Removal of aqueous As(V), Cr(III) and As(III) using magnetic iron oxide nanoparticles (MIONPs) as adsorbents

NASA Astrophysics Data System (ADS)

Lin, Sen; Lian, Cheng; Xu, Meng; Zhang, Wei; Liu, Lili; Lin, Kuangfei

2017-11-01

The adsorption and co-adsorption of As(V), Cr(VI) and As(III) onto the magnetic iron oxide nanoparticles (MIONPs) surface were investigated comprehensively to clarify the competitive processes. The results reflected that the MIONPs had remarkable preferential adsorption to As(V) compared with Cr(VI) and As(III). And it was determined, relying on the analysis of heavy metals variations on the MIONPs surface at different co-adsorption stages using FTIR and XPS, that the inner-sphere complexation made vital contribution to the preferential adsorption for As(V), corresponding with the replacement experiments where As(V) could grab extensively active sites on the MIONPs pre-occupied by As(III) or Cr(V) uniaxially. The desorption processes displayed that the strongest affinity between the MIONPs and As(V) where As(III) and Cr(VI) were more inclined to wash out. It is wish to provide a helpful direction with this study for the wastewater treatment involving multiple oxyacid-type heavy metals using MIONPs as adsorbents.

Synchrotron speciation of silver and zinc oxide nanoparticles aged in a kaolin suspension.

PubMed

Scheckel, Kirk G; Luxton, Todd P; El Badawy, Amro M; Impellitteri, Christopher A; Tolaymat, Thabet M

2010-02-15

Assessments of the environmental fate and mobility of nanoparticles must consider the behavior of nanoparticles in relevant environmental systems that may result in speciation changes over time. Environmental conditions may act on nanoparticles to change their size, shape, and surface chemistry. Changing these basic characteristics of nanoparticles may result in a final reaction product that is significantly different than the initial nanomaterial. As such, basing long-term risk and toxicity on the initial properties of a nanomaterial may lead to erroneous conclusions if nanoparticles change upon release to the environment. The influence of aging on the speciation and chemical stability of silver and zinc oxide nanoparticles in kaolin suspensions was examined in batch reactors for up to 18 months. Silver nanoparticles remained unchanged in sodium nitrate suspensions; however, silver chloride was identified with the metallic silver nanoparticles in sodium chloride suspensions and may be attributed to an in situ silver chloride surface coating. Zinc oxide nanoparticles were rapidly converted via destabilization/dissolution mechanisms to Zn(2+) inner-sphere sorption complexes within 1 day of reaction and these sorption complexes were maintained through the 12 month aging processes. Chemical and physical alteration of nanomaterials in the environment must be examined to understand fate, mobility, and toxicology.

THE POTENTIAL ROLE OF ENDOGENOUS STEM CELLS IN REGENERATION OF THE INNER EAR

PubMed Central

Martinez-Monedero, Rodrigo; Oshima, Kazuo; Heller, Stefan; Edge, Albert S.B.

2007-01-01

Stem cells in various mammalian tissues retain the capacity to renew themselves and may be able to restore damaged tissue. Their existence has been proven by genetic tracer studies that demonstrate their differentiation into multiple tissue types and by their ability to self-renew through proliferation. Stem cells from the adult nervous system proliferate to form clonal floating colonies called spheres in vitro, and recent studies have demonstrated sphere formation by cells in the cochlea in addition to the vestibular system and the auditory ganglia, indicating that these tissues contain cells with stem cell properties. The presence of stem cells in the inner ear raises the hope of regeneration of mammalian inner ear cells but is difficult to correlate with the lack spontaneous regeneration seen in the inner ear after tissue damage. Loss of stem cells postnatally in the cochlea may correlate with the loss of regenerative capacity and may limit our ability to stimulate regeneration. Retention of sphere forming capacity in adult vestibular tissues suggests that the limited capacity for repair may be attributed to the continued presence of progenitor cells. Future strategies for regeneration must consider the distribution of endogenous stem cells in the inner ear and whether cells with the capacity for regeneration are retained. PMID:17321086

Optical trapping forces of a focused azimuthally polarized Bessel-Gaussian beam on a double-layered sphere

NASA Astrophysics Data System (ADS)

Wu, F. P.; Zhang, B.; Liu, Z. L.; Tang, Y.; Zhang, N.

2017-12-01

We calculate the trapping forces exerted by a highly focused Bessel-Gaussian beam on a double-layered sphere by means of vector diffraction integral, T-matrix method and Maxwell stress tensor integral. The Bessel-Gaussian beam is azimuthally polarized. Numerical results predicate that the double-layered sphere with air core can be stably trapped in three-dimensions. The trapping forces and efficiencies are dependent on the refraction index and size of the inner core. The trapping efficiency can be optimized by choosing the refraction indices of the inner core and outer layer. Our computational method can be easily modified for other laser beams and particles with arbitrary geometries and multilayers.

A numerical test of the topographic bias

NASA Astrophysics Data System (ADS)

Sjöberg, L. E.; Joud, M. S. S.

2018-02-01

In 1962 A. Bjerhammar introduced the method of analytical continuation in physical geodesy, implying that surface gravity anomalies are downward continued into the topographic masses down to an internal sphere (the Bjerhammar sphere). The method also includes analytical upward continuation of the potential to the surface of the Earth to obtain the quasigeoid. One can show that also the common remove-compute-restore technique for geoid determination includes an analytical continuation as long as the complete density distribution of the topography is not known. The analytical continuation implies that the downward continued gravity anomaly and/or potential are/is in error by the so-called topographic bias, which was postulated by a simple formula of L E Sjöberg in 2007. Here we will numerically test the postulated formula by comparing it with the bias obtained by analytical downward continuation of the external potential of a homogeneous ellipsoid to an inner sphere. The result shows that the postulated formula holds: At the equator of the ellipsoid, where the external potential is downward continued 21 km, the computed and postulated topographic biases agree to less than a millimetre (when the potential is scaled to the unit of metre).

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

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

Cances, Benjamin; Benedetti, Marc; Farges, Francois

2007-02-02

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands atmore » pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

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

Cances, Benjamin; /Marne La Vallee U.; Benedetti, Marc

2006-12-13

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxyhydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au L{sub III}-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl){sub 4}), with dominantly OHmore » ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution--Multi Site Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Geochemical conditions and the occurrence of selected trace elements in groundwater basins used for public drinking-water supply, Desert and Basin and Range hydrogeologic provinces, 2006-11: California GAMA Priority Basin Project

USGS Publications Warehouse

Wright, Michael T.; Fram, Miranda S.; Belitz, Kenneth

2015-01-01

Concentrations of strontium, which exists primarily in a cationic form (Sr2+), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

The Rayleigh-Taylor instability in a self-gravitating two-layer viscous sphere

NASA Astrophysics Data System (ADS)

Mondal, Puskar; Korenaga, Jun

2018-03-01

The dispersion relation of the Rayleigh-Taylor instability in the spherical geometry is of profound importance in the context of the Earth's core formation. Here we present a complete derivation of this dispersion relation for a self-gravitating two-layer viscous sphere. Such relation is, however, obtained through the solution of a complex transcendental equation, and it is difficult to gain physical insights directly from the transcendental equation itself. We thus also derive an empirical formula to compute the growth rate, by combining the Monte Carlo sampling of the relevant model parameter space with linear regression. Our analysis indicates that the growth rate of Rayleigh-Taylor instability is most sensitive to the viscosity of inner layer in a physical setting that is most relevant to the core formation.

Results of a Hubble Space Telescope Search for Natural Satellites of Dwarf Planet 1 Ceres

NASA Astrophysics Data System (ADS)

DeMario, Benjamin; Schmidt, Britney E.; Mutchler, Maximilian J.; Li, Jian-Yang; McFadden, Lucy Ann; McLean, Brian; Russell, Christopher T.

2016-10-01

In order to prepare for the arrival of the Dawn spacecraft at Ceres, a search for satellites was undertaken by the Hubble Space Telescope (HST) to enhance the mission science return and to ensure spacecraft safety. Previous satellite searches from ground-based telescopes have detected no satellites within Ceres' Hill sphere down to a size of 3 km (Gehrels et al. 1987) and early HST investigations searched to a limit of 1-2 km (Bieryla et al. 2011). The Wide Field Camera 3 (WFC3) on board the HST was used to image Ceres between 14 April - 28 April 2014. These images cover approximately the inner third of Ceres' Hill sphere, where the Hill sphere is the region surrounding Ceres where stable satellite orbits are possible. We performed a deep search for possible companions orbiting Ceres. No natural companions were located down to a diameter of 48 meters, over most of the Hill sphere to a distance of 205,000 km (434 Ceres radii) from the surface of Ceres. It was impossible to search all the way to the surface of Ceres because of scattered light, but at a distance of 2865 km (five Ceres radii), the search limit was determined to be 925 meters. The absence of a satellite around Ceres could, in the future, support more refined theories about satellite formation or capture mechanisms in the solar system.

Alternative Way of Shifting Mass to Move a Spherical Robot

NASA Technical Reports Server (NTRS)

Lux, James

2005-01-01

The method proposed calls for suspending a payload by use of four or more cables that would be anchored to the inner surface of the sphere. In this method, the anchor points would not be diametrically opposite points defining Cartesian axes. The payload, which includes the functional analog of the aforementioned control box, would contain winches that would shorten or lengthen the cables in a coordinated manner to shift the position of the payload within the shell.

Competition Between Co(NH3)63+ and Inner Sphere Mg2+ Ions in the HDV Ribozyme

PubMed Central

Gong, Bo; Chen, Jui-Hui; Bevilacqua, Philip C.; Golden, Barbara L.; Carey, Paul R.

2009-01-01

Divalent cations play critical structural and functional roles in many RNAs. While the hepatitis delta virus (HDV) ribozyme can undergo self-cleavage in the presence of molar concentrations of monovalent cations, divalent cations such as Mg2+ are required for efficient catalysis under physiological conditions. Moreover, the cleavage reaction can be inhibited with Co(NH3)63+, an analog of Mg(H2O)62+. Here, the binding of Mg2+ and Co(NH3)63+ to the HDV ribozyme are studied by Raman microscopic analysis of crystals. Raman difference spectra acquired at different metal ion conditions reveal changes in the ribozyme. When Mg2+ alone is introduced to the ribozyme, inner sphere coordination of Mg(H2O)x2+ (x≤5) to non-bridging PO2− oxygen, and changes in base stretches and phosphodiester group conformation are observed. In addition, binding of Mg2+ induces deprotonation of a cytosine assigned to the general acid C75, consistent with solution studies. When Co(NH3)63+ alone is introduced, deprotonation of C75 is again observed, as are distinctive changes in base vibrational ring modes and phosphodiester backbone conformation. In contrast to Mg2+ binding, Co(NH3)63+ binding does not perturb PO2− group vibrations, consistent with its ability to make only outer sphere contacts. Surprisingly, competitive binding studies reveal that Co(NH3)63+ ions displace some inner sphere-coordinated magnesium species, including ions coordinated to PO2− groups or the N7 of a guanine, likely G1 at the active site. These observations contrast with the tenet that Co(NH3)63+ ions displace only outer sphere magnesium ions. Overall, our data support two classes of inner sphere Mg2+-PO2− binding sites: sites that Co(NH3)63+ can displace, and others it cannot. PMID:19888753

Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

PubMed

Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin

2010-09-21

In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

Rotational Splittings of Acoustic Modes in an Experimental Model of a Planetary Core

NASA Astrophysics Data System (ADS)

Adams, M. M.; Stone, D.; Lathrop, D. P.

2014-12-01

Planetary zonal flows can be probed in principle using the tools of helioseismology. We explore this technique using laboratory experiments where the measurement of zonal flows is also of geophysical relevance. The experiments are carried out in a device with a geometry similar to that of Earth's core. It consists of a 60 cm diameter outer spherical shell concentric with a 20 cm diameter inner sphere. Air between the inner sphere and outer shell is used as the working fluid. A turbulent shear flow is driven in the air by independently rotating the inner sphere and outer shell. Acoustic modes are excited in the vessel with a speaker, and microphones are used to measure the rotational splittings of these modes. The radial profile of azimuthal velocities is inferred from these splittings, in an approach analogous to that used in helioseismology to determine solar velocity profiles. By varying the inner and outer rotation rates, different turbulent states can be investigated. Comparison is made to previous experimental investigations of turbulent spherical Couette flow. These experiments also serve as a test of this diagnostic, which may be used in the future in liquid sodium experiments, providing information on zonal flows in hydromagnetic experiments.

Fabrication of sub-micrometer-sized jingle bell-shaped hollow spheres from multilayered core-shell particles.

PubMed

Gu, Shunchao; Kondo, Tomohiro; Mine, Eiichi; Nagao, Daisuke; Kobayashi, Yoshio; Konno, Mikio

2004-11-01

Jingle bell-shaped hollow spheres were fabricated starting from multilayered particles composed of a silica core, a polystyrene inner shell, and a titania outer shell. Composite particles of silica core-polystyrene shell, synthesized by coating a 339-nm-sized silica core with a polystyrene shell of thickness 238 nm in emulsion polymerization, were used as core particles for a succeeding titania-coating. A sol-gel method was employed to form the titania outer shell with a thickness of 37 nm. The inner polystyrene shell in the multilayered particles was removed by immersing them in tetrahydrofuran. These successive procedures could produce jingle bell-shaped hollow spheres that contained a silica core in the titania shell.

Monte Carlo simulation of Hamaker nanospheres coated with dipolar particles

NASA Astrophysics Data System (ADS)

Meyra, Ariel G.; Zarragoicoechea, Guillermo J.; Kuz, Victor A.

2012-01-01

Parallel tempering Monte Carlo simulation is carried out in systems of N attractive Hamaker spheres dressed with n dipolar particles, able to move on the surface of the spheres. Different cluster configurations emerge for given values of the control parameters. Energy per sphere, pair distribution functions of spheres and dipoles as function of temperature, density, external electric field, and/or the angular orientation of dipoles are used to analyse the state of aggregation of the system. As a consequence of the non-central interaction, the model predicts complex structures like self-assembly of spheres by a double crown of dipoles. This interesting result could be of help in understanding some recent experiments in colloidal science and biology.

Hemoglobin and Myoglobin as Reducing Agents in Biological Systems. Redox Reactions of Globins with Copper and Iron Salts and Complexes.

PubMed

Postnikova, G B; Shekhovtsova, E A

2016-12-01

In addition to reversible O2 binding, respiratory proteins of the globin family, hemoglobin (Hb) and myoglobin (Mb), participate in redox reactions with various metal complexes, including biologically significant ones, such as those of copper and iron. HbO 2 and MbO 2 are present in cells in large amounts and, as redox agents, can contribute to maintaining cell redox state and resisting oxidative stress. Divalent copper complexes with high redox potentials (E 0 , 200-600 mV) and high stability constants, such as [Cu(phen) 2 ] 2+ , [Cu(dmphen) 2 ] 2+ , and CuDTA oxidize ferrous heme proteins by the simple outer-sphere electron transfer mechanism through overlapping π-orbitals of the heme and the copper complex. Weaker oxidants, such as Cu2+, CuEDTA, CuNTA, CuCit, CuATP, and CuHis (E 0 ≤ 100-150 mV) react with HbO 2 and MbO 2 through preliminary binding to the protein with substitution of the metal ligands with protein groups and subsequent intramolecular electron transfer in the complex (the site-specific outer-sphere electron transfer mechanism). Oxidation of HbO 2 and MbO 2 by potassium ferricyanide and Fe(3) complexes with NTA, EDTA, CDTA, ATP, 2,3-DPG, citrate, and pyrophosphate PP i proceeds mainly through the simple outer-sphere electron transfer mechanism via the exposed heme edge. According to Marcus theory, the rate of this reaction correlates with the difference in redox potentials of the reagents and their self-exchange rates. For charged reagents, the reaction may be preceded by their nonspecific binding to the protein due to electrostatic interactions. The reactions of LbO 2 with carboxylate Fe complexes, unlike its reactions with ferricyanide, occur via the site-specific outer-sphere electron transfer mechanism, even though the same reagents oxidize structurally similar MbO 2 and cytochrome b 5 via the simple outer-sphere electron transfer mechanism. Of particular biological interest is HbO 2 and MbO 2 transformation into met-forms in the presence of small amounts of metal ions or complexes (catalysis), which, until recently, had been demonstrated only for copper compounds with intermediate redox potentials. The main contribution to the reaction rate comes from copper binding to the "inner" histidines, His97 (0.66 nm from the heme) that forms a hydrogen bond with the heme propionate COO - group, and the distal His64. The affinity of both histidines for copper is much lower than that of the surface histidines residues, and they are inaccessible for modification with chemical reagents. However, it was found recently that the high-potential Fe(3) complex, potassium ferricyanide (400 mV), at a 5 to 20% of molar protein concentration can be an efficient catalyst of MbO 2 oxidation into metMb. The catalytic process includes binding of ferrocyanide anion in the region of the His119 residue due to the presence there of a large positive local electrostatic potential and existence of a "pocket" formed by Lys16, Ala19, Asp20, and Arg118 that is sufficient to accommodate [Fe(CN) 6 ] 4- . Fast, proton-assisted reoxidation of the bound ferrocyanide by oxygen (which is required for completion of the catalytic cycle), unlike slow [Fe(CN) 6 ] 4- oxidation in solution, is provided by the optimal location of neighboring protonated His113 and His116, as it occurs in the enzyme active site.

Promoting the Adsorption of Metal Ions on Kaolinite by Defect Sites: A Molecular Dynamics Study

PubMed Central

Li, Xiong; Li, Hang; Yang, Gang

2015-01-01

Defect sites exist abundantly in minerals and play a crucial role for a variety of important processes. Here molecular dynamics simulations are used to comprehensively investigate the adsorption behaviors, stabilities and mechanisms of metal ions on defective minerals, considering different ionic concentrations, defect sizes and contents. Outer-sphere adsorbed Pb2+ ions predominate for all models (regular and defective), while inner-sphere Na+ ions, which exist sporadically only at concentrated solutions for regular models, govern the adsorption for all defective models. Adsorption quantities and stabilities of metal ions on kaolinite are fundamentally promoted by defect sites, thus explaining the experimental observations. Defect sites improve the stabilities of both inner- and outer-sphere adsorption, and (quasi) inner-sphere Pb2+ ions emerge only at defect sites that reinforce the interactions. Adsorption configurations are greatly altered by defect sites but respond weakly by changing defect sizes or contents. Both adsorption quantities and stabilities are enhanced by increasing defect sizes or contents, while ionic concentrations mainly affect adsorption quantities. We also find that adsorption of metal ions and anions can be promoted by each other and proceeds in a collaborative mechanism. Results thus obtained are beneficial to comprehend related processes for all types of minerals. PMID:26403873

Control of electroosmosis in coated quartz capillaries

NASA Technical Reports Server (NTRS)

Herren, Blair J.; Van Alstine, James; Snyder, Robert S.; Shafer, Steven G.; Harris, J. Milton

1987-01-01

The effectiveness of various coatings for controlling the electroosmotic fluid flow that hinders electrophoretic processes is studied using analytical particle microelectrophoresis. The mobilities of 2-micron diameter glass and polystyrene latex spheres (exhibiting both negative and zero effective surface charge) were measured in 2-mm diameter quartz capillaries filled with NaCl solutions within the 3.5-7.8 pH range. It is found that capillary inner surface coatings using 5000 molecular weight (or higher) poly(ethylene glycol): significantly reduced electroosmosis within the selected pH range, were stable for long time periods, and appeared to be more effective than dextran, methylcellulose, or silane coatings.

Assessing the contributions of surface waves and complex rays to far-field Mie scattering by use of the Debye series

NASA Technical Reports Server (NTRS)

Hovenac, Edward A.; Lock, James A.

1991-01-01

The contributions of complex rays and the secondary radiation shed by surface waves to scattering by a dielectric sphere are calculated in the context of the Debye series expansion of the Mie scattering amplitudes. Also, the contributions of geometrical rays are reviewed and compared with the Debye series. Interference effects between surface waves, complex waves, and geometrical waves are calculated, and the possibility of observing these interference effects is discussed. Experimental data supporting the observation of a surface wave-geometrical pattern is presented.

Distribution and mobility of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb) from ammunition residues on shooting ranges for small arms located on mires.

PubMed

Mariussen, Espen; Johnsen, Ida Vaa; Strømseng, Arnljot Einride

2017-04-01

An environmental survey was performed on shooting ranges for small arms located on minerotrophic mires. The highest mean concentrations of Pb (13 g/kg), Cu (5.2 g/kg), Zn (1.1 g/kg), and Sb (0.83 g/kg) in the top soil were from a range located on a poor minerotrophic and acidic mire. This range had also the highest concentrations of Pb, Cu, Zn, and Sb in discharge water (0.18 mg/L Pb, 0.42 mg/L Cu, 0.63 mg/L Zn, and 65 μg/L Sb) and subsurface soil water (2.5 mg/L Pb, 0.9 mg/L Cu, 1.6 mg/L Zn, and 0.15 mg/L Sb). No clear differences in the discharge of ammunition residues between the mires were observed based on the characteristics of the mires. In surface water with high pH (pH ~7), there was a trend with high concentrations of Sb and lower relative concentrations of Cu and Pb. The relatively low concentrations of ammunition residues both in the soil and soil water, 20 cm below the top soil, indicates limited vertical migration in the soil. Channels in the mires, made by plant roots or soil layer of less decomposed materials, may increase the rate of transport of contaminated surface water into deeper soil layers and ground water. A large portion of both Cu and Sb were associated to the oxidizable components in the peat, which may imply that these elements form inner-sphere complexes with organic matter. The largest portion of Pb and Zn were associated with the exchangeable and pH-sensitive components in the peat, which may imply that these elements form outer-sphere complexes with the peat.

Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation

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

Collins, Richard N.; Rosso, Kevin M.

Molecular-level pathways in the aqueous redox transformation of uranium by iron remain unclear, despite the importance of this knowledge for predicting uranium transport and distribution in natural and engineered environments. As the relative importance of homogeneous versus heterogeneous pathways is difficult to probe experimentally, here we apply computational molecular simulation to isolate rates of key one electron transfer reactions in the homogeneous pathway. By comparison to experimental observations the role of the heterogeneous pathway also becomes clear. Density functional theory (DFT) and Marcus theory calculations for all primary monomeric species at pH values ≤7 show for UO22+ and its hydrolysismore » species UO2OH+ and UO2(OH)20 that reduction by Fe2+ is thermodynamically favorable, though kinetically limited for UO22+. An inner-sphere encounter complex between UO2OH+ and Fe2+ was the most stable for the first hydrolysis species and displayed an electron transfer rate constant ket = 4.3 × 103 s-1. Three stable inner- and outer-sphere encounter complexes between UO2(OH)20 and Fe2+ were found, with electron transfer rate constants ranging from ket = 7.6 × 102 to 7.2 × 104 s-1. Homogeneous reduction of these U(VI) hydrolysis species to U(V) is, therefore, predicted to be facile. In contrast, homogeneous reduction of UO2+ by Fe2+ was found to be thermodynamically unfavorable, suggesting the possible importance of U(V)-U(V) disproportionation as a route to U(IV). Calculations on homogeneous disproportionation, however, while yielding a stable outer-sphere U(V)-U(V) encounter complex, indicate that this electron transfer reaction is not feasible at circumneutral pH. Protonation of both axial O atoms of acceptor U(V) (i.e., by H3O+) was found to be a prerequisite to stabilize U(IV), consistent with the experimental observation that the rate of this reaction is inversely correlated with pH. Thus, despite prevailing notions that U(V) is rapidly eliminated by homogeneous disproportionation, this pathway is irrelevant at environmental conditions.« less

Removal of Ciprofloxacin from Aqueous Solutions Using Pillared Clays

PubMed Central

Roca Jalil, Maria Eugenia; Baschini, Miria; Sapag, Karim

2017-01-01

Emerging contaminants in the environment have caused enormous concern in the last few decades, and among them, antibiotics have received special attention. On the other hand, adsorption has shown to be a useful, low-cost, and eco-friendly method for the removal of this type of contaminants from water. This work is focused on the study of ciprofloxacin (CPX) removal from water by adsorption on pillared clays (PILC) under basic pH conditions, where CPX is in its anionic form (CPX−). Four different materials were synthetized, characterized, and studied as adsorbents of CPX (Al-, Fe-, Si-, and Zr-PILC). The highest CPX adsorption capacities of 100.6 and 122.1 mg g−1 were obtained for the Si- and Fe-PILC (respectively), and can be related to the porous structure of the PILCs. The suggested adsorption mechanism involves inner-sphere complexes formation as well as van der Waals interactions between CPX− and the available adsorption sites on the PILC surfaces. PMID:29168798

Heat capacity of a self-gravitating spherical shell of radiations

NASA Astrophysics Data System (ADS)

Kim, Hyeong-Chan

2017-10-01

We study the heat capacity of a static system of self-gravitating radiations analytically in the context of general relativity. To avoid the complexity due to a conical singularity at the center, we excise the central part and replace it with a regular spherically symmetric distribution of matters of which specifications we are not interested in. We assume that the mass inside the inner boundary and the locations of the inner and the outer boundaries are given. Then, we derive a formula relating the variations of physical parameters at the outer boundary with those at the inner boundary. Because there is only one free variation at the inner boundary, the variations at the outer boundary are related, which determines the heat capacity. To get an analytic form for the heat capacity, we use the thermodynamic identity δ Srad=β δ Mrad additionally, which is derived from the variational relation of the entropy formula with the restriction that the mass inside the inner boundary does not change. Even if the radius of the inner boundary of the shell goes to zero, in the presence of a central conical singularity, the heat capacity does not go to the form of the regular sphere. An interesting discovery is that another legitimate temperature can be defined at the inner boundary which is different from the asymptotic one β-1.

Macroscopic and molecular approaches of enrofloxacin retention in soils in presence of Cu(II).

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2013-10-15

The co-adsorption of copper and the fluoroquinolone antibiotic enrofloxacin (ENR) at the water-soil interface was studied by means of batch adsorption experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The system was investigated over a pH range between 6 and 10, at different contact times, ionic strengths, and ENR concentrations. Adsorption coefficient - Kd - was determined at relevant environmental concentrations and the value obtained in water at a ionic strength imposed by the soil and at soil natural pH was equal to 0.66Lg(-1). ENR adsorption onto the soil showed strong pH dependence illustrating the influence of the electrostatic interactions in the sorption processes. The simultaneous co-adsorption of ENR and Cu(II) on the soil was also investigated. The presence of Cu(II) strongly influenced the retention of the antibiotic, leading to an increase up to 35% of adsorbed ENR amount. The combined quantitative and spectroscopic results showed that Cu(II) and ENR directly interacted at the water-soil interface to form ternary surface complexes. Cu K-edge EXAFS data indicated a molecular structure where the carboxylate and carbonyl groups of ENR coordinate to Cu(II) to form a 6-membered chelate ring and where Cu(II) bridges between ENR and the soil surface sites. Cu(II) bonds bidentately to the surface in an inner-sphere mode. Thus, the spectroscopic data allowed us to propose the formation of ternary surface complexes with the molecular architecture soil-Cu(II)-ENR. Copyright © 2013 Elsevier Inc. All rights reserved.

On the probability distribution function of the mass surface density of molecular clouds. I

NASA Astrophysics Data System (ADS)

Fischera, Jörg

2014-05-01

The probability distribution function (PDF) of the mass surface density is an essential characteristic of the structure of molecular clouds or the interstellar medium in general. Observations of the PDF of molecular clouds indicate a composition of a broad distribution around the maximum and a decreasing tail at high mass surface densities. The first component is attributed to the random distribution of gas which is modeled using a log-normal function while the second component is attributed to condensed structures modeled using a simple power-law. The aim of this paper is to provide an analytical model of the PDF of condensed structures which can be used by observers to extract information about the condensations. The condensed structures are considered to be either spheres or cylinders with a truncated radial density profile at cloud radius rcl. The assumed profile is of the form ρ(r) = ρc/ (1 + (r/r0)2)n/ 2 for arbitrary power n where ρc and r0 are the central density and the inner radius, respectively. An implicit function is obtained which either truncates (sphere) or has a pole (cylinder) at maximal mass surface density. The PDF of spherical condensations and the asymptotic PDF of cylinders in the limit of infinite overdensity ρc/ρ(rcl) flattens for steeper density profiles and has a power law asymptote at low and high mass surface densities and a well defined maximum. The power index of the asymptote Σ- γ of the logarithmic PDF (ΣP(Σ)) in the limit of high mass surface densities is given by γ = (n + 1)/(n - 1) - 1 (spheres) or by γ = n/ (n - 1) - 1 (cylinders in the limit of infinite overdensity). Appendices are available in electronic form at http://www.aanda.org

Solvent extraction: the coordination chemistry behind extractive metallurgy.

PubMed

Wilson, A Matthew; Bailey, Phillip J; Tasker, Peter A; Turkington, Jennifer R; Grant, Richard A; Love, Jason B

2014-01-07

The modes of action of the commercial solvent extractants used in extractive hydrometallurgy are classified according to whether the recovery process involves the transport of metal cations, M(n+), metalate anions, MXx(n-), or metal salts, MXx into a water-immiscible solvent. Well-established principles of coordination chemistry provide an explanation for the remarkable strengths and selectivities shown by most of these extractants. Reagents which achieve high selectivity when transporting metal cations or metal salts into a water-immiscible solvent usually operate in the inner coordination sphere of the metal and provide donor atom types or dispositions which favour the formation of particularly stable neutral complexes that have high solubility in the hydrocarbons commonly used in recovery processes. In the extraction of metalates, the structures of the neutral assemblies formed in the water-immiscible phase are usually not well defined and the cationic reagents can be assumed to operate in the outer coordination spheres. The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bonding interactions are favoured by the low polarity of the water-immiscible solvents.

Influence of ionic strength, anions, cations, and natural organic matter on the adsorption of pharmaceuticals to silica.

PubMed

Bui, Tung Xuan; Choi, Heechul

2010-08-01

The adsorption of four wide-use pharmaceuticals (carbamazepine, diclofenac, ibuprofen, and ketoprofen) onto a porous silica was investigated under varied ionic strengths, different anions, divalent cations (Ca(2+) and Mg(2+)), trivalent cations (Al(3+) and Fe(3+)), and natural organic matter (NOM). The experiments demonstrated that at a given pH the adsorption was most affected by ionic strength, trivalent cations, and properties of pharmaceuticals. The increase of ionic strength resulted in an increase in the adsorption of ketoprofen, but a decrease in the adsorption of carbamazepine. Trivalent metal cations made intense increases in the adsorption of three acidic pharmaceuticals, which could be due to the formation of inner-sphere complex of the cations on the surface and/or complexation of the pharmaceuticals with both surface and aqueous metal species. It was found that the adsorption of carbamazepine was not affected by divalent and trivalent cations, whereas the adsorption of diclofenac was solely impacted by the presence of Al(3+). Moreover, divalent cations at low concentration could slightly enhance the adsorption of ibuprofen and ketoprofen, whereas NOM caused a reduction in the adsorption of the tested pharmaceuticals except for diclofenac. These results suggest that ionic strength, divalent cations, trivalent cations, and NOM are notable factors affecting the adsorption of pharmaceuticals and thus the ultimate fate of pharmaceuticals in the aqueous environment. Copyright 2010 Elsevier Ltd. All rights reserved.

Phosphate uptake studies of cross-linked chitosan bead materials.

PubMed

Mahaninia, Mohammad H; Wilson, Lee D

2017-01-01

A systematic experimental study is reported that provides a molecular based understanding of cross-linked chitosan beads and their adsorption properties in aqueous solution containing phosphate dianion (HPO 4 2- ) species. Synthetically modified chitosan using epichlorohydrin and glutaraldehyde cross-linkers result in surface modified beads with variable hydrophile-lipophile character and tunable HPO 4 2- uptake properties. The kinetic and thermodynamic adsorption properties of cross-linked chitosan beads with HPO 4 2- species were studied in aqueous solution. Complementary structure and physicochemical characterization of chitosan beads via potentiometry, Raman spectroscopy, DSC, and dye adsorption measurements was carried out to establish structure-property relationships. The maximum uptake (Q m ) of bead systems with HPO 4 2- at equilibrium was 52.1mgg -1 ; whereas, kinetic uptake results for chitosan bead/phosphate systems are relatively rapid (0.111-0.113min -1 ) with an intraparticle diffusion rate-limiting step. The adsorption process follows a multi-step pathway involving inner- and outer-sphere complexes with significant changes in hydration. Phosphate uptake strongly depends on the composition and type of cross-linker used for preparation of chitosan beads. The adsorption isotherms and structural characterization of bead systems illustrate the role of surface charge, hydrophile-lipophile balance, adsorption site accessibility, and hydration properties of the chitosan bead surface. Copyright © 2016 Elsevier Inc. All rights reserved.

Sorptive Uptake Studies of an Aryl-Arsenical with Iron Oxide Composites on an Activated Carbon Support

PubMed Central

Kwon, Jae H.; Wilson, Lee D.; Sammynaiken, Ramaswami

2014-01-01

Sorption uptake kinetics and equilibrium studies for 4-hydroxy-3-nitrobenzene arsonic acid (roxarsone) was evaluated with synthetic magnetite (Mag-P), commercial magnetite (Mag-C), magnetite 10%, 19%, and 32% composite material (CM-10, -19, -32) that contains granular activated carbon (GAC), and synthetic goethite at pH 7.00 in water at 21 °C for 24 h. GAC showed the highest sorptive removal of roxarsone and the relative uptake for each sorbent material with roxarsone are listed in descending order as follows: GAC (471 mg/g) > goethite (418 mg/g) > CM-10 (377 mg/g) CM-19 (254 mg/g) > CM-32 (227 mg/g) > Mag-P (132 mg/g) > Mag-C (29.5 mg/g). The As (V) moiety of roxarsone is adsorbed onto the surface of the iron oxide/oxyhydrate and is inferred as inner-sphere surface complexes; monodentate-mononuclear, bidentate-mononuclear, and bidentate-binuclear depending on the protolytic speciation of roxarsone. The phenyl ring of roxarsone provides the primary driving force for the sorptive interaction with the graphene surface of GAC and its composites. Thus, magnetite composites are proposed as multi-purpose adsorbents for the co-removal of inorganic and organic arsenicals due to the presence of graphenic and iron oxide active adsorption sites. PMID:28788545

Elastodynamic cloaking and field enhancement for soft spheres

NASA Astrophysics Data System (ADS)

Diatta, Andre; Guenneau, Sebastien

2016-11-01

We propose a spherical cloak described by a non-singular asymmetric elasticity tensor {C} depending upon a small parameter η, that defines the softness of a region one would like to conceal from elastodynamic waves. By varying η, we generate a class of soft spheres dressed by elastodynamic cloaks, which are shown to considerably reduce the scattering of the soft spheres. Importantly, such cloaks also provide some wave protection except for a countable set of frequencies, for which some large elastic field enhancement can be observed within the soft spheres. Through an investigation of trapped modes in elasticity, we supply a good approximation of such Mie-type resonances by some transcendental equation. Our results, unlike previous studies that focused merely on the invisibility aspects, shed light on potential pitfalls of elastodynamic cloaks for earthquake protection designed via geometric transforms: a seismic cloak needs to be designed in such a way that its inner resonances differ from eigenfrequencies of the building one wishes to protect. In order to circumvent this downfall of field enhancement inside the cloaked area, we introduce a novel generation of cloaks, named here, mixed cloaks. Such mixed cloaks consist of a shell that detours incoming waves, hence creating an invisibility region, and of a perfectly matched layer (PML, located at the inner boundary of the cloaks) that absorbs residual wave energy in such a way that aforementioned resonances in the soft sphere are strongly attenuated. The designs of mixed cloaks with a non-singular elasticity tensor combined with an inner PML and non-vanishing density bring seismic cloaks one step closer to a practical implementation. Note in passing that the concept of mixed cloaks also applies in the case of singular cloaks and can be translated in other wave areas for a similar purpose (i.e. to smear down inner resonances within the invisibility region).

Arsenic behavior in river sediments under redox gradient: a review.

PubMed

Gorny, Josselin; Billon, Gabriel; Lesven, Ludovic; Dumoulin, David; Madé, Benoît; Noiriel, Catherine

2015-02-01

The fate of arsenic - a redox sensitive metalloid - in surface sediments is closely linked to early diagenetic processes. The review presents the main redox mechanisms and final products of As that have been evidenced over the last years. Oxidation of organic matter and concomitant reduction of oxidants by bacterial activity result in redox transformations of As species. The evolution of the sediment reactivity will also induce secondary abiotic reactions like complexation/de-complexation, sorption, precipitation/dissolution and biotic reactions that could, for instance, lead to the detoxification of some As species. Overall, abiotic redox reactions that govern the speciation of As mostly involve manganese (hydr)-oxides and reduced sulfur species produced by the sulfate-reducing bacteria. Bacterial activity is also responsible for the inter-conversion between As(V) and As(III), as well as for the production of methylated arsenic species. In surficial sediments, sorption processes also control the fate of inorganic As(V), through the formation of inner sphere complexes with iron (hydr)-oxides, that are biologically reduced in buried sediment. Arsenic species can also be bound to organic matter, either directly to functional groups or indirectly through metal complexes. Finally, even if the role of reduced sulfur species in the cycling of arsenic in sediments has been evidenced, some of the transformations remain hypothetical and deserve further investigation. Copyright © 2014 Elsevier B.V. All rights reserved.

Silicic acid competes for dimethylarsinic acid (DMA) immobilization by the iron hydroxide plaque mineral goethite.

PubMed

Kersten, Michael; Daus, Birgit

2015-03-01

A surface complexation modeling approach was used to extend the knowledge about processes that affect the availability of dimethylarsinic acid (DMA) in the soil rhizosphere in presence of a strong sorbent, e.g., Fe plaques on rice roots. Published spectroscopic and molecular modeling information suggest for the organoarsenical agent to form bidentate-binuclear inner-sphere surface complexes with Fe hydroxides similar to the inorganic As oxyanions. However, since also the ubiquitous silicic acid oxyanion form the same bidentate binuclear surface complexes, our hypothesis was that it may have an effect on the adsorption of DMA by Fe hydroxides in soil. Our experimental batch equilibrium data show that DMA is strongly adsorbed in the acidic pH range, with a steep adsorption edge in the circumneutral pH region between the DMA acidity constant (pKa=6.3) and the point of zero charge value of the goethite adsorbent (pHpzc=8.6). A 1-pK CD-MUSIC surface complexation model was chosen to fit the experimental adsorption vs. pH data. The same was done for silicic acid batch equilibrium data with our goethite adsorbent. Both model parameters for individual DMA and silicic acid adsorption were then merged into one CD-MUSIC model to predict the binary DMA+Si adsorption behavior. Silicic acid (500 μM) was thus predicted by the model to strongly compete for DMA with up to 60% mobilization of the latter at a pH6. This model result could be verified subsequently by experimental batch equilibrium data with zero adjustable parameters. The thus quantified antagonistic relation between DMA and silicic acid is discussed as one of factors to explain the increase of the DMA proportion in rice grains as observed upon silica fertilization of rice fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Goldfish and oscars have comparable responsiveness to dipole stimuli

NASA Astrophysics Data System (ADS)

Nauroth, Ines Eva; Mogdans, Joachim

2009-12-01

The relative roles of the fish lateral line and inner ear for the perception of hydrodynamic stimuli are poorly investigated. Here, we studied responsiveness to a 100 Hz vibrating sphere (dipole stimulus) of goldfish and oscars, two species that differ in peripheral lateral line morphology, inner ear morphology, mechanical linkage between inner ear and swim bladder, and inner ear sensitivity. We measured unconditioned dipole-evoked changes in breathing activity in still water and in the presence of a 5-cm s-1 background flow. In still water, individuals from both species responded to sound pressure levels (SPLs) between 92 and 109 dB SPL re 1 μPaRMS. Responsiveness was not affected by background flow or by temporary inactivation of the lateral line. The data suggest that fish with different lateral line and inner ear morphologies have similar sensitivities to vibrating sphere stimuli and can detect and respond to dipole sources equally well in still water and in moderate background flows. Moreover, behavioral responses were not dependent on a functional lateral line, suggesting that in this type of experiment, the inner ear is the dominant sense organ for the perception of hydrodynamic stimuli.

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

PubMed Central

Sutton, Rebecca; Sposito, Garrison

2002-01-01

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

Hard sphere packings within cylinders.

PubMed

Fu, Lin; Steinhardt, William; Zhao, Hao; Socolar, Joshua E S; Charbonneau, Patrick

2016-03-07

Arrangements of identical hard spheres confined to a cylinder with hard walls have been used to model experimental systems, such as fullerenes in nanotubes and colloidal wire assembly. Finding the densest configurations, called close packings, of hard spheres of diameter σ in a cylinder of diameter D is a purely geometric problem that grows increasingly complex as D/σ increases, and little is thus known about the regime for D > 2.873σ. In this work, we extend the identification of close packings up to D = 4.00σ by adapting Torquato-Jiao's adaptive-shrinking-cell formulation and sequential-linear-programming (SLP) technique. We identify 17 new structures, almost all of them chiral. Beyond D ≈ 2.85σ, most of the structures consist of an outer shell and an inner core that compete for being close packed. In some cases, the shell adopts its own maximum density configuration, and the stacking of core spheres within it is quasiperiodic. In other cases, an interplay between the two components is observed, which may result in simple periodic structures. In yet other cases, the very distinction between the core and shell vanishes, resulting in more exotic packing geometries, including some that are three-dimensional extensions of structures obtained from packing hard disks in a circle.

Spiral Ganglion Stem Cells Can Be Propagated and Differentiated Into Neurons and Glia

PubMed Central

Zecha, Veronika; Wagenblast, Jens; Arnhold, Stefan; Edge, Albert S. B.; Stöver, Timo

2014-01-01

Abstract The spiral ganglion is an essential functional component of the peripheral auditory system. Most types of hearing loss are associated with spiral ganglion cell degeneration which is irreversible due to the inner ear's lack of regenerative capacity. Recent studies revealed the existence of stem cells in the postnatal spiral ganglion, which gives rise to the hope that these cells might be useful for regenerative inner ear therapies. Here, we provide an in-depth analysis of sphere-forming stem cells isolated from the spiral ganglion of postnatal mice. We show that spiral ganglion spheres have characteristics similar to neurospheres isolated from the brain. Importantly, spiral ganglion sphere cells maintain their major stem cell characteristics after repeated propagation, which enables the culture of spheres for an extended period of time. In this work, we also demonstrate that differentiated sphere-derived cell populations not only adopt the immunophenotype of mature spiral ganglion cells but also develop distinct ultrastructural features of neurons and glial cells. Thus, our work provides further evidence that self-renewing spiral ganglion stem cells might serve as a promising source for the regeneration of lost auditory neurons. PMID:24940560

Eu(III) Complexes of Octadentate 1-Hydroxy-2-pyridinones: Stability and Improved Photophysical Performance[].

PubMed

Moore, Evan G; D'Aléo, Anthony; Xu, Jide; Raymond, Kenneth N

2009-10-13

The luminescence properties of lanthanoid ions can be dramatically enhanced by coupling them to antenna ligands that absorb light in the UV/visible and then efficiently transfer the energy to the lanthanoid center. The synthesis and the complexation of Ln(III) cations (Ln=Eu; Gd) for a ligand based on four 1-hydroxy-2-pyridinone (1,2-HOPO) chelators appended to a ligand backbone derived by linking two L-lysine units (3LI-bis-LYS) is described. This octadentate Eu(III) complex ([Eu(3LI-bis-LYS-1,2-HOPO)](-)) has been evaluated in terms of its thermodynamic stability, UV/visible absorption and luminescence properties. For this complex the conditional stability constant (pM) is 19.9, which is an order of magnitude higher than diethylenetriaminepentacetic acid (DTPA) at pH= 7.4. This Eu(III) complex also shows an almost two-fold increase in its luminescence quantum yield in aqueous solution (pH= 7.4) when compared to other octadentate ligands. Hence, despite a slight decrease of the molar absorption coefficient, a much higher brightness is obtained for [Eu(3LI-bis-LYS-1,2-HOPO)](-). This overall improvement was achieved by saturating the coordination sphere of the Eu(III) cation, yielding an increased metal centered efficiency by excluding solvent water molecules from the metal's inner sphere.

Polarized XANES and EXAFS spectroscopic investigation into copper(II) complexes on vermiculite

NASA Astrophysics Data System (ADS)

Furnare, Luca J.; Vailionis, Arturas; Strawn, Daniel G.

2005-11-01

Interaction of heavy metals with clay minerals can dominate solid-solution reactions in soil, controlling the fate of the metals in the environment. In this study we used powdered and polarized extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES) to investigate Cu sorbed on Llano vermiculite and compare the results to reported Cu sorption mechanism on Wyoming (WY) smectite and reduced South African (SA) vermiculite. Analysis of the Cu K-edge spectra revealed that Cu sorbed on Llano vermiculite at high ionic strength ( I) has the greatest degree of covalent bond character, followed by Cu sorbed on montmorillonite at high I, and Cu sorbed on reduced SA vermiculite at high I. Cu sorbed on clay minerals at low I has the least covalent character. EXAFS data from Cu sorbed Ca- and K-equilibrated Llano vermiculites showed the presence of a second-shell Al, Si, or Mg backscatterer at 3.02 Å. This distance is consistent with Cu sorbing via a corner-sharing monodentate or bidentate bond. Polarized XANES and EXAFS results revealed that the angle between the Cu atom and the mineral sorption sites is 68° with respect to the [001] direction. From the bond angle and the persistence of the second-shell backscatterer when the interlayer is collapsed (K-equilibration), we conclude that Cu adsorption on the Llano vermiculite is not occurring in the interlayer but rather Cu is adsorbing onto the edges of the vermiculite. Results from this research provide evidence that Cu forms inner-sphere and outer-sphere complexes on clay minerals, and does not form the vast multinuclear surface precipitates that have been observed for Co, Zn, and Ni.

Hyperfine coupling constants on inner-sphere water molecules of Gd(III)-based MRI contrast agents.

PubMed

Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Helm, Lothar; Platas-Iglesias, Carlos

2012-11-12

Herein we present a theoretical investigation of the hyperfine coupling constants (HFCCs) on the inner-sphere water molecules of [Gd(H(2)O)(8)](3+) and different Gd(III)-based magnetic resonance imaging contrast agents such as [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)]. DFT calculations performed on the [Gd(H(2)O)(8)](3+) model system show that both hybrid-GGA functionals (BH&HLYP, B3PW91 and PBE1PBE) and the hybrid meta-GGA functional TPSSh provide (17)O HFCCs in close agreement with the experimental data. The use of all-electron relativistic approaches based on the DKH2 approximation and the use of relativistic effective core potentials (RECP) provide results of essentially the same quality. The accurate calculation of HFCCs on the [Gd(DOTA)(H(2)O)](-), [Gd(DTPA)(H(2)O)](2-), [Gd(DTPA-BMA)(H(2)O)] and [Gd(HP-DO3A)(H(2)O)] complexes requires an adequate description of solvent effects. This was achieved by using a mixed cluster/continuum approach that includes explicitly two second-sphere water molecules. The calculated isotropic (17)O HFCCs (A(iso)) fall within the range 0.40-0.56 MHz, and show deviations from the corresponding experimental values typically lower than 0.05 MHz. The A(iso) values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the Gd(III) ion, as well as by the orientation of the water molecule plane with respect to the Gd-O vector. (1)H HFCCs of coordinated water molecules and (17)O HFCCs of second-sphere water molecules take values close to zero. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

GROWTH AND DIFFERENTIATION OF MITOCHONDRIA IN THE REGENERATING RAT ADRENAL CORTEX

PubMed Central

Yago, Nagasumi; Seki, Masatoshi; Sekiyama, Shigetaka; Kobayashi, Shigeru; Kurokawa, Hiromi; Iwai, Yuko; Sato, Fumiaki; Shiragai, Akihiro

1972-01-01

Diameters of the circular profiles of spherical mitochondria in parenchymal cells of the zona fasciculata in rat adrenal cortex were measured for intact controls and for the regenerating adrenal cortex on electron micrographs recorded at random. The diameter data were then processed by Bach's method which deals with the sphere size distribution. The structural parameters of the mitochondria were computed with the aid of an electronic computer. The total number of mitochondria in all the parenchymal cells of the zona fasciculata were calculated. The surface area of the inner mitochondrial membrane was then determined stereologically. Biochemical parameters were obtained for the protein, the phospholipid, and the cytochrome P-450 content, per averaged mitochondrion. The number of cytochrome P-450 molecules contained in the inner membrane was determined in terms of the unit surface area and of the unit amount of phospholipid. These correlated biochemical and stereological parameters have led to the following conclusions. (a) The genesis of the mitochondria after the adrenal enucleation is almost completed within 10 days. (b) During the period of mitochondrial proliferation, the mitochondria are small in size and also immature both in the structure and in the function of their inner membrane, (c) These small and immature mitochondria grow through an increase of the phospholipid and protein, and this increase is accompanied by expansion of the area of the membrane surface, (d) An enrichment of the inner membrane with cytochrome P-450 molecules occurs, thus indicating the differentiation of adrenocortical mitochondria. The process of membrane differentiation is not tightly coupled with that of membrane growth. PMID:5009515

Dynamics of an elastic sphere containing a thin creeping region and immersed in an acoustic region for similar viscous-elastic and acoustic time- and length-scales

NASA Astrophysics Data System (ADS)

Gat, Amir; Friedman, Yonathan

2017-11-01

The characteristic time of low-Reynolds number fluid-structure interaction scales linearly with the ratio of fluid viscosity to solid Young's modulus. For sufficiently large values of Young's modulus, both time- and length-scales of the viscous-elastic dynamics may be similar to acoustic time- and length-scales. However, the requirement of dominant viscous effects limits the validity of such regimes to micro-configurations. We here study the dynamics of an acoustic plane wave impinging on the surface of a layered sphere, immersed within an inviscid fluid, and composed of an inner elastic sphere, a creeping fluid layer and an external elastic shell. We focus on configurations with similar viscous-elastic and acoustic time- and length-scales, where the viscous-elastic speed of interaction between the creeping layer and the elastic regions is similar to the speed of sound. By expanding the linearized spherical Reynolds equation into the relevant spectral series solution for the hyperbolic elastic regions, a global stiffness matrix of the layered elastic sphere was obtained. This work relates viscous-elastic dynamics to acoustic scattering and may pave the way to the design of novel meta-materials with unique acoustic properties. ISF 818/13.

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.

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.

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

PubMed Central

Bai, Da-Chang; Yu, Fei-Le; Wang, Wan-Ying; Chen, Di; Li, Hao; Liu, Qing-Rong; Ding, Chang-Hua; Chen, Bo; Hou, Xue-Long

2016-01-01

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of β-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism—nucleophilic attack of enolate oxygen on Palladium followed by C–C bond-forming [3,3']-reductive elimination. PMID:27283477

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

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

Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a ( syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanisticmore » studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

DOE PAGES

Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying; ...

2016-06-10

The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a ( syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanisticmore » studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

On the probability distribution function of the mass surface density of molecular clouds. II.

NASA Astrophysics Data System (ADS)

Fischera, Jörg

2014-11-01

The probability distribution function (PDF) of the mass surface density of molecular clouds provides essential information about the structure of molecular cloud gas and condensed structures out of which stars may form. In general, the PDF shows two basic components: a broad distribution around the maximum with resemblance to a log-normal function, and a tail at high mass surface densities attributed to turbulence and self-gravity. In a previous paper, the PDF of condensed structures has been analyzed and an analytical formula presented based on a truncated radial density profile, ρ(r) = ρc/ (1 + (r/r0)2)n/ 2 with central density ρc and inner radius r0, widely used in astrophysics as a generalization of physical density profiles. In this paper, the results are applied to analyze the PDF of self-gravitating, isothermal, pressurized, spherical (Bonnor-Ebert spheres) and cylindrical condensed structures with emphasis on the dependence of the PDF on the external pressure pext and on the overpressure q-1 = pc/pext, where pc is the central pressure. Apart from individual clouds, we also consider ensembles of spheres or cylinders, where effects caused by a variation of pressure ratio, a distribution of condensed cores within a turbulent gas, and (in case of cylinders) a distribution of inclination angles on the mean PDF are analyzed. The probability distribution of pressure ratios q-1 is assumed to be given by P(q-1) ∝ q-k1/ (1 + (q0/q)γ)(k1 + k2) /γ, where k1, γ, k2, and q0 are fixed parameters. The PDF of individual spheres with overpressures below ~100 is well represented by the PDF of a sphere with an analytical density profile with n = 3. At higher pressure ratios, the PDF at mass surface densities Σ ≪ Σ(0), where Σ(0) is the central mass surface density, asymptotically approaches the PDF of a sphere with n = 2. Consequently, the power-law asymptote at mass surface densities above the peak steepens from Psph(Σ) ∝ Σ-2 to Psph(Σ) ∝ Σ-3. The corresponding asymptote of the PDF of cylinders for the large q-1 is approximately given by Pcyl(Σ) ∝ Σ-4/3(1 - (Σ/Σ(0))2/3)-1/2. The distribution of overpressures q-1 produces a power-law asymptote at high mass surface densities given by ∝ Σ-2k2 - 1 (spheres) or ∝ Σ-2k2 (cylinders). Appendices are available in electronic form at http://www.aanda.org

Boron removal from hydraulic fracturing wastewater by aluminum and iron coagulation: Mechanisms and limitations.

PubMed

Chorghe, Darpan; Sari, Mutiara Ayu; Chellam, Shankararaman

2017-12-01

One promising water management strategy during hydraulic fracturing is treatment and reuse of flowback/produced water. In particular, the saline flowback water contains many of the chemicals employed for fracking, which need to be removed before possible reuse as "frac water." This manuscript targets turbidity along with one of the additives; borate-based cross-linkers used to adjust the rheological characteristics of the frac-fluid. Alum and ferric chloride were evaluated as coagulants for clarification and boron removal from saline flowback water obtained from a well in the Eagle Ford shale. Extremely high dosages (> 9000 mg/L or 333 mM Al and 160 mM Fe) corresponding to Al/B and Fe/B mass ratios of ∼70 and molar ratios of ∼28 and 13 respectively were necessary to remove ∼80% boron. Hence, coagulation does not appear to be feasible for boron removal from high-strength waste streams. X-ray photoelectron spectroscopy revealed BO bonding on surfaces of freshly precipitated Al(OH) 3 (am) and Fe(OH) 3 (am) suggesting boron uptake was predominantly via ligand exchange. Attenuated total reflection-Fourier transform infrared spectroscopy provided direct evidence of inner-sphere boron complexation with surface hydroxyl groups on both amorphous aluminum and iron hydroxides. Only trigonal boron was detected on aluminum flocs since possible presence of tetrahedral boron was masked by severe AlO interferences. Both trigonal and tetrahedral conformation of boron complexes were identified on Fe(OH) 3 surfaces. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids

NASA Astrophysics Data System (ADS)

Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

2015-05-01

The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2]3+ (1), cis-[Co(dp)2(C12H25NH2)2]3+ (2), cis-[Co(trien)(C12H25NH2)2]3+ (3), cis-[Co(bpy)2(C12H25NH2)2]3+ (4) and cis-[Co(phen)2(C12H25NH2)2]3+ (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2‧-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe2+ ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323 K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH‡ and entropy of activation ΔS‡) of the reaction have been calculated which substantiate the kinetics of the reaction.

Continuous leaching modifies the surface properties and metal(loid) sorption of sludge-derived biochar.

PubMed

Feng, Mingyu; Zhang, Weihua; Wu, Xueyong; Jia, Yanming; Jiang, Chixiao; Wei, Hang; Qiu, Rongliang; Tsang, Daniel C W

2018-06-01

After the application of sludge derived biochar (SDBC) for soil stabilization, it is subjected to continuous leaching that may change its surface properties and metal(loid) immobilization performance. This study simulated the continuous leaching through the fresh SDBC sample in columns with unsaturated and saturated zones under flushing with 0.01M NaNO 3 solution (pH5.5) and acidic solution (pH adjusted to 3.2 by HNO 3 :H 2 SO 4 =1:2), respectively. The resultant changes were assessed in terms of the SDBC surface characteristics and metal(loid) sorption capacities. Continuous leaching was found to gradually decrease the density of basic functional groups and increase the density of carboxyl groups as well as cation exchange capacity on the SDBC surface. It was attributed to the surface acidification and oxidation process by the leaching process, yet it occurred to a lesser extent than the atmospheric exposure. Continuous leaching increased Pb(II), Cr(VI), and As(III) sorption capacity of the SDBC, probably because the increase in carboxyl groups promoted inner-sphere complexation and Fe oxidation as revealed by spectroscopic analysis. It was noteworthy that the SDBC in the unsaturated and saturated zones under continuous leaching displayed distinctive effects on metal(loid) sorption capacity than the atmospheric exposure. Future investigations are needed for understanding the fate and interactions of the SDBC under varying redox conditions and intermittent leaching process. Copyright © 2017. Published by Elsevier B.V.

Dust modeling of the combined ALMA and SPHERE datasets of HD 163296. Is HD 163296 really a Meeus group II disk?

NASA Astrophysics Data System (ADS)

Muro-Arena, G. A.; Dominik, C.; Waters, L. B. F. M.; Min, M.; Klarmann, L.; Ginski, C.; Isella, A.; Benisty, M.; Pohl, A.; Garufi, A.; Hagelberg, J.; Langlois, M.; Menard, F.; Pinte, C.; Sezestre, E.; van der Plas, G.; Villenave, M.; Delboulbé, A.; Magnard, Y.; Möller-Nilsson, O.; Pragt, J.; Rabou, P.; Roelfsema, R.

2018-06-01

Context. Multiwavelength observations are indispensable in studying disk geometry and dust evolution processes in protoplanetary disks. Aims: We aim to construct a three-dimensional model of HD 163296 that is capable of reproducing simultaneously new observations of the disk surface in scattered light with the SPHERE instrument and thermal emission continuum observations of the disk midplane with ALMA. We want to determine why the spectral energy distribution of HD 163296 is intermediary between the otherwise well-separated group I and group II Herbig stars. Methods: The disk was modeled using the Monte Carlo radiative transfer code MCMax3D. The radial dust surface density profile was modeled after the ALMA observations, while the polarized scattered light observations were used to constrain the inclination of the inner disk component and turbulence and grain growth in the outer disk. Results: While three rings are observed in the disk midplane in millimeter thermal emission at 80, 124, and 200 AU, only the innermost of these is observed in polarized scattered light, indicating a lack of small dust grains on the surface of the outer disk. We provide two models that are capable of explaining this difference. The first model uses increased settling in the outer disk as a mechanism to bring the small dust grains on the surface of the disk closer to the midplane and into the shadow cast by the first ring. The second model uses depletion of the smallest dust grains in the outer disk as a mechanism for decreasing the optical depth at optical and near-infrared wavelengths. In the region outside the fragmentation-dominated regime, such depletion is expected from state-of-the-art dust evolution models. We studied the effect of creating an artificial inner cavity in our models, and conclude that HD 163296 might be a precursor to typical group I sources.

An ultrasensitive hollow-silica-based biosensor for pathogenic Escherichia coli DNA detection.

PubMed

Ariffin, Eda Yuhana; Lee, Yook Heng; Futra, Dedi; Tan, Ling Ling; Karim, Nurul Huda Abd; Ibrahim, Nik Nuraznida Nik; Ahmad, Asmat

2018-03-01

A novel electrochemical DNA biosensor for ultrasensitive and selective quantitation of Escherichia coli DNA based on aminated hollow silica spheres (HSiSs) has been successfully developed. The HSiSs were synthesized with facile sonication and heating techniques. The HSiSs have an inner and an outer surface for DNA immobilization sites after they have been functionalized with 3-aminopropyltriethoxysilane. From field emission scanning electron microscopy images, the presence of pores was confirmed in the functionalized HSiSs. Furthermore, Brunauer-Emmett-Teller (BET) analysis indicated that the HSiSs have four times more surface area than silica spheres that have no pores. These aminated HSiSs were deposited onto a screen-printed carbon paste electrode containing a layer of gold nanoparticles (AuNPs) to form a AuNP/HSiS hybrid sensor membrane matrix. Aminated DNA probes were grafted onto the AuNP/HSiS-modified screen-printed electrode via imine covalent bonds with use of glutaraldehyde cross-linker. The DNA hybridization reaction was studied by differential pulse voltammetry using an anthraquinone redox intercalator as the electroactive DNA hybridization label. The DNA biosensor demonstrated a linear response over a wide target sequence concentration range of 1.0×10 -12 -1.0×10 -2 μM, with a low detection limit of 8.17×10 -14 μM (R 2 = 0.99). The improved performance of the DNA biosensor appeared to be due to the hollow structure and rough surface morphology of the hollow silica particles, which greatly increased the total binding surface area for high DNA loading capacity. The HSiSs also facilitated molecule diffusion through the silica hollow structure, and substantially improved the overall DNA hybridization assay. Graphical abstract Step-by-step DNA biosensor fabrication based on aminated hollow silica spheres.

A SYMMETRIC INNER CAVITY IN THE HD 141569A CIRCUMSTELLAR DISK

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

Mazoyer, J.; Choquet, É.; Perrin, M. D.

2016-02-20

Some circumstellar disks, called transitional or hybrid disks, present characteristics of both protoplanetary disks (significant amount of gas) and debris disks (evolved structures around young main-sequence stars, composed of second generation dust, from collisions between planetesimals). Therefore, they are ideal astrophysical laboratories to witness the last stages of planet formation. The circumstellar disk around HD 141569A was intensively observed and resolved in the past from space, but also from the ground. However, the recent implementation of high contrast imaging systems has opened up new opportunities to re-analyze this object. We analyzed Gemini archival data from the Near-infrared Coronagraphic Imager obtained inmore » 2011 in the H band, using several angular differential imaging techniques (classical ADI, LOCI, KLIP). These images reveal the complex structures of this disk with an unprecedented resolution. We also include archival Hubble Space Telescope images as an independent data set to confirm these findings. Using an analysis of the inner edge of the disk, we show that the inner disk is almost axisymmetrical. The measurement of an offset toward the east observed by previous authors is likely due to the fact that the eastern part of this disk is wider and more complex in substructure. Our precise reanalysis of the eastern side shows several structures, including a splitting of the disk and a small finger detached from the inner edge to the southeast. Finally, we find that the arc at 250 AU is unlikely to be a spiral, at least not at the inclination derived from the first ring, but instead could be interpreted as a third belt at a different inclination. If the very symmetrical inner disk edge is carved by a companion, the data presented here put additional constraints on its position. The observed very complex structures will be confirmed by the new generation of coronagraphic instrument (GPI, SPHERE). However, a full understanding of this system will require gas observations at millimetric wavelengths.« less

Microcalorimetric and potentiometric titration studies on the adsorption of copper by extracellular polymeric substances (EPS), minerals and their composites.

PubMed

Fang, Linchuan; Huang, Qiaoyun; Wei, Xing; Liang, Wei; Rong, Xinming; Chen, Wenli; Cai, Peng

2010-08-01

Equilibrium adsorption experiments, isothermal titration calorimetry and potentiometric titration techniques were employed to investigate the adsorption of Cu(II) by extracellular polymeric substances (EPS) extracted from Pseudomonas putida X4, minerals (montmorillonite and goethite) and their composites. Compared with predicted values of Cu(II) adsorption on composites, the measured values of Cu(II) on EPS-montmorillonite composite increased, however, those on EPS-goethite composite decreased. Potentiometric titration results also showed that more surface sites were observed on EPS-montmorillonite composite and less reactive sites were found on EPS-goethite composite. The adsorption of Cu(II) on EPS molecules and their composites with minerals was an endothermic reaction, while that on minerals was exothermic. The positive values of enthalpy change (Delta H) and entropy change (DeltaS) for Cu(II) adsorption on EPS and mineral-EPS composites indicated that Cu(II) mainly interacts with carboxyl and phosphoryl groups as inner-sphere complexes on EPS molecules and their composites with minerals. (c) 2010 Elsevier Ltd. All rights reserved.

Design of a Fission 99 Mo Recovery Process and Implications toward Mo Adsorption Mechanism on Titania and Alumina Sorbents

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

Stepinski, Dominique C.; Youker, Amanda J.; Krahn, Elizabeth O.

2017-03-01

Molybdenum-99 is a parent of the most widely used medical isotope technetium-99m. Proliferation concerns have prompted development of alternative Mo production methods utilizing low enriched uranium. Alumina and titania sorbents were evaluated for separation of Mo from concentrated uranyl nitrate solutions. System, mass transfer, and isotherm parameters were determined to enable design of Mo separation processes under a wide range of conditions. A model-based approach was utilized to design representative commercial-scale column processes. The designs and parameters were verified with bench-scale experiments. The results are essential for design of Mo separation processes from irradiated uranium solutions, selection of support materialmore » and process optimization. Mo uptake studies show that adsorption decreases with increasing concentration of uranyl nitrate; howeveL, examination of Mo adsorption as a function of nitrate ion concentration shows no dependency, indicating that uranium competes with Mo for adsorption sites. These results are consistent with reports indicating that Mo forms inner-sphere complexes with titania and alumina surface groups.« less

Highly Efficient Lead Distribution by Magnetic Sewage Sludge Biochar: Sorption Mechanisms and Bench Applications.

PubMed

Ifthikar, Jerosha; Wang, Jia; Wang, Qiliang; Wang, Ting; Wang, Huabin; Khan, Aimal; Jawad, Ali; Sun, Tingting; Jiao, Xiang; Chen, Zhuqi

2017-08-01

Highly efficient magnetic sewage sludge biochar (MSSBC) discloses feasible fabrication process with lower production cost, superior adsorption capacity, usage of waste sewage sludge as resource, selected by external magnetic field and exceptional regeneration property. 2gL -1 MSSBC exhibited a high adsorption capacity of 249.00mgg -1 in 200ppmPb(II) and the lead-MSSBC equilibrium was achieved within one hour, owing to the existence of the copious active sites. The adsorption kinetics was well described by the pseudo-second-order model while the adsorption isotherm could be fitted by Langmuir model. Mechanism study demonstrated the adsorption involved electrostatic attraction, ion exchange, inner-sphere complexation and formation of co-precipitates at the surface of MSSBC. Additionally, adsorption performance maintained remarkable in a broad pH window. These outcomes demonstrated the promising waste resource utilization by a feasible approach that turns the solid waste of sewage sludge into biochar adsorbent with auspicious applications in elimination of Pb(II) from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

PubMed

Othmane, Guillaume; Allard, Thierry; Morin, Guillaume; Sélo, Madeleine; Brest, Jessica; Llorens, Isabelle; Chen, Ning; Bargar, John R; Fayek, Mostafa; Calas, Georges

2013-11-19

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites. XANES and EXAFS data and transmission electron microscopy analyses of the samples with the highest uranium concentrations (∼400-700 mg kg(-1) of U) demonstrate that uranium primarily occurs as monomeric uranyl ions (UO2(2+)), forming inner-sphere surface complexes bound to ferrihydrite (50-70% of the total U) and to a lesser extent to chlorite (30-40% of the total U). Thus, the stability and mobility of uranium at the Gunnar site are mainly influenced by sorption/desorption processes. In this context, acidic pH or alkaline pH with the presence of UO2(2+)- and/or Fe(3+)-complexing agents (e.g., carbonate) could potentially solubilize U in the tailings pore waters.

Phosphinic derivative of DTPA conjugated to a G5 PAMAM dendrimer: an 17O and 1H relaxation study of its Gd(III) complex.

PubMed

Lebdusková, Petra; Sour, Angélique; Helm, Lothar; Tóth, Eva; Kotek, Jan; Lukes, Ivan; Merbach, André E

2006-07-28

A DTPA-based chelate containing one phosphinate group was conjugated to a generation 5 polyamidoamine (PAMAM) dendrimer via a benzylthiourea linkage. The Gd(III) complex of this novel conjugate has potential as a contrast agent for magnetic resonance imaging (MRI). The chelates bind Gd3+via three nitrogen atoms, four carboxylates and one phosphinate oxygen, and one water molecule completes the inner coordination sphere. The monomer Gd(III) chelates bearing nitrobenzyl and aminobenzyl groups ([Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-) as well as the dendrimeric Gd(III) complex G5-(Gd(DTTAP))63) were studied by multiple-field, variable temperature 17O and 1H NMR. The rate of water exchange is faster than that of [Gd(DTPA)(H2O)]2- and very similar on the two monomeric complexes (8.9 and 8.3 x 10(6) s-1 for [Gd(DTTAP-bz-NO2)(H2O)]2- and [Gd(DTTAP-bz-NH2)(H2O)]2-, respectively), while it is decreased on the dendrimeric conjugate (5.0 x 10(6) s-1). The Gd(III) complex of the dendrimer conjugate has a relaxivity of 26.8 mM-1 s-1 at 37 degrees C and 0.47 T (corresponding to 1H Larmor frequency of 20 MHz). Given the contribution of the second sphere water molecules to the overall relaxivity, this value is slightly higher than those reported for similar size dendrimers. The experimental 17O and 1H NMR data were fitted to the Solomon-Bloembergen-Morgan equations extended with a contribution from second coordination sphere water molecules. The rotational dynamics of the dendrimeric conjugate was described in terms of global and local motions with the Lipari-Szabo approach.

Shadows cast on the transition disk of HD 135344B. Multiwavelength VLT/SPHERE polarimetric differential imaging

NASA Astrophysics Data System (ADS)

Stolker, T.; Dominik, C.; Avenhaus, H.; Min, M.; de Boer, J.; Ginski, C.; Schmid, H. M.; Juhasz, A.; Bazzon, A.; Waters, L. B. F. M.; Garufi, A.; Augereau, J.-C.; Benisty, M.; Boccaletti, A.; Henning, Th.; Langlois, M.; Maire, A.-L.; Ménard, F.; Meyer, M. R.; Pinte, C.; Quanz, S. P.; Thalmann, C.; Beuzit, J.-L.; Carbillet, M.; Costille, A.; Dohlen, K.; Feldt, M.; Gisler, D.; Mouillet, D.; Pavlov, A.; Perret, D.; Petit, C.; Pragt, J.; Rochat, S.; Roelfsema, R.; Salasnich, B.; Soenke, C.; Wildi, F.

2016-11-01

Context. The protoplanetary disk around the F-type star HD 135344B (SAO 206462) is in a transition stage and shows many intriguing structures both in scattered light and thermal (sub-)millimeter emission which are possibly related to planet formation processes. Aims: We aim to study the morphology and surface brightness of the disk in scattered light to gain insight into the innermost disk regions, the formation of protoplanets, planet-disk interactions traced in the surface and midplane layers, and the dust grain properties of the disk surface. Methods: We have carried out high-contrast polarimetric differential imaging (PDI) observations with VLT/SPHERE and obtained polarized scattered light images with ZIMPOL in the R and I-bands and with IRDIS in the Y and J-bands. The scattered light images and surface brightness profiles are used to study in detail structures in the disk surface and brightness variations. We have constructed a 3D radiative transfer model to support the interpretation of several detected shadow features. Results: The scattered light images reveal with unprecedented angular resolution and sensitivity the spiral arms as well as the 25 au cavity of the disk. Multiple shadow features are discovered on the outer disk with one shadow only being present during the second observation epoch. A positive surface brightness gradient is observed in the stellar irradiation corrected (r2-scaled) images in southwest direction possibly due to an azimuthally asymmetric perturbation of the temperature and/or surface density by the passing spiral arms. The disk integrated polarized flux, normalized to the stellar flux, shows a positive trend towards longer wavelengths which we attribute to large (2πa ≳ λ) aggregate dust grains in the disk surface. Part of the non-azimuthal polarization signal in the Uφ image of the J-band observation can be attributed to multiple scattering in the disk. Conclusions: The detected shadow features and their possible variability have the potential to provide insight into the structure of and processes occurring in the innermost disk regions. Possible explanations for the presence of the shadows include a 22° misaligned inner disk, a warped disk region that connects the inner disk with the outer disk, and variable or transient phenomena such as a perturbation of the inner disk or an asymmetric accretion flow. The spiral arms are best explained by one or multiple protoplanets in the exterior of the disk although no gap is detected beyond the spiral arms up to 1.''0. Based on observations collected at the European Southern Observatory, Chile, ESO No. 095.C-0273(A) and 095.C-0273(D).

Surface and interior views on origins of two types of banded spherulites in poly(nonamethylene terephthalate).

PubMed

Woo, Eamor M; Nurkhamidah, Siti; Chen, Yu-Fan

2011-10-21

Top-surface and three-dimensional views of Type-1 and Type-2 of ring-banded spherulites in poly(nonamethylene terephthalate) (PNT) in thicker bulk crystallized on a nucleating potassium bromide (KBr) substrate were examined using various microscopy techniques: scanning electron microscopy (SEM), polarized-optical microscopy (POM), and atomic-force microscopy (AFM). In PNT crystallized at higher crystallization temperature (T(c)) with heterogeneous nucleating substrate, typically two types of ring-banded spherulites are present that differ significantly in patterns and ring spacings: Type-1 Type-2 (single- and double-ring-banded spherulites). Three-dimensional view on fractured spherulites in bulk PNT samples reveals that the single-ring-banded spherulite (Type-1) tends to be well-rounded spheres as they are nucleated homogeneously from bulk; the double-ring-banded spherulite (Type-2) is concentric hemisphere or truncated sphere shells owing to be nucleated from bottom. With confined thickness of films, the 3-D hemispheres in PNT may become truncated into multi-shell annular cones or arcs when thickness or growth is restricted. Based on the top-surface vs. interior views of banded lamellar assembly, origins and inner structures of dual types of ring bands in PNT were examined in greater details. This journal is © the Owner Societies 2011

Immobilization of tetracyclines in manure and manure-amended soils using aluminum-based drinking water treatment residuals.

PubMed

Punamiya, Pravin; Sarkar, Dibyendu; Rakshit, Sudipta; Elzinga, Evert J; Datta, Rupali

2016-02-01

Veterinary antibiotics (VAs) are emerging contaminants of concern in the environment, mainly due to the potential for development of antibiotic-resistant bacteria and effect on microbiota that could interfere with crucial ecosystem functions such as nutrient cycling and decomposition. High levels of VAs such as tetracyclines (TCs) have been reported in agricultural soils amended with manure, which also has the potential to cause surface and groundwater contamination. Several recent studies have focused on developing methods to immobilize VAs such as composting with straw, hardwood chips, commercial biochar, aeration, mixing, heat treatment, etc. The major shortcomings of these methods include high cost and limited effectiveness. In the current study, we assessed the effectiveness of aluminum-based drinking water treatment residuals (Al-WTR) as a "green" sorbent to immobilize TCs in manure and manure-applied soils with varying physicochemical properties by laboratory incubation study. Results show that Al-WTR is very effective in immobilizing tetracycline (TTC) and oxytetracycline (OTC). The presence of phosphate resulted in significant (p < 0.01) decrease in TTC/OTC sorption by Al-WTR, but the presence of sulfate did not. attenuated total reflection (ATR)-FTIR spectroscopy indicate that TTC and OTC likely forming surface complexes via inner-sphere-type bonds in soils, manure, and manure-applied soils amended with Al-WTR.

Efficient oxidation and sorption of arsenite using a novel titanium(IV)-manganese(IV) binary oxide sorbent.

PubMed

Zhang, Wei; Liu, Caihong; Zheng, Tong; Ma, Jun; Zhang, Gaosheng; Ren, Guohui; Wang, Lu; Liu, Yulei

2018-04-19

Owing to the high toxicity and mobility, the removal of arsenite (As(III)) is significantly more difficult than arsenate (As(V)), thus representing a major challenge in arsenite-contaminated water treatment. For efficient elimination of As(III), we successfully fabricated a novel Ti-Mn binary oxide via a simultaneous oxidation and coprecipitation process. The amorphous oxide was aggregated from nanosized particles with a high specific surface area of 349.5 m 2 /g. It could effectively oxidize As(III) to As(V) and had a high As(III) sorption capacity of 107.0 mg/g. As(III) sorption occurred rapidly and equilibrium was achieved within 24 h. The kinetic data was well fitted by the pseudo-second-order equation, indicating a chemical sorption process. The material was almost independent upon the presence of competitive ions. The As(III) removal by the sorbent is a combined process coupled oxidation with sorption, where the MnO 2 content is mainly responsible for oxidizing As(III) to As(V) and the formed As(V) is then adsorbed onto the surface of amorphous TiO 2 content, through replacing the surface hydroxyl group or the adsorbed As(III) and forming inner-sphere surface complexes. Furthermore, the arsenic-containing oxide could be effectively regenerated and reused. The bi-functional sorbent could be used as a potentially attractive sorbent for As(III) removal in drinking water treatment and environmental remediation. Copyright © 2018. Published by Elsevier B.V.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

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

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

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

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

PubMed Central

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; Sturchio, Neil C.

2017-01-01

Ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here we report temporal variation in the distribution of Rb+ species at the muscovite (001)–water interface during exchange with Na+. Time-resolved resonant anomalous X-ray reflectivity measurements at 25 °C reveal that Rb+ desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb+ slowly transforms to a less stable outer-sphere Rb+. In contrast, Rb+ adsorption is about twice as fast, proceeding from Rb+ in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55 °C shows that the pre-exponential factor for desorption is significantly smaller than that for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface. PMID:28598428

The assessment of accuracy of inner shapes manufactured by FDM

NASA Astrophysics Data System (ADS)

Gapiński, Bartosz; Wieczorowski, Michał; Båk, Agata; Domínguez, Alejandro Pereira; Mathia, Thomas

2018-05-01

3D printing created a totally new manufacturing possibilities. It is possible e.g. to produce closed inner shapes with different geometrical features. Unfortunately traditional methods are not suitable to verify the manufacturing accuracy, because it would be necessary to cut workpieces. In the paper the possibilities of computed tomography (x-ray micro-CT) application for accuracy assessment of inner shapes are presented. This was already reported in some papers. For research works hollow cylindrical samples with 20mm diameter and 300mm length were manufactured by means of FDM. A sphere, cone and cube were put inside these elements. All measurements were made with the application of CT. The measurement results enable us to obtain a full geometrical image of both inner and outer surfaces of a cylinder as well as shapes of inner elements. Additionally, it is possible to inspect the structure of a printed element - size and location of supporting net and all the other supporting elements necessary to hold up the walls created over empty spaces. The results obtained with this method were compared with CAD models which were a source of data for 3D printing. This in turn made it possible to assess the manufacturing accuracy of particular figures inserted into the cylinders. The influence of location of the inner supporting walls on a shape deformation was also investigated. The results obtained with this way show us how important CT can be during the assessment of 3D printing of objects.

Cs-137 immobilization in C-S-H gel nanopores.

PubMed

Duque-Redondo, Eduardo; Kazuo, Yamada; López-Arbeloa, Iñigo; Manzano, Hegoi

2018-04-04

Cementation is a widespread technique to immobilize nuclear waste due to the low leachability of cementitious materials. The capacity of calcium silicate hydrate (C-S-H), the main component of cement, to retain radionuclide Cs has been empirically studied at the macroscale, yet the specific molecular scale mechanisms that govern the retention have not been determined. In this work, we employed molecular dynamics simulations to investigate the adsorption and diffusivity of Cs into a C-S-H gel nanopore. From the simulations, it was possible to distinguish three types of Cs adsorption configurations on the C-S-H: an inner-sphere surface site where Cs is strongly bound, an outer-sphere surface site where Cs is loosely bound, and Cs free in the nanopore. For each configuration, we determined the sorption energy, and the diffusion coefficients, up to two orders of magnitude lower than in bulk water due to the effect of nanoconfinement in the worst case scenario. It has also proved that Cs cannot displace the intrinsic Ca from the C-S-H surface, and we calculated the binding strength and the residence time of the cations in the surface adsorption sites. Finally, we quantified the average number of adsorption sites per nm2 of the C-S-H surface. All these results are the first insights into Cs retention in cement at the molecular scale and will be useful to build macroscopic diffusion models and devise cement formulations to improve radionuclide Cs retention from spent nuclear fuel.

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.

Tailoring sphere density for high pressure physical property measurements on liquids

NASA Astrophysics Data System (ADS)

Secco, R. A.; Tucker, R. F.; Balog, S. P.; Rutter, M. D.

2001-04-01

We present a new method of tailoring the density of a sphere for use as a probe in high pressure-temperature physical property experiments on liquids. The method consists of a composite sphere made of an inner, high density, metallic, spherical core and an exterior, low density, refractory, spherical shell or mantle. Micromechanical techniques are used to fabricate the composite sphere. We describe a relatively simple mechanical device that can grind hemispherical recesses as small as 200 μm in diameter in sapphire and as small as 500 μm in diameter in ruby hemispheres. Examples of composite spheres made with a Pt or WC core and Al2O3 shell used in metallic liquids pressurized to 16 GPa and 1900 K are shown.

Inhibition and oxygen activation in copper amine oxidases.

PubMed

Shepard, Eric M; Dooley, David M

2015-05-19

Copper-containing amine oxidases (CuAOs) use both copper and 2,4,5-trihydroxyphenylalanine quinone (TPQ) to catalyze the oxidative deamination of primary amines. The CuAO active site is highly conserved and comprised of TPQ and a mononuclear type II copper center that exhibits five-coordinate, distorted square pyramidal coordination geometry with histidine ligands and equatorially and axially bound water in the oxidized, resting state. The active site is buried within the protein, and CuAOs from various sources display remarkable diversity with respect to the composition of the active site channel and cofactor accessibility. Structural and mechanistic factors that influence substrate preference and inhibitor sensitivity and selectivity have been defined. This Account summarizes the strategies used to design selective CuAO inhibitors based on active site channel characteristics, leading to either enhanced steric fits or the trapping of reactive electrophilic products. These findings provide a framework to support the future development of candidate molecules aimed at minimizing the negative side effects associated with drugs containing amine functionalities. This is vital given the existence of human diamine oxidase and vascular adhesion protein-1, which have distinct amine substrate preferences and are associated with different metabolic processes. Inhibition of these enzymes by antifungal or antiprotozoal agents, as well as classic monoamine oxidase (MAO) inhibitors, may contribute to the adverse side effects associated with drug treatment. These observations provide a rationale for the limited clinical value associated with certain amine-containing pharmaceuticals and emphasize the need for more selective AO inhibitors. This Account also discusses the novel roles of copper and TPQ in the chemistry of O2 activation and substrate oxidation. Reduced CuAOs exist in a redox equilibrium between the Cu(II)-TPQAMQ (aminoquinol) and Cu(I)-TPQSQ (semiquinone). Elucidating the roles of Cu(I), TPQSQ, and TPQAMQ in O2 activation, for example, distinguishing inner-sphere versus outer-sphere electron transfer mechanisms, has been actively investigated since the discovery of TPQSQ in 1991 and has only recently been clarified. Kinetics and spectroscopic studies encompassing metal substitution, stopped-flow and temperature-jump relaxation methods, and oxygen kinetic isotope experiments have provided strong support for an inner-sphere electron transfer step from Cu(I) to O2. Data for two enzymes support a mechanism wherein O2 prebinds to a three-coordinate Cu(I) site, yielding a [Cu(II)(η(1)-O2(-1))](+) intermediate, with H2O2 generated from ensuing rate-determining proton coupled electron transfer from TPQSQ. While kinetics data from the cobalt-substituted yeast enzyme indicated that O2 is reduced through an outer-sphere process involving TPQAMQ, new findings with a bacterial CuAO demonstrate that both the Cu(II) and Co(II) forms of the enzyme operate via parallel mechanisms involving metal-superoxide intermediates. Structural observations of a coordinated TPQSQ-Cu(I) complex in two CuAOs supports previous indications that Cu(II)/(I) ligand substitution chemistry may be mechanistically relevant. Substantial evidence indicates that rapid and reversible inner-sphere reduction of O2 at a three-coordinate Cu(I) site occurs, but the existence of a coordinated semiquinone in some AOs suggests that, in these enzymes, an outer-sphere reaction between O2 and TPQSQ may also be possible, since this is expected to be energetically favorable compared with outer-sphere electron transfer from TPQAMQ to O2.

Collection, processing and error analysis of Terrestrial Laser Scanning data from fluvial gravel surfaces

NASA Astrophysics Data System (ADS)

Hodge, R.; Brasington, J.; Richards, K.

2009-04-01

The ability to collect 3D elevation data at mm-resolution from in-situ natural surfaces, such as fluvial and coastal sediments, rock surfaces, soils and dunes, is beneficial for a range of geomorphological and geological research. From these data the properties of the surface can be measured, and Digital Terrain Models (DTM) can be constructed. Terrestrial Laser Scanning (TLS) can collect quickly such 3D data with mm-precision and mm-spacing. This paper presents a methodology for the collection and processing of such TLS data, and considers how the errors in this TLS data can be quantified. TLS has been used to collect elevation data from fluvial gravel surfaces. Data were collected from areas of approximately 1 m2, with median grain sizes ranging from 18 to 63 mm. Errors are inherent in such data as a result of the precision of the TLS, and the interaction of factors including laser footprint, surface topography, surface reflectivity and scanning geometry. The methodology for the collection and processing of TLS data from complex surfaces like these fluvial sediments aims to minimise the occurrence of, and remove, such errors. The methodology incorporates taking scans from multiple scanner locations, averaging repeat scans, and applying a series of filters to remove erroneous points. Analysis of 2.5D DTMs interpolated from the processed data has identified geomorphic properties of the gravel surfaces, including the distribution of surface elevations, preferential grain orientation and grain imbrication. However, validation of the data and interpolated DTMs is limited by the availability of techniques capable of collecting independent elevation data of comparable quality. Instead, two alternative approaches to data validation are presented. The first consists of careful internal validation to optimise filter parameter values during data processing combined with a series of laboratory experiments. In the experiments, TLS data were collected from a sphere and planes with different reflectivities to measure the accuracy and precision of TLS data of these geometrically simple objects. Whilst this first approach allows the maximum precision of TLS data from complex surfaces to be estimated, it cannot quantify the distribution of errors within the TLS data and across the interpolated DTMs. The second approach enables this by simulating the collection of TLS data from complex surfaces of a known geometry. This simulated scanning has been verified through systematic comparison with laboratory TLS data. Two types of surface geometry have been investigated: simulated regular arrays of uniform spheres used to analyse the effect of sphere size; and irregular beds of spheres with the same grain size distribution as the fluvial gravels, which provide a comparable complex geometry to the field sediment surfaces. A series of simulated scans of these surfaces has enabled the magnitude and spatial distribution of errors in the interpolated DTMs to be quantified, as well as demonstrating the utility of the different processing stages in removing errors from TLS data. As well as demonstrating the application of simulated scanning as a technique to quantify errors, these results can be used to estimate errors in comparable TLS data.

[Adsorption of Cu on Core-shell Structured Magnetic Particles: Relationship Between Adsorption Performance and Surface Properties].

PubMed

Li, Qiu-mei; Chen, Jing; Li, Hai-ning; Zhang, Xiao-lei; Zhang, Gao-sheng

2015-12-01

In order to reveal the relationship between the adsorption performance of adsorbents and their compositions, structure, and surface properties, the core-shell structured Fe₃O₄/MnO2 and Fe-Mn/Mn₂2 magnetic particles were systematically characterized using multiple techniques and their Cu adsorption behaviors as well as mechanism were also investigated in details. It was found that both Fe₃O4 and Fe-Mn had spinel structure and no obvious crystalline phase change was observed after coating with MnO₂. The introduction of Mn might improve the affinity between the core and the shell, and therefore enhanced the amount and distribution uniformity of the MnO₂ coated. Consequently, Fe-Mn/MnO₂ exhibited a higher BET specific surface area and a lower isoelectric point. The results of sorption experiments showed that Fe-Mn had a higher maximal Cu adsorption capacity of 33.7 mg · g⁻¹ at pH 5.5, compared with 17.5 mg · g⁻¹ of Fe₃O4. After coating, the maximal adsorption capacity of Fe-Mn/MnO₂ was increased to 58.2 mg · g⁻¹, which was 2.6 times as high as that of Fe₃O₄/MnO₂ and outperformed the majority of magnetic adsorbents reported in literature. In addition, a specific adsorption of Cu occurred at the surface of Fe₃O₄/MnO₂ or Fe-Mn/MnO₂ through the formation of inner-sphere complexes. In conclusion, the adsorption performance of the magnetic particles was positively related to their compositions, structure, and surface properties.

Water Surface Impact and Ricochet of Deformable Elastomeric Spheres

NASA Astrophysics Data System (ADS)

Hurd, Randy C.

Soft and deformable silicone rubber spheres ricochet from a water surface when rigid spheres and disks (or skipping stones) cannot. This dissertation investigates why these objects are able to skip so successfully. High speed cameras allow us to see that these unique spheres deform significantly as they impact the water surface, flattening into pancake-like shapes with greater area. Though the water entry behavior of deformable spheres deviates from that of rigid spheres, our research shows that if this deformation is accounted for, their behavior can be predicted from previously established methods. Soft spheres skip more easily because they deform significantly when impacting the water surface. We present a diagram which enables the prediction of a ricochet from sphere impact conditions such as speed and angle. Experiments and mathematical representations of the sphere skipping both show that these deformable spheres skip more readily because deformation momentarily increases sphere area and produces an attack angle with the water which is favorable to skipping. Predictions from our mathematical representation of sphere skipping agree strongly with observations from experiments. Even when a sphere was allowed to skip multiple times in the laboratory, the mathematical predictions show good agreement with measured impact conditions through subsequent skipping events. While studying multiple impact events in an outdoor setting, we discovered a previously unidentified means of skipping, which is unique to deformable spheres. This new skipping occurs when a relatively soft sphere first hits the water at a high speed and low impact angle and the sphere begins to rotate very quickly. This quick rotation causes the sphere to stretch into a shape similar to an American football and maintain this shape while it spins. The sphere is observed to move nearly parallel with the water surface with the tips of this "football" dipping into the water as it rotates and the sides passing just over the surface. This sequence of rapid impact events give the impression that the sphere is walking across the water surface.

Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems.

PubMed

Cheng, Hefa; Hu, Yuanan; Luo, Jian; Xu, Bin; Zhao, Jianfu

2009-06-15

Acid mine drainage (AMD) is often accompanied with elevated concentrations of arsenic, in the forms of arsenite, As(III), and/or arsenate, As(V), due to the high affinity of arsenic for sulfide mineral ores. This review summarizes the major geochemical processes controlling the release, speciation, fate, and distribution of inorganic arsenic in mine drainage and natural systems. Arsenic speciation depends highly on redox potential and pH of the solution, and arsenite can be oxidized to the less toxic arsenate form. Homogeneous oxidation of arsenite occurs rather slowly while its heterogeneous oxidation on mineral surfaces can greatly enhance the reaction rates. Little evidence suggests that precipitation reaction limits the concentrations of arsenic in natural water, while co-precipitation may lead to rapid arsenic removal when large amount of iron hydroxides precipitate out of the aqueous phase upon neutralization of the mine drainage. Both arsenate and arsenite adsorb on common metal oxides and clay minerals through formation of inner-sphere and/or outer-sphere complexes, controlling arsenic concentration in natural water bodies. Arsenite adsorbs less strongly than arsenate in the typical pH range of natural water and is more mobile. Part of the adsorbed arsenic species can be exchanged by common anions (e.g., PO(4)(3-) and SO(4)(2-)), especially phosphate, which leads to their re-mobilization. Understanding the geochemistry of arsenic is helpful for predicting its mobility and fate in AMD and natural systems, and for designing of cost-effective remediation/treatment strategies to reduce the occurrence and risk of arsenic contamination.

Surface gloss and color perception of 3D objects.

PubMed

Xiao, Bei; Brainard, David H

2008-01-01

Two experiments explore the color perception of objects in complex scenes. The first experiment examines the color perception of objects across variation in surface gloss. Observers adjusted the color appearance of a matte sphere to match that of a test sphere. Across conditions we varied the body color and glossiness of the test sphere. The data indicate that observers do not simply match the average light reflected from the test. Indeed, the visual system compensates for the physical effect of varying the gloss, so that appearance is stabilized relative to what is predicted by the spatial average. The second experiment examines how people perceive color across locations on an object. We replaced the test sphere with a soccer ball that had one of its hexagonal faces colored. Observers were asked to adjust the match sphere have the same color appearance as this test patch. The test patch could be located at either an upper or lower location on the soccer ball. In addition, we varied the surface gloss of the entire soccer ball (including the test patch). The data show that there is an effect of test patch location on observers' color matching, but this effect is small compared to the physical change in the average light reflected from the test patch across the two locations. In addition, the effect of glossy highlights on the color appearance of the test patch was consistent with the results from Experiment 1.

Surface gloss and color perception of 3D objects

PubMed Central

Xiao, Bei; Brainard, David H.

2008-01-01

Two experiments explore the color perception of objects in complex scenes. The first experiment examines the color perception of objects across variation in surface gloss. Observers adjusted the color appearance of a matte sphere to match that of a test sphere. Across conditions we varied the body color and glossiness of the test sphere. The data indicate that observers do not simply match the average light reflected from the test. Indeed, the visual system compensates for the physical effect of varying the gloss, so that appearance is stabilized relative to what is predicted by the spatial average. The second experiment examines how people perceive color across locations on an object. We replaced the test sphere with a soccer ball that had one of its hexagonal faces colored. Observers were asked to adjust the match sphere have the same color appearance as this test patch. The test patch could be located at either an upper or lower location on the soccer ball. In addition, we varied the surface gloss of the entire soccer ball (including the test patch). The data show that there is an effect of test patch location on observers’ color matching, but this effect is small compared to the physical change in the average light reflected from the test patch across the two locations. In addition, the effect of glossy highlights on the color appearance of the test patch was consistent with the results from Experiment 1. PMID:18598406

Reduction of adsorbed As(V) on nano-TiO2 by sulfate-reducing bacteria.

PubMed

Luo, Ting; Ye, Li; Ding, Cheng; Yan, Jinlong; Jing, Chuanyong

2017-11-15

Reduction of surface-bound arsenate [As(V)] and subsequent release into the aqueous phase contribute to elevated As in groundwater. However, this natural process is not fully understood, especially in the presence of sulfate-reducing bacteria (SRB). Gaining mechanistic insights into solid-As(V)-SRB interactions motivated our molecular level study on the fate of nano-TiO 2 bound As(V) in the presence of Desulfovibrio vulgaris DP4, a strain of SRB, using incubation and in situ ATR-FTIR experiments. The incubation results clearly revealed the reduction of As(V), either adsorbed on nano-TiO 2 or dissolved, in the presence of SRB. In contrast, this As(V) reduction was not observed in abiotic control experiments where sulfide was used as the reductant. Moreover, the reduction was faster for surface-bound As(V) than for dissolved As(V), as evidenced by the appearance of As(III) at 45h and 75h, respectively. ATR-FTIR results provided direct evidence that the surface-bound As(V) was reduced to As(III) on TiO 2 surfaces in the presence of SRB. In addition, the As(V) desorption from nano-TiO 2 was promoted by SRB relative to abiotic sulfide, due to the competition between As(V) and bacterial phosphate groups for TiO 2 surface sites. This competition was corroborated by the ATR-FTIR analysis, which showed inner-sphere surface complex formation by bacterial phosphate groups on TiO 2 surfaces. The results from this study highlight the importance of indirect bacteria-mediated As(V) reduction and release in geochemical systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

USGS Publications Warehouse

Arai, Yuji; Fuller, C.C.

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na2SO4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO42-]~13 mM L-1) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO2-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO2, there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO2 fluctuates between 1 and 2 pCO2%.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces.

PubMed

Arai, Yuji; Fuller, C C

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite-water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55-7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%. Copyright © 2011 Elsevier Inc. All rights reserved.

Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

USGS Publications Warehouse

Wang, Bronwen; Burau, Richard G.

1995-01-01

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

Foam morphology, frustration and topological defects in a Negatively curved Hele-Shaw geometry

NASA Astrophysics Data System (ADS)

Mughal, Adil; Schroeder-Turk, Gerd; Evans, Myfanwy

2014-03-01

We present preliminary simulations of foams and single bubbles confined in a narrow gap between parallel surfaces. Unlike previous work, in which the bounding surfaces are flat (the so called Hele-Shaw geometry), we consider surfaces with non-vanishing Gaussian curvature. We demonstrate that the curvature of the bounding surfaces induce a geometric frustration in the preferred order of the foam. This frustration can be relieved by the introduction of topological defects (disclinations, dislocations and complex scar arrangements). We give a detailed analysis of these defects for foams confined in curved Hele-Shaw cells and compare our results with exotic honeycombs, built by bees on surfaces of varying Gaussian curvature. Our simulations, while encompassing surfaces of constant Gaussian curvature (such as the sphere and the cylinder), focus on surfaces with negative Gaussian curvature and in particular triply periodic minimal surfaces (such as the Schwarz P-surface and the Schoen's Gyroid surface). We use the results from a sphere-packing algorithm to generate a Voronoi partition that forms the basis of a Surface Evolver simulation, which yields a realistic foam morphology.

ATR-FTIR Spectroscopic Evidence for Biomolecular Phosphorus and Carboxyl Groups Facilitating Bacterial Adhesion to Iron Oxides

PubMed Central

Parikh, Sanjai J.; Mukome, Fungai N.D.; Zhang, Xiaoming

2014-01-01

Attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to probe the binding of bacteria to hematite (α-Fe2O3) and goethite (α-FeOOH). In situ ATR-FTIR experiments with bacteria (Pseudomonas putida, P. aeruginosa, Escherichia coli), mixed amino acids, polypeptide extracts, deoxyribonucleic acid (DNA), and a suite of model compounds were conducted. These compounds represent carboxyl, catecholate, amide, and phosphate groups present in siderophores, amino acids, polysaccharides, phospholipids, and DNA. Due in part to the ubiquitous presence of carboxyl groups in biomolecules, numerous IR peaks corresponding to outer-sphere or unbound (1400 cm−1) and inner-sphere (1310-1320 cm−1) coordinated carboxyl groups are noted following reaction of bacteria and biomolecules with α-Fe2O3 and α-FeOOH. However, the data also reveal that the presence of low-level amounts (i.e., 0.45-0.79%) of biomolecular phosphorous groups result in strong IR bands at ~1043 cm−1, corresponding to inner-sphere Fe-O-P bonds, underscoring the importance of bacteria associated P-containing groups in biomolecule and cell adhesion. Spectral comparisons also reveal slightly greater P-O-Fe contributions for bacteria (Pseudomonad, E. coli) deposited on α-FeOOH, as compared to α-Fe2O3. This data demonstrates that slight differences in bacterial adhesion to Fe oxides can be attributed to bacterial species and Fe-oxide minerals. However, more importantly, the strong binding affinity of phosphate in all bacteria samples to both Fe-oxides results in the formation of inner-sphere Fe-O-P bonds, signifying the critical role of biomolecular P in the initiation of bacterial adhesion. PMID:24859052

Cation-Inhibited Transport of Graphene Oxide Nanomaterials in Saturated Porous Media: The Hofmeister Effects.

PubMed

Xia, Tianjiao; Qi, Yu; Liu, Jing; Qi, Zhichong; Chen, Wei; Wiesner, Mark R

2017-01-17

Transport of negatively charged nanoparticles in porous media is largely affected by cations. To date, little is known about how cations of the same valence may affect nanoparticle transport differently. We observed that the effects of cations on the transport of graphene oxide (GO) and sulfide-reduced GO (RGO) in saturated quartz sand obeyed the Hofmeister series; that is, transport-inhibition effects of alkali metal ions followed the order of Na + < K + < Cs + , and those of alkaline earth metal ions followed the order of Mg 2+ < Ca 2+ < Ba 2+ . With batch adsorption experiments and microscopic data, we verified that cations having large ionic radii (and thus being weakly hydrated) interacted with quartz sand and GO and RGO more strongly than did cations of small ionic radii. In particular, the monovalent Cs + and divalent Ca 2+ and Ba 2+ , which can form inner-sphere complexes, resulted in very significant deposition of GO and RGO via cation bridging between quartz sand and GO and RGO, and possibly via enhanced straining, due to the enhanced aggregation of GO and RGO from cation bridging. The existence of the Hofmeister effects was further corroborated with the interesting observation that cation bridging was more significant for RGO, which contained greater amounts of carboxyl and phenolic groups (i.e., metal-complexing moieties) than did GO. The findings further demonstrate that transport of nanoparticles is controlled by the complex interplay between nanoparticle surface functionalities and solution chemistry constituents.

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.; Piana, M.J.

2002-01-01

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatitebased in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 ??M was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations ???4700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 A??. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios ???0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.

Evidence of progenitor cells in the adult human cochlea: sphere formation and identification of ABCG2.

PubMed

Massucci-Bissoli, Milene; Lezirovitz, Karina; Oiticica, Jeanne; Bento, Ricardo Ferreira

2017-11-01

The aim of this study was to search for evidence of stem or progenitor cells in the adult human cochlea by testing for sphere formation capacity and the presence of the stem cell marker ABCG2. Cochleas removed from patients undergoing vestibular schwannoma resection (n=2) and from brain-dead organ donors (n=4) were dissociated for either flow cytometry analysis for the stem cell marker ABCG2 or a sphere formation assay that is widely used to test the sphere-forming capacity of cells from mouse inner ear tissue. Spheres were identified after 2-5 days in vitro, and the stem cell marker ABCG2 was detected using flow cytometric analysis after cochlear dissociation. Evidence suggests that there may be progenitor cells in the adult human cochlea, although further studies are required.

Kinetic and mechanism of the oxidation of chromium(III) complex with anthranil- N, N-diacetic acid by periodate ion in acidic aqueous solutions

NASA Astrophysics Data System (ADS)

Ali, Ismat H.

2015-06-01

The kinetics of oxidation of [CrIII(atda)(H2O)2] (atda = anthranil- N, N-diacetato) complex by IO{4/-} was studied spectrophotometrically in aqueous solutions with pH range 2.20-3.34, 0.30 M ionic strength and in 20.0-40.0°C temperature range. The rate law of the reaction exhibited saturation kinetics. Values of the rate constant for the electron transfer process, the equilibrium constant for dissociation of [CrIII (atda)(H2O)2] to [CrIII (atda) (H2O)OH]+ + H+ and the pre-equilibrium formation constant were calculated. The thermodynamic activation parameters are reported. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of the IVII to chromium(III).

The contour-buildup algorithm to calculate the analytical molecular surface.

PubMed

Totrov, M; Abagyan, R

1996-01-01

A new algorithm is presented to calculate the analytical molecular surface defined as a smooth envelope traced out by the surface of a probe sphere rolled over the molecule. The core of the algorithm is the sequential build up of multi-arc contours on the van der Waals spheres. This algorithm yields substantial reduction in both memory and time requirements of surface calculations. Further, the contour-buildup principle is intrinsically "local", which makes calculations of the partial molecular surfaces even more efficient. Additionally, the algorithm is equally applicable not only to convex patches, but also to concave triangular patches which may have complex multiple intersections. The algorithm permits the rigorous calculation of the full analytical molecular surface for a 100-residue protein in about 2 seconds on an SGI indigo with R4400++ processor at 150 Mhz, with the performance scaling almost linearly with the protein size. The contour-buildup algorithm is faster than the original Connolly algorithm an order of magnitude.

Scalable synthesis of Na3V2(PO4)(3)/C porous hollow spheres as a cathode for Na-ion batteries

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

Mao, JF; Luo, C; Gao, T

2015-01-01

Na3V2(PO4)(3) (NVP) has been considered as a very promising cathode material for sodium-ion batteries (SIBs) due to its typical NASICON structure, which provides an open and three dimensional (3D) framework for Na+ migration. However, the low electronic conductivity of NVP limits its rate capability and cycling ability. In this study, carbon coated hollow structured NVP/C composites are synthesized via a template-free and scalable ultrasonic spray pyrolysis process, where the carbon coated NVP particles are uniformly decorated on the inner and outer surfaces of the porous hollow carbon spheres. When evaluated as a cathode material for SIBs, the unique NVP/C porousmore » hollow sphere cathode delivers an initial discharge capacity of 99.2 mA h g(-1) and retains 89.3 mA h g(-1) after 300 charge/discharge cycles with a very low degradation rate of 0.035% per cycle. For comparison, the NVP/C composite, prepared by the traditional sol-gel method, delivers a lower initial discharge capacity of 97.4 mA h g(-1) and decreases significantly to 71.5 mA h g(-1) after 300 cycles. The superior electrochemical performance of NVP/C porous hollow spheres is attributed to their unique porous, hollow and spherical structures, as well as the carbon-coating layer, which provides a high contact area between electrode/electrolyte, high electronic conductivity, and high mechanical strength.« less

The Limitations of an Exclusively Colloidal View of Protein Solution Hydrodynamics and Rheology

PubMed Central

Sarangapani, Prasad S.; Hudson, Steven D.; Migler, Kalman B.; Pathak, Jai A.

2013-01-01

Proteins are complex macromolecules with dynamic conformations. They are charged like colloids, but unlike colloids, charge is heterogeneously distributed on their surfaces. Here we overturn entrenched doctrine that uncritically treats bovine serum albumin (BSA) as a colloidal hard sphere by elucidating the complex pH and surface hydration-dependence of solution viscosity. We measure the infinite shear viscosity of buffered BSA solutions in a parameter space chosen to tune competing long-range repulsions and short-range attractions (2 mg/mL ≤ [BSA] ≤ 500 mg/mL and 3.0 ≤ pH ≤ 7.4). We account for surface hydration through partial specific volume to define volume fraction and determine that the pH-dependent BSA intrinsic viscosity never equals the classical hard sphere result (2.5). We attempt to fit our data to the colloidal rheology models of Russel, Saville, and Schowalter (RSS) and Krieger-Dougherty (KD), which are each routinely and successfully applied to uniformly charged suspensions and to hard-sphere suspensions, respectively. We discover that the RSS model accurately describes our data at pH 3.0, 4.0, and 5.0, but fails at pH 6.0 and 7.4, due to steeply rising solution viscosity at high concentration. When we implement the KD model with the maximum packing volume fraction as the sole floating parameter while holding the intrinsic viscosity constant, we conclude that the model only succeeds at pH 6.0 and 7.4. These findings lead us to define a minimal framework for models of crowded protein solution viscosity wherein critical protein-specific attributes (namely, conformation, surface hydration, and surface charge distribution) are addressed. PMID:24268154

Complex Refractive Index of Ice Fog at a Radio Wavelength of 3 mm

DTIC Science & Technology

1974-10-01

particles on mirror surface 55 41. Liberally dusting mirror with 3-// polystyrene dust produces almost no effect 56 —" -.-.—-- ■ .■..^„^-^aa...spheres, as Debye (1929) did in his original theory. The rotation of these spheres in a viscous medium is opposed by forces related by Stoke’s law to...given by a relation of the form ,_ C „D/kT E/RT Z 0 where R k ■ M.C \\s only slightly temperature dependent, and n/w is the average time required by

Real-time observation of cation exchange kinetics and dynamics at the muscovite-water interface

DOE PAGES

Lee, Sang Soo; Fenter, Paul; Nagy, Kathryn L.; ...

2017-06-09

Here, ion exchange at charged solid–liquid interfaces is central to a broad range of chemical and transport phenomena. Real-time observations of adsorption/desorption at the molecular-scale elucidate exchange reaction pathways. Here, we report temporal variation in the distribution of Rb + species at the muscovite (001)–water interface during exchange with Na +. Time-resolved resonant anomalous X-ray reflectivity measurements reveal that Rb + desorption occurs over several tens of seconds during which thermodynamically stable inner-sphere Rb + slowly transforms to less stable outer-sphere Rb + at 25°C. In contrast, Rb + adsorption is about twice as fast, proceeding quickly from Rb +more » in the bulk solution to the stable inner-sphere species. The Arrhenius plot of the adsorption/desorption rate constants measured from 9 to 55°C shows that the pre-exponential factor for desorption is significantly smaller than for adsorption, indicating that this reduced attempt frequency of cation detachment largely explains the slow cation exchange processes at the interface.« less

Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

2017-05-01

The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope budget. In contrast, the isotopic composition of W in ancient seawater should have evolved in response to the extent of deposition of both Fe and Mn oxides; this is likely to be different compared with that of the Mo isotopes, which is strongly associated with the occurrence of Mn oxides relative to Fe oxides.

Application of identifying transmission spheres for spherical surface testing

NASA Astrophysics Data System (ADS)

Han, Christopher B.; Ye, Xin; Li, Xueyuan; Wang, Quanzhao; Tang, Shouhong; Han, Sen

2017-06-01

We developed a new application on Microsoft Foundation Classes (MFC) to identify correct transmission spheres (TS) for Spherical Surface Testing (SST). Spherical surfaces are important optical surfaces, and the wide application and high production rate of spherical surfaces necessitates an accurate and highly reliable measuring device. A Fizeau Interferometer is an appropriate tool for SST due to its subnanometer accuracy. It measures the contour of a spherical surface using a common path, which is insensitive to the surrounding circumstances. The Fizeau Interferometer transmits a wide laser beam, creating interference fringes from re-converging light from the transmission sphere and the test surface. To make a successful measurement, the application calculates and determines the appropriate transmission sphere for the test surface. There are 3 main inputs from the test surfaces that are utilized to determine the optimal sizes and F-numbers of the transmission spheres: (1) the curvatures (concave or convex), (2) the Radii of Curvature (ROC), and (3) the aperture sizes. The application will firstly calculate the F-numbers (i.e. ROC divided by aperture) of the test surface, secondly determine the correct aperture size of a convex surface, thirdly verify that the ROC of the test surface must be shorter than the reference surface's ROC of the transmission sphere, and lastly calculate the percentage of area that the test surface will be measured. However, the amount of interferometers and transmission spheres should be optimized when measuring large spherical surfaces to avoid requiring a large amount of interferometers and transmission spheres for each test surface. Current measuring practices involve tedious and potentially inaccurate calculations. This smart application eliminates human calculation errors, optimizes the selection of transmission spheres (including the least number required) and interferometer sizes, and increases efficiency.

Adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II), and As(V) on bacterially produced metal sulfides.

PubMed

Jong, Tony; Parry, David L

2004-07-01

The adsorption of Pb(II), Cu(II), Cd(II), Zn(II), Ni(II), Fe(II) and As(V) onto bacterially produced metal sulfide (BPMS) material was investigated using a batch equilibrium method. It was found that the sulfide material had adsorptive properties comparable with those of other adsorbents with respect to the specific uptake of a range of metals and, the levels to which dissolved metal concentrations in solution can be reduced. The percentage of adsorption increased with increasing pH and adsorbent dose, but decreased with increasing initial dissolved metal concentration. The pH of the solution was the most important parameter controlling adsorption of Cd(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), and As(V) by BPMS. The adsorption data were successfully modeled using the Langmuir adsorption isotherm. Desorption experiments showed that the reversibility of adsorption was low, suggesting high-affinity adsorption governed by chemisorption. The mechanism of adsorption for the divalent metals was thought to be the formation of strong, inner-sphere complexes involving surface hydroxyl groups. However, the mechanism for the adsorption of As(V) by BPMS appears to be distinct from that of surface hydroxyl exchange. These results have important implications to the management of metal sulfide sludge produced by bacterial sulfate reduction.

Cd(II) Sorption on Montmorillonite-Humic acid-Bacteria Composites

PubMed Central

Du, Huihui; Chen, Wenli; Cai, Peng; Rong, Xingmin; Dai, Ke; Peacock, Caroline L.; Huang, Qiaoyun

2016-01-01

Soil components (e.g., clays, bacteria and humic substances) are known to produce mineral-organic composites in natural systems. Herein, batch sorption isotherms, isothermal titration calorimetry (ITC), and Cd K-edge EXAFS spectroscopy were applied to investigate the binding characteristics of Cd on montmorillonite(Mont)-humic acid(HA)-bacteria composites. Additive sorption and non-additive Cd(II) sorption behaviour is observed for the binary Mont-bacteria and ternary Mont-HA-bacteria composite, respectively. Specifically, in the ternary composite, the coexistence of HA and bacteria inhibits Cd adsorption, suggesting a “blocking effect” between humic acid and bacterial cells. Large positive entropies (68.1 ~ 114.4 J/mol/K), and linear combination fitting of the EXAFS spectra for Cd adsorbed onto Mont-bacteria and Mont-HA-bacteria composites, demonstrate that Cd is mostly bound to bacterial surface functional groups by forming inner-sphere complexes. All our results together support the assertion that there is a degree of site masking in the ternary clay mineral-humic acid-bacteria composite. Because of this, in the ternary composite, Cd preferentially binds to the higher affinity components-i.e., the bacteria. PMID:26792640

Interactions between Silicon Oxide Nanoparticles (SONPs) and U(VI) Contaminations: Effects of pH, Temperature and Natural Organic Matters

PubMed Central

Wu, Hanyu; Li, Ping; Pan, Duoqiang; Yin, Zhuoxin; Fan, Qiaohui; Wu, Wangsuo

2016-01-01

The interactions between contaminations of U(VI) and silicon oxide nanoparticles (SONPs), both of which have been widely used in modern industry and induced serious environmental challenge due to their high mobility, bioavailability, and toxicity, were studied under different environmental conditions such as pH, temperature, and natural organic matters (NOMs) by using both batch and spectroscopic approaches. The results showed that the accumulation process, i.e., sorption, of U(VI) on SONPs was strongly dependent on pH and ionic strength, demonstrating that possible outer- and/or inner-sphere complexes were controlling the sorption process of U(VI) on SONPs in the observed pH range. Humic acid (HA), one dominated component of NOMs, bounded SONPs can enhance U(VI) sorption below pH~4.5, whereas restrain at high pH range. The reversible sorption of U(VI) on SONPs possibly indicated that the outer-sphere complexes were prevalent at pH 5. However, an irreversible interaction of U(VI) was observed in the presence of HA (Fig 1). It was mainly due to the ternary SONPs-HA-U(VI) complexes (Type A Complexes). After SONPs adsorbed U(VI), the particle size in suspension was apparently increased from ~240 nm to ~350 nm. These results showed that toxicity of both SONPs and U(VI) will decrease to some extent after the interaction in the environment. These findings are key for providing useful information on the possible mutual interactions among different contaminants in the environment. PMID:26930197

Adsorption behavior and mechanism of different arsenic species on mesoporous MnFe2O4 magnetic nanoparticles.

PubMed

Hu, Qingsong; Liu, Yuling; Gu, Xueyuan; Zhao, Yaping

2017-08-01

Arsenic pollution poses severe threat to human health, therefore dealing with the problem of arsenic contamination in water bodies is extremely important. The adsorption behaviors of different arsenic species, such as arsenate (As(V)), p-arsanilic acid (p-ASA), roxarsone (ROX), dimethylarsenate (DMA) from water using mesoporous bimetal oxide magnetic manganese ferrite nanoparticles (MnFe 2 O 4 ) have been detailedly investigated. The adsorbent was synthesized via a facile co-precipitation approach and recovered conveniently owing to its strong magnetic properties. The obtained MnFe 2 O 4 with large surface area and abundant hydroxyly functional groups exhibited excellent adsorption performance for As(V) and p-ASA, in contrast to ROX and DMA with the maximum adsorption capacities of As(V), p-ASA, ROX and DMA of 68.25 mg g -1 , 59.45 mg g -1 , 51.49 mg g -1 , and 35.77 mg g -1 , respectively. The Langmuir model and the pseudo-second-order kinetic model correlated satisfactorily with the adsorption thermodynamics and kinetics, and thermodynamic parameters depicted the spontaneous endothermic nature for the adsorption of different arsenic species. The adsorption mechanism of different arsenic species onto MnFe 2 O 4 nanoparticles at various pH values could be explained by surface complexation and molecular structural variations. Attenuated Total internal Reflectance Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) further proved that arsenic species were bonded to the surface of MnFe 2 O 4 through the formation of an inner-sphere complex between the arsenic acid moiety and surface metal centers. The results would help to know the interaction of arsenic species with iron-manganese minerals and the mobility of arsenic species in natural environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Experimental investigation of shock wave diffraction over a single- or double-sphere model

NASA Astrophysics Data System (ADS)

Zhang, L. T.; Wang, T. H.; Hao, L. N.; Huang, B. Q.; Chen, W. J.; Shi, H. H.

2017-01-01

In this study, the unsteady drag produced by the interaction of a shock wave with a single- and a double-sphere model is measured using imbedded accelerometers. The shock wave is generated in a horizontal circular shock tube with an inner diameter of 200 mm. The effect of the shock Mach number and the dimensionless distance between spheres is investigated. The time-history of the drag coefficient is obtained based on Fast Fourier Transformation (FFT) band-block filtering and polynomial fitting of the measured acceleration. The measured peak values of the drag coefficient, with the associated uncertainty, are reported.

Improved AFM Mapping of ICF Target Surfaces

NASA Astrophysics Data System (ADS)

Olson, D. K.; Drake, T.; Frey, D.; Huang, H.; Stephens, R. B.

2003-10-01

Targets for Inertial Confinement Fusion (ICF) research are made from spherical shells with very strict requirements on surface smoothness. Hydrodynamic instabilities are amplified by the presence of surface defects, greatly reducing the gain of ICF targets. Sub-micron variations in the surface can be examined using an Atomic Force Microscope. The current sphere mapping assembly at General Atomics is designed to trace near the equator of a rotating sphere under the AFM head. Spheres are traced on three mutually orthogonal planes. The ˜10 mm piezo-electric actuator range limits how far off the equator we can scan spheres of millimeter diameter. Because only a small fraction of the target's surface can be covered, localized high-mode defects are difficult to detect. In order to meet the needs of ICF research, we need to scan more surface area of the sphere with the AFM. By integrating an additional stepping motor to the sphere mapping assembly, we will be able to recenter the piezo driver of the AFM while mapping. This additional ability allows us to increase the amount of the sphere's surface we are able to scan with the AFM by extending the range of the AFM from the sphere's equator.

Adsorption of fatty acids on iron (hydr)oxides from aqueous solutions.

PubMed

Chernyshova, Irina V; Ponnurangam, Sathish; Somasundaran, Ponisseril

2011-08-16

The interaction of iron (hydr)oxides with fatty acids is related to many industrial and natural processes. To resolve current controversies about the adsorption configurations of fatty acids and the conditions of the maximum hydrophobicity of the minerals, we perform a detailed study of the adsorption of sodium laurate (dodecanoate) on 150 nm hematite (α-Fe(2)O(3)) particles as a model system. The methods used include in situ FTIR spectroscopy, ex situ X-ray photoelectron spectroscopy (XPS), measurements of the adsorption isotherm and contact angle, as well as the density functional theory (DFT) calculations. We found that the laurate adlayer is present as a mixture of inner-sphere monodentate mononuclear (ISMM) and outer-sphere (OS) hydration shared complexes independent of the solution pH. Protonation of the OS complexes does not influence the conformational order of the surfactant tails. One monolayer, which is filled through the growth of domains and is reached at the micellization/precipitation edge of laurate, makes the particles superhydrophobic. These results contradict previous models of the fatty acid adsorption and suggest new interpretation of literature data. Finally, we discovered that the fractions of both the OS laurate and its molecular form increase in D(2)O, which can be used for interpreting complex spectra. We discuss shortcomings of vibrational spectroscopy in determining the interfacial coordination of carboxylate groups. This work advances the current understanding of the oxide-carboxylate interactions and the research toward improving performance of fatty acids as surfactants, dispersants, lubricants, and anticorrosion reagents.

"Outer-sphere to inner-sphere" redox cycling for ultrasensitive immunosensors.

PubMed

Akanda, Md Rajibul; Choe, Yu-Lim; Yang, Haesik

2012-01-17

This paper reports chemical-chemical (CC) and electrochemical-chemical-chemical (ECC) redox cycling, for use in ultrasensitive biosensor applications. A triple chemical amplification approach using an enzymatic reaction, CC redox cycling, and ECC redox cycling is applied toward electrochemical immunosensors of cardiac troponin I. An enzymatic reaction, in which alkaline phosphatase converts 4-aminophenyl phosphate to 4-aminophenol (AP), triggers CC redox cycling in the presence of an oxidant and a reductant, and electrochemical signals are measured with ECC redox cycling after an incubation period of time in an air-saturated solution. To obtain high, selective, and reproducible redox cycling without using redox enzymes, two redox reactions [the reaction between AP and the oxidant and the reaction between the oxidized form of AP (4-quinone imine, QI) and the reductant] should be fast, but an unwanted reaction between the oxidant and reductant should be very slow. Because species that undergo outer-sphere reactions (OSR-philic species) react slowly with species that undergo inner-sphere reactions (ISR-philic species), highly OSR-philic Ru(NH(3))(6)(3+) and highly ISR-philic tris(2-carboxyethyl)phosphine (TCEP) are chosen as the oxidant and reductant, respectively. The OSR- and ISR-philic QI/AP couple allows fast redox reactions with both the OSR-philic Ru(NH(3))(6)(3+) and the ISR-philic TCEP. Highly OSR-philic indium-tin oxide (ITO) electrodes minimize unwanted electrochemical reactions with highly ISR-philic species. Although the formal potential of the Ru(NH(3))(6)(3+)/Ru(NH(3))(6)(2+) couple is lower than that of the QI/AP couple, the endergonic reaction between Ru(NH(3))(6)(3+) and AP is driven by the highly exergonic reaction between TCEP and QI (via a coupled reaction mechanism). Overall, the "outer-sphere to inner-sphere" redox cycling in the order of highly OSR-philic ITO, highly OSR-philic Ru(NH(3))(6)(3+)/Ru(NH(3))(6)(2+) couple, OSR- and ISR-philic QI/AP couple, and highly ISR-philic TCEP allows high, selective, and reproducible signal amplification. The electrochemical data obtained by chronocoulometry permit a lower detection limits than those obtained by cyclic voltammetry. The detection limit of an immunosensor for troponin I in serum, calculated from the anodic charges in chronocoulometry, is ca. 10 fg/mL.

In vitro and in vivo study of the application of volvox spheres to co-culture vehicles in liver tissue engineering.

PubMed

Chang, Siou Han; Huang, Han Hsiang; Kang, Pei Leun; Wu, Yu Chian; Chang, Ming-Huang; Kuo, Shyh Ming

2017-11-01

Volvox sphere is a biomimetic concept of a natural Volvox, wherein a large outer sphere contains smaller inner spheres, which can encapsulate cells and provide a double-layer three-dimensional environment for culturing cells. This study simultaneously encapsulated rat mesenchymal stem cells (MSCs) and AML12 hepatocytes in volvox spheres and extensively evaluated the effects of various culturing modes on cell functions and fates. The results showed that compared with a static flask culture, MSCs encapsulated in volvox spheres differentiated into hepatocyte-like cells with a 2-fold increase in albumin (ALB) expression and a 2.5-fold increase in cytokeratin 18 expression in a dynamic bioreactor. Moreover, the restorative effects of volvox spheres encapsulating cells on retrorsine-exposed CCl 4 -induced liver injuries in rats were evaluated. The data presented significant reductions in AST and ALT levels after the implantation of volvox spheres encapsulating both MSCs and AML12 hepatocytes in vivo. In contrast to the negative control group, histopathological analysis demonstrated liver repair and formation of the new liver tissue in groups implanted with volvox spheres containing cells. These results demonstrate that liver cells implanted with volvox spheres encapsulating both MSCs and AML12 hepatocytes promote liver repair and liver tissue regeneration in liver failure caused by necrotizing agents such as retrorsine and CCl 4 . Hence, volvox spheres encapsulating MSCs and liver cells can be a promising and clinically effective therapy for liver injury. In this study, we used a volvox sphere, which is a unique design that mimics the natural Volvox, that consists of a large outer sphere that contains smaller inner spheres, which provide a three-dimensional environment to culture cells. The purpose of this study is to co-culture mesenchymal stem cells (MSCs) and AML12 liver cells in volvox spheres and evaluate two different culture methods, dynamic bioreactor and static culture flask,on the cultured cells. In addition, we aimed to evaluate the restorative effects of volvox spheres encapsulating MSCs and/or AML12 liver cells on rats with retrorsine-exposed CCl 4 -induced liver injuries. The results showed that MSCs encapsulated in volvox spheres differentiated into hepatocyte-like cells with a 2-fold increase in albumin expression and a 2.5-fold increase in cytokeratin 18 expression ina dynamic bioreactor. Moreover, the data presented significant reductions in AST and ALT levels after the implantation of volvox spheres encapsulating both MSCs and AML12 hepatocytes in vivo. In contrast to the negative control group, histopathological analysis demonstrated liver repair and formation of new liver tissue in groups implanted with volvox spheres containing cells. These results demonstrate that liver cells implanted with volvox spheres encapsulating both MSCs and AML12 hepatocytes promote liver repair and liver tissue regeneration in liver failure caused by necrotizing agents such as retrorsine and CCl 4 . Hence, volvox spheres encapsulating MSCs and liver cells can be a promising and clinically effective therapy for liver injury. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Machine imparting complex rotary motion for lapping a spherical inner diameter

DOEpatents

Carroll, Thomas A.; Yetter, Harold H.

1986-01-01

An apparatus for imparting complex rotary motion is used to lap an inner spherical diameter surface of a workpiece. A lapping tool consists of a dome and rod mounted along the dome's vertical axis. The workpiece containing the lapping tool is held in a gimbal which uses power derived from a secondary takeoff means to impart rotary motion about a horizontal axis. The gimbal is rotated about a vertical axis by a take means while mounted at a radially outward position on a rotating arm.

Machine imparting complex rotary motion for lapping a spherical inner diameter

DOEpatents

Carroll, T.A.; Yetter, H.H.

1985-01-30

An apparatus for imparting complex rotary motion is used to lap an inner spherical diameter surface of a workpiece. A lapping tool consists of a dome and rod mounted along the dome's vertical axis. The workpiece containing the lapping tool is held in a gimbal which uses power derived from a secondary takeoff means to impart rotary motion about a horizontal axis. The gimbal is rotated about a vertical axis by a take means while mounted at a radially outward position on a rotating arm.

Mitochondrial Protein Synthesis, Import, and Assembly

PubMed Central

Fox, Thomas D.

2012-01-01

The mitochondrion is arguably the most complex organelle in the budding yeast cell cytoplasm. It is essential for viability as well as respiratory growth. Its innermost aqueous compartment, the matrix, is bounded by the highly structured inner membrane, which in turn is bounded by the intermembrane space and the outer membrane. Approximately 1000 proteins are present in these organelles, of which eight major constituents are coded and synthesized in the matrix. The import of mitochondrial proteins synthesized in the cytoplasm, and their direction to the correct soluble compartments, correct membranes, and correct membrane surfaces/topologies, involves multiple pathways and macromolecular machines. The targeting of some, but not all, cytoplasmically synthesized mitochondrial proteins begins with translation of messenger RNAs localized to the organelle. Most proteins then pass through the translocase of the outer membrane to the intermembrane space, where divergent pathways sort them to the outer membrane, inner membrane, and matrix or trap them in the intermembrane space. Roughly 25% of mitochondrial proteins participate in maintenance or expression of the organellar genome at the inner surface of the inner membrane, providing 7 membrane proteins whose synthesis nucleates the assembly of three respiratory complexes. PMID:23212899

Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores

NASA Astrophysics Data System (ADS)

Yang, Guomin; Neretnieks, Ivars; Holmboe, Michael

2017-08-01

During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and about eight water molecules in the first hydration shell within a radius of 3.3 Å at all higher hydration states. Moreover, the MD results show that the complete hydration shells are nearly spherical with an orthogonal coordination sphere. They could only be formed when the basal spacing d001 ≥ 18.7 Å, i.e., approximately, the interlayer separation h ≥ 10 Å. Comparison between DFT and MD simulations shows that DFT failed to reproduce the outer-sphere complexes in the Stern-layer (within ˜5.0 Å from the clay basal-plane), observed in the MD simulations.

Stability of barotropic vortex strip on a rotating sphere

PubMed Central

Sohn, Sung-Ik; Kim, Sun-Chul

2018-01-01

We study the stability of a barotropic vortex strip on a rotating sphere, as a simple model of jet streams. The flow is approximated by a piecewise-continuous vorticity distribution by zonal bands of uniform vorticity. The linear stability analysis shows that the vortex strip becomes stable as the strip widens or the rotation speed increases. When the vorticity constants in the upper and the lower regions of the vortex strip have the same positive value, the inner flow region of the vortex strip becomes the most unstable. However, when the upper and the lower vorticity constants in the polar regions have different signs, a complex pattern of instability is found, depending on the wavenumber of perturbations, and interestingly, a boundary far away from the vortex strip can be unstable. We also compute the nonlinear evolution of the vortex strip on the rotating sphere and compare with the linear stability analysis. When the width of the vortex strip is small, we observe a good agreement in the growth rate of perturbation at an early time, and the eigenvector corresponding to the unstable eigenvalue coincides with the most unstable part of the flow. We demonstrate that a large structure of rolling-up vortex cores appears in the vortex strip after a long-time evolution. Furthermore, the geophysical relevance of the model to jet streams of Jupiter, Saturn and Earth is examined. PMID:29507524

Stability of barotropic vortex strip on a rotating sphere.

PubMed

Sohn, Sung-Ik; Sakajo, Takashi; Kim, Sun-Chul

2018-02-01

We study the stability of a barotropic vortex strip on a rotating sphere, as a simple model of jet streams. The flow is approximated by a piecewise-continuous vorticity distribution by zonal bands of uniform vorticity. The linear stability analysis shows that the vortex strip becomes stable as the strip widens or the rotation speed increases. When the vorticity constants in the upper and the lower regions of the vortex strip have the same positive value, the inner flow region of the vortex strip becomes the most unstable. However, when the upper and the lower vorticity constants in the polar regions have different signs, a complex pattern of instability is found, depending on the wavenumber of perturbations, and interestingly, a boundary far away from the vortex strip can be unstable. We also compute the nonlinear evolution of the vortex strip on the rotating sphere and compare with the linear stability analysis. When the width of the vortex strip is small, we observe a good agreement in the growth rate of perturbation at an early time, and the eigenvector corresponding to the unstable eigenvalue coincides with the most unstable part of the flow. We demonstrate that a large structure of rolling-up vortex cores appears in the vortex strip after a long-time evolution. Furthermore, the geophysical relevance of the model to jet streams of Jupiter, Saturn and Earth is examined.

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.

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

USGS Publications Warehouse

Waychunas, G.A.; Fuller, C.C.; Davis, J.A.

2002-01-01

"Two-line" ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10-5 to 10-3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(0.2) A?? and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) A?? and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) A?? in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior. Copyright ?? 2002 Elsevier Science Ltd.

Interaction of a shock wave with multiple spheres suspended in different arrangements

NASA Astrophysics Data System (ADS)

Zhang, Li-Te; Sui, Zhen-Zhen; Shi, Hong-Hui

2018-03-01

In this study, the unsteady drag force, Fd, drag coefficient, Cd, and the relevant dynamic behaviors of waves caused by the interaction between a planar incident shock wave and a multi-sphere model are investigated by using imbedded accelerometers and a high-speed Schlieren system. The shock wave is produced in a horizontal 200 mm inner diameter circular shock tube with a 2000 mm × 200 mm × 200 mm transparent test section. The time history of Cd is obtained based on band-block and low-pass Fast Fourier Transformation filtering combined with Savitzky-Golay polynomial smoothing for the measured acceleration. The effects of shock Mach number, Ms, geometry of multi-sphere model, nondimensional distance between sphere centers, H, and channel blockage are analyzed. We find that all time histories of Cd have a similar double-peak shaped main structure. It is due to wave reflection, diffraction, interference, and convergence at different positions of the spheres. The peak Fd increases, whereas the peak Cd decreases monotonically with increasing Ms. The increase of shock strength due to shock focusing by upstream spheres increases the peak Fd of downstream spheres. Both the increase in sphere number and the decrease in distance between spheres promote wave interference between neighboring spheres. As long as the wave interference times are shorter than the peak times, the peak Fd and Cd are higher compared to a single sphere.

Measurement of steep aspheric surfaces using improved two-wavelength phase-shifting interferometer

NASA Astrophysics Data System (ADS)

Zhang, Liqiong; Wang, Shaopu; Hu, Yao; Hao, Qun

2017-10-01

Optical components with aspheric surfaces can improve the imaging quality of optical systems, and also provide extra advantages such as lighter weight, smaller volume and simper structure. In order to satisfy these performance requirements, the surface error of aspheric surfaces, especially high departure aspheric surfaces must be measured accurately and conveniently. The major obstacle of traditional null-interferometry for aspheric surface under test is that specific and complex null optics need to be designed to fully compensate for the normal aberration of the aspheric surface under test. However, non-null interferometry partially compensating for the aspheric normal aberration can test aspheric surfaces without specific null optics. In this work, a novel non-null test approach of measuring the deviation between aspheric surfaces and the best reference sphere by using improved two-wavelength phase shifting interferometer is described. With the help of the calibration based on reverse iteration optimization, we can effectively remove the retrace error and thus improve the accuracy. Simulation results demonstrate that this method can measure the aspheric surface with the departure of over tens of microns from the best reference sphere, which introduces approximately 500λ of wavefront aberration at the detector.

Triassico: A Sphere Positioning System for Surface Studies with IBA Techniques

NASA Astrophysics Data System (ADS)

Fontana, Cristiano L.; Doyle, Barney L.

We propose here a novel device, called the Triassico, to microscopically study the entire surface of millimeter-sized spheres. The sphere dimensions can be as small as 1 mm, and the upper limit defined only by the power and by the mechanical characteristics of the motors used. Three motorized driving rods are arranged so an equilateral triangle is formed by the rod's axes, on such a triangle the sphere sits. Movement is achieved by rotating the rods with precise relative speeds and by exploiting the friction between the sphere and the rods surfaces. The sphere can be held in place by gravity or by an opposing trio of rods. By rotating the rods with specific relative angular velocities, a net torque can be exerted on the sphere which then rotates. No repositioning of the sphere or of the motors is needed to cover the full surface with the investigating tools. An algorithm was developed to position the sphere at any arbitrary polar and azimuthal angle. The algorithm minimizes the number of rotations needed by the rods, in order to efficiently select a particular position on the sphere surface. A prototype Triassico was developed for the National Ignition Facility, of the Lawrence Livermore National Laboratory (Livermore, California, USA), as a sphere manipulation apparatus for ion microbeam analysis at Sandia National Laboratories (Albuquerque, NM, USA) of Xe-doped DT inertial confinement fusion fuel spheres. Other applications span from samples orientation, ball bearing manufacturing, or jewelry.

HD 169142 in the eyes of ZIMPOL/SPHERE

NASA Astrophysics Data System (ADS)

Bertrang, G. H.-M.; Avenhaus, H.; Casassus, S.; Montesinos, M.; Kirchschlager, F.; Perez, S.; Cieza, L.; Wolf, S.

2018-03-01

We present new data of the protoplanetary disc surrounding the Herbig Ae/Be star HD 169142 obtained in the very broad-band (VBB) with the Zurich imaging polarimeter (ZIMPOL), a subsystem of the Spectro-Polarimetric High-contrast Exoplanet REsearch instrument (SPHERE) at the Very Large Telescope (VLT). Our Polarimetric Differential Imaging (PDI) observations probe the disc as close as 0.03 arcsec (3.5 au) to the star and are able to trace the disc out to ˜1.08 arcsec (˜126 au). We find an inner hole, a bright ring bearing substructures around 0.18 arcsec (21 au), and an elliptically shaped gap stretching from 0.25 to 0.47 arcsec (29-55 au). Outside of 0.47 arcsec, the surface brightness drops off, discontinued only by a narrow annular brightness minimum at ˜0.63 to 0.74 arcsec (74-87 au). These observations confirm features found in less-well-resolved data as well as reveal yet undetected indications for planet-disc interactions, such as small-scale structures, star-disc offsets, and potentially moving shadows.

Investigation of mechanism and critical parameters for removal of arsenic from water using Zr-TiO2 composite.

PubMed

Anđelković, I; Amaizah, N R R; Marković, S B; Stanković, D; Marković, M; Kuzmanović, D; Roglić, G

2017-09-01

Using the microwave-hydrothermal method for the synthesis of composite, high surface density of hydroxyl groups, as an active adsorption sites for arsenic, was obtained. Adsorption mechanisms of As(III) and As(V) onto zirconium-doped titanium dioxide (Zr-TiO 2 ) were investigated and proposed using macroscopic and microscopic methods. Obtained results are suggesting inner-sphere and outer-sphere adsorption mechanisms for As(III) and As(V), respectively. This allowed us to identify parameters that are critical for the successful removal of arsenic from water, which is essential information for further optimization of the removal process. The composite was further applied for the removal of As(III) and As(V) from water in a dynamic flow through the reactor. Column study proved that the removal of both arsenic species below the value recommended by WHO can be achieved. Elution of As(III) and As(V) from the composite can be done by using small amounts of 0.01 M NaOH solution resulting in preconcentration of arsenic species and possible multiple usage of composite.

Surface similarity-based molecular query-retrieval

PubMed Central

Singh, Rahul

2007-01-01

Background Discerning the similarity between molecules is a challenging problem in drug discovery as well as in molecular biology. The importance of this problem is due to the fact that the biochemical characteristics of a molecule are closely related to its structure. Therefore molecular similarity is a key notion in investigations targeting exploration of molecular structural space, query-retrieval in molecular databases, and structure-activity modelling. Determining molecular similarity is related to the choice of molecular representation. Currently, representations with high descriptive power and physical relevance like 3D surface-based descriptors are available. Information from such representations is both surface-based and volumetric. However, most techniques for determining molecular similarity tend to focus on idealized 2D graph-based descriptors due to the complexity that accompanies reasoning with more elaborate representations. Results This paper addresses the problem of determining similarity when molecules are described using complex surface-based representations. It proposes an intrinsic, spherical representation that systematically maps points on a molecular surface to points on a standard coordinate system (a sphere). Molecular surface properties such as shape, field strengths, and effects due to field super-positioningcan then be captured as distributions on the surface of the sphere. Surface-based molecular similarity is subsequently determined by computing the similarity of the surface-property distributions using a novel formulation of histogram-intersection. The similarity formulation is not only sensitive to the 3D distribution of the surface properties, but is also highly efficient to compute. Conclusion The proposed method obviates the computationally expensive step of molecular pose-optimisation, can incorporate conformational variations, and facilitates highly efficient determination of similarity by directly comparing molecular surfaces and surface-based properties. Retrieval performance, applications in structure-activity modeling of complex biological properties, and comparisons with existing research and commercial methods demonstrate the validity and effectiveness of the approach. PMID:17634096

Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties.

PubMed

Zhang, Z; Fenter, P; Cheng, L; Sturchio, N C; Bedzyk, M J; Predota, M; Bandura, A; Kubicki, J D; Lvov, S N; Cummings, P T; Chialvo, A A; Ridley, M K; Bénézeth, P; Anovitz, L; Palmer, D A; Machesky, M L; Wesolowski, D J

2004-06-08

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

A two-dimensional phase separation on the spherical surface of the metallic glass Au55Pb22.5Sb22.5

NASA Technical Reports Server (NTRS)

Lee, M. C.; Johnson, W. L.

1982-01-01

Recent experiments indicate that a phase separation in a spherical sample of the metallic glass Au55Pb22.5Sb22.5 occurs near the surface of the sphere. This strongly suggests either a contribution of surface-free energy to the decomposition process or a possible influence of near surface impurities absorbed during synthesis of the sphere. The surface phase separation has been studied as a function of cooling rate of the sphere. At high cooling rates (small sphere sizes), the surface separation disappears altogether suggesting that the surface of the parent liquid droplet is initially homogeneous.

Using snowflake surface-area-to-volume ratio to model and interpret snowfall triple-frequency radar signatures

NASA Astrophysics Data System (ADS)

Gergely, Mathias; Cooper, Steven J.; Garrett, Timothy J.

2017-10-01

The snowflake microstructure determines the microwave scattering properties of individual snowflakes and has a strong impact on snowfall radar signatures. In this study, individual snowflakes are represented by collections of randomly distributed ice spheres where the size and number of the constituent ice spheres are specified by the snowflake mass and surface-area-to-volume ratio (SAV) and the bounding volume of each ice sphere collection is given by the snowflake maximum dimension. Radar backscatter cross sections for the ice sphere collections are calculated at X-, Ku-, Ka-, and W-band frequencies and then used to model triple-frequency radar signatures for exponential snowflake size distributions (SSDs). Additionally, snowflake complexity values obtained from high-resolution multi-view snowflake images are used as an indicator of snowflake SAV to derive snowfall triple-frequency radar signatures. The modeled snowfall triple-frequency radar signatures cover a wide range of triple-frequency signatures that were previously determined from radar reflectivity measurements and illustrate characteristic differences related to snow type, quantified through snowflake SAV, and snowflake size. The results show high sensitivity to snowflake SAV and SSD maximum size but are generally less affected by uncertainties in the parameterization of snowflake mass, indicating the importance of snowflake SAV for the interpretation of snowfall triple-frequency radar signatures.

Procedure for measuring simultaneously the solar and visible properties of glazing with complex internal or external structures.

PubMed

Gentle, A R; Smith, G B

2014-10-20

Accurate solar and visual transmittances of materials in which surfaces or internal structures are complex are often not easily amenable to standard procedures with laboratory-based spectrophotometers and integrating spheres. Localized "hot spots" of intensity are common in such materials, so data on small samples is unreliable. A novel device and simple protocols have been developed and undergone validation testing. Simultaneous solar and visible transmittance and reflectance data have been acquired for skylight components and multilayer polycarbonate roof panels. The pyranometer and lux sensor setups also directly yield "light coolness" in lumens/watt. Sample areas must be large, and, although mainly in sheet form, some testing has been done on curved panels. The instrument, its operation, and the simple calculations used are described. Results on a subset of diffuse and partially diffuse materials with no hot spots have been cross checked using 150 mm integrating spheres with a spectrophotometer and the Air Mass 1.5 spectrum. Indications are that results are as good or better than with such spheres for transmittance, but reflectance techniques need refinement for some sample types.

Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

PubMed Central

Behenna, Douglas C.; Mohr, Justin T.; Sherden, Nathaniel H.; Marinescu, Smaranda C.; Harned, Andrew M.; Tani, Kousuke; Seto, Masaki; Ma, Sandy; Novák, Zoltán; Krout, Michael R.; McFadden, Ryan M.; Roizen, Jennifer L.; Enquist, John A.; White, David E.; Levine, Samantha R.; Petrova, Krastina V.; Iwashita, Akihiko; Virgil, Scott C.; Stoltz, Brian M.

2012-01-01

α-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursors: enol carbonates, enol silanes, and racemic β-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center. PMID:22083969

Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate.

PubMed

Su, Chunming; Puls, Robert W

2004-05-01

Recent studies have shown that zerovalent iron (Fe0) may potentially be used as a chemical medium in permeable reactive barriers (PRBs) for groundwater nitrate remediation; however, the effects of commonly found organic and inorganic ligands in soil and sediments on nitrate reduction by Fe0 have not been well understood. A 25.0 mL nitrate solution of 20.0 mg of N L(-1) (1.43 mM nitrate) was reacted with 1.00 g of Peerless Fe0 at 200 rpm on a rotational shaker at 23 degrees C for up to 120 h in the presence of each of the organic acids (3.0 mM formic, 1.5 mM oxalic, and 1.0 mM citric acids) and inorganic acids (3.0 mM HCl, 1.5 mM H2SO4, 3.0 mM H3BO3, and 1.5 mM H3PO4). These acids provided an initial dissociable H+ concentration of 3.0 mM available for nitrate reduction reactions under conditions of final pH < 9.3. Nitrate reduction rates (pseudo-first-order) increased in the order: H3PO4 < citric acid < H3BO3 < oxalic acid < H2SO4 < formic acid < HCl, ranging from 0.00278 to 0.0913 h(-1), corresponding to surface area normalized rates ranging from 0.126 to 4.15 h(-1) m(-2) mL. Correlation analysis showed a negative linear relationship between the nitrate reduction rates for the ligands and the conditional stability constants for the soluble complexes of the ligands with Fe2+ (R2 = 0.701) or Fe3+ (R2 = 0.918) ions. This sequence of reactivity corresponds also to surface adsorption and complexation of the three organic ligands to iron oxides, which increase in the order formate < oxalate < citrate. The results are also consistent with the sequence of strength of surface complexation of the inorganic ligands to iron oxides, which increases in the order: chloride < sulfate < borate < phosphate. The blockage of reactive sites on the surface of Fe0 and its corrosion products by specific adsorption of the inner-sphere complex forming ligands (oxalate, citrate, sulfate, borate, and phosphate) may be responsible for the decreased nitrate reduction by Fe0 relative to the chloride system.

Demixing, surface nematization, and competing adsorption in binary mixtures of hard rods and hard spheres under confinement

NASA Astrophysics Data System (ADS)

Wu, Liang; Malijevský, Alexandr; Avendaño, Carlos; Müller, Erich A.; Jackson, George

2018-04-01

A molecular simulation study of binary mixtures of hard spherocylinders (HSCs) and hard spheres (HSs) confined between two structureless hard walls is presented. The principal aim of the work is to understand the effect of the presence of hard spheres on the entropically driven surface nematization of hard rod-like particles at surfaces. The mixtures are studied using a constant normal-pressure Monte Carlo algorithm. The surface adsorption at different compositions is examined in detail. At moderate hard-sphere concentrations, preferential adsorption of the spheres at the wall is found. However, at moderate to high pressure (density), we observe a crossover in the adsorption behavior with nematic layers of the rods forming at the walls leading to local demixing of the system. The presence of the spherical particles is seen to destabilize the surface nematization of the rods, and the degree of demixing increases on increasing the hard-sphere concentration.

Synthesis and enhanced humidity detection response of nanoscale Au-particle-decorated ZnS spheres

PubMed Central

2014-01-01

We successfully prepared Au-nanoparticle-decorated ZnS (ZnS-Au) spheres by sputtering Au ultrathin films on surfaces of hydrothermally synthesized ZnS spheres and subsequently postannealed the samples in a high-vacuum atmosphere. The Au nanoparticles were distributed on ZnS surfaces without substantial aggregation. The Au nanoparticle diameter range was 5 to 10 nm. Structural information showed that the surface of the annealed ZnS-Au spheres became more irregular and rough. A humidity sensor constructed using the Au-nanoparticle-decorated ZnS spheres demonstrated a substantially improved response to the cyclic change in humidity from 11% relative humidity (RH) to 33% to 95% RH at room temperature. The improved response was associated with the enhanced efficiency of water molecule adsorption onto the surfaces of the ZnS because of the surface modification of the ZnS spheres through noble-metal nanoparticle decoration. PMID:25520595

Demixing, surface nematization, and competing adsorption in binary mixtures of hard rods and hard spheres under confinement.

PubMed

Wu, Liang; Malijevský, Alexandr; Avendaño, Carlos; Müller, Erich A; Jackson, George

2018-04-28

A molecular simulation study of binary mixtures of hard spherocylinders (HSCs) and hard spheres (HSs) confined between two structureless hard walls is presented. The principal aim of the work is to understand the effect of the presence of hard spheres on the entropically driven surface nematization of hard rod-like particles at surfaces. The mixtures are studied using a constant normal-pressure Monte Carlo algorithm. The surface adsorption at different compositions is examined in detail. At moderate hard-sphere concentrations, preferential adsorption of the spheres at the wall is found. However, at moderate to high pressure (density), we observe a crossover in the adsorption behavior with nematic layers of the rods forming at the walls leading to local demixing of the system. The presence of the spherical particles is seen to destabilize the surface nematization of the rods, and the degree of demixing increases on increasing the hard-sphere concentration.

Nanoscale Hollow Spheres: Microemulsion-Based Synthesis, Structural Characterization and Container-Type Functionality

PubMed Central

Gröger, Henriette; Kind, Christian; Leidinger, Peter; Roming, Marcus; Feldmann, Claus

2010-01-01

A wide variety of nanoscale hollow spheres can be obtained via a microemulsion approach. This includes oxides (e.g., ZnO, TiO2, SnO2, AlO(OH), La(OH)3), sulfides (e.g., Cu2S, CuS) as well as elemental metals (e.g., Ag, Au). All hollow spheres are realized with outer diameters of 10−60 nm, an inner cavity size of 2−30 nm and a wall thickness of 2−15 nm. The microemulsion approach allows modification of the composition of the hollow spheres, fine-tuning their diameter and encapsulation of various ingredients inside the resulting “nanocontainers”. This review summarizes the experimental conditions of synthesis and compares them to other methods of preparing hollow spheres. Moreover, the structural characterization and selected properties of the as-prepared hollow spheres are discussed. The latter is especially focused on container-functionalities with the encapsulation of inorganic salts (e.g., KSCN, K2S2O8, KF), biomolecules/bioactive molecules (e.g., phenylalanine, quercetin, nicotinic acid) and fluorescent dyes (e.g., rhodamine, riboflavin) as representative examples. PMID:28883333

Coordinate measuring machine test standard apparatus and method

DOEpatents

Bieg, L.F.

1994-08-30

A coordinate measuring machine test standard apparatus and method are disclosed which includes a rotary spindle having an upper phase plate and an axis of rotation, a kinematic ball mount attached to the phase plate concentric with the axis of rotation of the phase plate, a groove mounted at the circumference of the phase plate, and an arm assembly which rests in the groove. The arm assembly has a small sphere at one end and a large sphere at the other end. The small sphere may be a coordinate measuring machine probe tip and may have variable diameters. The large sphere is secured in the kinematic ball mount and the arm is held in the groove. The kinematic ball mount includes at least three mounting spheres and the groove is an angular locating groove including at least two locking spheres. The arm may have a hollow inner core and an outer layer. The rotary spindle may be a ratio reducer. The device is used to evaluate the measuring performance of a coordinate measuring machine for periodic recertification, including 2 and 3 dimensional accuracy, squareness, straightness, and angular accuracy. 5 figs.

Coordinate measuring machine test standard apparatus and method

DOEpatents

Bieg, Lothar F.

1994-08-30

A coordinate measuring machine test standard apparatus and method which iudes a rotary spindle having an upper phase plate and an axis of rotation, a kinematic ball mount attached to the phase plate concentric with the axis of rotation of the phase plate, a groove mounted at the circumference of the phase plate, and an arm assembly which rests in the groove. The arm assembly has a small sphere at one end and a large sphere at the other end. The small sphere may be a coordinate measuring machine probe tip and may have variable diameters. The large sphere is secured in the kinematic ball mount and the arm is held in the groove. The kinematic ball mount includes at least three mounting spheres and the groove is an angular locating groove including at least two locking spheres. The arm may have a hollow inner core and an outer layer. The rotary spindle may be a ratio reducer. The device is used to evaluate the measuring performance of a coordinate measuring machine for periodic recertification, including 2 and 3 dimensional accuracy, squareness, straightness, and angular accuracy.

Ab Initio Metadynamics Study of the VO2+/VO2+ Redox Reaction Mechanism at the Graphite Edge/Water Interface.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2018-06-20

Redox flow batteries (RFBs) are promising electrochemical energy storage systems, for which development is impeded by a poor understanding of redox reactions occurring at electrode/electrolyte interfaces. Even for the conventional all-vanadium RFB chemistry employing V 2+ /V 3+ and VO 2 + /VO 2+ couples, there is still no consensus about the reaction mechanism, electrode active sites, and rate-determining step. Herein, we perform Car-Parrinello molecular dynamics-based metadynamics simulations to unravel the mechanism of the VO 2 + /VO 2+ redox reaction in water at the oxygen-functionalized graphite (112̅0) edge surface serving as a representative carbon-based electrode. Our results suggest that during the battery discharge aqueous VO 2 + /VO 2+ species adsorb at the surface C-O groups as inner-sphere complexes, exhibiting faster adsorption/desorption kinetics than V 2+ /V 3+ , at least at low vanadium concentrations considered in our study. We find that this is because (i) VO 2 + /VO 2+ conversion does not involve the slow transfer of an oxygen atom, (ii) protonation of VO 2 + is spontaneous and coupled to interfacial electron transfer in acidic conditions to enable VO 2+ formation, and (iii) V 3+ found to be strongly bound to oxygen groups of the graphite surface features unfavorable desorption kinetics. In contrast, the reverse process taking place upon charging is expected to be more sluggish for the VO 2 + /VO 2+ redox couple because of both unfavorable deprotonation of the VO 2+ water ligands and adsorption/desorption kinetics.

Performance of magnetic zirconium-iron oxide nanoparticle in the removal of phosphate from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Chang; Li, Yongqiu; Wang, Fenghua; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Ma, Chi; Li, Zihao; Xu, ZiYi; Zeng, Guangming

2017-02-01

In this study, magnetic zirconium-iron oxide nanoparticles (MZION) of different Fe/Zr molar ratios were successfully prepared using the co-precipitation method, and their performance for phosphate removal was systematically evaluated. The as-obtained adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Zeta potential analyzer, Fourier transform infrared spectroscopy (FT-IR) and Brunauer Emmett Teller (BET) specific surface area analysis. The effects of pH, ionic strength, and co-existing ions (including Cl-, SO42-, NO3- and HCO3-) were measured to evaluate the adsorption performance in batch experiments. The results showed that decreasing the Fe/Zr molar ratios increased the specific surface area that was propitious to adsorption process, but the adsorption capacity enhanced with the decrease of Fe/Zr molar ratios. Phosphate adsorption on MZION could be well described by the Freundlich equilibrium model and pseudo-second-order kinetics. The adsorption of phosphate was highly pH dependent and decreased with increasing pH from 1.5 to 10.0. The adsorption was slightly affected by ionic strength. With the exception of HCO3-, co-existing anions showed minimum or no effect on their adsorption performance. After adsorption, phosphate on these MZION could be easily desorbed by 0.1 M NaOH solution. The phosphate adsorption mechanism of MZION followed the inner-sphere complexing mechanism, and the surface sbnd OH groups played a significant role in the phosphate adsorption. Additionally, the main advantages of MZION consisted in its separation convenience and highly adsorption capacity compared to other adsorbents.

Pb(II), Cr(VI) and atrazine sorption behavior on sludge-derived biochar: role of humic acids.

PubMed

Zhou, Fengsa; Wang, Hong; Fang, Sheng'en; Zhang, Weihua; Qiu, Rongliang

2015-10-01

Pyrolyzing municipal wastewater treatment sludge into biochar can be a promising sludge disposal approach, especially as the produced sludge-derived biochar (SDBC) is found to be an excellent sorbent for heavy metals and atrazine. The aim of this study was to investigate how and why the coexisting humic acids influence the sorption capacity, kinetic, and binding of these contaminants on SDBC surface. Results showed humic acids enhanced Pb(II)/Cr(VI) sorption binding, and increased the corresponding Pb(II) Langmuir sorption capacity at pH 5.0 from 197 to 233 μmol g(-1), and from 688 to 738 μmol g(-1) for Cr(VI) at pH 2.0. It can be mainly attributed to the sorbed humic acids, whose active functional groups can offer the additional sites to form stronger inner-sphere complexes with Pb(2+), and supply more reducing agent to facilitate the transformation of Cr(VI) to Cr(III). However, humic acids reduced the atrazine adsorption Freundlich constant from 1.085 to 0.616 μmol g(-1). The pore blockage, confirmed by the decreased BET-specific surface area, as well as the more hydrophilic surface with more sorbed water molecules may be the main reasons for that suppression. Therefore, the coexisting humic acids may affect heavy metal stabilization or pesticide immobilization during SDBC application to contaminated water or soils, and its role thus should be considered especially when organic residues are also added significantly to increase the humic acid content there.

Equilibrium location for spherical DNA and toroidal cyclodextrin

NASA Astrophysics Data System (ADS)

Sarapat, Pakhapoom; Baowan, Duangkamon; Hill, James M.

2018-05-01

Cyclodextrin comprises a ring structure composed of glucose molecules with an ability to form complexes of certain substances within its central cavity. The compound can be utilised for various applications including food, textiles, cosmetics, pharmaceutics, and gene delivery. In gene transfer, the possibility of forming complexes depends upon the interaction energy between cyclodextrin and DNA molecules which here are modelled as a torus and a sphere, respectively. Our proposed model is derived using the continuum approximation together with the Lennard-Jones potential, and the total interaction energy is obtained by integrating over both the spherical and toroidal surfaces. The results suggest that the DNA prefers to be symmetrically situated about 1.2 Å above the centre of the cyclodextrin to minimise its energy. Furthermore, an optimal configuration can be determined for any given size of torus and sphere.

Spectroscopic study on the role of TiO{sub 2} in the adsorption of Eu(III) and U(VI) on silica surfaces in aqueous solutions

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

Im, Hee-Jung, E-mail: imhj@kaeri.re.kr; Park, Kyoung Kyun; Jung, Euo Chang

2014-10-15

Highlights: • Enhanced adsorption of Eu(III) and U(VI) onto TiO{sub 2}-coated silica. • Enhanced Eu(III) luminescence and lifetime on TiO{sub 2}-coated silica. • Energy transfer from TiO{sub 2} of TiO{sub 2}-coated silica to Eu(III) in solutions. - Abstract: To determine the effects of TiO{sub 2} on the adsorption of actinides onto mineral surfaces in groundwater, silica was partially coated with TiO{sub 2}, and Eu(III) and U(VI) were individually adsorbed from separate 0.1 mM concentration solutions. The TiO{sub 2}-coated silica showed higher Eu(III) and U(VI) adsorption capacities for increasing amounts of TiO{sub 2} coated on the silica surfaces, and thus themore » existence of TiO{sub 2} can decrease the mobility of Eu(III) and U(VI) contaminants. In luminescence studies, it was found that TiO{sub 2} considerably enhanced the luminescence of the adsorbed Eu(III) indicating that TiO{sub 2}–Eu(III) forms surface complexes which may decrease the number of water molecules at the inner sphere of Eu(III), but this was not observed for U(VI). An energy transfer from the TiO{sub 2} to the Eu(III) was confirmed in this case of amorphous TiO{sub 2}-coated silica in Eu(III) solutions, and an increase of the luminescence lifetime of Eu(III) for increasing concentrations of coated TiO{sub 2} was also observed.« less

Diagnosis of a Poorly Performing Liquid Hydrogen Bulk Storage Sphere

NASA Technical Reports Server (NTRS)

Krenn, Angela G.

2011-01-01

There are two 850,000 gallon Liquid Hydrogen (LH2) storage spheres used to support the Space Shuttle Program; one residing at Launch Pad A and the other at Launch Pad B. The LH2 Sphere at Pad B has had a high boiloff rate since being brought into service in the 1960's. The daily commodity loss was estimated to be approximately double that of the Pad A sphere, and well above the minimum required by the sphere's specification. Additionally, after being re-painted in the late 1990's a "cold spot" appeared on the outer sphere which resulted in a poor paint bond, and mold formation. Thermography was used to characterize the area, and the boiloff rate was continually evaluated. All evidence suggested that the high boiloff rate was caused by an excessive heat leak into the inner sphere due to an insulation void in the annulus. Pad B was recently taken out of Space Shuttle program service which provided a unique opportunity to diagnose the sphere's poor performance. The sphere was drained and inerted, and then opened from the annular relief device on the top where a series of boroscoping operations were accomplished. Boroscoping revealed a large Perlite insulation void in the region of the sphere where the cold spot was apparent. Perlite was then trucked in and off-loaded into the annular void region until the annulus was full. The sphere has not yet been brought back into service.

Specific surface area of overlapping spheres in the presence of obstructions

NASA Astrophysics Data System (ADS)

Jenkins, D. R.

2013-02-01

This study considers the random placement of uniform sized spheres, which may overlap, in the presence of another set of randomly placed (hard) spheres, which do not overlap. The overlapping spheres do not intersect the hard spheres. It is shown that the specific surface area of the collection of overlapping spheres is affected by the hard spheres, such that there is a minimum in the specific surface area as a function of the relative size of the two sets of spheres. The occurrence of the minimum is explained in terms of the break-up of pore connectivity. The configuration can be considered to be a simple model of the structure of a porous composite material. In particular, the overlapping particles represent voids while the hard particles represent fillers. Example materials are pervious concrete, metallurgical coke, ice cream, and polymer composites. We also show how the material properties of such composites are affected by the void structure.

Specific surface area of overlapping spheres in the presence of obstructions.

PubMed

Jenkins, D R

2013-02-21

This study considers the random placement of uniform sized spheres, which may overlap, in the presence of another set of randomly placed (hard) spheres, which do not overlap. The overlapping spheres do not intersect the hard spheres. It is shown that the specific surface area of the collection of overlapping spheres is affected by the hard spheres, such that there is a minimum in the specific surface area as a function of the relative size of the two sets of spheres. The occurrence of the minimum is explained in terms of the break-up of pore connectivity. The configuration can be considered to be a simple model of the structure of a porous composite material. In particular, the overlapping particles represent voids while the hard particles represent fillers. Example materials are pervious concrete, metallurgical coke, ice cream, and polymer composites. We also show how the material properties of such composites are affected by the void structure.

Volumes and surface areas of pendular rings

USGS Publications Warehouse

Rose, W.

1958-01-01

A packing of spheres is taken as a suitable model of porous media. The packing may be regular and the sphere size may be uniform, but in general, both should be random. Approximations are developed to give the volumes and surface areas of pendular rings that exist at points of sphere contact. From these, the total free volume and interfacial specific surface area are derived as expressive of the textural character of the packing. It was found that the log-log plot of volumes and surface areas of pendular rings vary linearly with the angle made by the line joining the sphere centers and the line from the center of the largest sphere to the closest edge of the pendular ring. The relationship, moreover, was found not to be very sensitive to variation in the size ratio of the spheres in contact. It also was found that the addition of pendular ring material to various sphere packings results in an unexpected decrease in the surface area of the boundaries that confine the resulting pore space. ?? 1958 The American Institute of Physics.

RESOLVING THE PLANET-HOSTING INNER REGIONS OF THE LkCa 15 DISK

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

Thalmann, C.; Garufi, A.; Quanz, S. P.

2016-09-10

LkCa 15 hosts a pre-transitional disk as well as at least one accreting protoplanet orbiting in its gap. Previous disk observations have focused mainly on the outer disk, which is cleared inward of ∼50 au. The planet candidates, on the other hand, reside at orbital radii around 15 au, where disk observations have been unreliable until recently. Here, we present new J -band imaging polarimetry of LkCa 15 with SPHERE IRDIS, yielding the most accurate and detailed scattered-light images of the disk to date down to the planet-hosting inner regions. We find what appear to be persistent asymmetric structures inmore » the scattering material at the location of the planet candidates, which could be responsible at least for parts of the signals measured with sparse-aperture masking. These images further allow us to trace the gap edge in scattered light at all position angles and search the inner and outer disks for morphological substructure. The outer disk appears smooth with slight azimuthal variations in polarized surface brightness, which may be due to shadowing from the inner disk or a two-peaked polarized phase function. We find that the near-side gap edge revealed by polarimetry matches the sharp crescent seen in previous ADI imaging very well. Finally, the ratio of polarized disk to stellar flux is more than six times larger in the J -band than in the RI bands.« less

The Escherichia coli Lpt transenvelope protein complex for lipopolysaccharide export is assembled via conserved structurally homologous domains.

PubMed

Villa, Riccardo; Martorana, Alessandra M; Okuda, Suguru; Gourlay, Louise J; Nardini, Marco; Sperandeo, Paola; Dehò, Gianni; Bolognesi, Martino; Kahne, Daniel; Polissi, Alessandra

2013-03-01

Lipopolysaccharide is a major glycolipid component in the outer leaflet of the outer membrane (OM), a peculiar permeability barrier of Gram-negative bacteria that prevents many toxic compounds from entering the cell. Lipopolysaccharide transport (Lpt) across the periplasmic space and its assembly at the Escherichia coli cell surface are carried out by a transenvelope complex of seven essential Lpt proteins spanning the inner membrane (LptBCFG), the periplasm (LptA), and the OM (LptDE), which appears to operate as a unique machinery. LptC is an essential inner membrane-anchored protein with a large periplasm-protruding domain. LptC binds the inner membrane LptBFG ABC transporter and interacts with the periplasmic protein LptA. However, its role in lipopolysaccharide transport is unclear. Here we show that LptC lacking the transmembrane region is viable and can bind the LptBFG inner membrane complex; thus, the essential LptC functions are located in the periplasmic domain. In addition, we characterize two previously described inactive single mutations at two conserved glycines (G56V and G153R, respectively) of the LptC periplasmic domain, showing that neither mutant is able to assemble the transenvelope machinery. However, while LptCG56V failed to copurify any Lpt component, LptCG153R was able to interact with the inner membrane protein complex LptBFG. Overall, our data further support the model whereby the bridge connecting the inner and outer membranes would be based on the conserved structurally homologous jellyroll domain shared by five out of the seven Lpt components.

The Escherichia coli Lpt Transenvelope Protein Complex for Lipopolysaccharide Export Is Assembled via Conserved Structurally Homologous Domains

PubMed Central

Villa, Riccardo; Martorana, Alessandra M.; Okuda, Suguru; Gourlay, Louise J.; Nardini, Marco; Sperandeo, Paola; Dehò, Gianni; Bolognesi, Martino; Kahne, Daniel

2013-01-01

Lipopolysaccharide is a major glycolipid component in the outer leaflet of the outer membrane (OM), a peculiar permeability barrier of Gram-negative bacteria that prevents many toxic compounds from entering the cell. Lipopolysaccharide transport (Lpt) across the periplasmic space and its assembly at the Escherichia coli cell surface are carried out by a transenvelope complex of seven essential Lpt proteins spanning the inner membrane (LptBCFG), the periplasm (LptA), and the OM (LptDE), which appears to operate as a unique machinery. LptC is an essential inner membrane-anchored protein with a large periplasm-protruding domain. LptC binds the inner membrane LptBFG ABC transporter and interacts with the periplasmic protein LptA. However, its role in lipopolysaccharide transport is unclear. Here we show that LptC lacking the transmembrane region is viable and can bind the LptBFG inner membrane complex; thus, the essential LptC functions are located in the periplasmic domain. In addition, we characterize two previously described inactive single mutations at two conserved glycines (G56V and G153R, respectively) of the LptC periplasmic domain, showing that neither mutant is able to assemble the transenvelope machinery. However, while LptCG56V failed to copurify any Lpt component, LptCG153R was able to interact with the inner membrane protein complex LptBFG. Overall, our data further support the model whereby the bridge connecting the inner and outer membranes would be based on the conserved structurally homologous jellyroll domain shared by five out of the seven Lpt components. PMID:23292770

Electric-field-induced forces between two surfaces filled with an insulating liquid: the role of adsorbed water

NASA Astrophysics Data System (ADS)

Wang, Yong Jian; Xu, Zuli; Sheng, Ping; Tong, Penger

2014-06-01

A systematic study of the electric-field-induced forces between a solid glass sphere and a flat gold-plated substrate filled with an insulating liquid has been carried out. Using atomic force microscopy, we measure the electrostatic force f(s, V) between the sphere and substrate as a function of the surface separation s and applied voltage V. The measured f(s, V) is found to be well described by an equation for a conducting sphere. Further force measurements for the "wet" porous glass spheres filled with an aqueous solution of urea and the dried porous glass spheres filled with (dry) air suggest that there is a water layer of a few nanometers in thickness adsorbed on the hydrophilic glass surface under ambient conditions. This adsorbed water layer is more conductive than the dielectric core of the glass sphere, making the sphere surface to be at a potential close to that of the cantilever electrode. As a result, the electric field is strongly concentrated in the gap region between the glass sphere and gold-plate substrate and thus their electrostatic attraction is enhanced. This surface conductivity effect is further supported by the thermal gravimetric analysis (TGA) and force response measurements to a time-dependent electric field. The experiment clearly demonstrates that the adsorption of a conductive water layer on a hydrophilic surface plays a dominant role in determining the electrostatic interaction between the dielectric sphere and substrate.

orbis (sphaera), circulus, via, iter, orbita -- on the terminological identification of the essential paradigm change in astronomy by Johannes Kepler. (German Title: orbis (sphaera), circulus, via, iter, orbita} -- zur terminologischen Kennzeichnung des wesentlichsten Paradigmawechsels in der Astronomie durch Johannes Kepler)

NASA Astrophysics Data System (ADS)

Krafft, Fritz

2011-08-01

The use of modern terminology hinders to understand historical astronomical texts and often misleads the reader. Therefore, this study tries to reconstruct the ideas of the way the planets seem to move against the sphere of fixed stars in a non-teleological manner, that means in the original view and with original terms. The study proceeds historically and explains: (1) Aristotle's system of homocentric spheres being hollow spheres of ether turning equally round the earth in the centre of the world, a number of which makes the apparatus of the movement of a planet which produces its apparently unequal motion. (2) Ptolemy's reductionistic system of geometric circles (eccentric deferents, epicycles etc.), which are indeed great circles on non-concentric hollow spheres, whereupon they turn around equally. The space which they take up in all is surrounded by an inner and an outer concentric spherical surface and makes the sphere of the planet. (3) John's of Sacrobosco transferring of the geometric astronomy to the Latin of Middle Ages and the commentators' precision of the Greek-Latin terms. (4) The tradition of the "Theorica planetarum" which makes this geometry physics by allotting every partial moving to a partial material hollow sphere (with spherical surfaces of different centricity) or full sphere of an epicycle (orbes particulares or partialis), a number of which makes the entire sphere of each planet (orbis totalis or totus). - Copernicus also stood within this tradition, except that his entire spheres differ from the earlier ones in size or thickness (because he eliminated the partly very big synodic epicycles and allocated their effect as a mere parallactic one to the yearly moving of the earth) and in the great intervening spaces between each other (a result of measuring the true distances of the planets on the basis of these parallactic effects). (5) Tycho Brahe's refutation of the unchangingness and unpermeableness and therefore solidity of all etherial spheres, what had been the fundamental condition for creating the indirect ways of the planets in all astronomical systems with partial or entire spheres engaging one another. It was particularly Kepler who recognizes that as a result celestial physics requires a complete change. (6) Kepler's replacement of celestial physics. He did not think any more that the apparent (unequal) way of a planet indirectly results from the combination of several equal movements of etherial partial and entire spheres. His planets move their true and real way caused directly by the joint effect of two corporal forces moving the planets both around the sun and to and from it, which latter makes the planet's speed indeed naturally unequal. For this "real way" he coins in late 1604 the specific term "orbita" (the modern "orbit", the German "Bahn". This term then little by little replaced the former non-specific, general description of the apparent or real way (as "via, iter, ambitus, circulus, circuitus" etc.), and Kepler used it increasingly from its introduction (initially frequently joined to a describing definition of this "way") up to the exclusive use in the fifth book of the "Epitome", after this "orbita" had changed its shape from a perfect eccentric circle to an oval and finally an elliptic form. This way Kepler marks the paradigm change of astronomy caused by himself also terminologically.

Image method for induced surface charge from many-body system of dielectric spheres

NASA Astrophysics Data System (ADS)

Qin, Jian; de Pablo, Juan J.; Freed, Karl F.

2016-09-01

Charged dielectric spheres embedded in a dielectric medium provide the simplest model for many-body systems of polarizable ions and charged colloidal particles. We provide a multiple scattering formulation for the total electrostatic energy for such systems and demonstrate that the polarization energy can be rapidly evaluated by an image method that generalizes the image methods for conducting spheres. Individual contributions to the total electrostatic energy are ordered according to the number of polarized surfaces involved, and each additional surface polarization reduces the energy by a factor of (a/R)3ɛ, where a is the sphere radius, R the average inter-sphere separation, and ɛ the relevant dielectric mismatch at the interface. Explicit expressions are provided for both the energy and the forces acting on individual spheres, which can be readily implemented in Monte Carlo and molecular dynamics simulations of polarizable charged spheres, thereby avoiding costly computational techniques that introduce a surface charge distribution that requires numerical solution.

IImage method for induced surface charge from many-body system of dielectric spheres

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

Qin, Jian; de Pablo, Juan J.; Freed, Karl F.

2016-09-28

Charged dielectric spheres embedded in a dielectric medium provide the simplest model for many-body systems of polarizable ions and charged colloidal particles. We provide a multiple scattering formulation for the total electrostatic energy for such systems and demonstrate that the polarization energy can be rapidly evaluated by an image method that generalizes the image methods for conducting spheres. Individual contributions to the total electrostatic energy are ordered according to the number of polarized surfaces involved, and each additional surface polarization reduces the energy by a factor of (a/R)(3) epsilon, where a is the sphere radius, R the average inter-sphere separation,more » and. the relevant dielectric mismatch at the interface. Explicit expressions are provided for both the energy and the forces acting on individual spheres, which can be readily implemented in Monte Carlo and molecular dynamics simulations of polarizable charged spheres, thereby avoiding costly computational techniques that introduce a surface charge distribution that requires numerical solution.« less

GAUGING APPARATUS

DOEpatents

Ruggles, C.A.

1957-08-27

A swinging arm gage designed to measure radial angles, tapering, sloping, or arcuate concave surfaces is described. The principle of the swinging arm gage is that in any spherical system, radii and radial lines established by them pass through the center of the sphere. Thus if an arm be made to pivot at the sphere center, the path of the swinging end can be guided by a can so set as to establish the proper center angle, and dial indicators on the arm can be zeroed on a master object, angular and dimensional manufacturing errors can be determined on a duplicate object. This device makes possible a considerable saving of time in measuring complex arcuate contours.

Actinide geochemistry: from the molecular level to the real system.

PubMed

Geckeis, Horst; Rabung, Thomas

2008-12-12

Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid-liquid interface reactions to obtain molecular level speciation insight. We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto gamma-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S-O-An(III)(OH)x(2-x)(H2O)5-x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions. The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide-colloid interaction. Kinetic stabilization of colloid bound actinides can be due to inclusion into inorganic colloid matrix or by macromolecular rearrangement in case of organic, humic/fulvic like colloids. Only a combination of spectroscopy, microscopy and classical batch sorption experiments can help to elucidate the actinide-colloid interaction mechanisms and thus contribute to the assessment of colloids for radionuclide migration.

A molecularly based theory for electron transfer reorganization energy.

PubMed

Zhuang, Bilin; Wang, Zhen-Gang

2015-12-14

Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule's permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory.

Characterization of the Inner Disk around HD 141569 A from Keck/NIRC2 L-Band Vortex Coronagraphy

NASA Astrophysics Data System (ADS)

Mawet, Dimitri; Choquet, Élodie; Absil, Olivier; Huby, Elsa; Bottom, Michael; Serabyn, Eugene; Femenia, Bruno; Lebreton, Jérémy; Matthews, Keith; Gomez Gonzalez, Carlos A.; Wertz, Olivier; Carlomagno, Brunella; Christiaens, Valentin; Defrère, Denis; Delacroix, Christian; Forsberg, Pontus; Habraken, Serge; Jolivet, Aissa; Karlsson, Mikael; Milli, Julien; Pinte, Christophe; Piron, Pierre; Reggiani, Maddalena; Surdej, Jean; Vargas Catalan, Ernesto

2017-01-01

HD 141569 A is a pre-main sequence B9.5 Ve star surrounded by a prominent and complex circumstellar disk, likely still in a transition stage from protoplanetary to debris disk phase. Here, we present a new image of the third inner disk component of HD 141569 A made in the L‧ band (3.8 μm) during the commissioning of the vector vortex coronagraph that has recently been installed in the near-infrared imager and spectrograph NIRC2 behind the W.M. Keck Observatory Keck II adaptive optics system. We used reference point-spread function subtraction, which reveals the innermost disk component from the inner working distance of ≃23 au and up to ≃70 au. The spatial scale of our detection roughly corresponds to the optical and near-infrared scattered light, thermal Q, N, and 8.6 μm PAH emission reported earlier. We also see an outward progression in dust location from the L‧ band to the H band (Very Large Telescope/SPHERE image) to the visible (Hubble Space Telescope (HST)/STIS image), which is likely indicative of dust blowout. The warm disk component is nested deep inside the two outer belts imaged by HST-NICMOS in 1999 (at 406 and 245 au, respectively). We fit our new L‧-band image and spectral energy distribution of HD 141569 A with the radiative transfer code MCFOST. Our best-fit models favor pure olivine grains and are consistent with the composition of the outer belts. While our image shows a putative very faint point-like clump or source embedded in the inner disk, we did not detect any true companion within the gap between the inner disk and the first outer ring, at a sensitivity of a few Jupiter masses.

Simulations of Solar Wind Turbulence

NASA Technical Reports Server (NTRS)

Goldstein, Melvyn L.; Usmanov, A. V.; Roberts, D. A.

2008-01-01

Recently we have restructured our approach to simulating magnetohydrodynamic (MHD) turbulence in the solar wind. Previously, we had defined a 'virtual' heliosphere that contained, for example, a tilted rotating current sheet, microstreams, quasi-two-dimensional fluctuations as well as Alfven waves. In this new version of the code, we use the global, time-stationary, WKB Alfven wave-driven solar wind model developed by Usmanov and described in Usmanov and Goldstein [2003] to define the initial state of the system. Consequently, current sheets, and fast and slow streams are computed self-consistently from an inner, photospheric, boundary. To this steady-state configuration, we add fluctuations close to, but above, the surface where the flow become super-Alfvenic. The time-dependent MHD equations are then solved using a semi-discrete third-order Central Weighted Essentially Non-Oscillatory (CWENO) numerical scheme. The computational domain now includes the entire sphere; the geometrical singularity at the poles is removed using the multiple grid approach described in Usmanov [1996]. Wave packets are introduced at the inner boundary such as to satisfy Faraday's Law [Yeh and Dryer, 1985] and their nonlinear evolution are followed in time.

Superspace models for S-3

NASA Astrophysics Data System (ADS)

McKeon, D. G. C.

2003-11-01

The simplest supersymmetric extension of the group SO(4) is discussed. The superalgebra is realized in a superspace whose Bosonic subspace is the surface of a sphere S-3 embedded in four-dimensional Euclidean space. By using Fermionic coordinates in this superspace, which are chiral symplectic Majorana spinors, it proves possible to devise superfield models involving a complex scalar, a pair of chiral symplectic Majorana spinors, and a complex auxiliary scalar. Kinetic terms involve operators that are isometry generators on S-3.

[Stabilization of Cadmium Contaminated Soils by Ferric Ion Modified Attapulgite (Fe/ATP)--Characterizations and Stabilization Mechanism].

PubMed

Rong, Yang; Li, Rong-bo; Zhou, Yong-li; Chen, Jing; Wang, Lin-ling; Lu, Xiao-hua

2015-08-01

Ferric ion modified attapulgite (Fe/ATP) was prepared by impregnation and its structure and morphology were characterized. The toxicity characteristic leaching procedure (TCLP) was used to evaluate the effect of Cadmium( Cd) stabilization in soil with the addition of attapulgite (ATP) and Fe/ATP. The stabilization mechanism of Cd was further elucidated by comparing the morphologies and structure of ATP and Fe/ATP before and after Cd adsorption. Fe/ATP exhibited much better adsorption capacity than ATP, suggesting different adsorption mechanisms occurred between ATP and Fe/ATP. The leaching concentrations of Cd in soil decreased by 45% and 91% respectively, with the addition of wt. 20% ATP and Fe/ATP. The former was attributed to the interaction between Cd2 and --OH groups by chemical binding to form inner-sphere complexes in ATP and the attachment between Cd2+ and the defect sites in ATP framework. Whereas Cd stabilization with Fe/ATP was resulted from the fact that the active centers (--OH bonds or O- sites) on ATP could react with Fe3+ giving Fe--O--Cd-- bridges, which helped stabilize Cd in surface soil. What'more, the ferric oxides and metal hydroxides on the surface of ATP could interact with Cd, probably by the formation of cadmium ferrite. In conclusion, Fe/ATP, which can be easily prepared, holds promise as a potential low-cost and environmental friendly stabilizing agent for remediation of soil contaminated with heavy metals.

Macroscopic and Microscopic Investigation of U(VI) and Eu(III) Adsorption on Carbonaceous Nanofibers.

PubMed

Sun, Yubing; Wu, Zhen-Yu; Wang, Xiangxue; Ding, Congcong; Cheng, Wencai; Yu, Shu-Hong; Wang, Xiangke

2016-04-19

The adsorption mechanism of U(VI) and Eu(III) on carbonaceous nanofibers (CNFs) was investigated using batch, IR, XPS, XANES, and EXAFS techniques. The pH-dependent adsorption indicated that the adsorption of U(VI) on the CNFs was significantly higher than the adsorption of Eu(III) at pH < 7.0. The maximum adsorption capacity of the CNFs calculated from the Langmuir model at pH 4.5 and 298 K for U(VI) and Eu(III) were 125 and 91 mg/g, respectively. The CNFs displayed good recyclability and recoverability by regeneration experiments. Based on XPS and XANES analyses, the enrichment of U(VI) and Eu(III) was attributed to the abundant adsorption sites (e.g., -OH and -COOH groups) of the CNFs. IR analysis further demonstrated that -COOH groups were more responsible for U(VI) adsorption. In addition, the remarkable reducing agents of the R-CH2OH groups were responsible for the highly efficient adsorption of U(VI) on the CNFs. The adsorption mechanism of U(VI) on the CNFs at pH 4.5 was shifted from inner- to outer-sphere surface complexation with increasing initial concentration, whereas the surface (co)precipitate (i.e., schoepite) was observed at pH 7.0 by EXAFS spectra. The findings presented herein play an important role in the removal of radionuclides on inexpensive and available carbon-based nanoparticles in environmental cleanup applications.

Novel synergistic hydrous iron-nickel-manganese (HINM) trimetal oxide for hazardous arsenite removal.

PubMed

Nasir, A M; Goh, P S; Ismail, A F

2018-06-01

A novel hydrous iron-nickel-manganese (HINM) trimetal oxide was successfully fabricated using oxidation and coprecipitation method for metalloid arsenite removal. The atomic ratio of Fe:Ni:Mn for this adsorbent is 3:2:1. HINM adsorbent was identified as an amorphous nanosized adsorbent with particle size ranged from 30 nm to 60 nm meanwhile the total active surface area and pore diameter of HINM area of 195.78 m 2 /g and 2.43 nm, respectively. Experimental data of arsenite adsorption is best fitted into pseudo-second order and Freundlich isotherm model. The maximum adsorption capacity of arsenite onto HINM was 81.9 mg/g. Thermodynamic study showed that the adsorption of arsenite was a spontaneous and endothermic reaction with enthalpy change of 14.04 kJ/mol and Gibbs energy of -12 to -14 kJ/mol. Zeta potential, thermal gravimetric (TGA) and Fourier transform infrared (FTIR) analysis were applied to elucidate the mechanism of arsenite adsorption by HINM. Mechanism of arsenite adsorption by HINM involved both chemisorption and physisorption based on the electrostatic attraction between arsenite ions and surface charge of HINM. It also involved the hydroxyl substitution by arsenite ions through the formation of inner-sphere complex. Reusability of HINM trimetal oxide was up to 89% after three cycles of testing implied that HINM trimetal oxide is a promising and practical adsorbent for arsenite. Copyright © 2018 Elsevier Ltd. All rights reserved.

Superparamagnetic magnesium ferrite nanoadsorbent for effective arsenic (III, V) removal and easy magnetic separation.

PubMed

Tang, Wenshu; Su, Yu; Li, Qi; Gao, Shian; Shang, Jian Ku

2013-07-01

By doping a proper amount of Mg(2+) (~10%) into α-Fe2O3 during a solvent thermal process, ultrafine magnesium ferrite (Mg0.27Fe2.50O4) nanocrystallites were successfully synthesized with the assistance of in situ self-formed NaCl "cage" to confine their crystal growth. Their ultrafine size (average size of ~3.7 nm) and relatively low Mg-content conferred on them a superparamagnetic behavior with a high saturation magnetization (32.9 emu/g). The ultrafine Mg0.27Fe2.50O4 nanoadsorbent had a high specific surface area of ~438.2 m(2)/g, and demonstrated a superior arsenic removal performance on both As(III) and As(V) at near neutral pH condition. Its adsorption capacities on As(III) and As(V) were found to be no less than 127.4 mg/g and 83.2 mg/g, respectively. Its arsenic adsorption mechanism was found to follow the inner-sphere complex mechanism, and abundant hydroxyl groups on its surface played the major role in its superior arsenic adsorption performance. It could be easily separated from treated water bodies with magnetic separation, and could be easily regenerated and reused while maintaining a high arsenic removal efficiency. This novel superparamagnetic magnesium ferrite nanoadsorbent may offer a simple single step adsorption treatment option to remove arsenic contamination from water without the pre-/post-treatment requirement for current industrial practice. Copyright © 2013 Elsevier Ltd. All rights reserved.

Ligand-Sensitive But Not Ligand-Diagnostic: Evaluating Cr Valence-to-Core X-ray Emission Spectroscopy as a Probe of Inner-Sphere Coordination

PubMed Central

2015-01-01

This paper explores the strengths and limitations of valence-to-core X-ray emission spectroscopy (V2C XES) as a probe of coordination environments. A library was assembled from spectra obtained for 12 diverse Cr complexes and used to calibrate density functional theory (DFT) calculations of V2C XES band energies. A functional dependence study was undertaken to benchmark predictive accuracy. All 7 functionals tested reproduce experimental V2C XES energies with an accuracy of 0.5 eV. Experimentally calibrated, DFT calculated V2C XES spectra of 90 Cr compounds were used to produce a quantitative spectrochemical series showing the V2C XES band energy ranges for ligands comprising 18 distinct classes. Substantial overlaps are detected in these ranges, which complicates the use of V2C XES to identify ligands in the coordination spheres of unknown Cr compounds. The ligand-dependent origins of V2C intensity are explored for a homologous series of [CrIII(NH3)5X]2+ (X = F, Cl, Br, and I) to rationalize the variable intensity contributions of these ligand classes. PMID:25496512

An analytical method for computing atomic contact areas in biomolecules.

PubMed

Mach, Paul; Koehl, Patrice

2013-01-15

We propose a new analytical method for detecting and computing contacts between atoms in biomolecules. It is based on the alpha shape theory and proceeds in three steps. First, we compute the weighted Delaunay triangulation of the union of spheres representing the molecule. In the second step, the Delaunay complex is filtered to derive the dual complex. Finally, contacts between spheres are collected. In this approach, two atoms i and j are defined to be in contact if their centers are connected by an edge in the dual complex. The contact areas between atom i and its neighbors are computed based on the caps formed by these neighbors on the surface of i; the total area of all these caps is partitioned according to their spherical Laguerre Voronoi diagram on the surface of i. This method is analytical and its implementation in a new program BallContact is fast and robust. We have used BallContact to study contacts in a database of 1551 high resolution protein structures. We show that with this new definition of atomic contacts, we generate realistic representations of the environments of atoms and residues within a protein. In particular, we establish the importance of nonpolar contact areas that complement the information represented by the accessible surface areas. This new method bears similarity to the tessellation methods used to quantify atomic volumes and contacts, with the advantage that it does not require the presence of explicit solvent molecules if the surface of the protein is to be considered. © 2012 Wiley Periodicals, Inc. Copyright © 2012 Wiley Periodicals, Inc.

Stem/progenitor cells derived from the cochlear sensory epithelium give rise to spheres with distinct morphologies and features.

PubMed

Diensthuber, Marc; Oshima, Kazuo; Heller, Stefan

2009-06-01

Nonmammalian vertebrates regenerate lost sensory hair cells by means of asymmetric division of supporting cells. Inner ear or lateral line supporting cells in birds, amphibians, and fish consequently serve as bona fide stem cells resulting in high regenerative capacity of hair cell-bearing organs. Hair cell regeneration does not happen in the mammalian cochlea, but cells with proliferative capacity can be isolated from the neonatal cochlea. These cells have the ability to form clonal floating colonies, so-called spheres, when cultured in nonadherent conditions. We noticed that the sphere population derived from mouse cochlear sensory epithelium cells was heterogeneous, consisting of morphologically distinct sphere types, hereby classified as solid, transitional, and hollow. Cochlear sensory epithelium-derived stem/progenitor cells initially give rise to small solid spheres, which subsequently transition into hollow spheres, a change that is accompanied by epithelial differentiation of the majority of sphere cells. Only solid spheres, and to a lesser extent, transitional spheres, appeared to harbor self-renewing stem cells, whereas hollow spheres could not be consistently propagated. Solid spheres contained significantly more rapidly cycling Pax-2-expressing presumptive otic progenitor cells than hollow spheres. Islet-1, which becomes upregulated in nascent sensory patches, was also more abundant in solid than in hollow spheres. Likewise, hair cell-like cells, characterized by the expression of multiple hair cell markers, differentiated in significantly higher numbers in cell populations derived from solid spheres. We conclude that cochlear sensory epithelium cell populations initially give rise to small solid spheres that have self-renewing capacity before they subsequently convert into hollow spheres, a process that is accompanied by loss of stemness and reduced ability to spontaneously give rise to hair cell-like cells. Solid spheres might, therefore, represent the most suitable sphere type for cell-based assays or animal model transplantation studies aimed at development of cell replacement therapies.

A Quantitative Raman Spectroscopic Signal for Metal–Phosphodiester Interactions in Solution†

PubMed Central

Christian, Eric L.; Anderson, Vernon E.; Carey, Paul R.; Harris, Michael E.

2011-01-01

Accurate identification and quantification of metal ion–phosphodiester interactions are essential for understanding the role of metal ions as determinants of three-dimensional folding of large RNAs and as cofactors in the active sites of both RNA and protein phosphodiesterases. Accomplishing this goal is difficult due to the dynamic and complex mixture of direct and indirect interactions formed with nucleic acids and other phosphodiesters in solution. To address this issue, Raman spectroscopy has been used to measure changes in bond vibrational energies due to metal interactions. However, the contributions of inner-sphere, H-bonding, and electrostatic interactions to the Raman spectrum of phosphoryl oxygens have not been analyzed quantitatively. Here, we report that all three forms of metal ion interaction result in attenuation of the Raman signal for the symmetric vibration of the nonbridging phosphate oxygens (νsPO2−), while only inner-sphere coordination gives rise to an apparent shift of νsPO2− to higher wavenumbers (νsPO2−M) in solution. Formation of νsPO2−M is shown to be both dependent on metal ion identity and an accurate measure of site-specific metal ion binding. In addition, the spectroscopic parameter reflecting the energetic difference between νsPO2− and νsPO2−M (ΔνM) is largely insensitive to changes in phosphodiester structure but strongly dependent on the absolute electronegativity and hardness of the interacting metal ion. Together, these studies provide strong experimental support for the use of νsPO2−M and ΔνM as general spectroscopic features for the quantitative analysis of metal binding affinity and the identification of metal ions associated with phosphodiesters in solution. PMID:20180599

Hemispherical map for the human brain cortex

NASA Astrophysics Data System (ADS)

Tosun, Duygu; Prince, Jerry L.

2001-07-01

Understanding the function of the human brain cortex is a primary goal in human brain mapping. Methods to unfold and flatten the cortical surface for visualization and measurement have been described in previous literature; but comparison across multiple subjects is still difficult because of the lack of a standard mapping technique. We describe a new approach that maps each hemisphere of the cortex to a portion of a sphere in a standard way, making comparison of anatomy and function across different subjects possible. Starting with a three-dimensional magnetic resonance image of the brain, the cortex is segmented and represented as a triangle mesh. Defining a cut around the corpus collosum identifies the left and right hemispheres. Together, the two hemispheres are mapped to the complex plane using a conformal mapping technique. A Mobius transformation, which is conformal, is used to transform the points on the complex plane so that a projective transformation maps each brain hemisphere onto a spherical segment comprising a sphere with a cap removed. We determined the best size of the spherical cap by minimizing the relative area distortion between hemispherical maps and original cortical surfaces. The relative area distortion between the hemispherical maps and the original cortical surfaces for fifteen human brains is analyzed.

Finite Element in Angle Unit Sphere Meshing for Charged Particle Transport.

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

Ortega, Mario Ivan; Drumm, Clifton R.

Finite element in angle formulations of the charged particle transport equation require the discretization of the unit sphere. In Sceptre, a three-dimensional surface mesh of a sphere is transformed into a two-dimensional mesh. Projection of a sphere onto a two-dimensional surface is well studied with map makers spending the last few centuries attempting to create maps that preserve proportion and area. Using these techniques, various meshing schemes for the unit sphere were investigated.

A novel approach for arsenic adsorbents regeneration using MgO.

PubMed

Tresintsi, Sofia; Simeonidis, Konstantinos; Katsikini, Maria; Paloura, Eleni C; Bantsis, Georgios; Mitrakas, Manassis

2014-01-30

An integrated procedure for the regeneration of iron oxy-hydroxide arsenic adsorbents by granulated MgO is proposed in this study. A continuous recirculation configuration, with a NaOH solution flowing sequentially through the saturated adsorbent (leaching step) and the MgO (adsorption step) column beds, was optimized by utilizing the high arsenic adsorption efficiency of MgO at strong alkaline environments. Experimental results indicated that the total amount of leached arsenic was captured by MgO whereas the regenerated iron oxy-hydroxide recovered around 80% of its removal capacity upon reuse. The improved adsorption capacity of MgO for As(V), which is maximized at pH 10, is explained by the intermediate hydration to Mg(OH)2 and the following As(V) oxy-anions adsorption on its surface through the formation of monodentate inner sphere complexes, as it is deduced from the AsK-edge X-ray absorption fine structure (EXAFS) analysis. In addition to the economical-benefits, corresponding tests proved that the solid wastes of this process, namely spent MgO/Mg(OH)2, can be environmentally safely disposed as stable additives in cement products, while the alkaline solution is completely detoxified and can be recycled to the regeneration task. Copyright © 2013 Elsevier B.V. All rights reserved.

Enhancing phosphate adsorption by Mg/Al layered double hydroxide functionalized biochar with different Mg/Al ratios.

PubMed

Li, Ronghua; Wang, Jim J; Zhou, Baoyue; Awasthi, Mukesh Kumar; Ali, Amjad; Zhang, Zengqiang; Gaston, Lewis A; Lahori, Altaf Hussain; Mahar, Amanullah

2016-07-15

Mg/Al ratio plays a significant role for anion adsorption by Mg/Al-layered double hydroxides (Mg/Al-LDHs) modified biochar. In this study, Mg/Al-LDHs biochar with different Mg/Al ratios (2, 3, 4) were prepared by co-precipitation for phosphate removal from aqueous solution. Factors on phosphate adsorption including Mg/Al ratio, pH, and the presence of other inorganic anions were investigated through batch experiments. Increasing Mg/Al ratio in the Mg/Al-LDHs biochar composites generally enhanced phosphate adsorption with Langmuir adsorption maximum calculated at 81.83mg phosphorous (P) per gram of 4:1Mg/Al-LDHs biochar at pH3.0. The adsorption process was best described by the pseudo-second-order kinetic model. Solution pH had greater effects on the phosphate adsorption by Mg/Al LDHs biochar composites with lower Mg/Al ratios. The presence of other inorganic anions decreased the phosphate adsorption efficiency in the order of F(-) > SO4(2-) > NO2(-) >Cl(-). Phosphate adsorption mechanism involves ion exchange, electrostatic attraction and surface inner-sphere complex formation. Overall, Mg/Al-LDHs biochar composites offer a potential alternative of carbon-based adsorbent for phosphate removal from aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Magnesium-binding architectures in RNA crystal structures: validation, binding preferences, classification and motif detection

PubMed Central

Zheng, Heping; Shabalin, Ivan G.; Handing, Katarzyna B.; Bujnicki, Janusz M.; Minor, Wladek

2015-01-01

The ubiquitous presence of magnesium ions in RNA has long been recognized as a key factor governing RNA folding, and is crucial for many diverse functions of RNA molecules. In this work, Mg2+-binding architectures in RNA were systematically studied using a database of RNA crystal structures from the Protein Data Bank (PDB). Due to the abundance of poorly modeled or incorrectly identified Mg2+ ions, the set of all sites was comprehensively validated and filtered to identify a benchmark dataset of 15 334 ‘reliable’ RNA-bound Mg2+ sites. The normalized frequencies by which specific RNA atoms coordinate Mg2+ were derived for both the inner and outer coordination spheres. A hierarchical classification system of Mg2+ sites in RNA structures was designed and applied to the benchmark dataset, yielding a set of 41 types of inner-sphere and 95 types of outer-sphere coordinating patterns. This classification system has also been applied to describe six previously reported Mg2+-binding motifs and detect them in new RNA structures. Investigation of the most populous site types resulted in the identification of seven novel Mg2+-binding motifs, and all RNA structures in the PDB were screened for the presence of these motifs. PMID:25800744

Increasing Helicity to Achieve a Dynamo State on the Three-Meter Model of the Earth's Core

NASA Astrophysics Data System (ADS)

Rojas, R.; Perevalov, A.; Lathrop, D. P.

2017-12-01

Dynamo theory describes the generation of magnetic fields in the flows of conducting fluids, for example, in stars and planetary cores. Spherical Couette flows, which are flows between two concentric and independently rotating spheres, is one of the experimental models for achieving this task in the laboratory. We have performed dynamo state search in our three-meter spherical-Couette model reaching up to Reynolds number near 108 with amplifications of the field between 10-30% but without a self-sustained dynamo magnetic field. A recent numerical work [K. Finke and A. Tilgner. Phys. Rev. E, 86:016310, Jul 2012] suggested that a roughened inner core reduces the threshold for dynamo action. The mean flow would have more poloidal component than the one we are generating with our current smooth sphere setup. With baffles flow would be expelled radially outward on the equatorial plane and returned at the poles, with opposite helicities in the two hemispheres. Baffles welded on our smooth inner sphere are proposed to achieve this task. We are working to perform experiments on a scaled water model of our experimental setup with Reynolds number near 105 to measure the helicity improvements of different baffle designs in support of upcoming Three-Meter modifications. We gratefully acknowledge support from NSF EAR-1417148.

Ceramic Spheres From Cation Exchange Beads

NASA Technical Reports Server (NTRS)

Dynys, F. W.

2003-01-01

Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

Surface complexation of carboxylate adheres Cryptosporidium parvum öocysts to the hematite-water interface

USGS Publications Warehouse

Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

2009-01-01

The interaction of viable Cryptosporidium parvum öocysts at the hematite (α-Fe2O3)−water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed öocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, öocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, öocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

Electrostatic theory of the assembly of PAMAM dendrimers and DNA.

PubMed

Perico, Angelo

2016-05-01

The electrostatic interactions mediated by counterions between a cationic PAMAM dendrimer, modelized as a sphere of radius and cationic surface charge highly increasing with generation, and a DNA, modelized as an anionic elastic line, are analytically calculated in the framework of condensation theory. Under these interactions the DNA is wrapped around the sphere. For excess phosphates relative to dendrimer primary amines, the free energy of the DNA-dendrimer complex displays an absolute minimum when the complex is weakly negatively overcharged. This overcharging opposes gene delivery. For a highly positive dendrimer and a DNA fixed by experimental conditions to a number of phosphates less than the number of dendrimer primary amines, excess amine charges, the dendrimer may at the same time bind stably DNA and interact with negative cell membranes to activate cell transfection in fair agreement with molecular simulations and experiments. © 2016 Wiley Periodicals, Inc.

Spontaneous light emission in complex nanostructures

NASA Astrophysics Data System (ADS)

Blanco, L. A.; García de Abajo, F. J.

2004-05-01

The spontaneous emission of an excited atom surrounded by different materials is studied in the framework of a semiclassical approach, where the transition dipole moment acts as the source of the emission field. The emission in the presence of semiinfinite media, metallic nanorings, spheres, gratings, and other complex geometries is investigated. Strong emission enhancement effects are obtained in some of these geometries associated to the excitation of plasmons (e.g., in nanorings or spheres). Furthermore, the emission is shown to take place only along narrow angular distributions when the atom is located inside a low-index dielectric and near its planar surface, or when metallic nanogratings are employed at certain resonant wave lengths. In particular, axially symmetric gratings made of real silver metal are considered, and both emission rate enhancement and focused far-field emission are achieved simultaneously when the grating is decorated with further nanostructures.

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.

Discrete Surface Evolution and Mesh Deformation for Aircraft Icing Applications

NASA Technical Reports Server (NTRS)

Thompson, David; Tong, Xiaoling; Arnoldus, Qiuhan; Collins, Eric; McLaurin, David; Luke, Edward; Bidwell, Colin S.

2013-01-01

Robust, automated mesh generation for problems with deforming geometries, such as ice accreting on aerodynamic surfaces, remains a challenging problem. Here we describe a technique to deform a discrete surface as it evolves due to the accretion of ice. The surface evolution algorithm is based on a smoothed, face-offsetting approach. We also describe a fast algebraic technique to propagate the computed surface deformations into the surrounding volume mesh while maintaining geometric mesh quality. Preliminary results presented here demonstrate the ecacy of the approach for a sphere with a prescribed accretion rate, a rime ice accretion, and a more complex glaze ice accretion.

The influence of size and charge of chitosan/polyglutamic acid hollow spheres on cellular internalization, viability and blood compatibility.

PubMed

Dash, Biraja C; Réthoré, Gildas; Monaghan, Michael; Fitzgerald, Kathleen; Gallagher, William; Pandit, Abhay

2010-11-01

Polymeric hollow spheres can be tailored as efficient carriers of various therapeutic molecules due to their tunable properties. However, the entry of these synthetic vehicles into cells, their cell viability and blood compatibility depend on their physical and chemical properties e.g. size, surface charge. Herein, we report the effect of size and surface charge on cell viability and cellular internalization behaviour and their effect on various blood components using chitosan/polyglutamic acid hollow spheres as a model system. Negatively charged chitosan/polyglutamic acid hollow spheres of various sizes 100, 300, 500 and 1000 nm were fabricated using a template based method and covalently surface modified using linear polyethylene glycol and methoxyethanol amine to create a gradient of surface charge from negative to neutrally charged spheres respectively. The results here suggest that both size and surface charge have a significant influence on the sphere's behaviour, most prominently on haemolysis, platelet activation, plasma recalcification time, cell viability and internalization over time. Additionally, cellular internalization behaviour and viability was found to vary with different cell types. These results are in agreement with those of inorganic spheres and liposomes, and can serve as guidelines for tailoring polymeric solid spheres for specific desired applications in biological and pharmaceutical fields, including the design of nanometer to submicron-sized delivery vehicles. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer

PubMed Central

Petrenko, Alexander; Stein, Matthias

2017-01-01

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron–sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from Density Functional Theory (DFT) calculations. The distal cubane FeS-cluster has a three-cysteine and one-histidine coordination [Fe4S4](His)(Cys)3 first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and an all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe4S4](Cys)4 case. The fast and efficient electron transfer from the distal iron–sulfur cluster is realized by a fine-tuned protein environment, which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering. PMID:28067774

Ball assisted device for analytical surface sampling

DOEpatents

ElNaggar, Mariam S; Van Berkel, Gary J; Covey, Thomas R

2015-11-03

A system for sampling a surface includes a sampling probe having a housing and a socket, and a rolling sampling sphere within the socket. The housing has a sampling fluid supply conduit and a sampling fluid exhaust conduit. The sampling fluid supply conduit supplies sampling fluid to the sampling sphere. The sampling fluid exhaust conduit has an inlet opening for receiving sampling fluid carried from the surface by the sampling sphere. A surface sampling probe and a method for sampling a surface are also disclosed.

Surface phenomena and the evolution of radiating fluid spheres in general relativity

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

Herrera, L.; Jimenez, J.; Esculpi, M.

1989-10-01

A method used to study the evolution of radiating spheres (Herrera, Jimenez, and Ruggeri) is extended to the case in which surface phenomena are taken into account. The equations have been integrated numerically for a model derived from the Schwarzschild interior solution, bringing out the effects of surface tension on the evolution of the spheres. 17 refs.

Ligand effects on the hydrogenation of biomass-inspired substrates with bifunctional Ru, Ir, and Rh complexes.

PubMed

Jansen, Eveline; Jongbloed, Linda S; Tromp, Dorette S; Lutz, Martin; de Bruin, Bas; Elsevier, Cornelis J

2013-09-01

We herein report on the application and structural investigation of a new set of complexes that contain bidentate N-heterocyclic carbenes (NHCs) and primary amine moieties of the type [M(arene)Cl(L)] [M=Ru, Ir, or Rh; arene=p-cymene or pentamethylcyclopentadienyl; L=1-(2-aminophenyl)-3-(n-alkyl)imidazol-2-ylidine]. These complexes were tested and compared in the hydrogenation of acetophenone with hydrogen. Structural variations in the chelate ring size of the heteroditopic ligand revealed that smaller chelate ring sizes in combination with ring conjugation in the ligand are beneficial for the activity of this type of catalyst, favoring an inner-sphere coordination pathway. Additionally, increasing the steric bulk of the alkyl substituent on the NHC aided the reaction, showing almost no induction period and formation of a more active catalyst for the n-butyl complex relative to complexes with smaller Me and Et substituents. As is common in hydrogenation reactions, the activity of the complexes decreases in the order Ru>Ir>Rh. The application of [Ru(p-cym)Cl(L)]PF6 , which outperforms its reported analogues, has been successfully extended to the hydrogenation of more challenging biomass-inspired substrates. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid

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

Heathman, Colt R.; Grimes, Travis S.; Zalupski, Peter R.

In this study, the coordination behavior and thermodynamic features of complexation of trivalent lanthanides and americium by ethylenediamine- N,N'-di(acetylglycine)- N,N'-diacetic acid (EDDAG-DA) (bisamide-substituted-EDTA) were investigated by potentiometric and spectroscopic techniques. Acid dissociation constants (K a) and complexation constants (β) of lanthanides (except Pm) were determined by potentiometric analysis. Absorption spectroscopy was used to determine stability constants for the binding of trivalent americium and neodymium by EDDAG-DA under similar conditions. The potentiometry revealed 5 discernible protonation constants and 3 distinct metal–ligand complexes (identified as ML –, MHL, and MH 2L +). Time-resolved fluorescence studies of Eu-(EDDAG-DA) solutions (at varying pH) identifiedmore » a constant inner-sphere hydration number of 3, suggesting that glycine functionalities contained in the amide pendant arms are not involved in metal complexation and are protonated under more acidic conditions. The thermodynamic studies identified that f-element coordination by EDDAG-DA is similar to that observed for ethylenediamine- N,N,N',N'-tetraacetic acid (EDTA). However, coordination via two amidic oxygens of EDDAG-DA lowers its trivalent f-element complex stability by roughly 3 orders of magnitude relative to EDTA.« less

Thermodynamic and Spectroscopic Studies of Trivalent f -element Complexation with Ethylenediamine- N,N '-di(acetylglycine)- N,N '-diacetic Acid

DOE PAGES

Heathman, Colt R.; Grimes, Travis S.; Zalupski, Peter R.

2016-03-21

In this study, the coordination behavior and thermodynamic features of complexation of trivalent lanthanides and americium by ethylenediamine- N,N'-di(acetylglycine)- N,N'-diacetic acid (EDDAG-DA) (bisamide-substituted-EDTA) were investigated by potentiometric and spectroscopic techniques. Acid dissociation constants (K a) and complexation constants (β) of lanthanides (except Pm) were determined by potentiometric analysis. Absorption spectroscopy was used to determine stability constants for the binding of trivalent americium and neodymium by EDDAG-DA under similar conditions. The potentiometry revealed 5 discernible protonation constants and 3 distinct metal–ligand complexes (identified as ML –, MHL, and MH 2L +). Time-resolved fluorescence studies of Eu-(EDDAG-DA) solutions (at varying pH) identifiedmore » a constant inner-sphere hydration number of 3, suggesting that glycine functionalities contained in the amide pendant arms are not involved in metal complexation and are protonated under more acidic conditions. The thermodynamic studies identified that f-element coordination by EDDAG-DA is similar to that observed for ethylenediamine- N,N,N',N'-tetraacetic acid (EDTA). However, coordination via two amidic oxygens of EDDAG-DA lowers its trivalent f-element complex stability by roughly 3 orders of magnitude relative to EDTA.« less

Identification of Residues in the Lipopolysaccharide ABC Transporter That Coordinate ATPase Activity with Extractor Function

PubMed Central

Simpson, Brent W.; Owens, Tristan W.; Orabella, Matthew J.; Davis, Rebecca M.; May, Janine M.; Trauger, Sunia A.

2016-01-01

ABSTRACT The surface of most Gram-negative bacteria is covered with lipopolysaccharide (LPS), creating a permeability barrier against toxic molecules, including many antimicrobials. To assemble LPS on their surface, Gram-negative bacteria must extract newly synthesized LPS from the inner membrane, transport it across the aqueous periplasm, and translocate it across the outer membrane. The LptA to -G proteins assemble into a transenvelope complex that transports LPS from the inner membrane to the cell surface. The Lpt system powers LPS transport from the inner membrane by using a poorly characterized ATP-binding cassette system composed of the ATPase LptB and the transmembrane domains LptFG. Here, we characterize a cluster of residues in the groove region of LptB that is important for controlling LPS transport. We also provide the first functional characterization of LptFG and identify their coupling helices that interact with the LptB groove. Substitutions at conserved residues in these coupling helices compromise both the assembly and function of the LptB2FG complex. Defects in LPS transport conferred by alterations in the LptFG coupling helices can be rescued by changing a residue in LptB that is adjacent to functionally important residues in the groove region. This suppression is achieved by increasing the ATPase activity of the LptB2FG complex. Taken together, these data identify a specific binding site in LptB for the coupling helices of LptFG that is responsible for coupling of ATP hydrolysis by LptB with LptFG function to achieve LPS extraction. PMID:27795402

17O nuclear quadrupole coupling constants of water bound to a metal ion: A gadolinium(III) case study

NASA Astrophysics Data System (ADS)

Yazyev, Oleg V.; Helm, Lothar

2006-08-01

Rotational correlation times of metal ion aqua complexes can be determined from O17 NMR relaxation rates if the quadrupole coupling constant of the bound water oxygen-17 nucleus is known. The rotational correlation time is an important parameter for the efficiency of Gd3+ complexes as magnetic resonance imaging contrast agents. Using a combination of density functional theory with classical and Car-Parrinello molecular dynamics simulations we performed a computational study of the O17 quadrupole coupling constants in model aqua ions and the [Gd(DOTA)(H2O)]- complex used in clinical diagnostics. For the inner sphere water molecule in the [Gd(DOTA)(H2O)]- complex the determined quadrupole coupling parameter χ√1+η2/3 of 8.7MHz is very similar to that of the liquid water (9.0MHz ). Very close values were also predicted for the the homoleptic aqua ions of Gd3+ and Ca2+. We conclude that the O17 quadrupole coupling parameters of water molecules coordinated to closed shell and lanthanide metal ions are similar to water molecules in the liquid state.

Lay Definitions of Happiness across Nations: The Primacy of Inner Harmony and Relational Connectedness

PubMed Central

Delle Fave, Antonella; Brdar, Ingrid; Wissing, Marié P.; Araujo, Ulisses; Castro Solano, Alejandro; Freire, Teresa; Hernández-Pozo, María Del Rocío; Jose, Paul; Martos, Tamás; Nafstad, Hilde E.; Nakamura, Jeanne; Singh, Kamlesh; Soosai-Nathan, Lawrence

2016-01-01

In well-being research the term happiness is often used as synonymous with life satisfaction. However, little is known about lay people's understanding of happiness. Building on the available literature, this study explored lay definitions of happiness across nations and cultural dimensions, analyzing their components and relationship with participants' demographic features. Participants were 2799 adults (age range = 30–60, 50% women) living in urban areas of Argentina, Brazil, Croatia, Hungary, India, Italy, Mexico, New Zealand, Norway, Portugal, South Africa, and United States. They completed the Eudaimonic and Hedonic Happiness Investigation (EHHI), reporting, among other information, their own definition of happiness. Answers comprised definitions referring to a broad range of life domains, covering both the contextual-social sphere and the psychological sphere. Across countries and with little variation by age and gender, inner harmony predominated among psychological definitions, and family and social relationships among contextual definitions. Whereas relationships are widely acknowledged as basic happiness components, inner harmony is substantially neglected. Nevertheless, its cross-national primacy, together with relations, is consistent with the view of an ontological interconnectedness characterizing living systems, shared by several conceptual frameworks across disciplines and cultures. At the methodological level, these findings suggest the potential of a bottom-up, mixed method approach to contextualize psychological dimensions within culture and lay understanding. PMID:26858677

Lay Definitions of Happiness across Nations: The Primacy of Inner Harmony and Relational Connectedness.

PubMed

Delle Fave, Antonella; Brdar, Ingrid; Wissing, Marié P; Araujo, Ulisses; Castro Solano, Alejandro; Freire, Teresa; Hernández-Pozo, María Del Rocío; Jose, Paul; Martos, Tamás; Nafstad, Hilde E; Nakamura, Jeanne; Singh, Kamlesh; Soosai-Nathan, Lawrence

2016-01-01

In well-being research the term happiness is often used as synonymous with life satisfaction. However, little is known about lay people's understanding of happiness. Building on the available literature, this study explored lay definitions of happiness across nations and cultural dimensions, analyzing their components and relationship with participants' demographic features. Participants were 2799 adults (age range = 30-60, 50% women) living in urban areas of Argentina, Brazil, Croatia, Hungary, India, Italy, Mexico, New Zealand, Norway, Portugal, South Africa, and United States. They completed the Eudaimonic and Hedonic Happiness Investigation (EHHI), reporting, among other information, their own definition of happiness. Answers comprised definitions referring to a broad range of life domains, covering both the contextual-social sphere and the psychological sphere. Across countries and with little variation by age and gender, inner harmony predominated among psychological definitions, and family and social relationships among contextual definitions. Whereas relationships are widely acknowledged as basic happiness components, inner harmony is substantially neglected. Nevertheless, its cross-national primacy, together with relations, is consistent with the view of an ontological interconnectedness characterizing living systems, shared by several conceptual frameworks across disciplines and cultures. At the methodological level, these findings suggest the potential of a bottom-up, mixed method approach to contextualize psychological dimensions within culture and lay understanding.

Zinc isotope fractionation during adsorption onto Mn oxyhydroxide at low and high ionic strength

NASA Astrophysics Data System (ADS)

Bryan, Allison L.; Dong, Shuofei; Wilkes, Elise B.; Wasylenki, Laura E.

2015-05-01

Marine ferromanganese sediments represent one of the largest sinks from global seawater for Zn, a critical trace metal nutrient. These sediments are variably enriched in heavier isotopes of Zn relative to deep seawater, and some are among the heaviest natural samples analyzed to date. New experimental results demonstrate that adsorption of Zn to poorly crystalline Mn oxyhydroxide results in preferential association of heavier isotopes with the sorbent phase. At low ionic strength our experimental system displayed a short-lived kinetic isotope effect, with light isotopes adsorbed to birnessite (Δ66/64Znadsorbed-dissolved ∼ -0.2‰). After 100 h the sense of fractionation was opposite, such that heavier isotopes were preferentially adsorbed at steady state, but the magnitude of Δ66/64Znadsorbed-dissolved was indistinguishable from zero (+0.05 ± 0.08‰). At high ionic strength, we observed preferential sorption of heavy isotopes, with a strong negative correlation between Δ66/64Znadsorbed-dissolved and the percentage of Zn on the birnessite. Values of Δ66/64Znadsorbed-dissolved ranged from nearly +3‰ at low surface loading to +0.16‰ at high surface loading. Based on previous EXAFS work we infer that Zn adsorbs first as tetrahedral, inner-sphere complexes at low surface loading, with preferential incorporation of heavier isotopes relative to the octahedral Zn species predominating in solution. As surface loading increases, so does the proportion of Zn adsorbing as octahedral complexes, thus diminishing the magnitude of fractionation between the dissolved and adsorbed pools of Zn. The magnitude of fractionation at high ionic strength is also governed by aqueous speciation of Zn in synthetic seawater; a substantial fraction of Zn ions reside in chloro complexes, which preferentially incorporate light Zn isotopes, and this drives the adsorbed pool to be heavier relative to the bulk solution than it was at low ionic strength. Our results explain the observation that ferromanganese sediments are enriched in heavier isotopes of Zn relative to deep seawater. This represents a step towards building a robust mass balance model for Zn isotopes in the oceans and potentially using Zn isotopes to trace biogeochemical cycling of this important element in the modern and ancient oceans.

Partitioning of uranyl between ferrihydrite and humic substances at acidic and circum-neutral pH

NASA Astrophysics Data System (ADS)

Dublet, Gabrielle; Lezama Pacheco, Juan; Bargar, John R.; Fendorf, Scott; Kumar, Naresh; Lowry, Gregory V.; Brown, Gordon E.

2017-10-01

As part of a larger study of the reactivity and mobility of uranyl (U(VI)O22+) cations in subsurface environments containing natural organic matter (NOM) and hydrous ferric oxides, we have examined the effect of reference humic and fulvic substances on the sorption of uranyl on 2-line ferrihydrite (Fh), a common, naturally occurring nano-Fe(III)-hydroxide. Uranyl was reacted with Fh at pH 4.6 and 7.0 in the presence and absence of Elliott Soil Humic Acid (ESHA) (0-835 ppm) or Suwanee River Fulvic Acid (SRFA) (0-955 ppm). No evidence was found for reduction of uranyl by either form of NOM after 24 h of exposure. The following three size fractions were considered in this study: (1) ≥0.2 μm (Fh-NOM aggregates), (2) 0.02-0.2 μm (dispersed Fh nanoparticles and NOM macro-molecules), and (3) <0.02 μm (dissolved). The extent to which U(VI) is sorbed in aggregates or dispersed as colloids was assessed by comparing U, Fe, and NOM concentrations in these three size fractions. Partitioning of uranyl between Fh and NOM was determined in size fraction (1) using X-ray absorption spectroscopy (XAS). Uranyl sorption on Fh-NOM aggregates was affected by the presence of NOM in different ways depending on pH and type of NOM (ESHA vs. SRFA). The presence of ESHA in the uranyl-Fh-NOM ternary system at pH 4.6 enhanced uranyl uptake more than the presence of SRFA. In contrast, neither form of NOM affected uranyl sorption at pH 7.0 over most of the NOM concentration range examined (0-500 ppm); at the highest NOM concentrations (500-955 ppm) uranyl uptake in the aggregates was slightly inhibited at pH 7.0, which is interpreted as being due to the dispersion of Fh aggregates. XAS at the U LIII-edge was used to characterize molecular-level changes in uranyl complexation as a result of sorption to the Fh-NOM aggregates. In the absence of NOM, uranyl formed dominantly inner-sphere, mononuclear, bidentate sorption complexes on Fh. However, when NOM concentration was increased at pH 4.6, the proportion of uranyl-Fh inner-sphere sorption complexes decreased relative to uranyl-ESHA or uranyl-SRFA complexes, which comprised up to ∼60% of the total uranyl in the systems studied. At pH 7.0, uranyl-NOM complexes were also present in the Fh-NOM aggregates in the concentration ranges of ESHA or SRFA considered; however, the proportion of these complexes was smaller at pH 7.0 than at pH 4.6 and did not increase significantly with increasing NOM concentration.

Controlled superficial assembly of DNA-amorphous calcium phosphate nanocomposite spheres for surface-mediated gene delivery.

PubMed

Oyane, Ayako; Araki, Hiroko; Nakamura, Maki; Shimizu, Yoshiki; Shubhra, Quazi T H; Ito, Atsuo; Tsurushima, Hideo

2016-05-01

Surface-mediated gene delivery systems have many potential applications in tissue engineering. We recently fabricated an assembly consisting of DNA-amorphous calcium phosphate (DNA-ACP) nanocomposite spheres on a polymer substrate via coprecipitation in a labile supersaturated calcium phosphate (CaP) solution and demonstrated the assembly's high gene delivery efficacy. In this study, we conducted a detailed investigation of the coprecipitation process in solution and revealed that the negatively charged DNA molecules were immobilized in the ACP spheres during the initial stage of coprecipitation and functioned as both sphere-dispersing and size-regulating agents. As a result, the DNA-ACP nanocomposites grew into size-regulated submicrospheres in solution and assembled onto the substrate via gravity sedimentation. The assembled nanocomposite spheres were chemically anchored to the substrate surface through an intermediate layer of CaP-based nanoparticles that was formed heterogeneously at the substrate surface. The coprecipitation conditions, i.e., coprecipitation time and Ca and P concentrations in solution, greatly affected the state of assembly of the nanocomposite spheres, thereby influencing the gene expression level of the cells cultured on the substrate. Increasing the number density and decreasing the size of the nanocomposite spheres did not always increase the assembly's gene delivery efficacy (per surface area of the substrate) due to adverse effects on cellular viability. As demonstrated herein, controlling the coprecipitation conditions is important for designing a cell-stimulating and biocompatible scaffold surface consisting of an assembly of DNA-ACP nanocomposite spheres. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Interactions between Hofmeister anions and the binding pocket of a protein.

PubMed

Fox, Jerome M; Kang, Kyungtae; Sherman, Woody; Héroux, Annie; Sastry, G Madhavi; Baghbanzadeh, Mostafa; Lockett, Matthew R; Whitesides, George M

2015-03-25

This paper uses the binding pocket of human carbonic anhydrase II (HCAII, EC 4.2.1.1) as a tool to examine the properties of Hofmeister anions that determine (i) where, and how strongly, they associate with concavities on the surfaces of proteins and (ii) how, upon binding, they alter the structure of water within those concavities. Results from X-ray crystallography and isothermal titration calorimetry show that most anions associate with the binding pocket of HCAII by forming inner-sphere ion pairs with the Zn(2+) cofactor. In these ion pairs, the free energy of anion-Zn(2+) association is inversely proportional to the free energetic cost of anion dehydration; this relationship is consistent with the mechanism of ion pair formation suggested by the "law of matching water affinities". Iodide and bromide anions also associate with a hydrophobic declivity in the wall of the binding pocket. Molecular dynamics simulations suggest that anions, upon associating with Zn(2+), trigger rearrangements of water that extend up to 8 Å away from their surfaces. These findings expand the range of interactions previously thought to occur between ions and proteins by suggesting that (i) weakly hydrated anions can bind complementarily shaped hydrophobic declivities, and that (ii) ion-induced rearrangements of water within protein concavities can (in contrast with similar rearrangements in bulk water) extend well beyond the first hydration shells of the ions that trigger them. This study paints a picture of Hofmeister anions as a set of structurally varied ligands that differ in size, shape, and affinity for water and, thus, in their ability to bind to—and to alter the charge and hydration structure of—polar, nonpolar, and topographically complex concavities on the surfaces of proteins.

Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

PubMed

Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

2017-07-01

Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

A novel approach for fabricating NiO hollow spheres for gas sensors

NASA Astrophysics Data System (ADS)

Kuang, Chengwei; Zeng, Wen; Ye, Hong; Li, Yanqiong

2018-03-01

Hollow spheres are usually fabricated by hard template methods or soft template methods with soft surfactants, which is quiet tedious and time-consuming. In this paper, NiO hollow spheres with fluffy surface were successfully synthesized by a facile hydrothermal method and subsequent calcination, where bubbles acted as the template. NiO hollow spheres exhibited excellent gas sensing performances, which results from its hollow structure and high specific surface area. In addition, a possible evolution mechanism of NiO hollow spheres was proposed based on experimental results.

Anti-gravity device

NASA Technical Reports Server (NTRS)

Palsingh, S. (Inventor)

1975-01-01

An educational toy useful in demonstrating fundamental concepts regarding the laws of gravity is described. The device comprises a sphere 10 of radius r resting on top of sphere 12 of radius R. The center of gravity of sphere 10 is displaced from its geometrical center by distance D. The dimensions are so related that D((R+r)/r) is greater than r. With the center of gravity of sphere 10 lying on a vertical line, the device is in equilibrium. When sphere 10 is rolled on the surface of sphere 12 it will return to its equilibrium position upon release. This creates an illusion that sphere 10 is defying the laws of gravity. In reality, due to the above noted relationship of D, R, and r, the center of gravity of sphere 10 rises from its equilibrium position as it rolls a short distance up or down the surface of sphere 12.

Research Of The Influence Of Reftinskii SDPP’S Ash On The Processes Of Cement Stone’S Structure Forming

NASA Astrophysics Data System (ADS)

Zimakova, G. A.; Solonina, V. A.; Zelig, M. P.

2017-01-01

The article describes the experimental research of cement stone. Cement stone forming involves highly dispersive mineral additive - ground ash. It is stated that the substitution of some part of cement with activated ash leaves cement strength high. This is possible due to the activity of ash in structure forming processes. Activation of ash provides the increase in its puzzolanic activity, complete hydration processes. it is stated that ash grinding leads to a selective crystallization hydrated neoformations. Their morthology is different on outer and inner surfaces of ash spheres. The usage of ash can provide cement economy on condition that rheological characteristics of concrete stay constant. Besides, the usage of ash will improve physical and mechanic characteristics of cement stone and concrete.

Multiple rings in the transition disk and companion candidates around RX J1615.3-3255. High contrast imaging with VLT/SPHERE

NASA Astrophysics Data System (ADS)

de Boer, J.; Salter, G.; Benisty, M.; Vigan, A.; Boccaletti, A.; Pinilla, P.; Ginski, C.; Juhasz, A.; Maire, A.-L.; Messina, S.; Desidera, S.; Cheetham, A.; Girard, J. H.; Wahhaj, Z.; Langlois, M.; Bonnefoy, M.; Beuzit, J.-L.; Buenzli, E.; Chauvin, G.; Dominik, C.; Feldt, M.; Gratton, R.; Hagelberg, J.; Isella, A.; Janson, M.; Keller, C. U.; Lagrange, A.-M.; Lannier, J.; Menard, F.; Mesa, D.; Mouillet, D.; Mugrauer, M.; Peretti, S.; Perrot, C.; Sissa, E.; Snik, F.; Vogt, N.; Zurlo, A.; SPHERE Consortium

2016-11-01

Context. The effects of a planet sculpting the disk from which it formed are most likely to be found in disks that are in transition between being classical protoplanetary and debris disks. Recent direct imaging of transition disks has revealed structures such as dust rings, gaps, and spiral arms, but an unambiguous link between these structures and sculpting planets is yet to be found. Aims: We aim to find signs of ongoing planet-disk interaction and study the distribution of small grains at the surface of the transition disk around RX J1615.3-3255 (RX J1615). Methods: We observed RX J1615 with VLT/SPHERE. From these observations, we obtained polarimetric imaging with ZIMPOL (R'-band) and IRDIS (J), and IRDIS (H2H3) dual-band imaging with simultaneous spatially resolved spectra with the IFS (YJ). Results: We image the disk for the first time in scattered light and detect two arcs, two rings, a gap and an inner disk with marginal evidence for an inner cavity. The shapes of the arcs suggest that they are probably segments of full rings. Ellipse fitting for the two rings and inner disk yield a disk inclination I = 47 ± 2° and find semi-major axes of 1.50 ± 0.01'' (278 au), 1.06 ± 0.01'' (196 au) and 0.30 ± 0.01'' (56 au), respectively. We determine the scattering surface height above the midplane, based on the projected ring center offsets. Nine point sources are detected between 2.1'' and 8.0'' separation and considered as companion candidates. With NACO data we recover four of the nine point sources, which we determine to be not co-moving, and therefore unbound to the system. Conclusions: We present the first detection of the transition disk of RX J1615 in scattered light. The height of the rings indicate limited flaring of the disk surface, which enables partial self-shadowing in the disk. The outermost arc either traces the bottom of the disk or it is another ring with semi-major axis ≳ 2.35'' (435 au). We explore both scenarios, extrapolating the complete shape of the feature, which will allow us to distinguish between the two in future observations. The most attractive scenario, where the arc traces the bottom of the outer ring, requires the disk to be truncated at r ≈ 360 au. If the closest companion candidate is indeed orbiting the disk at 540 au, then it would be the most likely cause for such truncation. This companion candidate, as well as the remaining four, all require follow up observations to determine if they are bound to the system. Based on observations made with ESO Telescopes at the La Silla Paranal Observatory under programme IDs 095.C-0298(A), 095.C-0298(B), and 095.C-0693(A) during guaranteed and open time observations of the SPHERE consortium, and on NACO observations: program IDs: 085.C-0012(A), 087.C-0111(A), and 089.C-0133(A). The reduced images as FITS files are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A114

Status of the Scorpion Planet Survey: Establishing the Frequency of HR8799b-Like Planets

NASA Astrophysics Data System (ADS)

Wagner, K. R.; Daniel, A.; Kasper, M.

2017-11-01

Wide-orbit giant planets will likely affect plant formation and habitability of inner planets. In this presentation we will review the existing evidence on the occurrence rates of super-Jupiters and present the status of our VLT/SPHERE survey.

Direct Observation of the BCC (100) Plane in Thin Films of Sphere-forming Diblock Copolymers

NASA Astrophysics Data System (ADS)

Ji, Shengxiang; Nagpal, Umang; Liao, Wen; de Pablo, Juan; Nealey, Paul

2010-03-01

In sphere-forming diblock copolymers, periodic arrays of spheres are arranged in a body-centred cubic (BCC) lattice structure in bulk. However, in thin films different surface morphologies were observed as a function of the film thickness, and the transition from the hexagonal array to the BCC (110) arrangement of spheres on film surfaces was located with respect to the increase of the film thickness. Here we report the first direct observation of the BCC (100) plane in thin films of poly (styrene-b-methyl methacrylate) diblock copolymers on homogeneous substrates. By balancing the surface energies of both blocks, the lower energy BCC (100) plane corresponding to a square arrangement of half spheres, formed on film surfaces when the film thickness was commensurate with the spacing, L100, between (100) planes or greater than 2 L100. A hexagonal arrangement of spheres was only observed when the thickness was less than 2 L100 and incommensurate with 1 L100. Monte Carlo (MC) simulation confirmed our experimental observation and was used to investigate the transition of the arrangement of spheres as a function of the film thickness.

Quantifying Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction.

PubMed

Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh

2018-05-15

We quantify changes in the interfacial pH local to the electrochemical double layer during electrocatalysis, using a concurrent non-faradaic probe reaction. In the absence of electrocatalysis, nanostructured Pt/C surfaces mediate the reaction of H2 with cis-2-butene-1,4-diol to form a mixture of 1,4-butanediol and n-butanol with a selectivity that is linearly dependent on the bulk solution pH. We show that kinetic branching occurs from a common surface-bound intermediate, ensuring that this probe reaction is uniquely sensitive to the interfacial pH within molecular length scales of the surface. We use the pH-dependent selectivity of this reaction to track changes in interfacial pH during concurrent hydrogen oxidation electrocatalysis and find that the local pH can vary dramatically, > 3 units, relative to the bulk value even at modest current densities in well-buffered electrolytes. This work highlights the key role that interfacial pH variation plays in modulating inner-sphere electrocatalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification and onset of inertial modes in the wide-gap spherical Couette system

NASA Astrophysics Data System (ADS)

Barik, A.; Wicht, J.; Triana, S. A.; Hoff, M.

2016-12-01

The spherical Couette system consists of two concentric rotating spheres with a fluid filling the shell in between. The system has been studied for a long time by fluid dynamicists and is ideal for studying flow instabilities due to differential rotation and the interaction of the same with magnetic fields - important for understanding dynamics of planetary and stellar interiors. The system is also a basis for a new generation of dynamo experiments because of its closer geometrical resemblance to real astrophysical objects as compared to past experiments. We simulate this system using the two different pseudo-spectral codes MagIC and XSHELLS. We focus here on a very interesting and general instability in this system - inertial modes. A rotating body of fluid is known to sustain oscillatory waves due to the restoring action of the Coriolis force. In a bounded container, these form a discrete spectrum called inertial modes. These modes have been analytically known for a rotating full sphere for over a century now. In a spherical shell, they cannot be formulated analytically. However, many of these inertial modes are observed in spherical Couette experiments as well as in simulations. Past studies have tried to explain the onset of these modes invoking wave over-reflection or critical layer instabilities on the cylinder tangent to the inner sphere. In this study, we present the inertial modes found in our simulations and try to explain their onset as secondary instabilities due to the destabilization of the fundamental non-axisymmetric instability, forming a triadic resonance with the fundamental instability. We run various simulations varying the rotation rate of the inner sphere, while keeping the rotation rate of the outer sphere constant. We track velocities and induced magnetic field and produce spectrograms similar to those of the experiments. Our results match very well the experimental data from spherical Couette set-ups at BTU Cottbus and the University of Maryland.

Electromagnetic Energy Localization and Characterization of Composites

DTIC Science & Technology

2013-01-01

polyhedrons ), and [39] (spheres and a complex yet symmetric structure). With time-domain EM analysis, regular shapes, such as cubes, spheres, and regular...spheres), [40] (spheres, crosses, cylinders, and polyhedrons ), and [41] (spheres and cylinders); and 3-D random mixtures using a frequency-domain finite...element method [42] ( polyhedrons ), and [43], [44] (spheres). Such steady-state analyses are limited as they, for example, do not capture temporal

Thermodynamic stability in elastic systems: Hard spheres embedded in a finite spherical elastic solid.

PubMed

Solano-Altamirano, J M; Goldman, Saul

2015-12-01

We determined the total system elastic Helmholtz free energy, under the constraints of constant temperature and volume, for systems comprised of one or more perfectly bonded hard spherical inclusions (i.e. "hard spheres") embedded in a finite spherical elastic solid. Dirichlet boundary conditions were applied both at the surface(s) of the hard spheres, and at the outer surface of the elastic solid. The boundary conditions at the surface of the spheres were used to describe the rigid displacements of the spheres, relative to their initial location(s) in the unstressed initial state. These displacements, together with the initial positions, provided the final shape of the strained elastic solid. The boundary conditions at the outer surface of the elastic medium were used to ensure constancy of the system volume. We determined the strain and stress tensors numerically, using a method that combines the Neuber-Papkovich spherical harmonic decomposition, the Schwartz alternating method, and Least-squares for determining the spherical harmonic expansion coefficients. The total system elastic Helmholtz free energy was determined by numerically integrating the elastic Helmholtz free energy density over the volume of the elastic solid, either by a quadrature, or a Monte Carlo method, or both. Depending on the initial position of the hard sphere(s) (or equivalently, the shape of the un-deformed stress-free elastic solid), and the displacements, either stationary or non-stationary Helmholtz free energy minima were found. The non-stationary minima, which involved the hard spheres nearly in contact with one another, corresponded to lower Helmholtz free energies, than did the stationary minima, for which the hard spheres were further away from one another.

Output-increasing, protective cover for a solar cell

DOEpatents

Hammerbacher, Milfred D.

1995-11-21

A flexible cover (14) for a flexible solar cell (12) protects the cell from the ambient and increases the cell's efficiency. The cell(12)includes silicon spheres (16) held in a flexible aluminum sheet matrix (20,22). The cover (14) is a flexible, protective layer (60) of light-transparent material having a relatively flat upper, free surface (64) and an irregular opposed surface (66). The irregular surface (66) includes first portions (68) which conform to the polar regions (31R) of the spheres (16) and second convex (72) or concave (90) portions (72 or 90) which define spaces (78) in conjunction with the reflective surface (20T) of one aluminum sheet (20). Without the cover (14) light (50) falling on the surface (20T) between the spheres (16) is wasted, that is, it does not fall on a sphere (16). The surfaces of the second portions are non-parallel to the direction of the otherwise wasted light (50), which fact, together with a selected relationship between the refractive indices of the cover and the spaces, result in sufficient diffraction of the otherwise wasted light (50) so that about 25% of it is reflected from the surface (20T) onto a sphere (16).

Effect of replacing a hydroxyl group with a methyl group on arsenic (V) species adsorption on goethite (alpha-FeOOH).

PubMed

Zhang, J S; Stanforth, R S; Pehkonen, S O

2007-02-01

Arsenate and methylated arsenicals, such as dimethylarsinate (DMA) and monomethylarsonate (MMA), are being found with increasing frequency in natural water systems. The mobility and bioavailability of these arsenic species in the environment are strongly influenced by their interactions with mineral surface, especially iron and aluminum oxides. Goethite (alpha-FeOOH), one of the most abundant ferric (hydr)oxides in natural systems, has a high retention capacity for arsenic species. Unfortunately, the sorption mechanism for the species is not completely understood, which limits our ability to model their behavior in natural systems. The purpose of this study is to investigate the effect of replacing a hydroxyl group with a methyl group on the adsorption behaviors of arsenic (V) species using adsorption edges, the influence of the background electrolyte on arsenic adsorption, and their effect on the zeta potential of goethite. The affinity of the three species to the goethite surface decreases in the order of AsO4=MMA>DMA. The uptake of DMA and MMA is independent of the concentration of background electrolyte, indicating that both species form inner-sphere complexes on the goethite surface and the most charge of adsorbed DMA and MMA locates at the surface plane. Arsenate uptake increases with increasing concentrations of background electrolyte at pH above 4, possibly due to that the charge of adsorbed arsenate is distributed between the surface plane and another electrostatic plane. DMA and lower concentrations of MMA have small effect on the zeta potential, whereas the zeta potential of goethite decreases in the presence of arsenate. The small effect on zeta potential of DMA or MMA adsorption suggests that the sorption sites for the anions is not important in controlling the surface charge. This observation is inconsistent with most adsorption models that postulate a singly coordinated hydroxyls contributing to both the adsorption and the surface charge, but supports the thesis that the charge on the goethite surface comes primarily from protonation of the triply bound oxygen atoms on the surface.

Formation of aggregated nanoparticle spheres through femtosecond laser surface processing

NASA Astrophysics Data System (ADS)

Tsubaki, Alfred T.; Koten, Mark A.; Lucis, Michael J.; Zuhlke, Craig; Ianno, Natale; Shield, Jeffrey E.; Alexander, Dennis R.

2017-10-01

A detailed structural and chemical analysis of a class of self-organized surface structures, termed aggregated nanoparticle spheres (AN-spheres), created using femtosecond laser surface processing (FLSP) on silicon, silicon carbide, and aluminum is reported in this paper. AN-spheres are spherical microstructures that are 20-100 μm in diameter and are composed entirely of nanoparticles produced during femtosecond laser ablation of material. AN-spheres have an onion-like layered morphology resulting from the build-up of nanoparticle layers over multiple passes of the laser beam. The material properties and chemical composition of the AN-spheres are presented in this paper based on scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX) analysis. There is a distinct difference in the density of nanoparticles between concentric rings of the onion-like morphology of the AN-sphere. Layers of high-density form when the laser sinters nanoparticles together and low-density layers form when nanoparticles redeposit while the laser ablates areas surrounding the AN-sphere. The dynamic nature of femtosecond laser ablation creates a variety of nanoparticles that make-up the AN-spheres including Si/C core-shell, nanoparticles that directly fragmented from the base material, nanoparticles with carbon shells that retarded oxidation, and amorphous, fully oxidized nanoparticles.

The electromagnetic radiation from simple sources in the presence of a homogeneous dielectric sphere

NASA Technical Reports Server (NTRS)

Mason, V. B.

1973-01-01

In this research, the effect of a homogeneous dielectric sphere on the electromagnetic radiation from simple sources is treated as a boundary value problem, and the solution is obtained by the technique of dyadic Green's functions. Exact representations of the electric fields in the various regions due to a source located inside, outside, or on the surface of a dielectric sphere are formulated. Particular attention is given to the effect of sphere size, source location, dielectric constant, and dielectric loss on the radiation patterns and directivity of small spheres (less than 5 wavelengths in diameter) using the Huygens' source excitation. The computed results are found to closely agree with those measured for waveguide-excited plexiglas spheres. Radiation patterns for an extended Huygens' source and for curved electric dipoles located on the sphere's surface are also presented. The resonance phenomenon associated with the dielectric sphere is studied in terms of the modal representation of the radiated fields. It is found that when the sphere is excited at certain frequencies, much of the energy is radiated into the sidelobes. The addition of a moderate amount of dielectric loss, however, quickly attenuates this resonance effect. A computer program which may be used to calculate the directivity and radiation pattern of a Huygens' source located inside or on the surface of a lossy dielectric sphere is listed.

[A history of internal medicine: medical specialization: as old as antiquity].

PubMed

Echenberg, Donald

2007-11-28

This article presents a short review of the history of medical specialization and the evolution of internal medicine within the last two centuries. Medical specialization, far from being a recent phenomenon, existed in the Hellenistic world and in Rome. The development of specialization during the latter part of the 19th century and early 20th century is credited to the rapid expansion of medical knowledge which made it impossible for a single doctor to encompass all the different spheres of the profession. The term innere medizin or internal medicine was adopted from German terminology in the 1880's. The Canadian society of internal medicine was formed in 1983 and its main goal is to promote a broad perspective of medical care and to master the complexity in medicine through a generalist approach.

K-band observations of boxy bulges - I. Morphology and surface brightness profiles

NASA Astrophysics Data System (ADS)

Bureau, M.; Aronica, G.; Athanassoula, E.; Dettmar, R.-J.; Bosma, A.; Freeman, K. C.

2006-08-01

In this first paper of a series on the structure of boxy and peanut-shaped (B/PS) bulges, Kn-band observations of a sample of 30 edge-on spiral galaxies are described and discussed. Kn-band observations best trace the dominant luminous galactic mass and are minimally affected by dust. Images, unsharp-masked images, as well as major-axis and vertically summed surface brightness profiles are presented and discussed. Galaxies with a B/PS bulge tend to have a more complex morphology than galaxies with other bulge types, more often showing centred or off-centred X structures, secondary maxima along the major-axis and spiral-like structures. While probably not uniquely related to bars, those features are observed in three-dimensional N-body simulations of barred discs and may trace the main bar orbit families. The surface brightness profiles of galaxies with a B/PS bulge are also more complex, typically containing three or more clearly separated regions, including a shallow or flat intermediate region (Freeman Type II profiles). The breaks in the profiles offer evidence for bar-driven transfer of angular momentum and radial redistribution of material. The profiles further suggest a rapid variation of the scaleheight of the disc material, contrary to conventional wisdom but again as expected from the vertical resonances and instabilities present in barred discs. Interestingly, the steep inner region of the surface brightness profiles is often shorter than the isophotally thick part of the galaxies, itself always shorter than the flat intermediate region of the profiles. The steep inner region is also much more prominent along the major-axis than in the vertically summed profiles. Similarly to other recent work but contrary to the standard `bulge + disc' model (where the bulge is both thick and steep), we thus propose that galaxies with a B/PS bulge are composed of a thin concentrated disc (a disc-like bulge) contained within a partially thick bar (the B/PS bulge), itself contained within a thin outer disc. The inner disc likely formed secularly through bar-driven processes and is responsible for the steep inner region of the surface brightness profiles, traditionally associated with a classic bulge, while the bar is responsible for the flat intermediate region of the surface brightness profiles and the thick complex morphological structures observed. Those components are strongly coupled dynamically and are formed mostly of the same (disc) material, shaped by the weak but relentless action of the bar resonances. Any competing formation scenario for galaxies with a B/PS bulge, which represent at least 45 per cent of the local disc galaxy population, must explain equally well and self-consistently the above morphological and photometric properties, the complex gas and stellar kinematics observed, and the correlations between them.

Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.

PubMed

Chen, Yiling; Zhang, Huichun

2013-10-01

Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom.

System and method for underwater radiography

DOEpatents

Hunter, James; Keck, Danny Lee; Sims, Jr., James Rae; Watson, Scott Avery

2015-01-20

A system for subsea imaging comprises a first plate having an inner surface, an outer surface, and a cavity formed in the inner surface. In addition, the system comprises a phosphor imaging plate disposed in the cavity. Further, the system comprises a second plate having an inner surface facing the inner surface of the first plate and an outer surface facing away from the outer surface of the first plate. Still further, the system comprises a seal member disposed between the inner surface of the first plate and the inner surface of the second plate. The seal member extends around the perimeter of the cavity and is configured to seal the phosphor imaging plate and the cavity from intrusion water.

Ultrastructure of the embryonic snake skin and putative role of histidine in the differentiation of the shedding complex.

PubMed

Alibardi, Lorenzo

2002-02-01

The morphogenesis and ultrastructure of the epidermis of snake embryos were studied at progressive stages of development through hatching to determine the time and modality of differentiation of the shedding complex. Scales form as symmetric epidermal bumps that become slanted and eventually very overlapped. During the asymmetrization of the bumps, the basal cells of the forming outer surface of the scale become columnar, as in an epidermal placode, and accumulate glycogen. Small dermal condensations are sometimes seen and probably represent primordia of the axial dense dermis of the growing tip of scales. Deep, dense, and superficial loose dermal regions are formed when the epidermis is bilayered (periderm and basal epidermis) and undifferentiated. Glycogen and lipids decrease from basal cells to differentiating suprabasal cells. On the outer scale surface, beneath the peridermis, a layer containing dense granules and sparse 25-30-nm thick coarse filaments is formed. The underlying clear layer does not contain keratohyalin-like granules but has a rich cytoskeleton of intermediate filaments. Small denticles are formed and they interdigitate with the oberhautchen spinulae formed underneath. On the inner scale surface the clear layer contains dense granules, coarse filaments, and does not form denticles with the aspinulated oberhautchen. On the inner side surface the oberhautchen only forms occasional spinulae. The sloughing of the periderm and embryonic epidermis takes place in ovo 5-6 days before hatching. There follow beta-, mesos-, and alpha-layers, not yet mature before hatching. No resting period is present but a new generation is immediately produced so that at 6-10 h posthatching an inner generation and a new shedding complex are forming beneath the outer generation. The first shedding complex differentiates 10-11 days before hatching. In hatchlings 6-10 h old, tritiated histidine is taken up in the epidermis 4 h after injection and is found mainly in the shedding complex, especially in the apposed membranes of the clear layer and oberhautchen cells. This indicates that a histidine-rich protein is produced in preparation for shedding, as previously seen in lizard epidermis. The second shedding (first posthatching) takes place at 7-9 days posthatching. It is suggested that the shedding complex in lepidosaurian reptiles has evolved after the production of a histidine-rich protein and of a beta-keratin layer beneath the former alpha-layer. Copyright 2002 Wiley-Liss, Inc.

A new 3D multi-fluid dust model: a study of the effects of activity and nucleus rotation on the dust grains' behavior in the cometary environment

NASA Astrophysics Data System (ADS)

Shou, Y.; Combi, M. R.; Toth, G.; Fougere, N.; Tenishev, V.; Huang, Z.; Jia, X.; Hansen, K. C.; Gombosi, T. I.; Bieler, A. M.; Rubin, M.

2016-12-01

Cometary dust observations may deepen our understanding of the role of dust in the formation of comets and in altering the cometary environment. Models including dust grains are in demand to interpret observations and test hypotheses. Several existing models have taken into account the gas-dust interaction, varying sizes of dust grains and the cometary gravitational force. In this work, we develop a multi-fluid dust model based on BATS-R-US in the University of Michigan's Space Weather Modeling Framework (SWMF). This model not only incorporates key features of previous dust models, but also has the capability of simulating time-dependent phenomena. Since the model is running in the rotating comet reference frame with a real shaped nucleus in the computational domain, the fictitious centrifugal and Coriolis forces are included. The boundary condition on the nucleus surface can be set according to the distribution of activity and the solar illumination. The Sun, which drives sublimation and the radiation pressure force, revolves around the comet in this frame. A newly developed numerical mesh is also used to resolve the real shaped nucleus in the center and to facilitate prescription of the outer boundary conditions that accommodate the rotating frame. The inner part of the grid is a box composed of Cartesian cells and the outer surface is a smooth sphere, with stretched cells filled in between the box and the sphere. The effects of the rotating nucleus and the activity region on the surface are discussed and preliminary results are presented. This work has been partially supported by grant NNX14AG84G from the NASA Planetary Atmospheres Program, and US Rosetta contracts JPL #1266313, JPL #1266314 and JPL #1286489.

A hybrid 3D SEM reconstruction method optimized for complex geologic material surfaces.

PubMed

Yan, Shang; Adegbule, Aderonke; Kibbey, Tohren C G

2017-08-01

Reconstruction methods are widely used to extract three-dimensional information from scanning electron microscope (SEM) images. This paper presents a new hybrid reconstruction method that combines stereoscopic reconstruction with shape-from-shading calculations to generate highly-detailed elevation maps from SEM image pairs. The method makes use of an imaged glass sphere to determine the quantitative relationship between observed intensity and angles between the beam and surface normal, and the detector and surface normal. Two specific equations are derived to make use of image intensity information in creating the final elevation map. The equations are used together, one making use of intensities in the two images, the other making use of intensities within a single image. The method is specifically designed for SEM images captured with a single secondary electron detector, and is optimized to capture maximum detail from complex natural surfaces. The method is illustrated with a complex structured abrasive material, and a rough natural sand grain. Results show that the method is capable of capturing details such as angular surface features, varying surface roughness, and surface striations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Space filling minimal surfaces and sphere packings

NASA Astrophysics Data System (ADS)

Elser, Veit

1994-05-01

A space filling minimal surface is defined to be any embedded minimal surface without boundary with the property that the area and genus enclosed by any large spherical region scales in proportion to the volume of the region. The triply periodic minimal surfaces are one realization, but not necessarily the only one. By using the genus per unit volume of the surface, a meaningful comparison of surface areas can be made even in cases where there is no unit cell. Of the known periodic minimal surfaces this measure of the surface area is smallest for Schoen's FRD surface. This surface is one of several that is closely related to packings of spheres. Its low area is largely due to the fact that the corresponding sphere packing (fcc) has the maximal kissing number.

The Shadow Knows: Using Shadows to Investigate the Structure of the Pretransitional Disk of HD 100453

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

Long, Zachary C.; Fernandes, Rachel B.; Sitko, Michael

2017-03-20

We present Gemini Planet Imager polarized intensity imagery of HD 100453 in Y , J , and K 1 bands that reveals an inner gap (9–18 au), an outer disk (18–39 au) with two prominent spiral arms, and two azimuthally localized dark features that are also present in Spectro-Polarimetric High-contrast Exoplanet REsearch (SPHERE) total intensity images. Spectral energy distribution fitting further suggests that the radial gap extends to 1 au. The narrow, wedge-like shape of the dark features appears similar to predictions of shadows cast by an inner disk that is misaligned with respect to the outer disk. Using themore » Monte Carlo radiative transfer code HOCHUNCK3D, we construct a model of the disk that allows us to determine its physical properties in more detail. From the angular separation of the features, we measure the difference in inclination between the disks (45°) and their major axes, PA = 140° east of north for the outer disk, and 100° for the inner disk. We find an outer-disk inclination of 25° ± 10° from face-on, in broad agreement with the Wagner et al. measurement of 34°. SPHERE data in J and H bands indicate a reddish disk, which indicates that HD 100453 is evolving into a young debris disk.« less

Development And Testing Of The Inertial Electrostatic Confinement Diffusion Thruster

NASA Technical Reports Server (NTRS)

Becnel, Mark D.; Polzin, Kurt A.

2013-01-01

The Inertial Electrostatic Confinement (IEC) diffusion thruster is an experiment in active development that takes advantage of physical phenomenon that occurs during operation of an IEC device. The IEC device has been proposed as a fusion reactor design that relies on traditional electrostatic ion acceleration and is typically arranged in a spherical geometry. The design incorporates two radially-symmetric spherical electrodes. Often the inner electrode utilizes a grid of wire shaped in a sphere with a radius 15 to 50 percent of the radius of the outer electrode. The inner electrode traditionally has 90 percent or more transparency to allow particles (ions) to pass to the center of the spheres and collide/recombine in the dense plasma core at r=0. When operating the IEC, an unsteady plasma leak is typically observed passing out one of the gaps in the lattice grid of the inner electrode. The IED diffusion thruster is based upon the idea that this plasma leak can be used for propulsive purposes. The IEC diffusion thruster utilizes the radial symmetry found in the IEC device. A cylindrical configuration is employed here as it will produce a dense core of plasma the length of the cylindrical grid while promoting the plasma leak to exhaust through an electromagnetic nozzle at one end of the apparatus. A proof-of-concept IEC diffusion thruster is operational and under testing using argon as propellant (Figure 1).

The Shadow Knows: Using Shadows to Investigate the Structure of the Pretransitional Disk of HD 100453

NASA Astrophysics Data System (ADS)

Long, Zachary C.; Fernandes, Rachel B.; Sitko, Michael; Wagner, Kevin; Muto, Takayuki; Hashimoto, Jun; Follette, Katherine; Grady, Carol A.; Fukagawa, Misato; Hasegawa, Yasuhiro; Kluska, Jacques; Kraus, Stefan; Mayama, Satoshi; McElwain, Michael W.; Oh, Daehyon; Tamura, Motohide; Uyama, Taichi; Wisniewski, John P.; Yang, Yi

2017-03-01

We present Gemini Planet Imager polarized intensity imagery of HD 100453 in Y, J, and K1 bands that reveals an inner gap (9-18 au), an outer disk (18-39 au) with two prominent spiral arms, and two azimuthally localized dark features that are also present in Spectro-Polarimetric High-contrast Exoplanet REsearch (SPHERE) total intensity images. Spectral energy distribution fitting further suggests that the radial gap extends to 1 au. The narrow, wedge-like shape of the dark features appears similar to predictions of shadows cast by an inner disk that is misaligned with respect to the outer disk. Using the Monte Carlo radiative transfer code HOCHUNCK3D, we construct a model of the disk that allows us to determine its physical properties in more detail. From the angular separation of the features, we measure the difference in inclination between the disks (45°) and their major axes, PA = 140° east of north for the outer disk, and 100° for the inner disk. We find an outer-disk inclination of 25° ± 10° from face-on, in broad agreement with the Wagner et al. measurement of 34°. SPHERE data in J and H bands indicate a reddish disk, which indicates that HD 100453 is evolving into a young debris disk.

The Shadow Knows: Using Shadows to Investigate the Structure of the Pretransitional Disk of HD 100453

NASA Technical Reports Server (NTRS)

Long, Zachary C.; Fernandes, Rachel B.; Sitko, Michael; Wagner, Kevin; Muto, Takayuki; Hashimoto, Jun; Follette, Katherine; Grady, Carol A.; Fukagawa, Misato; Hasegawa, Yasuhiro;

Complex Waves on 1D, 2D, and 3D Periodic Arrays of Lossy and Lossless Magnetodielectric Spheres

DTIC Science & Technology

2010-05-16

magnetic) dipole field. The radius of the spheres is denoted by a, and t he relative permittivity and permeability of the spheres are denoted by fr and...1-’" respectively, where fr and I-’r are in general complex. We denote the separation between the centers of adjacent spheres by d, take the z axis...fT and JJ.’i-ff become reciprocals) , both (~fT and J.’’i- fr should approach the value of + 1. However, a little t.hought and numerical examples

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

USGS Publications Warehouse

Fox, P.M.; Davis, J.A.; Luther, G. W.

2009-01-01

The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Arsenic Scavenging by Al-Substituted Ferrihydrites in a Circumneutral pH River Impacted by the Acid Mine Drainage of Carnoulès, Gard, France

NASA Astrophysics Data System (ADS)

ADRA, A.; Morin, G.; ona-Nguema, G.; Maillot, F.; Casiot, C.; Bruneel, O.

2013-12-01

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure and reactivity of aluminum-rich Fh from river-bed sediments collected in a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. EXAFS analysis indicates that Al(III) substitutes for Fe(III) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 20-37×7 mol%Al range, in agreement with bulk chemical compositions. Synthetic aluminous Fh analogues prepared in the present study are found to be less Al-substituted (14-18×4 mol%Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidences for the scavenging of arsenic by natural Al- Fh, with possible implications for other pollutants in natural or engineered systems.

Complex inner core of the Earth: The last frontier of global seismology

NASA Astrophysics Data System (ADS)

Tkalčić, Hrvoje

2015-03-01

The days when the Earth's inner core (IC) was viewed as a homogeneous solid sphere surrounded by the liquid outer core (OC) are now behind us. Due to a limited number of data sampling the IC and a lack of experimentally controlled conditions in the deep Earth studies, it has been difficult to scrutinize competitive hypotheses in this active area of research. However, a number of new concepts linking IC structure and dynamics has been proposed lately to explain different types of seismological observations. A common denominator of recent observational work on the IC is increased complexity seen in IC physical properties such as its isotropic and anisotropic structure, attenuation, inner core boundary (ICB) topography, and its rotational dynamics. For example, small-scale features have been observed to exist as a widespread phenomenon in the uppermost inner core, probably superimposed on much longer-scale features. The characterization of small-scale features sheds light on the nature of the solidification process and helps in understanding seismologically observed hemispherical dichotomy of the IC. The existence of variations in the rate and level of solidification is a plausible physical outcome in an environment where vigorous compositional convection in the OC and variations in heat exchange across the ICB may control the process of crystal growth. However, further progress is hindered by the fact that the current traveltime data of PKIKP waves traversing the IC do not allow discriminating between variations in isotropic P wave velocity and velocity anisotropy. Future studies of attenuation in the IC might provide crucial information about IC structure, although another trade-off exists—that of the relative contribution of scattering versus viscoelastic attenuation and the connection with the material properties. Future installations of dense arrays, cross paths of waves that sample the IC, and corresponding array studies will be a powerful tool to image and clearly distinguish between viscoelastic and scattering attenuation, and isotropic- and anisotropic-heterogeneity related effects on traveltimes of core-sensitive body waves. This will then inevitably contribute to a better understanding of what the IC is made of, how it solidifies and how it contributes to the generation and dynamics of the geomagnetic field.

Numerical implementation of isolated horizon boundary conditions

NASA Astrophysics Data System (ADS)

Jaramillo, José Luis; Ansorg, Marcus; Limousin, François

2007-01-01

We study the numerical implementation of a set of boundary conditions derived from the isolated horizon formalism, and which characterize a black hole whose horizon is in quasiequilibrium. More precisely, we enforce these geometrical prescriptions as inner boundary conditions on an excised sphere, in the numerical resolution of the conformal thin sandwich equations. As main results, we first establish the consistency of including in the set of boundary conditions a constant surface gravity prescription, interpretable as a lapse boundary condition, and second we assess how the prescriptions presented recently by Dain et al. for guaranteeing the well-posedness of the conformal transverse traceless equations with quasiequilibrium horizon conditions extend to the conformal thin sandwich elliptic system. As a consequence of the latter analysis, we discuss the freedom of prescribing the expansion associated with the ingoing null normal at the horizon.

Discrimination of Inner- and Outer-Sphere Electrode Reactions by Cyclic Voltammetry Experiments

ERIC Educational Resources Information Center

Tanimoto, Sachiko; Ichimura, Akio

2013-01-01

A laboratory experiment for undergraduate students who are studying homogeneous and heterogeneous electron-transfer reactions is described. Heterogeneous or electrode reaction kinetics can be examined by using the electrochemical reduction of three Fe[superscript III]/Fe[superscript II] redox couples at platinum and glassy carbon disk electrodes.…

Imaging Red Supergiants with VLT/SPHERE/ZIMPOL

NASA Astrophysics Data System (ADS)

Cannon, Emily

2018-04-01

In the red supergiant (RSG) phase of evolution massive stars show powerful stellar winds, which strongly influence the supernova (progenitor) properties and control the nature of the compact object that is left behind. Material that is lost in the stellar wind, together with that ejected in the final core collapse, contributes to the chemical enrichment of the local interstellar medium. The mass-loss properties of RSGs are however poorly constrained. Moreover, little is known about the wind driving mechanism. To provide better constraints on both mass-loss rates and physics, high angular resolution observations are needed to unveil the inner regions of the circumstellar environment, where the mass loss is triggered. Using the VLT-SPHERE/ZIMPOL adaptive optics imaging polarimeter, spatially resolved images of four nearby RSGs were obtained in four filters. From these data, we obtain information on geometrical structures in the inner wind, the onset radius and spatial distribution of dust grains, and dust properties such as grain size. As dust grains may play a role in initiating and/or driving the outflow, this could provide us with clues as to the wind driving mechanism.

Mn(II) based T1 and T2 potential MRI contrast agent appended with tryptamine: Recognition moiety for Aβ-plaques.

PubMed

Rastogi, Neeraj; Tyagi, Nidhi; Singh, Ovender; Hemanth Kumar, B S; Singh, Udai P; Ghosh, Kaushik; Roy, Raja

2017-12-01

We report the synthesis and characterization of manganese(II) complexes having pentadentate ligands L 1 (2,6-bis(1-(2-phenyl-2-(pyridin-2-yl)hydrazono)ethyl)pyridine), L 2 (methyl 2,6-bis((E)-1-(2-phenyl-2-(pyridin-2yl)hydrazono)ethyl)isonicotinate), L 3 (N-(2-(1H-indol-3-yl)ethyl)-2,6-bis((E)-1-(2-phenyl-2-(pyridin2yl)hydrazono)ethyl)isonicotiamide) and their application as dual contrast agents for simultaneous T 1 and T 2 weighted magnetic resonance imaging. Single crystal analysis of all the complexes [Mn II L 1 , Mn II L 2 and Mn II L 3 ] confirm the formation of novel seven-coordinate manganese complexes with an inner sphere water and perchlorate ion. The Magnetic Resonance Imaging (MRI) contrast agent [MnL 2 ] was further modified by incorporating tryptamine as a binding moiety specific to Amyloid Beta-fibrils (Aβ-fibrils) in Alzhiemer's disease (AD) and it's in vitro evaluation for specific binding with Aβ-fibrils indicated as a bio-marker of AD. Copyright © 2017 Elsevier Inc. All rights reserved.

Exploring the electrochemical performance of graphitic paste electrodes: graphene vs. graphite.

PubMed

Figueiredo-Filho, Luiz C S; Brownson, Dale A C; Gómez-Mingot, Maria; Iniesta, Jesús; Fatibello-Filho, Orlando; Banks, Craig E

2013-11-07

We report the fabrication, characterisation (SEM, TEM, XPS and Raman spectroscopy) and electrochemical implementation of a graphene paste electrode. The paste electrodes utilised are constructed by simply mixing graphene with mineral oil (which acts as a binder) prior to loading the resultant paste into a piston-driven polymeric-tubing electrode-shell, where this electrode configuration allows for rapid renewal of the electrode surface. The fabricated paste electrode is electrochemically characterised using both inner-sphere and outer-sphere redox probes, namely potassium ferrocyanide(ii), hexaammine-ruthenium(iii) chloride and hexachloroiridate(iii), in addition to the biologically relevant and electroactive analytes, l-ascorbic acid (AA) and uric acid (UA). Comparisons are made with a graphite paste alternative and the benefits of graphene implementation as a paste electrode within electrochemistry are explored, as well as the characterisation of their electroanalytical performances. We reveal no observable differences in the electrochemical performance and thus suggest that there are no advantages of using graphene over graphite in the fabrication of paste electrodes. Such work is highly important and informative for those working in the field of electroanalysis where electrochemistry can provide portable, rapid, reliable and accurate sensing protocols (bringing the laboratory into the field), with particular relevance to those searching for new electrode materials.

Component with inspection-facilitating features

DOEpatents

Marra, John J; Zombo, Paul J

2014-02-11

A turbine airfoil can be formed with features to facilitate measurement of its wall thickness. An outer wall of the airfoil can include an outer surface and an inner surface. The outer surface of the airfoil can have an outer inspection target surface, and the inner surface of the airfoil can have an inner inspection target surface. The inner and outer target surfaces can define substantially flat regions in surfaces that are otherwise highly contoured. The inner and outer inspection target surfaces can be substantially aligned with each other. The inner and outer target surfaces can be substantially parallel to each other. As a result of these arrangements, a highly accurate measurement of wall thickness can be obtained. In one embodiment, the outer inspection target surface can be defined by an innermost surface of a groove formed in the outer surface of the outer wall of the airfoil.

Fabrication of hexagonal star-shaped and ring-shaped patterns arrays by Mie resonance sphere-lens-lithography

NASA Astrophysics Data System (ADS)

Liu, Xianchao; Wang, Jun; Li, Ling; Gou, Jun; Zheng, Jie; Huang, Zehua; Pan, Rui

2018-05-01

Mie resonance sphere-lens-lithography has proved to be a good candidate for fabrication of large-area tunable surface nanopattern arrays. Different patterns on photoresist surface are obtained theoretically by adjusting optical coupling among neighboring spheres with different gap sizes. The effect of light reflection from the substrate on the pattern produced on the photoresist with a thin thickness is also discussed. Sub-micron hexagonal star-shaped and ring-shaped patterns arrays are achieved with close-packed spheres arrays and spheres arrays with big gaps, respectively. Changing of star-shaped vertices is induced by different polarization of illumination. Experimental results agree well with the simulation. By using smaller resonance spheres, sub-400 nm star-shaped and ring-shaped patterns can be realized. These tunable patterns are different from results of previous reports and have enriched pattern morphology fabricated by sphere-lens-lithography, which can find application in biosensor and optic devices.

Asteroid Bennu Temperature Maps for OSIRIS-REx Spacecraft and Instrument Thermal Analyses

NASA Technical Reports Server (NTRS)

Choi, Michael K.; Emery, Josh; Delbo, Marco

2014-01-01

A thermophysical model has been developed to generate asteroid Bennu surface temperature maps for OSIRIS-REx spacecraft and instrument thermal design and analyses at the Critical Design Review (CDR). Two-dimensional temperature maps for worst hot and worst cold cases are used in Thermal Desktop to assure adequate thermal design margins. To minimize the complexity of the Bennu geometry in Thermal Desktop, it is modeled as a sphere instead of the radar shape. The post-CDR updated thermal inertia and a modified approach show that the new surface temperature predictions are more benign. Therefore the CDR Bennu surface temperature predictions are conservative.

Forming MOFs into spheres by use of molecular gastronomy methods.

PubMed

Spjelkavik, Aud I; Aarti; Divekar, Swapnil; Didriksen, Terje; Blom, Richard

2014-07-14

A novel method utilizing hydrocolloids to prepare nicely shaped spheres of metal-organic frameworks (MOFs) has been developed. Microcrystalline CPO-27-Ni particles are dispersed in either alginate or chitosan solutions, which are added dropwise to solutions containing, respectively, either divalent group 2 cations or base that act as gelling agents. Well-shaped spheres are immediately formed, which can be dried into spheres containing mainly MOF (>95 wt %). The spheronizing procedures have been optimized with respect to maximum specific surface area, shape, and particle density of the final sphere. At optimal conditions, well-shaped 2.5-3.5 mm diameter CPO-27-Ni spheres with weight-specific surface areas <10 % lower than the nonformulated CPO-27-Ni precursor, and having sphere densities in the range 0.8 to 0.9 g cm(-3) and particle crushing strengths above 20 N, can be obtained. The spheres are well suited for use in fixed-bed catalytic or adsorption processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adjustable link for kinematic mounting systems

DOEpatents

Hale, Layton C.

1997-01-01

An adjustable link for kinematic mounting systems. The adjustable link is a low-cost, passive device that provides backlash-free adjustment along its single constraint direction and flexural freedom in all other directions. The adjustable link comprises two spheres, two sockets in which the spheres are adjustable retain, and a connection link threadly connected at each end to the spheres, to provide a single direction of restraint and to adjust the length or distance between the sockets. Six such adjustable links provide for six degrees of freedom for mounting an instrument on a support. The adjustable link has applications in any machine or instrument requiring precision adjustment in six degrees of freedom, isolation from deformations of the supporting platform, and/or additional structural damping. The damping is accomplished by using a hollow connection link that contains an inner rod and a viscoelastic separation layer between the two.

Adjustable link for kinematic mounting systems

DOEpatents

Hale, L.C.

1997-07-01

An adjustable link for kinematic mounting systems is disclosed. The adjustable link is a low-cost, passive device that provides backlash-free adjustment along its single constraint direction and flexural freedom in all other directions. The adjustable link comprises two spheres, two sockets in which the spheres are adjustable retain, and a connection link threadly connected at each end to the spheres, to provide a single direction of restraint and to adjust the length or distance between the sockets. Six such adjustable links provide for six degrees of freedom for mounting an instrument on a support. The adjustable link has applications in any machine or instrument requiring precision adjustment in six degrees of freedom, isolation from deformations of the supporting platform, and/or additional structural damping. The damping is accomplished by using a hollow connection link that contains an inner rod and a viscoelastic separation layer between the two. 3 figs.

A Mechanistic Investigation of the Gold(III)-Catalyzed Hydrofurylation of C-C Multiple Bonds.

PubMed

Hossein Bagi, Amin; Khaledi, Yousef; Ghari, Hossein; Arndt, Sebastian; Hashmi, A Stephen K; Yates, Brian F; Ariafard, Alireza

2016-11-09

The gold-catalyzed direct functionalization of aromatic C-H bonds has attracted interest for constructing organic compounds which have application in pharmaceuticals, agrochemicals, and other important fields. In the literature, two major mechanisms have been proposed for these catalytic reactions: inner-sphere syn-addition and outer-sphere anti-addition (Friedel-Crafts-type mechanism). In this article, the AuCl 3 -catalyzed hydrofurylation of allenyl ketone, vinyl ketone, ketone, and alcohol substrates is investigated with the aid of density functional theory calculations, and it is found that the corresponding functionalizations are best rationalized in terms of a novel mechanism called "concerted electrophilic ipso-substitution" (CEIS) in which the gold(III)-furyl σ-bond produced by furan auration acts as a nucleophile and attacks the protonated substrate via an outer-sphere mechanism. This unprecedented mechanism needs to be considered as an alternative plausible pathway for gold(III)-catalyzed arene functionalization reactions in future studies.

Marcus equation

DOE R&D Accomplishments Database

1998-09-21

In the late 1950s to early 1960s Rudolph A. Marcus developed a theory for treating the rates of outer-sphere electron-transfer reactions. Outer-sphere reactions are reactions in which an electron is transferred from a donor to an acceptor without any chemical bonds being made or broken. (Electron-transfer reactions in which bonds are made or broken are referred to as inner-sphere reactions.) Marcus derived several very useful expressions, one of which has come to be known as the Marcus cross-relation or, more simply, as the Marcus equation. It is widely used for correlating and predicting electron-transfer rates. For his contributions to the understanding of electron-transfer reactions, Marcus received the 1992 Nobel Prize in Chemistry. This paper discusses the development and use of the Marcus equation. Topics include self-exchange reactions; net electron-transfer reactions; Marcus cross-relation; and proton, hydride, atom and group transfers.

Hydrodynamic capture of microswimmers into sphere-bound orbits.

PubMed

Takagi, Daisuke; Palacci, Jérémie; Braunschweig, Adam B; Shelley, Michael J; Zhang, Jun

2014-03-21

Self-propelled particles can exhibit surprising non-equilibrium behaviors, and how they interact with obstacles or boundaries remains an important open problem. Here we show that chemically propelled micro-rods can be captured, with little change in their speed, into close orbits around solid spheres resting on or near a horizontal plane. We show that this interaction between sphere and particle is short-range, occurring even for spheres smaller than the particle length, and for a variety of sphere materials. We consider a simple model, based on lubrication theory, of a force- and torque-free swimmer driven by a surface slip (the phoretic propulsion mechanism) and moving near a solid surface. The model demonstrates capture, or movement towards the surface, and yields speeds independent of distance. This study reveals the crucial aspects of activity–driven interactions of self-propelled particles with passive objects, and brings into question the use of colloidal tracers as probes of active matter.

Type IX secretion: the generation of bacterial cell surface coatings involved in virulence, gliding motility and the degradation of complex biopolymers.

PubMed

Veith, Paul D; Glew, Michelle D; Gorasia, Dhana G; Reynolds, Eric C

2017-10-01

The Type IX secretion system (T9SS) is present in over 1000 sequenced species/strains of the Fibrobacteres-Chlorobi-Bacteroidetes superphylum. Proteins secreted by the T9SS have an N-terminal signal peptide for translocation across the inner membrane via the SEC translocon and a C-terminal signal for secretion across the outer membrane via the T9SS. Nineteen protein components of the T9SS have been identified including three, SigP, PorX and PorY that are involved in regulation. The inner membrane proteins PorL and PorM and the outer membrane proteins PorK and PorN interact and a complex comprising PorK and PorN forms a large ring structure of 50 nm in diameter. PorU, PorV, PorQ and PorZ form an attachment complex on the cell surface of the oral pathogen, Porphyromonas gingivalis. P. gingivalis T9SS substrates bind to PorV suggesting that after translocation PorV functions as a shuttle protein to deliver T9SS substrates to the attachment complex. The PorU component of the attachment complex is a novel Gram negative sortase which catalyses the cleavage of the C-terminal signal and conjugation of the protein substrates to lipopolysaccharide, anchoring them to the cell surface. This review presents an overview of the T9SS focusing on the function of T9SS substrates and machinery components. © 2017 John Wiley & Sons Ltd.

Nanoscale zero-valent iron for metal/metalloid removal from model hydraulic fracturing wastewater.

PubMed

Sun, Yuqing; Lei, Cheng; Khan, Eakalak; Chen, Season S; Tsang, Daniel C W; Ok, Yong Sik; Lin, Daohui; Feng, Yujie; Li, Xiang-Dong

2017-06-01

Nanoscale zero-valent iron (nZVI) was tested for the removal of Cu(II), Zn(II), Cr(VI), and As(V) in model saline wastewaters from hydraulic fracturing. Increasing ionic strength (I) from 0.35 to 4.10 M (Day-1 to Day-90 wastewaters) increased Cu(II) removal (25.4-80.0%), inhibited Zn(II) removal (58.7-42.9%), slightly increased and then reduced Cr(VI) removal (65.7-44.1%), and almost unaffected As(V) removal (66.7-75.1%) by 8-h reaction with nZVI at 1-2 g L -1 . The removal kinetics conformed to pseudo-second-order model, and increasing I decreased the surface area-normalized rate coefficient (k sa ) of Cu(II) and Cr(VI), probably because agglomeration of nZVI in saline wastewaters restricted diffusion of metal(loid)s to active surface sites. Increasing I induced severe Fe dissolution from 0.37 to 0.77% in DIW to 4.87-13.0% in Day-90 wastewater; and Fe dissolution showed a significant positive correlation with Cu(II) removal. With surface stabilization by alginate and polyvinyl alcohol, the performance of entrapped nZVI in Day-90 wastewater was improved for Zn(II) and Cr(VI), and Fe dissolution was restrained (3.20-7.36%). The X-ray spectroscopic analysis and chemical speciation modelling demonstrated that the difference in removal trends from Day-1 to Day-90 wastewaters was attributed to: (i) distinctive removal mechanisms of Cu(II) and Cr(VI) (adsorption, (co-)precipitation, and reduction), compared to Zn(II) (adsorption) and As(V) (bidentate inner-sphere complexation); and (ii) changes in solution speciation (e.g., from Zn 2+ to ZnCl 3 - and ZnCl 4 2- ; from CrO 4 2- to CaCrO 4 complex). Bare nZVI was susceptible to variations in wastewater chemistry while entrapped nZVI was more stable and environmentally benign, which could be used to remove metals/metalloids before subsequent treatment for reuse/disposal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anomalous optical scattering from intersecting fine particles

NASA Astrophysics Data System (ADS)

Paley, Alina V.; Radchik, Alex V.; Smith, Geoffrey B.

1995-09-01

There are many areas of science and technology where the scattering of electromagnetic waves by clusters or merging particles are of interest. The merging particles under study might be inclusions in high-density composites, liquid drops, biological cells, macroscopic ceramic particles, etc. As intersecting particles are bounded by a complex physical surface, the problem of scattering from these particles valid for any degree of merging, including touching, and for arbitrary materials of the constituents, has received limited attention. Here we present solutions which are valid and exact in the long wavelength limit compared with the size of intersecting spherical particles and cardioidal particles of similar dimensions. Both shapes are almost coincident everywhere except in the region of intersection. We treat the case when the waves are polarized along the common axis (longitudinal field). The solutions of Laplace's equation are integrals (spheres) or sums (cardioids) over continuous or discrete eigenvalue spectra respectively. The spectral dependencies of the resulting extinction coefficients and the scattering for the spherical and cardioidal particles are quite distinct. There is an enormous difference in the magnitude of absorption responses. Overall the cardioidal particle behaves as if it is almost invisible in terms of effects on the external field for a very broad band of optical frequencies. THe latter result was checked for a number of dielectric permittivities and seems to be universal. It scatters far more weakly than the isolated sphere. In constrast the intersecting sphere has an extinction band which is broad and is much enhanced at longer wavelegnths relative to the simple sphere. This result has significant implications for the design of surfaces with minimum scattering.

Radiation Budget Instrument (RBI) for JPSS-2

NASA Technical Reports Server (NTRS)

Georgieva, Elena; Priestley, Kory; Dunn, Barry; Cageao, Richard; Barki, Anum; Osmundsen, Jim; Turczynski, Craig; Abedin, Nurul

2015-01-01

Radiation Budget Instrument (RBI) will be one of five instruments flying aboard the JPSS-2 spacecraft, a polar-orbiting sun-synchronous satellite in Low Earth Orbit. RBI is a passive remote sensing instrument that will follow the successful legacy of the Clouds and Earth's Radiant Energy System (CERES) instruments to make measurement of Earth's short and longwave radiation budget. The goal of RBI is to provide an independent measurement of the broadband reflected solar radiance and Earth's emitted thermal radiance by using three spectral bands (Shortwave, Longwave, and Total) that will have the same overlapped point spread function (PSF) footprint on Earth. To ensure precise NIST-traceable calibration in space the RBI sensor is designed to use a visible calibration target (VCT), a solar calibration target (SCT), and an infrared calibration target (ICT) containing phase change cells (PCC) to enable on-board temperature calibration. The VCT is a thermally controlled integrating sphere with space grade Spectralon covering the inner surface. Two sides of the sphere will have fiber-coupled laser diodes in the UV to IR wavelength region. An electrical substitution radiometer on the integrating sphere will monitor the long term stability of the sources and the possible degradation of the Spectralon in space. In addition the radiometric calibration operations will use the Spectralon diffusers of the SCT to provide accurate measurements of Solar degradation. All those stable on-orbit references will ensure that calibration stability is maintained over the RBI sensor lifetime. For the preflight calibration the RBI will view five calibration sources - two integrating spheres and three CrIS (Cross-track Infrared Sounder ) -like blackbodies whose outputs will be validated with NIST calibration approach. Thermopile are the selected detectors for the RBI. The sensor has a requirement to perform lunar calibration in addition to solar calibration in space in a way similar to CERES instruments approach. To monitor climate change and to get stable and traceable results, it is critical to assure stable calibration over instrument lifetime.

Hydrocode Simulations of the Chesapeake Bay Impact

NASA Technical Reports Server (NTRS)

Collins, G. S.; Melosh, H. J.

2004-01-01

The Chesapeake Bay Impact Crater (CBIC) formed about 35 million years ago (late Eocene), in a shallow marine environment (400-600 m water depth). The crater is complex and developed in a multi-layer, rheologically-variable target that comprised 400-1000 meters of soft, water-saturated sediments overlying crystalline basement. Seismic reflection data illustrates that the Chesapeake Bay crater morphology - often described as an "inverted sombrero" - is similar to other marine-target impact craters. It consists of a approx. 1 - 1.5-km deep, highly disturbed central crater, surrounded by a shallower, less deformed basin. The inner crater has a diameter of approx. 40 km; the edge of the outer basin extends to 85-km diameter. The morphological divide between the inner and outer crater is termed the inner ring or peak ring. Little is known about the nature of the inner ring. Seismic reflection data show that the underlying basement is modestly uplifted; however, it is unclear whether the pristine surface expression of the inner ring was elevated above the floor of the outer crater.

Effect of acoustic streaming on the mass transfer from a sublimating sphere

NASA Astrophysics Data System (ADS)

Kawahara, N.; Yarin, A. L.; Brenn, G.; Kastner, O.; Durst, F.

2000-04-01

The effect of the acoustic streaming on the mass transfer from the surface of a sphere positioned in an ultrasonic acoustic levitator is studied both experimentally and theoretically. Acoustic levitation using standing ultrasonic waves is an experimental tool for studying the heat and mass transfer from small solid or liquid samples, because it allows an almost steady positioning of a sample at a fixed location in space. However, the levitator introduces some difficulties. One of the main problems with acoustic levitation is that an acoustic streaming is induced near the sample surface, which affects the heat and mass transfer rates, as characterized by increased Nusselt and Sherwood numbers. The transfer rates are not uniform along the sample surface, and the aim of the present study is to quantify the spatial Sherwood number distribution over the surface of a sphere. The experiments are based on the measurement of the surface shape of a sphere layered with a solid substance as a function of time using a charge-coupled device (CCD) camera with backlighting. The sphere used in this research is a glass sphere layered with a volatile solid substance (naphthalene or camphor). The local mass transfer from the surface both with and without an ultrasonic acoustic field is investigated in order to evaluate the effect of the acoustic streaming. The experimental results are compared with predictions following from the theory outlined [A. L. Yarin, M. Pfaffenlehner, and C. Tropea, J. Fluid Mech. 356, 65 (1998); A. L. Yarin, G. Brenn, O. Kastner, D. Rensink, and C. Tropea, ibid. 399, 151 (1999)] which describes the acoustic field and the resulting acoustic streaming, and the mass transfer at the surface of particles and droplets located in an acoustic levitator. The results are also compared with the experimental data and with the theoretical predictions of Burdukov and Nakoryakov [J. Appl. Mech. Tech. Phys. 6, 51 (1965)], which are valid only in the case of spherical particles much smaller than the sound wavelength. Good agreement between experiment and the theory of Yarin et al. is demonstrated. The time-averaged heat and mass transfer rates over a sphere surface are greatest at the sphere's equator and least at its poles in the experiment as predicted by the theory (the ultrasonic standing wave spans the vertical axis passing through the poles). The measured distribution of the mass transfer rate over the sphere surface also agrees with the theoretical predictions, which shows that in strong acoustic fields sublimation (or evaporation) results from the acoustic streaming.

Effects of elastic bed on hydrodynamic forces for a submerged sphere in an ocean of finite depth

NASA Astrophysics Data System (ADS)

Mohapatra, Smrutiranjan

2017-08-01

In this paper, we consider a hydroelastic model to examine the radiation of waves by a submerged sphere for both heave and sway motions in a single-layer fluid flowing over an infinitely extended elastic bottom surface in an ocean of finite depth. The elastic bottom is modeled as a thin elastic plate and is based on the Euler-Bernoulli beam equation. The effect of the presence of surface tension at the free-surface is neglected. In such situation, there exist two modes of time-harmonic waves: the one with a lower wavenumber (surface mode) propagates along the free-surface and the other with higher wavenumber (flexural mode) propagates along the elastic bottom surface. Based on the small amplitude wave theory and by using the multipole expansion method, we find the particular solution for the problem of wave radiation by a submerged sphere of finite depth. Furthermore, this method eliminates the need to use large and cumbersome numerical packages for the solution of such problem and leads to an infinite system of linear algebraic equations which are easily solved numerically by any standard technique. The added-mass and damping coefficients for both heave and sway motions are derived and plotted for different submersion depths of the sphere and flexural rigidity of the elastic bottom surface. It is observed that, whenever the sphere nearer to the elastic bed, the added-mass move toward to a constant value of 1, which is approximately twice of the value of added-mass of a moving sphere in a single-layer fluid flowing over a rigid and flat bottom surface.

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

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

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less

Thermodynamic, Spectroscopic, and Computational Studies of f -Element Complexation by N -Hydroxyethyl-diethylenetriamine- N,N ', N ", N"-tetraacetic Acid

DOE PAGES

Grimes, Travis S.; Heathman, Colt R.; Jansone-Popova, Santa; ...

2017-01-24

Potentiometric and spectroscopic techniques were combined with DFT calculations to probe the coordination environment and determine thermodynamic features of trivalent f-element complexation by N-hydroxyethyl-diethylenetriamine-N,N',N",N"-tetraacetic acid, HEDTTA. Ligand protonation constants and lanthanide stability constants were determined using potentiometry. Five protonation constants were accessible in I = 2.0 M (H +/Na +)ClO 4. UV–vis spectroscopy was used to determine stability constants for Nd 3+ and Am 3+ complexation with HEDTTA. Luminescence spectroscopy indicates two water molecules in the inner coordination sphere of the Eu/HEDTTA complex, suggesting HEDTTA is heptadentate. Luminescence data was supported by DFT calculations, which demonstrate that substitution of themore » acetate pendant arm by a N-hydroxyethyl group weakens the metal–nitrogen bond. This bond elongation is reflected in HEDTTA’s ability to differentiate trivalent actinides from trivalent lanthanides. The trans-lanthanide Ln/HEDTTA complex stability trend is analogous to Ln/DTPA complexation; however, the loss of one chelate ring resulting from structural substitution weakens the complexation by ~3 orders of magnitude. Successful separation of trivalent americium from trivalent lanthanides was demonstrated when HEDTTA was utilized as aqueous holdback complexant in a liquid–liquid system. Time-dependent extraction studies for HEDTTA were compared to diethylenetriamine-N,N,N',N",N"-pentaacetic acid (DTPA) and N-hydroxyethyl-ethylenediamine-N,N',N'-triacetic acid (HEDTA). The results presented here indicate substantially enhanced phase-transfer kinetic rates for mixtures containing HEDTTA.« less

How Does the Gibbs Inequality Condition Affect the Stability and Detachment of Floating Spheres from the Free Surface of Water?

PubMed

Feng, Dong-xia; Nguyen, Anh V

2016-03-01

Floating objects on the air-water interfaces are central to a number of everyday activities, from walking on water by insects to flotation separation of valuable minerals using air bubbles. The available theories show that a fine sphere can float if the force of surface tension and buoyancies can support the sphere at the interface with an apical angle subtended by the circle of contact being larger than the contact angle. Here we show that the pinning of the contact line at the sharp edge, known as the Gibbs inequality condition, also plays a significant role in controlling the stability and detachment of floating spheres. Specifically, we truncated the spheres with different angles and used a force sensor device to measure the force of pushing the truncated spheres from the interface into water. We also developed a theoretical modeling to calculate the pushing force that in combination with experimental results shows different effects of the Gibbs inequality condition on the stability and detachment of the spheres from the water surface. For small angles of truncation, the Gibbs inequality condition does not affect the sphere detachment, and hence the classical theories on the floatability of spheres are valid. For large truncated angles, the Gibbs inequality condition determines the tenacity of the particle-meniscus contact and the stability and detachment of floating spheres. In this case, the classical theories on the floatability of spheres are no longer valid. A critical truncated angle for the transition from the classical to the Gibbs inequality regimes of detachment was also established. The outcomes of this research advance our understanding of the behavior of floating objects, in particular, the flotation separation of valuable minerals, which often contain various sharp edges of their crystal faces.

Hard Spheres on the Primitive Surface

NASA Astrophysics Data System (ADS)

Dotera, Tomonari; Takahashi, Yusuke

2015-03-01

Recently hierarchical structures associated with the gyroid in several soft-matter systems have been reported. One of fundamental questions is regular arrangement or tiling on minimal surfaces. We have found certain numbers of hard spheres per unit cell on the gyroid surface are entropically self-organized. Here, new results for the primitive surface are presented. 56/64/72 per unit cell on the primitive minimal surface are entropically self-organized. Numerical evidences for the fluid-solid transition as a function of hard sphere radius are obtained in terms of the acceptance ratio of Monte Carlo moves and order parameters. These arrangements, which are the extensions of the hexagonal arrangement on a flat surface, can be viewed as hyperbolic tiling on the Poincaré disk with a negative Gaussian curvature.

Chemical and electrochemical behavior of the Cr(3)/Cr(2) half cell in the NASA Redox Energy Storage System

NASA Technical Reports Server (NTRS)

Johnson, D. A.; Reid, M. A.

1982-01-01

The Cr(III) complexes in the NASA Redox Energy Storage System were isolated and identified as Cr(H2O)6(+3) and Cr(H2O)5Cl(+2) by ion exchange chromatography and visible spectrophotometry. The cell reactions during charge-discharge cycles were followed by means of visible spectrophotometry. The spectral bands were resolved into component peaks and concentrations calculated using Beer's Law. During the charge mode Cr(H2O)5Cl(+2) is reduced to Cr(H2O)5Cl(+) and during the discharge mode Cr(H2O)5Cl(+) is oxidized back to Cr(H2O)5Cl(+2). Both electrode reactions occur via a chloride-bridge inner-sphere reaction pathway. Hysteresis effects can be explained by the slow attainment of equilibrium between Cr(H2O)6(+3) and Cr(H2O)5Cl(+2).

Vibrational spectra of carboxylato complexes—III. Trinuclear 'basic' acetates and formates of chromium(III), iron(III) and other transition metals

NASA Astrophysics Data System (ADS)

Johnson, M. K.; Powell, D. B.; Cannon, R. D.

The i.r. and Raman spectra of a series of complexes [M III3O(OOCR) 6L 3]X· xH 2O (M = Cr, Fe, Mn, Ru, Rh; L = H 2O, pyridine, γ-picoline; X = Cl, Br, I, NO 3, ClO 3, ClO 4, BF 4) have been analysed in detail. The vibrational modes of the central M 3O and the three surrounding MO 4 units, are identified. The metal—nitrogen stretching vibrations and the MOH 2 modes are assigned. The 'basic' chromium(III) formate is shown to be [Cr 3O(OOCH) 6(OH 2) 2(OOCH)] xH 2O, containing monodentate, inner-sphere coordinated formate ion. The use of the symmetric and asymmetric OCO stretching frequencies in characterizing bridging carboxylate ions is discussed.

Experimental investigation of burning rates of pure ethanol and ethanol blended fuels

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

Parag, Shintre; Raghavan, Vasudevan

2009-05-15

A fundamental experimental study to determine the burning rates of ethanol and ethanol-blended fossil fuels is presented. Pure liquid ethanol or its blends with liquid fossil fuels such as gasoline or diesel, has been transpired to the surface a porous sphere using an infusion pump. Burning of the fuel takes place on the surface of the porous sphere, which is placed in an air stream blowing upwards with a uniform velocity at atmospheric pressure and temperature under normal gravity conditions. At low air velocities, when ignited, a flame envelopes the sphere. For each sphere size, air stream velocity and fuelmore » type, the fuel feed rate will vary and the same is recorded as the burning rate for that configuration. The flame stand-off distances from the sphere surface are measured by post-processing the digital image of the flame photograph using suitable imaging software. The transition velocity at which the flame moves and establishes itself at the wake region of the sphere has been determined for different diameters and fuel types. Correlations of these parameters are also presented. (author)« less

Influence of the shell thickness and charge distribution on the effective interaction between two like-charged hollow spheres.

PubMed

Angelescu, Daniel G; Caragheorgheopol, Dan

2015-10-14

The mean-force and the potential of the mean force between two like-charged spherical shells were investigated in the salt-free limit using the primitive model and Monte Carlo simulations. Apart from an angular homogeneous distribution, a discrete charge distribution where point charges localized on the shell outer surface followed an icosahedral arrangement was considered. The electrostatic coupling of the model system was altered by the presence of mono-, trivalent counterions or small dendrimers, each one bearing a net charge of 9 e. We analyzed in detail how the shell thickness and the radial and angular distribution of the shell charges influenced the effective interaction between the shells. We found a sequence of the potential of the mean force similar to the like-charged filled spheres, ranging from long-range purely repulsive to short-range purely attractive as the electrostatic coupling increased. Both types of potentials were attenuated and an attractive-to-repulsive transition occurred in the presence of trivalent counterions as a result of (i) thinning the shell or (ii) shifting the shell charge from the outer towards the inner surface. The potential of the mean force became more attractive with the icosahedrally symmetric charge model, and additionally, at least one shell tended to line up with 5-fold symmetry axis along the longest axis of the simulation box at the maximum attraction. The results provided a basic framework of understanding the non-specific electrostatic origin of the agglomeration and long-range assembly of the viral nanoparticles.

Treatment of As(V) and As(III) by electrocoagulation using Al and Fe electrode.

PubMed

Kuan, W H; Hu, C Y; Chiang, M C

2009-01-01

A batch electrocoagulation (EC) process with bipolar electrode and potentiodynamic polarization tests with monopolar systems were investigated as methods to explore the effects of electrode materials and initial solution pH on the As(V) and As(III) removal. The results displayed that the system with Al electrode has higher reaction rate during the initial period from 0 to 25 minutes than that of Fe electrode for alkaline condition. The pH increased with the EC time because the As(V) and As(III) removal by either co-precipitation or adsorption resulted in that the OH positions in Al-hydroxide or Fe-hydroxide were substituted by As(V) and As(III). The pH in Fe electrode system elevate higher than that in Al electrode because the As(V) removal substitutes more OH position in Fe-hydroxide than that in Al-hydroxide. EC system with Fe electrode can successfully remove the As(III) but system with Al electrode cannot because As(III) can strongly bind to the surface of Fe-hydroxide with forming inner-sphere species but weakly adsorb to the Al-hydroxide surface with forming outer-sphere species. The acidic solution can destroy the deposited hydroxide passive film then allow the metallic ions liberate into the solution, therefore, the acidic initial solution can enhance the As(V) and As(III) removal. The over potential calculation and potentiodynamic polarization tests reveal that the Fe electrode systems possess higher over potential and pitting potential than that of Al electrode system due to the fast hydrolysis of and the occurrence of Fe-hydroxide passive film.

Identification of Residues in the Lipopolysaccharide ABC Transporter That Coordinate ATPase Activity with Extractor Function.

PubMed

Simpson, Brent W; Owens, Tristan W; Orabella, Matthew J; Davis, Rebecca M; May, Janine M; Trauger, Sunia A; Kahne, Daniel; Ruiz, Natividad

2016-10-18

The surface of most Gram-negative bacteria is covered with lipopolysaccharide (LPS), creating a permeability barrier against toxic molecules, including many antimicrobials. To assemble LPS on their surface, Gram-negative bacteria must extract newly synthesized LPS from the inner membrane, transport it across the aqueous periplasm, and translocate it across the outer membrane. The LptA to -G proteins assemble into a transenvelope complex that transports LPS from the inner membrane to the cell surface. The Lpt system powers LPS transport from the inner membrane by using a poorly characterized ATP-binding cassette system composed of the ATPase LptB and the transmembrane domains LptFG. Here, we characterize a cluster of residues in the groove region of LptB that is important for controlling LPS transport. We also provide the first functional characterization of LptFG and identify their coupling helices that interact with the LptB groove. Substitutions at conserved residues in these coupling helices compromise both the assembly and function of the LptB 2 FG complex. Defects in LPS transport conferred by alterations in the LptFG coupling helices can be rescued by changing a residue in LptB that is adjacent to functionally important residues in the groove region. This suppression is achieved by increasing the ATPase activity of the LptB 2 FG complex. Taken together, these data identify a specific binding site in LptB for the coupling helices of LptFG that is responsible for coupling of ATP hydrolysis by LptB with LptFG function to achieve LPS extraction. Lipopolysaccharide (LPS) is synthesized at the cytoplasmic membrane of Gram-negative bacteria and transported across several compartments to the cell surface, where it forms a barrier that protects these organisms from antibiotics. The LptB 2 FG proteins form an ATP-binding cassette (ABC) transporter that uses energy from ATP hydrolysis in the cytoplasm to facilitate extraction of LPS from the outer face of the cytoplasmic membrane prior to transport to the cell surface. How ATP hydrolysis is coupled with LPS release from the membrane is not understood. We have identified residues at the interface between the ATPase and the transmembrane domains of this heteromeric ABC complex that are important for LPS transport, some of which coordinate ATPase activity with LPS release. Copyright © 2016 Simpson et al.

An Inner-Sphere Mechanism for Molecular Oxygen Reduction Catalyzed by Copper Amine Oxidases

PubMed Central

Mukherjee, Arnab; Smirnov, Valeriy V.; Lanci, Michael P.; Brown, Doreen E.; Shepard, Eric M.; Dooley, David M.; Roth, Justine P.

2008-01-01

Copper and topaquinone (TPQ) containing amine oxidases utilize O2 for the metabolism of biogenic amines while concomitantly generating H2O2 for use by the cell. The mechanism of O2 reduction has been the subject of long-standing debate due to the obscuring influence of a proton-coupled electron transfer between the tyrosine-derived TPQ and copper, a rapidly established equilibrium precluding assignment of the enzyme in its reactive form. Here we show that substrate-reduced pea seedling amine oxidase (PSAO) exists predominantly in the CuI, TPQ semiquinone state. A new mechanistic proposal for O2 reduction is advanced on the basis of thermodynamic considerations together with kinetic studies (at varying pH, temperature and viscosity), the identification of steady-state intermediates and the analysis of competitive oxygen kinetic isotope effects: 18O KIEs, [kcat/KM(16,16O2)]/[kcat/KM(16,18O2)]. The 18O KIE = 1.0136 ± 0.0013 at pH 7.2 is independent of temperature from 5 to 47°C and insignificantly changed to 1.0122 ± 0.0020 upon raising the pH to 9, thus indicating the absence of kinetic complexity. Using density functional methods, the effect is found to be precisely in the range expected for reversible O2 binding to CuI to afford a superoxide, [CuII(η1-O2)−I]+, intermediate. Electron transfer from the TPQ semiquinone follows in the first irreversible step to form a peroxide, CuII(η1-O2)−II, intermediate driving the reduction of O2. The similar 18O KIEs reported for copper amine oxidases from other sources raise the possibility that all enzymes react by related inner-sphere mechanisms although additional experiments are needed to test this proposal. PMID:18582059

Inner-Helmholtz potential development at the hematite (α-Fe 2O 3) (0 0 1) surface

NASA Astrophysics Data System (ADS)

Boily, Jean-François; Chatman, Shawn; Rosso, Kevin M.

2011-08-01

Electric potentials of the (0 0 1) surface of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4-14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH 0 sites (p K1,1,0,int = -1.32). This site is resilient to deprotonation up to at least pH 14 (-p K-1,1,0,int ≫ 19). The associated Stern layer capacitance of 0.31-0.73 F/m 2 is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO 3 etches the (0 0 1) surface, yielding a convoluted surface populated by -OH20.5+ sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (0 0 1) dissolution. Associated electric potentials were strongly negative, with values as large as -0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7-11 range due to surface complexation and/or precipitation of iron species (0.0038 Fe/nm 2) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite surfaces.

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

NASA Astrophysics Data System (ADS)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral-water interface.

Studies of drag on the nanocomposite superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Brassard, Jean-Denis; Sarkar, D. K.; Perron, Jean

2015-01-01

The nanocomposite thin films of stearic acid (SA)-functionalized ZnO nanoparticles incorporated in epoxy polymer matrix have been achieved. The X-ray diffraction (XRD) studies show the formation of zinc stearate on ZnO nanoparticles as the confirmation of SA-functionalization of ZnO nanoparticles in the thin films. Morphological analyses reveal the presence of micro-holes with the presence of irregular nanoparticles. The measured root mean square (rms) roughness of the thin film is found to be 12 ± 1 μm with the adhesion of 5B on both glass and aluminum substrates. The wetting property shows that the surface of the film is superhydrophobic with the contact angle of water of 156 ± 4° having contact angle hysteresis (CAH) of 4 ± 2°. The average terminal velocity in the water of the as-received glass spheres and superhydrophobic spheres were found to be 0.66 ± 0.01 m/s and 0.72 ± 0.01 m/s respectively. Consequently, the calculated average coefficients of the surface drag of the as-received glass sphere and superhydrophobic glass sphere were 2.30 ± 0.01 and 1.93 ± 0.03, respectively. Hence, the drag reduction on the surface of superhydrophobic glass sphere is found to be approximately 16% lower than as-received glass sphere.

Use of Yb(III) Centered Near Infra-Red (NIR) Luminescence to Determine the Hydration State of a 3,2-HOPO based MRI-Contrast Agent

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

Moore, Evan G.; Seitz, Michael; Raymond, Kenneth N.

It has been more than a decade since the first reports of [Gd(Tren-Me-3,2-HOPO)(H{sub 2}O){sub 2}] as a potential new class of magnetic resonance imaging contrast agent (MRI-CA). The defining feature of these 1-methyl-3-hydroxypyridin-2-one (Me-3,2-HOPO) based compounds has been the use of a hexadentate ligand design, and hence an increase in the number of metal bound water molecules, without sacrificing complex stability compared to the typically octadentate contrast agents used commercially. Since that time, significant advances in the properties of these chelates have been steadily reported, including improvements in relaxivity, incorporation into macromolecular architectures and, recently, the first direct verification ofmore » solution structure using the discovery of Eu(III) centered luminescence with the isomeric 1-hydroxypyridin-2-one (1,2-HOPO) chelate as a sensitizing chromophore. Nonetheless, it has remained frustrating that direct measurements of the inner sphere hydration state, q, using luminescence techniques with the parent Me-3,2-HOPO compounds have remained elusive, even when direct laser excitation of weakly absorbing f-f transitions were employed (eg. for Eu(III) complexes). This failing can likely be traced to the presence of a low lying LMCT state which efficiently quenches metal based emission. Instead, estimates of the q and hence solution structure have relied on the fitting of relaxivity data to the Solomon-Bloembergen-Morgan equations or, where sufficiently soluble in aqueous solution, studies on the temperature dependence of the paramagnetic contribution to the water {sup 17}O NMR transverse relaxation rate. Recently, Beeby et al reported on a qualitative equation to determine inner sphere hydration based on the change in lifetimes for Yb(III) in going from H{sub 2}O to D{sub 2}O solution, and we reasoned that the lower energy accepting state of Yb(III) may lie below the LMCT state which quenches Eu(III) emission, and hence may facilitate sensitized emission from Yb(III). This hypothesis was borne out experimentally, and herein we describe for the first time sensitized luminescence in the Near Infra-Red (NIR) region from a [Yb(Tren-Me-3,2-HOPO)(H{sub 2}O){sub 2}] complex, and hence the direct measurement of q for the archetypical member of this family of compounds.« less

Structure and function of complex I in animals and plants - a comparative view.

PubMed

Senkler, Jennifer; Senkler, Michael; Braun, Hans-Peter

2017-09-01

The mitochondrial NADH dehydrogenase complex (complex I) has a molecular mass of about 1000 kDa and includes 40-50 subunits in animals, fungi and plants. It is composed of a membrane arm and a peripheral arm and has a conserved L-like shape in all species investigated. However, in plants and possibly some protists it has a second peripheral domain which is attached to the membrane arm on its matrix exposed side at a central position. The extra domain includes proteins resembling prokaryotic gamma-type carbonic anhydrases. We here present a detailed comparison of complex I from mammals and flowering plants. Forty homologous subunits are present in complex I of both groups of species. In addition, five subunits are present in mammalian complex I, which are absent in plants, and eight to nine subunits are present in plant complex I which do not occur in mammals. Based on the atomic structure of mammalian complex I and biochemical insights into complex I architecture from plants we mapped the species-specific subunits. Interestingly, four of the five animal-specific and five of the eight to nine plant-specific subunits are localized at the inner surface of the membrane arm of complex I in close proximity. We propose that the inner surface of the membrane arm represents a workbench for attaching proteins to complex I, which are not directly related to respiratory electron transport, like nucleoside kinases, acyl-carrier proteins or carbonic anhydrases. We speculate that further enzyme activities might be bound to this micro-location in other groups of organisms. © 2017 Scandinavian Plant Physiology Society.

Inner-Sphere Reorganization in Optical Electron Transfer.

DTIC Science & Technology

1984-03-01

systematic error on Et should not exceed *0.05 eV. Agreement between the & rG s and Et’s in Table I is as good as can be expected in view of the preceding...01.413183101 ~359/413-2 TECHNICAL REPORT DISTRIBUTION LIST, 359 Dr. David Aikens Dr. 0. H. Whitmore Chemistry Department Department of Materials

The Inner (and Unavoidable?) Violence of Reason: Re-Reading Heidegger via Education

ERIC Educational Resources Information Center

d'Agnese, Vasco

2015-01-01

Since Plato, Western thought has framed knowing as a method within "some realm of what is" and a predetermined "sphere of objects". The roots and the consequences of this stance towards reason and truth were noted by Heidegger, who equates the history of Western thought with the history of metaphysics. Since Plato, truth has…

Introducing Students to Inner Sphere Electron Transfer Concepts through Electrochemistry Studies in Diferrocene Mixed-Valence Systems

ERIC Educational Resources Information Center

Ventura, Karen; Smith, Mark B.; Prat, Jacob R.; Echegoyen, Lourdes E.; Villagran´, Dino

2017-01-01

We have designed a 4 h physical chemistry laboratory to introduce upper division students to electrochemistry concepts, including mixed valency and electron transfer (ET), using cyclic and differential pulse voltammetries. In this laboratory practice, students use a ferrocene dimer consisting of two ferrocene centers covalently bonded through a…

Surface effects on mean inner potentials studied using density functional theory.

PubMed

Pennington, Robert S; Boothroyd, Chris B; Dunin-Borkowski, Rafal E

2015-12-01

Quantitative materials characterization using electron holography frequently requires knowledge of the mean inner potential, but reported experimental mean inner potential measurements can vary widely. Using density functional theory, we have simulated the mean inner potential for materials with a range of different surface conditions and geometries. We use both "thin-film" and "nanowire" specimen geometries. We consider clean bulk-terminated surfaces with different facets and surface reconstructions using atom positions from both structural optimization and experimental data and we also consider surfaces both with and without adsorbates. We find that the mean inner potential is surface-dependent, with the strongest dependency on surface adsorbates. We discuss the outlook and perspective for future mean inner potential measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

Improving scattering layer through mixture of nanoporous spheres and nanoparticles in ZnO-based dye-sensitized solar cells.

PubMed

Kim, Chohui; Choi, Hongsik; Kim, Jae Ik; Lee, Sangheon; Kim, Jinhyun; Lee, Woojin; Hwang, Taehyun; Kang, Suji; Moon, Taeho; Park, Byungwoo

2014-01-01

A scattering layer is utilized by mixing nanoporous spheres and nanoparticles in ZnO-based dye-sensitized solar cells. Hundred-nanometer-sized ZnO spheres consisting of approximately 35-nm-sized nanoparticles provide not only effective light scattering but also a large surface area. Furthermore, ZnO nanoparticles are added to the scattering layer to facilitate charge transport and increase the surface area as filling up large voids. The mixed scattering layer of nanoparticles and nanoporous spheres on top of the nanoparticle-based electrode (bilayer geometry) improves solar cell efficiency by enhancing both the short-circuit current (J sc) and fill factor (FF), compared to the layer consisting of only nanoparticles or nanoporous spheres.

A novel shell-structure cell microcarrier (SSCM) for cell transplantation and bone regeneration medicine.

PubMed

Su, Kai; Gong, Yihong; Wang, Chunming; Wang, Dong-An

2011-06-01

The present study aims to develop a novel open and hollow shell-structure cell microcarrier (SSCM) to improve the anchorage-dependent cell (ADC) loading efficiency, increase the space for cell proliferation and tissue regeneration, and better propel its therapeutic effects. Gelatin particles were prepared with oil/water/oil (o/w/o) technique and modified by an adjustable surface crosslinking technique and subsequent release of uncrosslinked material. Optical microscopy and scanning electron microscopy (SEM) were utilized to observe the morphologies of the microcarriers. Cell loading tests were performed to evaluate the biocompatibilities and effect on osteogenesis of SSCM. SSCMs were successfully fabricated via the surface technique. The shell-structure could allow the cell to attach and grow on both outer and inner surface of sphere and provide adequate space for cell proliferation and extracellular matrix (ECM) secretion. The cell loading rate, proliferation rate and osteogenesis-related gene expressions on the SSCMs were higher than those on the spherical gelatin microcarriers. The outstanding performance of injectable SSCMs endowed with favorable micro-structure, desirable cytocompatibility and enhanced cell affinity makes them as a good choice as cell delivery vehicle for transplanting therapeutic cells towards the scope of tissue regeneration.

Drag crisis moderation by thin air layers sustained on superhydrophobic spheres falling in water.

PubMed

Jetly, Aditya; Vakarelski, Ivan U; Thoroddsen, Sigurdur T

2018-02-28

We investigate the effect of thin air layers naturally sustained on superhydrophobic surfaces on the terminal velocity and drag force of metallic spheres free falling in water. The surface of 20 mm to 60 mm steel or tungsten-carbide spheres is rendered superhydrophobic by a simple coating process that uses a commercially available hydrophobic agent. By comparing the free fall of unmodified spheres and superhydrophobic spheres in a 2.5 meter tall water tank, it is demonstrated that even a very thin air layer (∼1-2 μm) that covers the freshly dipped superhydrophobic sphere can reduce the drag force on the spheres by up to 80%, at Reynolds numbers from 10 5 to 3 × 10 5 , owing to an early drag crisis transition. This study complements prior investigations on the drag reduction efficiency of model gas layers sustained on heated metal spheres falling in liquid by the Leidenfrost effect. The drag reduction effects are expected to have significant implications for the development of sustainable air-layer-based energy saving technologies.

Scattering characteristics of relativistically moving concentrically layered spheres

NASA Astrophysics Data System (ADS)

Garner, Timothy J.; Lakhtakia, Akhlesh; Breakall, James K.; Bohren, Craig F.

2018-02-01

The energy extinction cross section of a concentrically layered sphere varies with velocity as the Doppler shift moves the spectral content of the incident signal in the sphere's co-moving inertial reference frame toward or away from resonances of the sphere. Computations for hollow gold nanospheres show that the energy extinction cross section is high when the Doppler shift moves the incident signal's spectral content in the co-moving frame near the wavelength of the sphere's localized surface plasmon resonance. The energy extinction cross section of a three-layer sphere consisting of an olivine-silicate core surrounded by a porous and a magnetite layer, which is used to explain extinction caused by interstellar dust, also depends strongly on velocity. For this sphere, computations show that the energy extinction cross section is high when the Doppler shift moves the spectral content of the incident signal near either of olivine-silicate's two localized surface phonon resonances at 9.7 μm and 18 μm.

A comparative study of the electrostatic potential of fullerene-like structures of Au 32 and Au 42

NASA Astrophysics Data System (ADS)

Wang, Dong-Lai; Sun, Xiao-Ping; Shen, Hong-Tao; Hou, Dong-Yan; Zhai, Yu-Chun

2008-05-01

By using density functional theory calculations, it is found that the most negative MEP inside the gold cage occurs at the center of the sphere. The largest regions with the most negative MEP outside the sphere are localized in the neighborhood of the bridge sites and the vertex regions of the five-coordinated are more positive. The absolute values of the most negative potentials in both the inner and outer cages as well as the vertex regions of the five-coordinated of Au 32 structure are much larger than those of Au 42, which means Au 32 is preferable for electrophilic attack or nucleophilic processes.

Formation of Ordered Arrays of Proteins on Surfaces

NASA Technical Reports Server (NTRS)

Lenhoff, A. M.

1996-01-01

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. While the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models, with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation and crystal growth.

Sequestration of Sr(II) By Calcium Oxalate - a Batch Uptake Study And EXAFS Analysis of Model Compounds And Reaction Products

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

Singer, D.M.; Johnson, S.B.; Catalano, J.G.

Calcium oxalate monohydrate (CaC{sub 2}O{sub 4}{center_dot}H{sub 2}O -- abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II){sub aq} following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4--10, with initial Sr solution concentrations, [Sr]{sub aq}, ranging from 1 x 10{sup -4} to 1 x 10{sup -3} M and ionic strengths ranging of 0.001--0.1more » M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr{sub aq} for two days, the solution Ca concentration, [Ca]{sup aq}, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr{sub aq} removed from solution was nearly equal to the total [Ca]{sup aq} after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC{sub 2}O{sub 4} of mixed hydration state (i.e. SrO{sub x}{center_dot}nH{sub 2}O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO3 phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.« less

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Multi-phase-field method for surface tension induced elasticity

NASA Astrophysics Data System (ADS)

Schiedung, Raphael; Steinbach, Ingo; Varnik, Fathollah

2018-01-01

A method, based on the multi-phase-field framework, is proposed that adequately accounts for the effects of a coupling between surface free energy and elastic deformation in solids. The method is validated via a number of analytically solvable problems. In addition to stress states at mechanical equilibrium in complex geometries, the underlying multi-phase-field framework naturally allows us to account for the influence of surface energy induced stresses on phase transformation kinetics. This issue, which is of fundamental importance on the nanoscale, is demonstrated in the limit of fast diffusion for a solid sphere, which melts due to the well-known Gibbs-Thompson effect. This melting process is slowed down when coupled to surface energy induced elastic deformation.

Sphere based fluid systems

NASA Technical Reports Server (NTRS)

Elleman, Daniel D. (Inventor); Wang, Taylor G. (Inventor)

1989-01-01

Systems are described for using multiple closely-packed spheres. In one system for passing fluid, a multiplicity of spheres lie within a container, with all of the spheres having the same outside diameter and with the spheres being closely nested in one another to create multiple interstitial passages of a known size and configuration and smooth walls. The container has an inlet and outlet for passing fluid through the interstitial passages formed between the nested spheres. The small interstitial passages can be used to filter out material, especially biological material such as cells in a fluid, where the cells can be easily destroyed if passed across sharp edges. The outer surface of the spheres can contain a material that absorbs a constitutent in the flowing fluid, such as a particular contamination gas, or can contain a catalyst to chemically react the fluid passing therethrough, the use of multiple small spheres assuring a large area of contact of these surfaces of the spheres with the fluid. In a system for storing and releasing a fluid such as hydrogen as a fuel, the spheres can include a hollow shell containing the fluid to be stored, and located within a compressable container that can be compressed to break the shells and release the stored fluid.

Nano-functionalization of protein microspheres

NASA Astrophysics Data System (ADS)

Yoon, Sungkwon; Nichols, William T.

2014-08-01

Protein microspheres are promising building blocks for the assembly of complex functional materials. Here we demonstrate a set of three techniques that add functionality to the surface of protein microspheres. In the first technique, a positive surface charge on the protein spheres is deposited by electrostatic adsorption. Negatively charged silica and gold nanoparticle colloids can then electrostatically bind reversibly to the microsphere surface. In the second technique, nanoparticles are covalently anchored to the protein shell using a simple one-pot process. The strong covalent bond between sulfur groups in cysteine in the protein shell irreversibly binds to the gold nanoparticles. In the third technique, surface morphology of the protein microsphere is tuned through hydrodynamic instability at the water-oil interface. This is accomplished through the degree of solubility of the oil phase in water. Taken together these three techniques form a platform to create nano-functionalized protein microspheres, which can then be used as building blocks for the assembly of more complex macroscopic materials.

Establishment of a long-term three-dimensional primary culture of mouse glandular stomach epithelial cells within the stem cell niche

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

Katano, Takahito; Ootani, Akifumi; Department of Internal Medicine, Faculty of Medicine, Saga University, 5-1-1 Nabeshima, Saga 849-8501

2013-03-22

Highlights: ► We established a 3D culture system to allow long-term culture of stomach cells. ► In this culture system, gastric epithelial cells grew for about 3 months. ► The cultured cells differentiated into multi-units of the stomach. ► This culture method should be useful for elucidating the cause of gastric diseases. -- Abstract: Compared to the small intestine and colon, little is known about stem cells in the stomach because of a lack of specific stem cell markers and an in vitro system that allows long-term culture. Here we describe a long-term three-dimensional (3D) primary gastric culture system withinmore » the stem cell niche. Glandular stomach cells from neonatal mice cultured in collagen gel yielded expanding sphere-like structures for 3 months. The wall of the gastrospheres consisted of a highly polarized epithelial monolayer with an outer lining of myofibroblasts. The epithelial cells showed a tall columnar cell shape, basal round nuclei, and mucus-filled cytoplasm as well as expression of MUC5AC, indicating differentiation into gastric surface mucous cells. These cells demonstrated the features of fully differentiated gastric surface mucous cells such as microvilli, junctional complexes, and glycogen and secretory granules. Fewer than 1% of cultured epithelial cells differentiated into enteroendocrine cells. Active proliferation of the epithelial cells and many apoptotic cells in the inner lumen revealed the rapid cell turnover in gastrospheres in vitro. This method enables us to investigate the role of signaling between cell–cell and epithelial–mesenchymal interactions in an environment that is extremely similar to the in vivo environment.« less

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.

PubMed

Kanel, Sushil Raj; Greneche, Jean-Mark; Choi, Heechul

2006-03-15

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation.

Alzheimer's disease: An acquired neurodegenerative laminopathy.

PubMed

Frost, Bess

2016-05-03

The nucleus is typically depicted as a sphere encircled by a smooth surface of nuclear envelope. For most cell types, this depiction is accurate. In other cell types and in some pathological conditions, however, the smooth nuclear exterior is interrupted by tubular invaginations of the nuclear envelope, often referred to as a "nucleoplasmic reticulum," into the deep nuclear interior. We have recently reported a significant expansion of the nucleoplasmic reticulum in postmortem human Alzheimer's disease brain tissue. We found that dysfunction of the nucleoskeleton, a lamin-rich meshwork that coats the inner nuclear membrane and associated invaginations, is causal for Alzheimer's disease-related neurodegeneration in vivo. Additionally, we demonstrated that proper function of the nucleoskeleton is required for survival of adult neurons and maintaining genomic architecture. Here, we elaborate on the significance of these findings in regard to pathological states and physiological aging, and discuss cellular causes and consequences of nuclear envelope invagination.

Numerical implementation of isolated horizon boundary conditions

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

Jaramillo, Jose Luis; Ansorg, Marcus; Limousin, Francois

2007-01-15

We study the numerical implementation of a set of boundary conditions derived from the isolated horizon formalism, and which characterize a black hole whose horizon is in quasiequilibrium. More precisely, we enforce these geometrical prescriptions as inner boundary conditions on an excised sphere, in the numerical resolution of the conformal thin sandwich equations. As main results, we first establish the consistency of including in the set of boundary conditions a constant surface gravity prescription, interpretable as a lapse boundary condition, and second we assess how the prescriptions presented recently by Dain et al. for guaranteeing the well-posedness of the conformalmore » transverse traceless equations with quasiequilibrium horizon conditions extend to the conformal thin sandwich elliptic system. As a consequence of the latter analysis, we discuss the freedom of prescribing the expansion associated with the ingoing null normal at the horizon.« less

Polymerization shrinkage and spherical glass mega fillers: effects on cuspal deflection

PubMed Central

BASSI, M. ANDREASI; SERRA, S.; ANDRISANI, C.; LICO, S.; BAGGI, L.; LAURITANO, D.

2016-01-01

SUMMARY Purpose The Authors analyzed the effect of spherical glass mega fillers (SGMF) on reducing contraction stress in dental composite resins, by means of a cavity model simulating the cuspal deflection which occurs on filled tooth cavity walls in clinical condition. Materials and methods 20 stylized MOD cavities (C-factor = 0.83) were performed in acrylic resin. The inner surface of each cavity was sand blasted and adhesively treated in order to ensure a valid bond with the composite resin. Three different diameter of SGMF were used (i.e. 1, 1,5, 2 mm). The samples were divided in 4 groups of 5 each: Group 1 samples filled with the composite only; Group 2 samples filled with composite added with SGMFs, Ø1mm (16 spheres for each sample); Group 3 samples filled with composite added with SGMFs, Ø1,5 mm (5 spheres for each sample); Group 4 samples filled with composite added with SGMFs, Ø2 mm (2 spheres for each sample). Digital pictures were taken, in standardized settings, before and immediately after the polymerization of the composite material, placed into the cavities. With a digital image analysis software the distances from the coronal reference points of the cavity walls were measured. Then the difference between the first and second measurement was calculated. The data were analyzed by means of the ANOVA test. Results A significative reduction on cavity walls deflection, when the composite resin is used in addiction with the SGMFs was observed. The SGMFs of smallest diameter (1mm) showed the better outcome. Conclusion The SGMFs are reliable in reducing contraction stress in dental composite resins. PMID:28280535

Apparatus for premixing in a gas turbine engine

DOEpatents

McCormick, Keith Alan; Smith, Duane A.

2002-01-01

An apparatus for mixing fuel with oxidizing agent is disclosed comprising an outer body and an inner body. The outer body has an interior surface extending between an inlet end toward an outlet end. The interior surface includes a first plurality of openings. The inner body has an exterior surface extending between the first end and the second end of the inner body. The exterior surface of the inner body includes a second plurality of openings. At least a portion of the exterior surface of the inner body is positioned within the outer body to define a mixing channel between the exterior surface of the inner body and the interior surface of the outer body. In one form the first and second plurality of openings substantially longitudinally span at least one of the outer body and the inner body. In another form the first and second plurality of openings are substantially radially oriented. In yet another form the first and second plurality of openings are offset from one another.

Insight into the core-shell structures of Cu-In-S microspheres

NASA Astrophysics Data System (ADS)

Wochnik, Angela S.; Frank, Anna; Heinzl, Christoph; Häusler, Jonas; Schneider, Julian; Hoffmann, Ramona; Matich, Sonja; Scheu, Christina

2013-12-01

In this study we report about the inner and outer structure of CuInS2 microspheres which might be used e.g. in pastes for simple, low-cost solar cell preparation, as well as in electrodes for light-driven water splitting. The microspheres are synthesized via a mild, template-free solvothermal synthesis route and characterised by electron and focused ion beam microscopy, X-ray diffraction, inductively coupled plasma atomic emission and energy dispersive X-ray spectroscopy. The investigations of cross sections prepared by focused ion beam showed that the spheres consist of compact cores and flaky surface structures. Depending on the reaction time, the core possesses a stoichiometric or Cu-rich chemical composition surrounded by an In-rich shell. The flaky surface always comprises a stoichiometric composition in tetragonal chalcopyrite crystal structure, whereas the other areas additionally show minor contributions of CuS, and CuInS2 in hexagonal wurtzite structure. The presence of different phases can be beneficial for future applications since they offer different absorption behaviour in the visible range.

Atomistic Simulations of Complex DNA DSBs and the Interactions with Ku70/80 Heterodimer

NASA Technical Reports Server (NTRS)

Hu, Shaowen; Cucinotta, Francis A.

2011-01-01

Compared to DNA with simple DSBs, the complex lesions can enhance the hydrogen bonds opening rate at the DNA terminus, and increase the mobility of the whole duplex. Binding of Ku drastically reduces the structural disruption and flexibility caused by the complex lesions. In all complex DSBs systems, the binding of DSB terminus with Ku70 is softened while the binding of the middle duplex with Ku80 is tightened. Binding of Ku promotes the rigidity of DNA duplexes, due to the clamp structure of the inner surface of the rings of Ku70/80.

Attachment device for an inflatable protective cushion

DOEpatents

Nelsen, J.M.; Luna, D.A.; Gwinn, K.W.

1997-11-18

An inflatable cushion assembly for use with an inflator comprises an inflatable cushion having an inner surface, outer surface, and at least one protrusion extending from one of the inner or outer surfaces. The inflatable cushion defines an opening between the inner surface and the outer surface for receiving the inflator. An attachment member contacts the one of the inner or outer surfaces adjacent the opening and includes a groove for receiving the protrusion, the attachment member securing the inflator within the opening. 22 figs.

Attachment device for an inflatable protective cushion

DOEpatents

Nelsen, J.M.; Luna, D.A.; Gwinn, K.W.

1998-12-08

An inflatable cushion assembly for use with an inflator comprises an inflatable cushion having an inner surface, outer surface, and at least one protrusion extending from one of the inner or outer surfaces. The inflatable cushion defines an opening between the inner surface and the outer surface for receiving the inflator. An attachment member contacts the one of the inner or outer surfaces adjacent the opening and includes a groove for receiving the protrusion, the attachment member securing the inflator within the opening. 22 figs.

Radiation induced deposition of copper nanoparticles inside the nanochannels of poly(acrylic acid)-grafted poly(ethylene terephthalate) track-etched membranes

NASA Astrophysics Data System (ADS)

Korolkov, Ilya V.; Güven, Olgun; Mashentseva, Anastassiya A.; Atıcı, Ayse Bakar; Gorin, Yevgeniy G.; Zdorovets, Maxim V.; Taltenov, Abzal A.

2017-01-01

Poly(ethylene terephthalate) PET, track-etched membranes (TeMs) with 400 nm average pore size were UV-grafted with poly(acrylic acid) (PAA) after oxidation of inner surfaces by H2O2/UV system. Carboxylate groups of grafted PAA chains were easily complexed with Cu2+ ions in aqueous solutions. These ions were converted into metallic copper nanoparticles (NPs) by radiation-induced reduction of copper ions in aqueous-alcohol solution by gamma rays in the dose range of 46-250 kGy. Copper ions chelating with -COOH groups of PAA chains grafted on PET TeMs form polymer-metal ion complex that prevent the formation of agglomerates during reduction of copper ions to metallic nanoparticles. The detailed analysis by X-Ray diffraction technique (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) confirmed the deposition of copper nanoparticles with the average size of 70 nm on the inner surface of nanochannels of PET TeMs. Samples were also investigated by FTIR, ESR spectroscopies to follow copper ion reduction.

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors.

PubMed

Wilgosz, Karolina; Chen, Xuecheng; Kierzek, Krzysztof; Machnikowski, Jacek; Kalenczuk, Ryszard J; Mijowska, Ewa

2012-05-29

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors.

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

NASA Astrophysics Data System (ADS)

Wilgosz, Karolina; Chen, Xuecheng; Kierzek, Krzysztof; Machnikowski, Jacek; Kalenczuk, Ryszard J.; Mijowska, Ewa

2012-05-01

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors.

High photocatalytic activity of hierarchical SiO2@C-doped TiO2 hollow spheres in UV and visible light towards degradation of rhodamine B.

PubMed

Zhang, Ying; Chen, Juanrong; Hua, Li; Li, Songjun; Zhang, Xuanxuan; Sheng, Weichen; Cao, Shunsheng

2017-10-15

Ongoing research activities are targeted to explore high photocatalytic activity of TiO 2 -based photocatalysts for the degradation of environmental contaminants under UV and visible light irradiation. In this work, we devise a facile, cost-effective technique to in situ synthesize hierarchical SiO 2 @C-doped TiO 2 (SCT) hollow spheres for the first time. This strategy mainly contains the preparation of monodisperse cationic polystyrene spheres (CPS), sequential deposition of inner SiO 2 , the preparation of the sandwich-like CPS@SiO 2 @CPS particles, and formation of outer TiO 2 . After the one-step removal of CPS templates by calcination at 450°C, hierarchical SiO 2 @C-doped TiO 2 hollow spheres are in situ prepared. The morphology, hierarchical structure, and properties of SCT photocatalyst were characterized by TEM. SEM, STEM Mapping, BET, XRD, UV-vis spectroscopy, and XPS. Results strongly confirm the carbon doping in the outer TiO 2 lattice of SCT hollow spheres. When the as-synthesized SCT hollow spheres were employed as a photocatalyst for the degradation of Rhodamine B under visible-light and ultraviolet irradiation, the SCT photocatalyst exhibits a higher photocatalytic activity than commercial P25, effectively overcoming the limitations of poorer UV activity for many previous reported TiO 2 -based photocatalysts due to doping. Copyright © 2017 Elsevier B.V. All rights reserved.

Differential regulation of cellulose orientation at the inner and outer face of epidermal cells in the Arabidopsis hypocotyl.

PubMed

Crowell, Elizabeth Faris; Timpano, Hélène; Desprez, Thierry; Franssen-Verheijen, Tiny; Emons, Anne-Mie; Höfte, Herman; Vernhettes, Samantha

2011-07-01

It is generally believed that cell elongation is regulated by cortical microtubules, which guide the movement of cellulose synthase complexes as they secrete cellulose microfibrils into the periplasmic space. Transversely oriented microtubules are predicted to direct the deposition of a parallel array of microfibrils, thus generating a mechanically anisotropic cell wall that will favor elongation and prevent radial swelling. Thus far, support for this model has been most convincingly demonstrated in filamentous algae. We found that in etiolated Arabidopsis thaliana hypocotyls, microtubules and cellulose synthase trajectories are transversely oriented on the outer surface of the epidermis for only a short period during growth and that anisotropic growth continues after this transverse organization is lost. Our data support previous findings that the outer epidermal wall is polylamellate in structure, with little or no anisotropy. By contrast, we observed perfectly transverse microtubules and microfibrils at the inner face of the epidermis during all stages of cell expansion. Experimental perturbation of cortical microtubule organization preferentially at the inner face led to increased radial swelling. Our study highlights the previously underestimated complexity of cortical microtubule organization in the shoot epidermis and underscores a role for the inner tissues in the regulation of growth anisotropy.

Differential Regulation of Cellulose Orientation at the Inner and Outer Face of Epidermal Cells in the Arabidopsis Hypocotyl[W

PubMed Central

Crowell, Elizabeth Faris; Timpano, Hélène; Desprez, Thierry; Franssen-Verheijen, Tiny; Emons, Anne-Mie; Höfte, Herman; Vernhettes, Samantha

2011-01-01

It is generally believed that cell elongation is regulated by cortical microtubules, which guide the movement of cellulose synthase complexes as they secrete cellulose microfibrils into the periplasmic space. Transversely oriented microtubules are predicted to direct the deposition of a parallel array of microfibrils, thus generating a mechanically anisotropic cell wall that will favor elongation and prevent radial swelling. Thus far, support for this model has been most convincingly demonstrated in filamentous algae. We found that in etiolated Arabidopsis thaliana hypocotyls, microtubules and cellulose synthase trajectories are transversely oriented on the outer surface of the epidermis for only a short period during growth and that anisotropic growth continues after this transverse organization is lost. Our data support previous findings that the outer epidermal wall is polylamellate in structure, with little or no anisotropy. By contrast, we observed perfectly transverse microtubules and microfibrils at the inner face of the epidermis during all stages of cell expansion. Experimental perturbation of cortical microtubule organization preferentially at the inner face led to increased radial swelling. Our study highlights the previously underestimated complexity of cortical microtubule organization in the shoot epidermis and underscores a role for the inner tissues in the regulation of growth anisotropy. PMID:21742992

A reference standard for bidirectional reflection distribution function and bidirectional transmission distribution function measurement

NASA Technical Reports Server (NTRS)

Witherow, William K. (Inventor)

1988-01-01

A Lambertian reference standard for uniformly scattering a beam of light is constructed of a plate having a planar surface with a layer of glue disposed on the surface. An evenly packed layer of monodisperse spheres is set in the layer, and when the standard is used for bi-directional (BRDF) measurements, the spheres are coated with a layer of highly relective substance, such as gold or silver. When the standard is used for bi-directional transmittance distribution function (BTDF) measurements, the spheres are of a transparent material and are provided with a roughened surface, as by acid etching. In this case, the layer of glue is an optical cement, and the plate is of glass, with the spheres, the layer, and the plate all possessing a similar refractive index.

Nature and regional significance of unconformities associated with the Middle Ordovician Hagan K-bentonite complex in the North American midcontinent

USGS Publications Warehouse

Kolata, Dennis R.; Huff, W.D.; Bergstrom, Stig M.

1998-01-01

Stratal patterns of the Middle Ordovician Hagan K-bentonite complex and associated rocks show that the Black River-Trenton unconformity in the North American midcontinent formed through the complex interplay of eustasy, sediment accumulation rates, siliciclastic influx, bathymetry, seawater chemistry, and perhaps local tectonic uplift. The unconformity is diachronous and is an amalgamated surface that resulted from local late Turinian lowstand exposure followed by regional early Chatfieldian transgressive drowning and sediment starvation. The duration of the unconformity is greatest in southern Wisconsin, northern Illinois, and northern Indiana, where the Deicke and Millbrig K-bentonite Beds converge at the unconformity. On the basis of published isotopic ages for the Deicke and Millbrig beds, it is possible that in these regions erosion and non-deposition spanned a period of as much as 3.2 m.y. Two broad coeval depositional settings are recognized within the North American midcontinent during early Chatfieldian time. 1) An inner shelf, subtidal facies of fossiliferous shale (Spechts Ferry Shale Member and Ion Shale Member of the Decorah Formation) and argillaceous lime mudstone and skeletal wackestone (Guttenberg and Kings Lake Limestone Members) extended from the Canadian shield and Transcontinental arch southeastward through Minnesota, Wisconsin, Iowa, and Missouri. 2) A seaward, relatively deep subtidal, sediment-starved, middle shelf extended eastward from the Mississippi Valley region to the Taconian foreland basins in the central and southern Appalachians and southward through the pericratonic Arkoma and Black Warrior basins. In the inner shelf region, the Black River-Trenton unconformity is a composite of at least two prominent hardground omission surfaces, one at the top of the Castlewood and Carimona Limestone Members and the other at the top of the Guttenberg and Kings Lake Limestone Members, both merging to a single surface in the middle shelf region. The inner and middle shelves redeveloped later in approximately the same regions during Devonian and Mississippian time.

Modelling study of sea breezes in a complex coastal environment

NASA Astrophysics Data System (ADS)

Cai, X.-M.; Steyn, D. G.

This study investigates a mesoscale modelling of sea breezes blowing from a narrow strait into the lower Fraser valley (LFV), British Columbia, Canada, during the period of 17-20 July, 1985. Without a nudging scheme in the inner grid, the CSU-RAMS model produces satisfactory wind and temperature fields during the daytime. In comparison with observation, the agreement indices for surface wind and temperature during daytime reach about 0.6 and 0.95, respectively, while the agreement indices drop to 0.4 at night. In the vertical, profiles of modelled wind and temperature generally agree with tethersonde data collected on 17 and 19 July. The study demonstrates that in late afternoon, the model does not capture the advection of an elevated warm layer which originated from land surfaces outside of the inner grid. Mixed layer depth (MLD) is calculated from model output of turbulent kinetic energy field. Comparison of MLD results with observation shows that the method generates a reliable MLD during the daytime, and that accurate estimates of MLD near the coast require the correct simulation of wind conditions over the sea. The study has shown that for a complex coast environment like the LFV, a reliable modelling study depends not only on local surface fluxes but also on elevated layers transported from remote land surfaces. This dependence is especially important when local forcings are weak, for example, during late afternoon and at night.

Design and Synthesis of Hierarchical SiO2@C/TiO2 Hollow Spheres for High-Performance Supercapacitors.

PubMed

Zhang, Ying; Zhao, Yan; Cao, Shunsheng; Yin, Zhengliang; Cheng, Li; Wu, Limin

2017-09-06

TiO 2 has been widely investigated as an electrode material because of its long cycle life and good durability, but the relatively low theoretical capacity restricts its practical application. Herein, we design and synthesize novel hierarchical SiO 2 @C/TiO 2 (HSCT) hollow spheres via a template-directed method. These unique HSCT hollow spheres combine advantages from both TiO 2 such as cycle stability and SiO 2 with a high accessible area and ionic transport. In particular, the existence of a C layer is able to enhance the electrical conductivity. The SiO 2 layer with a porous structure can increase the ion diffusion channels and accelerate the ion transfer from the outer to the inner layers. The electrochemical measurements demonstrate that the HSCT-hollow-sphere-based electrode manifests a high specific capacitance of 1018 F g -1 at 1 A g -1 which is higher than those for hollow TiO 2 (113 F g -1 ) and SiO 2 /TiO 2 (252 F g -1 ) electrodes, and substantially higher than those of all the previously reported TiO 2 -based electrodes.

Transferable ordered ni hollow sphere arrays induced by electrodeposition on colloidal monolayer.

PubMed

Duan, Guotao; Cai, Weiping; Li, Yue; Li, Zhigang; Cao, Bingqiang; Luo, Yuanyuan

2006-04-13

We report an electrochemical synthesis of two-dimensionally ordered porous Ni arrays based on polystyrene sphere (PS) colloidal monolayer. The morphology can be controlled from bowl-like to hollow sphere-like structure by changing deposition time under a constant current. Importantly, such ordered Ni arrays on a conducting substrate can be transferred integrally to any other desired substrates, especially onto an insulting substrate or curved surface. The magnetic measurements of the two-dimensional hollow sphere array show the coercivity values of 104 Oe for the applied field parallel to the film, and 87 Oe for the applied field perpendicular to the film, which is larger than those of bulk Ni and hollow Ni submicrometer-sized spheres. The formation of hollow sphere arrays is attributed to preferential nucleation on the interstitial sites between PS in the colloidal monolayer and substrate, and growth along PSs' surface. The transferability of the arrays originates from partial contact between the Ni hollow spheres and substrate. Such novel Ni ordered nanostructured arrays with transferability and high magnetic properties should be useful in applications such as data storage, catalysis, and magnetics.

Vented Cavity Radiant Barrier Assembly And Method

DOEpatents

Dinwoodie, Thomas L.; Jackaway, Adam D.

2000-05-16

A vented cavity radiant barrier assembly (2) includes a barrier (12), typically a PV module, having inner and outer surfaces (18, 22). A support assembly (14) is secured to the barrier and extends inwardly from the inner surface of the barrier to a building surface (14) creating a vented cavity (24) between the building surface and the barrier inner surface. A low emissivity element (20) is mounted at or between the building surface and the barrier inner surface. At least part of the cavity exit (30) is higher than the cavity entrance (28) to promote cooling air flow through the cavity.

Acoustic scattering by arbitrary distributions of disjoint, homogeneous cylinders or spheres.

PubMed

Hesford, Andrew J; Astheimer, Jeffrey P; Waag, Robert C

2010-05-01

A T-matrix formulation is presented to compute acoustic scattering from arbitrary, disjoint distributions of cylinders or spheres, each with arbitrary, uniform acoustic properties. The generalized approach exploits the similarities in these scattering problems to present a single system of equations that is easily specialized to cylindrical or spherical scatterers. By employing field expansions based on orthogonal harmonic functions, continuity of pressure and normal particle velocity are directly enforced at each scatterer using diagonal, analytic expressions to eliminate the need for integral equations. The effect of a cylinder or sphere that encloses all other scatterers is simulated with an outer iterative procedure that decouples the inner-object solution from the effect of the enclosing object to improve computational efficiency when interactions among the interior objects are significant. Numerical results establish the validity and efficiency of the outer iteration procedure for nested objects. Two- and three-dimensional methods that employ this outer iteration are used to measure and characterize the accuracy of two-dimensional approximations to three-dimensional scattering of elevation-focused beams.

Hierarchical Porous Carbon Spheres for High-Performance Na-O2 Batteries.

PubMed

Sun, Bing; Kretschmer, Katja; Xie, Xiuqiang; Munroe, Paul; Peng, Zhangquan; Wang, Guoxiu

2017-12-01

As a new family member of room-temperature aprotic metal-O 2 batteries, Na-O 2 batteries, are attracting growing attention because of their relatively high theoretical specific energy and particularly their uncompromised round-trip efficiency. Here, a hierarchical porous carbon sphere (PCS) electrode that has outstanding properties to realize Na-O 2 batteries with excellent electrochemical performances is reported. The controlled porosity of the PCS electrode, with macropores formed between PCSs and nanopores inside each PCS, enables effective formation/decomposition of NaO 2 by facilitating the electrolyte impregnation and oxygen diffusion to the inner part of the oxygen electrode. In addition, the discharge product of NaO 2 is deposited on the surface of individual PCSs with an unusual conformal film-like morphology, which can be more easily decomposed than the commonly observed microsized NaO 2 cubes in Na-O 2 batteries. A combination of coulometry, X-ray diffraction, and in situ differential electrochemical mass spectrometry provides compelling evidence that the operation of the PCS-based Na-O 2 battery is underpinned by the formation and decomposition of NaO 2 . This work demonstrates that employing nanostructured carbon materials to control the porosity, pore-size distribution of the oxygen electrodes, and the morphology of the discharged NaO 2 is a promising strategy to develop high-performance Na-O 2 batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Layer-by-Layer Assembled Architecture of Polyelectrolyte Multilayers and Graphene Sheets on Hollow Carbon Spheres/Sulfur Composite for High-Performance Lithium-Sulfur Batteries.

PubMed

Wu, Feng; Li, Jian; Su, Yuefeng; Wang, Jing; Yang, Wen; Li, Ning; Chen, Lai; Chen, Shi; Chen, Renjie; Bao, Liying

2016-09-14

In the present work, polyelectrolyte multilayers (PEMs) and graphene sheets are applied to sequentially coat on the surface of hollow carbon spheres/sulfur composite by a flexible layer-by-layer (LBL) self-assembly strategy. Owing to the strong electrostatic interactions between the opposite charged materials, the coating agents are very stable and the coating procedure is highly efficient. The LBL film shows prominent impact on the stability of the cathode by acting as not only a basic physical barrier, and more importantly, an ion-permselective film to block the polysulfides anions by Coulombic repulsion. Furthermore, the graphene sheets can help to stabilize the polyelectrolytes film and greatly reduce the inner resistance of the electrode by changing the transport of the electrons from a "point-to-point" mode to a more effective "plane-to-point'' mode. On the basis of the synergistic effect of the PEMs and graphene sheets, the fabricated composite electrode exhibits very stable cycling stability for over 200 cycles at 1 A g(-1), along with a high average Coulombic efficiency of 99%. With the advantages of rapid and controllable fabrication of the LBL coating film, the multifunctional architecture developed in this study should inspire the design of other lithium-sulfur cathodes with unique physical and chemical properties.

Periplasmic orientation of nascent lipid A in the inner membrane of an Escherichia coli LptA mutant

PubMed Central

Ma, Bing; Reynolds, C. Michael; Raetz, Christian R. H.

2008-01-01

The core-lipid A domain of Escherichia coli lipopolysaccharide (LPS) is synthesized on the inner surface of the inner membrane (IM) and flipped to its outer surface by the ABC transporter MsbA. Recent studies with deletion mutants implicate the periplasmic protein LptA, the cytosolic protein LptB, and the IM proteins LptC, LptF, and LptG in the subsequent transport of nascent LPS to the outer membrane (OM), where the LptD/LptE complex flips LPS to the outer surface. We have isolated a temperature-sensitive mutant (MB1) harboring the S22C and Q111P substitutions in LptA. MB1 stops growing after 30 min at 42°C. 32Pi and [35S]methionine labeling show that export of newly synthesized phospholipids and proteins is not severely impaired, but export of LPS is defective. Using the lipid A 1-phosphatase LpxE as a periplasmic IM marker and the lipid A 3-O-deacylase PagL as an OM marker, we show that core-lipid A reaches the periplasmic side of the IM at 42°C in MB1 but not the outer surface of the OM. Electron microscopy of MB1 reveals dense periplasmic material and a smooth OM at 42°C, consistent with a role for LptA in shuttling LPS across the periplasm. PMID:18768814

Periplasmic orientation of nascent lipid A in the inner membrane of an Escherichia coli LptA mutant.

PubMed

Ma, Bing; Reynolds, C Michael; Raetz, Christian R H

2008-09-16

The core-lipid A domain of Escherichia coli lipopolysaccharide (LPS) is synthesized on the inner surface of the inner membrane (IM) and flipped to its outer surface by the ABC transporter MsbA. Recent studies with deletion mutants implicate the periplasmic protein LptA, the cytosolic protein LptB, and the IM proteins LptC, LptF, and LptG in the subsequent transport of nascent LPS to the outer membrane (OM), where the LptD/LptE complex flips LPS to the outer surface. We have isolated a temperature-sensitive mutant (MB1) harboring the S22C and Q111P substitutions in LptA. MB1 stops growing after 30 min at 42 degrees C. (32)P(i) and [(35)S]methionine labeling show that export of newly synthesized phospholipids and proteins is not severely impaired, but export of LPS is defective. Using the lipid A 1-phosphatase LpxE as a periplasmic IM marker and the lipid A 3-O-deacylase PagL as an OM marker, we show that core-lipid A reaches the periplasmic side of the IM at 42 degrees C in MB1 but not the outer surface of the OM. Electron microscopy of MB1 reveals dense periplasmic material and a smooth OM at 42 degrees C, consistent with a role for LptA in shuttling LPS across the periplasm.

Surface term effects on mass estimators

NASA Astrophysics Data System (ADS)

Membrado, M.; Pacheco, A. F.

2016-05-01

Context. We propose a way of estimating the mass contained in the volume occupied by a sample of galaxies in a virialized system. Aims: We analyze the influence of surface effects and the contribution of the cosmological constant terms on our mass estimations of galaxy systems. Methods: We propose two equations that contain surface terms to estimate galaxy sample masses. When the surface terms are neglected, these equations provide the so-called virial and projected masses. Both equations lead to a single equation that allows sample masses to be estimated without the need for calculating surface terms. Sample masses for some nearest galaxy groups are estimated and compared with virialized masses determined from turn-around radii and results of a spherical infall model. Results: Surface effects have a considerable effect on the mass estimations of the studied galaxy groups. According to our results, they lead sample masses of some groups to being less than half the virial mass estimations and even less than 10% of projected mass estimations. However, the contributions of cosmological constant terms to mass estimations are smaller than 2% for the majority of the virialized groups studied. Our estimations are in agreement with virialized masses calculated from turn-around radii. Virialized masses for complexes were found to be: (8.9 ± 2.8) × 1011 M⊙ for the Milky Way - M 31; (12.5 ± 2.5) × 1011 M⊙ for M 81 - NGC 2403; (21.5 ± 7.7) × 1011 M⊙. for Cantaurs A - M 83; and (7.9 ± 2.6) × 1011 M⊙. for IC 324 - Maffei. Conclusions: The nearest galaxy groups located inside a sphere of 5 Mpc have been addressed to explore the performance of our mass estimator. We have seen that surface effects make mass estimations of galaxy groups rather smaller than both virial and projected masses. In mass calculations, cosmological constant terms can be neglected; nevertheless, the collapse of cold dark matter leading to virialized structures is strongly affected by the cosmological constant. We have also seen that, if mass density were proportional to luminosity density on different scales in the Universe, the 5 Mpc sphere would have a mean density close to that of the sphere region containing galaxies and systems of galaxies; thus, the rest of the sphere could contain regions of low-mass dark halos with similar mass density. This mass density would be about 4.5 times greater than that of the matter background of the Universe at present.

The edge artifact in the point-spread function-based PET reconstruction at different sphere-to-background ratios of radioactivity.

PubMed

Kidera, Daisuke; Kihara, Ken; Akamatsu, Go; Mikasa, Shohei; Taniguchi, Takafumi; Tsutsui, Yuji; Takeshita, Toshiki; Maebatake, Akira; Miwa, Kenta; Sasaki, Masayuki

2016-02-01

The aim of this study was to quantitatively evaluate the edge artifacts in PET images reconstructed using the point-spread function (PSF) algorithm at different sphere-to-background ratios of radioactivity (SBRs). We used a NEMA IEC body phantom consisting of six spheres with 37, 28, 22, 17, 13 and 10 mm in inner diameter. The background was filled with (18)F solution with a radioactivity concentration of 2.65 kBq/mL. We prepared three sets of phantoms with SBRs of 16, 8, 4 and 2. The PET data were acquired for 20 min using a Biograph mCT scanner. The images were reconstructed with the baseline ordered subsets expectation maximization (OSEM) algorithm, and with the OSEM + PSF correction model (PSF). For the image reconstruction, the number of iterations ranged from one to 10. The phantom PET image analyses were performed by a visual assessment of the PET images and profiles, a contrast recovery coefficient (CRC), which is the ratio of SBR in the images to the true SBR, and the percent change in the maximum count between the OSEM and PSF images (Δ % counts). In the PSF images, the spheres with a diameter of 17 mm or larger were surrounded by a dense edge in comparison with the OSEM images. In the spheres with a diameter of 22 mm or smaller, an overshoot appeared in the center of the spheres as a sharp peak in the PSF images in low SBR. These edge artifacts were clearly observed in relation to the increase of the SBR. The overestimation of the CRC was observed in 13 mm spheres in the PSF images. In the spheres with a diameter of 17 mm or smaller, the Δ % counts increased with an increasing SBR. The Δ % counts increased to 91 % in the 10-mm sphere at the SBR of 16. The edge artifacts in the PET images reconstructed using the PSF algorithm increased with an increasing SBR. In the small spheres, the edge artifact was observed as a sharp peak at the center of spheres and could result in overestimation.

Measurement of the Casimir Force between Two Spheres

NASA Astrophysics Data System (ADS)

Garrett, Joseph L.; Somers, David A. T.; Munday, Jeremy N.

2018-01-01

Complex interaction geometries offer a unique opportunity to modify the strength and sign of the Casimir force. However, measurements have traditionally been limited to sphere-plate or plate-plate configurations. Prior attempts to extend measurements to different geometries relied on either nanofabrication techniques that are limited to only a few materials or slight modifications of the sphere-plate geometry due to alignment difficulties of more intricate configurations. Here, we overcome this obstacle to present measurements of the Casimir force between two gold spheres using an atomic force microscope. Force measurements are alternated with topographical scans in the x -y plane to maintain alignment of the two spheres to within approximately 400 nm (˜1 % of the sphere radii). Our experimental results are consistent with Lifshitz's theory using the proximity force approximation (PFA), and corrections to the PFA are bounded using nine sphere-sphere and three sphere-plate measurements with spheres of varying radii.

Computation of resistive instabilities by matched asymptotic expansions

DOE PAGES

Glasser, A. H.; Wang, Z. R.; Park, J. -K.

2016-11-17

Here, we present a method for determining the linear resistive magnetohydrodynamic (MHD) stability of an axisymmetric toroidal plasma, based on the method of matched asymptotic expansions. The plasma is partitioned into a set of ideal MHD outer regions, connected through resistive MHD inner regions about singular layers where q = m/n, with m and n toroidal mode numbers, respectively, and q the safety factor. The outer regions satisfy the ideal MHD equations with zero-frequency, which are identical to the Euler-Lagrange equations for minimizing the potential energy delta W. The solutions to these equations go to infinity at the singular surfaces.more » The inner regions satisfy the equations of motion of resistive MHD with a finite eigenvalue, resolving the singularity. Both outer and inner regions are solved numerically by newly developed singular Galerkin methods, using specialized basis functions. These solutions are matched asymptotically, providing a complex dispersion relation which is solved for global eigenvalues and eigenfunctions in full toroidal geometry. The dispersion relation may have multiple complex unstable roots, which are found by advanced root-finding methods. These methods are much faster and more robust than the previous numerical methods. The new methods are applicable to more challenging high-pressure and strongly shaped plasma equilibria and generalizable to more realistic inner region dynamics. In the thermonuclear regime, where the outer and inner regions overlap, they are also much faster and more accurate than the straight-through methods, which treat the resistive MHD equations in the whole plasma volume.« less

Micro-mesoporous carbon spheres derived from carrageenan as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Fan, Yang; Yang, Xin; Zhu, Bing; Liu, Pei-Fang; Lu, Hai-Ting

2014-12-01

The polysaccharide carrageenan is used as a natural precursor to prepare micro-mesoporous carbon spheres. The carbon spheres were synthesized by hydrothermal carbonization of carrageenan, and subsequent chemical activation by KOH at different temperatures. The obtained micro-mesoporous carbon spheres have high surface area (up to 2502 m2 g-1) and large pore volume (up to 1.43 cm3 g-1). Moreover, the micro- and mesoporosity can be finely tuned be modifying the activation temperatures in the range of 700-900 °C. The carbon spheres activated at 900 °C present high specific capacitance of 230 F g-1 at a current density of 1 A g-1 and good ion transport kinetics. The good capacitive performance can be ascribed to the high specific surface area, well-controlled micro- and mesoporosity and narrow pore size distribution.

Solvent-induced synthesis of nitrogen-doped hollow carbon spheres with tunable surface morphology for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Feng; Yuan, Ren-Lu; Zhang, Ning; Ke, Chang-Ce; Ma, Shao-Xia; Zhang, Ru-Liang; Liu, Lei

2018-04-01

Nitrogen doped hollow carbon spheres (NHCSs) with tunable surface morphology have been prepared through one-pot carbonization method by using melamine-formaldehyde spheres as template and resorcinol-based resin as carbon precursor in ethanol-water solution. Well-dispersed NHCSs with particle size of 800 nm were obtained and the surface of NHCSs turn from smooth to tough, wrinkled, and finally concave by increasing the ethanol concentration. The fabricated NHCSs possessed high nitrogen content (3.99-4.83%) and hierarchical micro-dual mesoporous structure with surface area range of 265-405 m2 g-1 and total pore volume of 0.18-0.29 cm3 g-1, which contributed to high specific capacitance, excellent rate capability and long cycle life.

Rapid and highly efficient preconcentration of Eu(III) by core-shell structured Fe3O4@humic acid magnetic nanoparticles.

PubMed

Yang, Shitong; Zong, Pengfei; Ren, Xuemei; Wang, Qi; Wang, Xiangke

2012-12-01

In this study, humic acid-coated Fe(3)O(4) magnetic nanoparticles (Fe(3)O(4)@HA MNPs) were synthesized using a chemical coprecipitation method and characterized in detail. The XRD analysis results showed that HA coating did not change the phase of Fe(3)O(4) cores. The TEM image suggested that Fe(3)O(4)@HA MNPs had nearly uniform size without the observation of aggregation. The Fe(3)O(4)@HA MNPs were stable in solution and could be easily separated from aqueous solution using a magnetic separation method. A batch technique was adopted to investigate the removal efficiency of Fe(3)O(4)@HA MNPs toward Eu(III) under various environmental conditions. The kinetic process of Eu(III) sorption on Fe(3)O(4)@HA MNPs reached equilibrium within <30 min. The fast sorption kinetics and high sorption amount were attributed to the plentiful surface sites provided by the surface-coated HA macromolecules. The Fe(3)O(4)@HA MNPs was able to remove ~99% of Eu(III) in aqueous solution at pH 8.5. Except for SO(4)(2-) anions, the coexisting electrolyte ions had no significant competition effects on the removal of Eu(III) by Fe(3)O(4)@HA MNPs. The obvious sorption-desorption hysteresis suggested that the removal of Eu(III) was dominated by inner-sphere surface complexation. The sorption isotherm agreed well with the Langmuir model, having a maximum sorption capacity of 6.95 × 10(-5) mol g(-1). The leaching test showed that the Eu(III)-loaded Fe(3)O(4)@HA colloids were capable to maintain high thermodynamic stability for long aging times. The findings herein suggested that Fe(3)O(4)@HA MNPs could be potentially used as a highly effective material for the enrichment and preconcentration of radionuclide Eu(III) or other trivalent lanthanides/actinides in geological repositories or in nuclear waste management.

Interaction of Tim23 with Tim50 Is essential for protein translocation by the mitochondrial TIM23 complex.

PubMed

Gevorkyan-Airapetov, Lada; Zohary, Keren; Popov-Celeketic, Dusan; Mapa, Koyeli; Hell, Kai; Neupert, Walter; Azem, Abdussalam; Mokranjac, Dejana

2009-02-20

The TIM23 complex is the major translocase of the mitochondrial inner membrane responsible for the import of essentially all matrix proteins and a number of inner membrane proteins. Tim23 and Tim50, two essential proteins of the complex, expose conserved domains into the intermembrane space that interact with each other. Here, we describe in vitro reconstitution of this interaction using recombinantly expressed and purified intermembrane space domains of Tim50 and Tim23. We established two independent methods, chemical cross-linking and surface plasmon resonance, to track their interaction. In addition, we identified mutations in Tim23 that abolish its interaction with Tim50 in vitro. These mutations also destabilized the interaction between the two proteins in vivo, leading to defective import of preproteins via the TIM23 complex and to cell death at higher temperatures. This is the first study to describe the reconstitution of the Tim50-Tim23 interaction in vitro and to identify specific residues of Tim23 that are vital for the interaction with Tim50.

Fast RBF OGr for solving PDEs on arbitrary surfaces

NASA Astrophysics Data System (ADS)

Piret, Cécile; Dunn, Jarrett

2016-10-01

The Radial Basis Functions Orthogonal Gradients method (RBF-OGr) was introduced in [1] to discretize differential operators defined on arbitrary manifolds defined only by a point cloud. We take advantage of the meshfree character of RBFs, which give us a high accuracy and the flexibility to represent complex geometries in any spatial dimension. A large limitation of the RBF-OGr method was its large computational complexity, which greatly restricted the size of the point cloud. In this paper, we apply the RBF-Finite Difference (RBF-FD) technique to the RBF-OGr method for building sparse differentiation matrices discretizing continuous differential operators such as the Laplace-Beltrami operator. This method can be applied to solving PDEs on arbitrary surfaces embedded in ℛ3. We illustrate the accuracy of our new method by solving the heat equation on the unit sphere.

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

PubMed Central

2012-01-01

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors. PMID:22643113

Migration of 75Se(IV) in crushed Beishan granite: Effects of the iron content.

PubMed

He, Jiangang; Ma, Bin; Kang, Mingliang; Wang, Chunli; Nie, Zhe; Liu, Chunli

2017-02-15

The diffusion of selenite (labeled with 75 Se) in compacted Beishan granite (BsG) was investigated using the in-diffusion capillary method at pH values from ∼2.0 to ∼11.0 under oxic and anoxic conditions. The results indicate that the apparent diffusion coefficient (D a ) values of selenite in BsG always reached the minimum at approximately pH 5. Unexpectedly, the D a values under oxic conditions are nearly one order of magnitude lower than those under the anoxic conditions. Further characterization reveals the existence of redox-sensitive Fe(II)-containing components, which can be responsible for the great difference in D a values. Fe(2p) X-ray photoelectron spectroscopy (XPS) results show that more Fe(III)-oxyhydroxide coating is formed on the granite's surface under aerobic conditions than is formed under anaerobic conditions. Correspondingly, Se(3d) spectra indicate that more selenium is sorbed under oxic conditions, and the sorbed amount always reached the maximum at pH values from ∼4 to ∼5. A linear combination fit of X-ray absorption near edge structure (XANES) spectroscopy data revealed that Se(0) was formed under anoxic condition and that selenite preferred to form inner-sphere complexes with Fe(III)-oxyhydroxide. Overall, this study indicates that natural Fe-bearing minerals can greatly attenuate selenite diffusion and the retardation would be enhanced under aerobic conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

Arsenic scavenging by aluminum-substituted ferrihydrites in a circumneutral pH river impacted by acid mine drainage.

PubMed

Adra, Areej; Morin, Guillaume; Ona-Nguema, Georges; Menguy, Nicolas; Maillot, Fabien; Casiot, Corinne; Bruneel, Odile; Lebrun, Sophie; Juillot, Farid; Brest, Jessica

2013-11-19

Ferrihydrite (Fh) is a nanocrystalline ferric oxyhydroxide involved in the retention of pollutants in natural systems and in water-treatment processes. The status and properties of major chemical impurities in natural Fh is however still scarcely documented. Here we investigated the structure of aluminum-rich Fh, and their role in arsenic scavenging in river-bed sediments from a circumneutral river (pH 6-7) impacted by an arsenic-rich acid mine drainage (AMD). Extended X-ray absorption fine structure (EXAFS) spectroscopy at the Fe K-edge shows that Fh is the predominant mineral phase forming after neutralization of the AMD, in association with minor amount of schwertmannite transported from the AMD. TEM-EDXS elemental mapping and SEM-EDXS analyses combined with EXAFS analysis indicates that Al(3+) substitutes for Fe(3+) ions into the Fh structure in the natural sediment samples, with local aluminum concentration within the 25-30 ± 10 mol %Al range. Synthetic aluminous Fh prepared in the present study are found to be less Al-substituted (14-20 ± 5 mol %Al). Finally, EXAFS analysis at the arsenic K-edge indicates that As(V) form similar inner-sphere surface complexes on the natural and synthetic Al-substituted Fh studied. Our results provide direct evidence for the scavenging of arsenic by natural Al-Fh, which emphasize the possible implication of such material for scavenging pollutants in natural or engineered systems.

Swirling structure for mixing two concentric fluid flows at nozzle outlet

DOEpatents

Mensink, Daniel L.

1993-01-01

A nozzle device for causing two fluids to mix together. In particular, a spray nozzle comprise two hollow, concentric housings, an inner housing and an outer housing. The inner housing has a channel formed therethrough for a first fluid. Its outer surface cooperates with the interior surface of the outer housing to define the second channel for a second fluid. The outer surface of the inner housing and the inner surface of the outer housing each carry a plurality of vanes that interleave but do not touch, each vane of one housing being between two vanes of the other housing. The vanes are curved and the inner surface of the outer housing and the outer surface of the inner housing converge to narrow the second channel. The shape of second channel results in a swirling, accelerating second fluid that will impact the first fluid just past the end of the nozzle where mixing will take place.

Assessment of cell death mechanisms triggered by 177Lu-anti-CD20 in lymphoma cells.

PubMed

Azorín-Vega, E; Rojas-Calderón, E; Martínez-Ventura, B; Ramos-Bernal, J; Serrano-Espinoza, L; Jiménez-Mancilla, N; Ordaz-Rosado, D; Ferro-Flores, G

2018-08-01

The aim of this research was to evaluate the cell cycle redistribution and activation of early and late apoptotic pathways in lymphoma cells after treatment with 177 Lu-anti-CD20. Experimental and computer models were used to calculate the radiation absorbed dose to cancer cell nuclei. The computer model (Monte Carlo, PENELOPE) consisted of twenty spheres representing cells with an inner sphere (cell nucleus) embedded in culture media. Radiation emissions of the radiopharmaceutical located in cell membranes and in culture media were considered for nuclei dose calculations. Flow cytometric analyses demonstrated that doses as low as 4.8Gy are enough to induce cell cycle arrest and activate late apoptotic pathways. Copyright © 2017 Elsevier Ltd. All rights reserved.

Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework

DOE PAGES

Bogart, Justin A.; Lippincott, Connor A.; Carroll, Patrick J.; ...

2015-10-27

Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C 6 H 4 CH 2 ) 3 N] 3- (TriNO x 3- ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNO x )thf][BAr F 4 ], in which Ar F =3,5-(CF 3 ) 2 -C 6 H 3 , and [Ce(TriNO x )py][OTf] . A rare complete Ce-halide series, Ce(TriNO x )X, in which X=F - , Clmore » - , Br - , I - , was also synthesized. We explored the solution chemistry of these complexes through detailed solution-phase electrochemistry and 1 H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X - group. DFT calculations on the series of calculations corroborated the experimental findings. Also, the use of a bulky and strongly donating tethered tripodal nitroxide ligand allowed the controlled redox chemistry at cerium. As a result, rare examples of cationic Ce IV complexes were synthesized and fully characterized. The full Ce-halide series supported by the tripodal ligand framework is also reported (see scheme).« less

Temporal Change of Seismic Earth's Inner Core Phases: Inner Core Differential Rotation Or Temporal Change of Inner Core Surface?

NASA Astrophysics Data System (ADS)

Yao, J.; Tian, D.; Sun, L.; Wen, L.

2017-12-01

Since Song and Richards [1996] first reported seismic evidence for temporal change of PKIKP wave (a compressional wave refracted in the inner core) and proposed inner core differential rotation as its explanation, it has generated enormous interests in the scientific community and the public, and has motivated many studies on the implications of the inner core differential rotation. However, since Wen [2006] reported seismic evidence for temporal change of PKiKP wave (a compressional wave reflected from the inner core boundary) that requires temporal change of inner core surface, both interpretations for the temporal change of inner core phases have existed, i.e., inner core rotation and temporal change of inner core surface. In this study, we discuss the issue of the interpretation of the observed temporal changes of those inner core phases and conclude that inner core differential rotation is not only not required but also in contradiction with three lines of seismic evidence from global repeating earthquakes. Firstly, inner core differential rotation provides an implausible explanation for a disappearing inner core scatterer between a doublet in South Sandwich Islands (SSI), which is located to be beneath northern Brazil based on PKIKP and PKiKP coda waves of the earlier event of the doublet. Secondly, temporal change of PKIKP and its coda waves among a cluster in SSI is inconsistent with the interpretation of inner core differential rotation, with one set of the data requiring inner core rotation and the other requiring non-rotation. Thirdly, it's not reasonable to invoke inner core differential rotation to explain travel time change of PKiKP waves in a very small time scale (several months), which is observed for repeating earthquakes in Middle America subduction zone. On the other hand, temporal change of inner core surface could provide a consistent explanation for all the observed temporal changes of PKIKP and PKiKP and their coda waves. We conclude that the observed temporal changes of the inner core phases are caused by temporal changes of inner core surface. The temporal changes of inner core surface are found to occur in some localized regions within a short time scale (years to months), a phenomenon that should provide important clues to a potentially fundamental change of our understanding of core dynamics.

Endotoxin deposits on the inner surfaces of closed-face cassettes during bioaerosol sampling: a field investigation at composting facilities.

PubMed

Duquenne, Philippe; Simon, Xavier; Demange, Valérie; Harper, Martin; Wild, Pascal

2015-05-01

A set of 270 bioaerosol samples was taken from 15 composting facilities using polystyrene closed-face filter cassettes (CFCs). The objective was to measure the quantity of endotoxin deposits on the inner surfaces of the cassettes (sometimes referred to as 'wall deposits'). The results show that endotoxins are deposited on the inner surfaces of the CFCs through sampling and/or handling of samples. The quantity of endotoxins measured on inner surfaces range between 0.05 (the limit of detection of the method) and 3100 endotoxin units per cassette. The deposits can represent a large and variable percentage of the endotoxins sampled. More than a third of the samples presented a percentage of inner surface deposits >40% of the total quantity of endotoxins collected (filter + inner surfaces). Omitting these inner surface deposits in the analytical process lead to measurement errors relative to sampling all particles entering the CFC sampler, corresponding to a developing consensus on matching the inhalable particulate sampling convention. The result would be underestimated exposures and could affect the decision as to whether or not a result is acceptable in comparison to airborne concentration limits defined in terms of the inhalability convention. The results of this study suggest including the endotoxins deposited on the inner surfaces of CFCs during analysis. Further researches are necessary to investigate endotoxin deposits on the inner cassette surfaces in other working sectors. © The Author 2014. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

A New 3D Multi-fluid Dust Model: A Study of the Effects of Activity and Nucleus Rotation on Dust Grain Behavior at Comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Shou, Y.; Combi, M.; Toth, G.; Tenishev, V.; Fougere, N.; Jia, X.; Rubin, M.; Huang, Z.; Hansen, K.; Gombosi, T.

2017-11-01

Improving our capability to interpret observations of cometary dust is necessary to deepen our understanding of the role of dust in the formation of comets and in altering the cometary environments. Models including dust grains are in demand to interpret observations and test hypotheses. Several existing models have taken into account the gas-dust interaction, varying sizes of dust grains and the cometary gravitational force. In this work, we develop a multi-fluid dust model based on the BATS-R-US code. This model not only incorporates key features of previous dust models, but also has the capability of simulating time-dependent phenomena. Since the model is run in the rotating comet reference frame, the centrifugal and Coriolis forces are included. The boundary conditions on the nucleus surface can be set according to the distribution of activity and the solar illumination. The Sun revolves around the comet in this frame. A newly developed numerical mesh is also used to resolve the real-shaped nucleus in the center and to facilitate prescription of the outer boundary conditions that accommodate the rotating frame. The inner part of the mesh is a box composed of Cartesian cells and the outer surface is a smooth sphere, with stretched cells filled in between the box and the sphere. Our model achieved comparable results to the Direct Simulation Monte Carlo method and the Rosetta/OSIRIS observations. It is also applied to study the effects of the rotating nucleus and the cometary activity and offers interpretations of some dust observations of comet 67P/Churyumov-Gerasimenko.

CHARACTERIZATION OF THE INNER DISK AROUND HD 141569 A FROM KECK/NIRC2 L-BAND VORTEX CORONAGRAPHY

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

Mawet, Dimitri; Bottom, Michael; Matthews, Keith

HD 141569 A is a pre-main sequence B9.5 Ve star surrounded by a prominent and complex circumstellar disk, likely still in a transition stage from protoplanetary to debris disk phase. Here, we present a new image of the third inner disk component of HD 141569 A made in the L ′ band (3.8 μ m) during the commissioning of the vector vortex coronagraph that has recently been installed in the near-infrared imager and spectrograph NIRC2 behind the W.M. Keck Observatory Keck II adaptive optics system. We used reference point-spread function subtraction, which reveals the innermost disk component from the innermore » working distance of ≃23 au and up to ≃70 au. The spatial scale of our detection roughly corresponds to the optical and near-infrared scattered light, thermal Q , N , and 8.6 μ m PAH emission reported earlier. We also see an outward progression in dust location from the L ′ band to the H band (Very Large Telescope/SPHERE image) to the visible ( Hubble Space Telescope ( HST )/STIS image), which is likely indicative of dust blowout. The warm disk component is nested deep inside the two outer belts imaged by HST-NICMOS in 1999 (at 406 and 245 au, respectively). We fit our new L ′-band image and spectral energy distribution of HD 141569 A with the radiative transfer code MCFOST. Our best-fit models favor pure olivine grains and are consistent with the composition of the outer belts. While our image shows a putative very faint point-like clump or source embedded in the inner disk, we did not detect any true companion within the gap between the inner disk and the first outer ring, at a sensitivity of a few Jupiter masses.« less

Quantitative study of protein-protein interactions by quartz nanopipettes

NASA Astrophysics Data System (ADS)

Tiwari, Purushottam Babu; Astudillo, Luisana; Miksovska, Jaroslava; Wang, Xuewen; Li, Wenzhi; Darici, Yesim; He, Jin

2014-08-01

In this report, protein-modified quartz nanopipettes were used to quantitatively study protein-protein interactions in attoliter sensing volumes. As shown by numerical simulations, the ionic current through the conical-shaped nanopipette is very sensitive to the surface charge variation near the pore mouth. With the appropriate modification of negatively charged human neuroglobin (hNgb) onto the inner surface of a nanopipette, we were able to detect concentration-dependent current change when the hNgb-modified nanopipette tip was exposed to positively charged cytochrome c (Cyt c) with a series of concentrations in the bath solution. Such current change is due to the adsorption of Cyt c to the inner surface of the nanopipette through specific interactions with hNgb. In contrast, a smaller current change with weak concentration dependence was observed when Cyt c was replaced with lysozyme, which does not specifically bind to hNgb. The equilibrium dissociation constant (KD) for the Cyt c-hNgb complex formation was derived and the value matched very well with the result from surface plasmon resonance measurement. This is the first quantitative study of protein-protein interactions by a conical-shaped nanopore based on charge sensing. Our results demonstrate that nanopipettes can potentially be used as a label-free analytical tool to quantitatively characterize protein-protein interactions.In this report, protein-modified quartz nanopipettes were used to quantitatively study protein-protein interactions in attoliter sensing volumes. As shown by numerical simulations, the ionic current through the conical-shaped nanopipette is very sensitive to the surface charge variation near the pore mouth. With the appropriate modification of negatively charged human neuroglobin (hNgb) onto the inner surface of a nanopipette, we were able to detect concentration-dependent current change when the hNgb-modified nanopipette tip was exposed to positively charged cytochrome c (Cyt c) with a series of concentrations in the bath solution. Such current change is due to the adsorption of Cyt c to the inner surface of the nanopipette through specific interactions with hNgb. In contrast, a smaller current change with weak concentration dependence was observed when Cyt c was replaced with lysozyme, which does not specifically bind to hNgb. The equilibrium dissociation constant (KD) for the Cyt c-hNgb complex formation was derived and the value matched very well with the result from surface plasmon resonance measurement. This is the first quantitative study of protein-protein interactions by a conical-shaped nanopore based on charge sensing. Our results demonstrate that nanopipettes can potentially be used as a label-free analytical tool to quantitatively characterize protein-protein interactions. Electronic supplementary information (ESI) available: Determination of nanopipette diameter; surface modification scheme; numerical simulation; noise analysis; SPR experiments. See DOI: 10.1039/c4nr02964j

Super-Resolution Imaging by Arrays of High-Index Spheres Embedded in Transparent Matrices

DTIC Science & Technology

2014-06-25

microsphere-assisted imaging. Roles of surface excitations, plasmons, polaritons and Tamm-states, as well as the role of nanoscale gap separating the object...nanometric gap between the object and spheres and the role of surface polariton -plasmons in the metallic nanostructures. Our results, however, show that

Polarization Utilization in Radar Target Reconstruction: C-Wide (Multi-Frequency) Band Relationship of a Target’s Characteristic Operators with Its Unique Set of Natural Eigenfrequencies.

DTIC Science & Technology

1983-12-14

the left half of the s- plane . These are representation independent. We shall be interested in these poles only. These poles are the complex...on the Left Half Plane Asymptotic Behavior of the SEM Expansion of Surface Currents, Published in Special Issue on the Singularity Expansion Method...precisely, the polarization chart is an orthogonal projection of the Poincare Sphere on a plane , having polar coordinates p= cos (2-) and

Textural timbre

PubMed Central

Hollins, Mark

2009-01-01

During haptic exploration of surfaces, complex mechanical oscillations—of surface displacement and air pressure—are generated, which are then transduced by receptors in the skin and in the inner ear. Tactile and auditory signals thus convey redundant information about texture, partially carried in the spectral content of these signals. It is no surprise, then, that the representation of temporal frequency is linked in the auditory and somatosensory systems. An emergent hypothesis is that there exists a supramodal representation of temporal frequency, and by extension texture. PMID:19721886

Terminal velocity and drag reduction measurements on superhydrophobic spheres

NASA Astrophysics Data System (ADS)

McHale, G.; Shirtcliffe, N. J.; Evans, C. R.; Newton, M. I.

2009-02-01

Super water-repellent surfaces occur naturally on plants and aquatic insects and are created in the laboratory by combining micro- or nanoscale surface topographic features with hydrophobic surface chemistry. When such types of water-repellent surfaces are submerged they can retain a film of air (a plastron). In this work, we report measurements of the terminal velocity of solid acrylic spheres with various surface treatments settling under the action of gravity in water. We observed increases in terminal velocity corresponding to drag reduction of between 5% and 15% for superhydrophobic surfaces that carry plastrons.

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

Tao Xia; Liu Bing; Hou Qian

A new route for the economic and efficient treatment of azo dye pollutants is reported, in which surface-modified organic-inorganic hybrid mesoporous silica (MS) spheres were chosen as microreactors for the accumulation and subsequent photodegradation of pollutants in defined regions. The surface-modified silica materials were prepared by anchoring the polycationic species such as poly(allylamine hydrochloride) on MS spheres via a simple wet impregnation method. The as-synthesized spheres with well-defined porous structures exhibited 15 times of accumulating capacity for orange II and Congo red compared to that of the pure MS spheres. Diffuse reflectance UV-vis spectroscopy and confocal laser scanning microscopy demonstratedmore » that the accumulated orange II and CR in defined MS spheres were rapidly degraded in the presence of Fenton reagent under visible radiation. Kinetics analysis in recycling degradation showed that the as-synthesized materials might be utilized as environment-friendly preconcentrators/microreactors for the remediation of dye wastewater.« less

The Escherichia coli Peripheral Inner Membrane Proteome*

PubMed Central

Papanastasiou, Malvina; Orfanoudaki, Georgia; Koukaki, Marina; Kountourakis, Nikos; Sardis, Marios Frantzeskos; Aivaliotis, Michalis; Karamanou, Spyridoula; Economou, Anastassios

2013-01-01

Biological membranes are essential for cell viability. Their functional characteristics strongly depend on their protein content, which consists of transmembrane (integral) and peripherally associated membrane proteins. Both integral and peripheral inner membrane proteins mediate a plethora of biological processes. Whereas transmembrane proteins have characteristic hydrophobic stretches and can be predicted using bioinformatics approaches, peripheral inner membrane proteins are hydrophilic, exist in equilibria with soluble pools, and carry no discernible membrane targeting signals. We experimentally determined the cytoplasmic peripheral inner membrane proteome of the model organism Escherichia coli using a multidisciplinary approach. Initially, we extensively re-annotated the theoretical proteome regarding subcellular localization using literature searches, manual curation, and multi-combinatorial bioinformatics searches of the available databases. Next we used sequential biochemical fractionations coupled to direct identification of individual proteins and protein complexes using high resolution mass spectrometry. We determined that the proposed cytoplasmic peripheral inner membrane proteome occupies a previously unsuspected ∼19% of the basic E. coli BL21(DE3) proteome, and the detected peripheral inner membrane proteome occupies ∼25% of the estimated expressed proteome of this cell grown in LB medium to mid-log phase. This value might increase when fleeting interactions, not studied here, are taken into account. Several proteins previously regarded as exclusively cytoplasmic bind membranes avidly. Many of these proteins are organized in functional or/and structural oligomeric complexes that bind to the membrane with multiple interactions. Identified proteins cover the full spectrum of biological activities, and more than half of them are essential. Our data suggest that the cytoplasmic proteome displays remarkably dynamic and extensive communication with biological membrane surfaces that we are only beginning to decipher. PMID:23230279

Van der Waals Interactions Involving Proteins

NASA Technical Reports Server (NTRS)

Roth, Charles M.; Neal, Brian L.; Lenhoff, Abraham M.

1996-01-01

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models. with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth.

Targeting Prostate Cancer Stemlike Cells through Cell Surface Expressed GRP78

DTIC Science & Technology

2016-12-01

NOTES 14. ABSTRACT This study investigated a function for cell surface GRP78 in regulating prostate cancer stem -like cells . In year 1, we showed that...enrichment of cell surface GRP78+ cancer stem like cells in sphere culture. We also showed that the signaling axis activated by cell surface GRP78 is...but not the GRP78(-) cells , exhibited cancer stem -like cell behavior. Furthermore an GRP78 monoclonal antibody inhibited sphere forming ability of

Interactions of praseodymium and neodymium with nucleosides and nucleotides: absorption difference and comparative absorption spectral study.

PubMed

Misra, S N; Anjaiah, K; Joseph, G; Abdi, S H

1992-02-01

The interactions of praseodymium(III) and neodymium(III) with nucleosides and nucleotides have been studied in different stoichiometry in water and water-DMF mixtures by employing absorption difference and comparative absorption spectrophotometry. The 4f-4f bands were analysed by linear curve analysis followed by gaussian curve analysis, and various spectral parameters were computed, using partial and multiple regression method. The magnitude of changes in both energy interaction and intensity were used to explore the degree of outer and inner sphere coordination, incidence of covalency and the extent of metal 4f-orbital involvement in chemical bonding. Crystalline complexes of the type [Ln(nucleotide)2(H2O)2]- (where nucleotide--GMP or IMP) were characterized by IR, 1H NMR, 31P NMR data. These studies indicated that the binding of the nucleotide is through phosphate oxygen in a bidentate manner and the complexes undergo substantial ionisation in aqueous medium, thereby supporting the observed weak 4f-4f bands and lower values for nephelauxetic effect (1-beta), bonding (b) and covalency (delta) parameters derived from coulombic and spin orbit interaction parameters.

Complex Chern-Simons from M5-branes on the squashed three-sphere

NASA Astrophysics Data System (ADS)

Córdova, Clay; Jafferis, Daniel L.

2017-11-01

We derive an equivalence between the (2,0) superconformal M5-brane field theory dimensionally reduced on a squashed three-sphere, and Chern-Simons theory with complex gauge group. In the reduction, the massless fermions obtain an action which is second order in derivatives and are reinterpreted as ghosts for gauge fixing the emergent non-compact gauge symmetry. A squashing parameter in the geometry controls the imaginary part of the complex Chern-Simons level.

Evidence of the no-slip boundary condition of water flow between hydrophilic surfaces using atomic force microscopy.

PubMed

Maali, Abdelhamid; Wang, Yuliang; Bhushan, Bharat

2009-10-20

In this study we present measurements of the hydrodynamic force exerted on a glass sphere glued to an atomic force microscopy (AFM) cantilever approaching a mica surface in water. A large sphere was used to reduce the impact of the cantilever beam on the measurement. An AFM cantilever with large stiffness was used to accurately determine the actual contact position between the sphere and the sample surface. The measured hydrodynamic force with different approach velocities is in good agreement with the Taylor force calculated in the lubrication theory with the no-slip boundary conditions, which verifies that there is no boundary slip on the glass and mica surfaces. Moreover, a detailed procedure of how to subtract the electrostatic double-layer force is presented.

The effect of ultrasound irradiation on the convective heat transfer rate during immersion cooling of a stationary sphere.

PubMed

Kiani, Hossein; Sun, Da-Wen; Zhang, Zhihang

2012-11-01

It has been proven that ultrasound irradiation can enhance the rate of heat transfer processes. The objective of this work was to study the heat transfer phenomenon, mainly the heat exchange at the surface, as affected by ultrasound irradiation around a stationary copper sphere (k=386W m(-1)K(-1), C(p)=384J kg(-1)K(-1), ρ=8660kg m(-3)) during cooling. The sphere (0.01m in diameter) was immersed in an ethylene glycol-water mixture (-10°C) in an ultrasonic cooling system that included a refrigerated circulator, a flow meter, an ultrasound generator and an ultrasonic bath. The temperature of the sphere was recorded using a data logger equipped with a T-type thermocouple in the center of the sphere. The temperature of the cooling medium was also monitored by four thermocouples situated at different places in the bath. The sphere was located at different positions (0.02, 0.04 and 0.06m) above the transducer surface of the bath calculated considering the center of the sphere as the center of the reference system and was exposed to different intensities of ultrasound (0, 120, 190, 450, 890, 1800, 2800, 3400 and 4100W m(-2)) during cooling. The frequency of the ultrasound was 25kHz. It was demonstrated that ultrasound irradiation can increase the rate of heat transfer significantly, resulting in considerably shorter cooling times. Higher intensities caused higher cooling rates, and Nu values were increased from about 23-27 to 25-108 depending on the intensity of ultrasound and the position of the sphere. However, high intensities of ultrasound led to the generation of heat at the surface of the sphere, thus limiting the lowest final temperature achieved. An analytical solution was developed considering the heat generation and was fitted to the experimental data with R(2) values in the range of 0.910-0.998. Visual observations revealed that both cavitation and acoustic streaming were important for heat transfer phenomenon. Cavitation clouds at the surface of the sphere were the main cause of heating effect. The results showed that closer distances to the transducer surface showed higher cooling rates. On the other hand, despite having a bigger distance from the transducer, when the sphere was located close to the gas-liquid interface the enhancement factor of heat transfer was higher. Ultrasound irradiation showed promising effect for the enhancement of convective heat transfer rate during immersion cooling. More investigations are required to demonstrate the behavior of ultrasound assisted heat transfer and resolve the proper way of the application of ultrasound to assist the cooling and/or freezing processes. Copyright © 2012 Elsevier B.V. All rights reserved.

Silver nanoparticle deposition on inverse opal SiO2 films embedded in protective polypropylene micropits for SERS applications

NASA Astrophysics Data System (ADS)

Ammosova, Lena; Ankudze, Bright; Philip, Anish; Jiang, Yu; Pakkanen, Tuula T.; Pakkanen, Tapani A.

2018-01-01

Common methods to fabricate surface enhanced Raman scattering (SERS) substrates with controlled micro-nanohierarchy are often complex and expensive. In this study, we demonstrate a simple and cost effective method to fabricate SERS substrates with complex geometries. Microworking robot structuration is used to pattern a polypropylene (PP) substrate with micropits, facilitating protective microenvironment for brittle SiO2 inverse opal (IO) structure. Hierarchical SiO2 IO patterns were obtained using polystyrene (PS) spheres as a sacrificial template, and were selectively embedded into the hydrophilized PP micropits. The same microworking robot technique was subsequently used to deposit silver nanoparticle ink into the SiO2 IO cavities. The fabricated multi-level micro-nanohierarchy surface was studied to enhance Raman scattering of the 4-aminothiophenol (4-ATP) analyte molecule. The results show that the SERS performance of the micro-nanohierarchical substrate increases significantly the Raman scattering intensity compared to substrates with structured 2D surface geometries.

Evaluating inner surface roughness of inline/picoliter fiber optic spectrometer fabricated by an NUV femtosecond laser drilling

NASA Astrophysics Data System (ADS)

Shiraishi, Masahiko; Kubodera, Shoichi; Watanabe, Kazuhiro

2017-05-01

We have evaluated inner surface roughness of inline/picoliter fiber optic spectrometer fabricated by an NUV femtosecond laser drilling. A microhole fabricated by the femtosecond laser without breaking off works as inline/picoliter fiber optic spectrometer. The attractive feature of the spectrometer is very small sensing volume which has several tens of picoliter. A second harmonic 400 nm femtosecond laser with 350 fs pulse duration launched onto the glass fiber optic. A high aspect ratio of the microhole was fabricated after 1000 pulse shots, but there was inner surface roughness. Although the repetition rate was changed 10 to 1000 Hz in order to control the inner surface roughness, the inner surface roughness was occurred in each case. It was confirmed that ablated fused silica particles deposited on the inner surface of microhole. The depth of microhole was deepened with 1 kHz of repetition rate and number of 1000 shots. In comparison to 10 Hz, the depth of microhole was increased by approximately 80%. It was assumed that heat accumulation effect enlarged the length of drilling. In order to minimize inner surface roughness, the best method is to use low number laser shots. After 100 pulse shots with 30 μJ of pulse energy, an optical inner surface quality of microhole was acquired. The optical inner surface quality of microhole was verified by measuring the transmittance of 94% of infrared light emission launched from superluminescent diode in the case of 100 pulse shots with 20 μJ. The transmittance decreased to 52% changing the microhole fabricated by 30 μJ with 100 laser shots because of increasing interaction area between the microhole and propagating light.

Exact Solution for Capillary Bridges Properties by Shooting Method

NASA Astrophysics Data System (ADS)

Qiang-Nian, Li; Jia-Qi, Zhang; Feng-Xi, Zhou

2017-04-01

The investigation of liquid bridge force acting between wet particles has great significance in many fields. In this article, the exact solution of capillary force between two unequal-sized spherical particles is investigated. Firstly, The Young-Laplace equation with moving boundary is converted into a set of ordinary differential equations with two fix point boundary using variable substitution technique, in which the gravity effects have been neglected. The geometry of the liquid bridge between two particles is solved by shooting method. After that, the gorge method is applied to calculate the capillary-bridge force that is consists of contributions from the capillary suction and surface tension. Finally, the effect of various parameters including distance between two spheres, radii of spheres, and contact angles on the capillary force are investigated. It is shown that the presented approach is an efficient and accurate algorithm for capillary force between two particles in complex situations.

Social Justice and Education in the Public and Private Spheres

ERIC Educational Resources Information Center

Power, Sally; Taylor, Chris

2013-01-01

This paper explores the complex relationship between social justice and education in the public and private spheres. The politics of education is often presented as a battle between left and right, the state and the market. In this representation, the public and the private spheres are neatly aligned on either side of the line of battle, and…

Self-enhanced plasma discharge effect in the deposition of diamond-like carbon films on the inner surface of slender tube

NASA Astrophysics Data System (ADS)

Xu, Yi; Li, Liuhe; Luo, Sida; Lu, Qiuyuan; Gu, Jiabin; Lei, Ning; Huo, Chunqin

2017-01-01

Enhanced glow discharge plasma immersion ion implantation and deposition (EGD-PIII&D) have been proved to be highly effective for depositing diamond-like carbon (DLC) films on the inner surface of the slender quartz tube with a deposition rate of 1.3 μm/min. Such a high-efficiency DLC films deposition was explained previously as the short electrons mean free path to cause large collision frequency between electrons and neutral particles. However, in this paper, we found that the inner surface material of the tube itself play a vital role on the films deposition. To disclose the mechanism of this phenomenon, the effect of different inner surface materials on plasma discharge was experimentally and theoretically investigated. Then a self-enhancing plasma discharge is discovered. It is found that secondary electrons emitted from the inner surface material, whatever it is the tube inner surface or deposited DLC films, can dramatically enhance the plasma discharge to improve the DLC films deposition rate.

Swirling structure for mixing two concentric fluid flows at nozzle outlet

DOEpatents

Mensink, D.L.

1993-07-20

A nozzle device is described for causing two fluids to mix together. In particular, a spray nozzle comprises two hollow, concentric housings, an inner housing and an outer housing. The inner housing has a channel formed therethrough for a first fluid. Its outer surface cooperates with the interior surface of the outer housing to define the second channel for a second fluid. The outer surface of the inner housing and the inner surface of the outer housing each carry a plurality of vanes that interleave but do not touch, each vane of one housing being between two vanes of the other housing. The vanes are curved and the inner surface of the outer housing and the outer surface of the inner housing converge to narrow the second channel. The shape of second channel results in a swirling, accelerating second fluid that will impact the first fluid just past the end of the nozzle where mixing will take place.

Structures and Properties of As(OH)3 Adsorption Complexes on Hydrated Mackinawite (FeS) Surfaces: A DFT-D2 Study

PubMed Central

2017-01-01

Reactive mineral–water interfaces exert control on the bioavailability of contaminant arsenic species in natural aqueous systems. However, the ability to accurately predict As surface complexation is limited by the lack of molecular-level understanding of As–water–mineral interactions. In the present study, we report the structures and properties of the adsorption complexes of arsenous acid (As(OH)3) on hydrated mackinawite (FeS) surfaces, obtained from density functional theory (DFT) calculations. The fundamental aspects of the adsorption, including the registries of the adsorption complexes, adsorption energies, and structural parameters are presented. The FeS surfaces are shown to be stabilized by hydration, as is perhaps to be expected because the adsorbed water molecules stabilize the low-coordinated surface atoms. As(OH)3 adsorbs weakly at the water–FeS(001) interface through a network of hydrogen-bonded interactions with water molecules on the surface, with the lowest-energy structure calculated to be an As–up outer-sphere complex. Compared to the water–FeS(001) interface, stronger adsorption was calculated for As(OH)3 on the water–FeS(011) and water–FeS(111) interfaces, characterized by strong hybridization between the S-p and O-p states of As(OH)3 and the surface Fe-d states. The As(OH)3 molecule displayed a variety of chemisorption geometries on the water–FeS(011) and water–FeS(111) interfaces, where the most stable configuration at the water–FeS(011) interface is a bidentate Fe–AsO–Fe complex, but on the water–FeS(111) interface, a monodentate Fe–O–Fe complex was found. Detailed information regarding the adsorption mechanisms has been obtained via projected density of states (PDOS) and electron density difference iso-surface analyses and vibrational frequency assignments of the adsorbed As(OH)3 molecule. PMID:28233994

Calculation of Latitude and Longitude for Points on Perimeter of a Circle on a Sphere

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

Morris, Heidi E.

2015-08-14

This document describes the calculation of the Earth-Centered Earth Fixed (ECEF) coordinates for points lying on the perimeter of a circle. Here, the perimeter of the circle lies on the surface of the sphere and the center of the planar circle is below the surface. These coordinates are converted to latitude and longitude for mapping fields on the surface of the earth.

Floating nut retention system

NASA Technical Reports Server (NTRS)

Charles, J. F.; Theakston, H. A. (Inventor)

1980-01-01

A floating nut retention system includes a nut with a central aperture. An inner retainer plate has an opening which is fixedly aligned with the nut aperture. An outer retainer member is formed of a base plate having an opening and a surface adjacent to a surface of the inner retainer plate. The outer retainer member includes a securing mechanism for retaining the inner retainer plate adjacent to the outer retainer member. The securing mechanism enables the inner retainer plate to float with respect to the outer retainer number, while simultaneously forming a bearing surface for inner retainer plate.

Biominerals and waxes of Calamagrostis epigejos and Phragmites australis leaves from post-industrial habitats.

PubMed

Talik, Ewa; Guzik, Adam; Małkowski, Eugeniusz; Woźniak, Gabriela; Sierka, Edyta

2018-05-01

Vascular plants are able to conduct biomineralization processes and collect synthesized compounds in their internal tissues or to deposit them on their epidermal surfaces. This mechanism protects the plant from fluctuations of nutrient levels caused by different levels of supply and demand for them. The biominerals reflect both the metabolic characteristics of a vascular plant species and the environmental conditions of the plant habitat. The SEM/EDX method was used to examine the surface and cross-sections of the Calamagrostis epigejos and Phragmites australis leaves from post-industrial habitats (coal and zinc spoil heaps). The results from this study have showed the presence of mineral objects on the surfaces of leaves of both grass species. The calcium oxalate crystals, amorphous calcium carbonate spheres, and different silica forms were also found in the inner tissues. The high variety of mineral forms in the individual plants of both species was shown. The waxes observed on the leaves of the studied plants might be the initializing factor for the crystalline forms and structures that are present. For the first time, wide range of crystal forms is presented for C. epigejos. The leaf samples of P. australis from the post-industrial areas showed an increased amount of mineral forms with the presence of sulfur.

Evaluation of the constant potential method in simulating electric double-layer capacitors

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Yang, Yang; Olmsted, David L.; Asta, Mark; Laird, Brian B.

2014-11-01

A major challenge in the molecular simulation of electric double layer capacitors (EDLCs) is the choice of an appropriate model for the electrode. Typically, in such simulations the electrode surface is modeled using a uniform fixed charge on each of the electrode atoms, which ignores the electrode response to local charge fluctuations in the electrolyte solution. In this work, we evaluate and compare this Fixed Charge Method (FCM) with the more realistic Constant Potential Method (CPM), [S. K. Reed et al., J. Chem. Phys. 126, 084704 (2007)], in which the electrode charges fluctuate in order to maintain constant electric potential in each electrode. For this comparison, we utilize a simplified LiClO4-acetonitrile/graphite EDLC. At low potential difference (ΔΨ ⩽ 2 V), the two methods yield essentially identical results for ion and solvent density profiles; however, significant differences appear at higher ΔΨ. At ΔΨ ⩾ 4 V, the CPM ion density profiles show significant enhancement (over FCM) of "inner-sphere adsorbed" Li+ ions very close to the electrode surface. The ability of the CPM electrode to respond to local charge fluctuations in the electrolyte is seen to significantly lower the energy (and barrier) for the approach of Li+ ions to the electrode surface.

Bushy sphere dendrites with husk-shaped branches axially spreading out from the core for photo-catalytic oxidation/remediation of toxins.

PubMed

Shenashen, Mohamed A; Kawada, Satoshi; Selim, Mahmoud M; Morsy, Wafaa M; Yamaguchi, Hitoshi; Alhamid, Abdulaziz A; Ohashi, Naoki; Ichinose, Izumi; El-Safty, Sherif A

2017-06-14

This work describes densely interlinked bushy "tree-like chains" characterized by neatly branched sphere dendrites (bushy sphere dendrites, BSD) with long fan-like, husk-shaped branching paths that extend longitudinally from the core axis of the {110}-exposed plane. We confirmed that the hierarchical dendrite surfaces created bowls of swirled caves along the tree-tube in the mat-like branches. These surfaces had high-index catalytic site facets associated with the formation of ridges/defects on the dominant {110}-top-cover surface. These swirled caves along the branches were completely filled with 50-100 nm poly-CN nano-sphere-fossils with orb-like appearance. Such structural features are key issues of the inherent surface reactivity of a powerful catalyst/trapper, enabling photocatalytic oxidation and trapping of extremely toxic arsenite (AsO 3 3- ) species and photo-induced recovery of arsenate (AsO 4 3- ) products from catalyst surfaces. The light-induced release of produced AsO 4 3- from BSD indicates (i) highly controlled waste collection/management (i.e., recovery), (ii) low cost and ecofriendly photo-adsorbent, (iii) selective trapping of real sample water to produce water-free arsenite species; (iv) multiple reuse cycles of catalysts (i.e., reduced waste volume). Matrixed dendrites, covered with 3D microscopic sphere cores that capture solar-light, trap toxins, and are triggered by light, were designed. These dendrites can withstand indoor and outdoor recovery of toxins from water sources.

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.

Spectral studies, thermal investigation and biological activity of some metal complexes derived from (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide

NASA Astrophysics Data System (ADS)

El-Samanody, El-Sayed A.; Polis, Magdy W.; Emara, Esam M.

2017-09-01

A new series of biologically active Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes derived from the novel thiosemicarbazone ligand; (E)-N‧-(1-(4-aminophenyl)ethylidene)morpholine-4-carbothiohydrazide (HL) were synthesized. The mode of bonding of the ligand and the geometrical structures of its metal complexes were achieved by different analytical and spectral methods. The ligand coordinated with metal ions in a neutral bidentate fashion through the thione sulfur and azomethine nitrogen atoms. All metal complexes adopted octahedral geometry, except Cu(II) complexes (3, 6, 7) which have a square planar structure. The general thermal decomposition pathways of the ligand along with its metal complexes were explained. The thermal stability of the complexes is controlled by the number of outer and inner sphere water molecules, ionic radii and the steric hindrance. The activation thermodynamic parameters; (activation energy (E*), enthalpy of activation (ΔH*), entropy of activation (ΔS*) and Gibbs free energy (ΔG*)) along with order of reaction (n) were estimated from DTG curves. The ESR spectra of Cu(II) complexes indicated that (dx2-y2)1 is the ground state with covalence character of metal-ligand bonds. The molluscicidal and biochemical effects of the ligand and its Ni(II); Cu(II) complexes (2; 3, 5, 7) along with their combinations with metaldehyde were screened in vitro on the mucous gland of Eobania vermiculata. The tested compounds exhibited a significant toxicity against the tested animals and have almost the same toxic effect of metaldehyde which increases the mucous secretion of the snails and leads to death.

Radar Transponder Antenna Systems Evaluation Handbook

DTIC Science & Technology

2006-07-01

Poincare Sphere Usage. The plane geometry... Poincare Sphere any coupling factor is numerically equal to the cosine of half the distance between states on the spherical surface. 5-52 Then in...Erhcp, Elhcp) on the Poincare sphere (Paragraph 5.14.1). As such, any antenna whose polarization lies on this plane receives the same

Modelling mass diffusion for a multi-layer sphere immersed in a semi-infinite medium: application to drug delivery.

PubMed

Carr, Elliot J; Pontrelli, Giuseppe

2018-04-12

We present a general mechanistic model of mass diffusion for a composite sphere placed in a large ambient medium. The multi-layer problem is described by a system of diffusion equations coupled via interlayer boundary conditions such as those imposing a finite mass resistance at the external surface of the sphere. While the work is applicable to the generic problem of heat or mass transfer in a multi-layer sphere, the analysis and results are presented in the context of drug kinetics for desorbing and absorbing spherical microcapsules. We derive an analytical solution for the concentration in the sphere and in the surrounding medium that avoids any artificial truncation at a finite distance. The closed-form solution in each concentric layer is expressed in terms of a suitably-defined inverse Laplace transform that can be evaluated numerically. Concentration profiles and drug mass curves in the spherical layers and in the external environment are presented and the dependency of the solution on the mass transfer coefficient at the surface of the sphere analyzed. Copyright © 2018 Elsevier Inc. All rights reserved.

Isolation and characterization of a uranium(VI)-nitride triple bond

NASA Astrophysics Data System (ADS)

King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

2013-06-01

The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium-ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)-nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)-nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.