High-Order Ca(II)-Chloro Complexes in Mixed CaCl2-LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations.

PubMed

Wang, Yu-Lin; Wang, Ying; Yi, Hai-Bo

2016-07-21

In this study, the structural characteristics of high-coordinated Ca-Cl complexes present in mixed CaCl2-LiCl aqueous solution were investigated using density functional theory (DFT) and molecular dynamics (MD) simulations. The DFT results show that [CaClx](2-x) (x = 4-6) clusters are quite unstable in the gas phase, but these clusters become metastable when hydration is considered. The MD simulations show that high-coordinated Ca-chloro complexes are possible transient species that exist for up to nanoseconds in concentrated (11.10 mol·kg(-1)) Cl(-) solution at 273 and 298 K. As the temperature increases to 423 K, these high-coordinated structures tend to disassociate and convert into smaller clusters and single free ions. The presence of high-order Ca-Cl species in concentrated LiCl solution can be attributed to their enhanced hydration shell and the inadequate hydration of ions. The probability of the [CaClx](2-x)aq (x = 4-6) species being present in concentrated LiCl solution decreases greatly with increasing temperature, which also indicates that the formation of the high-coordinated Ca-Cl structure is related to its hydration characteristics.

Mixed ligand complex formation of 2-aminobenzamide with Cu(II) in the presence of some amino acids: Synthesis, structural, biological, pH-metric, spectrophotometric and thermodynamic studies

NASA Astrophysics Data System (ADS)

Dharmaraja, Jeyaprakash; Esakkidurai, Thirugnanasamy; Subbaraj, Paramasivam; Shobana, Sutha

2013-10-01

Mixed ligand Cu(II) complexes of 2-aminobenzamide (2AB) and amino acids viz., glycine (gly), L-alanine (ala), L-valine (val) and L-phenylalanine (phe) have been synthesised and characterized by various physico-chemical and spectral techniques. The calculated g-tensor values for Cu(II) complexes at 77 K and 300 K, show the distorted octahedral geometry which has been confirmed from the absorption studies. Consequently, the thermal studies illustrate that the loss of water and acetate molecules in the initial stage which are followed by the decomposition of organic residues. The powder X-ray diffraction and SEM analysis reflect that all the complexes have well-defined crystallinity nature with homogeneous morphology. The binding activities of CT DNA with CuAB complexes have been examined by absorption studies. Further, the oxidative cleavage interactions of 2-aminobenzamide and CuAB complexes with DNA were studied by gel electrophoresis method in H2O2 medium. Also, the complex formation of Cu(II) involving 2-aminobenzamide and amino acids were carried out by a combined pH-metric and spectrophotometric techniques in 50% (v/v) water-ethanol mixture at 300, 310, 320 and 330 ± 0.1 K with I = 0.15 mol dm-3 (NaClO4). In solution, CuAB and CuAB2 species has been detected and the binding modes of 2-aminobenzamide and amino acids in both binary and mixed ligand complexes are same. The calculated stabilization value of Δ log K, log X and log X' indicates higher stabilities for the mixed ligand complexes rather than their binary species. The thermodynamic parameters like ΔG, ΔH and ΔS have been determined from temperature dependence of the stability constant. In vitro biological activities of 2-aminobenzamide, CuA and CuAB complexes show remarkable activities against some bacterial and fungal strains. The percentage distribution of various binary and mixed ligand species in solution at dissimilar pH intervals were also evaluated.

Contrasting intermolecular and intramolecular exciplex formation of a 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad.

PubMed

Imoto, Mitsutaka; Ikeda, Hiroshi; Fujii, Takayuki; Taniguchi, Hisaji; Tamaki, Akihiro; Takeda, Motonori; Mizuno, Kazuhiko

2010-05-07

An intramolecular exciplex is formed upon excitation of the cyclohexane solution of the 1,4-dicyano-2-methylnaphthalene-N,N-dimethyl-p-toluidine dyad, but little if any intramolecular CT complex exists in the ground state of this substance in solution. In contrast, in the crystalline state, the dyad forms an intermolecular mixed-stack CT complex in the ground state and an intermolecular exciplex when it is photoexcited.

Direct observation of bis(dicarbollyl)nickel conformers in solution by fluorescence spectroscopy: an approach to redox-controlled metallacarborane molecular motors.

PubMed

Safronov, Alexander V; Shlyakhtina, Natalia I; Everett, Thomas A; VanGordon, Monika R; Sevryugina, Yulia V; Jalisatgi, Satish S; Hawthorne, M Frederick

2014-10-06

As a continuation of work on metallacarborane-based molecular motors, the structures of substituted bis(dicarbollyl)nickel complexes in Ni(III) and Ni(IV) oxidation states were investigated in solution by fluorescence spectroscopy. Symmetrically positioned cage-linked pyrene molecules served as fluorescent probes to enable the observation of mixed meso-trans/dl-gauche (pyrene monomer fluorescence) and dl-cis/dl-gauche (intramolecular pyrene excimer fluorescence with residual monomer fluorescence) cage conformations of the nickelacarboranes in the Ni(III) and Ni(IV) oxidation states, respectively. The absence of energetically disfavored conformers in solution--dl-cis in the case of nickel(III) complexes and meso-trans in the case of nickel(IV)--was demonstrated based on spectroscopic data and conformer energy calculations in solution. The conformational persistence observed in solution indicates that bis(dicarbollyl)nickel complexes may provide attractive templates for building electrically driven and/or photodriven molecular motors.

Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

PubMed

Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

2016-09-13

For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions.

A Signature of Spatial Correlations between rare earth ions and single-wall nanotubes wrapped with DNA in their mixed solution

NASA Astrophysics Data System (ADS)

Ignatova, Tetyana; Rotkin, Slava V.

2012-02-01

We propose that the fluorescence resonance energy transfer (FRET) between the rare earth ions (REI) and single-wall nanotubes (SWNT) can be used to measure their Coulomb correlation in solution. As a calibration experiment the FRET between two different REIs, being the energy donor and the acceptor, in their mixed solution has been used. From the photoluminescence decay time we were able to extract the characteristic distance between unlike REIs. Our study revealed negative correlation (the repulsion) for Tb-Eu solution. In the case of the solution containing the REI and the SWNTs wrapped with DNA we observed a significant positive correlation (the attraction and the complex formation). The data is in a good agreement with the theoretical estimates and allows to propose REIs and their FRET as a sensitive tool for detecting kinetics of interaction of SWNTs in aqueous solutions.

URANIUM RECOVERY PROCESS

DOEpatents

Hyman, H.H.; Dreher, J.L.

1959-07-01

The recovery of uranium from the acidic aqueous metal waste solutions resulting from the bismuth phosphate carrier precipitation of plutonium from solutions of neutron irradiated uranium is described. The waste solutions consist of phosphoric acid, sulfuric acid, and uranium as a uranyl salt, together with salts of the fission products normally associated with neutron irradiated uranium. Generally, the process of the invention involves the partial neutralization of the waste solution with sodium hydroxide, followed by conversion of the solution to a pH 11 by mixing therewith sufficient sodium carbonate. The resultant carbonate-complexed waste is contacted with a titanated silica gel and the adsorbent separated from the aqueous medium. The aqueous solution is then mixed with sufficient acetic acid to bring the pH of the aqueous medium to between 4 and 5, whereby sodium uranyl acetate is precipitated. The precipitate is dissolved in nitric acid and the resulting solution preferably provided with salting out agents. Uranyl nitrate is recovered from the solution by extraction with an ether such as diethyl ether.

The enthalpies of interactions of Ca2+(aq) and C2O{4/2-} (aq) ions in complexon solutions: Competition between complexation and precipitation

NASA Astrophysics Data System (ADS)

Kustov, A. V.; Smirnova, N. L.; Berezin, B. D.; Trostin, V. N.

2010-04-01

The thermal effects of mixing of aqueous calcium chloride with sodium citrate and ethylenedi-aminetetraacetate in the absence and presence of sodium oxalate have been measured at 25°C. The thermal effects of dilution of aqueous calcium chloride solutions were determined. The thermal effects of calcium oxalate precipitation and formation of calcium complexes with citrate and ethylenediaminetetraacetate ions were calculated. The 1% solution of sodium citrate inhibited the formation of CaC2O4 (s); in a 1% solution of sodium ethylenediaminetetraacetate with [Ca2+][C2O{4/2-}] > 10-5, the endothermal formation of the [CaEdta]2- complex quickly changed to exothermal precipitation. The 3 and 5% solutions of complexons showed a pronounced inhibiting effect on the formation of urinary stones even when the concentration of calcium and oxalate ions in solution exceeded the product of solubility of CaC2O4 by four and more orders of magnitude.

Compatible-strain mixed finite element methods for incompressible nonlinear elasticity

NASA Astrophysics Data System (ADS)

Faghih Shojaei, Mostafa; Yavari, Arash

2018-05-01

We introduce a new family of mixed finite elements for incompressible nonlinear elasticity - compatible-strain mixed finite element methods (CSFEMs). Based on a Hu-Washizu-type functional, we write a four-field mixed formulation with the displacement, the displacement gradient, the first Piola-Kirchhoff stress, and a pressure-like field as the four independent unknowns. Using the Hilbert complexes of nonlinear elasticity, which describe the kinematics and the kinetics of motion, we identify the solution spaces of the independent unknown fields. In particular, we define the displacement in H1, the displacement gradient in H (curl), the stress in H (div), and the pressure field in L2. The test spaces of the mixed formulations are chosen to be the same as the corresponding solution spaces. Next, in a conforming setting, we approximate the solution and the test spaces with some piecewise polynomial subspaces of them. Among these approximation spaces are the tensorial analogues of the Nédélec and Raviart-Thomas finite element spaces of vector fields. This approach results in compatible-strain mixed finite element methods that satisfy both the Hadamard compatibility condition and the continuity of traction at the discrete level independently of the refinement level of the mesh. By considering several numerical examples, we demonstrate that CSFEMs have a good performance for bending problems and for bodies with complex geometries. CSFEMs are capable of capturing very large strains and accurately approximating stress and pressure fields. Using CSFEMs, we do not observe any numerical artifacts, e.g., checkerboarding of pressure, hourglass instability, or locking in our numerical examples. Moreover, CSFEMs provide an efficient framework for modeling heterogeneous solids.

Superconductor precursor mixtures made by precipitation method

DOEpatents

Bunker, Bruce C.; Lamppa, Diana L.; Voigt, James A.

1989-01-01

Method and apparatus for preparing highly pure homogeneous precursor powder mixtures for metal oxide superconductive ceramics. The mixes are prepared by instantaneous precipitation from stoichiometric solutions of metal salts such as nitrates at controlled pH's within the 9 to 12 range, by addition of solutions of non-complexing pyrolyzable cations, such as alkyammonium and carbonate ions.

Photodamage of a Mn(III/IV)-oxo mixed-valence compound and photosystem II: evidence that a high-valent manganese species is responsible for UV-induced photodamage of the oxygen-evolving complex in photosystem II.

PubMed

Wei, Zi; Cady, Clyde W; Brudvig, Gary W; Hou, Harvey J M

2011-01-01

The Mn cluster in photosystem II (PS II) is believed to play an important role in the UV photoinhibition of green plants, but the mechanism is still not clear at a molecular level. In this work, the photochemical stability of [Mn(III)(O)(2)Mn(IV)(H(2)O)(2)(Terpy)(2)](NO(3))(3) (Terpy=2,2':6',2''-terpyridine), designated as Mn-oxo mixed-valence dimer, a well characterized functional model of the oxygen-evolving complex in PS II, was examined in aqueous solution by exposing the complex to excess light irradiation at six different wavelengths in the range of 250 to 700 nm. The photodamage of the Mn-oxo mixed-valence dimer was confirmed by the decrease of its oxygen-evolution activity measured in the presence of the chemical oxidant oxone. Ultraviolet light irradiation induced a new absorption peak at around 400-440 nm of the Mn-oxo mixed-valence dimer. Visible light did not have the same effect on the Mn-oxo mixed-valence dimer. We speculate that the spectral change may be caused by conversion of the Mn(III)O(2)Mn(IV) dimer into a new structure--Mn(IV)O(2)Mn(IV). In the processes, the appearance of a 514 nm fluorescence peak was observed in the solution and may be linked to the hydration or protonation of Terpy ligand in the Mn-oxo dimer. In comparing the response of the PS II functional model compound and the PS II complex to excess light radiation, our results support the idea that UV photoinhibition is triggered at the Mn(4)Ca center of the oxygen-evolution complex in PS II by forming a modified structure, possibly a Mn(IV) species, and that the reaction of Mn ions is likely the initial step. Published by Elsevier B.V.

Evaluation of sulfate reduction at experimentally induced mixing interfaces using small-scale push-pull tests in an aquifer-wetland system

USGS Publications Warehouse

Kneeshaw, T.A.; McGuire, J.T.; Smith, E.W.; Cozzarelli, I.M.

2007-01-01

This paper presents small-scale push-pull tests designed to evaluate the kinetic controls on SO42 - reduction in situ at mixing interfaces between a wetland and aquifer impacted by landfill leachate at the Norman Landfill research site, Norman, OK. Quantifying the rates of redox reactions initiated at interfaces is of great interest because interfaces have been shown to be zones of increased biogeochemical transformations and thus may play an important role in natural attenuation. To mimic the aquifer-wetland interface and evaluate reaction rates, SO42 --rich anaerobic aquifer water (??? 100 mg / L SO42 -) was introduced into SO42 --depleted wetland porewater via push-pull tests. Results showed SO42 - reduction was stimulated by the mixing of these waters and first-order rate coefficients were comparable to those measured in other push-pull studies. However, rate data were complex involving either multiple first-order rate coefficients or a more complex rate order. In addition, a lag phase was observed prior to SO42 - reduction that persisted until the mixing interface between test solution and native water was recovered, irrespective of temporal and spatial constraints. The lag phase was not eliminated by the addition of electron donor (acetate) to the injected test solution. Subsequent push-pull tests designed to elucidate the nature of the lag phase support the importance of the mixing interface in controlling terminal electron accepting processes. These data suggest redox reactions may occur rapidly at the mixing interface between injected and native waters but not in the injected bulk water mass. Under these circumstances, push-pull test data should be evaluated to ensure the apparent rate is actually a function of time and that complexities in rate data be considered. ?? 2007 Elsevier Ltd. All rights reserved.

Copper(II) Thiosemicarbazone Complexes and Their Proligands upon UVA Irradiation: An EPR and Spectrophotometric Steady-State Study.

PubMed

Hricovíni, Michal; Mazúr, Milan; Sîrbu, Angela; Palamarciuc, Oleg; Arion, Vladimir B; Brezová, Vlasta

2018-03-21

X- and Q-band electron paramagnetic resonance (EPR) spectroscopy was used to characterize polycrystalline Cu(II) complexes that contained sodium 5-sulfonate salicylaldehyde thiosemicarbazones possessing a hydrogen, methyl, ethyl, or phenyl substituent at the terminal nitrogen. The ability of thiosemicarbazone proligands to generate superoxide radical anions and hydroxyl radicals upon their exposure to UVA irradiation in aerated aqueous solutions was evidenced by the EPR spin trapping technique. The UVA irradiation of proligands in neutral or alkaline solutions and dimethylsulfoxide (DMSO) caused a significant decrease in the absorption bands of aldimine and phenolic chromophores. Mixing of proligand solutions with the equimolar amount of copper(II) ions resulted in the formation of 1:1 Cu(II)-to-ligand complex, with the EPR and UV-Vis spectra fully compatible with those obtained for the dissolved Cu(II) thiosemicarbazone complexes. The formation of the complexes fully inhibited the photoinduced generation of reactive oxygen species, and only subtle changes were found in the electronic absorption spectra of the complexes in aqueous and DMSO solutions upon UVA steady-state irradiation. The dark redox activity of copper(II) complexes and proligand/Cu(II) aqueous solutions towards hydrogen peroxide which resulted in the generation of hydroxyl radicals, was confirmed by spin trapping experiments.

Structures of Cu surfaces developing in benzotriazole solutions: Effect of pH

NASA Astrophysics Data System (ADS)

Kondoh, Eiichi; Kawakami, Tatsuya; Watanabe, Mitsuhiro; Jin, Linhua; Hamada, Satomi; Shima, Shohei; Hiyama, Hirokuni

2017-07-01

The effect of pH on layer formation onto clean Cu surfaces in benzotriazole (BTA) aqueous solutions was studied by in situ spectroscopic ellipsometry. The effect of H2O2 addition was also investigated. Time changes in the ellipsometric parameters Ψ and Δ, which correspond to the structural changes of the layers on Cu, were discussed. In acidic solutions, a BTA or a Cu-BTA complex layer grows directly on Cu. The out-diffusion of Cu is suppressed at the Cu layer interface. When H2O2 was mixed, the Cu surface is eroded in acidic solutions. In alkaline solutions, the BTA layer grows on the oxidized Cu layer, or no growth occurs, depending on the composition of the solutions. In neutral solutions, the Cu-BTA complex layer forms on Cu, and the uncovered part is oxidized in the presence of H2O2.

Removal of acidic or basic α-amino acids in water by poorly water soluble scandium complexes.

PubMed

Hayashi, Nobuyuki; Jin, Shigeki; Ujihara, Tomomi

2012-11-02

To recognize α-amino acids with highly polar side chains in water, poorly water soluble scandium complexes with both Lewis acidic and basic portions were synthesized as artificial receptors. A suspension of some of these receptor molecules in an α-amino acid solution could remove acidic and basic α-amino acids from the solution. The compound most efficient at preferentially removing basic α-amino acids (arginine, histidine, and lysine) was the receptor with 7,7'-[1,3-phenylenebis(carbonylimino)]bis(2-naphthalenesulfonate) as the ligand. The neutral α-amino acids were barely removed by these receptors. Removal experiments using a mixed amino acid solution generally gave results similar to those obtained using solutions containing a single amino acid. The results demonstrated that the scandium complex receptors were useful for binding acidic and basic α-amino acids.

Complexation equilibria and coordination aspects of Zn(II) complexes contain 2-aminobenzamide and some bioactive amino acid mixed ligands: pH-metric, spectroscopic and thermodynamic studies.

PubMed

Dharmaraja, Jeyaprakash; Subbaraj, Paramasivam; Esakkidurai, Thirugnanasamy; Shobana, Sutha; Raji, Saravanan

2014-01-01

Mixed ligand complexation of 2-aminobenzamide (2AB) as ligand [L] with Zn(II) in the presence of some bio-relevant amino acid constituents like glycine (gly), L-alanine (ala), L-valine (val) and L-phenylalanine (phe) as ligand [B] have been investigated using pH-metric measurements with a combined pH electrode at different temperatures (300, 310, 320 and 330 ± 0.1 K) in 50% (v/v) ethanol-water mixture containing I = 0.15 M NaClO(4) as supporting electrolyte. Computer assisted analysis of the experimental titration data showed the presence of ZnLB and ZnLB2 species as mixed ligand complexes in addition to various binary species. In ZnLB/ZnLB(2) species, both primary and secondary ligands act as bidentate to form a stable six, five membered chelate ring. The calculated stabilization parameter Deltalog K, log X, log X' and % R.S. values clearly show the mixed ligand complexes have higher stabilities than their binary. Thermodynamic parameters DeltaG, DeltaH and DeltaS have been derived from the temperature dependence of the stability constants. The complexation behavior of ZnLB species has been studied by means of electronic spectra. The percentage distribution of various binary and mixed ligand species of each type of the complexes in solution depending on pH and the ratio of Zn(II) to 2-aminobenzamide/amino acid of the systems.

The Ellipticity Filter-A Proposed Solution to the Mixed Event Problem in Nuclear Seismic Discrimination

DTIC Science & Technology

1974-09-07

ellipticity filter. The source waveforms are recreated by an inverse transform of those complex ampli- tudes associated with the same azimuth...terms of the three complex data points and the ellipticity. Having solved the equations for all frequency bins, the inverse transform of...Transform of those complex amplitudes associated with Source 1, yielding the signal a (t). Similarly, take the inverse Transform of all

A mixed-mode crack analysis of rectilinear anisotropic solids using conservation laws of elasticity

NASA Technical Reports Server (NTRS)

Wang, S. S.; Yau, J. F.; Corten, H. T.

1980-01-01

A very simple and convenient method of analysis for studying two-dimensional mixed-mode crack problems in rectilinear anisotropic solids is presented. The analysis is formulated on the basis of conservation laws of anisotropic elasticity and of fundamental relationships in anisotropic fracture mechanics. The problem is reduced to a system of linear algebraic equations in mixed-mode stress intensity factors. One of the salient features of the present approach is that it can determine directly the mixed-mode stress intensity solutions from the conservation integrals evaluated along a path removed from the crack-tip region without the need of solving the corresponding complex near-field boundary value problem. Several examples with solutions available in the literature are solved to ensure the accuracy of the current analysis. This method is further demonstrated to be superior to other approaches in its numerical simplicity and computational efficiency. Solutions of more complicated and practical engineering problems dealing with the crack emanating from a circular hole in composites are presented also to illustrate the capacity of this method.

Optical limiting device and method of preparation thereof

DOEpatents

Wang, Hsing-Lin; Xu, Su; McBranch, Duncan W.

2003-01-01

Optical limiting device and method of preparation thereof. The optical limiting device includes a transparent substrate and at least one homogeneous layer of an RSA material in polyvinylbutyral attached to the substrate. The device may be produced by preparing a solution of an RSA material, preferably a metallophthalocyanine complex, and a solution of polyvinylbutyral, and then mixing the two solutions together to remove air bubbles. The resulting solution is layered onto the substrate and the solvent is evaporated. The method can be used to produce a dual tandem optical limiting device.

Removal of Cr(VI) from Aqueous Environments Using Micelle-Clay Adsorption

PubMed Central

Qurie, Mohannad; Khamis, Mustafa; Manassra, Adnan; Ayyad, Ibrahim; Nir, Shlomo; Scrano, Laura; Bufo, Sabino A.; Karaman, Rafik

2013-01-01

Removal of Cr(VI) from aqueous solutions under different conditions was investigated using either clay (montmorillonite) or micelle-clay complex, the last obtained by adsorbing critical micelle concentration of octadecyltrimethylammonium ions onto montmorillonite. Batch experiments showed the effects of contact time, adsorbent dosage, and pH on the removal efficiency of Cr(VI) from aqueous solutions. Langmuir adsorption isotherm fitted the experimental data giving significant results. Filtration experiments using columns filled with micelle-clay complex mixed with sand were performed to assess Cr(VI) removal efficiency under continuous flow at different pH values. The micelle-clay complex used in this study was capable of removing Cr(VI) from aqueous solutions without any prior acidification of the sample. Results demonstrated that the removal effectiveness reached nearly 100% when using optimal conditions for both batch and continuous flow techniques. PMID:24222757

Study of complexation process between 4'-nitrobenzo-15-crown-5 and yttrium(III) cation in binary mixed non-aqueous solvents using conductometric method

NASA Astrophysics Data System (ADS)

Habibi, N.; Rounaghi, G. H.; Mohajeri, M.

2012-12-01

The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

Third-order nonlinear optical properties of soluble Cr(III)-dioxolene complexes

NASA Astrophysics Data System (ADS)

Noro, Shin-ichiro; Sassa, Takafumi; Aoyama, Tetsuya; Chang, Ho-Chol; Kitagawa, Susumu; Wada, Tatsuo

2004-10-01

We synthesized novel ligand-based mixed valence (LBMV) CrIII-dioxolene complexes, [Cr(X4SQ)(X4Cat)(4,4'-di-tert-butyl-2,2'-bpy)] (SQ = semiquinone, Cat = catecohol, 2,2'-bpy = 2,2'-bipyridine; X = Cl (2a) and Br (2b)) and [Cr(X4SQ)(X4Cat)(4,4'-dinonyl-2,2'-bpy)] (X = Cl (3a) and Br (3b)), and prepared thin films for investigating their third-order nonlinear optical (NLO) properties in terms of the mixed valence states. Electronic absorption spectra of these complexes in solution and solid states showed an intervalence charge-transfer (IVCT) band from Cat2- to SQ"- at the IR region, indicating of a coexistence of SQ and Cat ligands, namely, LBMV state of the complexes. These complexes were well soluble in nonpolar organic solvent, which allowed us to prepare thin films by spin coating. The obtained films showed the electronic absorption spectra similar to those in solution and were amorphous because of steric hindrance of halogen and alkyl substituents in o-dioxolene and 2,2'-bpy moieties, respectively. The x(3) values of the films of 3a and 3b with a thickness of 30 ~ 40 nm were determined for 1.0 × 10-12 esu at 1.907 μm.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

PubMed

El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) < Ni(2+) < Cu(2+) > Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands

PubMed Central

El-Sherif, Ahmed A.; Shehata, Mohamed R.; Shoukry, Mohamed M.; Barakat, Mohammad H.

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO3) using a potentiometric technique. The order of –ΔG0 and –ΔH0 was found to obey Co2+ < Ni2+ < Cu2+ > Zn2+, in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K. PMID:23226992

The Control of Orbital Mixing in Ruthenium Complexes Containing Quinone Related Ligands

DTIC Science & Technology

1991-04-04

and sodium, respectively. Tetrabutylammonium perchlorate (TBAP) and tetrabutylammonium hexafluorophosphate (Kodak; TBAH) were recrystallized from...solution. Lithium perchlorate trihydrate (0.036 g; 0.23 mmol) in methanol (2 mL) was added to the hot reaction mixture. The mixture was cooled to room...and lithium aluminum hydride suspension in THF (this required the use of the 4,5-dimethylated orthophenylenediamine complex for solubility reasons

Investigation of solvent-free MALDI-TOFMS sample preparation methods for the analysis of organometallic and coordination compounds.

PubMed

Hughes, Laura; Wyatt, Mark F; Stein, Bridget K; Brenton, A Gareth

2009-01-15

An investigation of various solvent-free matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample preparation methods for the characterization of organometallic and coordination compounds is described. Such methods are desirable for insoluble materials, compounds that are only soluble in disadvantageous solvents, or complexes that dissociate in solution, all of which present a major "difficulty" to most mass spectrometry techniques. First-row transition metal acetylacetonate complexes, which have been characterized previously by solution preparation MALDI-TOFMS, were used to evaluate the various solvent-free procedures. These procedures comprise two distinct steps: the first being the efficient "solids mixing" (the mixing of sample and matrix), and the second being the effective transfer of the sample/matrix mixture to the MALDI target plate. This investigation shows that vortex mixing is the most efficient first step and that smearing using a microspatula is the most effective second step. In addition, the second step is shown to be much more critical than the first step in obtaining high-quality data. Case studies of truly insoluble materials highlight the importance of these techniques for the wider chemistry community.

Lagrangian turbulence: Structures and mixing in admissible model flows

NASA Astrophysics Data System (ADS)

Ottino, Julio M.

1991-12-01

The goal of our research was to bridge the gap between modern ideas from dynamical systems and chaos and more traditional approaches to turbulence. In order to reach this objective we conducted theoretical and computational work on two systems: (1) a perturbed-Kelvin cat eyes flow, and (2) prototype solutions of the Navier-Stokes equations near solid walls. The main results obtained are two-fold: we have been able to produce flows capable of producing complex distributions of vorticity, and we have been able to construct flowfields, based on solutions of the Navier-Stokes equations, which are capable of displaying both Eulerian and Lagrangian turbulence. These results exemplify typical mechanisms of mixing enhancement in transitional flows.

Chemical composition of an aqueous oxalato-/citrato-VO(2+) solution as determinant for vanadium oxide phase formation.

PubMed

Peys, Nick; Maurelli, Sara; Reekmans, Gunter; Adriaensens, Peter; De Gendt, Stefan; Hardy, An; Van Doorslaer, Sabine; Van Bael, Marlies K

2015-01-05

Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C.

Transient modeling/analysis of hyperbolic heat conduction problems employing mixed implicit-explicit alpha method

NASA Technical Reports Server (NTRS)

Tamma, Kumar K.; D'Costa, Joseph F.

1991-01-01

This paper describes the evaluation of mixed implicit-explicit finite element formulations for hyperbolic heat conduction problems involving non-Fourier effects. In particular, mixed implicit-explicit formulations employing the alpha method proposed by Hughes et al. (1987, 1990) are described for the numerical simulation of hyperbolic heat conduction models, which involves time-dependent relaxation effects. Existing analytical approaches for modeling/analysis of such models involve complex mathematical formulations for obtaining closed-form solutions, while in certain numerical formulations the difficulties include severe oscillatory solution behavior (which often disguises the true response) in the vicinity of the thermal disturbances, which propagate with finite velocities. In view of these factors, the alpha method is evaluated to assess the control of the amount of numerical dissipation for predicting the transient propagating thermal disturbances. Numerical test models are presented, and pertinent conclusions are drawn for the mixed-time integration simulation of hyperbolic heat conduction models involving non-Fourier effects.

Thermodynamic study of complex formation between Ce3+ and cryptand 222 in some binary mixed nonaqueous solvents

NASA Astrophysics Data System (ADS)

Rounaghi, G. H.; Dolatshahi, S.; Tarahomi, S.

2014-12-01

The stoichiometry, stability and the thermodynamic parameters of complex formation between cerium(III) cation and cryptand 222 (4,7,13,16,21,24-hexaoxa-1,10-diazabycyclo[8.8.8]-hexacosane) were studied by conductometric titration method in some binary solvent mixtures of dimethylformamide (DMF), 1,2-dichloroethane (DCE), ethyl acetate (EtOAc) and methyl acetate (MeOAc) with methanol (MeOH), at 288, 298, 308, and 318 K. A model based on 1: 1 stoichiometry has been used to analyze the conductivity data. The data have been fitted according to a non-linear least-squares analysis that provide the stability constant, K f, for the cation-ligand inclusion complex. The results revealed that the stability order of [Ce(cryptand 222)]3+ complex changes with the nature and composition of the solvent system. A non-linear relationship was observed between the stability constant (log K f) of [Ce(cryptand 222)]3+ complex versus the composition of the binary mixed solvent. Standard thermodynamic values were obtained from temperature dependence of the stability constant of the complex, show that the studied complexation process is mainly entropy governed and are influenced by the nature and composition of the binary mixed solvent solutions.

A TDDFT study of the ruthenium(II) polyazaaromatic complex [Ru(dppz)(phen) 2] 2+ in solution

NASA Astrophysics Data System (ADS)

Fantacci, Simona; De Angelis, Filippo; Sgamellotti, Antonio; Re, Nazzareno

2004-09-01

DFT/TDDFT calculations were performed to investigate the structural, electronic and optical properties of the [Ru(dppz)(phen) 2] 2+ complex in solution. TDDFT calculations in water show two groups of metal-to-ligand charge transfer (MLCT) transitions at ≈450 and 415 nm whose superposition gives account of the broad absorption band experimentally characterized at 440 nm. Also, a group of almost coincident MLCT transitions partially mixed with dppz intraligand π-π ∗ transitions centered at ≈380 nm is found to give rise to the narrow absorption band experimentally found at 380 nm. Our results provide insight into the hypochromic shifts experimentally characterized upon intercalation of the title complex into DNA.

Method of tagging excipients with /sup 99m/Tc

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

Bardy, A.; Beydon, J.; Gobin, R.

1977-11-08

A method of using /sup 99m/technetium for tagging excipients in medical diagnosis by scintigraphy comprises mixing, in an aqueous solution of alkali-metal pertechnetate, an excipient and a reducing agent in the form of a complex, which complex is such that the association constant of the anion with reduced techetium is less than the association constant of the excipient with reduced technetium, thereby forming a radio-pharmaceutical substance which is a complex between the excipient and /sup 99m/technetium.

Remediation of cadmium- and lead-contaminated agricultural soil by composite washing with chlorides and citric acid.

PubMed

Li, Yu-jiao; Hu, Peng-jie; Zhao, Jie; Dong, Chang-xun

2015-04-01

Composite washing of cadmium (Cd)- and lead (Pb)-contaminated agricultural soil from Hunan province in China using mixtures of chlorides (FeCl3, CaCl2) and citric acid (CA) was investigated. The concentrations of composite washing agents for metal removal were optimized. Sequential extraction was conducted to study the changes in metal fractions after soil washing. The removal of two metals at optimum concentration was reached. Using FeCl3 mixed with CA, 44% of Cd and 23% of Pb were removed, and 49 and 32% by CaCl2 mixed with CA, respectively. The mechanism of composite washing was postulated. A mixture of chlorides and CA enhanced metal extraction from soil through the formation of metal-chloride and metal-citrate complexes. CA in extract solutions promoted the formation of metal-chloride complexes and reduced the solution pH. Composite washing reduced Cd and Pb in Fe-Mn oxide forms significantly. Chlorides and CA exerted a synergistic effect on metal extraction during composite washing.

Halide ions complex and deprotonate dipicolinamides and isophthalamides: assessment by mass spectrometry and UV-visible spectroscopy.

PubMed

Carasel, I Alexandru; Yamnitz, Carl R; Winter, Rudolph K; Gokel, George W

2010-12-03

The F(-), Cl(-), and Br(-) binding selectivity of bis(p-nitroanilide)s of dipicolinic and isophthalic acids was studied by using competitive electrospray mass spectrometry and UV-Visible spectroscopy. Both hosts prefer binding Cl(-) over either F(-) or Br(-). Host deprotonation was observed to some extent in all experiments in which the host was exposed to halide ions. When F(-) was present, host deprotonation was often the major process, whereas little deprotonation was observed by Cl(-) or Br(-), which preferred complexation. A solution of either host changed color when mixed with a F(-), H(2)PO(4)(-), di- or triphenylacetate solution.

Electrogenerated chemiluminescence. 58. Ligand-sensitized electrogenerated chemiluminescence in europium labels

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

Richter, M.M.; Bard, A.J.

The electrochemistry and electrogenerated chemiluminescence (ECL) of a series of europium chelates, cryptates, and mixed-ligand chelate/cryptand complexes were studied. The complexes were of the following general forms: EuL{sub 4}{sup -}, where L = {beta}-diketonate, a bis-chelating ligand (such as dibenzoylmethide), added as salts (A)EuL{sub 4}, where A= tetrabutylammonium ion or piperidinium ion (pipH{sup +}); Eu(crypt){sup 3+}, where crypt = a cryptand ligand, e.g., 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8,8,5]-tricosa ne; and Eu(crypt)(L){sup 2+} for the mixed-ligand systems. ECL was obtained for the chelates and mixed-ligand systems by reducing the complexes at a Pt electrode in the presence of peroxydisulfate in acetonitrile solutions and was attributedmore » to the electron-transfer reaction between the reduced bound ligands and SO{sub 4}{sup .-}, followed by intramolecular excitation transfer from the excited ligand orbitals to the metal-centered 4f states. No ECL was observed under the same conditions for the europium complexes incorporating only the cryptand ligands in aqueous solution. The ECL spectra matched the photoluminescence spectra with a narrow emission band observed at 612 nm, corresponding to a metal-centered 4f-4f transition. The ECL efficiencies for the ECL-active species were low, about 10{sup -1}-10{sup -4}% of that of the Ru-(bpy){sub 3}{sup 2+}/S{sub 2}O{sub 8}{sup 2-} system under similar conditions. 38 refs., 6 figs., 2 tabs.« less

A hybrid structured-unstructured grid method for unsteady turbomachinery flow computations

NASA Technical Reports Server (NTRS)

Mathur, Sanjay R.; Madavan, Nateri K.; Rajagopalan, R. G.

1993-01-01

A hybrid grid technique for the solution of 2D, unsteady flows is developed. This technique is capable of handling complex, multiple component geometries in relative motion, such as those encountered in turbomachinery. The numerical approach utilizes a mixed structured-unstructured zonal grid topology along with modeling equations and solution methods that are most appropriate in the individual domains, therefore combining the advantages of both structured and unstructured grid techniques.

Synthesis, spectroscopic characterization, electrochemical behavior and computational analysis of mixed diamine ligand gold(III) complexes: antiproliferative and in vitro cytotoxic evaluations against human cancer cell lines.

PubMed

Al-Jaroudi, Said S; Monim-ul-Mehboob, M; Altaf, Muhammad; Al-Saadi, Abdulaziz A; Wazeer, Mohammed I M; Altuwaijri, Saleh; Isab, Anvarhusein A

2014-12-01

The gold(III) complexes of the type [(DACH)Au(en)]Cl3, 1,2-Diaminocyclohexane ethylenediamine gold(III) chloride [where 1,2-DACH = cis-, trans-1,2- and S,S-1,2diaminocyclohexane and en = ethylenediamine] have been synthesized and characterized using various analytical and spectroscopic techniques including elemental analysis, UV-Vis and FTIR spectra; and solution as well as solid-state NMR measurements. The solid-state (13)C NMR shows that 1,2-diaminocyclohexane (1,2-DACH) and ethylenediamine (en) are strongly bound to the gold(III) center via N donor atoms. The stability of the mixed diamine ligand gold(III) was determined by (1)H and (13)C NMR spectra. Their electrochemical behavior was studied by cyclic voltammetry. The structural details and relative stabilities of the four possible isomers of the complexes were also reported at the B3LYP/LANL2DZ level of theory. The coordination sphere of these complexes around gold(III) center adopts distorted square planar geometry. The computational study also demonstrates that trans- conformations is slightly more stable than the cis-conformations. The antiproliferative effects and cytotoxic properties of the mixed diamine ligand gold(III) complexes were evaluated in vitro on human gastric SGC7901 and prostate PC3 cancer cells using MTT assay. The antiproliferative study of the gold(III) complexes on PC3 and SGC7901 cells indicate that complex 1 is the most effective antiproliferative agent among mixed ligand based gold(III) complexes 1-3. The IC50 data reveal that the in vitro cytotoxicity of complexes 1 and 3 against SGC7901 cancer cells are fairly better than that of cisplatin.

Enhanced nonlinear optical responses in donor-acceptor ionic complexes via photo induced energy transfer.

PubMed

Mamidala, Venkatesh; Polavarapu, Lakshminarayana; Balapanuru, Janardhan; Loh, Kian Ping; Xu, Qing-Hua; Ji, Wei

2010-12-06

By complexion of donor and acceptor using ionic interactions, the enhanced nonlinear optical responses of donor-acceptor ionic complexes in aqueous solution were studied with 7-ns laser pulses at 532 nm. The optical limiting performance of negatively charged gold nanoparticles or graphene oxide (Acceptor) was shown to be improved significantly when they were mixed with water-soluble, positively-charged porphyrin (Donor) derivative. In contrast, no enhancement was observed when mixing with negatively-charged porphyrin. Transient absorption studies of the donor-acceptor complexes confirmed that the addition of energy transfer pathway were responsible for excited-state deactivation, which results in the observed enhancement. Fluence, angle-dependent scattering and time correlated single photon counting measurements suggested that the enhanced nonlinear scattering due to faster nonradiative decay should play a major role in the enhanced optical limiting responses.

Self-Assembly of Porphyrin J-Aggregates

NASA Astrophysics Data System (ADS)

Snitka, Valentinas; Rackaitis, Mindaugas; Navickaite, Gintare

2006-03-01

The porphyrin nanotubes were built by ionic self-assembly of two oppositely charged porphyrins in aqueous solution. The porphyrins in the acid aqueous solution self-assemble into J-aggregates, wheels or other structures. The electrostatic forces between these porphyrin blocks contribute to the formation of porphyrin aggregates in the form of nanotubes, enhance the structural stability of these nanostructures. The nanotubes were composed mixing aqueous solutions of the two porphyrins - anionic Meso-tetra(4- sulfonatophrnyl)porhine dihydrochloride (TPPS4) and cationic Meso-tetra(4-pyridyl)porphine (T4MPyP). The porphyrin nanotubes obtained are hollow structures with the length of 300 nm and diameter 50 nm. Photocatalytic porphyrins are used to reduce metal complexes from aqueous solution and to control the deposition of Au from AuHCl4 and Au nanoparticles colloid solutions onto porphyrin nanotubes. Porphyrin nanotubes are shown to reduce metal complexes and deposit the metal selectively onto the inner or outer surface of the tubes, leading to nanotube-metal composite structures.

A multi-species reactive transport model to estimate biogeochemical rates based on single-well push-pull test data

NASA Astrophysics Data System (ADS)

Phanikumar, Mantha S.; McGuire, Jennifer T.

2010-08-01

Push-pull tests are a popular technique to investigate various aquifer properties and microbial reaction kinetics in situ. Most previous studies have interpreted push-pull test data using approximate analytical solutions to estimate (generally first-order) reaction rate coefficients. Though useful, these analytical solutions may not be able to describe important complexities in rate data. This paper reports the development of a multi-species, radial coordinate numerical model (PPTEST) that includes the effects of sorption, reaction lag time and arbitrary reaction order kinetics to estimate rates in the presence of mixing interfaces such as those created between injected "push" water and native aquifer water. The model has the ability to describe an arbitrary number of species and user-defined reaction rate expressions including Monod/Michelis-Menten kinetics. The FORTRAN code uses a finite-difference numerical model based on the advection-dispersion-reaction equation and was developed to describe the radial flow and transport during a push-pull test. The accuracy of the numerical solutions was assessed by comparing numerical results with analytical solutions and field data available in the literature. The model described the observed breakthrough data for tracers (chloride and iodide-131) and reactive components (sulfate and strontium-85) well and was found to be useful for testing hypotheses related to the complex set of processes operating near mixing interfaces.

[Nasal submicron emulsion of Scutellariae Radix extract preparation technology research based on phase transfer of solute technology].

PubMed

Shi, Ya-jun; Shi, Jun-hui; Chen, Shi-bin; Yang, Ming

2015-07-01

Based on the demand of nasal drug delivery high drug loadings, using the unique phase transfer of solute, integrating the phospholipid complex preparation and submicron emulsion molding process of Scutellariae Radix extract, the study obtained the preparation of the high drug loadings submicron emulsion of Scutellariae Radix extract. In the study of drug solution dispersion method, the uniformity of drug dispersed as the evaluation index, the traditional mixing method, grinding, homogenate and solute phase transfer technology were investigated, and the solute phase transfer technology was adopted in the last. With the adoption of new technology, the drug loading capacity reached 1.33% (phospholipid complex was 4%). The drug loading capacity was improved significantly. The transfer of solute method and timing were studied as follows,join the oil phase when the volume of phospholipid complex anhydrous ethanol solution remaining 30%, the solute phase transfer was completed with the continued recycling of anhydrous ethanol. After drug dissolved away to oil phase, the preparation technology of colostrum was determined with the evaluation index of emulsion droplet form. The particle size of submicron emulsion, PDI and stability parameters were used as evaluation index, orthogonal methodology were adopted to optimize the submicron emulsion ingredient and main influential factors of high pressure homogenization technology. The optimized preparation technology of Scutellariae Radix extract nasal submicron emulsion is practical and stable.

Copper-phospholipid interaction at cell membrane model hydrophobic surfaces.

PubMed

Mlakar, Marina; Cuculić, Vlado; Frka, Sanja; Gašparović, Blaženka

2018-04-01

Detailed investigation of Cu (II) binding with natural lipid phosphatidylglycerol (PG) in aqueous solution was carried out by voltammetric measurements at the mercury drop electrode, complemented by monolayer studies in a Langmuir trough and electrophoretic measurements, all used as models for hydrophobic cell membranes. Penetration of copper ions into the PG layer was facilitated by the formation of hydrophilic Cu-Phenanthroline (Phen) complex in the subphase, followed by the mixed ligand Cu-Phen-PG complex formation at the hydrophobic interface. Electrophoretic measurements indicated a comparatively low abundance of the formed mixed ligand complex within the PG vesicles, resulting it the zeta potential change of +0.83mV, while monolayer studies confirmed their co-existence at the interface. The Cu-Phen-PG complex was identified in the pH range from 6 to 9. The stoichiometry of the complex ([PhenCuOHPG]), as well as its stability and kinetics of formation, were determined at the mercury drop electrode. Cu-Phen-PG reduces quasireversibly at about -0.7V vs. Ag/AgCl including reactant adsorption, followed by irreversible mixed complex dissociation, indicating a two-electron transfer - chemical reaction (EC mechanism). Consequently, the surface concentration (γ) of the adsorbed [PhenCuOHPG] complex at the hydrophobic electrode surface was calculated to be (3.35±0.67)×10 -11 molcm -2 . Information on the mechanism of Cu (II) - lipid complex formation is a significant contribution to the understanding of complex processes at natural cell membranes. Copyright © 2017 Elsevier B.V. All rights reserved.

AFM Structural Characterization of Drinking Water Biofilm ...

EPA Pesticide Factsheets

Due to the complexity of mixed culture drinking water biofilm, direct visual observation under in situ conditions has been challenging. In this study, atomic force microscopy (AFM) revealed the three dimensional morphology and arrangement of drinking water relevant biofilm in air and aqueous solution. Operating parameters were optimized to improve imaging of structural details for a mature biofilm in liquid. By using a soft cantilever (0.03 N/m) and slow scan rate (0.5 Hz), biofilm and individual bacterial cell’s structural topography were resolved and continuously imaged in liquid without loss of spatial resolution or sample damage. The developed methodology will allow future in situ investigations to temporally monitor mixed culture drinking water biofilm structural changes during disinfection treatments. Due to the complexity of mixed culture drinking water biofilm, direct visual observation under in situ conditions has been challenging. In this study, atomic force microscopy (AFM) revealed the three dimensional morphology and arrangement of drinking water relevant biofilm in air and aqueous solution. Operating parameters were optimized to improve imaging of structural details for a mature biofilm in liquid. By using a soft cantilever (0.03 N/m) and slow scan rate (0.5 Hz), biofilm and individual bacterial cell’s structural topography were resolved and continuously imaged in liquid without loss of spatial resolution or sample damage. The developed methodo

Generalized dark-bright vector soliton solution to the mixed coupled nonlinear Schrödinger equations.

PubMed

Manikandan, N; Radhakrishnan, R; Aravinthan, K

2014-08-01

We have constructed a dark-bright N-soliton solution with 4N+3 real parameters for the physically interesting system of mixed coupled nonlinear Schrödinger equations. Using this as well as an asymptotic analysis we have investigated the interaction between dark-bright vector solitons. Each colliding dark-bright one-soliton at the asymptotic limits includes more coupling parameters not only in the polarization vector but also in the amplitude part. Our present solution generalizes the dark-bright soliton in the literature with parametric constraints. By exploiting the role of such coupling parameters we are able to control certain interaction effects, namely beating, breathing, bouncing, attraction, jumping, etc., without affecting other soliton parameters. Particularly, the results of the interactions between the bound state dark-bright vector solitons reveal oscillations in their amplitudes under certain parametric choices. A similar kind of effect was also observed experimentally in the BECs. We have also characterized the solutions with complicated structure and nonobvious wrinkle to define polarization vector, envelope speed, envelope width, envelope amplitude, grayness, and complex modulation. It is interesting to identify that the polarization vector of the dark-bright one-soliton evolves on a spherical surface instead of a hyperboloid surface as in the bright-bright case of the mixed coupled nonlinear Schrödinger equations.

Stress-intensity factor calculations using the boundary force method

NASA Technical Reports Server (NTRS)

Tan, P. W.; Raju, I. S.; Newman, J. C., Jr.

1987-01-01

The Boundary Force Method (BFM) was formulated for the three fundamental problems of elasticity: the stress boundary value problem, the displacement boundary value problem, and the mixed boundary value problem. Because the BFM is a form of an indirect boundary element method, only the boundaries of the region of interest are modeled. The elasticity solution for the stress distribution due to concentrated forces and a moment applied at an arbitrary point in a cracked infinite plate is used as the fundamental solution. Thus, unlike other boundary element methods, here the crack face need not be modeled as part of the boundary. The formulation of the BFM is described and the accuracy of the method is established by analyzing a center-cracked specimen subjected to mixed boundary conditions and a three-hole cracked configuration subjected to traction boundary conditions. The results obtained are in good agreement with accepted numerical solutions. The method is then used to generate stress-intensity solutions for two common cracked configurations: an edge crack emanating from a semi-elliptical notch, and an edge crack emanating from a V-notch. The BFM is a versatile technique that can be used to obtain very accurate stress intensity factors for complex crack configurations subjected to stress, displacement, or mixed boundary conditions. The method requires a minimal amount of modeling effort.

Multilayer Films and Capsules of Sodium Carboxymethylcellulose and Polyhexamethylenguanidine Hydrochloride

NASA Astrophysics Data System (ADS)

Guzenko, Nataliia; Gabchak, Oleksandra; Pakhlov, Evgenij

The complexation of polyhexamethylenguanidine hydrochloride (PHMG) and sodium carboxymethylcellulose (CMC) was investigated for different conditions. Mixing of equiconcentrated aqueous solutions of the polyelectrolytes was found to result in the formation of an insoluble interpolyelectrolyte complex with an overweight of carboxymethylcellulose. A step-by-step formation of stable, irreversibly adsorbed multilayer film of the polymers was demonstrated using the quartz crystal microbalance method. Unusually thick polymer shells with a large number of loops and tails of the polyanion were formed by the method of layer-by-layer self-assembly of PHMG and CMC on spherical CaCO3 particles. Hollow multilayer capsules stable in neutral media were obtained by dissolution of the inorganic matrix in EDTA solution.

The Systematics of Activity-Composition Relations in Mg-Fe2+ Oxide and Silicate Solid Solutions

NASA Astrophysics Data System (ADS)

O'Neill, H. S.

2006-12-01

The need to quantify activity-composition relations of mineral solid solutions for petrologic modelling has prompted many experimental studies, but different studies on the same system often appear to show a startling lack of consistency. A good example is Mg-Fe2+ mixing in garnet (the pyrope-almandine join). This is understandable because the energies of mixing in solid solutions are often obtained experimentally as small difference between large numbers. In particular, the fallacy of using a sequential approach to data fitting to a thermodynamic model leads to the accumulated errors being artificially concentrated onto the last step of the fitting process, which is usually that part of the model dealing with the excess energies of mixing. This gives rise to erroneous activity-composition relations, often apparently showing complex deviations from ideality. Systemizing the results of many studies can reveal underlying patterns of behaviour while also identifying outliers and anomalies that may be worth reinvestigating. Davies and Navrotsky [1] showed that the energies of mixing of many different pairs of ions with the same charge correlated well with the difference in molar volumes of the end-members, within a particular crystal structure. This empirical work is now supported by theoretical calculations. It underlies the modern approach to melt/crystal trace-element partitioning. Provided an internally consistent dataset is used, an analogous correlation may be demonstrated across different crystal structures for the mixing of one pair of ions, such as Mg and Fe2+. Activity-composition relations in MgO-"FeO" magnesiowuestite solutions in equilibrium with iron metal were used to obtain the properties of Mg-Fe olivine solutions from magnesiowuestite/olivine partitioning [2]. New results at 1400 K, 1 bar and 1473 K, 25 kb (O'Neill and Pownceby, in prep.) confirm previous work that mixing in Mg-Fe olivine is regular (symmetrical) with W Mg-Fe = 2.5 kJ/mol, with an accuracy including possible systematic errors of 0.5 kJ/mol (1 st. dev.). Any asymmetry is unambiguously constrained to be very small. These results were combined with experimental data (all at or above 900ºC), for partitioning of Mg and Fe between olivine and one of ilmenite (Pownceby and O'Neill, in prep.), Ti-, Al- or Cr-spinel (O'Neill, unpublished) and pyroxenes, garnet, and various high-pressure phases (literature). Internal consistency can be checked using other available partitioning data between pairs of these phases (i.e., without olivine). Except for some of the high-pressure phases, the ferromagnesian solutions are symmetrical with W Mg-Fe decreasing with the difference in the volumes of the end-members, which in turn depends on the atomic (Mg+Fe)/O ratio. This suggests that mixing in binary amphiboles, micas and other complex ferromagnesian silicates should be nearly ideal. The discrepancies shown by the high-pressure phases may be due to Fe3+ substitutions. As a working hypothesis, it is proposed that solid solutions between cations of the same charge and roughly similar size have simple thermodynamic mixing properties, with little asymmetry, modest excess entropies and excess enthalpies proportional to the volume difference of the end-members. Order-disorder phenomena have surprisingly little effect in the high temperature regime for which experimental data are available. Refs: [1] Davies and Navrotsky, J Sol State Chem 46, 1-22, 1983. [2] O'Neill et al., CMP 146, 308-325, 2003.

Influence of the preparation method on the physicochemical properties of indomethacin and methyl-β-cyclodextrin complexes.

PubMed

Rudrangi, Shashi Ravi Suman; Bhomia, Ruchir; Trivedi, Vivek; Vine, George J; Mitchell, John C; Alexander, Bruce David; Wicks, Stephen Richard

2015-02-20

The main objective of this study was to investigate different manufacturing processes claimed to promote inclusion complexation between indomethacin and cyclodextrins in order to enhance the apparent solubility and dissolution properties of indomethacin. Especially, the effectiveness of supercritical carbon dioxide processing for preparing solid drug-cyclodextrin inclusion complexes was investigated and compared to other preparation methods. The complexes were prepared by physical mixing, co-evaporation, freeze drying from aqueous solution, spray drying and supercritical carbon dioxide processing methods. The prepared complexes were then evaluated by scanning electron microscopy, differential scanning calorimetry, X-ray powder diffraction, solubility and dissolution studies. The method of preparation of the inclusion complexes was shown to influence the physicochemical properties of the formed complexes. Indomethacin exists in a highly crystalline solid form. Physical mixing of indomethacin and methyl-β-cyclodextrin appeared not to reduce the degree of crystallinity of the drug. The co-evaporated and freeze dried complexes had a lower degree of crystallinity than the physical mix; however the lowest degree of crystallinity was achieved in complexes prepared by spray drying and supercritical carbon dioxide processing methods. All systems based on methyl-β-cyclodextrin exhibited better dissolution properties than the drug alone. The greatest improvement in drug dissolution properties was obtained from complexes prepared using supercritical carbon dioxide processing, thereafter by spray drying, freeze drying, co-evaporation and finally by physical mixing. Supercritical carbon dioxide processing is well known as an energy efficient alternative to other pharmaceutical processes and may have application for the preparation of solid-state drug-cyclodextrin inclusion complexes. It is an effective and economic method that allows the formation of solid complexes with a high yield, without the use of organic solvents and problems associated with their residues. Copyright © 2015 Elsevier B.V. All rights reserved.

Minimization of required model runs in the Random Mixing approach to inverse groundwater flow and transport modeling

NASA Astrophysics Data System (ADS)

Hoerning, Sebastian; Bardossy, Andras; du Plessis, Jaco

2017-04-01

Most geostatistical inverse groundwater flow and transport modelling approaches utilize a numerical solver to minimize the discrepancy between observed and simulated hydraulic heads and/or hydraulic concentration values. The optimization procedure often requires many model runs, which for complex models lead to long run times. Random Mixing is a promising new geostatistical technique for inverse modelling. The method is an extension of the gradual deformation approach. It works by finding a field which preserves the covariance structure and maintains observed hydraulic conductivities. This field is perturbed by mixing it with new fields that fulfill the homogeneous conditions. This mixing is expressed as an optimization problem which aims to minimize the difference between the observed and simulated hydraulic heads and/or concentration values. To preserve the spatial structure, the mixing weights must lie on the unit hyper-sphere. We present a modification to the Random Mixing algorithm which significantly reduces the number of model runs required. The approach involves taking n equally spaced points on the unit circle as weights for mixing conditional random fields. Each of these mixtures provides a solution to the forward model at the conditioning locations. For each of the locations the solutions are then interpolated around the circle to provide solutions for additional mixing weights at very low computational cost. The interpolated solutions are used to search for a mixture which maximally reduces the objective function. This is in contrast to other approaches which evaluate the objective function for the n mixtures and then interpolate the obtained values. Keeping the mixture on the unit circle makes it easy to generate equidistant sampling points in the space; however, this means that only two fields are mixed at a time. Once the optimal mixture for two fields has been found, they are combined to form the input to the next iteration of the algorithm. This process is repeated until a threshold in the objective function is met or insufficient changes are produced in successive iterations.

Analytical Solution for Interface Flow to a Sink With an Upconed Saline Water Lens: Strack's Regimes Revisited

NASA Astrophysics Data System (ADS)

Kacimov, A. R.; Obnosov, Y. V.

2018-01-01

A study is made of a steady, two-dimensional groundwater flow with a horizontal well (drain), which pumps out freshwater from an aquifer sandwiched between a horizontal bedrock and ponded soil surface, and containing a lens-shaped static volume of a heavier saline water (DNAPL-dense nonaqueous phase liquid) as a free surface. For flow toward a line sink, an explicit analytical solution is obtained by a conformal mapping of the hexagon in the complex potential plane onto a reference plane and the Keldysh-Sedov integral representation of a mixed boundary-value problem for a complex physical coordinate. The interface is found as a function of the pumping rate, the well locus, the ratio of liquid densities, and the hydraulic heads at the soil surface and in the well. The shape with two inflexion points and fronts varies from a small-thickness bedrock-spread pancake to a critical curvilinear triangle, which cusps toward the sink. The problem is mathematically solvable in a relatively narrow band of geometric and hydraulic parameters. A similar analytic solution for a static heavy bubble confined by a closed-curve interface (no contact with the bedrock) is outlined as an illustration of the method to solve a mixed boundary-value problem.

Structure and Properties of Melt-spun Bio-based Polyamide/Eu(TTA)3Phen Composite fibers

NASA Astrophysics Data System (ADS)

Li, Yunye; Lou, Pengfei; Jia, Qingxiu

2018-02-01

In this paper, the bio-based polyamide (PA ) was melt polymerized from four bio-based monomers. Composites of the bio-based PA and europium complex Eu(TTA)3Phen were prepared through solution mixing using N, N-Dimethylformamide (DMF) and formic acid as the mixed solvent, and then composite fibers were obtained by melt spinning method. The structure and properties of the melt-spun composite fibers were characterized by FTIR and SEM. The results indicated that the Eu(TTA)3Phen complex, with the average diameter below 300 nm, was homogeneously dispersed in the PA matrix. FTIR spectra indicated that the coordination bond between carbonyl of BDIS and Eu(TTA)3Phen complex formed, which was also confirmed by the mechanical properties. The initial modulus and breaking strength of these fibers can arrived at 2.5GPa and 0.3GPa, respectively.

Alginate encapsulation of Begonia microshoots for short-term storage and distribution

USDA-ARS?s Scientific Manuscript database

Synthetic seeds were formed from in vitro grown Begonia cultivars (Sweetheart Mix and BabyWing White) shoot tips using 3% sodium alginate in Murashige and Skoog medium (MS) salt solution as the gel matrix and 100 mM calcium chloride for complexation. Synthetic seed formation was achieved by releasin...

Hepa filter dissolution process

DOEpatents

Brewer, Ken N.; Murphy, James A.

1994-01-01

A process for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal.

From Mixed-Metal MOFs to Carbon-Coated Core-Shell Metal Alloy@Metal Oxide Solid Solutions: Transformation of Co/Ni-MOF-74 to CoxNi1-x@CoyNi1-yO@C for the Oxygen Evolution Reaction.

PubMed

Sun, Dengrong; Ye, Lin; Sun, Fangxiang; García, Hermenegildo; Li, Zhaohui

2017-05-01

Calcination of the mixed-metal species Co/Ni-MOF-74 leads to the formation of carbon-coated Co x Ni 1-x @Co y Ni 1-y O with a metal core diameter of ∼3.2 nm and a metal oxide shell thickness of ∼2.4 nm embedded uniformly in the ligand-derived carbon matrix. The close proximity of Co and Ni in the mixed-metal Co/Ni-MOF-74 promotes the metal alloying and the formation of a solid solution of metal oxide during the calcination process. The presence of the tightly coated carbon shell prohibits particle agglomeration and stabilizes the Co x Ni 1-x @Co y Ni 1-y O nanoparticles in small size. The Co x Ni 1-x @Co y Ni 1-y O@C derived from Co/Ni-MOF-74 nanocomposites show superior performance for the oxygen evolution reaction (OER). The use of mixed-metal MOFs as precursors represents a powerful strategy for the fabrication of metal alloy@metal oxide solid solution nanoparticles in small size. This method also holds great promise in the development of multifunctional carbon-coated complex core-shell metal/metal oxides owing to the diversified MOF structures and their flexible chemistry.

The phase behavior of cationic lipid-DNA complexes.

PubMed Central

May, S; Harries, D; Ben-Shaul, A

2000-01-01

We present a theoretical analysis of the phase behavior of solutions containing DNA, cationic lipids, and nonionic (helper) lipids. Our model allows for five possible structures, treated as incompressible macroscopic phases: two lipid-DNA composite (lipoplex) phases, namely, the lamellar (L(alpha)(C)) and hexagonal (H(II)(C)) complexes; two binary (cationic/neutral) lipid phases, that is, the bilayer (L(alpha)) and inverse-hexagonal (H(II)) structures, and uncomplexed DNA. The free energy of the four lipid-containing phases is expressed as a sum of composition-dependent electrostatic, elastic, and mixing terms. The electrostatic free energies of all phases are calculated based on Poisson-Boltzmann theory. The phase diagram of the system is evaluated by minimizing the total free energy of the three-component mixture with respect to all the compositional degrees of freedom. We show that the phase behavior, in particular the preferred lipid-DNA complex geometry, is governed by a subtle interplay between the electrostatic, elastic, and mixing terms, which depend, in turn, on the lipid composition and lipid/DNA ratio. Detailed calculations are presented for three prototypical systems, exhibiting markedly different phase behaviors. The simplest mixture corresponds to a rigid planar membrane as the lipid source, in which case, only lamellar complexes appear in solution. When the membranes are "soft" (i.e., low bending modulus) the system exhibits the formation of both lamellar and hexagonal complexes, sometimes coexisting with each other, and with pure lipid or DNA phases. The last system corresponds to a lipid mixture involving helper lipids with strong propensity toward the inverse-hexagonal phase. Here, again, the phase diagram is rather complex, revealing a multitude of phase transitions and coexistences. Lamellar and hexagonal complexes appear, sometimes together, in different regions of the phase diagram. PMID:10733951

Competition and enhancement effect in coremoval of atenolol and copper by an easily regenerative magnetic cation exchange resin.

PubMed

Li, Qimeng; Wang, Zheng; Li, Qiang; Shuang, Chendong; Zhou, Qing; Li, Aimin; Gao, Canzhu

2017-07-01

This paper aimed to investigate the removal of combined Cu 2+ and atenolol (ATL) in aqueous solution by using a newly synthesized magnetic cation exchange resin (MCER) as the adsorbent. The MCER exhibited efficient removal performance in sole, binary, pre-loading and saline systems. The adsorption kinetics of Cu 2+ and ATL fitted both pseudo-first-order and pseudo-second order model, while better described by pseudo-second order model in binary system. In mixed Cu 2+ and ATL solution, the adsorption of ATL was suppressed due to direct competition of carboxylic groups, while Cu 2+ adsorption was enhanced because of the formation of surface complexes. This increasing in heterogeneity was demonstrated by adsorption isotherms, which were more suitable for Freundlich model in binary system, while better described by Langmuir model in sole system. As proved by FTIR and XPS spectra, both amino and hydroxyl groups of ATL could form complexes with Cu 2+ . Decomplexing-bridging interaction was elucidated as the leading mechanism in coremoval of Cu 2+ and ATL, which involved [Cu-ATL] decomplexing and newly created Cu- or ATL sites for additional bridging. For saline system, the resulting competition and enhancement effects in mixed solution were amplified with the addition of co-existing cations. Moreover, the MCER could be effectively regenerated by 0.01 M HCl solution and maintain high stability over 5 adsorption-desorption cycles, which render it great potential for practical applications. Copyright © 2017. Published by Elsevier Ltd.

Synthesis, characterization and electrochemical investigations of mixed-ligand copper(II)-organic supramolecular frameworks

NASA Astrophysics Data System (ADS)

Singh, Sandeep K.; Srivastava, Ashish Kumar; Srivastava, Krishna; Banerjee, Rahul; Prasad, Jagdish

2017-11-01

Two mixed-ligand copper(II)-organic coordination compounds with 5,5‧-dimethyl-2,2‧-bipyridine (5,5‧-Me2bpy) as a primary ligand while aliphatic malonate (Hmal) and aromatic 2-hydroxynicotinate (2-OHNA) as secondary ligands, were synthesized. These complexes are formulated as: [Cu(Hmal)(5,5‧-Me2bpy)(H2O)](ClO4) 1 and [Cu2(2-OHNA)2(5,5‧-Me2bpy)2(NO3)](NO3) 2. These two complexes were structurally characterized by single crystal X-ray diffraction analysis. Characterization was further supported by powder X-ray diffraction analysis, elemental analyses, FT-IR, FAB-MASS and TGA, DSC studies. Cyclic voltammetric and UV-visible spectral studies of these two complexes have also been done. The electrochemical studies of complex 1 in DMSO and DMF have shown that this complex undergoes quasi-reversible diffusion-controlled one-electron transfer reaction without any chemical complication while complex 2 in DMSO undergoes quasi-reversible diffusion-controlled one electron transfer reaction, following EC mechanism. The electrochemical behaviour of complex 2 in DMF is complicated probably due to presence of more than one species in solution phase.

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

DTIC Science & Technology

2012-02-28

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

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

DTIC Science & Technology

2012-02-28

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

Energy-exchange collisions of dark-bright-bright vector solitons.

PubMed

Radhakrishnan, R; Manikandan, N; Aravinthan, K

2015-12-01

We find a dark component guiding the practically interesting bright-bright vector one-soliton to two different parametric domains giving rise to different physical situations by constructing a more general form of three-component dark-bright-bright mixed vector one-soliton solution of the generalized Manakov model with nine free real parameters. Moreover our main investigation of the collision dynamics of such mixed vector solitons by constructing the multisoliton solution of the generalized Manakov model with the help of Hirota technique reveals that the dark-bright-bright vector two-soliton supports energy-exchange collision dynamics. In particular the dark component preserves its initial form and the energy-exchange collision property of the bright-bright vector two-soliton solution of the Manakov model during collision. In addition the interactions between bound state dark-bright-bright vector solitons reveal oscillations in their amplitudes. A similar kind of breathing effect was also experimentally observed in the Bose-Einstein condensates. Some possible ways are theoretically suggested not only to control this breathing effect but also to manage the beating, bouncing, jumping, and attraction effects in the collision dynamics of dark-bright-bright vector solitons. The role of multiple free parameters in our solution is examined to define polarization vector, envelope speed, envelope width, envelope amplitude, grayness, and complex modulation of our solution. It is interesting to note that the polarization vector of our mixed vector one-soliton evolves in sphere or hyperboloid depending upon the initial parametric choices.

Application of Mortar Coupling in Multiscale Modelling of Coupled Flow, Transport, and Biofilm Growth in Porous Media

NASA Astrophysics Data System (ADS)

Laleian, A.; Valocchi, A. J.; Werth, C. J.

2017-12-01

Multiscale models of reactive transport in porous media are capable of capturing complex pore-scale processes while leveraging the efficiency of continuum-scale models. In particular, porosity changes caused by biofilm development yield complex feedbacks between transport and reaction that are difficult to quantify at the continuum scale. Pore-scale models, needed to accurately resolve these dynamics, are often impractical for applications due to their computational cost. To address this challenge, we are developing a multiscale model of biofilm growth in which non-overlapping regions at pore and continuum spatial scales are coupled with a mortar method providing continuity at interfaces. We explore two decompositions of coupled pore-scale and continuum-scale regions to study biofilm growth in a transverse mixing zone. In the first decomposition, all reaction is confined to a pore-scale region extending the transverse mixing zone length. Only solute transport occurs in the surrounding continuum-scale regions. Relative to a fully pore-scale result, we find the multiscale model with this decomposition has a reduced run time and consistent result in terms of biofilm growth and solute utilization. In the second decomposition, reaction occurs in both an up-gradient pore-scale region and a down-gradient continuum-scale region. To quantify clogging, the continuum-scale model implements empirical relations between porosity and continuum-scale parameters, such as permeability and the transverse dispersion coefficient. Solutes are sufficiently mixed at the end of the pore-scale region, such that the initial reaction rate is accurately computed using averaged concentrations in the continuum-scale region. Relative to a fully pore-scale result, we find accuracy of biomass growth in the multiscale model with this decomposition improves as the interface between pore-scale and continuum-scale regions moves downgradient where transverse mixing is more fully developed. Also, this decomposition poses additional challenges with respect to mortar coupling. We explore these challenges and potential solutions. While recent work has demonstrated growing interest in multiscale models, further development is needed for their application to field-scale subsurface contaminant transport and remediation.

Carotenoid stoichiometry in the LH2 crystal: no spectral evidence for the presence of the second molecule in the alpha/beta-apoprotein dimer.

PubMed

Gall, Andrew; Gardiner, Alastair T; Cogdell, Richard J; Robert, Bruno

2006-07-10

In this work we have investigated the carotenoid-protein interactions in LH2 complexes of Rhodopseudomonas acidophila both in "free in solution" mixed-micelles and in three-dimensional crystals by Raman spectroscopy in resonance with the carotenoid (Car) molecules. We show that the Car molecules when bound to their binding pockets show no significant differences when the complexes are "free in solution" or packed in crystalline arrays. Furthermore, there is no significant wavelength dependence in the Raman spectrum of the Car molecules of LH2. This indicates that there is only one Car configuration in LH2 and thus only one molecule per alpha/beta-heterodimer.

Thermometric titration studies of mixed ligand complexes of thorium.

PubMed

Kugler, G C; Carey, G H

1970-10-01

Mixed-ligand chelates consisting of two different multidentate ligands linked to a central thorium(IV) ion have been prepared in aqueous solution and their heats of formation studied thermo metrically. Pyrocatechol, tiron, chromotropic acid, potassium hydrogen phthalate, 8-hydroxyquinoline-S-sulphonic acid, iminodiacetic acid, 5-sulphosalicylic acid and salicylic acid were used as the secondary ligands, while ethylenediaminetetra-acetate and 1, 2-diaminocyclohexane-N,N,N',N'-tetra-acetate were used as primary ligands. DeltaH values for the overall reactions are given, and where possible, the DeltaH and DeltaS values for the specific secondary ligand addition were calculated. The overall stability of the mixed-ligand chelates and the enhanced stability of EDTA mixed chelates relative to the analogous DCTA chelates were found to be due to entropy rather than enthalpy effects.

Thermoresponsive complex amphiphilic block copolymer micelles investigated by laser light scattering.

PubMed

Zhao, Fang; Xie, Dinghai; Zhang, Guangzhao; Pispas, Stergios

2008-05-22

Poly(isoprene)-block-poly(ethylene oxide) (PI-b-PEO) diblock copolymers form micelles in water. The introduction of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-b-PPO-b-PEO) triblock copolymer leads to the formation of mixed micelles through hydrophobic interaction. The dimension of the mixed micelles varies with the weight ratio (r) of PEO-b-PPO-b-PEO to PI-b-PEO. By use of laser light scattering, we have investigated the temperature dependence of the structural evolution of the micelles at different r. At r<10, the size of the mixed micelles decreases with temperature. At r>10, due to the excessive PEO-b-PPO-b-PEO chains in solution, as temperature increases, the mixed micelles aggregate into larger micelle clusters.

Mixing of two solutions combined by gravity drainage.

PubMed

Leuptow, R M; Smith, K; Mockros, L F

1995-01-01

A variety of medical therapies require the mixing of solutions from two separate bags before use. One scenario for the mixing is to drain the solution from one bag into the other by gravity through a short connecting tube. The degree of mixing in the lower bag depends on the relative densities of the two solutions, the geometry of the two bags and the connecting tube, and the placement of the connecting tube. Solutions with densities differing by as much as 12% were mixed by draining the solution from an upper bag into a lower bag for a particular geometric configuration. The two solutions had different electrical conductivities, and the conductivity of the combined solution as it exited from the lower bag was used as a measure of the effectiveness of mixing. When the more dense solution was drained from the upper bag into the less dense solution in a lower bag, mixing was very effective. The incoming jet of high density solution entrained the low density solution. Flow visualization indicated that the incoming jet penetrated to the bottom of the lower bag, and resulting large vortical structures enhanced mixing. When the less dense solution was drained from the upper bag into the more dense solution in the lower bag mixing was less effective. The buoyancy force reduced the momentum of the incoming jet such that it did not penetrate to the bottom of the lower bag, resulting in stratification of the solutions.

Mechanical properties of bulk graphene oxide/poly(acrylic acid)/poly(ethylenimine) ternary polyelectrolyte complex.

PubMed

Duan, Yipin; Wang, Chao; Zhao, Mengmeng; Vogt, Bryan D; Zacharia, Nicole S

2018-05-30

Ternary complexes formed in a single pot process through the mixing of cationic (branched polyethylenimine, BPEI) and anionic (graphene oxide, GO, and poly(acrylic acid), PAA) aqueous solutions exhibit superior mechanical performance in comparison to their binary analogs. The composition of the ternary complex can be simply tuned through the composition of the anionic solution, which influences the water content and mechanical properties of the complex. Increasing the PAA content in the complex decreases the overall water content due to improved charge compensation with the BPEI, but this change also significantly improves the toughness of the complex. Ternary complexes containing ≤32 wt% PAA were too brittle to generate samples for tensile measurements, while extension in excess of 250% could be reached with 57 wt% PAA. From this work, the influence of GO and PAA on the mechanical properties of GO/PAA/BPEI complexes were elucidated with GO sheets acting to restrain the viscous flow and improve the mechanical strength at low loading (<12.6 wt%) and PAA more efficiently complexes with BPEI than GO to generate a less swollen and stronger network. This combination overcomes the brittle nature of GO-BPEI complexes and viscous creep of PAA-BPEI complexes. Ternary nanocomposite complexes appear to provide an effective route to toughen and strengthen bulk polyelectrolyte complexes.

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

PubMed

Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

2016-08-25

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules of arbitrary structure.

Dispersive—diffusive transport of non-sorbed solute in multicomponent solutions

NASA Astrophysics Data System (ADS)

Hu, Qinhong; Brusseau, Mark L.

1995-10-01

The composition of fuels, mixed-solvent wastes and other contaminants that find their way into the subsurface are frequently chemically complex. The dispersion and diffusion characteristics of multicomponent solutions in soil have rarely been compared to equivalent single-solute systems. The purpose of this work was to examine the diffusive and dispersive transport of single- and multi-component solutions in homogeneous porous media. The miscible displacement technique was used to investigate the transport behavior of 14C-labelled 2,4-dichlorophenoxyacetic acid ( 2,4-D) in two materials for which sorption of 2,4-D was minimal. Comparison of breakthrough curves collected for 2,4-D in single- and multi-component solutions shows that there is little, if any, difference in transport behavior over a wide range of pore-water velocities (70, 7, 0.66 and 0.06 cm h -1). Thus, dispersivities measured with a non-sorbing single-solute solution should be applicable to multicomponent systems.

Simultaneous injection effective mixing flow analysis of urinary albumin using dye-binding reaction.

PubMed

Ratanawimarnwong, Nuanlaor; Ponhong, Kraingkrai; Teshima, Norio; Nacapricha, Duangjai; Grudpan, Kate; Sakai, Tadao; Motomizu, Shoji

2012-07-15

A new four-channel simultaneous injection effective mixing flow analysis (SIEMA) system has been assembled for the determination of urinary albumin. The SIEMA system consisted of a syringe pump, two 5-way cross connectors, four holding coils, five 3-way solenoid valves, a 50-cm long mixing coil and a spectrophotometer. Tetrabromophenol blue anion (TBPB) in Triton X-100 micelle reacted with albumin at pH 3.2 to form a blue ion complex with a λ(max) 625nm. TBPB, Triton X-100, acetate buffer and albumin standard solutions were aspirated into four individual holding coils by a syringe pump and then the aspirated zones were simultaneously pushed in the reverse direction to the detector flow cell. Baseline drift, due to adsorption of TBPB-albumin complex on the wall of the hydrophobic PTFE tubing, was minimized by aspiration of Triton X-100 and acetate buffer solutions between samples. The calibration graph was linear in the range of 10-50μg/mL and the detection limit for albumin (3σ) was 0.53μg/mL. The RSD (n=11) at 30μg/mL was 1.35%. The sample throughput was 37/h. With a 10-fold dilution, interference from urine matrix was removed. The proposed method has advantages in terms of simple automation operation and short analysis time. Copyright © 2012 Elsevier B.V. All rights reserved.

Distributed mixed-integer fuzzy hierarchical programming for municipal solid waste management. Part I: System identification and methodology development.

PubMed

Cheng, Guanhui; Huang, Guohe; Dong, Cong; Xu, Ye; Chen, Xiujuan; Chen, Jiapei

2017-03-01

Due to the existence of complexities of heterogeneities, hierarchy, discreteness, and interactions in municipal solid waste management (MSWM) systems such as Beijing, China, a series of socio-economic and eco-environmental problems may emerge or worsen and result in irredeemable damages in the following decades. Meanwhile, existing studies, especially ones focusing on MSWM in Beijing, could hardly reflect these complexities in system simulations and provide reliable decision support for management practices. Thus, a framework of distributed mixed-integer fuzzy hierarchical programming (DMIFHP) is developed in this study for MSWM under these complexities. Beijing is selected as a representative case. The Beijing MSWM system is comprehensively analyzed in many aspects such as socio-economic conditions, natural conditions, spatial heterogeneities, treatment facilities, and system complexities, building a solid foundation for system simulation and optimization. Correspondingly, the MSWM system in Beijing is discretized as 235 grids to reflect spatial heterogeneity. A DMIFHP model which is a nonlinear programming problem is constructed to parameterize the Beijing MSWM system. To enable scientific solving of it, a solution algorithm is proposed based on coupling of fuzzy programming and mixed-integer linear programming. Innovations and advantages of the DMIFHP framework are discussed. The optimal MSWM schemes and mechanism revelations will be discussed in another companion paper due to length limitation.

HEPA filter dissolution process

DOEpatents

Brewer, K.N.; Murphy, J.A.

1994-02-22

A process is described for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal. 4 figures.

Tuning of protein-surfactant interaction to modify the resultant structure.

PubMed

Mehan, Sumit; Aswal, Vinod K; Kohlbrecher, Joachim

2015-09-01

Small-angle neutron scattering and dynamic light scattering studies have been carried out to examine the interaction of bovine serum albumin (BSA) protein with different surfactants under varying solution conditions. We show that the interaction of anionic BSA protein (pH7) with surfactant and the resultant structure are strongly modified by the charge head group of the surfactant, ionic strength of the solution, and mixed surfactants. The protein-surfactant interaction is maximum when two components are oppositely charged, followed by components being similarly charged through the site-specific binding, and no interaction in the case of a nonionic surfactant. This interaction of protein with ionic surfactants is characterized by the fractal structure representing a bead-necklace structure of micellelike clusters adsorbed along the unfolded protein chain. The interaction is enhanced with ionic strength only in the case of site-specific binding of an anionic surfactant with an anionic protein, whereas it is almost unchanged for other complexes of cationic and nonionic surfactants with anionic proteins. Interestingly, the interaction of BSA protein with ionic surfactants is significantly suppressed in the presence of nonionic surfactant. These results with mixed surfactants thus can be used to fold back the unfolded protein as well as to prevent surfactant-induced protein unfolding. For different solution conditions, the results are interpreted in terms of a change in fractal dimension, the overall size of the protein-surfactant complex, and the number of micelles attached to the protein. The interplay of electrostatic and hydrophobic interactions is found to govern the resultant structure of complexes.

Tuning of protein-surfactant interaction to modify the resultant structure

NASA Astrophysics Data System (ADS)

Mehan, Sumit; Aswal, Vinod K.; Kohlbrecher, Joachim

2015-09-01

Small-angle neutron scattering and dynamic light scattering studies have been carried out to examine the interaction of bovine serum albumin (BSA) protein with different surfactants under varying solution conditions. We show that the interaction of anionic BSA protein (p H 7 ) with surfactant and the resultant structure are strongly modified by the charge head group of the surfactant, ionic strength of the solution, and mixed surfactants. The protein-surfactant interaction is maximum when two components are oppositely charged, followed by components being similarly charged through the site-specific binding, and no interaction in the case of a nonionic surfactant. This interaction of protein with ionic surfactants is characterized by the fractal structure representing a bead-necklace structure of micellelike clusters adsorbed along the unfolded protein chain. The interaction is enhanced with ionic strength only in the case of site-specific binding of an anionic surfactant with an anionic protein, whereas it is almost unchanged for other complexes of cationic and nonionic surfactants with anionic proteins. Interestingly, the interaction of BSA protein with ionic surfactants is significantly suppressed in the presence of nonionic surfactant. These results with mixed surfactants thus can be used to fold back the unfolded protein as well as to prevent surfactant-induced protein unfolding. For different solution conditions, the results are interpreted in terms of a change in fractal dimension, the overall size of the protein-surfactant complex, and the number of micelles attached to the protein. The interplay of electrostatic and hydrophobic interactions is found to govern the resultant structure of complexes.

Simple and complex mental subtraction: strategy choice and speed-of-processing differences in younger and older adults.

PubMed

Geary, D C; Frensch, P A; Wiley, J G

1993-06-01

Thirty-six younger adults (10 male, 26 female; ages 18 to 38 years) and 36 older adults (14 male, 22 female; ages 61 to 80 years) completed simple and complex paper-and-pencil subtraction tests and solved a series of simple and complex computer-presented subtraction problems. For the computer task, strategies and solution times were recorded on a trial-by-trial basis. Older Ss used a developmentally more mature mix of problem-solving strategies to solve both simple and complex subtraction problems. Analyses of component scores derived from the solution times suggest that the older Ss are slower at number encoding and number production but faster at executing the borrow procedure. In contrast, groups did not appear to differ in the speed of subtraction fact retrieval. Results from a computational simulation are consistent with the interpretation that older adults' advantage for strategy choices and for the speed of executing the borrow procedure might result from more practice solving subtraction problems.

Multidimensional Solitons in Complex Media with Variable Dispersion: Structure and Evolution

DTIC Science & Technology

2003-07-20

the results of numerical experiments on Kadomtsev - Petviashvili (KP) equation study of structure and evolution of the nonlinear waves Sx described by...the KP equation with 13 = 3 (t,r) are con- at + auaxu + 03’u =K fAjudx, (1) sidered distracting from a concrete type of media. The -o• numerical...0i)(cot 0- mIM). It is well known that cluding the solutions of the mixed "soliton - non-soliton" the ID solutions of the KdV equation with 3 = const

Formation and stability of water-soluble, molecular polyelectrolyte complexes: effects of charge density, mixing ratio, and polyelectrolyte concentration.

PubMed

Shovsky, Alexander; Varga, Imre; Makuska, Ricardas; Claesson, Per M

2009-06-02

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC's are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Potentiometric study of binary complexes of 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride with some lanthanide ions in aqueous and mixed solutions

NASA Astrophysics Data System (ADS)

Sharma, S. S.; Kadia, M. V.

2014-12-01

The complexation of lanthanide ions (Y3+, La3+, Ce3+, Pr3+, Nd3+, Sm3+, Gd3+, Tb3+, and Dy3+) with 3-[(1 R)-1-hydroxy-2-(methylamino)ethyl]phenol hydrochloride was studied at different temperatures and different ionic strengths in aqueous solutions by Irving-Rossotti pH titration technique. Stepwise calculation, PKAS and BEST Fortran IV computer programs were used for determination of proton-ligand and metal-ligand stability constants. The formation of species like MA, MA2, and MA(OH) is considered in SPEPLOT. Thermodynamic parameters of complex formation (Δ G, Δ H, and Δ S) are also evaluated. Negative Δ G and Δ H values indicate that complex formation is favourable in these experimental conditions. The stability of complexes is also studied at in different solvent-aqueous (vol/vol). The stability series of lanthanide complexes has shown to have the "gadolinium break." Stability of complexes decreases with increase in ionic strength and temperature. Effect of systematic errors like effect of dissolved carbon dioxide, concentration of alkali, concentration of acid, concentration of ligand and concentration of metal have also been explained.

Some difficulties in the assessment of electric arc welding fume.

PubMed

Hewitt, P J; Gray, C N

1983-10-01

During electric arc welding of metals, particulate fume in a variety of chemical compositions and physical forms is produced with consequent complex solution chemistry. Mechanisms of fume formation include condensation of vaporized metals to produce submicron diameter chains, and spatter of larger particles with subsequent oxidation to yield mixed metal oxide fumes in the respirable range. Complete dissolution of certain constituent metals such as chromium, can be achieved by fusion with potassium hydrogen sulphate. Extraction of hexavalent chromium by sodium carbonate/hydroxide solution is efficient and rapid, while some other extractants give erroneous results. Investigations show that constituent metals are released from the fume at different rates both in vitro and in vivo. The implications arising from the complex nature of welding fume for industrial hygiene assessment are discussed.

Spatial Heterogeneity and Imperfect Mixing in Chemical Reactions: Visualization of Density-Driven Pattern Formation

DOE PAGES

Sobel, Sabrina G.; Hastings, Harold M.; Testa, Matthew

2009-01-01

Imore » mperfect mixing is a concern in industrial processes, everyday processes (mixing paint, bread machines), and in understanding salt water-fresh water mixing in ecosystems. The effects of imperfect mixing become evident in the unstirred ferroin-catalyzed Belousov-Zhabotinsky reaction, the prototype for chemical pattern formation. Over time, waves of oxidation (high ferriin concentration, blue) propagate into a background of low ferriin concentration (red); their structure reflects in part the history of mixing in the reaction vessel. However, it may be difficult to separate mixing effects from reaction effects. We describe a simpler model system for visualizing density-driven pattern formation in an essentially unmixed chemical system: the reaction of pale yellow Fe 3 + with colorless SCN − to form the blood-red Fe ( SCN ) 2 + complex ion in aqueous solution. Careful addition of one drop of Fe ( NO 3 ) 3 to KSCN yields striped patterns after several minutes. The patterns appear reminiscent of Rayleigh-Taylor instabilities and convection rolls, arguing that pattern formation is caused by density-driven mixing.« less

Spatial Heterogeneity and Imperfect Mixing in Chemical Reactions: Visualization of Density-Driven Pattern Formation

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

Sobel, Sabrina G.; Hastings, Harold M.; Testa, Matthew

Imore » mperfect mixing is a concern in industrial processes, everyday processes (mixing paint, bread machines), and in understanding salt water-fresh water mixing in ecosystems. The effects of imperfect mixing become evident in the unstirred ferroin-catalyzed Belousov-Zhabotinsky reaction, the prototype for chemical pattern formation. Over time, waves of oxidation (high ferriin concentration, blue) propagate into a background of low ferriin concentration (red); their structure reflects in part the history of mixing in the reaction vessel. However, it may be difficult to separate mixing effects from reaction effects. We describe a simpler model system for visualizing density-driven pattern formation in an essentially unmixed chemical system: the reaction of pale yellow Fe 3 + with colorless SCN − to form the blood-red Fe ( SCN ) 2 + complex ion in aqueous solution. Careful addition of one drop of Fe ( NO 3 ) 3 to KSCN yields striped patterns after several minutes. The patterns appear reminiscent of Rayleigh-Taylor instabilities and convection rolls, arguing that pattern formation is caused by density-driven mixing.« less

Solute mixing regulates heterogeneity of mineral precipitation in porous media: Effect of Solute Mixing on Precipitation

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

Cil, Mehmet B.; Xie, Minwei; Packman, Aaron I.

Synchrotron X-ray microtomography was used to track the spatiotemporal evolution of mineral precipitation and the consequent alteration of the pore structure. Column experiments were conducted by injecting CaCl2 and NaHCO3 solutions into granular porous media either as a premixed supersaturated solution (external mixing) or as separate solutions that mixed within the specimen (internal mixing). The two mixing modes produced distinct mineral growth patterns. While internal mixing promoted transverse heterogeneity with precipitation at the mixing zone, external mixing favored relatively homogeneous precipitation along the flow direction. The impact of precipitation on pore water flow and permeability was assessed via 3-D flowmore » simulations, which indicated anisotropic permeability evolution for both mixing modes. Under both mixing modes, precipitation decreased the median pore size and increased the skewness of the pore size distribution. Such similar pore-scale evolution patterns suggest that the clogging of individual pores depends primarily on local supersaturation state and pore geometry.« less

Synergistic Growth of Giant Wormlike Micelles in Ternary Mixed Surfactant Solutions: Effect of Octanoic Acid.

PubMed

Georgieva, Gergana S; Anachkov, Svetoslav E; Lieberwirth, Ingo; Koynov, Kaloian; Kralchevsky, Peter A

2016-12-06

The synergistic growth of giant wormlike micelles in ternary mixed solutions composed of an anionic surfactant (sodium laurylethersulfate, SLES), a zwitterionic surfactant (cocamidopropyl betaine, CAPB), and octanoic acid (HC8) is studied. Rheological data and their analysis in terms of Cole-Cole plots and micellar characteristic times are presented, and the micellar structures behind the observed rheological behavior are revealed by cryo-TEM micrographs. The surfactant composition is fixed near the maximal micelle size of the binary SLES + CAPB system, whereas the concentration of HC8 is varied. At a given HC8 concentration, the viscosity of the ternary micellar solutions exhibits a very high and sharp peak. Polarized-light optical microscopy indicates that all investigated solutions are isotropic rather than liquid-crystalline. The cryo-TEM imaging shows complex phase behavior: wormlike micelles to the left of the peak, giant entangled wormlike micelles at the peak, and long wormlike micelles coexisting with multiconnected micellar aggregates to the right of the peak. The formation of multiconnected micelles leads to a drop in viscosity at the higher concentrations. The results contribute to a better understanding of the structure-rheology relations in micellar surfactant solutions and could be useful for controlling the properties of formulations in personal-care and house-hold detergency.

Chitosan/pectin/gum Arabic polyelectrolyte complex: process-dependent appearance, microstructure analysis and its application.

PubMed

Tsai, Ruei-Yi; Chen, Pin-Wen; Kuo, Ting-Yun; Lin, Che-Min; Wang, Da-Ming; Hsien, Tzu-Yang; Hsieh, Hsyue-Jen

2014-01-30

Novel chitosan/pectin/gum Arabic polyelectrolyte complex (PEC) solutions and membranes with various compositions were prepared for biomedical applications. The appearance of the PEC solutions, either clear or turbid, was process-dependent and depended on how the three components were dissolved and mixed. The addition of gum Arabic to the chitosan and pectin significantly decreased the viscosities of the resultant PEC solutions due to the formation of globe-like microstructures that was accompanied by network-like microstructures and other molecular entanglements. The mechanical strength and hydrophilicity of the PEC membranes manufactured from the PEC solutions, especially for a weight ratio of 84/8/8 (chitosan/pectin/gum Arabic), were enhanced compared to pure chitosan membranes. Moreover, the use of the 84/8/8 PEC membranes as a drug carrier exhibited steady and fairly complete release of a drug (insulin) for 6h. Based on these promising results, the chitosan/pectin/gum Arabic PEC membranes have great potential in controlled drug release applications. Copyright © 2013 Elsevier Ltd. All rights reserved.

Coordination properties of tridentate (N,O,O) heterocyclic alcohol (PDC) with Cu(II). Mixed ligand complex formation reactions of Cu(II) with PDC and some bio-relevant ligands.

PubMed

El-Sherif, Ahmed A; Shoukry, Mohamed M

2007-03-01

The formation equilibria of copper(II) complexes and the ternary complexes Cu(PDC)L (PDC=2,6-bis-(hydroxymethyl)-pyridine, HL=amino acid, amides or DNA constituents) have been investigated. Ternary complexes are formed by a simultaneous mechanism. The results showed the formation of Cu(PDC)L, Cu(PDC, H(-1))(L) and Cu(PDC, H(-2))(L) complexes. The concentration distribution of the complexes in solution is evaluated as a function of pH. The effect of dioxane as a solvent on the protonation constant of PDC and the formation constants of Cu(II) complexes are discussed. The thermodynamic parameters DeltaH degrees and DeltaS degrees calculated from the temperature dependence of the equilibrium constants are investigated.

Mixed oxide solid solutions

DOEpatents

Magno, Scott; Wang, Ruiping; Derouane, Eric

2003-01-01

The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents, and divalent metal ions.

PubMed

Svanedal, Ida; Boija, Susanne; Norgren, Magnus; Edlund, Håkan

2014-06-10

The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg(2+) and Ni(2+) complexes with the chelating surfactant 4-C12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter β(σ) for mixed monolayer formation and the phase-transfer efficiency of Ni(2+) complexes with 4-C12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+) and Zn(2+), the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu(2+)) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C12-DTPA.

Interrelation of Entropic Contributors to π -Stacking in Solution

NASA Astrophysics Data System (ADS)

Starodub, Maria A.; Lantushenko, Anastasia O.; Evstigneev, Vladislav P.; Golovchenko, Igor V.; Mykhina, Yulia V.; Savin, Valery V.; Evstigneev, Maxim P.

2016-08-01

The recently published most complete set of thermodynamical data on self- and hetero-complexation of aromatic molecules measured under comparable experimental conditions were analyzed. The main aim of this study is to get insights into contribution of various entropic factors to π -stacking in aqueous solution. It was found that the experimental entropy change on π -stacking is determined by counterbalancing effects of two principal factors, i.e., the hydrophobic interaction (positive contribution) and the loss of degrees of freedom (negative contribution) modulated by the electrostatic contribution. Other factors, including the mixing entropy contribution, were shown to be less important.

Lagrangian turbulence near walls: Structures and mixing in admissible model flows

NASA Astrophysics Data System (ADS)

Ottino, J. M.

1989-05-01

The general objective of work during this period was to bridge the gap between modern ideas from dynamical systems and chaos and more traditional approaches to turbulence. In order to reach this objective we conducted theoretical and computational work on two systems: a perturbed Kelvin cat eyes flow, and prototype solutions of the Navier-Stokes equations near solid walls. The main results obtained are two-fold: production flows capable of producing complex distributions of vorticity, and constructed flow fields, based on solutions of the Navier Stokes equations, which are capable of displaying both Eulerian and Lagrangian turbulence.

Synthesis, spectral and thermal studies of some transition metal mixed ligand complexes: Modeling of equilibrium composition and biological activity

NASA Astrophysics Data System (ADS)

Neelakantan, M. A.; Sundaram, M.; Nair, M. Sivasankaran

2011-09-01

Several mixed ligand Ni(II), Cu(II) and Zn(II) complexes of 2-amino-3-hydroxypyridine (AHP) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) have been synthesized and characterized by elemental and spectral (vibrational, electronic, 1H NMR and EPR) data as well as by magnetic moment values. On the basis of elemental analysis and molar conductance values, all the complexes can be formulated as [MAB]Cl except histidine complexes as MAB. Thermogravimetric studies reveal the presence of coordinated water molecules in most of the complexes. From the magnetic measurements and electronic spectral data, octahedral structure was proposed for Ni(II) and Cu(II)-AHP-his, tetrahedral for Cu(II)-AHP-him/bim/hist, but square planar for the Cu(II)-AHP complex. The g∥/ A∥ calculated supports tetrahedral environment around the Cu(II) in Cu(II)-AHP-him/bim/hist and distorted octahedral for Cu(II)-AHP-his complexes. The morphology of the reported metal complexes was investigated by scanning electron micrographs (SEM). The potentiometric study has been performed in aqueous solution at 37 °C and I = 0.15 mol dm -3 NaClO 4. MABH, MAB and MAB 2 species has been identified in the present systems. Proton dissociation constants of AHP and stability constants of metal complexes were determined using MINIQUAD-75. The most probable structure of the mixed ligand species is discussed based upon their stability constants. The in vitro biological activity of the complexes was tested against the Gram positive and Gram negative bacteria, fungus and yeast. The oxidative DNA cleavage studies of the complexes were performed using gel electrophoresis method. Cu(II) complexes have been found to promote DNA cleavage in presence of biological reductant such as ascorbate and oxidant like hydrogen peroxide.

A Comparison of Analytical and Numerical Methods for Modeling Dissolution and Other Reactions in Transport Limited Systems

NASA Astrophysics Data System (ADS)

Hochstetler, D. L.; Kitanidis, P. K.

2009-12-01

Modeling the transport of reactive species is a computationally demanding problem, especially in complex subsurface media, where it is crucial to improve understanding of geochemical processes and the fate of groundwater contaminants. In most of these systems, reactions are inherently fast and actual rates of transformations are limited by the slower physical transport mechanisms. There have been efforts to reformulate multi-component reactive transport problems into systems that are simpler and less demanding to solve. These reformulations include defining conservative species and decoupling of reactive transport equations so that fewer of them must be solved, leaving mostly conservative equations for transport [e.g., De Simoni et al., 2005; De Simoni et al., 2007; Kräutle and Knabner, 2007; Molins et al., 2004]. Complex and computationally cumbersome numerical codes used to solve such problems have also caused De Simoni et al. [2005] to develop more manageable analytical solutions. Furthermore, this work evaluates reaction rates and has reaffirmed that the mixing rate,▽TuD▽u, where u is a solute concentration and D is the dispersion tensor, as defined by Kitanidis [1994], is an important and sometimes dominant factor in determining reaction rates. Thus, mixing of solutions is often reaction-limiting. We will present results from analytical and computational modeling of multi-component reactive-transport problems. The results have applications to dissolution of solid boundaries (e.g., calcite), dissolution of non-aqueous phase liquids (NAPLs) in separate phases, and mixing of saltwater and freshwater (e.g. saltwater intrusion in coastal carbonate aquifers). We quantify reaction rates, compare numerical and analytical results, and analyze under what circumstances which approach is most effective for a given problem. References: DeSimoni, M., et al. (2005), A procedure for the solution of multicomponent reactive transport problems, Water Resources Research, 41(W11410). DeSimoni, M., et al. (2007), A mixing ratios-based formulation for multicomponent reactive transport, Water Resources Research, 43(W07419). Kitanidis, P. (1994), The Concept of the Dilution Index, Water Resources Research, 30(7), 2011-2026. Kräutle, S., and P. Knabner (2007), A reduction scheme for coupled multicomponent transport-reaction problems in porous media: Generalization to problems with heterogeneous equilibrium reactions Water Resources Research, 43. Molins, S., et al. (2004), A formulation for decoupling components in reactive transport porblems, Water Resources Research, 40, 13.

Mixed Reality with HoloLens: Where Virtual Reality Meets Augmented Reality in the Operating Room.

PubMed

Tepper, Oren M; Rudy, Hayeem L; Lefkowitz, Aaron; Weimer, Katie A; Marks, Shelby M; Stern, Carrie S; Garfein, Evan S

2017-11-01

Virtual reality and augmented reality devices have recently been described in the surgical literature. The authors have previously explored various iterations of these devices, and although they show promise, it has become clear that virtual reality and/or augmented reality devices alone do not adequately meet the demands of surgeons. The solution may lie in a hybrid technology known as mixed reality, which merges many virtual reality and augmented realty features. Microsoft's HoloLens, the first commercially available mixed reality device, provides surgeons intraoperative hands-free access to complex data, the real environment, and bidirectional communication. This report describes the use of HoloLens in the operating room to improve decision-making and surgical workflow. The pace of mixed reality-related technological development will undoubtedly be rapid in the coming years, and plastic surgeons are ideally suited to both lead and benefit from this advance.

Evidence of an inverted hexagonal phase in self-assembled phospholipid-DNA-metal complexes

NASA Astrophysics Data System (ADS)

Francescangeli, O.; Pisani, M.; Stanic, V.; Bruni, P.; Weiss, T. M.

2004-08-01

We report the first observation of an inverted hexagonal phase of phospholipid-DNA-metal complexes. These ternary complexes are formed in a self-assembled manner when water solutions of neutral lipid dioleoylphosphatidylethanolamine (DOPE), DNA and divalent metal cations (Me2+; Me=Fe, Co, Mg, Mn) are mixed, which represents a striking example of supramolecular chemistry. The structure, derived from synchrotron X-ray diffraction, consists of cylindrical DNA strands coated by neutral lipid monolayers and arranged on a two-dimensional hexagonal lattice (HIIc). Besides the fundamental aspects, DOPE-DNA-Me2+ complexes may be of great interest as efficient nonviral delivery systems in gene therapy applications because of the low inherent cytotoxicity and the potential high transfection efficiency.

Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes.

PubMed

Tamaki, Yusuke; Morimoto, Tatsuki; Koike, Kazuhide; Ishitani, Osamu

2012-09-25

Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes-a photosensitizer and a catalyst-were synthesized. These complexes can photocatalyze the reduction of CO(2) to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide-triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO(2) reduction (Φ(HCOOH) = 0.061, TON(HCOOH) = 671) with the fastest reaction rate (TOF(HCOOH) = 11.6 min(-1)). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit.

Experimental testing and modeling analysis of solute mixing at water distribution pipe junctions.

PubMed

Shao, Yu; Jeffrey Yang, Y; Jiang, Lijie; Yu, Tingchao; Shen, Cheng

2014-06-01

Flow dynamics at a pipe junction controls particle trajectories, solute mixing and concentrations in downstream pipes. The effect can lead to different outcomes of water quality modeling and, hence, drinking water management in a distribution network. Here we have investigated solute mixing behavior in pipe junctions of five hydraulic types, for which flow distribution factors and analytical equations for network modeling are proposed. First, based on experiments, the degree of mixing at a cross is found to be a function of flow momentum ratio that defines a junction flow distribution pattern and the degree of departure from complete mixing. Corresponding analytical solutions are also validated using computational-fluid-dynamics (CFD) simulations. Second, the analytical mixing model is further extended to double-Tee junctions. Correspondingly the flow distribution factor is modified to account for hydraulic departure from a cross configuration. For a double-Tee(A) junction, CFD simulations show that the solute mixing depends on flow momentum ratio and connection pipe length, whereas the mixing at double-Tee(B) is well represented by two independent single-Tee junctions with a potential water stagnation zone in between. Notably, double-Tee junctions differ significantly from a cross in solute mixing and transport. However, it is noted that these pipe connections are widely, but incorrectly, simplified as cross junctions of assumed complete solute mixing in network skeletonization and water quality modeling. For the studied pipe junction types, analytical solutions are proposed to characterize the incomplete mixing and hence may allow better water quality simulation in a distribution network. Published by Elsevier Ltd.

Fingering dynamics on the adsorbed solute with influence of less viscous and strong sample solvent.

PubMed

Rana, Chinar; Mishra, Manoranjan

2014-12-07

Viscous fingering is a hydrodynamic instability that sets in when a low viscous fluid displaces a high viscous fluid and creates complex patterns in porous media flows. Fundamental facets of the displacement process, such as the solute concentration distribution, spreading length, and the solute mixing, depend strongly on the type of pattern created by the unstable interface of the underlying fluids. In the present study, the frontal interface of the sample shows viscous fingering and the strong solvent causes the retention of the solute to depend on the solvent concentration. This work presents a computational investigation to explore the effect of the underlying physico-chemical phenomena, (i.e., the combined effects of solvent strength, retention, and viscous fingering) on the dynamics of the adsorbed solute. A linear adsorption isotherm has been assumed between the mobile and stationary phases of the solute. We carried out the numerical simulations by considering a rectangular Hele-Shaw cell as an analog to 2D-porous media containing a three component system (displacing fluid, sample solvent, solute) to map out the evolution of the solute concentration. We observed that viscous fingering at the frontal interface of the strong sample solvent intensifies the band broadening of the solute zone. Also notable increase in the spreading dynamics of the solute has been observed for less viscous and strong sample solvent as compared to the high viscous sample slices or in the pure dispersive case. On the contrary, the solute gets intensively mixed at early times for more viscous sample in comparison to less viscous one. The results of the simulations are in qualitative agreement with the behavior observed in the liquid chromatography column experiments.

Quantification of mixing in vesicle suspensions using numerical simulations in two dimensions.

PubMed

Kabacaoğlu, G; Quaife, B; Biros, G

2017-02-01

We study mixing in Stokesian vesicle suspensions in two dimensions on a cylindrical Couette apparatus using numerical simulations. The vesicle flow simulation is done using a boundary integral method, and the advection-diffusion equation for the mixing of the solute is solved using a pseudo-spectral scheme. We study the effect of the area fraction, the viscosity contrast between the inside (the vesicles) and the outside (the bulk) fluid, the initial condition of the solute, and the mixing metric. We compare mixing in the suspension with mixing in the Couette apparatus without vesicles. On the one hand, the presence of vesicles in most cases slightly suppresses mixing. This is because the solute can be only diffused across the vesicle interface and not advected. On the other hand, there exist spatial distributions of the solute for which the unperturbed Couette flow completely fails to mix whereas the presence of vesicles enables mixing. We derive a simple condition that relates the velocity and solute and can be used to characterize the cases in which the presence of vesicles promotes mixing.

Quantification of mixing in vesicle suspensions using numerical simulations in two dimensions

PubMed Central

Quaife, B.; Biros, G.

2017-01-01

We study mixing in Stokesian vesicle suspensions in two dimensions on a cylindrical Couette apparatus using numerical simulations. The vesicle flow simulation is done using a boundary integral method, and the advection-diffusion equation for the mixing of the solute is solved using a pseudo-spectral scheme. We study the effect of the area fraction, the viscosity contrast between the inside (the vesicles) and the outside (the bulk) fluid, the initial condition of the solute, and the mixing metric. We compare mixing in the suspension with mixing in the Couette apparatus without vesicles. On the one hand, the presence of vesicles in most cases slightly suppresses mixing. This is because the solute can be only diffused across the vesicle interface and not advected. On the other hand, there exist spatial distributions of the solute for which the unperturbed Couette flow completely fails to mix whereas the presence of vesicles enables mixing. We derive a simple condition that relates the velocity and solute and can be used to characterize the cases in which the presence of vesicles promotes mixing. PMID:28344432

The importance of flow history in mixed shear and extensional flows

NASA Astrophysics Data System (ADS)

Wagner, Caroline; McKinley, Gareth

2015-11-01

Many complex fluid flows of experimental and academic interest exhibit mixed kinematics with regions of shear and elongation. Examples include flows through planar hyperbolic contractions in microfluidic devices and through porous media or geometric arrays. Through the introduction of a ``flow-type parameter'' α which varies between 0 in pure shear and 1 in pure elongation, the local velocity fields of all such mixed flows can be concisely characterized. It is tempting to then consider the local stress field and interpret the local state of stress in a complex fluid in terms of shearing or extensional material functions. However, the material response of such fluids exhibit a fading memory of the entire deformation history. We consider a dilute solution of Hookean dumbbells and solve the Oldroyd-B model to obtain analytic expressions for the entire stress field in any arbitrary mixed flow of constant strain rate and flow-type parameter α. We then consider a more complex flow for which the shear rate is constant but the flow-type parameter α varies periodically in time (reminiscent of flow through a periodic array or through repeated contractions and expansions). We show that the flow history and kinematic sequencing (in terms of whether the flow was initialized as shearing or extensional) is extremely important in determining the ensuing stress field and rate of dissipated energy in the flow, and can only be ignored in the limit of infinitely slow flow variations.

A digital front-end and readout microsystem for calorimetry at LHC

NASA Astrophysics Data System (ADS)

Alippi, C.; Appelquist, G.; Berglund, S.; Bohm, C.; Breveglieri, L.; Brigati, S.; Carlson, P.; Cattaneo, P.; Dadda, L.; David, J.; Del Buono, L.; Dell'Acqua, A.; Engström, M.; Fumagalli, G.; Gatti, U.; Genat, J. F.; Goggi, G.; Hansen, M.; Hentzell, H.; Höglund, I.; Inkinen, S.; Kerek, A.; Lebbolo, H.; LeDortz, O.; Lofstedt, B.; Maloberti, F.; Nayman, P.; Persson, S.-T.; Piuri, V.; Salice, F.; Sami, M.; Savoy-Navarro, A.; Stefanelli, R.; Sundblad, R.; Svensson, C.; Torelli, G.; Vanuxem, J. P.; Yamdagni, N.; Yuan, J.; Zitoun, R.

1994-04-01

A digital solution to the front-end electronics for calorimetric detectors at future supercolliders is presented. The solution is based on high speed {A}/{D} converters, a fully programmable pipeline/digital filter chain and local intelligence. Questions of error correction, fault-tolerance and system redundancy are also being considered. A system integration of a multichannel device in a multichip, Silicon-on-Silicon Microsystem hybrid, is used. This solution allows a new level of integration of complex analogue and digital functions, with an excellent flexibility in mixing technologies for the different functional blocks. It also allows a high degree of programmability at both the function and the system level, and offers the possibility of customising the microsystem with detector-specific functions.

Fully constrained Majorana neutrino mass matrices using \\varvec{Σ(72× 3)}

NASA Astrophysics Data System (ADS)

Krishnan, R.; Harrison, P. F.; Scott, W. G.

2018-01-01

In 2002, two neutrino mixing ansatze having trimaximally mixed middle (ν _2) columns, namely tri-chi-maximal mixing ( {T}χ {M}) and tri-phi-maximal mixing ( {T}φ {M}), were proposed. In 2012, it was shown that {T}χ {M} with χ =± π /16 as well as {T}φ {M} with φ = ± π /16 leads to the solution, sin ^2 θ _{13} = 2/3 sin ^2 π /16, consistent with the latest measurements of the reactor mixing angle, θ _{13}. To obtain {T}χ {M}_{(χ =± π /16)} and {T}φ {M}_{(φ =± π /16)}, the type I see-saw framework with fully constrained Majorana neutrino mass matrices was utilised. These mass matrices also resulted in the neutrino mass ratios, m_1:m_2:m_3=( 2+√{2}) /1+√{2(2+√{2)}}:1:( 2+√{2}) /-1+√{2(2+√{2)}}. In this paper we construct a flavour model based on the discrete group Σ (72× 3) and obtain the aforementioned results. A Majorana neutrino mass matrix (a symmetric 3× 3 matrix with six complex degrees of freedom) is conveniently mapped into a flavon field transforming as the complex six-dimensional representation of Σ (72× 3). Specific vacuum alignments of the flavons are used to arrive at the desired mass matrices.

Spectroscopic evidence for organic diacid complexation with dissolved silica in aqueous systems—I. Oxalic acid

USGS Publications Warehouse

Marley, N.A.; Bennett, P.; Janecky, D.R.; Gaffney, J.S.

1989-01-01

Increased solubility of quartz and mobilization in contaminated groundwater due to the complexation with dissolved organic acids has been recently proposed [Bennett and Siegel, Nature326, 684–686 (1987)]. Using laser Raman and Fourier transform infrared spectroscopies, we have examined mixed solutions of oxalic and silicic acids at near neutral pH in the tenth molar concentration ranges in an attempt to directly observe the proposed organo-silicate complexes.In both laser Raman and infrared spectra, product bands were observed that indicate an oxalate/silicic acid ester is being formed in the reaction. These data support the observation that organic diacids can lead to enhanced solubility of quartz in hydrogeological systems.

Chirality-selected phase behaviour in ionic polypeptide complexes

DOE PAGES

Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; ...

2015-01-14

In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with amore » β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.« less

DFT study of uranyl peroxo complexes with H2O, F-, OH-, CO3(2-), and NO3(-).

PubMed

Odoh, Samuel O; Schreckenbach, Georg

2013-05-06

The structural and electronic properties of monoperoxo and diperoxo uranyl complexes with aquo, fluoride, hydroxo, carbonate, and nitrate ligands have been studied using scalar relativistic density functional theory (DFT). Only the complexes in which the peroxo ligands are coordinated to the uranyl moiety in a bidentate mode were considered. The calculated binding energies confirm that the affinity of the peroxo ligand for the uranyl group far exceeds that of the F(-), OH(-), CO3(2-), NO3(-), and H2O ligands. The formation of the monoperoxo complexes from UO2(H2O)5(2+) and HO2(-) were found to be exothermic in solution. In contrast, the formation of the monouranyl-diperoxo, UO2(O2)2X2(4-) or UO2(O2)2X(4-/3-) (where X is any of F(-), OH(-), CO3(2-), or NO3(-)), complexes were all found to be endothermic in aqueous solution. This suggests that the monoperoxo species are the terminal monouranyl peroxo complexes in solution, in agreement with recent experimental work. Overall, we find that the properties of the uranyl-peroxo complexes conform to well-known trends: the coordination of the peroxo ligand weakens the U-O(yl) bonds, stabilizes the σ(d) orbitals and causes a mixing between the uranyl π- and peroxo σ- and π-orbitals. The weakening of the U-O(yl) bonds upon peroxide coordination results in uranyl stretching vibrational frequencies that are much lower than those obtained after the coordination of carbonato or hydroxo ligands.

Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands

PubMed Central

2016-01-01

The structure–property relationship study of a series of cationic Ir(III) complexes in the form of [Ir(C^N)2(dtBubpy)]PF6 [where dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = cyclometallating ligand bearing an electron-withdrawing group (EWG) at C4 of the phenyl substituent, i.e., −CF3 (1), −OCF3 (2), −SCF3 (3), −SO2CF3 (4)] has been investigated. The physical and optoelectronic properties of the four complexes were comprehensively characterized, including by X-ray diffraction analysis. All the complexes exhibit quasireversible dtBubpy-based reductions from −1.29 to −1.34 V (vs SCE). The oxidation processes are likewise quasireversible (metal + C^N ligand) and are between 1.54 and 1.72 V (vs SCE). The relative oxidation potentials follow a general trend associated with the Hammett parameter (σ) of the EWGs. Surprisingly, complex 4 bearing the strongest EWG does not adhere to the expected Hammett behavior and was found to exhibit red-shifted absorption and emission maxima. Nevertheless, the concept of introducing EWGs was found to be generally useful in blue-shifting the emission maxima of the complexes (λem = 484–545 nm) compared to that of the prototype complex [Ir(ppy)2(dtBubpy)]PF6 (where ppy = 2-phenylpyridinato) (λem = 591 nm). The complexes were found to be bright emitters in solution at room temperature (ΦPL = 45–66%) with microsecond excited-state lifetimes (τe = 1.14–4.28 μs). The photophysical properties along with density functional theory (DFT) calculations suggest that the emission of these complexes originates from mixed contributions from ligand-centered (LC) transitions and mixed metal-to-ligand and ligand-to-ligand charge transfer (LLCT/MLCT) transitions, depending on the EWG. In complexes 1, 3, and 4 the 3LC character is prominent over the mixed 3CT character, while in complex 2, the mixed 3CT character is much more pronounced, as demonstrated by DFT calculations and the observed positive solvatochromism effect. Due to the quasireversible nature of the oxidation and reduction waves, fabrication of light-emitting electrochemical cells (LEECs) using these complexes as emitters was possible with the LEECs showing moderate efficiencies. PMID:27681985

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, J.W.

1995-04-11

A process is described for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to expose additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal. 2 figures.

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, J.W.

1994-01-01

A process for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to exposure additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal.

Process for removing cadmium from scrap metal

DOEpatents

Kronberg, James W.

1995-01-01

A process for the recovery of a metal, in particular, cadmium contained in scrap, in a stable form. The process comprises the steps of mixing the cadmium-containing scrap with an ammonium carbonate solution, preferably at least a stoichiometric amount of ammonium carbonate, and/or free ammonia, and an oxidizing agent to form a first mixture so that the cadmium will react with the ammonium carbonate to form a water-soluble ammine complex; evaporating the first mixture so that ammine complex dissociates from the first mixture leaving carbonate ions to react with the cadmium and form a second mixture that includes cadmium carbonate; optionally adding water to the second mixture to form a third mixture; adjusting the pH of the third mixture to the acid range whereby the cadmium carbonate will dissolve; and adding at least a stoichiometric amount of sulfide, preferably in the form of hydrogen sulfide or an aqueous ammonium sulfide solution, to the third mixture to precipitate cadmium sulfide. This mixture of sulfide is then preferably digested by heating to facilitate precipitation of large particles of cadmium sulfide. The scrap may be divided by shredding or breaking up to expose additional surface area. Finally, the precipitated cadmium sulfide can be mixed with glass formers and vitrified for permanent disposal.

Modulating surface rheology by electrostatic protein/polysaccharide interactions.

PubMed

Ganzevles, Renate A; Zinoviadou, Kyriaki; van Vliet, Ton; Cohen, Martien A; de Jongh, Harmen H

2006-11-21

There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.

Mixed bilayer containing dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylserine: lipid complexation, ion binding, and electrostatics.

PubMed

Pandit, Sagar A; Bostick, David; Berkowitz, Max L

2003-11-01

Two mixed bilayers containing dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylserine at a ratio of 5:1 are simulated in NaCl electrolyte solutions of different concentration using the molecular dynamics technique. Direct NH.O and CH.O hydrogen bonding between lipids was observed to serve as the basis of interlipid complexation. It is deduced from our results and previous studies that dipalmitoylphosphatidylcholine alone is less likely to form interlipid complexes than in the presence of bound ions or other bilayer "impurities" such as dipalmitoylphosphatidylserine. The binding of counterions is observed and quantitated. Based upon the calculated ion binding constants, the Gouy-Chapman surface potential (theta) is calculated. In addition we calculated the electrostatic potential profile (Phi) by twice integrating the system charge distribution. A large discrepancy between and the value of Phi at the membrane surface is observed. However, at "larger" distance from the bilayer surface, a qualitative similarity in the z-profiles of Phi and psi(GC) is seen. The discrepancy between the two potential profiles near the bilayer surface is attributed to the discrete and nonbulk-like nature of water in the interfacial region and to the complex geometry of this region.

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

Morgan, Rhodri M. L.; Pal, Mohinder; Roe, S. Mark

A helix swap involving the fifth helix between two adjacently bound Tah1 molecules restores the normal binding environment of the conserved MEEVD peptide of Hsp90. Dimerization also explains how other monomeric TPR-domain proteins are excluded from forming inappropriate mixed co-chaperone complexes with Hsp90 and Tah1. Specific co-chaperone adaptors facilitate the recruitment of client proteins to the Hsp90 system. Tah1 binds the C-terminal conserved MEEVD motif of Hsp90, thus linking an eclectic set of client proteins to the R2TP complex for their assembly and regulation by Hsp90. Rather than the normal complement of seven α-helices seen in other tetratricopeptide repeat (TPR)more » domains, Tah1 unusually consists of the first five only. Consequently, the methionine of the MEEVD peptide remains exposed to solvent when bound by Tah1. In solution Tah1 appears to be predominantly monomeric, and recent structures have failed to explain how Tah1 appears to prevent the formation of mixed TPR domain-containing complexes such as Cpr6–(Hsp90){sub 2}–Tah1. To understand this further, the crystal structure of Tah1 in complex with the MEEVD peptide of Hsp90 was determined, which shows a helix swap involving the fifth α-helix between two adjacently bound Tah1 molecules. Dimerization of Tah1 restores the normal binding environment of the bound Hsp90 methionine residue by reconstituting a TPR binding site similar to that in seven-helix-containing TPR domain proteins. Dimerization also explains how other monomeric TPR-domain proteins are excluded from forming inappropriate mixed co-chaperone complexes.« less

pH-sensitive polymer-modified liposome-based immunity-inducing system: Effects of inclusion of cationic lipid and CpG-DNA.

PubMed

Yoshizaki, Yuta; Yuba, Eiji; Sakaguchi, Naoki; Koiwai, Kazunori; Harada, Atsushi; Kono, Kenji

2017-10-01

Efficient vaccine carriers for cancer immunotherapy require two functions: antigen delivery to dendritic cells (DCs) and the activation of DCs, a so-called adjuvant effect. We previously reported antigen delivery system using liposomes modified with pH-sensitive polymers, such as 3-methylglutarylated hyperbranched poly(glycidol) (MGlu-HPG), for the induction of antigen-specific immune responses. We reported that inclusion of cationic lipids to MGlu-HPG-modified liposomes activates DCs and enhances antitumor effects. In this study, CpG-DNA, a ligand to Toll-like receptor 9 (TLR9) expressing in endosomes of DCs, was introduced to MGlu-HPG-modified liposomes containing cationic lipids using two complexation methods (Pre-mix and Post-mix) for additional activation of antigen-specific immunity. For Pre-mix, thin membrane of lipids and polymers were dispersed by a mixture of antigen/CpG-DNA. For Post-mix, CpG-DNA was added to pre-formed liposomes. Both Pre-mix and Post-mix delivered CpG-DNA to DC endosomes, where TLR9 is expressing, more efficiently than free CpG-DNA solution did. These liposomes promoted cytokine production from DCs and the expression of co-stimulatory molecules in vitro and induced antigen-specific immune responses in vivo. Both Pre-mix and Post-mix exhibited strong antitumor effects compared with conventional pH-sensitive polymer-modified liposomes. Results show that inclusion of multiple adjuvant molecules into pH-sensitive polymer-modified liposomes and suitable CpG-DNA complexation methods are important to design potent vaccine carriers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermodynamic analysis of energy density in pressure retarded osmosis: The impact of solution volumes and costs

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

Reimund, Kevin K.; McCutcheon, Jeffrey R.; Wilson, Aaron D.

A general method was developed for estimating the volumetric energy efficiency of pressure retarded osmosis via pressure-volume analysis of a membrane process. The resulting model requires only the osmotic pressure, π, and mass fraction, w, of water in the concentrated and dilute feed solutions to estimate the maximum achievable specific energy density, uu, as a function of operating pressure. The model is independent of any membrane or module properties. This method utilizes equilibrium analysis to specify the volumetric mixing fraction of concentrated and dilute solution as a function of operating pressure, and provides results for the total volumetric energy densitymore » of similar order to more complex models for the mixing of seawater and riverwater. Within the framework of this analysis, the total volumetric energy density is maximized, for an idealized case, when the operating pressure is π/(1+√w⁻¹), which is lower than the maximum power density operating pressure, Δπ/2, derived elsewhere, and is a function of the solute osmotic pressure at a given mass fraction. It was also found that a minimum 1.45 kmol of ideal solute is required to produce 1 kWh of energy while a system operating at “maximum power density operating pressure” requires at least 2.9 kmol. Utilizing this methodology, it is possible to examine the effects of volumetric solution cost, operation of a module at various pressure, and operation of a constant pressure module with various feed.« less

The Prediction and Analysis of Jet Flows and Scattered Turbulent Mixing Noise about Flight Vehicle Airframes

NASA Technical Reports Server (NTRS)

Miller, Steven A. E.

2014-01-01

Jet flows interacting with nearby surfaces exhibit a complex behavior in which acoustic and aerodynamic characteristics are altered. The physical understanding and prediction of these characteristics are essential to designing future low noise aircraft. A new approach is created for predicting scattered jet mixing noise that utilizes an acoustic analogy and steady Reynolds-averaged Navier-Stokes solutions. A tailored Green's function accounts for the propagation of mixing noise about the airframe and is calculated numerically using a newly developed ray tracing method. The steady aerodynamic statistics, associated unsteady sound source, and acoustic intensity are examined as jet conditions are varied about a large flat plate. A non-dimensional number is proposed to estimate the effect of the aerodynamic noise source relative to jet operating condition and airframe position.The steady Reynolds-averaged Navier-Stokes solutions, acoustic analogy, tailored Green's function, non-dimensional number, and predicted noise are validated with a wide variety of measurements. The combination of the developed theory, ray tracing method, and careful implementation in a stand-alone computer program result in an approach that is more first principles oriented than alternatives, computationally efficient, and captures the relevant physics of fluid-structure interaction.

The Prediction and Analysis of Jet Flows and Scattered Turbulent Mixing Noise About Flight Vehicle Airframes

NASA Technical Reports Server (NTRS)

Miller, Steven A.

2014-01-01

Jet flows interacting with nearby surfaces exhibit a complex behavior in which acoustic and aerodynamic characteristics are altered. The physical understanding and prediction of these characteristics are essential to designing future low noise aircraft. A new approach is created for predicting scattered jet mixing noise that utilizes an acoustic analogy and steady Reynolds-averaged Navier-Stokes solutions. A tailored Green's function accounts for the propagation of mixing noise about the air-frame and is calculated numerically using a newly developed ray tracing method. The steady aerodynamic statistics, associated unsteady sound source, and acoustic intensity are examined as jet conditions are varied about a large at plate. A non-dimensional number is proposed to estimate the effect of the aerodynamic noise source relative to jet operating condition and airframe position. The steady Reynolds-averaged Navier-Stokes solutions, acoustic analogy, tailored Green's function, non- dimensional number, and predicted noise are validated with a wide variety of measurements. The combination of the developed theory, ray tracing method, and careful implementation in a stand-alone computer program result in an approach that is more first principles oriented than alternatives, computationally efficient, and captures the relevant physics of fluid-structure interaction.

The speciation of antimony in sulfidic solutions: A theoretical study

NASA Astrophysics Data System (ADS)

Tossell, J. A.

1994-12-01

To assist in identifying the Sb sulfide species present in alkaline sulfide solutions, we have used ab initio quantum mechanical methods to calculate the structures, stabilities and vibrational spectra of a number of monomeric and oligomeric Sb(III) sulfides. In agreement with the interpretation of WOOD (1989), we assign a prominent feature observed at 369 cm -1 in the Raman spectrum of sulfidic Sb solutions to Sb-S stretching vibrations in a monomeric complex, although our calculations are most consistent with its assignment to the SbS 2(SH) -2 complex, rather than the fully deprotonated complex SbS 3-3. A shoulder observed at 380 cm -1 is best assigned to SbS(SH) 2-. Raman features observed at 314 and 350 cm 3-1 are assigned to Sb-S(H) symmetric stretching vibrations of the dimeric species Sb 2S 2(SH) 2, which is calculated to be thermodynamically stable, with respect to both the monomer Sb(SH) 3 and the trimer Sb 3S 3(SH) 3. The mixed-ligand complex Sb 2S 2(OH) 2 is calculated to become stable compared to Sb 2S 2(SH) 2 at high temperatures, in agreement with experimental solubility data. The Sb sulfide monomers are found to H-bond to water through their -SH or -S groups, but with only small changes in the Sb-S distances and Sb-S stretching frequencies. Accurate gas-phase proton affinities and estimated solution proton affinities are presented for the anionic species in solution and the estimated energetics are consistent with the presence of SbS 2(SH) -2, SbS(SH) 2-1 and Sb 2S 2(SH) 2 suggested by the Raman data.

Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes

PubMed Central

Tamaki, Yusuke; Morimoto, Tatsuki; Koike, Kazuhide; Ishitani, Osamu

2012-01-01

Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes—a photosensitizer and a catalyst—were synthesized. These complexes can photocatalyze the reduction of CO2 to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide–triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO2 reduction (ΦHCOOH = 0.061, TONHCOOH = 671) with the fastest reaction rate (TOFHCOOH = 11.6 min-1). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit. PMID:22908243

Effect of complexation conditions on microcapsulation of Lactobacillus acidophilus in xanthan-chitosan polyelectrolyte complex gels.

PubMed

Chen, He; Song, Yajuan; Liu, Nina; Wan, Hongchang; Shu, Guowei; Liao, Na

2015-01-01

Lactobacillus acidophilus has become increasingly popular because of their beneficial effects on health of their host, and are called proboscis. In order to exert beneficial effects for probiotics, they must be able to tolerate the acidic conditions of the stomach environment and the bile in the small intestine. Microencapsulated form has received reasonable attention, since it can protect probiotic organisms against an unfavourable environment, and to allow their release in a viable and metabolically active state in the intestine. The aim of this study was to investigate some factores, such as chitosan solution pH and concentration, xanthan concentration, cell suspension-xanthan ratio, mixed bacteria glue liquid-chitosan ratio, which impacted the process of microencapsulation of L. acidophilus. In this study, L. acidophilus was immobilized with xanthan⁄chitosan gel using extrusion method. The viable counts and encapsulation yield of L. acidophilus encapsulated in different chitosan solution pH (4.5, 5, 5.5 and 6), in different chitosan concentration (0.5%, 0.7%, 0.9% and 1.1%), in different xanthan concentration (0.5%, 0.7%, 0.9% and 1.1%), in different cell suspension-xanthan ratios (1:5, 1:10, 1:15 and 1:20), in different mixed bacteria glue liquid-chitosan ratios (1:3, 1:4, 1:5 and 1:6), have been investigated by single factor experiment method. The optimum conditions of microencapsulated L. acidophilus have been observed. The optimum chitosan solution pH for L. acidophilus was 5.5; the optimum chitosan concentration was 0.9%; the optimum xanthan concentration was 0.7%; the optimum cell suspension-xanthan ratio was 1:10; the optimum mixed bacteria glue liquid-chitosan ratio was 1:3. These results will be helpful to further optimize the process of L. acidophilus microencapsulation, and provide reference for obtaining higher viable counts and entrapped yield of L. acidophilus microcapsules.

Experimental Testing and Modeling Analysis of Solute Mixing at Water Distribution Pipe Junctions

EPA Science Inventory

Flow dynamics at a pipe junction controls particle trajectories, solute mixing and concentrations in downstream pipes. Here we have categorized pipe junctions into five hydraulic types, for which flow distribution factors and analytical equations for describing the solute mixing ...

Rack 'em, pack 'em and stack 'em: challenges and opportunities in teaching large classes in higher education.

PubMed

Kumar, Saravana

2013-01-01

The higher education sector is undergoing tremendous change, driven by complex driving forces including financial, administrative, and organisational and stakeholder expectations. It is in this challenging environment, educators are required to maintain and improve the quality of teaching and learning outcomes while contending with increasing class sizes. Despite mixed evidence on the effectiveness of large classes on student outcomes, large classes continue to play an important part in higher education. While large classes pose numerous challenges, they also provide opportunities for innovative solutions. This paper provides an overview of these challenges and highlights opportunities for innovative solutions.

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

PubMed

Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

2009-04-01

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

Effects of turbulent hyporheic mixing on reach-scale solute transport

NASA Astrophysics Data System (ADS)

Roche, K. R.; Li, A.; Packman, A. I.

2017-12-01

Turbulence rapidly mixes solutes and fine particles into coarse-grained streambeds. Both hyporheic exchange rates and spatial variability of hyporheic mixing are known to be controlled by turbulence, but it is unclear how turbulent mixing influences mass transport at the scale of stream reaches. We used a process-based particle-tracking model to simulate local- and reach-scale solute transport for a coarse-bed stream. Two vertical mixing profiles, one with a smooth transition from in-stream to hyporheic transport conditions and a second with enhanced turbulent transport at the sediment-water interface, were fit to steady-state subsurface concentration profiles observed in laboratory experiments. The mixing profile with enhanced interfacial transport better matched the observed concentration profiles and overall mass retention in the streambed. The best-fit mixing profiles were then used to simulate upscaled solute transport in a stream. Enhanced mixing coupled in-stream and hyporheic solute transport, causing solutes exchanged into the shallow subsurface to have travel times similar to the water column. This extended the exponential region of the in-stream solute breakthrough curve, and delayed the onset of the heavy power-law tailing induced by deeper and slower hyporheic porewater velocities. Slopes of observed power-law tails were greater than those predicted from stochastic transport theory, and also changed in time. In addition, rapid hyporheic transport velocities truncated the hyporheic residence time distribution by causing mass to exit the stream reach via subsurface advection, yielding strong exponential tempering in the in-stream breakthrough curves at the timescale of advective hyporheic transport through the reach. These results show that strong turbulent mixing across the sediment-water interface violates the conventional separation of surface and subsurface flows used in current models for solute transport in rivers. Instead, the full distribution of flow and mixing over the surface-subsurface continuum must be explicitly considered to properly interpret solute transport in coarse-bed streams.

Quadrant CFD Analysis of a Mixer-Ejector Nozzle for HSCT Applications

NASA Technical Reports Server (NTRS)

Yoder, Dennis A.; Georgiadis, Nicholas J.; Wolter, John D.

2005-01-01

This study investigates the sidewall effect on flow within the mixing duct downstream of a lobed mixer-ejector nozzle. Simulations which model only one half-chute width of the ejector array are compared with those which model one complete quadrant of the nozzle geometry and with available experimental data. These solutions demonstrate the applicability of the half-chute technique to model the flowfield far away from the sidewall and the necessity of a full-quadrant simulation to predict the formation of a low-energy flow region near the sidewall. The quadrant solutions are further examined to determine the cause of this low-energy region, which reduces the amount of mixing and lowers the thrust of the nozzle. Grid resolution and different grid topologies are also examined. Finally, an assessment of the half-chute and quadrant approaches is made to determine the ability of these simulations to provide qualitative and/or quantitative predictions for this type of complex flowfield.

Building Bridges to Integrate Care (BRIDGES): Incubating Health Service Innovation across the Continuum of Care for Patients with Multiple Chronic Conditions.

PubMed

Bhattacharyya, Onil; Schull, Michael; Shojania, Kaveh; Stergiopoulos, Vicky; Naglie, Gary; Webster, Fiona; Brandao, Ricardo; Mohammed, Tamara; Christian, Jennifer; Hawker, Gillian; Wilson, Lynn; Levinson, Wendy

2016-01-01

Integrating care for people with complex needs is challenging. Indeed, evidence of solutions is mixed, and therefore, well-designed, shared evaluation approaches are needed to create cumulative learning. The Toronto-based Building Bridges to Integrate Care (BRIDGES) collaborative provided resources to refine and test nine new models linking primary, hospital and community care. It used mixed methods, a cross-project meta-evaluation and shared outcome measures. Given the range of skills required to develop effective interventions, a novel incubator was used to test and spread opportunities for system integration that included operational expertise and support for evaluation and process improvement.

Effects of the pH and Concentration on the Stability of Standard Solutions of Proteinogenic Amino Acid Mixtures.

PubMed

Kato, Megumi; Yamazaki, Taichi; Kato, Hisashi; Yamanaka, Noriko; Takatsu, Akiko; Ihara, Toshihide

2017-01-01

To prepare metrologically traceable amino acid mixed standard solutions, it is necessary to determine the stability of each amino acid present in the mixed solutions. In the present study, we prepared amino acid mixed solutions using certified reference standards of 17 proteinogenic amino acids, and examined the stability of each of these amino acids in 0.1 N HCl. We found that the concentration of glutamic acid decreased significantly during storage. LC/MS analysis indicated that the instability of glutamic acid was due to the partial degradation of glutamic acid to pyroglutamic acid in 0.1 N HCl. Using accelerated degradation tests, we investigated several solvent compositions to improve the stability of glutamic acid in amino acid mixed solution, and determined that the change of the pH by diluting the mixed solution improved the stability of glutamic acid.

Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes

NASA Astrophysics Data System (ADS)

Bhattacharjee, Chira R.; Goswami, Pankaj; Pramanik, Harun A. R.; Paul, Pradip C.; Mondal, Paritosh

2011-05-01

Two new mixed-ligand iron(III) complexes, [Fe(L n)(acac)(C 2H 5OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac) 3] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H 2L 1) or 2-aminobenzoic acid (H 2L 2). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L n)(acac)X] ( n = 1, 2; X = Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, 1H and 13C NMR spectroscopy. Room temperature magnetic susceptibility measurements ( μeff ˜ 5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (Δ Ep > 100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential ( E1/2) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level.

Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

DOEpatents

Hu, Michael Z.

2006-05-23

Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.

Rapid determination of tannins in tanning baths by adaptation of BSA method.

PubMed

Molinari, R; Buonomenna, M G; Cassano, A; Drioli, E

2001-01-01

A rapid and reproducible method for the determination of tannins in vegetable tanning baths is proposed as a modification of the BSA method for grain tannins existing in literature. The protein BSA was used instead of leather powder employed in the Filter Method, which is adopted in Italy and various others countries of Central Europe. In this rapid method the tannin contents is determined by means a spectrophotometric reading and not by means a gravimetric analysis of the Filter Method. The BSA method, which belongs to mixed methods (which use both precipitation and complexation of tannins), consists of selective precipitation of tannin from a solution containing also non tannins by BSA, the dissolution of precipitate and the quantification of free tannin amount by its complexation with Fe(III) in hydrochloric solutions. The absorbance values, read at 522 nm, have been expressed in terms of tannic acid concentration by using a calibration curve made with standard solutions of tannic acid; these have been correlated with the results obtained by using the Filter Method.

A controlled genetic algorithm by fuzzy logic and belief functions for job-shop scheduling.

PubMed

Hajri, S; Liouane, N; Hammadi, S; Borne, P

2000-01-01

Most scheduling problems are highly complex combinatorial problems. However, stochastic methods such as genetic algorithm yield good solutions. In this paper, we present a controlled genetic algorithm (CGA) based on fuzzy logic and belief functions to solve job-shop scheduling problems. For better performance, we propose an efficient representational scheme, heuristic rules for creating the initial population, and a new methodology for mixing and computing genetic operator probabilities.

Combined Microfluidic-Eectric Diffused Mixing of Living Cells in Continuous Flow

NASA Astrophysics Data System (ADS)

Ming-Wen Wang,

2010-02-01

The mixing process is a crucially important stage in the operation of biological and chemical microfluidic devices. If the mixing is inadequate, reactants do not fully interact with each other, and the device may not operate properly. This paper describes a simplified microfluidic mixer (different from a chaotic mixer) which can uniformly mix a buffer solution with living cells by applying an AC electric charge. Diffusion of the living cells into the buffer solution occurs rapidly following the interface of the flow stream with the electric charge; no further agitating step is needed. To accomplish this, an asymmetric pair of electrodes was integrated at the inlets of the buffer solution and the cells fluid. When the buffer solution and the cells fluid were introduced into one flow path, they remained limited to that flow stream. When the electrodes were charged, however, the cells in a short distance were efficiently moved into the solution flow, and the original fluids were mixed. The mixing efficiency depends on the polarizability of the cells, and this in turn is governed by the dielectric properties of the cells, the medium, and the solvent. This micro device, capable of efficiently mixing living cells with a buffer solution, may potentially allow biological mixing to be done outside of hospitals, in facilities without biological analyzing instruments.

Single-phase and well-dispersed Cu1.75S nanocrystals by ambient pressure diethylene glycol solution synthesis

NASA Astrophysics Data System (ADS)

Zheng, Xuerong; Jin, Zhengguo; Liu, Hui; Wang, Yueqiu; Wang, Xin; Du, Haiyan

2013-02-01

Single-phase, well-dispersed Cu1.75S nanocrystals were synthesized by an ambient pressure, hydrazine hydrate and ethylenediamine co-assisted diethylene glycol based solution chemical process using copper chloride and thioacetamide as precursors at the temperature range from 180 to 210 °C. Influence of hydrazine hydrate and ethylenediamine adding amounts, synthetic temperature on crystal growth, size distribution and optical properties of the synthesized Cu1.75S nanocrystals were investigated by XRD, TEM, HRTEM, EDX and UV-vis measurements. The synthetic reaction at above 200 °C grew flaky-shaped nanocrystals with relatively narrow size distribution. The formation of single-phase Cu1.75S nanocrystals in the diethylene glycol based solution process might be involved in the presence of intermediate [Cu(en)n]1+ and [Cu(NH3)4]2+ complexes in reaction solution, providing a stable Cu(I) and Cu(II) valent-mixed precursor.

Discrimination of Mixed Taste Solutions using Ultrasonic Wave and Soft Computing

NASA Astrophysics Data System (ADS)

Kojima, Yohichiro; Kimura, Futoshi; Mikami, Tsuyoshi; Kitama, Masataka

In this study, ultrasonic wave acoustic properties of mixed taste solutions were investigated, and the possibility of taste sensing based on the acoustical properties obtained was examined. In previous studies, properties of solutions were discriminated based on sound velocity, amplitude and frequency characteristics of ultrasonic waves propagating through the five basic taste solutions and marketed beverages. However, to make this method applicable to beverages that contain many taste substances, further studies are required. In this paper, the waveform of an ultrasonic wave with frequency of approximately 5 MHz propagating through mixed solutions composed of sweet and salty substance was measured. As a result, differences among solutions were clearly observed as differences in their properties. Furthermore, these mixed solutions were discriminated by a self-organizing neural network. The ratio of volume in their mixed solutions was estimated by a distance-type fuzzy reasoning method. Therefore, the possibility of taste sensing was shown by using ultrasonic wave acoustic properties and the soft computing, such as the self-organizing neural network and the distance-type fuzzy reasoning method.

Polyelectrolyte Properties in Mono and Multi-Valent Ionic Media: Brushes and Complex Coacervates

NASA Astrophysics Data System (ADS)

Farina, Robert M.

Materials composed of polyelectrolytes have unique and interesting physical properties resulting primarily from their charged monomer segments. Polyelectrolytes, which exist in many different biological and industrial forms, have also been shown to be highly responsive to external environmental changes. Here, two specific polyelectrolyte systems, brushes and complex coacervates, are discussed in regards to how their properties can be tailored by adjusting the surrounding ionic environment with mono and multi-valent ions. End-tethered polyelectrolyte brushes, which constitute an interesting and substantial portion of polyelectrolyte applications, are well known for their ability to provide excellent lubrication and low friction when coated onto surfaces (e.g. articular cartilage and medical devices), as well as for their ability to stabilize colloidal particles in solution (e.g. paint and cosmetic materials). These properties have been extensively studied with brushes in pure mono-valent ionic media. However, polyelectrolyte brush interactions with multi-valent ions in solution are much less understood, although highly relevant considering mono and multi-valent counterions are present in most applications. Even at very low concentrations of multi-valent ions in solution, dramatic polyelectrolyte brush physical property changes can occur, resulting in collapsed chains which also adhere to one another via multi-valent bridging. Here, the strong polyelectrolyte poly(sodium styrene sulfonate) was studied using the Surface Forces Apparatus (SFA) and electrochemistry in order to investigate brush height and intermolecular interactions between two brushes as a function of multi-valent counterion population inside a brush. Complex coacervates are formed when polyanions and polycations are mixed together in proper conditions of an aqueous solution. This mixing results in a phase separation of a polymer-rich, coacervate phase composed of a chain network held together via electrostatic interactions. Complex coacervates are highly regarded for their extremely low interfacial energy resulting in an ability to spread and adhere to surfaces under water, utilized by marine organisms (e.g. mussels and tubeworms), as well as many encapsulation applications (e.g. pigment encapsulation for carbon-less paper and electronic paper displays). Here, the interfacial energy of coacervates composed of oppositely charged polypeptides, poly(L-lysine) and poly(L-glutamic acid), was investigated using the SFA in regards to changes in bulk mono-valent salt concentrations.

A spectral-Tchebychev solution for three-dimensional dynamics of curved beams under mixed boundary conditions

NASA Astrophysics Data System (ADS)

Bediz, Bekir; Aksoy, Serdar

2018-01-01

This paper presents the application of the spectral-Tchebychev (ST) technique for solution of three-dimensional dynamics of curved beams/structures having variable and arbitrary cross-section under mixed boundary conditions. To accurately capture the vibrational behavior of curved structures, a three-dimensional (3D) solution approach is required since these structures generally exhibit coupled motions. In this study, the integral boundary value problem (IBVP) governing the dynamics of the curved structures is found using extended Hamilton's principle where the strain energy is expressed using 3D linear elasticity equation. To solve the IBVP numerically, the 3D spectral Tchebychev (3D-ST) approach is used. To evaluate the integral and derivative operations defined by the IBVP and to render the complex geometry into an equivalent straight beam with rectangular cross-section, a series of coordinate transformations are applied. To validate and assess the performance of the presented solution approach, two case studies are performed: (i) curved beam with rectangular cross-section, (ii) curved and pretwisted beam with airfoil cross-section. In both cases, the results (natural frequencies and mode shapes) are also found using a finite element (FE) solution approach. It is shown that the difference in predicted natural frequencies are less than 1%, and the mode shapes are in excellent agreement based on the modal assurance criteria (MAC) analyses; however, the presented spectral-Tchebychev solution approach significantly reduces the computational burden. Therefore, it can be concluded that the presented solution approach can capture the 3D vibrational behavior of curved beams as accurately as an FE solution, but for a fraction of the computational cost.

Stable supersaturated aqueous solutions of silatecan 7-t-butyldimethylsilyl-10-hydroxycamptothecin via chemical conversion in the presence of a chemically modified beta-cyclodextrin.

PubMed

Xiang, Tian-Xiang; Anderson, Bradley D

2002-08-01

A method for obtaining clear supersaturated aqueous solutions for parenteral administration of the poorly soluble experimental anti-cancer drug silatecan 7-t-butyldimethylsilyl-10-hydroxycamptothecin (DB-67) has been developed. Equilibrium solubilities of DB-67 were determined in various solvents and pH values, and in the presence of chemically modified water-soluble beta-cyclodextrins. The stoichiometry and binding constants for complexes of the lactone form of DB-67 and its ring-opened carboxylate with sulfobutyl ether and 2-hydroxypropyl substituted beta-cyclodextrins (SBE-CD and HP-CD) were obtained by solubility and circular dichroism spectroscopy, respectively. Kinetics for the reversible ring-opening of DB-67 in aqueous solution and for lactone precipitation were determined by HPLC with UV detection. Solubilities of DB-67 lactone in various injectable solvent systems were found to be at least one order of magnitude below the target concentration (2 mg/ml). DB-67 forms inclusion complexes with SBE-CD and HP-CD but the solubilization attainable is substantially less than the target concentration. Slow addition of DB-67/ DMSO into 22.2% (w/v) SBE-CD failed to yield stable supersaturated solutions due to precipitation. Stable supersatured solutions were obtained, however, by mixing a concentrated alkaline aqueous solution of DB-67 carboxylate with an acidified 22.2% (w/v) SBE-CD solution. Ring-closure yielded supersaturated solutions that could be lyophilized and reconstituted to clear, stable, supersaturated solutions. The method developed provides an alternative to colloidal dispersions (e.g., liposomal suspensions, emulsions, etc.) for parenteral administration of lipophilic camptothecin analogs.

Investigation of Compressibility Effect for Aeropropulsive Shear Flows

NASA Technical Reports Server (NTRS)

Balasubramanyam, M. S.; Chen, C. P.

2005-01-01

Rocket Based Combined Cycle (RBCC) engines operate within a wide range of Mach numbers and altitudes. Fundamental fluid dynamic mechanisms involve complex choking, mass entrainment, stream mixing and wall interactions. The Propulsion Research Center at the University of Alabama in Huntsville is involved in an on- going experimental and numerical modeling study of non-axisymmetric ejector-based combined cycle propulsion systems. This paper attempts to address the modeling issues related to mixing, shear layer/wall interaction in a supersonic Strutjet/ejector flow field. Reynolds Averaged Navier-Stokes (RANS) solutions incorporating turbulence models are sought and compared to experimental measurements to characterize detailed flow dynamics. The effect of compressibility on fluids mixing and wall interactions were investigated using an existing CFD methodology. The compressibility correction to conventional incompressible two- equation models is found to be necessary for the supersonic mixing aspect of the ejector flows based on 2-D simulation results. 3-D strut-base flows involving flow separations were also investigated.

Simulation of Reacting Flow with a Discontinuous Spectral Element Method

NASA Astrophysics Data System (ADS)

Ghiasi, Zia; Mashayek, Farzad; Komperda, Jonathan

2013-11-01

While using high order methods is desirable in order to accurately capture the small scale mixing effects in reacting flows, the challenge is to develop and implement such methods for complex geometries. In this work, a high-order Discontinuous Spectral Element Method (DSEM) code, which solves for the Navier-Stokes equations, has been modified by adding the appropriate components to solve for scalar transport equations in order to simulate the chemical reaction. Dealing with discontinuous solution at element interfaces is a challenge that is met by patching the fluxes at mortars thus making them continuous on interfaces. The patching is performed using the Lax-Fredrichs numerical flux for scalars, whereas a generalized Riemann solver is used for the Navier-Stokes equations. Direct numerical simulation is conducted in a temporally developing mixing layer to validate the method for a single step reaction (F + rO --> [ 1 + r ] P). Next, the method is implemented to simulate a subsonic reacting flow in a slanted cavity combustor with gaseous fuel injectors to demonstrate the capability of the method to handle complex geometries. The results will be used for physical understanding of mixing and reaction in this type of combustors.

Enhancing the water dispersibility of paclitaxel by complexation with hydrophobic peptides.

PubMed

Inada, Asuka; Oshima, Tatsuya; Baba, Yoshinari

2015-11-01

The complex between paclitaxel (Ptx) and a peptide mixture (Pep) was prepared to enhance of the water-dispersibility of Ptx. Pep was prepared by enzymatic hydrolysis of casein, followed by fractionation using ammonium sulfate precipitation and ultrafiltration. The Ptx and Pep complex (Ptx-Pep) was prepared by mixing an ethanol solution of Ptx and an aqueous solution of Pep followed by lyophilization. The water dispersibility test of Ptx-Pep prepared using different fractions of Pep demonstrated that a fraction (Pep-A), containing relatively hydrophobic peptides with high molecular weights, was effective in enhancing the water dispersibility of Ptx. The sequences of the major peptides in Pep-A were identified by matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry with "LIFT" technique. The water dispersibility of the complex between Ptx and Pep-A (Ptx-Pep-A) was independent of pH, even though it is positively or negatively charged under strongly acidic and neutral conditions. As the particle size of Ptx-Pep-A in aqueous media was 147-215 nm, Ptx-Pep-A was present as a hydrocolloidal material in aqueous media. Copyright © 2015 Elsevier B.V. All rights reserved.

Specific and Non-Specific Protein Association in Solution: Computation of Solvent Effects and Prediction of First-Encounter Modes for Efficient Configurational Bias Monte Carlo Simulations

PubMed Central

Cardone, Antonio; Pant, Harish; Hassan, Sergio A.

2013-01-01

Weak and ultra-weak protein-protein association play a role in molecular recognition, and can drive spontaneous self-assembly and aggregation. Such interactions are difficult to detect experimentally, and are a challenge to the force field and sampling technique. A method is proposed to identify low-population protein-protein binding modes in aqueous solution. The method is designed to identify preferential first-encounter complexes from which the final complex(es) at equilibrium evolves. A continuum model is used to represent the effects of the solvent, which accounts for short- and long-range effects of water exclusion and for liquid-structure forces at protein/liquid interfaces. These effects control the behavior of proteins in close proximity and are optimized based on binding enthalpy data and simulations. An algorithm is described to construct a biasing function for self-adaptive configurational-bias Monte Carlo of a set of interacting proteins. The function allows mixing large and local changes in the spatial distribution of proteins, thereby enhancing sampling of relevant microstates. The method is applied to three binary systems. Generalization to multiprotein complexes is discussed. PMID:24044772

Mixing high-viscosity fluids via acoustically driven bubbles

NASA Astrophysics Data System (ADS)

Orbay, Sinem; Ozcelik, Adem; Lata, James; Kaynak, Murat; Wu, Mengxi; Huang, Tony Jun

2017-01-01

We present an acoustofluidic micromixer which can perform rapid and homogeneous mixing of highly viscous fluids in the presence of an acoustic field. In this device, two high-viscosity polyethylene glycol (PEG) solutions were co-injected into a three-inlet PDMS microchannel with the center inlet containing a constant stream of nitrogen flow which forms bubbles in the device. When these bubbles were excited by an acoustic field generated via a piezoelectric transducer, the two solutions mixed homogenously due to the combination of acoustic streaming, droplet ejection, and bubble eruption effects. The mixing efficiency of this acoustofluidic device was evaluated using PEG-700 solutions which are ~106 times more viscous than deionized (DI) water. Our results indicate homogenous mixing of the PEG-700 solutions with a ~0.93 mixing index. The acoustofluidic micromixer is compact, inexpensive, easy to operate, and has the capacity to mix highly viscous fluids within 50 ms.

Synthesis, structures and properties of three copper complexes with dibutyldithiocarbamate ligand

NASA Astrophysics Data System (ADS)

Wang, Chen; Niu, Jiao; Li, Jun; Ma, Xiaoxun

2017-05-01

Three copper complexes constructed with sulfur-containing dibutyldithiocarbamate ligand (DDTC), [(Et2NCS2)4Cu2] (1), [(Et2NCS2)(EtO)Cu]2 (2) and [(Et2NCS2)6Cu13I10]n (3) have been synthesized through the reaction of CuI with different mole ratios of DDTC under solution-diffusion conditions. The single crystal X-ray diffraction revealed that divalent Cu cations in complexes 1 and 2 imply that the reactant, Cu(I), was involved in the redox process. They formed binuclear complexes according to bridging S from DDTC ligands and O atoms from ethanol molecules respectively. The mixed valence Cu cations had two types of coordination environments in complex 3 and formed a two-dimensional layered coordination polymer by bridging the five-core Cu(I) clusters and Cu(II). The powder X-ray diffraction, luminescent, thermogravimetric analysis, etc. were also studied in this paper.

Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: Stability and interaction with SDS micelles

NASA Astrophysics Data System (ADS)

Vignoli Muniz, Gabriel S.; Incio, Jimmy Llontop; Alves, Odivaldo C.; Krambrock, Klaus; Teixeira, Letícia R.; Louro, Sonia R. W.

2018-01-01

The stability of ternary copper(II) complexes of a heterocyclic ligand, L (L being 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)) and the fluorescent antibacterial agent norfloxacin (NFX) as the second ligand was studied at pH 7.4 and different ionic strengths. Fluorescence quenching upon titration of NFX with the binary complexes allowed to obtain stability constants for NFX binding, Kb, as a function of ionic strength. The Kb values vary by more than two orders of magnitude when buffer concentration varies from 0.5 to 100 mM. It was observed that previously synthesized ternary complexes dissociate in buffer according with the obtained stability constants. This shows that equimolar solutions of NFX and binary complexes are equivalent to solutions of synthesized ternary complexes. The interaction of the ternary copper complexes with anionic SDS (sodium dodecyl sulfate) micelles was studied by fluorescence and electron paramagnetic resonance (EPR). Titration of NFX-loaded SDS micelles with the complexes Cu:L allowed to determine the stability constants inside the micelles. Fluorescence quenching demonstrated that SDS micelles increase the stability constants by factors around 50. EPR spectra gave details of the copper(II) local environment, and demonstrated that the structure of the ternary complexes inside SDS micelles is different from that in buffer. Mononuclear ternary complexes formed inside the micelles, while in buffer most ternary complexes are binuclear. The results show that anionic membrane interfaces increase formation of copper fluoroquinolone complexes, which can influence bioavailability, membrane diffusion, and mechanism of action of the antibiotics.

Lipopeptide biosurfactants from Paenibacillus polymyxa inhibit single and mixed species biofilms.

PubMed

Quinn, Gerry A; Maloy, Aaron P; McClean, Stephen; Carney, Brian; Slater, John W

2012-01-01

Although biofilms are recognised as important in microbial colonisation, solutions to their inhibition are predominantly based on planktonic assays. These solutions have limited efficacy against biofilms. Here, a series of biofilm-orientated tests were used to identify anti-biofilm compounds from marine micro-flora. This led to the isolation of a complex of anti-biofilm compounds from an extract of Paenibacillus polymyxa (PPE). A combination of rpHPLC and mass spectrometry identified the principle components of PPE as fusaricidin B (LI-FO4b) and polymyxin D1, with minor contributions from surfactins. This complex (PPE) reduced the biofilm biomass of Bacillus subtilis, Micrococcus luteus, Pseudomonas aeruginosa, Staphylococcus aureus and Streptococcus bovis. In contrast, ampicillin was only effective against S. aureus. PPE also inhibited a self-assembling marine biofilm (SAMB) in co-incubation assays by 99.3% ± 1.9 and disrupted established SAMB by 72.4% ± 4.4, while ampicillin showed no significant reduction. The effectiveness of this complex of lipopeptides against single and multispecies biofilms suggests a future role in biofilm prevention strategies.

Thermodynamic studies of aqueous solutions of 2,2,2-cryptand at 298.15 K: enthalpy-entropy compensation, partial entropies, and complexation with K+ ions.

PubMed

Shaikh, Vasim R; Terdale, Santosh S; Ahamad, Abdul; Gupta, Gaurav R; Dagade, Dilip H; Hundiwale, Dilip G; Patil, Kesharsingh J

2013-12-19

The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.

Use of Carboxymethyl-beta-cyclodextrin (CMCD) as Flushing Agent for Remediation of Metal Contaminated Soil

NASA Astrophysics Data System (ADS)

Skold, M. E.; Thyne, G. D.; McCray, J. E.; Drexler, J. W.

2005-12-01

One of the major challenges in remediating soil and ground water is the presence of mixed organic and inorganic contaminants. Due to their very different behavior, research has to a large extent focused on remediation of either organic or inorganic contaminants rather than mixed waste. Cyclodextrins (CDs) are a group of non-toxic sugar based molecules that do not sorb to soil particles and do not experience pore size exclusion. Thus, they have good hydraulic properties. CDs enhance the solubility of organic compounds by forming inclusion complexes between organic contaminants and the non-polar cavity at the center of the CD. By substituting functional groups to the cyclodextrin molecule it can form complexes with heavy metals. Previous studies have shown that carboxymethyl-beta-cyclodextrin (CMCD) can simultaneously complex organic and inorganic contaminants. The aim of this study is to compare how strongly CMCD complexes several common heavy metals, radioactive elements and a common divalent cation. Results from batch experiments show that CMCD has the ability to complex a wide array of heavy metals and radioactive elements. The solubility of metal oxalates and metal oxides clearly increased in the presence of CMCD. Logarithmic conditional formation constants ranged from 3.5 to 6 for heavy metals and from 3 to 6 for radioactive elements. Calcium, which may compete for binding sites, has a logarithmic conditional formation constant of 3.1. Batch experiments performed at 10 and 25 degrees C showed little temperature effect on conditional formation constants. Results from batch experiments were compared to results from column experiments where Pb was sorbed onto hydrous ferric oxide coated sand and subsequently removed by a CMCD solution. The results indicate that CMCD is a potential flushing agent for remediation of mixed waste sites.

Electrical Resistivity Imaging and Hydrodynamic Modeling of Convective Fingering in a Sabkha Aquifer

NASA Astrophysics Data System (ADS)

Van Dam, Remke; Eustice, Brian; Hyndman, David; Wood, Warren; Simmons, Craig

2014-05-01

Free convection, or fluid motion driven by density differences, is an important groundwater flow mechanism that can enhance transport and mixing of heat and solutes in the subsurface. Various issues of environmental and societal relevance are exacerbated convective mixing; it has been studied in the context of dense contaminant plumes, nuclear waste disposal, greenhouse gas sequestration, the impacts of sea level rise and saline intrusion on drinking water resources. The basic theory behind convective flow in porous media is well understood, but important questions regarding this process in natural systems remain unanswered. Most previous research on this topic has focused on theory and modeling, with only limited attention to experimental studies and field measurements. The few published studies present single snapshots, making it difficult to quantify transient changes in these systems. Non-invasive electrical methods have the potential to exploit the relation between solute concentrations and electrical conductance of a fluid, and thereby estimate fluid salinity differences in time and space. We present the results of a two-year experimental study at a shallow sabkha aquifer in the United Arab Emirates, about 50 km southwest of the city of Abu Dhabi along the coast of the Arabian Gulf, that was designed to explore the transient nature of free convection. Electrical resistivity tomography (ERT) data documented the presence of convective fingers following a significant rainfall event. One year later, the complex fingering pattern had completely disappeared. This observation is supported by analysis of the aquifer solute budget as well as hydrodynamic modeling of the system. The transient dynamics of the gravitational instabilities in the modeling results are in agreement with the timing observed in the time-lapse ERT data. Our experimental observations and modeling are consistent with the hypothesis that the instabilities arose from a dense brine that infiltrated into the aquifer from a surficial source and that the finite nature of this brine and dispersive mixing led to the decay of the complex fingers with time. Our work provides direct field measurements in a discipline where such data are quite rare. This work is likely the first to provide such direct evidence, coupled with time series data from numerical modeling, to allow quantification of the speed and the dynamics of complex free convective fingering in a field setting. This is a major step forward for this field.

Mixed-Timescale Per-Group Hybrid Precoding for Multiuser Massive MIMO Systems

NASA Astrophysics Data System (ADS)

Teng, Yinglei; Wei, Min; Liu, An; Lau, Vincent; Zhang, Yong

2018-05-01

Considering the expensive radio frequency (RF) chain, huge training overhead and feedback burden issues in massive MIMO, in this letter, we propose a mixed-timescale per-group hybrid precoding (MPHP) scheme under an adaptive partially-connected RF precoding structure (PRPS), where the RF precoder is implemented using an adaptive connection network (ACN) and M analog phase shifters (APSs), where M is the number of antennas at the base station (BS). Exploiting the mixed-time stage channel state information (CSI) structure, the joint-design of ACN and APSs is formulated as a statistical signal-to-leakage-and-noise ratio (SSLNR) maximization problem, and a heuristic group RF precoding (GRFP) algorithm is proposed to provide a near-optimal solution. Simulation results show that the proposed design advances at better energy efficiency (EE) and lower hardware cost, CSI signaling overhead and computational complexity than the conventional hybrid precoding (HP) schemes.

Separation and recovery of lead from a low concentration solution of lead(II) and zinc(II) using the hydrolysis production of poly styrene-co-maleic anhydride.

PubMed

Liang, Xing; Su, Yibing; Yang, Ying; Qin, Wenwu

2012-02-15

The PbZn separation/preconcentration technique, based on the complex formation reaction of Pb(II) and Zn(II), using a copolymer poly(styrene-co-maleic anhydride) (PSMA), without adding any carrier element was developed. The effects of several experimental parameters such as solution pH, temperature and adsorption time were studied. The experimental results show that the PSMA resin-Pb equilibrium was achieved in 2 min and the Pb(II) loading capacity is up to 641.62 mg g(-1) in aqueous solution under optimum conditions, which is much higher than the Zn(II) loading capacity within 80 min. The adsorption test for Pb(II) indicates that PSMA can recover Pb(II) from a mixed solution of Pb(II), Zn(II) and light metals such as Ca(II) and Mg(II) with higher adsorption rate and larger selective coefficient. A further study indicates that PSMA as chelating resins recovering Pb(II) can be regenerated via mineral acid (6M H(2)SO(4)). PSMA was synthesized by radical polymerization and tested as an adsorbent for the selective recovery of Pb(II). In addition, the formation procedure and structure of Pb-PSMA complex were also studied. Both the PSMA and the Pb-PSMA complex were characterized by means of FTIR spectroscopy, elemental analysis, gel permeation chromatography (GPC) and atomic absorption spectrometry (AAS). Copyright © 2011 Elsevier B.V. All rights reserved.

Fracturing fluid cleanup by controlled release of enzymes from polyelectrolyte complex nanoparticles

NASA Astrophysics Data System (ADS)

Barati Ghahfarokhi, Reza

Guar-based polymer gels are used in the oil and gas industry to viscosify fluids used in hydraulic fracturing of production wells, in order to reduce leak-off of fluids and pressure, and improve the transport of proppants. After fracturing, the gel and associated filter cake must be degraded to very low viscosities using breakers to recover the hydraulic conductivity of the well. Enzymes are widely used to achieve this but injecting high concentrations of enzyme may result in premature degradation, or failure to gel; denaturation of enzymes at alkaline pH and high temperature conditions can also limit their applicability. In this study, application of polyelectrolyte nanoparticles for entrapping, carrying, releasing and protecting enzymes for fracturing fluids was examined. The objective of this research is to develop nano-sized carriers capable of carrying the enzymes to the filter cake, delaying the release of enzyme and protecting the enzyme against pH and temperature conditions inhospitable to native enzyme. Polyethylenimine-dextran sulfate (PEI-DS) polyelectrolyte complexes (PECs) were used to entrap two enzymes commonly used in the oil industry in order to obtain delayed release and to protect the enzyme from conditions inhospitable to native enzyme. Stability and reproducibility of PEC nanoparticles was assured over time. An activity measurement method was used to measure the entrapment efficiency of enzyme using PEC nanoparticles. This method was confirmed using a concentration measurement method (SDS-PAGE). Entrapment efficiencies of pectinase and a commercial high-temperature enzyme mixture in polyelectrolyte complex nanoparticles were maximized. Degradation, as revealed by reduction in viscoelastic moduli of borate-crosslinked hydroxypropyl guar (HPG) gel by commercial enzyme loaded in polyelectrolyte nanoparticles, was delayed, compared to equivalent systems where the enzyme mixture was not entrapped. This indicates that PEC nanoparticles delay the activity of enzymes by entrapping them. It was also observed that control PEC nanoparticles decreased both viscoelastic moduli, but with a slower rate compared to the PEC nanoparticles loaded with enzyme. Preparation shear and applied shear showed no significant effect on activity of enzyme-loaded PEC nanoparticles mixed with HPG solutions. However, fast addition of chemicals during the preparations showed smaller particle size compared to the drop-wise method. PEC nanoparticles (PECNPs) also protected both enzymes from denaturation at elevated temperature and pH. Following preparation, enzyme-loaded PEC nanoparticles were mixed with borate crosslinked HPG and the mixture was injected through a shear loop. Pectinase-loaded nanoparticles mixed with gelled HPG showed no sensitivity to shear applied along the shear loop at 25 °C. However, EL2X-loaded PEC nanoparticles showed sensitivity to shear applied along the shear loop at 40 °C. Filter cake was formed and degraded in a fluid loss cell for borate crosslinked HPG solutions mixed with either enzymes or enzyme-loaded PEC nanoparticles. Cleanup slopes of filter cake degraded using enzyme-loaded PEC nanoparticles and systems with enzymes mixed with HPG gel were significantly higher than for the filter cake formed with HPG gel mixed with no enzyme. In a different application, enzyme-loaded PEC nanoparticles showed significantly slower reduction in viscosity of HPG solution over time compared to the HPG systems mixed with enzyme. Increasing the viscosity of low concentration HPG, used as slick-water, decreases the proppant settling velocity. This is of specific interest in fracturing fluids used for unconventional reservoirs.

Evolution of mixed surfactant aggregates in solutions and at solid/solution interfaces

NASA Astrophysics Data System (ADS)

Zhang, Rui

Surfactant systems have been widely used in such as enhanced oil recovery, waste treatment and metallurgy, etc., in order to solve the problem of global energy crisis, to remove the pollutants and to generate novel energy resources. Almost all surfactant systems are invariably mixtures due to beneficial and economic considerations. The sizes and shapes of aggregates in solutions and at solid/solution interfaces become important, since the nanostructures of mixed aggregates determine solution and adsorption properties. A major hurdle in science is the lack of information on the type of complexes and aggregates formed by mixtures and the lack of techniques for deriving such information. Using techniques such as analytical ultracentrifuge, small angle neutron scattering, surface tension, fluorescence, cryo-TEM, light scattering and ultrafiltration, the nanostructures of aggregates of sugar based n-dodecyl-beta-D-maltoside (DM) and nonionic pentaethyleneglycol monododecyl ether or nonyl phenol ethoxylated decyl ether (NP-10) and their mixtures have been investigated to prove the hypothesis that the aggregation behavior is linked to packing of the surfactant governed by the molecular interactions as well as the molecular structures. The results from both sedimentation velocity and sedimentation equilibrium experiments suggest coexistence of two types of micelles in nonyl phenol ethoxylated decyl ether solutions and its mixtures with n-dodecyl-beta-D-maltoside while only one micellar species is present in n-dodecyl-beta-D-maltoside solutions, in good agreement with those from small angle neutron scattering, cryo-TEM, light scattering and ultrafiltration. Type I micelles were primary micelles at cmc while type II micelles were elongated micelles. On the other hand, the nanostructures of mixed surface aggregates have been quantitatively predicted for the first time using a modified packing index. As a continuation of the Somasundaran-Fuersteneau adsorption model, a modified one-step model has been developed to fully understand the adsorption behavior of surfactant mixtures and obtained thermodynamic information on aggregation number and standard free energy for surface aggregation. The findings are expected to provide fundamental basis for the design optimal surfactant schemes for desired purposes.

Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

PubMed

Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

2018-05-07

Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

Expanding Thorium Hydride Chemistry Through Th²⁺, Including the Synthesis of a Mixed-Valent Th⁴⁺/Th³⁺ Hydride Complex.

PubMed

Langeslay, Ryan R; Fieser, Megan E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2016-03-30

The reactivity of the recently discovered Th(2+) complex [K(18-crown-6)(THF)2][Cp″3Th], 1 [Cp'' = C5H3(SiMe3)2-1,3], with hydrogen reagents has been investigated and found to provide syntheses of new classes of thorium hydride compounds. Complex 1 reacts with [Et3NH][BPh4] to form the terminal Th(4+) hydride complex Cp″3ThH, 2, a reaction that formally involves a net two-electron reduction. Complex 1 also reacts in the solid state and in solution with H2 to form a mixed-valent bimetallic product, [K(18-crown-6)(Et2O)][Cp″2ThH2]2, 3, which was analyzed by X-ray crystallography, electron paramagnetic resonance and optical spectroscopy, and density functional theory. The existence of 3, which formally contains Th(3+) and Th(4+), suggested that KC8 could reduce [(C5Me5)2ThH2]2. In the presence of 18-crown-6, this reaction forms an analogous mixed-valent product formulated as [K(18-crown-6)(THF)][(C5Me5)2ThH2]2, 4. A similar complex with (C5Me4H)(1-) ligands was not obtained, but reaction of (C5Me4H)3Th with H2 in the presence of KC8 and 2.2.2-cryptand at -45 °C produced two monometallic hydride products, namely, (C5Me4H)3ThH, 5, and [K(2.2.2-cryptand)]{(C5Me4H)2[η(1):η(5)-C5Me3H(CH2)]ThH]}, 6. Complex 6 contains a metalated tetramethylcyclopentadienyl dianion, [C5Me3H(CH2)](2-), that binds in a tuck-in mode.

Communication Architecture in Mixed-Reality Simulations of Unmanned Systems

PubMed Central

2018-01-01

Verification of the correct functionality of multi-vehicle systems in high-fidelity scenarios is required before any deployment of such a complex system, e.g., in missions of remote sensing or in mobile sensor networks. Mixed-reality simulations where both virtual and physical entities can coexist and interact have been shown to be beneficial for development, testing, and verification of such systems. This paper deals with the problems of designing a certain communication subsystem for such highly desirable realistic simulations. Requirements of this communication subsystem, including proper addressing, transparent routing, visibility modeling, or message management, are specified prior to designing an appropriate solution. Then, a suitable architecture of this communication subsystem is proposed together with solutions to the challenges that arise when simultaneous virtual and physical message transmissions occur. The proposed architecture can be utilized as a high-fidelity network simulator for vehicular systems with implicit mobility models that are given by real trajectories of the vehicles. The architecture has been utilized within multiple projects dealing with the development and practical deployment of multi-UAV systems, which support the architecture’s viability and advantages. The provided experimental results show the achieved similarity of the communication characteristics of the fully deployed hardware setup to the setup utilizing the proposed mixed-reality architecture. PMID:29538290

Communication Architecture in Mixed-Reality Simulations of Unmanned Systems.

PubMed

Selecký, Martin; Faigl, Jan; Rollo, Milan

2018-03-14

Verification of the correct functionality of multi-vehicle systems in high-fidelity scenarios is required before any deployment of such a complex system, e.g., in missions of remote sensing or in mobile sensor networks. Mixed-reality simulations where both virtual and physical entities can coexist and interact have been shown to be beneficial for development, testing, and verification of such systems. This paper deals with the problems of designing a certain communication subsystem for such highly desirable realistic simulations. Requirements of this communication subsystem, including proper addressing, transparent routing, visibility modeling, or message management, are specified prior to designing an appropriate solution. Then, a suitable architecture of this communication subsystem is proposed together with solutions to the challenges that arise when simultaneous virtual and physical message transmissions occur. The proposed architecture can be utilized as a high-fidelity network simulator for vehicular systems with implicit mobility models that are given by real trajectories of the vehicles. The architecture has been utilized within multiple projects dealing with the development and practical deployment of multi-UAV systems, which support the architecture's viability and advantages. The provided experimental results show the achieved similarity of the communication characteristics of the fully deployed hardware setup to the setup utilizing the proposed mixed-reality architecture.

40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section for...

40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section for...

40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section for...

40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section for...

40 CFR 721.10104 - Halophosphate mixed metal complex (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halophosphate mixed metal complex... Specific Chemical Substances § 721.10104 Halophosphate mixed metal complex (generic). (a) Chemical... as halophosphate mixed metal complex (PMN P-04-254) is subject to reporting under this section for...

Numerical studies of unsteady two dimensional subsonic flows using the ICE method. Ph.D. Thesis - Toledo Univ.

NASA Technical Reports Server (NTRS)

Wieber, P. R.

1973-01-01

A numerical program was developed to compute transient compressible and incompressible laminar flows in two dimensions with multicomponent mixing and chemical reaction. The algorithm used the Los Alamos Scientific Laboratory ICE (Implicit Continuous-Fluid Eulerian) method as its base. The program can compute both high and low speed compressible flows. The numerical program incorporating the stabilization techniques was quite successful in treating both old and new problems. Detailed calculations of coaxial flow very close to the entry plane were possible. The program treated complex flows such as the formation and downstream growth of a recirculation cell. An implicit solution of the species equation predicted mixing and reaction rates which compared favorably with the literature.

Analytical solution for reactive solute transport considering incomplete mixing within a reference elementary volume

NASA Astrophysics Data System (ADS)

Chiogna, Gabriele; Bellin, Alberto

2013-05-01

The laboratory experiments of Gramling et al. (2002) showed that incomplete mixing at the pore scale exerts a significant impact on transport of reactive solutes and that assuming complete mixing leads to overestimation of product concentration in bimolecular reactions. Successively, several attempts have been made to model this experiment, either considering spatial segregation of the reactants, non-Fickian transport applying a Continuous Time Random Walk (CTRW) or an effective upscaled time-dependent kinetic reaction term. Previous analyses of these experimental results showed that, at the Darcy scale, conservative solute transport is well described by a standard advection dispersion equation, which assumes complete mixing at the pore scale. However, reactive transport is significantly affected by incomplete mixing at smaller scales, i.e., within a reference elementary volume (REV). We consider here the family of equilibrium reactions for which the concentration of the reactants and the product can be expressed as a function of the mixing ratio, the concentration of a fictitious non reactive solute. For this type of reactions we propose, in agreement with previous studies, to model the effect of incomplete mixing at scales smaller than the Darcy scale assuming that the mixing ratio is distributed within an REV according to a Beta distribution. We compute the parameters of the Beta model by imposing that the mean concentration is equal to the value that the concentration assumes at the continuum Darcy scale, while the variance decays with time as a power law. We show that our model reproduces the concentration profiles of the reaction product measured in the Gramling et al. (2002) experiments using the transport parameters obtained from conservative experiments and an instantaneous reaction kinetic. The results are obtained applying analytical solutions both for conservative and for reactive solute transport, thereby providing a method to handle the effect of incomplete mixing on multispecies reactive solute transport, which is simpler than other previously developed methods.

Many-body calculations of low energy eigenstates in magnetic and periodic systems with self healing diffusion Monte Carlo: steps beyond the fixed-phase

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

Reboredo, Fernando A.

The self-healing diffusion Monte Carlo algorithm (SHDMC) [Reboredo, Hood and Kent, Phys. Rev. B {\\bf 79}, 195117 (2009), Reboredo, {\\it ibid.} {\\bf 80}, 125110 (2009)] is extended to study the ground and excited states of magnetic and periodic systems. A recursive optimization algorithm is derived from the time evolution of the mixed probability density. The mixed probability density is given by an ensemble of electronic configurations (walkers) with complex weight. This complex weigh allows the amplitude of the fix-node wave function to move away from the trial wave function phase. This novel approach is both a generalization of SHDMC andmore » the fixed-phase approximation [Ortiz, Ceperley and Martin Phys Rev. Lett. {\\bf 71}, 2777 (1993)]. When used recursively it improves simultaneously the node and phase. The algorithm is demonstrated to converge to the nearly exact solutions of model systems with periodic boundary conditions or applied magnetic fields. The method is also applied to obtain low energy excitations with magnetic field or periodic boundary conditions. The potential applications of this new method to study periodic, magnetic, and complex Hamiltonians are discussed.« less

A brief introduction to mixed effects modelling and multi-model inference in ecology

PubMed Central

Donaldson, Lynda; Correa-Cano, Maria Eugenia; Goodwin, Cecily E.D.

2018-01-01

The use of linear mixed effects models (LMMs) is increasingly common in the analysis of biological data. Whilst LMMs offer a flexible approach to modelling a broad range of data types, ecological data are often complex and require complex model structures, and the fitting and interpretation of such models is not always straightforward. The ability to achieve robust biological inference requires that practitioners know how and when to apply these tools. Here, we provide a general overview of current methods for the application of LMMs to biological data, and highlight the typical pitfalls that can be encountered in the statistical modelling process. We tackle several issues regarding methods of model selection, with particular reference to the use of information theory and multi-model inference in ecology. We offer practical solutions and direct the reader to key references that provide further technical detail for those seeking a deeper understanding. This overview should serve as a widely accessible code of best practice for applying LMMs to complex biological problems and model structures, and in doing so improve the robustness of conclusions drawn from studies investigating ecological and evolutionary questions. PMID:29844961

A brief introduction to mixed effects modelling and multi-model inference in ecology.

PubMed

Harrison, Xavier A; Donaldson, Lynda; Correa-Cano, Maria Eugenia; Evans, Julian; Fisher, David N; Goodwin, Cecily E D; Robinson, Beth S; Hodgson, David J; Inger, Richard

2018-01-01

The use of linear mixed effects models (LMMs) is increasingly common in the analysis of biological data. Whilst LMMs offer a flexible approach to modelling a broad range of data types, ecological data are often complex and require complex model structures, and the fitting and interpretation of such models is not always straightforward. The ability to achieve robust biological inference requires that practitioners know how and when to apply these tools. Here, we provide a general overview of current methods for the application of LMMs to biological data, and highlight the typical pitfalls that can be encountered in the statistical modelling process. We tackle several issues regarding methods of model selection, with particular reference to the use of information theory and multi-model inference in ecology. We offer practical solutions and direct the reader to key references that provide further technical detail for those seeking a deeper understanding. This overview should serve as a widely accessible code of best practice for applying LMMs to complex biological problems and model structures, and in doing so improve the robustness of conclusions drawn from studies investigating ecological and evolutionary questions.

Modeling Bimolecular Reactive Transport With Mixing-Limitation: Theory and Application to Column Experiments

NASA Astrophysics Data System (ADS)

Ginn, T. R.

2018-01-01

The challenge of determining mixing extent of solutions undergoing advective-dispersive-diffusive transport is well known. In particular, reaction extent between displacing and displaced solutes depends on mixing at the pore scale, that is, generally smaller than continuum scale quantification that relies on dispersive fluxes. Here a novel mobile-mobile mass transfer approach is developed to distinguish diffusive mixing from dispersive spreading in one-dimensional transport involving small-scale velocity variations with some correlation, such as occurs in hydrodynamic dispersion, in which short-range ballistic transports give rise to dispersed but not mixed segregation zones, termed here ballisticules. When considering transport of a single solution, this approach distinguishes self-diffusive mixing from spreading, and in the case of displacement of one solution by another, each containing a participant reactant of an irreversible bimolecular reaction, this results in time-delayed diffusive mixing of reactants. The approach generates models for both kinetically controlled and equilibrium irreversible reaction cases, while honoring independently measured reaction rates and dispersivities. The mathematical solution for the equilibrium case is a simple analytical expression. The approach is applied to published experimental data on bimolecular reactions for homogeneous porous media under postasymptotic dispersive conditions with good results.

New classes of solutions in the coupled PT symmetric nonlocal nonlinear Schrödinger equations with four wave mixing

NASA Astrophysics Data System (ADS)

Vinayagam, P. S.; Radha, R.; Al Khawaja, U.; Ling, Liming

2018-06-01

We investigate generalized nonlocal coupled nonlinear Schorödinger equation containing Self-Phase Modulation, Cross-Phase Modulation and four wave mixing involving nonlocal interaction. By means of Darboux transformation we obtained a family of exact breathers and solitons including the Peregrine soliton, Kuznetsov-Ma breather, Akhmediev breather along with all kinds of soliton-soliton and breather-soltion interactions. We analyze and emphasize the impact of the four-wave mixing on the nature and interaction of the solutions. We found that the presence of four wave mixing converts a two-soliton solution into an Akhmediev breather. In particular, the inclusion of four wave mixing results in the generation of a new solutions which is spatially and temporally periodic called "Soliton (Breather) lattice".

Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes.

PubMed

Bhattacharjee, Chira R; Goswami, Pankaj; Pramanik, Harun A R; Paul, Pradip C; Mondal, Paritosh

2011-05-01

Two new mixed-ligand iron(III) complexes, [Fe(L(n))(acac)(C(2)H(5)OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)(3)] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H(2)L(1)) or 2-aminobenzoic acid (H(2)L(2)). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L(n))(acac)X] (n=1, 2; X=Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, (1)H and (13)C NMR spectroscopy. Room temperature magnetic susceptibility measurements (μ(eff)∼5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (ΔE(p)>100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E(1/2)) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level. Copyright © 2011 Elsevier B.V. All rights reserved.

The effect of intra-wellbore head losses in a vertical well

NASA Astrophysics Data System (ADS)

Wang, Quanrong; Zhan, Hongbin

2017-05-01

Flow to a partially penetrating vertical well is made more complex by intra-wellbore losses. These are caused not only by the frictional effect, but also by the kinematic effect, which consists of the accelerational and fluid inflow effects inside a wellbore. Existing models of flow to a partially penetrating vertical well assume either a uniform-flux boundary condition (UFBC) or a uniform-head boundary condition (UHBC) for treating the flow into the wellbore. Neither approach considers intra-wellbore losses. In this study a new general solution, named the mixed-type boundary condition (MTBC) solution, is introduced to include intra-wellbore losses. It is developed from the existing solutions using a hybrid analytical-numerical method. The MTBC solution is capable of modeling various types of aquifer tests (constant-head tests, constant-rate tests, and slug tests) for partially or fully penetrating vertical wells in confined aquifers. Results show that intra-wellbore losses (both frictional and kinematic) can be significant in the early pumping stage. At later pumping times the UHBC solution is adequate because the difference between the MTBC and UHBC solutions becomes negligible.

Multispectroscopic DNA-Binding studies and antimicrobial evaluation of new mixed-ligand Silver(I) complex and nanocomplex: A comparative study

NASA Astrophysics Data System (ADS)

Movahedi, Elaheh; Rezvani, Ali Reza

2018-05-01

A novel mixed-ligand Ag(I) complex, , has been synthesized and characterized by the elemental analysis, IR spectroscopy and 1HNMR. In the formula, dian and phen are N-(4,5-diazafluoren-9-ylidene)aniline and 1,10-phenanthroline, respectively. This complex also has been prepared at nano size by sonochemical technique and characterized by the FTIR and scanning electron microscopy (SEM). To evaluate the biological preferences of the Ag(I) complex and nanocomplex and verify the relationships between the structure and biological function, in vitro DNA binding and antibacterial experiments have been carried out. DNA-complex interaction has been pursued by electronic absorption titration, luminescence titration, competitive binding experiment, effect of ionic strength, thermodynamic studies, viscometric evaluation and circular dichroism spectroscopy in the physiological pH. Each compound displays significant binding trend to the CT-DNA. The mode of binding to the CT-DNA probably is a moderate intercalation mode with the partial insertion of the planar ligands between the base stacks of double-stranded DNA. The relative viscosities and circular dichroism spectra of the CT-DNA with the complex solutions, confirm the intense interactions of the Ag(I) complex and nanocomplex with DNA. An in vitro antibacterial test of the complex and nanocomplex on a series of the Gram-positive bacteria (Staphylococcus aureus, Enterococcus faecalis) and the Gram-negative bacteria (Escherichia coli, Pseudomonas aeruginosa) shows a remarkable antibacterial feature of the Ag(I) complex. The MIC values (minimum inhibitory concentration) of the compounds compare with silver nitrate and silver sulfadiazine. The bacterial inhibitions of the Ag(I) complex and nanocomplex are agreed to their DNA binding affinities.

Zeolite crystal growth in space - What has been learned

NASA Technical Reports Server (NTRS)

Sacco, A., Jr.; Thompson, R. W.; Dixon, A. G.

1993-01-01

Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.

Hydroxypropyl-β-cyclodextrin for Delivery of Baicalin via Inclusion Complexation by Supercritical Fluid Encapsulation.

PubMed

Li, Ying; He, Zhen-Dan; Zheng, Qian-En; Hu, Chengshen; Lai, Wing-Fu

2018-05-14

Over the years, various methods have been developed to enhance the solubility of insoluble drugs; however, most of these methods are time-consuming and labor intensive or involve the use of toxic materials. A method that can safely and effectively enhance the solubility of insoluble drugs is lacking. This study adopted baicalin as an insoluble drug model, and used hydroxypropyl-β-cyclodextrin for the delivery of baicalin via the inclusion complexation by supercritical fluid encapsulation. Different parameters for the complex preparation as well as the physicochemical properties of the complex have been investigated. Our results showed that when compared to the conventional solution mixing approach, supercritical fluid encapsulation enables a more precise control of the properties of the complex, and gives higher loading and encapsulation efficiency. It is anticipated that our reported method can be useful in enhancing the preparation efficiency of inclusion complexes, and can expand the application potential of insoluble herbal ingredients in treatment development and pharmaceutical formulation.

Structure and dynamics of water in mixed solutions including laponite and PEO

NASA Astrophysics Data System (ADS)

Morikubo, Satoshi; Sekine, Yurina; Ikeda-Fukazawa, Tomoko

2011-01-01

To investigate the structure and dynamics of water in mixed solutions including laponite clay particles and poly(ethylene oxide) (PEO), we measured the Raman spectra of the mixed solutions in the temperature range 283-313 K. The results show that the vibrational energies of the O-H stretching modes in the mixed solutions depend on the water content and temperature. The energy shifts of the O-H stretching modes are attributed to changes in the water structure. By applying a structural model of bulk water to the spectra in the O-H stretching region, the local structures of water in the solutions were analyzed. The result shows that the formation probability of hydrogen bonds in the solutions decreases as the water content decreases. Laponite and PEO have effects to disrupt the network structure of hydrogen bonds between water molecules. Further, it was found that laponite and PEO cause increase in the strength of hydrogen bonds of surrounding water,although the strength of the hydrogen bonds increases with the order water-laponite < water-water < water-PEO. It is concluded that water in laponite-PEO mixed solutions has a less-networked structure with strong hydrogen bonds compared with bulk water.

Ice recrystallization inhibition in ice cream as affected by ice structuring proteins from winter wheat grass.

PubMed

Regand, A; Goff, H D

2006-01-01

Ice recrystallization in quiescently frozen sucrose solutions that contained some of the ingredients commonly found in ice cream and in ice cream manufactured under commercial conditions, with or without ice structuring proteins (ISP) from cold-acclimated winter wheat grass extract (AWWE), was assessed by bright field microscopy. In sucrose solutions, critical differences in moisture content, viscosity, ionic strength, and other properties derived from the presence of other ingredients (skim milk powder, corn syrup solids, locust bean gum) caused a reduction in ice crystal growth. Significant ISP activity in retarding ice crystal growth was observed in all solutions (44% for the most complex mix) containing 0.13% total protein from AWWE. In heat-shocked ice cream, ice recrystallization rates were significantly reduced 40 and 46% with the addition of 0.0025 and 0.0037% total protein from AWWE. The ISP activity in ice cream was not hindered by its inclusion in mix prior to pasteurization. A synergistic effect between ISP and stabilizer was observed, as ISP activity was reduced in the absence of stabilizer in ice cream formulations. A remarkably smoother texture for ice creams containing ISP after heat-shock storage was evident by sensory evaluation. The efficiency of ISP from AWWE in controlling ice crystal growth in ice cream has been demonstrated.

Automatic design of synthetic gene circuits through mixed integer non-linear programming.

PubMed

Huynh, Linh; Kececioglu, John; Köppe, Matthias; Tagkopoulos, Ilias

2012-01-01

Automatic design of synthetic gene circuits poses a significant challenge to synthetic biology, primarily due to the complexity of biological systems, and the lack of rigorous optimization methods that can cope with the combinatorial explosion as the number of biological parts increases. Current optimization methods for synthetic gene design rely on heuristic algorithms that are usually not deterministic, deliver sub-optimal solutions, and provide no guaranties on convergence or error bounds. Here, we introduce an optimization framework for the problem of part selection in synthetic gene circuits that is based on mixed integer non-linear programming (MINLP), which is a deterministic method that finds the globally optimal solution and guarantees convergence in finite time. Given a synthetic gene circuit, a library of characterized parts, and user-defined constraints, our method can find the optimal selection of parts that satisfy the constraints and best approximates the objective function given by the user. We evaluated the proposed method in the design of three synthetic circuits (a toggle switch, a transcriptional cascade, and a band detector), with both experimentally constructed and synthetic promoter libraries. Scalability and robustness analysis shows that the proposed framework scales well with the library size and the solution space. The work described here is a step towards a unifying, realistic framework for the automated design of biological circuits.

Addressing tomorrow's DMO technical challenges today

NASA Astrophysics Data System (ADS)

Milligan, James R.

2009-05-01

Distributed Mission Operations (DMO) is essentially a type of networked training that pulls in participants from all the armed services and, increasingly, allies to permit them to "game" and rehearse highly complex campaigns, using a mix of local, distant, and virtual players. The United States Air Force Research Laboratory (AFRL) is pursuing Science and Technology (S&T) solutions to address technical challenges associated with distributed communications and information management as DMO continues to progressively scale up the number, diversity, and geographic dispersal of participants in training and rehearsal exercises.

Using Neural Networks in the Mapping of Mixed Discrete/Continuous Design Spaces With Application to Structural Design

DTIC Science & Technology

1994-02-01

desired that the problem to which the design space mapping techniques were applied be easily analyzed, yet provide a design space with realistic complexity...consistent fully stressed solution. 3 DESIGN SPACE MAPPING In order to reduce the computational expense required to optimize design spaces, neural networks...employed in this study. Some of the issues involved in using neural networks to do design space mapping are how to configure the neural network, how much

Receptivity of the compressible mixing layer

NASA Astrophysics Data System (ADS)

Barone, Matthew F.; Lele, Sanjiva K.

2005-09-01

Receptivity of compressible mixing layers to general source distributions is examined by a combined theoretical/computational approach. The properties of solutions to the adjoint Navier Stokes equations are exploited to derive expressions for receptivity in terms of the local value of the adjoint solution. The result is a description of receptivity for arbitrary small-amplitude mass, momentum, and heat sources in the vicinity of a mixing-layer flow, including the edge-scattering effects due to the presence of a splitter plate of finite width. The adjoint solutions are examined in detail for a Mach 1.2 mixing-layer flow. The near field of the adjoint solution reveals regions of relatively high receptivity to direct forcing within the mixing layer, with receptivity to nearby acoustic sources depending on the source type and position. Receptivity ‘nodes’ are present at certain locations near the splitter plate edge where the flow is not sensitive to forcing. The presence of the nodes is explained by interpretation of the adjoint solution as the superposition of incident and scattered fields. The adjoint solution within the boundary layer upstream of the splitter-plate trailing edge reveals a mechanism for transfer of energy from boundary-layer stability modes to Kelvin Helmholtz modes. Extension of the adjoint solution to the far field using a Kirchhoff surface gives the receptivity of the mixing layer to incident sound from distant sources.

Direct effect of chlorine dioxide, zinc chloride and chlorhexidine solution on the gaseous volatile sulfur compounds.

PubMed

Kim, Ju-Sik; Park, Ji-Woon; Kim, Dae-Jung; Kim, Young-Ku; Lee, Jeong-Yun

2014-11-01

This study focused on the ability of aqueous anti-volatile-sulfur-compound (VSC) solutions to eliminate gaseous VSCs by direct contact in a sealed space to describe possible mode of action of anti-VSC agents. Twenty milliliters of each experimental solution, 0.16% sodium chlorite, 0.25% zinc chloride, 0.1% chlorhexidine and distilled water, was injected into a Teflon bag containing mixed VSCs, hydrogen sulfide, methyl mercaptan and dimethyl sulfide and mixed vigorously for 30 s. The VSC concentration was measured by gas chromatography before, immediately after, 30 min and 60 min after mixing. The sodium chlorite solution reduced the VSC concentration remarkably. After mixing, nearly all VSCs were eliminated immediately and no VSCs were detected at 30 and 60 min post-mixing. However, in the other solutions, the VSC concentration decreased by ∼30% immediately after mixing and there was no further decrease. The results suggest that sodium chlorite solution has the effect of eliminating gaseous VSCs directly. This must be because it can release chlorine dioxide gas which can react directly with gaseous VSCs. In the case of other solutions that have been proved to be effective to reduce halitosis clinically, it can be proposed that their anti-VSC effect is less likely due to the direct chemical elimination of gaseous VSCs in the mouth.

Investigating the synthesis of ligated metal clusters in solution using a flow reactor and electrospray ionization mass spectrometry.

PubMed

Olivares, Astrid; Laskin, Julia; Johnson, Grant E

2014-09-18

The scalable synthesis of ligated subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic, and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth, and postreduction etching are still not well understood. Herein, we demonstrate a prototype temperature-controlled flow reactor for qualitatively studying cluster formation in solution at steady-state conditions. Employing this technique, methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand, and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with a known length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates, and products synthesized in real time was characterized qualitatively using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged organometallic complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged organometallic complexes while reducing the abundance of triply charged species. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of batch reduction synthesis in solution.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Solvent microextraction-flame atomic absorption spectrometry (SME-FAAS) for determination of ultratrace amounts of cadmium in meat and fish samples.

PubMed

Goudarzi, Nasser

2009-02-11

A simple, low cost and highly sensitive method based on solvent microextraction (SME) for separation/preconcentration and flame atomic absorption spectrometry (FAAS) was proposed for the determination of ultratrace amounts of cadmium in meat and fish samples. The analytical procedure involved the formation of a hydrophobic complex by mixing the analyte solution with an ammonium pyrrolidinedithiocarbamate (APDC) solution. In suitable conditions, the complex of cadmium-APDC entered the micro organic phase, and thus, separation of the analyte from the matrix was achieved. Under optimal chemical and instrumental conditions, a detection limit (3 sigma) of 0.8 ng L(-1) and an enrichment factor of 93 were achieved. The relative standard deviation for the method was found to be 2.2% for Cd. The interference effects of some anions and cations were also investigated. The developed method has been applied to the determination of trace Cd in meat and fish samples.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

The efficacy of nimodipine drug delivery using mPEG-PLA micelles and mPEG-PLA/TPGS mixed micelles.

PubMed

Huang, Shuling; Yu, Xiaohong; Yang, Linlin; Song, Fenglan; Chen, Gang; Lv, Zhufen; Li, Tiao; Chen, De; Zhu, Wanhua; Yu, Anan; Zhang, Yongming; Yang, Fan

2014-10-15

In order to develop and compare mPEG-PLA micelles and mPEG-PLA/TPGS mixed micelles, with the intention to develop a highly efficient formulation for nimodipine (NIM), NIM-loaded micelles and mixed micelles were made and their pharmacokinetics were studied. Single factor experiments and orthogonal experiments were designed to optimize the final preparation process, characterizations and drug release behaviors were studied. Pharmacokinetics of NIM micelles, NIM mixed micelles were researched and were compared to NIM solution. Micelles and mixed micelles were prepared by solvent evaporation method, with relatively high drug loading efficiency and within nano-particle size range. The CMC value of mPEG-PLA was lower than that of mPEG-PLA/TPGS. The results of FTIR and TEM confirmed the spherical core-shell structure of micelles as well as mixed micelles, and the encapsulation of NIM inside the cores. In vitro release showed that micelles and mixed micelles had sustained release effect in the forms of passive diffusion and dissolution process, respectively. Following intraperitoneal administration (5mg/kg), micelles and mixed micelles were absorbed faster than solution, and with larger MRT(0-t), smaller CLz and larger AUC(0-t) as compared to that of solution, which showed micelles and mixed micelles had higher retention, slower elimination and higher bioavailability. This experiment also showed that mixed micelles released NIM more stably than micelles. By evaluate the bioequivalence, NIM micelles and NIM mixed micelles were testified non-bioequivalent to NIM solution. Micelles and mixed micelles could sustain the NIM concentrations more efficiently in plasma as compared to solution. Mixed micelles were the best ones since they had high loading content and released more stably. Thus, apprehending micelles and mixed micelles were suited as poor aqueous solubility drug carriers, and mixed micelles were better due to their high loading content and more stable release. Copyright © 2014 Elsevier B.V. All rights reserved.

Using a hybrid model to predict solute transfer from initially saturated soil into surface runoff with controlled drainage water.

PubMed

Tong, Juxiu; Hu, Bill X; Yang, Jinzhong; Zhu, Yan

2016-06-01

The mixing layer theory is not suitable for predicting solute transfer from initially saturated soil to surface runoff water under controlled drainage conditions. By coupling the mixing layer theory model with the numerical model Hydrus-1D, a hybrid solute transfer model has been proposed to predict soil solute transfer from an initially saturated soil into surface water, under controlled drainage water conditions. The model can also consider the increasing ponding water conditions on soil surface before surface runoff. The data of solute concentration in surface runoff and drainage water from a sand experiment is used as the reference experiment. The parameters for the water flow and solute transfer model and mixing layer depth under controlled drainage water condition are identified. Based on these identified parameters, the model is applied to another initially saturated sand experiment with constant and time-increasing mixing layer depth after surface runoff, under the controlled drainage water condition with lower drainage height at the bottom. The simulation results agree well with the observed data. Study results suggest that the hybrid model can accurately simulate the solute transfer from initially saturated soil into surface runoff under controlled drainage water condition. And it has been found that the prediction with increasing mixing layer depth is better than that with the constant one in the experiment with lower drainage condition. Since lower drainage condition and deeper ponded water depth result in later runoff start time, more solute sources in the mixing layer are needed for the surface water, and larger change rate results in the increasing mixing layer depth.

Resource allocation in shared spectrum access communications for operators with diverse service requirements

NASA Astrophysics Data System (ADS)

Kibria, Mirza Golam; Villardi, Gabriel Porto; Ishizu, Kentaro; Kojima, Fumihide; Yano, Hiroyuki

2016-12-01

In this paper, we study inter-operator spectrum sharing and intra-operator resource allocation in shared spectrum access communication systems and propose efficient dynamic solutions to address both inter-operator and intra-operator resource allocation optimization problems. For inter-operator spectrum sharing, we present two competent approaches, namely the subcarrier gain-based sharing and fragmentation-based sharing, which carry out fair and flexible allocation of the available shareable spectrum among the operators subject to certain well-defined sharing rules, traffic demands, and channel propagation characteristics. The subcarrier gain-based spectrum sharing scheme has been found to be more efficient in terms of achieved throughput. However, the fragmentation-based sharing is more attractive in terms of computational complexity. For intra-operator resource allocation, we consider resource allocation problem with users' dissimilar service requirements, where the operator supports users with delay constraint and non-delay constraint service requirements, simultaneously. This optimization problem is a mixed-integer non-linear programming problem and non-convex, which is computationally very expensive, and the complexity grows exponentially with the number of integer variables. We propose less-complex and efficient suboptimal solution based on formulating exact linearization, linear approximation, and convexification techniques for the non-linear and/or non-convex objective functions and constraints. Extensive simulation performance analysis has been carried out that validates the efficiency of the proposed solution.

Extraction of cesium, strontium and the platinium group metals from acidic high activity nuclear waste using a Purex process compatible organic extractant. Final report, December 15, 1980-August 15, 1983

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

Davis, M.W. Jr.; Van Brunt, V.

1984-09-14

Purex process compatible organic systems which selectively and reversibly extract cesium, strontium, and palladium from synthetic mixed fission product solutions containing 3M HNO/sub 3/ have been developed. This advance makes the development of continuous solvent extraction processes for their recovery more likely. The most favorable cesium and strontium complexing solutions have been tested for radiation stability to 10/sup 7/ rad using a 0.4 x 10/sup 7/ rad/h /sup 60/Co source. The distribution coefficients dropped somewhat but remained above unity. For cesium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % kerosenemore » containing 0.05m Bis 4,4',(5')(1-hydroxy 2-ethylhexyl)-benzo 18-crown-6 (Crown XVII). The NNS is a sulfonic acid cation exchanger. With an aqueous phase containing 0.006M Cs/sup +1/ in contact with an equal volume of extractant the D org/aq = 1.6 at a temperature of 25 to 35/sup 0/C. For strontium the complexing organic solution is 5 vol % (0.1M) NNS, 27 vol % TBP and 68 vol % Kerosene containing 0.02M Bis 4,4'(5') (1-hydroxyheptyl)cyclohexo 18-crown-6 (Crown XVI). With an aqueous phase containing 0.003M Sr/sup +2/ in contact with an equal volume of extractant the D org/aq = 1.98 at a temperature of 25 to 35/sup 0/C. For palladium the complexing organic solution consisted of a ratio of TBP/kerosene of 0.667 containing 0.3M Alamine 336 which is a tertiary amine anion exchanger. With an aqueous phase containing 0.0045M Pd/sup +/ in contact with an equal volume of extractant the D org/aq = 1.95 at a temperature of 25 to 35/sup 0/C.« less

Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

PubMed Central

Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

2015-01-01

Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

An investigation of paper based microfluidic devices for size based separation and extraction applications.

PubMed

Zhong, Z W; Wu, R G; Wang, Z P; Tan, H L

2015-09-01

Conventional microfluidic devices are typically complex and expensive. The devices require the use of pneumatic control systems or highly precise pumps to control the flow in the devices. This work investigates an alternative method using paper based microfluidic devices to replace conventional microfluidic devices. Size based separation and extraction experiments conducted were able to separate free dye from a mixed protein and dye solution. Experimental results showed that pure fluorescein isothiocyanate could be separated from a solution of mixed fluorescein isothiocyanate and fluorescein isothiocyanate labeled bovine serum albumin. The analysis readings obtained from a spectrophotometer clearly show that the extracted tartrazine sample did not contain any amount of Blue-BSA, because its absorbance value was 0.000 measured at a wavelength of 590nm, which correlated to Blue-BSA. These demonstrate that paper based microfluidic devices, which are inexpensive and easy to implement, can potentially replace their conventional counterparts by the use of simple geometry designs and the capillary action. These findings will potentially help in future developments of paper based microfluidic devices. Copyright © 2015 Elsevier B.V. All rights reserved.

Detection of Foreign Matter in Transfusion Solution Based on Gaussian Background Modeling and an Optimized BP Neural Network

PubMed Central

Zhou, Fuqiang; Su, Zhen; Chai, Xinghua; Chen, Lipeng

2014-01-01

This paper proposes a new method to detect and identify foreign matter mixed in a plastic bottle filled with transfusion solution. A spin-stop mechanism and mixed illumination style are applied to obtain high contrast images between moving foreign matter and a static transfusion background. The Gaussian mixture model is used to model the complex background of the transfusion image and to extract moving objects. A set of features of moving objects are extracted and selected by the ReliefF algorithm, and optimal feature vectors are fed into the back propagation (BP) neural network to distinguish between foreign matter and bubbles. The mind evolutionary algorithm (MEA) is applied to optimize the connection weights and thresholds of the BP neural network to obtain a higher classification accuracy and faster convergence rate. Experimental results show that the proposed method can effectively detect visible foreign matter in 250-mL transfusion bottles. The misdetection rate and false alarm rate are low, and the detection accuracy and detection speed are satisfactory. PMID:25347581

Comparing solute and particulate transport in streams using Notre Dame Linked Experimental Ecosystem Facility (ND-LEEF)

NASA Astrophysics Data System (ADS)

Shogren, A.; Tank, J. L.; Aubeneau, A. F.; Bolster, D.

2016-12-01

in streams and rivers. These processes co-vary across systems and are thus difficult to isolate. Therefore, to improve our understanding of drivers of fine-scale transport and retention of particles and solutes in streams, we experimentally compared transport and retention dynamics of two different particles (brewers yeast, 7μm; corn pollen, 70μm), a non-reactive solute (RhodamineWT), and a biologically reactive solute, nitrate (NO3-). We conducted experiments in four semi-natural constructed streams at the Notre Dame Linked Ecosystem Experimental Facility (ND-LEEF) in South Bend, Indiana. Each of the four 50 m replicate stream was lined with a unique configuration of substrate: pea gravel (PG, D50 = 0.5cm) and cobble (COB, D50 = 5cm) and structural complexity: alternating 2m sections of PG and COB substrates (ALT) and a random 50/50 mix (MIX). We allowed the experimental streams to naturally colonize with biofilm and periphyton throughout the summer sampling season. For particles, we estimated transport distance (Sp) and deposition velocity (vdep) and for solutes, we estimated uptake lengths (Sw) and uptake velocity (vf) using a short-term pulse addition technique. Sp and vdep were variable for particles, and were most strongly predicted by biofilm colonization on substrata in each stream. Biofilm accumulation also increased uptake of the reactive solute, though in contrast to particles, there were no significant differences in Sw or vf among streams suggesting that substrate type was not the main driver of reactive solute retention. These results emphasize the dynamic relationship between the physical and biological drivers influencing particle and solute retention in streams. Differential uptake of particles and solutes highlights the non stationarity of controlling variables along spatial or temporal continua. Even in highly controlled systems like those at ND-LEEF, physical vs. biological drivers are difficult to isolate.

A Method To Determine the Kinetics of Solute Mixing in Liquid/Liquid Formulation Dual-Chamber Syringes.

PubMed

Werk, Tobias; Mahler, Hanns-Christian; Ludwig, Imke Sonja; Luemkemann, Joerg; Huwyler, Joerg; Hafner, Mathias

Dual-chamber syringes were originally designed to separate a solid substance and its diluent. However, they can also be used to separate liquid formulations of two individual drug products, which cannot be co-formulated due to technical or regulatory issues. A liquid/liquid dual-chamber syringe can be designed to achieve homogenization and mixing of both solutions prior to administration, or it can be used to sequentially inject both solutions. While sequential injection can be easily achieved by a dual-chamber syringe with a bypass located at the needle end of the syringe barrel, mixing of the two fluids may provide more challenges. Within this study, the mixing behavior of surrogate solutions in different dual-chamber syringes is assessed. Furthermore, the influence of parameters such as injection angle, injection speed, agitation, and sample viscosity were studied. It was noted that mixing was poor for the commercial dual-chamber syringes (with a bypass designed as a longitudinal ridge) when the two liquids significantly differ in their physical properties (viscosity, density). However, an optimized dual-chamber syringe design with multiple bypass channels resulted in improved mixing of liquids. Dual-chamber syringes were originally designed to separate a solid substance and its diluent. However, they can also be used to separate liquid formulations of two individual drug products. A liquid/liquid dual-chamber syringe can be designed to achieve homogenization and mixing of both solutions prior to administration, or it can be used to sequentially inject both solutions. While sequential injection can be easily achieved by a dual-chamber syringe with a bypass located at the needle end of the syringe barrel, mixing of the two fluids may provide more challenges. Within this study, the mixing behavior of surrogate solutions in different dual-chamber syringes is assessed. Furthermore, the influence of parameters such as injection angle, injection speed, agitation, and sample viscosity were studied. It was noted that mixing was poor for the commercially available dual-chamber syringes when the two liquids significantly differ in viscosity and density. However, an optimized dual-chamber syringe design resulted in improved mixing of liquids. © PDA, Inc. 2017.

Entertaining Chemistry--Two Colorful Reactions.

ERIC Educational Resources Information Center

Elsworth, John F.

2000-01-01

Describes two related color-change reactions that are relatively easy and safe to demonstrate. In the "Sunday School Reaction", a black and a white solution are mixed to form a white solution. In the "South Africa Reaction", a series of black, brown, red, and white solutions are mixed to form a clear, colorless solution. (WRM)

Domain growth of carbon nanotubes assisted by dewetting of thin catalyst precursor films

NASA Astrophysics Data System (ADS)

Srivastava, Alok Kumar; Sachan, Priyanka; Samanta, Chandan; Mukhopadhyay, Kingsuk; Sharma, Ashutosh

2014-01-01

We explore self-organized dewetting of ultrathin films of a novel metal complex as a one step surface patterning method to create nanoislands of iron, using which spatially separated carbon nanostructures were synthesized. Dewetting of ultrathin metal complex films was induced by two different methods: liquid solvent exposure and thermal annealing to engender surface patterning. For thermal dewetting, thin films of the iron oleate complex were dewetted at high temperature. In the case of liquid solvent assisted dewetting, the metal complex, mixed with a sacrificial polymer (polystyrene) was spin coated as thin films (<40 nm) and then dewetted under an optimal solution mixture consisting of methyl ethyl ketone, acetone and water. The carrier polymer was then selectively removed to produce the iron metal islands. These metal islands were used for selective growth of discrete patches of multiwall CNTs and CNFs by a chemical vapor deposition (CVD) process. Solvent induced dewetting showed clear advantages over thermal dewetting owing to reduced size of catalyst domains formed by dewetting, an improved control over CNT growth as well as in its ability to immobilize the seed particles. The generic solution mediated dewetting and pattern generation in thin films of various catalytic precursors can thus be a powerful method for selective domain growth of a variety of functional nanomaterials.

Analytical Solution for Reactive Solute Transport Considering Incomplete Mixing

NASA Astrophysics Data System (ADS)

Bellin, A.; Chiogna, G.

2013-12-01

The laboratory experiments of Gramling et al. (2002) showed that incomplete mixing at the pore scale exerts a significant impact on transport of reactive solutes and that assuming complete mixing leads to overestimation of product concentration in bimolecular reactions. We consider here the family of equilibrium reactions for which the concentration of the reactants and the product can be expressed as a function of the mixing ratio, the concentration of a fictitious non reactive solute. For this type of reactions we propose, in agreement with previous studies, to model the effect of incomplete mixing at scales smaller than the Darcy scale assuming that the mixing ratio is distributed within an REV according to a Beta distribution. We compute the parameters of the Beta model by imposing that the mean concentration is equal to the value that the concentration assumes at the continuum Darcy scale, while the variance decays with time as a power law. We show that our model reproduces the concentration profiles of the reaction product measured in the Gramling et al. (2002) experiments using the transport parameters obtained from conservative experiments and an instantaneous reaction kinetic. The results are obtained applying analytical solutions both for conservative and for reactive solute transport, thereby providing a method to handle the effect of incomplete mixing on multispecies reactive solute transport, which is simpler than other previously developed methods. Gramling, C. M., C. F. Harvey, and L. C. Meigs (2002), Reactive transport in porous media: A comparison of model prediction with laboratory visualization, Environ. Sci. Technol., 36(11), 2508-2514.

Perforator chimerism for the reconstruction of complex defects: A new chimeric free flap classification system.

PubMed

Kim, Jeong Tae; Kim, Youn Hwan; Ghanem, Ali M

2015-11-01

Complex defects present structural and functional challenges to reconstructive surgeons. When compared to multiple free flaps or staged reconstruction, the use of chimeric flaps to reconstruct such defects have many advantages such as reduced number of operative procedures and donor site morbidity as well as preservation of recipient vessels. With increased popularity of perforator flaps, chimeric flaps' harvest and design has benefited from 'perforator concept' towards more versatile and better reconstruction solutions. This article discusses perforator based chimeric flaps and presents a practice based classification system that incorporates the perforator flap concept into "Perforator Chimerism". The authors analyzed a variety of chimeric patterns used in 31 consecutive cases to present illustrative case series and their new classification system. Accordingly, chimeric flaps are classified into four types. Type I: Classical Chimerism, Type II: Anastomotic Chimerism, Type III: Perforator Chimerism and Type IV Mixed Chimerism. Types I on specific source vessel anatomy whilst Type II requires microvascular anastomosis to create the chimeric reconstructive solution. Type III chimeric flaps utilizes the perforator concept to raise two components of tissues without microvascular anastomosis between them. Type IV chimeric flaps are mixed type flaps comprising any combination of Types I to III. Incorporation of the perforator concept in planning and designing chimeric flaps has allowed safe, effective and aesthetically superior reconstruction of complex defects. The new classification system aids reconstructive surgeons and trainees to understand chimeric flaps design, facilitating effective incorporation of this important reconstructive technique into the armamentarium of the reconstruction toolbox. Copyright © 2015 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

VAVUQ, Python and Matlab freeware for Verification and Validation, Uncertainty Quantification

NASA Astrophysics Data System (ADS)

Courtney, J. E.; Zamani, K.; Bombardelli, F. A.; Fleenor, W. E.

2015-12-01

A package of scripts is presented for automated Verification and Validation (V&V) and Uncertainty Quantification (UQ) for engineering codes that approximate Partial Differential Equations (PDFs). The code post-processes model results to produce V&V and UQ information. This information can be used to assess model performance. Automated information on code performance can allow for a systematic methodology to assess the quality of model approximations. The software implements common and accepted code verification schemes. The software uses the Method of Manufactured Solutions (MMS), the Method of Exact Solution (MES), Cross-Code Verification, and Richardson Extrapolation (RE) for solution (calculation) verification. It also includes common statistical measures that can be used for model skill assessment. Complete RE can be conducted for complex geometries by implementing high-order non-oscillating numerical interpolation schemes within the software. Model approximation uncertainty is quantified by calculating lower and upper bounds of numerical error from the RE results. The software is also able to calculate the Grid Convergence Index (GCI), and to handle adaptive meshes and models that implement mixed order schemes. Four examples are provided to demonstrate the use of the software for code and solution verification, model validation and uncertainty quantification. The software is used for code verification of a mixed-order compact difference heat transport solver; the solution verification of a 2D shallow-water-wave solver for tidal flow modeling in estuaries; the model validation of a two-phase flow computation in a hydraulic jump compared to experimental data; and numerical uncertainty quantification for 3D CFD modeling of the flow patterns in a Gust erosion chamber.

A new sensitive method of dissociation constants determination based on the isohydric solutions principle.

PubMed

Michałowski, Tadeusz; Pilarski, Bogusław; Asuero, Agustin G; Dobkowska, Agnieszka

2010-10-15

The paper provides a new formulation and analytical proposals based on the isohydric solutions concept. It is particularly stated that a mixture formed, according to titrimetric mode, from a weak acid (HX, C(0)mol/L) and a strong acid (HB, Cmol/L) solutions, assumes constant pH, independently on the volumes of the solutions mixed, provided that the relation C(0)=C+C(2)·10(pK(1)) is valid, where pK(1)=-log K(1), K(1) the dissociation constant for HX. The generalized formulation, referred to the isohydric solutions thus obtained, was extended also to more complex acid-base systems. Particularly in the (HX, HB) system, the titration occurs at constant ionic strength (I) value, not resulting from presence of a basal electrolyte. This very advantageous conjunction of the properties provides, among others, a new, very sensitive method for verification of pK(1) value. The new method is particularly useful for weak acids HX characterized by low pK(1) values. The method was tested experimentally on four acid-base systems (HX, HB), in aqueous and mixed-solvent media and compared with the literature data. Some useful (linear and hyperbolic) correlations were stated and applied for validation of pK(1) values. Finally, some practical applications of analytical interest of the isohydricity (pH constancy) principle as one formulated in this paper were enumerated, proving the usefulness of such a property which has its remote roots in the Arrhenius concept. Copyright © 2010 Elsevier B.V. All rights reserved.

Evaluating the effects of variable water chemistry on bacterial transport during infiltration.

PubMed

Zhang, Haibo; Nordin, Nahjan Amer; Olson, Mira S

2013-07-01

Bacterial infiltration through the subsurface has been studied experimentally under different conditions of interest and is dependent on a variety of physical, chemical and biological factors. However, most bacterial transport studies fail to adequately represent the complex processes occurring in natural systems. Bacteria are frequently detected in stormwater runoff, and may present risk of microbial contamination during stormwater recharge into groundwater. Mixing of stormwater runoff with groundwater during infiltration results in changes in local solution chemistry, which may lead to changes in both bacterial and collector surface properties and subsequent bacterial attachment rates. This study focuses on quantifying changes in bacterial transport behavior under variable solution chemistry, and on comparing the influences of chemical variability and physical variability on bacterial attachment rates. Bacterial attachment rate at the soil-water interface was predicted analytically using a combined rate equation, which varies temporally and spatially with respect to changes in solution chemistry. Two-phase Monte Carlo analysis was conducted and an overall input-output correlation coefficient was calculated to quantitatively describe the importance of physiochemical variation on the estimates of attachment rate. Among physical variables, soil particle size has the highest correlation coefficient, followed by porosity of the soil media, bacterial size and flow velocity. Among chemical variables, ionic strength has the highest correlation coefficient. A semi-reactive microbial transport model was developed within HP1 (HYDRUS1D-PHREEQC) and applied to column transport experiments with constant and variable solution chemistries. Bacterial attachment rates varied from 9.10×10(-3)min(-1) to 3.71×10(-3)min(-1) due to mixing of synthetic stormwater (SSW) with artificial groundwater (AGW), while bacterial attachment remained constant at 9.10×10(-3)min(-1) in a constant solution chemistry (AGW only). The model matched observed bacterial breakthrough curves well. Although limitations exist in the application of a semi-reactive microbial transport model, this method represents one step towards a more realistic model of bacterial transport in complex microbial-water-soil systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Boosting-Based Optimization as a Generic Framework for Novelty and Fraud Detection in Complex Strategies

NASA Astrophysics Data System (ADS)

Gavrishchaka, Valeriy V.; Kovbasinskaya, Maria; Monina, Maria

2008-11-01

Novelty detection is a very desirable additional feature of any practical classification or forecasting system. Novelty and rare patterns detection is the main objective in such applications as fault/abnormality discovery in complex technical and biological systems, fraud detection and risk management in financial and insurance industry. Although many interdisciplinary approaches for rare event modeling and novelty detection have been proposed, significant data incompleteness due to the nature of the problem makes it difficult to find a universal solution. Even more challenging and much less formalized problem is novelty detection in complex strategies and models where practical performance criteria are usually multi-objective and the best state-of-the-art solution is often not known due to the complexity of the task and/or proprietary nature of the application area. For example, it is much more difficult to detect a series of small insider trading or other illegal transactions mixed with valid operations and distributed over long time period according to a well-designed strategy than a single, large fraudulent transaction. Recently proposed boosting-based optimization was shown to be an effective generic tool for the discovery of stable multi-component strategies/models from the existing parsimonious base strategies/models in financial and other applications. Here we outline how the same framework can be used for novelty and fraud detection in complex strategies and models.

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Highly accurate symplectic element based on two variational principles

NASA Astrophysics Data System (ADS)

Qing, Guanghui; Tian, Jia

2018-02-01

For the stability requirement of numerical resultants, the mathematical theory of classical mixed methods are relatively complex. However, generalized mixed methods are automatically stable, and their building process is simple and straightforward. In this paper, based on the seminal idea of the generalized mixed methods, a simple, stable, and highly accurate 8-node noncompatible symplectic element (NCSE8) was developed by the combination of the modified Hellinger-Reissner mixed variational principle and the minimum energy principle. To ensure the accuracy of in-plane stress results, a simultaneous equation approach was also suggested. Numerical experimentation shows that the accuracy of stress results of NCSE8 are nearly the same as that of displacement methods, and they are in good agreement with the exact solutions when the mesh is relatively fine. NCSE8 has advantages of the clearing concept, easy calculation by a finite element computer program, higher accuracy and wide applicability for various linear elasticity compressible and nearly incompressible material problems. It is possible that NCSE8 becomes even more advantageous for the fracture problems due to its better accuracy of stresses.

A hybrid binary particle swarm optimization for large capacitated multi item multi level lot sizing (CMIMLLS) problem

NASA Astrophysics Data System (ADS)

Mishra, S. K.; Sahithi, V. V. D.; Rao, C. S. P.

2016-09-01

The lot sizing problem deals with finding optimal order quantities which minimizes the ordering and holding cost of product mix. when multiple items at multiple levels with all capacity restrictions are considered, the lot sizing problem become NP hard. Many heuristics were developed in the past have inevitably failed due to size, computational complexity and time. However the authors were successful in the development of PSO based technique namely iterative improvement binary particles swarm technique to address very large capacitated multi-item multi level lot sizing (CMIMLLS) problem. First binary particle Swarm Optimization algorithm is used to find a solution in a reasonable time and iterative improvement local search mechanism is employed to improvise the solution obtained by BPSO algorithm. This hybrid mechanism of using local search on the global solution is found to improve the quality of solutions with respect to time thus IIBPSO method is found best and show excellent results.

Single evolution equation in a light-matter pairing system

NASA Astrophysics Data System (ADS)

Bugaychuk, S.; Tobisch, E.

2018-03-01

The coupled system including wave mixing and nonlinear dynamics of a nonlocal optical medium is usually studied (1) numerically, with the medium being regarded as a black box, or (2) experimentally, making use of some empirical assumptions. In this paper we deduce for the first time a single evolution equation describing the dynamics of the pairing system as a holistic complex. For a non-degenerate set of parameters, we obtain the nonlinear Schrödinger equation with coefficients being written out explicitly. Analytical solutions of this equation can be experimentally realized in any photorefractive medium, e.g. in photorefractive, liquid or photonic crystals. For instance, a soliton-like solution can be used in dynamical holography for designing an artificial grating with maximal amplification of an image.

Conversion of radioactive ferrocyanide compounds to immobile glasses

DOEpatents

Schulz, W.W.; Dressen, A.L.

1975-11-21

A method is described for converting complex radioactive ferrocyanide compounds of /sup 134/Cs and /sup 137/Cs to immobile glass that is resistant to leaching by water. The /sup 134/Cs and /sup 137/Cs are separated from nuclear waste solutions by precipitation from alkaline solutions by the addition of a soluble Ni/sup 2 +/, Zn/sup 2 +/, Cu/sup 2 +/, Co/sup 2 +/, UO/sub 2//sup 2 +/, or Mn/sup 2 +/ and K/sub 4/Fe(CN)/sub 6/. The dried, finely ground precipitate is mixed with Na/sub 2/CO/sub 3/ and a mixture of (a) basalt and B/sub 2/O/sub 3/ or (b) SiO/sub 2/ and CaO, melted, and allowed to solidify. (BLM)

Acid-switched Eu(III) coordination inside reverse aggregates: Insights into a synergistic liquid-liquid extraction system

DOE PAGES

Ellis, Ross J.

2016-08-09

Determining the structure of complex solutions bearing metal ions is challenging, but crucial for developing important technologies such as liquid-liquid extraction for metal refining and separation purposes. Herein, the structure of an organic Eu(III) solution consisting a binary mixture of lipophilic ligands di-2-ethylhexyl phosphoric acid (HDEHP) and tetraoctyl diglycolamide (TODGA) in dodecane is studied using synchrotron small angle X-ray scattering (SAXS) and X-ray absorption fine structure spectroscopy (EXAFS). This system is of technological importance in f-element separation for nuclear fuel cycle applications, where extraction is controlled by varying nitric acid concentration. Extraction is promoted at low and high concentration, butmore » is retarded at intermediate concentration, leading to a U-shaped function; the structural origins of which we investigate. At the nanoscale, the solution is apparently comprised of reverse micelles with polar cores of approximately 1 nm in size, and these remain virtually unchanged as acid concentration is varied. Inside the polar cores, the coordination environment of Eu(III) switches from a 9-coordinate [Eu(TODGA) 3] 3+ motif at high acid, to a 6-coordinate HDEHP-dominated complex resembling Eu(HDEHP·DEHP) 3 at low acid. The results show that extraction is controlled within the coordination sphere, where it is promoted under conditions that favor coordination of either one of the two organic ligands, but is retarded under conditions that encourage mixed complexes. Lastly, our results link solution structure with ion transport properties in a technologically-important liquid-liquid ion extraction system.« less

Structure, stability, and thermodynamics of lamellar DNA-lipid complexes.

PubMed Central

Harries, D; May, S; Gelbart, W M; Ben-Shaul, A

1998-01-01

We develop a statistical thermodynamic model for the phase evolution of DNA-cationic lipid complexes in aqueous solution, as a function of the ratios of charged to neutral lipid and charged lipid to DNA. The complexes consist of parallel strands of DNA intercalated in the water layers of lamellar stacks of mixed lipid bilayers, as determined by recent synchrotron x-ray measurements. Elastic deformations of the DNA and the lipid bilayers are neglected, but DNA-induced spatial inhomogeneities in the bilayer charge densities are included. The relevant nonlinear Poisson-Boltzmann equation is solved numerically, including self-consistent treatment of the boundary conditions at the polarized membrane surfaces. For a wide range of lipid compositions, the phase evolution is characterized by three regions of lipid to DNA charge ratio, rho: 1) for low rho, the complexes coexist with excess DNA, and the DNA-DNA spacing in the complex, d, is constant; 2) for intermediate rho, including the isoelectric point rho = 1, all of the lipid and DNA in solution is incorporated into the complex, whose inter-DNA distance d increases linearly with rho; and 3) for high rho, the complexes coexist with excess liposomes (whose lipid composition is different from that in the complex), and their spacing d is nearly, but not completely, independent of rho. These results can be understood in terms of a simple charging model that reflects the competition between counterion entropy and inter-DNA (rho < 1) and interbilayer (rho > 1) repulsions. Finally, our approach and conclusions are compared with theoretical work by others, and with relevant experiments. PMID:9649376

Cloud point extraction thermospray flame quartz furnace atomic absorption spectrometry for determination of ultratrace cadmium in water and urine

NASA Astrophysics Data System (ADS)

Wu, Peng; Zhang, Yunchang; Lv, Yi; Hou, Xiandeng

2006-12-01

A simple, low cost and highly sensitive method based on cloud point extraction (CPE) for separation/preconcentration and thermospray flame quartz furnace atomic absorption spectrometry was proposed for the determination of ultratrace cadmium in water and urine samples. The analytical procedure involved the formation of analyte-entrapped surfactant micelles by mixing the analyte solution with an ammonium pyrrolidinedithiocarbamate (APDC) solution and a Triton X-114 solution. When the temperature of the system was higher than the cloud point of Triton X-114, the complex of cadmium-PDC entered the surfactant-rich phase and thus separation of the analyte from the matrix was achieved. Under optimal chemical and instrumental conditions, the limit of detection was 0.04 μg/L for cadmium with a sample volume of 10 mL. The analytical results of cadmium in water and urine samples agreed well with those by ICP-MS.

[Selected enhancement of different order stokes lines of SRS by using fluorescence of mixed dye solution].

PubMed

Zuo, Hao-yi; Gao, Jie; Yang, Jing-guo

2007-03-01

A new method to enhance the intensity of the different orders of Stokes lines of SRS by using mixed dye fluorescence is reported. The Stokes lines from the second-order to the fifth-order of CCl4 were enhanced by the fluorescence of mixed R6G and RB solutions in different proportions of 20:2, 20:13 and 20:40 (R6g:Rb), respectively. It is considered that the Stokes lines from the second-order to the fifth-order are near the fluorescence peaks of the three mixed solutions, and far from the absorption peaks of R6g and Rb, so the enhancement effect dominates the absorption effect; as a result, these stokes lines are enhanced. On the contrary, the first-order stokes line is near the absorption peak of RB and far from the fluorescence peaks of the mixed solutions, which leads to the weakening of this stokes line. It is also reported that the first-order, the second-order and the third-order Stokes lines of benzene were enhanced by the fluorescence of mixed solutions of R6g and DCM with of different proportions. The potential application of this method is forecasted.

Grid Convergence of High Order Methods for Multiscale Complex Unsteady Viscous Compressible Flows

NASA Technical Reports Server (NTRS)

Sjoegreen, B.; Yee, H. C.

2001-01-01

Grid convergence of several high order methods for the computation of rapidly developing complex unsteady viscous compressible flows with a wide range of physical scales is studied. The recently developed adaptive numerical dissipation control high order methods referred to as the ACM and wavelet filter schemes are compared with a fifth-order weighted ENO (WENO) scheme. The two 2-D compressible full Navier-Stokes models considered do not possess known analytical and experimental data. Fine grid solutions from a standard second-order TVD scheme and a MUSCL scheme with limiters are used as reference solutions. The first model is a 2-D viscous analogue of a shock tube problem which involves complex shock/shear/boundary-layer interactions. The second model is a supersonic reactive flow concerning fuel breakup. The fuel mixing involves circular hydrogen bubbles in air interacting with a planar moving shock wave. Both models contain fine scale structures and are stiff in the sense that even though the unsteadiness of the flows are rapidly developing, extreme grid refinement and time step restrictions are needed to resolve all the flow scales as well as the chemical reaction scales.

Modeling hyporheic zone processes

USGS Publications Warehouse

Runkel, Robert L.; McKnight, Diane M.; Rajaram, Harihar

2003-01-01

Stream biogeochemistry is influenced by the physical and chemical processes that occur in the surrounding watershed. These processes include the mass loading of solutes from terrestrial and atmospheric sources, the physical transport of solutes within the watershed, and the transformation of solutes due to biogeochemical reactions. Research over the last two decades has identified the hyporheic zone as an important part of the stream system in which these processes occur. The hyporheic zone may be loosely defined as the porous areas of the stream bed and stream bank in which stream water mixes with shallow groundwater. Exchange of water and solutes between the stream proper and the hyporheic zone has many biogeochemical implications, due to differences in the chemical composition of surface and groundwater. For example, surface waters are typically oxidized environments with relatively high dissolved oxygen concentrations. In contrast, reducing conditions are often present in groundwater systems leading to low dissolved oxygen concentrations. Further, microbial oxidation of organic materials in groundwater leads to supersaturated concentrations of dissolved carbon dioxide relative to the atmosphere. Differences in surface and groundwater pH and temperature are also common. The hyporheic zone is therefore a mixing zone in which there are gradients in the concentrations of dissolved gasses, the concentrations of oxidized and reduced species, pH, and temperature. These gradients lead to biogeochemical reactions that ultimately affect stream water quality. Due to the complexity of these natural systems, modeling techniques are frequently employed to quantify process dynamics.

Compatibility and osmolality of inhaled N-acetylcysteine nebulizing solution with fenoterol and ipratropium.

PubMed

Lee, Tzung-Yi; Chen, Chi-Ming; Lee, Chun-Nin; Chiang, Yi-Chun; Chen, Hsiang-Yin

2005-04-15

The compatibility, pH, and osmolality of N-acetylcysteine (NAC) nebulizing solution in the presence of ipratropium bromide or fenoterol hydrobromide were studied. Portions (400 microL) of each mixture were sampled immediately upon mixing and one, two, three, four, five, six, and seven hours after mixing and assayed by high-performance liquid chromatography. Osmolality was measured by sampling 100 microL from the filling cup at a five-minute interval during nebulization and by the freezing-point-depression method. Adding NAC solution to fenoterol solution raised the pH from 3.20 to 7.90 and the osmolality to a mean +/- S.D. of 1400.67 +/- 4.51 mOsm/kg. Fenoterol concentrations decreased to 93.71% and NAC concentrations to 92.54% of initial concentrations after seven hours. Mixing ipratropium with NAC solution raised the pH from 3.74 to 7.95 and the osmolality to a mean +/- S.D. of 1413 +/- 11.79 mOsm/kg. The initial ipratropium concentration declined 7.39% and 10.91% one and two hours after mixing with NAC solution, respectively. NAC and ipratropium were stable in nebulizing solution within one hour of mixing. NAC and fenoterol were compatible for at least seven hours.

Rapid and efficient mixing in a slip-driven three-dimensional flow in a rectangular channel

NASA Astrophysics Data System (ADS)

Pacheco, J. Rafael; Ping Chen, Kang; Hayes, Mark A.

2006-08-01

A method for generating mixing in an electroosmotic flow of an electrolytic solution in a three-dimensional channel is proposed. When the width-to-height aspect ratio of the channel cross-section is large, mixing of a blob of a solute in a slip-driven three-dimensional flow in a rectangular channel can be used to model and assess the effectiveness of this method. It is demonstrated through numerical simulations that under certain operating conditions, rapid and efficient mixing can be achieved. Future investigation will include the solution of the exact equations and experimentation.

Adsorption of saturated fatty acid in urea complexation: Kinetics and equilibrium studies

NASA Astrophysics Data System (ADS)

Setyawardhani, Dwi Ardiana; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

2018-02-01

Urea complexation is fractionation process for concentrating poly-unsaturated fatty acids (PUFAs) from vegetable oil or animal fats. For process design and optimization in commercial industries, it is necessary to provide kinetics and equilibrium data. Urea inclusion compounds (UICs) as the product is a unique complex form which one molecule (guest) is enclosed within another molecule (host). In urea complexation, the guest-host bonding exists between saturated fatty acids (SFAs) and crystalline urea. This research studied the complexation is analogous to an adsorption process. The Batch adsorption process was developed to obtain the experimental data. The ethanolic urea solution was mixed with SFA in certain compositions and adsorption times. The mixture was heated until it formed homogenous and clear solution, then it cooled very slowly until the first numerous crystal appeared. Adsorption times for the kinetic data were determined since the crystal formed. The temperature was maintained constant at room temperature. Experimental sets of data were observed with adsorption kinetics and equilibrium models. High concentration of saturated fatty acid (SFA) was used to represent adsorption kinetics and equilibrium parameters. Kinetic data were examined with pseudo first-order, pseudo second-order and intra particle diffusion models. Linier, Freundlich and Langmuir isotherm were used to study the equilibrium model of this adsorption. The experimental data showed that SFA adsorption in urea crystal followed pseudo second-order model. The compatibility of the data with Langmuir isotherm showed that urea complexation was a monolayer adsorption.

Superstructure-based Design and Optimization of Batch Biodiesel Production Using Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Nuh, M. Z.; Nasir, N. F.

2017-08-01

Biodiesel as a fuel comprised of mono alkyl esters of long chain fatty acids derived from renewable lipid feedstock, such as vegetable oil and animal fat. Biodiesel production is complex process which need systematic design and optimization. However, no case study using the process system engineering (PSE) elements which are superstructure optimization of batch process, it involves complex problems and uses mixed-integer nonlinear programming (MINLP). The PSE offers a solution to complex engineering system by enabling the use of viable tools and techniques to better manage and comprehend the complexity of the system. This study is aimed to apply the PSE tools for the simulation of biodiesel process and optimization and to develop mathematical models for component of the plant for case A, B, C by using published kinetic data. Secondly, to determine economic analysis for biodiesel production, focusing on heterogeneous catalyst. Finally, the objective of this study is to develop the superstructure for biodiesel production by using heterogeneous catalyst. The mathematical models are developed by the superstructure and solving the resulting mixed integer non-linear model and estimation economic analysis by using MATLAB software. The results of the optimization process with the objective function of minimizing the annual production cost by batch process from case C is 23.2587 million USD. Overall, the implementation a study of process system engineering (PSE) has optimized the process of modelling, design and cost estimation. By optimizing the process, it results in solving the complex production and processing of biodiesel by batch.

Sequential energy and charge transfer processes in mixed host-guest complexes of subphthalocyanine, porphyrin and phthalocyanine chromophores.

PubMed

Menting, Roel; Ng, Dennis K P; Röder, Beate; Ermilov, Eugeny A

2012-11-14

Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(IV) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

Efficient modeling of photonic crystals with local Hermite polynomials

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

Boucher, C. R.; Li, Zehao; Albrecht, J. D.

2014-04-21

Developing compact algorithms for accurate electrodynamic calculations with minimal computational cost is an active area of research given the increasing complexity in the design of electromagnetic composite structures such as photonic crystals, metamaterials, optical interconnects, and on-chip routing. We show that electric and magnetic (EM) fields can be calculated using scalar Hermite interpolation polynomials as the numerical basis functions without having to invoke edge-based vector finite elements to suppress spurious solutions or to satisfy boundary conditions. This approach offers several fundamental advantages as evidenced through band structure solutions for periodic systems and through waveguide analysis. Compared with reciprocal space (planemore » wave expansion) methods for periodic systems, advantages are shown in computational costs, the ability to capture spatial complexity in the dielectric distributions, the demonstration of numerical convergence with scaling, and variational eigenfunctions free of numerical artifacts that arise from mixed-order real space basis sets or the inherent aberrations from transforming reciprocal space solutions of finite expansions. The photonic band structure of a simple crystal is used as a benchmark comparison and the ability to capture the effects of spatially complex dielectric distributions is treated using a complex pattern with highly irregular features that would stress spatial transform limits. This general method is applicable to a broad class of physical systems, e.g., to semiconducting lasers which require simultaneous modeling of transitions in quantum wells or dots together with EM cavity calculations, to modeling plasmonic structures in the presence of EM field emissions, and to on-chip propagation within monolithic integrated circuits.« less

Influence of sodium borate on the early age hydration of calcium sulfoaluminate cement

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

Champenois, Jean-Baptiste; Dhoury, Mélanie; Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr

Calcium sulfoaluminate (CSA) cements are potential candidates for the conditioning of radioactive wastes with high sodium borate concentrations. This work thus investigates early age hydration of two CSA cements with different gypsum contents (0 to 20%) as a function of the mixing solution composition (borate and NaOH concentrations). Gypsum plays a key role in controlling the reactivity of cement. When the mixing solution is pure water, increasing the gypsum concentration accelerates cement hydration. However, the reverse is observed when the mixing solution contains sodium borate. Until gypsum exhaustion, the pore solution pH remains constant at ~ 10.8, and a poorlymore » crystallized borate compound (ulexite) precipitates. A correlation is established between this transient precipitation and the hydration delay. Decreasing the gypsum content in the binder, or increasing the sodium content in the mixing solution, are two ways of reducing the stability of ulexite, thus decreasing the hydration delay.« less

Synthesis, structural elucidation, biological, antioxidant and nuclease activities of some 5-Fluorouracil-amino acid mixed ligand complexes

NASA Astrophysics Data System (ADS)

Shobana, Sutha; Subramaniam, Perumal; Mitu, Liviu; Dharmaraja, Jeyaprakash; Arvind Narayan, Sundaram

2015-01-01

Some biologically active mixed ligand complexes (1-9) have been synthesized from 5-Fluorouracil (5-FU; A) and amino acids (B) such as glycine (gly), L-alanine (ala) and L-valine (val) with Ni(II), Cu(II) and Zn(II) ions. The synthesized mixed ligand complexes (1-9) were characterized by various physico-chemical, spectral, thermal and morphological studies. 5-Fluorouracil and its mixed ligand complexes have been tested for their in vitro biological activities against some pathogenic bacterial and fungal species by the agar well diffusion method. The in vitro antioxidant activities of 5-Fluorouracil and its complexes have also been investigated by using the DPPH assay method. The results demonstrate that Cu(II) mixed ligand complexes (4-6) exhibit potent biological as well as antioxidant activities compared to 5-Fluorouracil and Ni(II) (1-3) and Zn(II) (7-9) mixed ligand complexes. Further, the cleaving activities of CT DNA under aerobic conditions show moderate activity with the synthesized Cu(II) and Ni(II) mixed ligand complexes (1-6) while no activity is seen with Zn(II) complexes (7-9). Binding studies of CT DNA with these complexes show a decrease in intensity of the charge transfer band to the extent of 5-15% along with a minor red shift. The free energy change values (Δ‡G) calculated from intrinsic binding constants indicate that the interaction between mixed ligand complex and DNA is spontaneous.

Asymptotic solution of the turbulent mixing layer for velocity ratio close to unity

NASA Technical Reports Server (NTRS)

Higuera, F. J.; Jimenez, J.; Linan, A.

1996-01-01

The equations describing the first two terms of an asymptotic expansion of the solution of the planar turbulent mixing layer for values of the velocity ratio close to one are obtained. The first term of this expansion is the solution of the well-known time-evolving problem and the second, which includes the effects of the increase of the turbulence scales in the stream-wise direction, obeys a linear system of equations. Numerical solutions of these equations for a two-dimensional reacting mixing layer show that the correction to the time-evolving solution may explain the asymmetry of the entrainment and the differences in product generation observed in flip experiments.

Mixed mosaic membranes prepared by layer-by-layer assembly for ionic separations.

PubMed

Rajesh, Sahadevan; Yan, Yu; Chang, Hsueh-Chia; Gao, Haifeng; Phillip, William A

2014-12-23

Charge mosaic membranes, which possess distinct cationic and anionic domains that traverse the membrane thickness, are capable of selectively separating dissolved salts from similarly sized neutral solutes. Here, the generation of charge mosaic membranes using facile layer-by-layer assembly methodologies is reported. Polymeric nanotubes with pore walls lined by positively charged polyethylenimine moieties or negatively charged poly(styrenesulfonate) moieties were prepared via layer-by-layer assembly using track-etched membranes as sacrificial templates. Subsequently, both types of nanotubes were deposited on a porous support in order to produce mixed mosaic membranes. Scanning electron microscopy demonstrates that the facile deposition techniques implemented result in nanotubes that are vertically aligned without overlap between adjacent elements. Furthermore, the nanotubes span the thickness of the mixed mosaic membranes. The effects of this unique nanostructure are reflected in the transport characteristics of the mixed mosaic membranes. The hydraulic permeability of the mixed mosaic membranes in piezodialysis operations was 8 L m(-2) h(-1) bar(-1). Importantly, solute rejection experiments demonstrate that the mixed mosaic membranes are more permeable to ionic solutes than similarly sized neutral molecules. In particular, negative rejection of sodium chloride is observed (i.e., the concentration of NaCl in the solution that permeates through a mixed mosaic membrane is higher than in the initial feed solution). These properties illustrate the ability of mixed mosaic membranes to permeate dissolved ions selectively without violating electroneutrality and suggest their utility in ionic separations.

Chip Design Process Optimization Based on Design Quality Assessment

NASA Astrophysics Data System (ADS)

Häusler, Stefan; Blaschke, Jana; Sebeke, Christian; Rosenstiel, Wolfgang; Hahn, Axel

2010-06-01

Nowadays, the managing of product development projects is increasingly challenging. Especially the IC design of ASICs with both analog and digital components (mixed-signal design) is becoming more and more complex, while the time-to-market window narrows at the same time. Still, high quality standards must be fulfilled. Projects and their status are becoming less transparent due to this complexity. This makes the planning and execution of projects rather difficult. Therefore, there is a need for efficient project control. A main challenge is the objective evaluation of the current development status. Are all requirements successfully verified? Are all intermediate goals achieved? Companies often develop special solutions that are not reusable in other projects. This makes the quality measurement process itself less efficient and produces too much overhead. The method proposed in this paper is a contribution to solve these issues. It is applied at a German design house for analog mixed-signal IC design. This paper presents the results of a case study and introduces an optimized project scheduling on the basis of quality assessment results.

Analysis of Protein-Phenolic Compound Modifications Using Electrochemistry Coupled to Mass Spectrometry.

PubMed

Kallinich, Constanze; Schefer, Simone; Rohn, Sascha

2018-01-29

In the last decade, electrochemical oxidation coupled with mass spectrometry has been successfully used for the analysis of metabolic studies. The application focused in this study was to investigate the redox potential of different phenolic compounds such as the very prominent chlorogenic acid. Further, EC/ESI-MS was used as preparation technique for analyzing adduct formation between electrochemically oxidized phenolic compounds and food proteins, e.g., alpha-lactalbumin or peptides derived from a tryptic digestion. In the first step of this approach, two reactant solutions are combined and mixed: one contains the solution of the digested protein, and the other contains the phenolic compound of interest, which was, prior to the mixing process, electrochemically transformed to several oxidation products using a boron-doped diamond working electrode. As a result, a Michael-type addition led to covalent binding of the activated phenolic compounds to reactive protein/peptide side chains. In a follow-up approach, the reaction mix was further separated chromatographically and finally detected using ESI-HRMS. Compound-specific, electrochemical oxidation of phenolic acids was performed successfully, and various oxidation and reaction products with proteins/peptides were observed. Further optimization of the reaction (conditions) is required, as well as structural elucidation concerning the final adducts, which can be phenolic compound oligomers, but even more interestingly, quite complex mixtures of proteins and oxidation products.

Optical response of mixed methylammonium lead iodide and formamidinium tin iodide perovskite thin films

DOE PAGES

Ghimire, Kiran; Zhao, Dewei; Yan, Yanfa; ...

2017-07-13

Here, mixed tin (Sn) and lead (Pb) based perovskite thin films have been prepared by solution processing combining methylammonium lead iodide (MAPbI 3) and formamidinium tin iodide (FASnI 3) precursors. Optical response in the form of complex dielectric function (ε = ε 1 + iε 2) spectra and absorption coefficient (α) spectra of (FASnI 3) 1-x(MAPbI 3) x based perovskite films have been extracted over a spectral range 0.74 to 5.89 eV using spectroscopic ellipsometry. Absorption band edge energy changes as a function of composition for films including FASnI 3, MAPbI 3, and mixed x = 0.20, 0.35, 0.40, andmore » 0.6 (FASnI 3) 1-x(MAPbI 3) x perovskites. (FASnI 3) 0.60(MAPbI 3) 0.4 is found to have the minimum absorption band edge energy near ~1.2 eV.« less

A general method to determine sampling windows for nonlinear mixed effects models with an application to population pharmacokinetic studies.

PubMed

Foo, Lee Kien; McGree, James; Duffull, Stephen

2012-01-01

Optimal design methods have been proposed to determine the best sampling times when sparse blood sampling is required in clinical pharmacokinetic studies. However, the optimal blood sampling time points may not be feasible in clinical practice. Sampling windows, a time interval for blood sample collection, have been proposed to provide flexibility in blood sampling times while preserving efficient parameter estimation. Because of the complexity of the population pharmacokinetic models, which are generally nonlinear mixed effects models, there is no analytical solution available to determine sampling windows. We propose a method for determination of sampling windows based on MCMC sampling techniques. The proposed method attains a stationary distribution rapidly and provides time-sensitive windows around the optimal design points. The proposed method is applicable to determine sampling windows for any nonlinear mixed effects model although our work focuses on an application to population pharmacokinetic models. Copyright © 2012 John Wiley & Sons, Ltd.

Effect of mixing, concentration and temperature on the formation of mesostructured solutions and their role in the nucleation of DL-valine crystals.

PubMed

Jawor-Baczynska, Anna; Moore, Barry D; Sefcik, Jan

2015-01-01

We report investigations on the formation of mesostructured solutions in DL-valine-water-2-propanol mixtures, and the crystallization of DL-valine from these solutions. Mesostructured liquid phases, similar to those previously observed in aqueous solutions of glycine and DL-alanine, were observed using Dynamic Light Scattering and Brownian microscopy, in both undersaturated and supersaturated solutions below a certain transition temperature. Careful experimentation was used to demonstrate that the optically clear mesostructured liquid phase, comprising colloidal mesoscale clusters dispersed within bulk solution, is thermodynamically stable and present in equilibrium with the solid phase at saturation conditions. Solutions prepared by slow cooling contained mesoscale clusters with a narrow size distribution and a mean hydrodynamic diameter of around 200 nm. Solutions of identical composition prepared by rapid isothermal mixing of valine aqueous solutions with 2-propanol contained mesoscale clusters which were significantly larger than those observed in slowly cooled solutions. The presence of larger mesoscale clusters was found to correspond to faster nucleation. Observed induction times were strongly dependent on the rapid initial mixing step, although solutions were left undisturbed afterwards and the induction times observed were up to two orders of magnitude longer than the initial mixing period. We propose that mesoscale clusters above a certain critical size are likely to be the location of productive nucleation events.

Picoliter Drop-On-Demand Dispensing for Multiplex Liquid Cell Transmission Electron Microscopy

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

Patterson, Joseph P.; Parent, Lucas R.; Cantlon, Joshua

2016-05-03

Abstract Liquid cell transmission electron microscopy (LCTEM) provides a unique insight into the dynamics of nanomaterials in solution. Controlling the addition of multiple solutions to the liquid cell remains a key hurdle in our ability to increase throughput and to study processes dependent on solution mixing including chemical reactions. Here, we report that a piezo dispensing technique allows for mixing of multiple solutions directly within the viewing area. This technique permits deposition of 50 pL droplets of various aqueous solutions onto the liquid cell window, before assembly of the cell in a fully controlled manner. This proof-of-concept study highlights themore » great potential of picoliter dispensing in combination with LCTEM for observing nanoparticle mixing in the solution phase and the creation of chemical gradients.« less

Higher and lowest order mixed finite element approximation of subsurface flow problems with solutions of low regularity

NASA Astrophysics Data System (ADS)

Bause, Markus

2008-02-01

In this work we study mixed finite element approximations of Richards' equation for simulating variably saturated subsurface flow and simultaneous reactive solute transport. Whereas higher order schemes have proved their ability to approximate reliably reactive solute transport (cf., e.g. [Bause M, Knabner P. Numerical simulation of contaminant biodegradation by higher order methods and adaptive time stepping. Comput Visual Sci 7;2004:61-78]), the Raviart- Thomas mixed finite element method ( RT0) with a first order accurate flux approximation is popular for computing the underlying water flow field (cf. [Bause M, Knabner P. Computation of variably saturated subsurface flow by adaptive mixed hybrid finite element methods. Adv Water Resour 27;2004:565-581, Farthing MW, Kees CE, Miller CT. Mixed finite element methods and higher order temporal approximations for variably saturated groundwater flow. Adv Water Resour 26;2003:373-394, Starke G. Least-squares mixed finite element solution of variably saturated subsurface flow problems. SIAM J Sci Comput 21;2000:1869-1885, Younes A, Mosé R, Ackerer P, Chavent G. A new formulation of the mixed finite element method for solving elliptic and parabolic PDE with triangular elements. J Comp Phys 149;1999:148-167, Woodward CS, Dawson CN. Analysis of expanded mixed finite element methods for a nonlinear parabolic equation modeling flow into variably saturated porous media. SIAM J Numer Anal 37;2000:701-724]). This combination might be non-optimal. Higher order techniques could increase the accuracy of the flow field calculation and thereby improve the prediction of the solute transport. Here, we analyse the application of the Brezzi- Douglas- Marini element ( BDM1) with a second order accurate flux approximation to elliptic, parabolic and degenerate problems whose solutions lack the regularity that is assumed in optimal order error analyses. For the flow field calculation a superiority of the BDM1 approach to the RT0 one is observed, which however is less significant for the accompanying solute transport.

High-speed pulsed mixing in a short distance with high-frequency switching of pumping from three inlets

NASA Astrophysics Data System (ADS)

Sugano, K.; Nakata, A.; Tsuchiya, T.; Tabata, O.

2015-08-01

In this study, we propose a mixing method using alternate pulsed flows from three inlets with flow direction control. In conventional pulsed mixing, a residual flow near the sidewalls inhibits the rapid mixing of two solutions at high switching frequency. In this study, we addressed this issue in order to perform rapid mixing in a short distance with a low Reynolds number. We fabricated a microfluidic mixing device consisting of a cross-shaped mixing channel with three inlet microchannels and three valveless micropumps. In conventional T-shaped or Y-shaped mixing channels, a residual flow is observed because of the incomplete switching of solutions. The three inlet configuration enabled us to split the residual flow at a switching frequency of pumping of up to 200 Hz, thus resulting in rapid mixing. Furthermore, by controlling the flow direction at the confluent area using the reverse flow of the micropump, the mixing speed was dramatically increased because of the complete switching of the two solutions. As a result, we achieved the mixing time of 3.6 ms and the mixing length of 20.7 µm, which were necessary to achieve a 90% mixing ratio at a high micropump switching frequency of 400 Hz and reverse flow ratio of 1/4.

Enhanced Antimicrobial Activity Of Antibiotics Mixed With Metal Nanoparticles

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Kumar, Neeraj; Bhanjana, Gaurav; Thakur, Rajesh; Dilbaghi, Neeraj

2011-12-01

Current producers of antimicrobial technology have a long lasting, environmentally safe, non-leaching, water soluble solution that will eventually replace all poisons and heavy metals. The transition metal ions inevitably exist as metal complexes in biological systems by interaction with the numerous molecules possessing groupings capable of complexation or chelation. Nanoparticles of metal oxides offer a wide variety of potential applications in medicine due to the unprecedented advances in nanobiotechnology research. the bacterial action of antibiotics like penicillin, erythryomycin, ampicillin, streptomycin, kanamycin etc. and that of a mixture of antibiotics and metal and metal oxide nanoparticles like zinc oxide, zirconium, silver and gold on microbes was examined by the agar-well-diffusion method, enumeration of colony-forming units (CFU) and turbidimetry.

Association of riboflavin, caffeine, and sodium salicylate in aqueous solution

NASA Astrophysics Data System (ADS)

Baranovskii, S. F.; Bolotin, P. A.

2007-03-01

We have used UV and visible spectrophotometry to study self-association of aromatic riboflavin molecules (RFN, vitamin B2, 7,8-dimethyl-10-N-(1'-D-ribityl)isoalloxazine) in aqueous solution (pH 6.86) at T = 298 K, using a dimer model. We have determined the equilibrium dimerization constant for riboflavin, KdB = 125 ± 40 M-1. We have studied heteroassociation in the system of molecules of 7,8-dimethyl-10-ribitylisoalloxazine with 1,3,7-trimethylxanthine (caffeine) and sodium salicylate (NAS) in aqueous solution (pH 6.86; T = 298 K). We have determined the heteroassociation constants for RFN-NAS and RFN-caffeine molecules in the absence and in the presence of urea in solutions using a modified Benesi-Hildebrand equation: 25 ± 4, 17 ± 3, and 74 ± 11, 53 ± 7 M-1 respectively. We have determined the dimerization constants for NAS (2.7 ± 0.5 M-1) and caffeine (17.0 ± 1.5 M-1). We conclude that heteroassociation of the aromatic molecules leads to a lower effective riboflavin concentration in solution, and the presence of urea in mixed solutions leads to an decrease in the complexation constants for the RFN-NAS and RFN-caffeine systems.

Simulation of acid mine drainage generation around Küre VMS Deposits, Northern Turkey

NASA Astrophysics Data System (ADS)

Demirel, Cansu; Kurt, Mehmet Ali; Çelik Balci, Nurgül

2015-04-01

This study investigated comparative leaching characteristics of acidophilic bacterial strains under shifting environmental conditions at proposed two stages as formation stage or post acidic mine drainage (AMD) generation. At the first stage, initial reactions associated with AMD generation was simulated in shaking flasks containing massive pyritic chalcopyrite ore by using a pure strain Acidithiobacillus ferrooxidans and a mixed culture of Acidithiobacillus sp. mostly dominated by A. ferrooxidans and A. thiooxidans at 26oC. At the second stage, long term bioleaching experiments were carried out with the same strains at 26oC and 40oC to investigate the leaching characteristics of pyritic chalcopyrite ore under elevated heavy metal and temperature conditions. During the experiments, physicochemical characteristics (e.i. Eh, pH, EC) metal (Fe, Co, Cu, Zn) and sulfate concentration of the experimental solution were monitored during 180 days. Significant acid generation and sulfate release were determined during bioleaching of the ore by mixed acidophilic cultures containing both iron and sulfur oxidizers. In the early stage of the experiments, heavy metal release from the ore was caused by generation of acid due to accelerated bacterial oxidation of the ore. Generally high concentrations of Co and Cu were released into the solution from the experiments conducted by pure cultures of Acidithiobacillus ferrooxidans whereas high Zn and Fe was released into the solution from the mixed culture experiments. In the later stage of AMD generation and post AMD, chemical oxidation is accelerated causing excessive amounts of contamination, even exceeding the amounts resulted from bacterial oxidation by mixed cultures. Acidithibacillus ferrooxidans was found to be more effective in leaching Cu, Fe and Co at higher temperatures in contrary to mixed acidophiles that are more prone to operate at optimal moderate conditions. Moreover, decreasing Fe values are noted in bioleaching experiments with mixed acidophiles at higher temperatures. Further depleted Fe(III) values coinciding with decreasing pH may point to precipitation of secondary phases (i.e. jarosite). This study revealed that the metals (Fe, Cu, Co and Zn) released during short term leaching of the ore (34 days) are generally caused by acid produced by dissolution reactions rather than oxidation. In the long term experiments a more complex biogeochemical reactions (oxidation and dissolution) take place in conjunction. Key words: Bioleaching, AMD, heavy metal release, environment, acidophilic bacteria, Küre copper ore deposits, volcanogenic massive sulfide deposits

Complex analysis of concentrated antibody-gold nanoparticle conjugates' mixtures using asymmetric flow field-flow fractionation.

PubMed

Safenkova, Irina V; Slutskaya, Elvira S; Panferov, Vasily G; Zherdev, Anatoly V; Dzantiev, Boris B

2016-12-16

Conjugates of gold nanoparticles (GNPs) with antibodies are powerful analytical tools. It is crucial to know the conjugates' state in both the concentrated and mixed solutions used in analytical systems. Herein, we have applied asymmetrical flow field-flow fractionation (AF4) to identify the conjugates' state. The influence of a conjugate's composition and concentration on aggregation was studied in a true analytical solution (a concentrated mixture with stabilizing components). GNPs with an average diameter of 15.3±1.2nm were conjugated by adsorption with eight antibodies of different specificities. We found that, while the GNPs have a zeta potential of -31.6mV, the conjugates have zeta potentials ranging from -5.8 to -11.2mV. Increased concentrations (up to 184nM, OD 520 =80) of the mixed conjugate (mixture of eight conjugates) did not change the form of fractograms, and the peak areas' dependence on concentration was strongly linear (R 2 values of 0.99919 and 0.99845 for absorption signal and light scattering, respectively). Based on the gyration (R g ) and hydrodynamic (R h ) radii measured during fractionation, we found that the nanoparticles were divided into two populations: (1) those with constant radii (R g =9.9±0.9nm; R h =14.3±0.5nm); and (2) those with increased radii from 9.9 to 24.4nm for R g and from 14.3 to 28.1nm for R h . These results confirm that the aggregate state of the concentrated and mixed conjugates' preparations is the same as that of diluted preparations and that AF4 efficiently characterizes the conjugates' state in a true analytical solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

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

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

Bismuth(III) 5-sulfosalicylate complexes: structure, solubility and activity against Helicobacter pylori.

PubMed

Andrews, Philip C; Deacon, Glen B; Ferrero, Richard L; Junk, Peter C; Karrar, Abdulgader; Kumar, Ish; MacLellan, Jonathan G

2009-08-28

Treatment of 5-sulfosalicylic acid (H(3)Ssal) with BiPh(3) results in the formation of the first dianionic carboxylate-sulfonate bismuth complex, [PhBi(HSsal)H(2)O](infinity) 1a, and its ethanol analogue [PhBi(HSsal)EtOH](infinity) 1b (space group P2(1)/c), while Bi(OAc)(3) gives the mixed monoanionic and dianionic complex, {[Bi(HSsal)(H(2)Ssal)(H(2)O)(3)](2) x 2 H(2)O}(infinity) 2 (space group P1). The three complexes are all polymeric in the solid state as determined by single crystal X-ray diffraction, with extended frameworks constructed from dimeric [Bi(HSsal)](2), 1a and 1b, or from [Bi(HSsal)(H(2)Ssal)](2) units, 2. The heteroleptic bismuth complexes 1a and 2 display remarkable aqueous solubility, 10 and 2.5 mg ml(-1) respectively, resulting in a clear solution of pH 1.5. In contrast, 1b is essentially insoluble in aqueous environments. All three complexes show significant activity against the bacterium Helicobacter pylori of <6.25 microg ml(-1).

Solvent influence on complex formation between Cd2+ and 2-hydroxy-1,4-naphthoquinone in binary mixed nonaqueous solvents at 15-45°C

NASA Astrophysics Data System (ADS)

Farazandeh, R.; Rounaghi, G. H.; Ebrahimi, M.; Basafa, S.

2017-04-01

The complexation reaction of Cd2+ cation with 2-hydroxy-1,4-naphthoquinone (HNQ) was studied in acetonitrile (AN), 2-PrOH, ethyl acetate (EtOAc), EtOH, dimethylformamide (DMF) and in binary solutions AN-2-PrOH, AN-DMF, AN-EtOH, and AN-EtOAc using conductometric method at 15-45°C. The conductance data show that the stoichiometry of the Cd2+ complex with HNQ in all solvent systems is 1 : 1. In the pure solvents the stability of the complex changes in the order AN > 2-PrOH > EtOH > DMF. The stability of the complex at 25°C in the studied mixtures changes in the following order : AN-EtOAc > AN-2-PrOH > AN-EtOH > AN-DMF. These orders are affected by the nature and composition of the solvent systems and by the temperature. From the temperature dependence data, the thermodynamic functions values (Δ H° and Δ S°) for the complex formation were calculated.

Automatic Design of Synthetic Gene Circuits through Mixed Integer Non-linear Programming

PubMed Central

Huynh, Linh; Kececioglu, John; Köppe, Matthias; Tagkopoulos, Ilias

2012-01-01

Automatic design of synthetic gene circuits poses a significant challenge to synthetic biology, primarily due to the complexity of biological systems, and the lack of rigorous optimization methods that can cope with the combinatorial explosion as the number of biological parts increases. Current optimization methods for synthetic gene design rely on heuristic algorithms that are usually not deterministic, deliver sub-optimal solutions, and provide no guaranties on convergence or error bounds. Here, we introduce an optimization framework for the problem of part selection in synthetic gene circuits that is based on mixed integer non-linear programming (MINLP), which is a deterministic method that finds the globally optimal solution and guarantees convergence in finite time. Given a synthetic gene circuit, a library of characterized parts, and user-defined constraints, our method can find the optimal selection of parts that satisfy the constraints and best approximates the objective function given by the user. We evaluated the proposed method in the design of three synthetic circuits (a toggle switch, a transcriptional cascade, and a band detector), with both experimentally constructed and synthetic promoter libraries. Scalability and robustness analysis shows that the proposed framework scales well with the library size and the solution space. The work described here is a step towards a unifying, realistic framework for the automated design of biological circuits. PMID:22536398

Thermodynamic Parameters of the Dissolution of 4-Hydroxy-L-Proline and L-Phenylalanine in Mixed Aqueous Solvents at 298 K

NASA Astrophysics Data System (ADS)

Smirnov, V. I.; Badelin, V. G.

2018-01-01

The enthalpies of solution of 4-hydroxy-L-proline and L-phenylalanine in binary mixed aqueous solvents containing acetonitrile (AN), 1,4-dioxane (1,4-DO), or acetone (AC) at mole fractions of 0 to 0.25 are determined at T = 298.15 K via isothermal calorimetry. The standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of 4-hydroxy-L-proline and L-phenylalanine from water to mixed aqueous solvents are calculated using the experimental calorimetric data, as are the enthalpy coefficients of paired interactions ( h xy ) between the molecules of the investigated amino acids and the organic solvents. The effects the mixed aqueous solvent composition and the structure of the organic solvent molecules have on the enthalpies of solution and transfer for the investigated amino acids are considered. The correlation between the enthalpy of solution of the amino acids and the electron-donating properties of the organic solvents in the mixed aqueous solvent systems is established.

Using mixed methods to develop and evaluate complex interventions in palliative care research.

PubMed

Farquhar, Morag C; Ewing, Gail; Booth, Sara

2011-12-01

there is increasing interest in combining qualitative and quantitative research methods to provide comprehensiveness and greater knowledge yield. Mixed methods are valuable in the development and evaluation of complex interventions. They are therefore particularly valuable in palliative care research where the majority of interventions are complex, and the identification of outcomes particularly challenging. this paper aims to introduce the role of mixed methods in the development and evaluation of complex interventions in palliative care, and how they may be used in palliative care research. the paper defines mixed methods and outlines why and how mixed methods are used to develop and evaluate complex interventions, with a pragmatic focus on design and data collection issues and data analysis. Useful texts are signposted and illustrative examples provided of mixed method studies in palliative care, including a detailed worked example of the development and evaluation of a complex intervention in palliative care for breathlessness. Key challenges to conducting mixed methods in palliative care research are identified in relation to data collection, data integration in analysis, costs and dissemination and how these might be addressed. the development and evaluation of complex interventions in palliative care benefit from the application of mixed methods. Mixed methods enable better understanding of whether and how an intervention works (or does not work) and inform the design of subsequent studies. However, they can be challenging: mixed method studies in palliative care will benefit from working with agreed protocols, multidisciplinary teams and engaging staff with appropriate skill sets.

Superlubricity of a Mixed Aqueous Solution

NASA Astrophysics Data System (ADS)

Ma, Zhi-Zuo; Zhang, Chen-Hui; Luo, Jian-Bin; Lu, Xin-Chun; Wen, Shi-Zhu

2011-05-01

A super-low friction coefficient of 0.0028 is measured under a pressure of 300 MPa when the friction pair (the silicon nitride ball sliding on the silicate glass) is lubricated by the mixed aqueous solution of glycerol and boric acid. The morphorlogies of the hydroxylated glass plate are observed by an atomic force microscope (AFM) in deionized water, glycerol, boric acid and their mixed aqueous solution. Bonding peaks of the retained liquids adhered on the surface of the sliding track are detected by an infrared spectrum apparatus and a Raman spectrum apparatus. The mechanism of the superlubricity of the glycerol and boric acid mixed aqueous solution is discussed. It is deduced that the formation of the lubricant film has enough strength to support higher loads, the hydration effect offering the super lower shear resistance. Key words: superlubricity, water based lubricant, ultra-low friction

CFD study of mixing miscible liquid with high viscosity difference in a stirred tank

NASA Astrophysics Data System (ADS)

Madhania, S.; Cahyani, A. B.; Nurtono, T.; Muharam, Y.; Winardi, S.; Purwanto, W. W.

2018-03-01

The mixing process of miscible liquids with high viscosity difference is crucial role even though the solution mutually dissolved. This paper describes the mixing behaviour of the water-molasses system in a conical-bottomed cylindrical stirred tank (D = 0.28 m and H = 0.395 m) equipped with a side-entry Marine propeller (d = 0.036 m) under the turbulence regime using a three-dimensional and transient CFD-simulation. The objective of this work is to compare the solution strategies was applied in the computational analysis to capture the detail phenomena of mixing two miscible liquid with high viscosity difference. Four solution strategies that have been used are the RANS Standards k-ε (SKE) model as the turbulence model coupled with the Multiple Reference Frame (MRF) method for impeller motion, the RANS Realizable k-ε (RKE) combine with the MRF, the Large Eddy Simulation (LES) coupled with the Sliding Mesh (SM) method and the LES-MRF combination. The transient calculations were conducted with Ansys Fluent 17.1 version. The mixing behaviour and the propeller characteristic are to be compared and discussed in this work. The simulation results show the differences of flow pattern and the molasses distribution profile for every solution strategy. The variation of the flow pattern which happened in each solution strategy showing an instability of the mixing process in stirred tank. The LES-SM strategy shows the realistic direction of flow than another solution strategies.

Arsenic in hydrothermal apatite: Oxidation state, mechanism of uptake, and comparison between experiments and nature

NASA Astrophysics Data System (ADS)

Liu, Weihua; Mei, Yuan; Etschmann, Barbara; Brugger, Joël; Pearce, Mark; Ryan, Chris G.; Borg, Stacey; Wykes, Jeremey; Kappen, Peter; Paterson, David; Boesenberg, Ulrike; Garrevoet, Jan; Moorhead, Gareth; Falkenberg, Gerald

2017-01-01

Element substitution that occurs during fluid-rock interaction permits assessment of fluid composition and interaction conditions in ancient geological systems, and provides a way to fix contaminants from aqueous solutions. We conducted a series of hydrothermal mineral replacement experiments to determine whether a relationship can be established between arsenic (As) distribution in apatite and fluid chemistry. Calcite crystals were reacted with phosphate solutions spiked with As(V), As(III), and mixed As(III)/As(V) species at 250 °C and water-saturated pressure. Arsenic-bearing apatite rims formed in several hours, and within 48 h the calcite grains were fully replaced. X-ray Absorption Near-edge Spectroscopy (XANES) data show that As retained the trivalent oxidation state in the fully-reacted apatite grown from solutions containing only As(III). Extended X-ray Fine Spectroscopy (EXAFS) data reveal that these As(III) ions are surrounded by about three oxygen atoms at an Assbnd O bond length close to that of an arsenate group (AsO43-), indicating that they occupy tetrahedral phosphate sites. The three-coordinated As(III)-O3 structure, with three oxygen atoms and one lone electron pair around As(III), was confirmed by geometry optimization using ab initio molecular simulations. The micro-XANES imaging data show that apatite formed from solutions spiked with mixed As(III) and As(V) retained only As(V) after completion of the replacement reaction; in contrast, partially reacted samples revealed a complex distribution of As(V)/As(III) ratios, with As(V) concentrated in the center of the grain and As(III) towards the rim. Most natural apatites from the Ernest Henry iron oxide copper gold deposit, Australia, show predominantly As(V), but two grains retained some As(III) in their core. The As-anomalous amphibolite-facies gneiss from Binntal, Switzerland, only revealed As(V), despite the fact that these apatites in both cases formed under conditions where As(III) is expected to be the dominant As form in hydrothermal fluids. These results show that incorporation of As in apatite is a complicated process, and sensitive to the local fluid composition during crystallization, and that some of the complexity in As zoning in partially reacted apatite may be due to local fluctuations of As(V)/As(III) ratios in the fluid and to kinetic effects during the mineral replacement reaction. Our study shows for the first time that As(III) can be incorporated into the apatite structure, although not as efficiently as As(V). Uptake of As(III) is probably highly dependent on the reaction mechanism. As(III)O33- moieties replace phosphate groups, but cause a high strain on the lattice; as a result, As(III) is easily exchanged (or oxidized) for As(V) during hydrothermal recrystallization, and the fully reacted grains only record the preferred oxidation state (i.e., As(V)) from mixed-oxidation state solutions. Overall this study shows that the observed oxidation state of As in apatite may not reflect the original As(III)/As(V) ratio of the parent fluid, due to the complex nature of As(III) uptake and possible in situ oxidation during recrystallization.

How Does a Hydrophobic Macromolecule Respond to Mixed Osmolyte Environment?

PubMed

Tah, Indrajit; Mondal, Jagannath

2016-10-04

The role of the protecting osmolyte Trimethyl N-oxide (TMAO) in counteracting the denaturing effect of urea on a protein is quite well established. However, the mechanistic role of osmolytes on the hydrophobic interaction underlying protein folding is a topic of contention and is emerging as a key area of biophysical interest. Although recent experiment and computer simulation have established that individual aqueous solution of TMAO and urea respectively stabilizes and destabilizes the collapsed conformation of a hydrophobic polymer, it remains to be explored how a mixed aqueous solution of protecting and denaturing osmolytes influences the conformations of the polymer. In order to bridge the gap, we have simulated the conformational behavior of both a model hydrophobic polymer and a synthetic polymer polystyrene in an aqueous mixture of TMAO and urea. Intriguingly, our free energy based simulations on both the systems show that even though a pure aqueous solution of TMAO stabilizes the collapsed or globular conformation of the hydrophobic polymer, addition of TMAO to an aqueous solution of urea further destabilizes the collapsed conformation of the hydrophobic polymer. We also observe that the extent of destabilization in a mixed osmolyte solution is relatively higher than that in pure aqueous urea solution. The reinforcement of the denaturation effect of the hydrophobic macromolecule in a mixed osmolyte solution is in stark contrast to the well-known counteracting role of TMAO in proteins under denaturing condition of urea. In both model and realistic systems, our results show that in a mixed aqueous solution, greater number of cosolutes preferentially bind to the extended conformation of the polymer relative to that in the collapsed conformation, thereby complying with Tanford-Wyman preferential solvation theory disfavoring the collapsed conformation. The results are robust across a range of osmolyte concentrations and multiple cosolute forcefields. Our findings unequivocally imply that the action of mixed osmolyte solution on hydrophobic polymer is significantly distinct from that of proteins.

Numerical Technology for Large-Scale Computational Electromagnetics

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

Sharpe, R; Champagne, N; White, D

The key bottleneck of implicit computational electromagnetics tools for large complex geometries is the solution of the resulting linear system of equations. The goal of this effort was to research and develop critical numerical technology that alleviates this bottleneck for large-scale computational electromagnetics (CEM). The mathematical operators and numerical formulations used in this arena of CEM yield linear equations that are complex valued, unstructured, and indefinite. Also, simultaneously applying multiple mathematical modeling formulations to different portions of a complex problem (hybrid formulations) results in a mixed structure linear system, further increasing the computational difficulty. Typically, these hybrid linear systems aremore » solved using a direct solution method, which was acceptable for Cray-class machines but does not scale adequately for ASCI-class machines. Additionally, LLNL's previously existing linear solvers were not well suited for the linear systems that are created by hybrid implicit CEM codes. Hence, a new approach was required to make effective use of ASCI-class computing platforms and to enable the next generation design capabilities. Multiple approaches were investigated, including the latest sparse-direct methods developed by our ASCI collaborators. In addition, approaches that combine domain decomposition (or matrix partitioning) with general-purpose iterative methods and special purpose pre-conditioners were investigated. Special-purpose pre-conditioners that take advantage of the structure of the matrix were adapted and developed based on intimate knowledge of the matrix properties. Finally, new operator formulations were developed that radically improve the conditioning of the resulting linear systems thus greatly reducing solution time. The goal was to enable the solution of CEM problems that are 10 to 100 times larger than our previous capability.« less

HYDRAULICS AND MIXING EVALUATIONS FOR NT-21/41 TANKS

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

Lee, S.; Barnes, O.

2014-11-17

The hydraulic results demonstrate that pump head pressure of 20 psi recirculates about 5.6 liters/min flowrate through the existing 0.131-inch orifice when a valve connected to NT-41 is closed. In case of the valve open to NT-41, the solution flowrates to HB-Line tanks, NT-21 and NT-41, are found to be about 0.5 lpm and 5.2 lpm, respectively. The modeling calculations for the mixing operations of miscible fluids contained in the HB-Line tank NT-21 were performed by taking a three-dimensional Computational Fluid Dynamics (CFD) approach. The CFD modeling results were benchmarked against the literature results and the previous SRNL test resultsmore » to validate the model. Final performance calculations were performed for the nominal case by using the validated model to quantify the mixing time for the HB-Line tank. The results demonstrate that when a pump recirculates a solution volume of 5.7 liters every minute out of the 72-liter tank contents containing two acid solutions of 2.7 M and 0 M concentrations (i.e., water), a minimum mixing time of 1.5 hours is adequate for the tank contents to get the tank contents adequately mixed. In addition, the sensitivity results for the tank contents of 8 M existing solution and 1.5 M incoming species show that the mixing time takes about 2 hours to get the solutions mixed.« less

(Zr,Ti)O2 interface structure in ZrO2-TiO2 nanolaminates with ultrathin periodicity

NASA Astrophysics Data System (ADS)

Aita, C. R.; DeLoach, J. D.; Yakovlev, V. V.

2002-07-01

A mixed cation interfacial structure in ZrO2-TiO2 nanolaminate films with ultrathin bilayer periodicity grown by sputter deposition at 297 K was identified by x-ray diffraction and nonresonant Raman spectroscopy. This structure consists of an amorphous phase at a ZrO2-on-TiO2 bilayer interface, followed by an extensive crystalline monoclinic (Zr,Ti)O2 solid solution predicted by Vegard's law. Monoclinic (Zr,Ti)O2 has previously been reported only once, in bulk powder of a single composition (ZrTiO4) at high pressure. Its stabilization in the nanolaminates is explained by the Gibbs-Thomson effect. This complex interfacial structure is shown to be a means of accommodating chemical mixing in the absence of a driving force for heteroepitaxy.

Fabrication of three-dimensional helical microchannels with arbitrary length and uniform diameter inside fused silica.

PubMed

He, Shengguan; Chen, Feng; Liu, Keyin; Yang, Qing; Liu, Hewei; Bian, Hao; Meng, Xiangwei; Shan, Chao; Si, Jinhai; Zhao, Yulong; Hou, Xun

2012-09-15

We demonstrate an improved femtosecond laser irradiation followed by chemical etching process to create complex three-dimensional (3D) microchannels with arbitrary length and uniform diameter inside fused silica. A segmented chemical etching method of introducing extra access ports and a secondary power compensation is presented, which enables the fabrication of uniform 3D helical microchannels with length of 1.140 cm and aspect-ratio of 522. Based on this method, a micromixer which consists of a long helical microchannel and a y-tape microchannel was created inside the fused silica. We measured the mixing properties of the micromixer by injecting the phenolphthalein and NaOH solution through the two inlets of the y-tape microchannel. A rapid and efficient mixing was achieved in the 3D micromixer at a low Reynolds number.

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

NASA Astrophysics Data System (ADS)

Usher, Al; McPhail, D. C.; Brugger, Joël

2009-06-01

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0.05. The results of our study increase the understanding of gold aqueous geochemistry, with the potential to lead to new methods for mineral exploration, hydrometallurgy and medicine.

Ligand protons in a frozen solution of copper histidine relax via a T1e-driven three-spin mechanism

NASA Astrophysics Data System (ADS)

Stoll, S.; Epel, B.; Vega, S.; Goldfarb, D.

2007-10-01

Davies electron-nuclear double resonance spectra can exhibit strong asymmetries for long mixing times, short repetition times, and large thermal polarizations. These asymmetries can be used to determine nuclear relaxation rates in paramagnetic systems. Measurements of frozen solutions of copper(L-histidine)2 reveal a strong field dependence of the relaxation rates of the protons in the histidine ligand, increasing from low (g‖) to high (g⊥) field. It is shown that this can be attributed to a concentration-dependent T1e-driven relaxation process involving strongly mixed states of three spins: the histidine proton, the Cu(II) electron spin of the same complex, and another distant electron spin with a resonance frequency differing from the spectrometer frequency approximately by the proton Larmor frequency. The protons relax more efficiently in the g⊥ region, since the number of distant electrons able to participate in this relaxation mechanism is higher than in the g‖ region. Analytical expressions for the associated nuclear polarization decay rate Teen-1 are developed and Monte Carlo simulations are carried out, reproducing both the field and the concentration dependences of the nuclear relaxation.

Evolutions and equilibrium parameters of foam films from individual solutions of Bovine serum albumin, n-dodecyl-β-D-maltoside and from their mixed solutions

NASA Astrophysics Data System (ADS)

Gerasimova, Anelia Tsvetanova; Angarska, Jana Krumova; Tachev, Krasimir Dimov

2017-03-01

The evolutions of thinning of films from individual solutions of BSA, C12G2 and from their mixed solutions with molar ratios 1:1, 1:7.5, 1:50 and 1:100 with pH = 4.9 were recorded by modified (with video camera) interferometric method. Based on them the stages through which the film goes from its formation to the equilibrium state were distinguished. It was shown that: (i) the difference between the kinetic of drainage of films stabilized by high and low molecular surfactants is drastic; (ii) only the change of the pH solution under or above isoelectric point strongly retards the film drainage; (iii) the transition of the kinetic of thinning of films from mixed solutions from a kinetic typical for high molecular substances towards a kinetic for low substances depends on the molar ratio between the components in the solution. From the picture of film corresponding to its equilibrium state the type of film was determined. From the analysis of this picture the equilibrium thickness and contact angle were calculated. It was found that the criterion for Newtonium black films (based on the values of film thickness and contact angle) is not directly applicable for films from protein solutions or mixed solutions with the participation of proteins.

Toxicological evaluation of the effects of waste-to-energy ash-concrete on two marine species

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

Hamilton, K.L.; Nelson, W.G.; Curley, J.L.

1993-10-01

The toxicological effects of waste-to-energy ash-concrete on survivorship, growth, and fecundity (end-point parameters) of Mysidopsis bahia and on survivorship and growth of Menidia beryllina were evaluated with the 7-d static-renewal toxicity test. Leachate and elutriate solutions were prepared from experimental ash-concrete test cylinders constructed from concrete with additions of either bottom ash (mix BA), mixed bottom ash and scrubber residue, or mixed bottom ash and fly ash (60:40%, mix BA:FA). Control experiments with concrete (without ash) and pH (7-9.5) were conducted to assess any toxic effects of the stabilization process. pH did not affect end-point parameters of Mysidopsis bahia ormore » Menidia beryllina. However, the 100% elutriate solution made from concrete reduced survivorship of Mysidopsis bahia. For experiments with ash-concrete test cylinders with the BA mixture, 10-d leachate solution reduced survivorship of Mysidopsis bahia and the 100% elutriate solutions reduced survivorship of Mysidopsis bahia and Manidia beryllina. With the BA:SR mixture, the 100 and 50% elutriate solutions reduced survivorship of Menidia beryllina. The BA:FA 10- and 5-d leachate solutions and the 100, 50, and 25% elutriate solutions reduced survivorship of Menidia beryllina. The BA:FA 10- and 5-d leachate solutions and the 100, 50, 25% elutriate solutions reduced survivorship of Mysidopsis bahia.« less

Options for refractive index and viscosity matching to study variable density flows

NASA Astrophysics Data System (ADS)

Clément, Simon A.; Guillemain, Anaïs; McCleney, Amy B.; Bardet, Philippe M.

2018-02-01

Variable density flows are often studied by mixing two miscible aqueous solutions of different densities. To perform optical diagnostics in such environments, the refractive index of the fluids must be matched, which can be achieved by carefully choosing the two solutes and the concentration of the solutions. To separate the effects of buoyancy forces and viscosity variations, it is desirable to match the viscosity of the two solutions in addition to their refractive index. In this manuscript, several pairs of index matched fluids are compared in terms of viscosity matching, monetary cost, and practical use. Two fluid pairs are studied in detail, with two aqueous solutions (binary solutions of water and a salt or alcohol) mixed into a ternary solution. In each case: an aqueous solution of isopropanol mixed with an aqueous solution of sodium chloride (NaCl) and an aqueous solution of glycerol mixed with an aqueous solution of sodium sulfate (Na_2SO_4). The first fluid pair allows reaching high-density differences at low cost, but brings a large difference in dynamic viscosity. The second allows matching dynamic viscosity and refractive index simultaneously, at reasonable cost. For each of these four solutes, the density, kinematic viscosity, and refractive index are measured versus concentration and temperature, as well as wavelength for the refractive index. To investigate non-linear effects when two index-matched, binary solutions are mixed, the ternary solutions formed are also analyzed. Results show that density and refractive index follow a linear variation with concentration. However, the viscosity of the isopropanol and NaCl pair deviates from the linear law and has to be considered. Empirical correlations and their coefficients are given to create index-matched fluids at a chosen temperature and wavelength. Finally, the effectiveness of the refractive index matching is illustrated with particle image velocimetry measurements performed for a buoyant jet in a linearly stratified environment. The creation of the index-matched solutions and linear stratification in a large-scale experimental facility are detailed, as well as the practical challenges to obtain precise refractive index matching.

A Generalized Deduction of the Ideal-Solution Model

ERIC Educational Resources Information Center

Leo, Teresa J.; Perez-del-Notario, Pedro; Raso, Miguel A.

2006-01-01

A new general procedure for deriving the Gibbs energy of mixing is developed through general thermodynamic considerations, and the ideal-solution model is obtained as a special particular case of the general one. The deduction of the Gibbs energy of mixing for the ideal-solution model is a rational one and viewed suitable for advanced students who…

New influence factor inducing difficulty in selective flotation separation of Cu-Zn mixed sulfide minerals

NASA Astrophysics Data System (ADS)

Deng, Jiu-shuai; Mao, Ying-bo; Wen, Shu-ming; Liu, Jian; Xian, Yong-jun; Feng, Qi-cheng

2015-02-01

Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satisfactory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mechanisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions released from the ancient fluids reached 1.02 × 10-6 mol/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 × 10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.

Optimisation of spray-drying process variables for dry powder inhalation (DPI) formulations of corticosteroid/cyclodextrin inclusion complexes.

PubMed

Cabral-Marques, Helena; Almeida, Rita

2009-09-01

This study aims to develop and characterise a beclomethasone diproprionate:gamma-cyclodextrin (BDP:gamma-CYD) complex and to optimise the variables on the spray-drying process, in order to obtain a powder with the most suitable characteristics for lung delivery. The spray-dried powder--in a mass ratio of 2:5 (BDP:gamma-CYD)--was physically mixed with three carriers of different particle sizes and in different ratios. Particle-size distribution, shape and morphology, moisture content, and uniformity in BDP content of formulations were studied. In vitro aerolisation behaviour of the formulations was evaluated using the Rotahaler, and the performance was characterised based on the uniformity of emitted dose and aerodynamic particle-size distribution (respirable fraction (RF), as a percentage of nominal dose (RFN) and emitted dose (RFE)). The most suitable conditions for the preparation of BDP:gamma-CYD complexes were obtained with the solution flow of 5 ml/min, T(in) of 70 degrees C and T(out) of 50 degrees C. Statistically significant differences in the aerodynamic performances were obtained for formulations containing BDP:gamma-CYD complexes prepared using different solution flows and different T(in) (p<0.05). RFN and RFE vary in direct proportion with T(in), while an inverse relationship was observed for the solution flow. A direct correlation between the RFE and the T(out) was identified. Performance of the formulations was compared with an established commercial product (Beclotaide Rotacaps 100 microg) with improved performance of RF: formulations with respitose carrier attained RFN and RFE twofold greater, and formulations based on 63-90 microm fraction lactose and trehalose achieved a threefold improvement; also, all formulations showed that the percentage of dose of BDP deposited in the "oropharynx" compartment was reduced to half.

Contrasting coordination behavior of Group 12 perchlorate salts with an acyclic N3O2 donor ligand by X-ray crystallography and (1)H NMR.

PubMed

Tice, Daniel B; Pike, Robert D; Bebout, Deborah C

2016-08-09

An unbranched N3O2 ligand 2,6-bis[((2-pyridinylmethyl)oxy)methyl]pyridine (L1) was used to prepare new mononuclear heteroleptic Group 12 perchlorate complexes characterized by IR, (1)H NMR and X-ray crystallography. Racemic complexes with pentadentate L1 and one to four oxygens from either water or perchlorate bound to a metal ion were structurally characterized. Octahedral [Zn(L1)(OH2)](ClO4)2 (1) and pentagonal bipyramidal [Cd(L1)(OH2)(OClO3)]ClO4 (2) structures were found with lighter congeners. The polymorphic forms of [Hg(L1)(ClO4)2] characterized (3 in P1[combining macron] and 4 in P21/c) had a mix of monodentate, anisobidentate and bidentate perchlorates, providing the first examples of a tricapped trigonal prismatic Hg(ii) coordination geometry, as well as additional examples of a rare square antiprismatic Hg(ii) coordination geometry. Solution state (1)H NMR characterization of the Group 12 complexes in CD3CN indicated intramolecular reorganization remained rapid under conditions where intermolecular M-L1 exchange was slow on the chemical shift time scale for Zn(ii) and on the J(M(1)H) time scale for Cd(ii) and Hg(ii). Solution studies with more than one equivalent of ligand also suggested that a complex with a 1 : 2 ratio of M : L1 contributed significantly to solution equilibria with Hg(ii) but not the other metal ions. The behavior of related linear pentadentate ligands with Group 12 perchlorate salts is discussed.

Multicomponent Oxide Systems for Corrosion Protection.

DTIC Science & Technology

1980-11-15

hydroxides on film growth. New types of mixed oxide coatings deposited from nonaqueous solutions of organometallic compounds were developed. Titanium -aluminum...mixed oxide coatings, deposited from solutions of titanium alkoxides in isopropanol, served as a prototype system for much of this work. It was found...45 13. Coating Steps and Analysis... ...................... 50 14. Auger Depth Profiles of Titanium -Aluminum Mixed Oxide *Coatings Deposited

Synthesis and characterization of homo- and heterobimetallic niobium v and tantalum v peroxo-polyaminocarboxylato complexes and their use as single or multiple molecular precursors for Nb-Ta mixed oxides

NASA Astrophysics Data System (ADS)

Bayot, Daisy; Degand, Matthieu; Devillers, Michel

2005-09-01

New water-soluble bimetallic peroxo complexes of niobium V and/or tantalum V with high-denticity polyaminocarboxylate ligands have been prepared, characterized from the spectroscopic point of view, and used as molecular precursors for Nb-Ta mixed oxides. Four new homobimetallic complexes, (gu) 3[Nb 2(O 2) 4(dtpaO 3)]·3H 2O 1, (gu) 3[Ta 2(O 2) 4(dtpaO 3)]·5H 2O 2, (gu) 3[Nb 2(O 2) 4(HtthaO 4)]·2H 2O 4 and (gu) 3[Ta 2(O 2) 4(HtthaO 4)]·3H 2O 5 and the corresponding heterometallic complexes, (gu) 3[NbTa(O 2) 4(dtpaO 3)]·2.5H 2O 3 and (gu) 3[NbTa(O 2) 4(HtthaO 4)]·2H 2O 6 have been obtained. In these compounds, the in situ oxidation of the nitrogen atoms of the PAC ligands into N-oxide groups has been evidenced by IR spectroscopy and mass spectrometry. The thermal treatment of the homonuclear complexes in air at 700 or 800 °C, depending on the Ta content, provided Nb 2O 5 or Ta 2O 5 while the heteronuclear compounds led to the solid solution TaNbO 5. BET and SEM measurements have been carried out and comparison of the morphology of the samples prepared from homo- and heterometallic precursors is discussed.

Calculating excess volumes of binary solutions with allowance for structural differences between mixed components

NASA Astrophysics Data System (ADS)

Balankina, E. S.

2016-06-01

Analytical dependences of a volume's properties on the differences between the geometric structures of initial monosystems are obtained for binary systems simulated by a grain medium. The effect of microstructural parameter k (the ratio of volumes of molecules of mixed components) on the concentration behavior of the relative excess molar volume of different types of real binary solutions is analyzed. It is established that the contribution due to differences between the volumes of molecules and coefficients of the packing density of mixed components is ~80-100% for mutual solutions of n-alkanes and ~55-80% of the experimental value of the relative excess molar volume for water solutions of n-alcohols.

Understanding cellulose dissolution: energetics of interactions of ionic liquids and cellobiose revealed by solution microcalorimetry.

PubMed

de Oliveira, Heitor Fernando Nunes; Rinaldi, Roberto

2015-05-11

In this report, the interactions between fifteen selected ionic liquids (ILs) and cellobiose (CB) are examined by high-precision solution microcalorimetry. The heat of mixing (Δmix H) of CB and ILs, or CB and IL/molecular solvent (MS) solutions, provides the first ever-published measure of the affinity of CB with ILs. Most importantly, we found that there is a very good correlation between the nature of the results found for Δmix H(CB) and the solubility behavior of cellulose. This correlation suggests that Δmix H(CB) offers a good estimate of the enthalpy of dissolution of cellulose even in solvents in which cellulose is insoluble. Therefore, the current findings open up new horizons for unravelling the intricacies of the thermodynamic factors accounting for the spontaneity of cellulose dissolution in ILs or IL/MS solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of Hi-C results using in-solution versus in-nucleus ligation.

PubMed

Nagano, Takashi; Várnai, Csilla; Schoenfelder, Stefan; Javierre, Biola-Maria; Wingett, Steven W; Fraser, Peter

2015-08-26

Chromosome conformation capture and various derivative methods such as 4C, 5C and Hi-C have emerged as standard tools to analyze the three-dimensional organization of the genome in the nucleus. These methods employ ligation of diluted cross-linked chromatin complexes, intended to favor proximity-dependent, intra-complex ligation. During development of single-cell Hi-C, we devised an alternative Hi-C protocol with ligation in preserved nuclei rather than in solution. Here we directly compare Hi-C methods employing in-nucleus ligation with the standard in-solution ligation. We show in-nucleus ligation results in consistently lower levels of inter-chromosomal contacts. Through chromatin mixing experiments we show that a significantly large fraction of inter-chromosomal contacts are the result of spurious ligation events formed during in-solution ligation. In-nucleus ligation significantly reduces this source of experimental noise, and results in improved reproducibility between replicates. We also find that in-nucleus ligation eliminates restriction fragment length bias found with in-solution ligation. These improvements result in greater reproducibility of long-range intra-chromosomal and inter-chromosomal contacts, as well as enhanced detection of structural features such as topologically associated domain boundaries. We conclude that in-nucleus ligation captures chromatin interactions more consistently over a wider range of distances, and significantly reduces both experimental noise and bias. In-nucleus ligation creates higher quality Hi-C libraries while simplifying the experimental procedure. We suggest that the entire range of 3C applications are likely to show similar benefits from in-nucleus ligation.

Incomplete Mixing and Reactions - A Lagrangian Approach in a Pure Shear Flow

NASA Astrophysics Data System (ADS)

Paster, A.; Aquino, T.; Bolster, D.

2014-12-01

Incomplete mixing of reactive solutes is well known to slow down reaction rates relative to what would be expected from assuming perfect mixing. As reactions progress in a system and deplete reactant concentrations, initial fluctuations in the concentrations of reactions can be amplified relative to mean background concentrations and lead to spatial segregation of reactants. As the system evolves, in the absence of sufficient mixing, this segregation will increase, leading to a persistence of incomplete mixing that fundamentally changes the effective rate at which overall reactions will progress. On the other hand, non-uniform fluid flows are known to affect mixing between interacting solutes. Thus a natural question arises: Can non-uniform flows sufficiently enhance mixing to suppress incomplete mixing effects, and if so, under what conditions? In this work we address this question by considering one of the simplest possible flows, a laminar pure shear flow, which is known to significantly enhance mixing relative to diffusion alone. To study this system we adapt a novel Lagrangian particle-based random walk method, originally designed to simulate reactions in purely diffusive systems, to the case of advection and diffusion in a shear flow. To interpret the results we develop a semi-analytical solution, by proposing a closure approximation that aims to capture the effect of incomplete mixing. The results obtained via the Lagrangian model and the semi-analytical solutions consistently highlight that if shear effects in the system are not sufficiently strong, incomplete mixing effects initially similar to purely diffusive systems will occur, slowing down the overall reaction rate. Then, at some later time, dependent on the strength of the shear, the system will return to behaving as if it were well-mixed, but represented by a reduced effective reaction rate. If shear effects are sufficiently strong, the incomplete mixing regime never emerges and the system can behave as well-mixed at all times.

Incomplete Mixing and Reactions - A Lagrangian Approach in a Pure Shear Flow

NASA Astrophysics Data System (ADS)

Paster, Amir; Bolster, Diogo; Aquino, Tomas

2015-04-01

Incomplete mixing of reactive solutes is well known to slow down reaction rates relative to what would be expected from assuming perfect mixing. As reactions progress in a system and deplete reactant concentrations, initial fluctuations in the concentrations of reactions can be amplified relative to mean background concentrations and lead to spatial segregation of reactants. As the system evolves, in the absence of sufficient mixing, this segregation will increase, leading to a persistence of incomplete mixing that fundamentally changes the effective rate at which overall reactions will progress. On the other hand, nonuniform fluid flows are known to affect mixing between interacting solutes. Thus a natural question arises: Can non-uniform flows sufficiently enhance mixing to suppress incomplete mixing effects, and if so, under what conditions? In this work we address this question by considering one of the simplest possible flows, a laminar pure shear flow, which is known to significantly enhance mixing relative to diffusion alone. To study this system we adapt a novel Lagrangian particle-based random walk method, originally designed to simulate reactions in purely diffusive systems, to the case of advection and diffusion in a shear flow. To interpret the results we develop a semi-analytical solution, by proposing a closure approximation that aims to capture the effect of incomplete mixing. The results obtained via the Lagrangian model and the semi-analytical solutions consistently highlight that if shear effects in the system are not sufficiently strong, incomplete mixing effects initially similar to purely diffusive systems will occur, slowing down the overall reaction rate. Then, at some later time, dependent on the strength of the shear, the system will return to behaving as if it were well-mixed, but represented by a reduced effective reaction rate. If shear effects are sufficiently strong, the incomplete mixing regime never emerges and the system can behave as well-mixed at all times.

PWC-ICA: A Method for Stationary Ordered Blind Source Separation with Application to EEG.

PubMed

Ball, Kenneth; Bigdely-Shamlo, Nima; Mullen, Tim; Robbins, Kay

2016-01-01

Independent component analysis (ICA) is a class of algorithms widely applied to separate sources in EEG data. Most ICA approaches use optimization criteria derived from temporal statistical independence and are invariant with respect to the actual ordering of individual observations. We propose a method of mapping real signals into a complex vector space that takes into account the temporal order of signals and enforces certain mixing stationarity constraints. The resulting procedure, which we call Pairwise Complex Independent Component Analysis (PWC-ICA), performs the ICA in a complex setting and then reinterprets the results in the original observation space. We examine the performance of our candidate approach relative to several existing ICA algorithms for the blind source separation (BSS) problem on both real and simulated EEG data. On simulated data, PWC-ICA is often capable of achieving a better solution to the BSS problem than AMICA, Extended Infomax, or FastICA. On real data, the dipole interpretations of the BSS solutions discovered by PWC-ICA are physically plausible, are competitive with existing ICA approaches, and may represent sources undiscovered by other ICA methods. In conjunction with this paper, the authors have released a MATLAB toolbox that performs PWC-ICA on real, vector-valued signals.

PWC-ICA: A Method for Stationary Ordered Blind Source Separation with Application to EEG

PubMed Central

Bigdely-Shamlo, Nima; Mullen, Tim; Robbins, Kay

2016-01-01

Independent component analysis (ICA) is a class of algorithms widely applied to separate sources in EEG data. Most ICA approaches use optimization criteria derived from temporal statistical independence and are invariant with respect to the actual ordering of individual observations. We propose a method of mapping real signals into a complex vector space that takes into account the temporal order of signals and enforces certain mixing stationarity constraints. The resulting procedure, which we call Pairwise Complex Independent Component Analysis (PWC-ICA), performs the ICA in a complex setting and then reinterprets the results in the original observation space. We examine the performance of our candidate approach relative to several existing ICA algorithms for the blind source separation (BSS) problem on both real and simulated EEG data. On simulated data, PWC-ICA is often capable of achieving a better solution to the BSS problem than AMICA, Extended Infomax, or FastICA. On real data, the dipole interpretations of the BSS solutions discovered by PWC-ICA are physically plausible, are competitive with existing ICA approaches, and may represent sources undiscovered by other ICA methods. In conjunction with this paper, the authors have released a MATLAB toolbox that performs PWC-ICA on real, vector-valued signals. PMID:27340397

Pentavalent neptunyl ([OΞNpΞO] +) cation–cation interactions in aqueous/polar organic mixed-solvent media

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

Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O] +) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalentmore » linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al 3+, Sc 3+, Cr 3+, Fe 3+, In 3+ and UO 2+ 2) and the pentavalent neptunyl cation (NpO + 2, whose coordination chemistry is similar to that of AmO + 2 while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. As a result, the Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the NpO + 2 • Cr 3+ complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.« less

Pentavalent neptunyl ([OΞNpΞO] +) cation–cation interactions in aqueous/polar organic mixed-solvent media

DOE PAGES

Burn, Adam G.; Martin, Leigh R.; Nash, Kenneth L.

2017-06-17

Bonding interactions between polyvalent cations and oxo-anions are well known and characterized by predictably favorable Gibbs energies in solution-phase coordination chemistry. In contrast, interactions between ions of like charge are generally expected to be repulsive and strongly influenced by cation solvation. An exception to this instinctive rule is found in the existence of complexes resulting from interactions of pentavalent actinyl cations ([O≡An≡O] +) with selected polyvalent cations. Such cation–cation complexes have been known to exist since the 1960s, when they were first reported by Sullivan and co-workers. The weak actinyl cation–cation complex, resulting from a bonding interaction between a pentavalentmore » linear dioxo actinyl cation donor and hexavalent actinyl or trivalent/tetravalent metal cation acceptor, has been most commonly seen in media in which water activities are reduced, principally highly-salted aqueous media. Such interactions of pentavalent actinides are of relevance in ongoing research that focuses on advanced nuclear fuel processing systems based on the upper oxidation states of americium. This investigation focuses on exploring the thermodynamic stability of complexes between selected highly-charged metal cations (Al 3+, Sc 3+, Cr 3+, Fe 3+, In 3+ and UO 2+ 2) and the pentavalent neptunyl cation (NpO + 2, whose coordination chemistry is similar to that of AmO + 2 while exhibiting significantly greater oxidation state stability) in aqueous–polar organic mixed-solvents. As a result, the Gibbs energies for the cation–cation complexation reactions are correlated with general features of electrostatic bonding models; the NpO + 2 • Cr 3+ complex exhibits unexpectedly strong interactions that may indicate significant covalency in the cation–cation bonding interaction.« less

Conformal complex singlet extension of the Standard Model: scenario for dark matter and a second Higgs boson

NASA Astrophysics Data System (ADS)

Wang, Zhi-Wei; Steele, T. G.; Hanif, T.; Mann, R. B.

2016-08-01

We consider a conformal complex singlet extension of the Standard Model with a Higgs portal interaction. The global U(1) symmetry of the complex singlet can be either broken or unbroken and we study each scenario. In the unbroken case, the global U(1) symmetry protects the complex singlet from decaying, leading to an ideal cold dark matter candidate with approximately 100 GeV mass along with a significant proportion of thermal relic dark matter abundance. In the broken case, we have developed a renormalization-scale optimization technique to significantly narrow the parameter space and in some situations, provide unique predictions for all the model's couplings and masses. We have found there exists a second Higgs boson with a mass of approximately 550 GeV that mixes with the known 125 GeV Higgs with a large mixing angle sin θ ≈ 0.47 consistent with current experimental limits. The imaginary part of the complex singlet in the broken case could provide axion dark matter for a wide range of models. Upon including interactions of the complex scalar with an additional vector-like fermion, we explore the possibility of a diphoton excess in both the unbroken and the broken cases. In the unbroken case, the model can provide a natural explanation for diphoton excess if extra terms are introduced providing extra contributions to the singlet mass. In the broken case, we find a set of coupling solutions that yield a second Higgs boson of mass 720 GeV and an 830 GeV extra vector-like fermion F , which is able to address the 750 GeV LHC diphoton excess. We also provide criteria to determine the symmetry breaking pattern in both the Higgs and hidden sectors.

Mixed copper-platinum complex formation could explain synergistic antiproliferative effect exhibited by binary mixtures of cisplatin and copper-1,10-phenanthroline compounds: An ESI-MS study.

PubMed

Pivetta, Tiziana; Lallai, Viola; Valletta, Elisa; Trudu, Federica; Isaia, Francesco; Perra, Daniela; Pinna, Elisabetta; Pani, Alessandra

2015-10-01

Cisplatin, cis-diammineplatinum(II) dichloride, is a metal complex used in clinical practice for the treatment of cancer. Despite its great efficacy, it causes adverse reactions and most patients develop a resistance to cisplatin. To overcome these issues, a multi-drug therapy was introduced as a modern approach to exploit the drug synergy. A synergistic effect had been previously found when testing binary combinations of cisplatin and three copper complexes in vitro, namely, Cu(phen)(OH2)2(OClO3)2, [Cu(phen)2(OH2)](ClO4)2 and [Cu(phen)2(H2dit)](ClO4)2,(phen=1,10-phenanthroline, H2dit=imidazolidine-2-thione), against the human acute T-lymphoblastic leukaemia cell line (CCRF-CEM). In this work [Cu(phen)2(OH2)](ClO4)2 was also tested in combination with cisplatin against cisplatin-resistant sublines of CCRF-CEM (CCRF-CEM-res) and ovarian (A2780-res) cancer cell lines. The tested combinations show a synergistic effect against both the types of resistant cells. The possibility that this effect was caused by the formation of new adducts was considered and mass spectra of solutions containing cisplatin and one of the three copper complexes at a time were measured using electrospray ionisation at atmospheric-pressure mass spectrometry (ESI-MS). A mixed complex was detected and its stoichiometry was assessed on the basis of the isotopic pattern and the results of tandem mass spectrometry experiments. The formed complex was found to be [Cu(phen)(OH)μ-(Cl)2Pt(NH3)(H2O)](+). Copyright © 2015 Elsevier Inc. All rights reserved.

Pore-scale and Continuum Simulations of Solute Transport Micromodel Benchmark Experiments

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

Oostrom, Martinus; Mehmani, Yashar; Romero Gomez, Pedro DJ

Four sets of micromodel nonreactive solute transport experiments were conducted with flow velocity, grain diameter, pore-aspect ratio, and flow focusing heterogeneity as the variables. The data sets were offered to pore-scale modeling groups to test their simulators. Each set consisted of two learning experiments, for which all results was made available, and a challenge experiment, for which only the experimental description and base input parameters were provided. The experimental results showed a nonlinear dependence of the dispersion coefficient on the Peclet number, a negligible effect of the pore-aspect ratio on transverse mixing, and considerably enhanced mixing due to flow focusing.more » Five pore-scale models and one continuum-scale model were used to simulate the experiments. Of the pore-scale models, two used a pore-network (PN) method, two others are based on a lattice-Boltzmann (LB) approach, and one employed a computational fluid dynamics (CFD) technique. The learning experiments were used by the PN models to modify the standard perfect mixing approach in pore bodies into approaches to simulate the observed incomplete mixing. The LB and CFD models used these experiments to appropriately discretize the grid representations. The continuum model use published non-linear relations between transverse dispersion coefficients and Peclet numbers to compute the required dispersivity input values. Comparisons between experimental and numerical results for the four challenge experiments show that all pore-scale models were all able to satisfactorily simulate the experiments. The continuum model underestimated the required dispersivity values and, resulting in less dispersion. The PN models were able to complete the simulations in a few minutes, whereas the direct models needed up to several days on supercomputers to resolve the more complex problems.« less

Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes.

PubMed

Vijayakumar, M; Li, Liyu; Nie, Zimin; Yang, Zhenguo; Hu, JianZhi

2012-08-07

The vanadium(III) cation structure in mixed acid based electrolyte solution from vanadium redox flow batteries is studied by (17)O and (35/37)Cl nuclear magnetic resonance (NMR) spectroscopy, electronic spectroscopy and density functional theory (DFT) based computational modelling. Both computational and experimental results reveal that the V(III) species can complex with counter anions (sulfate/chlorine) depending on the composition of its solvation sphere. By analyzing the powder precipitate it was found that the formation of sulfate complexed V(III) species is the crucial process in the precipitation reaction. The precipitation occurs through nucleation of neutral species formed through deprotonation and ion-pair formation process. However, the powder precipitate shows a multiphase nature which warrants multiple reaction pathways for precipitation reaction.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor.

PubMed

von Rohr, Fabian; Winiarski, Michał J; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-11-15

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.

Impact of Spatial Pumping Patterns on Groundwater Management

NASA Astrophysics Data System (ADS)

Yin, J.; Tsai, F. T. C.

2017-12-01

Challenges exist to manage groundwater resources while maintaining a balance between groundwater quantity and quality because of anthropogenic pumping activities as well as complex subsurface environment. In this study, to address the impact of spatial pumping pattern on groundwater management, a mixed integer nonlinear multi-objective model is formulated by integrating three objectives within a management framework to: (i) maximize total groundwater withdrawal from potential wells; (ii) minimize total electricity cost for well pumps; and (iii) attain groundwater level at selected monitoring locations as close as possible to the target level. Binary variables are used in the groundwater management model to control the operative status of pumping wells. The NSGA-II is linked with MODFLOW to solve the multi-objective problem. The proposed method is applied to a groundwater management problem in the complex Baton Rouge aquifer system, southeastern Louisiana. Results show that (a) non-dominated trade-off solutions under various spatial distributions of active pumping wells can be achieved. Each solution is optimal with regard to its corresponding objectives; (b) operative status, locations and pumping rates of pumping wells are significant to influence the distribution of hydraulic head, which in turn influence the optimization results; (c) A wide range of optimal solutions is obtained such that decision makers can select the most appropriate solution through negotiation with different stakeholders. This technique is beneficial to finding out the optimal extent to which three objectives including water supply concern, energy concern and subsidence concern can be balanced.

Micromixer based on viscoelastic flow instability at low Reynolds number.

PubMed

Lam, Y C; Gan, H Y; Nguyen, N T; Lie, H

2009-03-30

We exploited the viscoelasticity of biocompatible dilute polymeric solutions, namely, dilute poly(ethylene oxide) solutions, to significantly enhance mixing in microfluidic devices at a very small Reynolds number, i.e., Re approximately 0.023, but large Peclet and elasticity numbers. With an abrupt contraction microgeometry (8:1 contraction ratio), two different dilute poly(ethylene oxide) solutions were successfully mixed with a short flow length at a relatively fast mixing time of <10 mus. Microparticle image velocimetry was employed in our investigations to characterize the flow fields. The increase in velocity fluctuation with an increase in flow rate and Deborah number indicates the increase in viscoelastic flow instability. Mixing efficiency was characterized by fluorescent concentration measurements. Our results showed that enhanced mixing can be achieved through viscoelastic flow instability under situations where molecular-diffusion and inertia effects are negligible. This approach bypasses the laminar flow limitation, usually associated with a low Reynolds number, which is not conducive to mixing.

Micromixer based on viscoelastic flow instability at low Reynolds number

PubMed Central

Lam, Y. C.; Gan, H. Y.; Nguyen, N. T.; Lie, H.

2009-01-01

We exploited the viscoelasticity of biocompatible dilute polymeric solutions, namely, dilute poly(ethylene oxide) solutions, to significantly enhance mixing in microfluidic devices at a very small Reynolds number, i.e., Re≈0.023, but large Peclet and elasticity numbers. With an abrupt contraction microgeometry (8:1 contraction ratio), two different dilute poly(ethylene oxide) solutions were successfully mixed with a short flow length at a relatively fast mixing time of <10 μs. Microparticle image velocimetry was employed in our investigations to characterize the flow fields. The increase in velocity fluctuation with an increase in flow rate and Deborah number indicates the increase in viscoelastic flow instability. Mixing efficiency was characterized by fluorescent concentration measurements. Our results showed that enhanced mixing can be achieved through viscoelastic flow instability under situations where molecular-diffusion and inertia effects are negligible. This approach bypasses the laminar flow limitation, usually associated with a low Reynolds number, which is not conducive to mixing. PMID:19693399

Establishment of Donor Chimerism Using Allogeneic Bone Marrow with AMP Cell Co-infusion

DTIC Science & Technology

2016-09-01

specific immunosuppression. Induction of tolerance to the CTA is the ideal solution. Combined mixed allogeneic chimerism induction and kidney ...transplantation has been shown to induce robust tolerance to the kidney allograft despite transient mixed chimerism in non-human primates and humans...solution. Mixed chimerism induction via hematopoietic cell transplantation (HCT) has been shown to facilitate tolerance induction to kidney allografts

Polythermal investigation of viscosity of solution of metal carboxylates in VIK-grade mixed carboxylic acids: Yttrium and gadolinium carboxylates

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

Mezhov, E.A.; Samatov, A.V.; Troyanovskii, L.V.

Kinematic viscosities have been measured for solutions of yttrium and gadolinium carboxylates in grade VIK mixed carboxylic acids (MCA). It has been established that the optimal fluidity of these metal carboxylate solutions for application to articles is reached at 333 K. A regression model has been developed to describe the concentration and temperature dependences of the viscosity of yttrium- and gadolinium-containing MCA solutions. 2 refs., 3 tabs.

Molecular interactions in gelatin/chitosan composite films.

PubMed

Qiao, Congde; Ma, Xianguang; Zhang, Jianlong; Yao, Jinshui

2017-11-15

Gelatin and chitosan were mixed at different mass ratios in solution forms, and the rheological properties of these film-forming solutions, upon cooling, were studied. The results indicate that the significant interactions between gelatin and chitosan promote the formation of multiple complexes, reflected by an increase in the storage modulus of gelatin solution. Furthermore, these molecular interactions hinder the formation of gelatin networks, consequently decreasing the storage modulus of polymer gels. Both hydrogen bonds and electrostatic interactions are formed between gelatin and chitosan, as evidenced by the shift of the amide-II bands of polymers. X-ray patterns of composite films indicate that the contents of triple helices decrease with increasing chitosan content. Only one glass transition temperature (T g ) was observed in composite films with different composition ratios, and it decreases gradually with an increase in chitosan proportion, indicating that gelatin and chitosan have good miscibility and form a wide range of blends. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluating a digital ship design tool prototype: Designers' perceptions of novel ergonomics software.

PubMed

Mallam, Steven C; Lundh, Monica; MacKinnon, Scott N

2017-03-01

Computer-aided solutions are essential for naval architects to manage and optimize technical complexities when developing a ship's design. Although there are an array of software solutions aimed to optimize the human element in design, practical ergonomics methodologies and technological solutions have struggled to gain widespread application in ship design processes. This paper explores how a new ergonomics technology is perceived by naval architecture students using a mixed-methods framework. Thirteen Naval Architecture and Ocean Engineering Masters students participated in the study. Overall, results found participants perceived the software and its embedded ergonomics tools to benefit their design work, increasing their empathy and ability to understand the work environment and work demands end-users face. However, participant's questioned if ergonomics could be practically and efficiently implemented under real-world project constraints. This revealed underlying social biases and a fundamental lack of understanding in engineering postgraduate students regarding applied ergonomics in naval architecture. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of mixing techniques on bacterial attachment and disinfection time of polyether impression material

PubMed Central

Guler, Umut; Budak, Yasemin; Ruh, Emrah; Ocal, Yesim; Canay, Senay; Akyon, Yakut

2013-01-01

Objective: The aim of this study was 2-fold. The first aim was to evaluate the effects of mixing technique (hand-mixing or auto-mixing) on bacterial attachment to polyether impression materials. The second aim was to determine whether bacterial attachment to these materials was affected by length of exposure to disinfection solutions. Materials and Methods: Polyether impression material samples (n = 144) were prepared by hand-mixing or auto-mixing. Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa were used in testing. After incubation, the bacterial colonies were counted and then disinfectant solution was applied. The effect of disinfection solution was evaluated just after the polymerization of impression material and 30 min after polymerization. Differences in adherence of bacteria to the samples prepared by hand-mixing and to those prepared by auto-mixing were assessed by Kruskal-Wallis and Mann-Whitney U-tests. For evaluating the efficiency of the disinfectant, Kruskal-Wallis multiple comparisons test was used. Results: E. coli counts were higher in hand-mixed materials (P < 0.05); no other statistically significant differences were found between hand- and auto-mixed materials. According to the Kruskal-Wallis test, significant differences were found between the disinfection procedures (Z > 2.394). Conclusion: The methods used for mixing polyether impression material did not affect bacterial attachment to impression surfaces. In contrast, the disinfection procedure greatly affects decontamination of the impression surface. PMID:24966729

Effect of mixing techniques on bacterial attachment and disinfection time of polyether impression material.

PubMed

Guler, Umut; Budak, Yasemin; Ruh, Emrah; Ocal, Yesim; Canay, Senay; Akyon, Yakut

2013-09-01

The aim of this study was 2-fold. The first aim was to evaluate the effects of mixing technique (hand-mixing or auto-mixing) on bacterial attachment to polyether impression materials. The second aim was to determine whether bacterial attachment to these materials was affected by length of exposure to disinfection solutions. Polyether impression material samples (n = 144) were prepared by hand-mixing or auto-mixing. Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa were used in testing. After incubation, the bacterial colonies were counted and then disinfectant solution was applied. The effect of disinfection solution was evaluated just after the polymerization of impression material and 30 min after polymerization. Differences in adherence of bacteria to the samples prepared by hand-mixing and to those prepared by auto-mixing were assessed by Kruskal-Wallis and Mann-Whitney U-tests. For evaluating the efficiency of the disinfectant, Kruskal-Wallis multiple comparisons test was used. E. coli counts were higher in hand-mixed materials (P < 0.05); no other statistically significant differences were found between hand- and auto-mixed materials. According to the Kruskal-Wallis test, significant differences were found between the disinfection procedures (Z > 2.394). The methods used for mixing polyether impression material did not affect bacterial attachment to impression surfaces. In contrast, the disinfection procedure greatly affects decontamination of the impression surface.

Incompatibility of Contrast Medium and Trisodium Citrate

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

Delcour, Christian, E-mail: christian.delcour@chu-charleroi.be; Bruninx, Guy

2013-02-15

To test the compatibility of trisodium citrate, a catheter lock solution, with iodinated contrast medium. Iohexol, iobitridol, iodixanol, ioxaglate, ioxithalamate, iomeprol, and iopromide were tested. In all tests, 2 ml of contrast medium were mixed with 2 ml of trisodium citrate solution. Iodixanol and ioxaglate provoked a highly viscous gluelike precipitation when mixed with trisodium citrate. A brief transient precipitate was observed with iohexol, iomeprol, and ioxithalamate. Permanent precipitation occurred with iobitridol and iopromide. One must be aware of the potential for precipitation when contrast medium is mixed with trisodium citrate solution. Before trisodium citrate solution is injected, the cathetermore » should be thoroughly flushed with saline if a contrast medium has previously been injected through it.« less

Automated Processing of Plasma Samples for Lipoprotein Separation by Rate-Zonal Ultracentrifugation.

PubMed

Peters, Carl N; Evans, Iain E J

2016-12-01

Plasma lipoproteins are the primary means of lipid transport among tissues. Defining alterations in lipid metabolism is critical to our understanding of disease processes. However, lipoprotein measurement is limited to specialized centers. Preparation for ultracentrifugation involves the formation of complex density gradients that is both laborious and subject to handling errors. We created a fully automated device capable of forming the required gradient. The design has been made freely available for download by the authors. It is inexpensive relative to commercial density gradient formers, which generally create linear gradients unsuitable for rate-zonal ultracentrifugation. The design can easily be modified to suit user requirements and any potential future improvements. Evaluation of the device showed reliable peristaltic pump accuracy and precision for fluid delivery. We also demonstrate accurate fluid layering with reduced mixing at the gradient layers when compared to usual practice by experienced laboratory personnel. Reduction in layer mixing is of critical importance, as it is crucial for reliable lipoprotein separation. The automated device significantly reduces laboratory staff input and reduces the likelihood of error. Overall, this device creates a simple and effective solution to formation of complex density gradients. © 2015 Society for Laboratory Automation and Screening.

Hollow silica microspheres for buoyancy-assisted separation of infectious pathogens from stool.

PubMed

Weigum, Shannon E; Xiang, Lichen; Osta, Erica; Li, Linying; López, Gabriel P

2016-09-30

Separation of cells and microorganisms from complex biological mixtures is a critical first step in many analytical applications ranging from clinical diagnostics to environmental monitoring for food and waterborne contaminants. Yet, existing techniques for cell separation are plagued by high reagent and/or instrumentation costs that limit their use in many remote or resource-poor settings, such as field clinics or developing countries. We developed an innovative approach to isolate infectious pathogens from biological fluids using buoyant hollow silica microspheres that function as "molecular buoys" for affinity-based target capture and separation by floatation. In this process, antibody functionalized glass microspheres are mixed with a complex biological sample, such as stool. When mixing is stopped, the target-bound, low-density microspheres float to the air/liquid surface, which simultaneously isolates and concentrates the target analytes from the sample matrix. The microspheres are highly tunable in terms of size, density, and surface functionality for targeting diverse analytes with separation times of ≤2min in viscous solutions. We have applied the molecular buoy technique for isolation of a protozoan parasite that causes diarrheal illness, Cryptosporidium, directly from stool with separation efficiencies over 90% and low non-specific binding. This low-cost method for phenotypic cell/pathogen separation from complex mixtures is expected to have widespread use in clinical diagnostics as well as basic research. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption of Nucleic Acid/Protein Supramolecular Complexes on Goethite: The Influence of Solution Interactions on Behavior at the Solution-Mineral Interface

NASA Astrophysics Data System (ADS)

Schmidt, M.; Martinez, C. E.

2017-12-01

Adsorption of biomolecule rich supramolecular complexes onto mineral surfaces plays an important role in the development of organo-mineral associations in soils. In this study, a series of supramolecular complexes of a model nucleic acid (deoxyribonucleic acid (DNA)) and protein (bovine serum albumin (BSA)) are synthesized, characterized and exposed to goethite to probe their adsorption behavior. To synthesize DNA/BSA complexes, a fixed DNA concentration (0.1 mg/mL) was mixed with a range of BSA concentrations (0.025-0.5 mg/mL) in 5 mM KCl at pH=5.0. Circular dichroism spectroscopy demonstrates strong, cooperative, Hill-type binding between DNA and BSA (Ka= 4.74 x 105 M-1) with DNA saturation achieved when BSA concentration reaches 0.4 mg/mL. Dynamic light scattering measurements of DNA/BSA complexes suggest binding accompanies disruption of DNA-DNA intermolecular electrostatic repulsion, resulting in a decrease of the DNA slow relaxation mode with increasing amount of BSA. Zeta potential measurements show increasing amounts of BSA lead to a reduction of negative charge on DNA/BSA complexes, in line with light scattering results. In situ attenuated total reflectance Fourier transform infrared spectroscopic studies of adsorption of DNA/BSA complexes onto goethite show that complexation of BSA with DNA appears to hinder direct coordination of DNA backbone phosphodiester groups with goethite, relative to DNA by itself. Furthermore, increasing amount of BSA (up to 0.4 mg/mL) in DNA/BSA complexes enhances DNA adsorption, possibly as a result of reduced repulsion between adsorbed DNA helices. When BSA concentration exceeds 0.4 mg/mL, a decrease in adsorbed DNA is observed. We hypothesize that this discrepancy in behavior between systems with BSA concentrations below and above saturation of DNA is caused by initial fast adsorption of loosely associated BSA on goethite, restricting access to goethite surface sites. Overall, these results highlight the impact of solution interaction between biomolecules on subsequent behavior at mineral surfaces. This work represents a bridge between model experiments with individual biomolecules and more complex natural systems, yielding a fundamental viewpoint of the formation of organo-mineral associations in soils.

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

PubMed

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Sustained release of antibiotic complexed by multivalent ion: in vitro and in vivo study for the treatment of peritonitis.

PubMed

Na, Seung Yeon; Oh, Se Heang; Kim, Tae Ho; Yoon, Jin A; Lee, In Soo; Lee, Jin Ho

2014-12-10

The main aims of this study are (i) the development of an antibiotic complexed with multivalent ion, which can allow sustained release of the antibiotic without any additional matrix or difficult process and (ii) the feasibility study of the ion-complexed antibiotic as a therapeutic technique for peritonitis treatment. An ion-complexed antibiotic is prepared by simple mixing of two aqueous solutions containing an ionized (water-soluble) drug (tetracycline) and a multivalent counter ionic compound. The ion-complexed antibiotic shows a continuous release of the antibiotic up to 21 days, and thus prolonged anti-bacterial effect by gradual ionic exchange between the multivalent ions in the complex and same-charged monovalent ions in surrounding medium. From the in vivo animal study using a cecum perforated peritonitis mouse model, the ion-complexed antibiotic group shows sufficient anti-bacterial effect and thus effectively treat the peritonitis because of the extermination of the contaminated enteric bacteria in the peritoneum during wound healing of injury cecum (by the sustained release of antibiotic from the ion complex). These results suggest that the ion-complexed antibiotic system may be promising for the effective treatment of the peritonitis caused by frequent gastrointestinal defect in clinical fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Numerical simulation for peristalsis of Carreau-Yasuda nanofluid in curved channel with mixed convection and porous space

PubMed Central

Tanveer, Anum; Hayat, T.; Alsaedi, A.; Ahmad, B.

2017-01-01

Main theme of present investigation is to model and analyze the peristaltic activity of Carraeu-Yasuda nanofluid saturating porous space in a curved channel. Unlike the traditional approach, the porous medium effects are characterized by employing modified Darcy’s law for Carreau-Yasuda fluid. To our knowledge this is first attempt in this direction for Carreau-Yasuda fluid. Heat and mass transfer are further considered. Simultaneous effects of heat and mass transfer are examined in presence of mixed convection, viscous dissipation and thermal radiation. The compliant characteristics for channel walls are taken into account. The resulting complex mathematical system has been discussed for small Reynolds number and large wavelength concepts. Numerical approximation to solutions are thus plotted in graphs and the physical description is presented. It is concluded that larger porosity in a medium cause an enhancement in fluid velocity and reduction in concentration. PMID:28151968

Metal–organic framework based mixed matrix membranes: a solution for highly efficient CO2 capture?† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4cs00437j Click here for additional data file.

PubMed Central

Seoane, Beatriz; Coronas, Joaquin; Gascon, Ignacio; Benavides, Miren Etxeberria; Karvan, Oğuz; Caro, Jürgen; Kapteijn, Freek

2015-01-01

The field of metal–organic framework based mixed matrix membranes (M4s) is critically reviewed, with special emphasis on their application in CO2 capture during energy generation. After introducing the most relevant parameters affecting membrane performance, we define targets in terms of selectivity and productivity based on existing literature on process design for pre- and post-combustion CO2 capture. Subsequently, the state of the art in M4s is reviewed against these targets. Because final application of these membranes will only be possible if thin separation layers can be produced, the latest advances in the manufacture of M4 hollow fibers are discussed. Finally, the recent efforts in understanding the separation performance of these complex composite materials and future research directions are outlined. PMID:25692487

IMMIGRATION ENFORCEMENT AND MIXED-STATUS FAMILIES: THE EFFECTS OF RISK OF DEPORTATION ON MEDICAID USE

PubMed Central

Vargas, Edward D.

2015-01-01

As Congress priorities the immigration debate on increased border security, the fate of an estimated 11 million undocumented citizens remains uncertain. Stuck in between partisan politics and practical solutions are mixed-status families in which some members of the family are U.S. citizens while other members are in the country without proper authorization. This paper, examines the relationship between risk of deportation and Medicaid use drawing from a nationally sample of mothers from the Fragile Families and Child Wellbeing Survey. These data are then merged with data from the U.S. Citizenship and Immigration Services to create a contextual risk of deportation measure. Findings suggest that an increase in risk of deportation is associated with a decrease in Medicaid use. The implications of this work have tremendous impacts for health service providers and policy makers interested in preventing and reducing health disparities in complex family structures. PMID:26435562

Numerical simulation for peristalsis of Carreau-Yasuda nanofluid in curved channel with mixed convection and porous space.

PubMed

Tanveer, Anum; Hayat, T; Alsaedi, A; Ahmad, B

2017-01-01

Main theme of present investigation is to model and analyze the peristaltic activity of Carraeu-Yasuda nanofluid saturating porous space in a curved channel. Unlike the traditional approach, the porous medium effects are characterized by employing modified Darcy's law for Carreau-Yasuda fluid. To our knowledge this is first attempt in this direction for Carreau-Yasuda fluid. Heat and mass transfer are further considered. Simultaneous effects of heat and mass transfer are examined in presence of mixed convection, viscous dissipation and thermal radiation. The compliant characteristics for channel walls are taken into account. The resulting complex mathematical system has been discussed for small Reynolds number and large wavelength concepts. Numerical approximation to solutions are thus plotted in graphs and the physical description is presented. It is concluded that larger porosity in a medium cause an enhancement in fluid velocity and reduction in concentration.

A hybrid Jaya algorithm for reliability-redundancy allocation problems

NASA Astrophysics Data System (ADS)

Ghavidel, Sahand; Azizivahed, Ali; Li, Li

2018-04-01

This article proposes an efficient improved hybrid Jaya algorithm based on time-varying acceleration coefficients (TVACs) and the learning phase introduced in teaching-learning-based optimization (TLBO), named the LJaya-TVAC algorithm, for solving various types of nonlinear mixed-integer reliability-redundancy allocation problems (RRAPs) and standard real-parameter test functions. RRAPs include series, series-parallel, complex (bridge) and overspeed protection systems. The search power of the proposed LJaya-TVAC algorithm for finding the optimal solutions is first tested on the standard real-parameter unimodal and multi-modal functions with dimensions of 30-100, and then tested on various types of nonlinear mixed-integer RRAPs. The results are compared with the original Jaya algorithm and the best results reported in the recent literature. The optimal results obtained with the proposed LJaya-TVAC algorithm provide evidence for its better and acceptable optimization performance compared to the original Jaya algorithm and other reported optimal results.

Direct power production from a water salinity difference in a membrane-modified supercapacitor flow cell.

PubMed

Sales, B B; Saakes, M; Post, J W; Buisman, C J N; Biesheuvel, P M; Hamelers, H V M

2010-07-15

The entropy increase of mixing two solutions of different salt concentrations can be harnessed to generate electrical energy. Worldwide, the potential of this resource, the controlled mixing of river and seawater, is enormous, but existing conversion technologies are still complex and expensive. Here we present a small-scale device that directly generates electrical power from the sequential flow of fresh and saline water, without the need for auxiliary processes or converters. The device consists of a sandwich of porous "supercapacitor" electrodes, ion-exchange membranes, and a spacer and can be further miniaturized or scaled-out. Our results demonstrate that alternating the flow of saline and fresh water through a capacitive cell allows direct autogeneration of voltage and current and consequently leads to power generation. Theoretical calculations aid in providing directions for further optimization of the properties of membranes and electrodes.

Facile fabrication of high-quality Ag/PS coaxial nanocables based on the mixed mode of soft/hard templates

NASA Astrophysics Data System (ADS)

Wan, Mimi; Zhao, Wenbo; Peng, Fang; Wang, Qi; Xu, Ping; Mao, Chun; Shen, Jian

2016-08-01

A new kind of high-quality Ag/PS coaxial nanocables can be facilely synthesized by using soft/hard templates method. In order to effectively introduce Ag sources into porous polystyrene (PS) nanotubes which were trapped in porous anodic aluminum oxide (AAO) hard template, Pluronic F127 (F127) was used as guiding agent, soft template and reductant. Meanwhile, ethylene glycol solution was also used as solvent and co-reducing agent to assist in the formation of silver nanowires. The influences of concentration of F127 and reducing reaction time on the formation of Ag/PS coaxial nanocables were discussed. Results indicated that the high-quality Ag/PS coaxial nanocables can be obtained by the mixed mode of soft/hard templates under optimized conditions. This strategy is expected to be extended to design more metal/polymer coaxial nanocables for the benefit of creation of complex and functional nanoarchitectures and components.

Solute Transport Dynamics in a Large Hyporheic Corridor System

NASA Astrophysics Data System (ADS)

Zachara, J. M.; Chen, X.; Murray, C. J.; Shuai, P.; Rizzo, C.; Song, X.; Dai, H.

2016-12-01

A hyporheic corridor is an extended zone of groundwater surface water-interaction that occurs within permeable aquifer sediments in hydrologic continuity with a river. These systems are dynamic and tightly coupled to river stage variations that may occur over variable time scales. Here we describe the behavior of a persistent uranium (U) contaminant plume that exists within the hyporheic corridor of a large, managed river system - the Columbia River. Temporally dense monitoring data were collected for a two year period from wells located within the plume at varying distances up to 400 m from the river shore. Groundwater U originates from desorption of residual U in the lower vadose zone during periods of high river stage and associated elevated water table. U is weakly adsorbed to aquifer sediments because of coarse texture, and along with specific conductance, serves as a tracer of vadose zone source terms, solute transport pathways, and groundwater-surface water mixing. Complex U concentration and specific conductance trends were observed for all wells that varied with distance from the river shoreline and the river hydrograph, although trends for each well were generally repeatable for each year during the monitoring period. Statistical clustering analysis was used to identify four groups of wells that exhibited common trends in dissolved U and specific conductance. A flow and reactive transport code, PFLOTRAN, was implemented within a hydrogeologic model of the groundwater-surface water interaction zone to provide insights on hydrologic processes controlling monitoring trends and cluster behavior. The hydrogeologic model was informed by extensive subsurface characterization, with the spatially variable topography of a basal aquitard being one of several key parameters. Numerical tracer experiments using PFLOTRAN revealed the presence of temporally complex flow trajectories, spatially variable domains of groundwater - river water mixing, and locations of enhanced groundwater - river exchange that helped to explain monitoring trends. Observations and modeling results are integrated into a conceptual model of this highly complex and dynamic system with applicability to hyporheic corridor systems elsewhere.

Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

USGS Publications Warehouse

Stollenwerk, Kenneth G.

1998-01-01

A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where pH (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as pH increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

Pilot Study Report, Cape Canaveral Air Station, Florida. Permeable Reactive Treatment (PeRT) Wall Pilot Study. Revision 2

DTIC Science & Technology

1999-11-01

slurry was made from mixing iron, guar gum , an enzyme and borax. The guar gum was Hercules Supercol™ food grade fine (200-mesh size) powder . It was...Florida The guar gum was mixed with water in batches in a stirred open top tank to form 2 to 3% solutions. The guar gum solution was pumped first to a...holding tank, then into a truck-mounted batch mixing plant. A positive displacement pump controlled the feed rate of guar gum to the batch mixing plant

In-situ laser-induced synthesis of associated YVO4:Eu3+@SiO2@Au-Ag/C nanohybrids with enhanced luminescence

NASA Astrophysics Data System (ADS)

Kolesnikov, I. E.; lvanova, T. Yu.; Ivanov, D. A.; Kireev, A. A.; Mamonova, D. V.; Golyeva, E. V.; Mikhailov, M. D.; Manshina, A. A.

2018-02-01

Associated luminescence/plasmonic nanoparticles were prepared in a single step process as a result of laser illumination (low intensity CW He-Cd laser) of colloidal solution of YVO4:Eu3+@SiO2 mixed with heterometallic supramolecular complex. The results of SEM-EDX analysis, absorption, steady-state luminescence and luminescence decay measurements revealed formation of associated nanohybrids with core/shell morphology. The obtained nanostructures demonstrated metal enhanced luminescence with enhancement factor of 1.6. The theoretical calculations revealed strong correlation of enhancement factor and plasmonic nanoparticles number.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

NASA Astrophysics Data System (ADS)

Zhul'Kina, A. L.; Ivantsova, E. L.; Filatova, A. G.; Kosenko, R. Yu.; Gumargalieva, K. Z.; Iordanskii, A. L.

2009-05-01

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

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

Zhul'kina, A. L.; Ivantsova, E. L.; Filatova, A. G.

2009-05-15

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Coiling, Entrainment, and Hydrodynamic Coupling of Decelerated Fluid Jets

NASA Astrophysics Data System (ADS)

Dombrowski, Christopher; Lewellyn, Braddon; Pesci, Adriana I.; Restrepo, Juan M.; Kessler, John O.; Goldstein, Raymond E.

2005-10-01

From algal suspensions to magma upwellings, one finds jets which exhibit complex symmetry-breaking instabilities as they are decelerated by their surroundings. We consider here a model system—a saline jet descending through a salinity gradient—which produces dynamics unlike those of standard momentum jets or plumes. The jet coils like a corkscrew within a conduit of viscously entrained fluid, whose upward recirculation braids the jet, and nearly confines transverse mixing to the narrow conduit. We show that the underlying jet structure and certain scaling relations follow from similarity solutions to the fluid equations and the physics of Kelvin-Helmholtz instabilities.

Lump solutions and interaction phenomenon to the third-order nonlinear evolution equation

NASA Astrophysics Data System (ADS)

Kofane, T. C.; Fokou, M.; Mohamadou, A.; Yomba, E.

2017-11-01

In this work, the lump solution and the kink solitary wave solution from the (2 + 1) -dimensional third-order evolution equation, using the Hirota bilinear method are obtained through symbolic computation with Maple. We have assumed that the lump solution is centered at the origin, when t = 0 . By considering a mixing positive quadratic function with exponential function, as well as a mixing positive quadratic function with hyperbolic cosine function, interaction solutions like lump-exponential and lump-hyperbolic cosine are presented. A completely non-elastic interaction between a lump and kink soliton is observed, showing that a lump solution can be swallowed by a kink soliton.

Device and method for screening crystallization conditions in solution crystal growth

NASA Technical Reports Server (NTRS)

Carter, Daniel C. (Inventor)

1995-01-01

A device and method for detecting optimum protein crystallization conditions and for growing protein crystals in either 1g or microgravity environments comprising a housing, defining at least one pair of chambers for containing crystallization solutions is presented. The housing further defines an orifice therein for providing fluid communication between the chambers. The orifice is adapted to receive a tube which contains a gelling substance for limiting the rate of diffusive mixing of the crystallization solutions. The solutions are diffusively mixed over a period of time defined by the quantity of gelling substance sufficient to achieve equilibration and to substantially reduce density driven convection disturbances therein. The device further includes endcaps to seal the first and second chambers. One of the endcaps includes a dialysis chamber which contains protein solution in which protein crystals are grown. Once the endcaps are in place, the protein solution is exposed to the crystallization solutions wherein the solubility of the protein solution is reduced at a rate responsive to the rate of diffusive mixing of the crystallization solutions. This allows for a controlled approach to supersaturation and allows for screening of crystal growth conditions at preselected intervals.

Device and Method for Screening Crystallization Conditions in Solution Crystal Growth

NASA Technical Reports Server (NTRS)

Carter, Daniel C. (Inventor)

1997-01-01

A device and method for detecting optimum protein crystallization conditions and for growing protein crystals in either 1 g or microgravity environments comprising a housing defining at least one pair of chambers for containing crystallization solutions. The housing further defines an orifice therein for providing fluid communication between the chambers. The orifice is adapted to receive a tube which contains a gelling substance for limiting the rate of diffusive mixing of the crystallization solutions. The solutions are diffusively mixed over a period of time defined by the quantity of gelling substance sufficient to achieve equilibration and to substantially reduce density driven convection disturbances therein. The device further includes endcaps to seal the first and second chambers. One of the endcaps includes a dialysis chamber which contains protein solution in which protein crystals are grown. Once the endcaps are in place. the protein solution is exposed to the crystallization solutions wherein the solubility of the protein solution is reduced at a rate responsive to the rate of diffusive mixing of the crystallization solutions. This allows for a controlled approach to supersaturation and allows for screening of crystal growth conditions at preselected intervals.

Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy.

PubMed

Kwak, Kyungwon; Rosenfeld, Daniel E; Chung, Jean K; Fayer, Michael D

2008-11-06

Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.

Rare earth element behavior during groundwater – seawater mixing along the Kona Coast of Hawaii

USGS Publications Warehouse

Johannesson, Karen H.; Palmore, C. Dianne; Fackrell, Joseph; Prouty, Nancy G.; Swarzenski, Peter W.; Chevis, Darren A.; Telfeyan, Katherine; White, Christopher D.; Burdige, David J.

2017-01-01

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previous investigations showed that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries. Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were mixed with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO3)2-] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Taken together, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3 – 2.6 mmol Nd day-1) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.

[Improvement of patient adherence by mixing oral itraconazole solution with a beverage (orange juice)].

PubMed

Adachi, Yoko; Sumikuma, Toshiya; Kagami, Ryogo; Nishio, Akira; Akasaka, Koji; Tsunemine, Hiroko; Kodaka, Taiichi; Hiramatsu, Yasushi; Tada, Hiroshi

2010-05-01

There have been some reports on the efficacy and tolerability of an oral itraconazole (ITCZ) solution as prophylaxis for fungal infection in patients with hematological malignancies. However, there are some cases where the bitter taste of oral ITCZ solution leads to an interruption of administration because the patient refuses to take this medicine. Therefore, we prospectively investigated the pharmacokinetics and promotion of treatment adherence in patients taking oral ITCZ solution mixed with a beverage. Compared with the responses of patients taking oral ITCZ solution with water, the taste of the agent was improved significantly when mixed with orange juice, although the plasma concentration of the agent did not differ between the two groups. Using this method, we can expect an improvement in treatment adherence and this method can easily be applied in clinical practice. This method is highly useful and should become common knowledge.

A mixed-mode crack analysis of isotropic solids using conservation laws of elasticity

NASA Technical Reports Server (NTRS)

Yau, J. F.; Wang, S. S.; Corten, H. T.

1980-01-01

A simple and convenient method of analysis for studying two-dimensional mixed-mode crack problems is presented. The analysis is formulated on the basis of conservation laws of elasticity and of fundamental relationships in fracture mechanics. The problem is reduced to the determination of mixed-mode stress-intensity factor solutions in terms of conservation integrals involving known auxiliary solutions. One of the salient features of the present analysis is that the stress-intensity solutions can be determined directly by using information extracted in the far field. Several examples with solutions available in the literature are solved to examine the accuracy and other characteristics of the current approach. This method is demonstrated to be superior in its numerical simplicity and computational efficiency to other approaches. Solutions of more complicated and practical engineering fracture problems dealing with the crack emanating from a circular hole are presented also to illustrate the capacity of this method

Method for low temperature preparation of a noble metal alloy

DOEpatents

Even, Jr., William R.

2002-01-01

A method for producing fine, essentially contamination free, noble metal alloys is disclosed. The alloys comprise particles in a size range of 5 to 500 nm. The method comprises 1. A method for preparing a noble metal alloy at low temperature, the method comprising the steps of forming solution of organometallic compounds by dissolving the compounds into a quantity of a compatible solvent medium capable of solvating the organometallic, mixing a portion of each solution to provide a desired molarity ratio of ions in the mixed solution, adding a support material, rapidly quenching droplets of the mixed solution to initiate a solute-solvent phase separation as the solvent freezes, removing said liquid cryogen, collecting and freezing drying the frozen droplets to produce a dry powder, and finally reducing the powder to a metal by flowing dry hydrogen over the powder while warming the powder to a temperature of about 150.degree. C.

Process and apparatus for producing ultrafine explosive particles

DOEpatents

McGowan, Michael J.

1992-10-20

A method and an improved eductor apparatus for producing ultrafine explosive particles is disclosed. The explosive particles, which when incorporated into a binder system, have the ability to propagate in thin sheets, and have very low impact sensitivity and very high propagation sensitivity. A stream of a solution of the explosive dissolved in a solvent is thoroughly mixed with a stream of an inert nonsolvent by obtaining nonlaminar flow of the streams by applying pressure against the flow of the nonsolvent stream, to thereby diverge the stream as it contacts the explosive solution, and violently agitating the combined stream to rapidly precipitate the explosive particles from the solution in the form of generally spheroidal, ultrafine particles. The two streams are injected coaxially through continuous, concentric orifices of a nozzle into a mixing chamber. Preferably, the nonsolvent stream is injected centrally of the explosive solution stream. The explosive solution stream is injected downstream of and surrounds the nonsolvent solution stream for a substantial distance prior to being ejected into the mixing chamber.

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

Metal-assisted in situ formation of a tridentate acetylacetone ligand for complexation of fac-Re(CO)3+ for radiopharmaceutical applications.

PubMed

Benny, Paul D; Fugate, Glenn A; Barden, Adam O; Morley, Jennifer E; Silva-Lopez, Elsa; Twamley, Brendan

2008-04-07

Reaction of [NEt4]2[ReBr3(CO)3] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)3 (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)3 complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)3 was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)3(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)3Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4]2[ReBr3(CO)3], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water.

URANIUM LEACHING AND RECOVERY PROCESS

DOEpatents

McClaine, L.A.

1959-08-18

A process is described for recovering uranium from carbonate leach solutions by precipitating uranium as a mixed oxidation state compound. Uranium is recovered by adding a quadrivalent uranium carbon;te solution to the carbonate solution, adjusting the pH to 13 or greater, and precipitating the uranium as a filterable mixed oxidation state compound. In the event vanadium occurs with the uranium, the vanadium is unaffected by the uranium precipitation step and remains in the carbonate solution. The uranium-free solution is electrolyzed in the cathode compartment of a mercury cathode diaphragm cell to reduce and precipitate the vanadium.

Gallium metal affinity capture tandem mass spectrometry for the selective detection of phosphopeptides in complex mixtures

PubMed Central

Blacken, Grady R.; Sadílek, Martin; Tureček, František

2008-01-01

Metal affinity capture tandem mass spectrometry (MAC-MSMS) is evaluated in a comparative study of a lysine-derived nitrilotriacetic acid (Nα, Nα-bis-(carboxymethyl)lysine, LysNTA) and an aspartic-acid-related iminodiacetic acid (N-(4-aminobutyl)aspartic acid, AspIDA) as selective phosphopeptide detection reagents. Both LysNTA and AspIDA spontaneously form ternary complexes with GaIII and phosphorylated amino acids and phosphopeptides upon mixing in solution. Collision-induced dissociation of positive complex ions produced by electrospray produces common fragments (LysNTA + H)+ or (AspIDA + H)+ at m/z 263 and 205, respectively. MSMS precursor scans using these fragments as reporter ions allow one to selectively detect multiple charge states of phosphopeptides in mixtures. It follows from this comparative study that LysNTA is superior to AspIDA in detecting phosphopeptides, possibly because of the higher coordination number and greater stability constant for GaIII – phosphopeptide complexation of the former reagent. In a continuing development of MAC-MSMS for proteomics applications, we demonstrate its utility in a post-column reaction format. Using a simple post-column-reaction ‘T’ and syringe pump to deliver our chelating reagents, α-casein tryptic phosphopeptides can be selectively analyzed from a solution containing a twofold molar excess of bovine serum albumin. The MAC-MSMS method is shown to be superior to the commonly used neutral loss scan for the common loss of phosphoric acid. PMID:18265438

Adsorption mechanism of mixed cationic/anionic collectors in feldspar-quartz flotation system.

PubMed

Vidyadhar, A; Hanumantha Rao, K

2007-02-15

The adsorption mechanism of mixed cationic alkyl diamine and anionic sulfonate/oleate collectors at acidic pH values was investigated on microcline and quartz minerals through Hallimond flotation, electrokinetic and diffuse reflectance FTIR studies. In the presence of anionic collectors, neither of the minerals responded to flotation but the diamine flotation of the minerals was observed to be pH and concentration dependent. The presence of sulfonate enhanced the diamine flotation of the minerals by its co-adsorption. The difference in surface charge between the minerals at pH 2 was found to be the basis for preferential feldspar flotation from quartz in mixed diamine/sulfonate collectors. The infrared spectra revealed no adsorption of sulfonate collector when used alone but displayed its co-adsorption as diamine-sulfonate complex when used with diamine. The presence of sulfonate increased the diamine adsorption due to a decrease in the electrostatic head-head repulsion between the adjacent surface ammonium ions and thereby increasing the lateral tail-tail hydrophobic bonds. The mole ratio of diamine/sulfonate was found to be an important factor in the orientation of alkyl chains and thus the flotation response of minerals. The increase in sulfonate concentration beyond diamine concentration leads to the formation of soluble 1:2 diamine-sulfonate complex or precipitate and the adsorption of these species decreased the flotation since the alkyl chains are in chaotical orientation with a conceivable number of head groups directing towards the solution phase.

Prescribing the mixed scalar curvature of a foliated Riemann-Cartan manifold

NASA Astrophysics Data System (ADS)

Rovenski, Vladimir Y.; Zelenko, Leonid

2018-03-01

The mixed scalar curvature is the simplest curvature invariant of a foliated Riemannian manifold. We explore the problem of prescribing the leafwise constant mixed scalar curvature of a foliated Riemann-Cartan manifold by conformal change of the structure in tangent and normal to the leaves directions. Under certain geometrical assumptions and in two special cases: along a compact leaf and for a closed fibered manifold, we reduce the problem to solution of a nonlinear leafwise elliptic equation for the conformal factor. We are looking for its solutions that are stable stationary solutions of the associated parabolic equation. Our main tool is using of majorizing and minorizing nonlinear heat equations with constant coefficients and application of comparison theorems for solutions of Cauchy's problem for parabolic equations.

Development of a novel wet oxidation process for hazardous and mixed wastes

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

Dhooge, P.M.

1994-12-31

Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. The over all objective of the effort described here is to develop a novel catalytic wet oxidation process for the treatment of these multi-component wastes, with the aim of providing a versatile, non-thermal method which will destroy hazardous organic compounds while simultaneously containing and concentrating toxic and radioactive metals for recovery or disposal in a readily stabilized matrix. The DETOX process usesmore » a unique combination of metal catalysts to increase the rate of oxidation of organic materials. The metal catalysts are in the form of salts dissolved in a dilute acid solution. A typical catalyst composition is 60% ferric chloride, 3--4% hydrochloric acid, 0.13% platinum ions, and 0.13% ruthenium ions in a water solution. The catalyst solution is maintained at 423--473 K. Wastes are introduced into contact with the solution, where their organic portion is oxidized to carbon dioxide and water. If the organic portion is chlorinated, hydrogen chloride will be produced as a product. The process is a viable alternative to incineration for the treatment of organic mixed wastes. Estimated costs for waste treatment using the process are from $2.50/kg to $25.00/kg, depending on the size of the unit and the amount of waste processed. Process units can be mobile for on-site treatment of wastes. Results from phase 1 and 2, design and engineering studies, are described.« less

Measuring case-mix complexity of tertiary care hospitals using DRGs.

PubMed

Park, Hayoung; Shin, Youngsoo

2004-02-01

The objectives of the study were to develop a model that measures and evaluates case-mix complexity of tertiary care hospitals, and to examine the characteristics of such a model. Physician panels defined three classes of case complexity and assigned disease categories represented by Adjacent Diagnosis Related Groups (ADRGs) to one of three case complexity classes. Three types of scores, indicating proportions of inpatients in each case complexity class standardized by the proportions at the national level, were defined to measure the case-mix complexity of a hospital. Discharge information for about 10% of inpatient episodes at 85 hospitals with bed size larger than 400 and their input structure and research and education activity were used to evaluate the case-mix complexity model. Results show its power to predict hospitals with the expected functions of tertiary care hospitals, i.e. resource intensive care, expensive input structure, and high levels of research and education activities.

Improved sugar beet pectin-stabilized emulsions through complexation with sodium caseinate.

PubMed

Li, Xiangyang; Fang, Yapeng; Phillips, Glyn O; Al-Assaf, Saphwan

2013-02-13

The study investigates the complexes formed between sodium caseinate (SC) and sugar beet pectin (SBP) and to harness them to stabilize SBP emulsions. We find that both hydrophobic and electrostatic interactions are involved in the complexation. In SC/SBP mixed solution, soluble SC/SBP complexes first form on acidification and then aggregate into insoluble complexes, which disassociate into soluble polymers upon further decreasing pH. The critical pH's for the formation of soluble and insoluble complexes and disappearance of insoluble complexes are designated as pH(c), pH(φ), and pH(d), respectively. These critical pH values define four regions in the phase diagram of complexation, and SC/SBP emulsions were prepared in these regions. The results show that the stability of SBP-stabilized emulsion is greatly improved at low SC/SBP ratios and acidic pH's. This enhancement can be attributed to an increase in the amount of adsorbed SBP as a result of cooperative adsorption to sodium caseinate. Using a low ratio of SC/SBP ensured that all caseinate molecules are completely covered by adsorbed SBP chains, which eliminates possible instability induced by thermal aggregation of caseinate molecules resulting from stress acceleration at elevated temperatures. A mechanistic model for the behavior is proposed.

Off-shell amplitudes as boundary integrals of analytically continued Wilson line slope

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

Kotko, P.; Serino, M.; Stasto, A. M.

We consider a conformal complex singlet extension of the Standard Model with a Higgs portal interaction. The global U(1) symmetry of the complex singlet can be either broken or unbroken and we study each scenario. In the unbroken case, the global U(1) symmetry protects the complex singlet from decaying, leading to an ideal cold dark matter candidate with approximately 100 GeV mass along with a significant proportion of thermal relic dark matter abundance. In the broken case, we have developed a renormalization-scale optimization technique to significantly narrow the parameter space and in some situations, provide unique predictions for all themore » model’s couplings and masses. We have found there exists a second Higgs boson with a mass of approximately 550 GeV that mixes with the known 125 GeV Higgs with a large mixing angle sin θ ≈ 0.47 consistent with current experimental limits. The imaginary part of the complex singlet in the broken case could provide axion dark matter for a wide range of models. Upon including interactions of the complex scalar with an additional vector-like fermion, we explore the possibility of a diphoton excess in both the unbroken and the broken cases. In the unbroken case, the model can provide a natural explanation for diphoton excess if extra terms are introduced providing extra contributions to the singlet mass. In the broken case, we find a set of coupling solutions that yield a second Higgs boson of mass 720 GeV and an 830 GeV extra vector-like fermion F , which is able to address the 750 GeV LHC diphoton excess. We also provide criteria to determine the symmetry breaking pattern in both the Higgs and hidden sectors.« less

Application of the Fokker-Planck molecular mixing model to turbulent scalar mixing using moment methods

NASA Astrophysics Data System (ADS)

Madadi-Kandjani, E.; Fox, R. O.; Passalacqua, A.

2017-06-01

An extended quadrature method of moments using the β kernel density function (β -EQMOM) is used to approximate solutions to the evolution equation for univariate and bivariate composition probability distribution functions (PDFs) of a passive scalar for binary and ternary mixing. The key element of interest is the molecular mixing term, which is described using the Fokker-Planck (FP) molecular mixing model. The direct numerical simulations (DNSs) of Eswaran and Pope ["Direct numerical simulations of the turbulent mixing of a passive scalar," Phys. Fluids 31, 506 (1988)] and the amplitude mapping closure (AMC) of Pope ["Mapping closures for turbulent mixing and reaction," Theor. Comput. Fluid Dyn. 2, 255 (1991)] are taken as reference solutions to establish the accuracy of the FP model in the case of binary mixing. The DNSs of Juneja and Pope ["A DNS study of turbulent mixing of two passive scalars," Phys. Fluids 8, 2161 (1996)] are used to validate the results obtained for ternary mixing. Simulations are performed with both the conditional scalar dissipation rate (CSDR) proposed by Fox [Computational Methods for Turbulent Reacting Flows (Cambridge University Press, 2003)] and the CSDR from AMC, with the scalar dissipation rate provided as input and obtained from the DNS. Using scalar moments up to fourth order, the ability of the FP model to capture the evolution of the shape of the PDF, important in turbulent mixing problems, is demonstrated. Compared to the widely used assumed β -PDF model [S. S. Girimaji, "Assumed β-pdf model for turbulent mixing: Validation and extension to multiple scalar mixing," Combust. Sci. Technol. 78, 177 (1991)], the β -EQMOM solution to the FP model more accurately describes the initial mixing process with a relatively small increase in computational cost.

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

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

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

PubMed Central

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; Klimczuk, Tomasz; Cava, Robert Joseph

2016-01-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellent intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials. PMID:27803330

Birds of a Feather: Supporting Secure Systems

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

Braswell III, H V

2006-04-24

Over the past few years Lawrence Livermore National Laboratory has begun the process of moving to a diskless environment in the Secure Computer Support realm. This movement has included many moving targets and increasing support complexity. We would like to set up a forum for Security and Support professionals to get together from across the Complex and discuss current deployments, lessons learned, and next steps. This would include what hardware, software, and hard copy based solutions are being used to manage Secure Computing. The topics to be discussed include but are not limited to: Diskless computing, port locking and management,more » PC, Mac, and Linux/UNIX support and setup, system imaging, security setup documentation and templates, security documentation and management, customer tracking, ticket tracking, software download and management, log management, backup/disaster recovery, and mixed media environments.« less

Effect of electron count and chemical complexity in the Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor

DOE PAGES

von Rohr, Fabian; Winiarski, Michał J.; Tao, Jing; ...

2016-11-01

High-entropy alloys are made from random mixtures of principal elements on simple lattices, stabilized by a high mixing entropy. The recently discovered body-centered cubic (BCC) Ta-Nb-Hf-Zr-Ti high-entropy alloy superconductor appears to display properties of both simple crystalline intermetallics and amorphous materials; e.g., it has a well-defined superconducting transition along with an exceptional robustness against disorder. Here we show that the valence electron count dependence of the superconducting transition temperature in the high-entropy alloy falls between those of analogous simple solid solutions and amorphous materials and test the effect of alloy complexity on the superconductivity. We propose high-entropy alloys as excellentmore » intermediate systems for studying superconductivity as it evolves between crystalline and amorphous materials.« less

Experimental evidence for excess entropy discontinuities in glass-forming solutions.

PubMed

Lienhard, Daniel M; Zobrist, Bernhard; Zuend, Andreas; Krieger, Ulrich K; Peter, Thomas

2012-02-21

Glass transition temperatures T(g) are investigated in aqueous binary and multi-component solutions consisting of citric acid, calcium nitrate (Ca(NO(3))(2)), malonic acid, raffinose, and ammonium bisulfate (NH(4)HSO(4)) using a differential scanning calorimeter. Based on measured glass transition temperatures of binary aqueous mixtures and fitted binary coefficients, the T(g) of multi-component systems can be predicted using mixing rules. However, the experimentally observed T(g) in multi-component solutions show considerable deviations from two theoretical approaches considered. The deviations from these predictions are explained in terms of the molar excess mixing entropy difference between the supercooled liquid and glassy state at T(g). The multi-component mixtures involve contributions to these excess mixing entropies that the mixing rules do not take into account. © 2012 American Institute of Physics

Competitive adsorption from mixed hen egg-white lysozyme/surfactant solutions at the air-water interface studied by tensiometry, ellipsometry, and surface dilational rheology.

PubMed

Alahverdjieva, V S; Grigoriev, D O; Fainerman, V B; Aksenenko, E V; Miller, R; Möhwald, H

2008-02-21

The competitive adsorption at the air-water interface from mixed adsorption layers of hen egg-white lysozyme with a non-ionic surfactant (C10DMPO) was studied and compared to the mixture with an ionic surfactant (SDS) using bubble and drop shape analysis tensiometry, ellipsometry, and surface dilational rheology. The set of equilibrium and kinetic data of the mixed solutions is described by a thermodynamic model developed recently. The theoretical description of the mixed system is based on the model parameters for the individual components.

Bioavailable concentrations of germanium and rare earth elements in soil as affected by low molecular weight organic acids and root exudates

NASA Astrophysics Data System (ADS)

Wiche, Oliver; Székely, Balázs; Kummer, Nicolai-Alexeji; Heinemann, Ute; Tesch, Silke; Heilmeier, Hermann

2014-05-01

Availability of elements in soil to plant is generally dependent on the solubility and mobility of elements in soil solution which is controlled by soil, elemental properties and plant-soil interactions. Low molecular organic acids or other root exudates may increase mobility and availability of certain elements for plants as an effect of lowering pH in the rhizosphere and complexation. However, these processes take place in a larger volume in soil, therefore to understand their nature, it is also important to know in which layers of the soil what factors modify these processes. In this work the influence of citric acid and root exudates of white lupin (Lupinus albus L.) on bioavailable concentrations of germanium, lanthan, neodymium, gadolinium and erbium in soil solution and uptake in root and shoot of rape (Brassica napus L.), comfrey (Symphytum officinale L.), common millet (Panicum milliaceum L.) and oat (Avena sativa L.) was investigated. Two different pot experiments were conducted: (1) the mentioned plant species were treated with nutrient solutions containing various amount of citric acid; (2) white lupin was cultivated in mixed culture (0 % lupin, 33 % lupin) with oat (Avena sativa L.) and soil solution was obtained by plastic suction cups placed at various depths. As a result, addition of citric acid significantly increased germanium concentrations in plant tissue of comfrey and rape and increased translocation of germanium, lanthan, neodymium, gadolinium and erbium from root to shoot. The cultivation of white lupin in mixed culture with oat led to significantly higher concentrations of germanium and increasing concentrations of lanthan, neodymium, gadolinium and erbium in soil solution and aboveground plant tissue. In these pots concentrations of citric acid in soil solution were significantly higher than in the control. The results show, that low molecular organic acids exuded by plant roots are of great importance for the mobilization of germanium, lanthan, neodymium, gadolinium and erbium in the rhizosphere and therefore the enhancement of bioavailability of the mentioned elements to plants. Based on the suction cup experiment we conclude that in vertical soil profile the bioavailable germanium is heavily affected by the activity of exudates, as the complexation processes of germanium take place at the root zone and below affected by the interplay of the infiltration of citric acid solutions and the actually produced exudates. These studies have been carried out in the framework of the PhytoGerm project, financed by the Federal Ministry of Education and Research, Germany. BS contributed as an Alexander von Humboldt Research Fellow. The authors are grateful to students and laboratory assistants contributing in the field work and sample preparation.

Improvement of the tetrachloromercurate absorption technique for measuring low atmospheric SO2 mixing ratios

NASA Astrophysics Data System (ADS)

Jaeschke, W.; Beltz, N.; Haunold, W.; Krischke, U.

1997-07-01

During the Gas-Phase Sulfur Intercomparison Experiment (GASIE) in 1994 an analytical system for measuring sulfur dioxide mixing ratios at low parts per trillion (pptv) levels was employed. It is based on the absorption of SO2 on a tetrachloromercurate(II)-impregnated filter. The subsequent analysis uses a chemiluminescence reaction by treating the resulting disulfitomercurate(II) complex with an acidic cerium sulfate solution. An improved sampling device has been introduced that increases the maximum sampling volume from 200 L to 500 L. It is also possible to determine the blank value accurately for each sample. The absorption efficiency of the sampling system is 98.7±6.4% at a nominal flow rate of 10 L/min. The calculated (3σ) detection limit is 3±1 pptv SO2. The sample solution is stable for up to 30 days, which allows the samples to be safely stored or shipped before analysis. This permits the use of a sensitive, compact, and reliable sampling system in the field with subsequent analysis under optimal conditions in the laboratory. A continuous flow chemiluminescence (CFCL) analyzer for on-line measurements is also presented. The system is based on the same chemical principles as the described filter technique.

Modeling of Flow, Transport and Controlled Sedimentation Phenomena during Mixing of Salt Solutions in Complex Porous Formations

NASA Astrophysics Data System (ADS)

Skouras, Eugene D.; Jaho, Sofia; Pavlakou, Efstathia I.; Sygouni, Varvara; Petsi, Anastasia; Paraskeva, Christakis A.

2015-04-01

The deposition of salts in porous media is a major engineering phenomenon encountered in a plethora of industrial and environmental applications where in some cases is desirable and in other not (oil production, geothermal systems, soil stabilization etc). Systematic approach of these problems requires knowledge of the key mechanisms of precipitating salts within the porous structures, in order to develop new methods to control the process. In this work, the development and the solution of spatiotemporally variable mass balances during salt solution mixing along specific pores were performed. Both analytical models and finite differences CFD models were applied for the study of flow and transport with simultaneous homogeneous and heterogeneous nucleation (by crystal growth on the surface of the pores) in simple geometries, while unstructured finite elements and meshless methods were developed and implemented for spatial discretization, reconstruction, and solution of transport equations and homogeneous / heterogeneous reactions in more complex geometries. At initial stages of this work, critical problem parameters were identified, such as the characteristics of the porosity, the number of dissolved components, etc. The parameters were then used for solving problems which correspond to available experimental data. For each combination of ions and materials, specific data and process characteristics were included: (a) crystal kinetics (nucleation, growth rates or reaction surface rates of crystals, critical suspension concentrations), (b) physico-chemical properties (bulk density, dimensions of generated crystals, ion diffusion coefficients in the solution), (c) operating parameters (macroscopic velocity, flow, or pressure gradient of the solution, ion concentration) (d) microfluidic data (geometry, flow area), (e) porosity data in Darcy description (initial porosity, specific surface area, tortuosity). During the modeling of flow and transport in three-dimensional pore network, the dependence of the mass balance in all major directions is taken into account, either as a three-dimensional network of pores with specific geometry (cylinders, sinusoidal cells), or as a homogeneous random medium (Darcy description). The distribution of the crystals along the porous medium was calculated in the case of selective crystallization on the walls, which is the predominant effect to date in the experiments. The crystals distribution was also examined in the case where crystallization was carried out in the bulk solution. Salts sedimentation experiments were simulated both in an unsaturated porous medium and in a medium saturated with an oil phase. A comparison of the simulation results with corresponding experimental results was performed in order to design improved selective sedimentation of salts systems in porous formations. ACKNOWLEDGMENTS This research was partially funded by the European Union (European Social Fund-ESF) and Greek National Funds through the Operational program "Education and Lifelong Learning" under the action Aristeia II (Code No 4420).

Phase formation and UV luminescence of Gd3+ doped perovskite-type YScO3

NASA Astrophysics Data System (ADS)

Shimizu, Yuhei; Ueda, Kazushige

2016-10-01

Synthesis of pure and Gd3+doped perovskite-type YScO3 was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd3+ doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phase at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO3 formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO3. Because Gd3+ ions were also dissolved into the single C-type phase in Gd3+ doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase.

The Mitosis and Neurodevelopment Proteins NDE1 and NDEL1 Form Dimers, Tetramers, and Polymers with a Folded Back Structure in Solution*

PubMed Central

Soares, Dinesh C.; Bradshaw, Nicholas J.; Zou, Juan; Kennaway, Christopher K.; Hamilton, Russell S.; Chen, Zhuo A.; Wear, Martin A.; Blackburn, Elizabeth A.; Bramham, Janice; Böttcher, Bettina; Millar, J. Kirsty; Barlow, Paul N.; Walkinshaw, Malcolm D.; Rappsilber, Juri; Porteous, David J.

2012-01-01

Paralogs NDE1 (nuclear distribution element 1) and NDEL1 (NDE-like 1) are essential for mitosis and neurodevelopment. Both proteins are predicted to have similar structures, based upon high sequence similarity, and they co-complex in mammalian cells. X-ray diffraction studies and homology modeling suggest that their N-terminal regions (residues 8–167) adopt continuous, extended α-helical coiled-coil structures, but no experimentally derived information on the structure of their C-terminal regions or the architecture of the full-length proteins is available. In the case of NDE1, no biophysical data exists. Here we characterize the structural architecture of both full-length proteins utilizing negative stain electron microscopy along with our established paradigm of chemical cross-linking followed by tryptic digestion, mass spectrometry, and database searching, which we enhance using isotope labeling for mixed NDE1-NDEL1. We determined that full-length NDE1 forms needle-like dimers and tetramers in solution, similar to crystal structures of NDEL1, as well as chain-like end-to-end polymers. The C-terminal domain of each protein, required for interaction with key protein partners dynein and DISC1 (disrupted-in-schizophrenia 1), includes a predicted disordered region that allows a bent back structure. This facilitates interaction of the C-terminal region with the N-terminal coiled-coil domain and is in agreement with previous results showing N- and C-terminal regions of NDEL1 and NDE1 cooperating in dynein interaction. It sheds light on recently identified mutations in the NDE1 gene that cause truncation of the encoded protein. Additionally, analysis of mixed NDE1-NDEL1 complexes demonstrates that NDE1 and NDEL1 can interact directly. PMID:22843697

Osmotically Induced Reversible Transitions in Lipid-DNA Mesophases

PubMed Central

Danino, Dganit; Kesselman, Ellina; Saper, Gadiel; Petrache, Horia I.; Harries, Daniel

2009-01-01

We follow the effect of osmotic pressure on isoelectric complexes that self-assemble from mixtures of DNA and mixed neutral and cationic lipids. Using small angle x-ray diffraction and freeze-fracture cryo-electron microscopy, we find that lamellar complexes known to form in aqueous solutions can reversibly transition to hexagonal mesophases under high enough osmotic stress exerted by adding a neutral polymer. Using molecular spacings derived from x-ray diffraction, we estimate the reversible osmotic pressure-volume (Π-V) work needed to induce this transition. We find that the transition free energy is comparable to the work required to elastically bend lipid layers around DNA. Consistent with this, the required work is significantly lowered by an addition of hexanol, which is known to soften lipid bilayers. Our findings not only help to resolve the free-energy contributions associated with lipid-DNA complex formation, but they also demonstrate the importance that osmotic stress can have to the macromolecular phase geometry in realistic biological environments. PMID:19348739

Phases, periphases, and interphases equilibrium by molecular modeling. I. Mass equilibrium by the semianalytical stochastic perturbations method and application to a solution between (120) gypsum faces

NASA Astrophysics Data System (ADS)

Pedesseau, Laurent; Jouanna, Paul

2004-12-01

The SASP (semianalytical stochastic perturbations) method is an original mixed macro-nano-approach dedicated to the mass equilibrium of multispecies phases, periphases, and interphases. This general method, applied here to the reflexive relation Ck⇔μk between the concentrations Ck and the chemical potentials μk of k species within a fluid in equilibrium, leads to the distribution of the particles at the atomic scale. The macroaspects of the method, based on analytical Taylor's developments of chemical potentials, are intimately mixed with the nanoaspects of molecular mechanics computations on stochastically perturbed states. This numerical approach, directly linked to definitions, is universal by comparison with current approaches, DLVO Derjaguin-Landau-Verwey-Overbeek, grand canonical Monte Carlo, etc., without any restriction on the number of species, concentrations, or boundary conditions. The determination of the relation Ck⇔μk implies in fact two problems: a direct problem Ck⇒μk and an inverse problem μk⇒Ck. Validation of the method is demonstrated in case studies A and B which treat, respectively, a direct problem and an inverse problem within a free saturated gypsum solution. The flexibility of the method is illustrated in case study C dealing with an inverse problem within a solution interphase, confined between two (120) gypsum faces, remaining in connection with a reference solution. This last inverse problem leads to the mass equilibrium of ions and water molecules within a 3 Å thick gypsum interface. The major unexpected observation is the repulsion of SO42- ions towards the reference solution and the attraction of Ca2+ ions from the reference solution, the concentration being 50 times higher within the interphase as compared to the free solution. The SASP method is today the unique approach able to tackle the simulation of the number and distribution of ions plus water molecules in such extreme confined conditions. This result is of prime importance for all coupled chemical-mechanical problems dealing with interfaces, and more generally for a wide variety of applications such as phase changes, osmotic equilibrium, surface energy, etc., in complex chemical-physics situations.

AQUO-OXALATO-SULFATE COMPOUNDS OF URANIUM (in Russian)

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

Chernyaev, I.I.; Golovnya, V.A.; Shchelokov, R.N.

1960-07-01

The following mixed aquo-acido complex uranyl compounds containing an oxalate and a sulfate group were synthesized for the first time: K/sub 2/STAUO/ sub 2/(C/sub 2/O/sub 4/) (SO/sub 4/ (H/sub 2/O)/sub 2/!. H/sub 2/O, Rb/sub 2/ STAUO/sub 2/(C/sub 2/O/sub 4/)(SO/sub 4/)(H/sub 2/O)/sub 2/!, Cs/sub 2/STAUO/sub 2/(C/sub 2/O/sub 4/)(SO/sub 4/)(H/sub 2/O)/sub 2/)!, and Cs(NH/sub 4/) (UO/sub 2/ (C/sub 2/O/sub 4/) (SO/sub 4/)(H/sub 2/O)/sub 2/!. T he molecular conductivity and pH were determined in dilute solutions, and it was concluded that the decrease in stability of these complexes in aqueous solution is as follows: STAUO/ sub 2/(C/sub 2/O/sub 4/)/sub 2/(H/sub 2/O)/sub 2/!/sup 2-/more » > STAUO/sub 2/(C/su b 2/O/sub 4/)(SO/sub 4)(H/sub 2/O)/sub 2/!/sup 2-/ > STAUO/sub 2/(SO/sub 4/)/sub 2/ (H/sub 2O)/sub 2/!/sup 2-. (TTT)« less

Joint physical and numerical modeling of water distribution networks.

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

Zimmerman, Adam; O'Hern, Timothy John; Orear, Leslie Jr.

2009-01-01

This report summarizes the experimental and modeling effort undertaken to understand solute mixing in a water distribution network conducted during the last year of a 3-year project. The experimental effort involves measurement of extent of mixing within different configurations of pipe networks, measurement of dynamic mixing in a single mixing tank, and measurement of dynamic solute mixing in a combined network-tank configuration. High resolution analysis of turbulence mixing is carried out via high speed photography as well as 3D finite-volume based Large Eddy Simulation turbulence models. Macroscopic mixing rules based on flow momentum balance are also explored, and in somemore » cases, implemented in EPANET. A new version EPANET code was developed to yield better mixing predictions. The impact of a storage tank on pipe mixing in a combined pipe-tank network during diurnal fill-and-drain cycles is assessed. Preliminary comparison between dynamic pilot data and EPANET-BAM is also reported.« less

Improved source apportionment of organic aerosols in complex urban air pollution using the multilinear engine (ME-2)

NASA Astrophysics Data System (ADS)

Zhu, Qiao; Huang, Xiao-Feng; Cao, Li-Ming; Wei, Lin-Tong; Zhang, Bin; He, Ling-Yan; Elser, Miriam; Canonaco, Francesco; Slowik, Jay G.; Bozzetti, Carlo; El-Haddad, Imad; Prévôt, André S. H.

2018-02-01

Organic aerosols (OAs), which consist of thousands of complex compounds emitted from various sources, constitute one of the major components of fine particulate matter. The traditional positive matrix factorization (PMF) method often apportions aerosol mass spectrometer (AMS) organic datasets into less meaningful or mixed factors, especially in complex urban cases. In this study, an improved source apportionment method using a bilinear model of the multilinear engine (ME-2) was applied to OAs collected during the heavily polluted season from two Chinese megacities located in the north and south with an Aerodyne high-resolution aerosol mass spectrometer (HR-ToF-AMS). We applied a rather novel procedure for utilization of prior information and selecting optimal solutions, which does not necessarily depend on other studies. Ultimately, six reasonable factors were clearly resolved and quantified for both sites by constraining one or more factors: hydrocarbon-like OA (HOA), cooking-related OA (COA), biomass burning OA (BBOA), coal combustion (CCOA), less-oxidized oxygenated OA (LO-OOA) and more-oxidized oxygenated OA (MO-OOA). In comparison, the traditional PMF method could not effectively resolve the appropriate factors, e.g., BBOA and CCOA, in the solutions. Moreover, coal combustion and traffic emissions were determined to be primarily responsible for the concentrations of PAHs and BC, respectively, through the regression analyses of the ME-2 results.

Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution.

PubMed

Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J; Golovanov, Alexander P

2016-07-14

The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (Sos(Cat)) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of Sos(Cat), while Sos(Cat) also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos.

Labeling and Functionalizing Amphipols for Biological Applications

PubMed Central

Bon, Christel Le; Popot, Jean-Luc; Giusti, Fabrice

2014-01-01

Amphipols (APols) are short amphipathic polymers developed as an alternative to detergents for handling membrane proteins (MPs) in aqueous solution. MPs are, as a rule, much more stable following trapping with APols than they are in detergent solutions. The best-characterized APol to date, called A8-35, is a mixture of short-chain sodium polyacrylates randomly derivatized with octylamine and isopropylamine. Its solution properties have been studied in detail, and it has been used extensively for biochemical and biophysical studies of MPs. One of the attractive characteristics of APols is that it is relatively easy to label them, isotopically or otherwise, without affecting their physical-chemical properties. Furthermore, several variously modified APols can be mixed, achieving multiple functionalization of MP/APol complexes in the easiest possible manner. Labeled or tagged APols are being used to study the solution properties of APols, their miscibility, their biodistribution upon injection into living organisms, their association with MPs and the composition, structure and dynamics of MP/APol complexes, examining the exchange of surfactants at the surface of MPs, labeling MPs to follow their distribution in fractionation experiments or to immobilize them, increasing the contrast between APols and solvent or MPs in biophysical experiments, improving NMR spectra, etc. Labeling or functionalization of APols can take various courses, each of which has its specific constraints and advantages regarding both synthesis and purification. The present review offers an overview of the various derivatives of A8-35 and its congeners that have been developed in our laboratory and discusses the pros and cons of various synthetic routes. PMID:24696186

Flow of wormlike micellar solutions around confined microfluidic cylinders.

PubMed

Zhao, Ya; Shen, Amy Q; Haward, Simon J

2016-10-26

Wormlike micellar (WLM) solutions are frequently used in enhanced oil and gas recovery applications in porous rock beds where complex microscopic geometries result in mixed flow kinematics with strong shear and extensional components. Experiments with WLM solutions through model microfluidic porous media have revealed a variety of complex flow phenomena, including the formation of stable gel-like structures known as a Flow-Induced Structured Phase (FISP), which undoubtedly play an important role in applications of WLM fluids, but are still poorly understood. A first step in understanding flows of WLM fluids through porous media can be made by examining the flow around a single micro-scale cylinder aligned on the flow axis. Here we study flow behavior of an aqueous WLM solution consisting of cationic surfactant cetyltrimethylammonium bromide (CTAB) and a stable hydrotropic salt 3-hydroxy naphthalene-2-carboxylate (SHNC) in microfluidic devices with three different cylinder blockage ratios, β. We observe a rich sequence of flow instabilities depending on β as the Weissenberg number (Wi) is increased to large values while the Reynolds number (Re) remains low. Instabilities upstream of the cylinder are associated with high stresses in fluid that accelerates into the narrow gap between the cylinder and the channel wall; vortex growth upstream is reminiscent of that seen in microfluidic contraction geometries. Instability downstream of the cylinder is associated with stresses generated at the trailing stagnation point and the resulting flow modification in the wake, coupled with the onset of time-dependent flow upstream and the asymmetric division of flow around the cylinder.

Sol-gel type synthesis of Bi.sub.2 (Sr,Ta.sub.2)O.sub.9 using an acetate based system

DOEpatents

Boyle, Timothy J.

1997-01-01

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen.

Sol-gel type synthesis of Bi{sub 2}(Sr,Ta{sub 2})O{sub 9} using an acetate based system

DOEpatents

Boyle, T.J.

1997-11-04

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen. 6 figs.

MBSSAS: A code for the computation of margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

USGS Publications Warehouse

Glynn, P.D.

1991-01-01

The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henry's law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system. ?? 1991.

A Comparison of Blood Factor XII Autoactivation in Buffer, Protein Cocktail, Serum, and Plasma Solutions

PubMed Central

Golas, Avantika; Yeh, Chyi-Huey Josh; Pitakjakpipop, Harit; Siedlecki, Christopher A.; Vogler, Erwin A.

2012-01-01

Activation of blood plasma coagulation in vitro by contact with material surfaces is demonstrably dependent on plasma-volume-to-activator-surface-area ratio. The only plausible explanation consistent with current understanding of coagulation-cascade biochemistry is that procoagulant stimulus arising from the activation complex of the intrinsic pathway is dependent on activator surface area. And yet, it is herein shown that activation of the blood zymogen factor XII (Hageman factor, FXII) dissolved in buffer, protein cocktail, heat-denatured serum, and FXI deficient plasma does not exhibit activator surface-area dependence. Instead, a highly-variable burst of procoagulant-enzyme yield is measured that exhibits no measurable kinetics, sensitivity to mixing, or solution-temperature dependence. Thus, FXII activation in both buffer and protein-containing solutions does not exhibit characteristics of a biochemical reaction but rather appears to be a “mechanochemical” reaction induced by FXII molecule interactions with hydrophilic activator particles that do not formally adsorb blood proteins from solution. Results of this study strongly suggest that activator surface-area dependence observed in contact activation of plasma coagulation does not solely arise at the FXII activation step of the intrinsic pathway. PMID:23117212

An ignored variable: solution preparation temperature in protein crystallization.

PubMed

Chen, Rui-Qing; Lu, Qin-Qin; Cheng, Qing-Di; Ao, Liang-Bo; Zhang, Chen-Yan; Hou, Hai; Liu, Yong-Ming; Li, Da-Wei; Yin, Da-Chuan

2015-01-19

Protein crystallization is affected by many parameters, among which certain parameters have not been well controlled. The temperature at which the protein and precipitant solutions are mixed (i.e., the ambient temperature during mixing) is such a parameter that is typically not well controlled and is often ignored. In this paper, we show that this temperature can influence protein crystallization. The experimental results showed that both higher and lower mixing temperatures can enhance the success of crystallization, which follows a parabolic curve with an increasing ambient temperature. This work illustrates that the crystallization solution preparation temperature is also an important parameter for protein crystallization. Uncontrolled or poorly controlled room temperature may yield poor reproducibility in protein crystallization.

Temperature and pH effects on plant uptake of benzotriazoles by sunflowers in hydroponic culture.

PubMed

Castro, Sigifredo; Davis, Lawrence C; Erickson, Larry E

2004-01-01

This article describes a systematic approach to understanding the effect of environmental variables on plant uptake (phyto-uptake) of organic contaminants. Uptake (and possibly phytotransformation) of xenobiotics is a complex process that may differ from nutrient uptake. A specific group of xenobiotics (benzotriazoles) were studied using sunflowers grown hydroponically with changes of environmental conditions including solution volume, temperature, pH, and mixing. The response of plants to these stimuli was evaluated and compared using physiological changes (biomass production and water uptake) and estimated uptake rates (influx into plants), which define the uptake characteristics for the xenobiotic. Stirring of the hydroponic solution had a significant impact on plant growth and water uptake. Plants were healthier, probably because of a combination of factors such as improved aeration and increase in temperature. Uptake and possibly phytotransformation of benzotriazoles was increased accordingly. Experiments at different temperatures allowed us to estimate an activation energy for the reaction leading to triazole disappearance from the solution. The estimated activation energy was 43 kJ/mol, which indicates that the uptake process is kinetically limited. Culturing plants in triazole-amended hydroponic solutions at different pH values did not strongly affect the biomass production, water uptake, and benzotriazole uptake characteristics. The sunflowers showed an unexpected capacity to buffer the solution pH.

Multiobjective optimization of urban water resources: Moving toward more practical solutions

NASA Astrophysics Data System (ADS)

Mortazavi, Mohammad; Kuczera, George; Cui, Lijie

2012-03-01

The issue of drought security is of paramount importance for cities located in regions subject to severe prolonged droughts. The prospect of "running out of water" for an extended period would threaten the very existence of the city. Managing drought security for an urban water supply is a complex task involving trade-offs between conflicting objectives. In this paper a multiobjective optimization approach for urban water resource planning and operation is developed to overcome practically significant shortcomings identified in previous work. A case study based on the headworks system for Sydney (Australia) demonstrates the approach and highlights the potentially serious shortcomings of Pareto optimal solutions conditioned on short climate records, incomplete decision spaces, and constraints to which system response is sensitive. Where high levels of drought security are required, optimal solutions conditioned on short climate records are flawed. Our approach addresses drought security explicitly by identifying approximate optimal solutions in which the system does not "run dry" in severe droughts with expected return periods up to a nominated (typically large) value. In addition, it is shown that failure to optimize the full mix of interacting operational and infrastructure decisions and to explore the trade-offs associated with sensitive constraints can lead to significantly more costly solutions.

Comparison of solution-mixed and sequentially processed P3HT: F4TCNQ films: effect of doping-induced aggregation on film morphology

DOE PAGES

Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.; ...

2016-03-23

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly moremore » uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. In conclusion, we propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.« less

Comparison of solution-mixed and sequentially processed P3HT: F4TCNQ films: effect of doping-induced aggregation on film morphology

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

Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly moremore » uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. In conclusion, we propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.« less

Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

PubMed

Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

2015-11-01

Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound.

Adsorption performance of mixed dyes on alkalization loofah fibers

NASA Astrophysics Data System (ADS)

Wang, Yongli; Liu, Jinyan; Li, Xingxing

2018-02-01

When the polyporous structures of loofah fiber is adequately exposed after alkali treatment,lignin, hemicellulose and pectin are removed. Specific surface area is increased to maximum, which means the efficiency of absorptivity is highest. In this paper, by using alkalization loofah (AL) as adsorbent, the effect of loofah fiber on waste water treatment is studied under the efficiency of loofah fiber which contain acridine yellow, methylene blue, mixed solution of the two dyes. The optimum treatment conditions of loofah fiber were studied from five aspects which include dosage, temperature, mixing time, pH and concentration. The results showed that the optimal conditions are 30°C, pH 8.0, 20mg dosage of loofah fiber in 40ml solution and mixing time 25min. The optimal treatment conditions of mixed dyes were studied from the aspects of mixing time, the dosage of AL and the molar ratio of the two components in the mixed dyes.

Rare earth element behavior during groundwater–seawater mixing along the Kona Coast of Hawaii

DOE PAGES

Johannesson, Karen H.; Palmore, C. Dianne; Fackrell, Joseph; ...

2016-11-14

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previously we saw that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries.more » Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were conducted with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO 3) 2 -] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Altogether, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3–2.6 mmol Nd day -1) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.« less

Rare earth element behavior during groundwater–seawater mixing along the Kona Coast of Hawaii

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

Johannesson, Karen H.; Palmore, C. Dianne; Fackrell, Joseph

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previously we saw that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries.more » Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were conducted with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO 3) 2 -] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are between 10 and 50 times higher than previously reported open-ocean seawater values from the North Pacific, further demonstrating the importance of SGD fluxes of REEs to these coastal waters. Altogether, these observations indicate that large-scale removal of REEs, which characterizes the behavior of REEs in the low salinity reaches of many surface estuaries, is not a feature of the subterranean estuary along the Kona Coast. A large positive gadolinium (Gd) anomaly characterizes groundwater from the vicinity of the WWTF. The positive Gd anomaly can be traced to the coastal ocean, providing further evidence of the impact of SGD on the coastal waters. Estimates of the SGD fluxes of the REEs to the coastal ocean along the Kona Coast (i.e., 1.3–2.6 mmol Nd day -1) are similar to recent estimates of SGD fluxes of REEs along Florida’s east coast and to Rhode Island Sound, all of which points to the importance of SGD as significant flux of REEs to the coastal ocean.« less

Local environment around gold (III) in aqueous chloride solutions: An EXAFS spectroscopy study

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Sharps, Julia A.; Brown, Gordon E., Jr.

1993-03-01

The local environment around Au (III) in aqueous solutions containing 1 M NaCl was determined as a function of pH and Au concentration using X-ray absorption spectroscopy (XAS) at ambient temperature and pressure. The solution Au concentrations studied were 10 - to 10 -3 M and the pH ranged between 2 and 9.2. No significant changes of Au speciation were detected with increasing Au concentration; however, major speciation changes were caused by variations in pH. At pH = 2, Au is coordinated by four Cl atoms ( mean d [AuCl] = 2.28 -2.29 ± 0.01 Å), whereas at pH 7.5 and 9.2, Au is coordinated by three Cl and one O (or OH) and by two Cl and two O (or OH), respectively ( mean d[AuCl] = 2.28 ± 0.02 Å; mean d[AuO or AuOH] = 1.97 ± 0.02 Å), indicating replacement of Cl by O (or OH) with increasing pH. In all solutions studied, the number of first-neighbors around Au(III) is close to four. XANES analysis suggests the presence of a square-planar geometry for AuX 4 ( X = Cl, O) at all pH values studied. These results are in excellent agreement with those from our previous Raman, resonance Raman, and UV/visible spectroscopy study of gold(III)-chloride solutions (PECK et al., 1991), which found that AuCl 4-, AuCl 3(OH) -, and AuCl 2(OH) 2- are the majority species in the pH ranges 2-6, 6-8.5, and 8.5-11, respectively. We did not find evidence for Au(I)Cl 2- or Au(I)Cl(OH) - complexes in our pH 7.5 and 9.2 solutions, as was recently suggested by PAN and WOOD (1991) for acidic gold chloride solutions at temperatures > 100°C, although we can't rule these complexes out as minority species (<10% of the total Au in solution). Our EXAFS results also provide the first direct evidence for Cl second neighbors around AuCl 4- complexes in the most acidic solutions studied ( pH = 2 and 4.5). These second-neighbor Cl atoms were also detected at low Au concentrations (10 -3 M) and are similar in number and arrangement to those observed in crystalline KAuCL 4·2H 2O (two Cl at a mean d[Au-Cl(2)] = 4.42 ± 0.03 Å). No evidence was found for second-neighbor Au atoms, which indicates little or no Au polymers or colloidal particles in any of the solutions studied. Our EXAFS results are in broad agreement with earlier predictions of Au speciation based on a variety of chemical measurements. Moreover, they directly confirm that mixed chloro-hydroxo Au (III) complexes are more stable than predicted on the basis of thermodynamically estimated stability constants.

Small-angle neutron scattering study of the structure of mixed micellar solutions based on heptaethylene glycol monotetradecyl ether and cesium dodecyl sulfate

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

Rajewska, A., E-mail: aldonar@jinr.ru; Medrzycka, K.; Hallmann, E.

2016-01-15

The micellization in mixed aqueous systems based on a nonionic surfactant, heptaethylene glycol monotetradecyl ether (C{sub 14}E{sub 7}), and an anionic surfactant, cesium dodecyl sulfate, has been investigated by small-angle neutron scattering. Preliminary data on the behavior of the C{sub 14}E{sub 7} aqueous solutions (with three concentrations, 0.17, 0.5, and 1%) mixed with a small amount of anionic surfactant, cesium dodecyl sulfate, are reported.

Comparison of Node-Centered and Cell-Centered Unstructured Finite-Volume Discretizations: Viscous Fluxes

NASA Technical Reports Server (NTRS)

Diskin, Boris; Thomas, James L.; Nielsen, Eric J.; Nishikawa, Hiroaki; White, Jeffery A.

2010-01-01

Discretization of the viscous terms in current finite-volume unstructured-grid schemes are compared using node-centered and cell-centered approaches in two dimensions. Accuracy and complexity are studied for four nominally second-order accurate schemes: a node-centered scheme and three cell-centered schemes - a node-averaging scheme and two schemes with nearest-neighbor and adaptive compact stencils for least-square face gradient reconstruction. The grids considered range from structured (regular) grids to irregular grids composed of arbitrary mixtures of triangles and quadrilaterals, including random perturbations of the grid points to bring out the worst possible behavior of the solution. Two classes of tests are considered. The first class of tests involves smooth manufactured solutions on both isotropic and highly anisotropic grids with discontinuous metrics, typical of those encountered in grid adaptation. The second class concerns solutions and grids varying strongly anisotropically over a curved body, typical of those encountered in high-Reynolds number turbulent flow simulations. Tests from the first class indicate the face least-square methods, the node-averaging method without clipping, and the node-centered method demonstrate second-order convergence of discretization errors with very similar accuracies per degree of freedom. The tests of the second class are more discriminating. The node-centered scheme is always second order with an accuracy and complexity in linearization comparable to the best of the cell-centered schemes. In comparison, the cell-centered node-averaging schemes may degenerate on mixed grids, have a higher complexity in linearization, and can fail to converge to the exact solution when clipping of the node-averaged values is used. The cell-centered schemes using least-square face gradient reconstruction have more compact stencils with a complexity similar to that of the node-centered scheme. For simulations on highly anisotropic curved grids, the least-square methods have to be amended either by introducing a local mapping based on a distance function commonly available in practical schemes or modifying the scheme stencil to reflect the direction of strong coupling. The major conclusion is that accuracies of the node centered and the best cell-centered schemes are comparable at equivalent number of degrees of freedom.

From Carbonatite to Ikaite: How high-T carbonates are transformed into low-T carbonate minerals in SW Greenland

NASA Astrophysics Data System (ADS)

Stockmann, G. J.; Tollefsen, E.; Ranta, E.; Skelton, A.; Sturkell, E.; Lundqvist, L.

2015-12-01

The 1300 Ma Grønnedal-Íka igneous complex in southwest Greenland comprises nepheline syenites and carbonatites. It belongs to a suite of intrusions formed 1300-1100 Ma ago referred to as the Gardar period. In modern time (the last ca. 8000 years), fluid-rock interactions involving the nepheline syenites and carbonatites gives rise to about one thousand submarine columns made of the rare low-T mineral ikaite (CaCO3x6H2O). The columns are found in a shallow, narrow fjord named Ikka Fjord and their distribution clearly follows the outcrop of the Grønnedal-Íka complex. When meteoric water percolates through the highly fractured complex, a sodium carbonate solution of pH 10 is formed through hitherto unknown fluid-rock reactions. This basic solution seeps up through fractures at the bottom of Ikka Fjord and when mixed with seawater, the mineral ikaite is formed. As the seepage water has a lower density than seawater, there is an upwards flow that creates columns. What is peculiar about ikaite is its limited stability making it unstable above +6 °C. Isotopic studies of ikaite reveal a seawater origin for the Ca2+ ions, and the carbonatite being the most likely source for the CO32- ions. The carbonatite is mainly of søvite composition (CaCO3) with high contents of siderite and ankerite in certain areas. The nepheline syenites contain Na,K-rich minerals like nepheline, alkali-feldspar, aegirine-augite, katophorite and biotite. Nepheline is mainly replaced by muscovite, and aegirine-augite partly by chlorite, which could release sodium into solution. A dolerite dyke of unknown age prompted extensive mineralization of magnetite by activating hydrothermal fluid convection. The fluid interacted with the carbonatite, replacing siderite and ankerite by magnetite and later hematite. In a newly launched project at Stockholm University, we are trying to unravel the chemical reactions taking place inside the Grønnedal-Íka igneous complex leading to the formation of the sodium carbonate solution issuing in Ikka Fjord.

38. DETAIL OF RUINS OF CYANIDE MIXING AND EXTRACTION SHED, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

38. DETAIL OF RUINS OF CYANIDE MIXING AND EXTRACTION SHED, LOOKING SOUTHEAST. CYANIDE SOLUTION WAS PREPARED HERE AND PUMPED UP INTO THE PROCESSING TANKS, AND THE PREGNANT SOLUTION WAS ALSO EXTRACTED HERE AFTER THE LEACHING PROCESS WAS COMPLETE - Skidoo Mine, Park Route 38 (Skidoo Road), Death Valley Junction, Inyo County, CA

Application of precipitation methods for the production of water-insoluble drug nanocrystals: production techniques and stability of nanocrystals.

PubMed

Xia, Dengning; Gan, Yong; Cui, Fude

2014-01-01

This review focuses on using precipitation (bottom-up) method to produce water-insoluble drug nanocrystals, and the stability issues of nanocrystals. The precipitation techniques for production of ultra-fine particles have been widely researched for last few decades. In these techniques, precipitation of solute is achieved by addition of a non-solvent for solute called anti-solvent to decrease the solvent power for the solute dissolved in a solution. The anti-solvent can be water, organic solvents or supercritical fluids. In this paper, efforts have been made to review the precipitation techniques involving the anti-solvent precipitation by simple mixing, impinging jet mixing, multi-inlet vortex mixing, the using of high-gravity, ultrasonic waves and supercritical fluids. The key to the success of yielding stable nanocrystals in these techniques is to control the nucleation kinetics and particle growth through mixing during precipitation based on crystallization theories. The stability issues of the nanocrystals, such as sedimentation, Ostwald ripening, agglomeration and cementing of crystals, change of crystalline state, and the approaches to stabilizing nanocrystals are also discussed in detail.

NMR study on the network structure of a mixed gel of kappa and iota carrageenans.

PubMed

Hu, Bingjie; Du, Lei; Matsukawa, Shingo

2016-10-05

The temperature dependencies of the (1)H T2 and diffusion coefficient (D) of a mixed solution of kappa-carrageenan and iota-carrageenan were measured by NMR. Rheological and NMR measurements suggested an exponential formation of rigid aggregates of kappa-carrageenan and a gradual formation of fine aggregates of iota-carrageenan during two step increases of G'. The results also suggested that longer carrageenan chains are preferentially involved in aggregation, thus resulting in a decrease in the average Mw of solute carrageenans. The results of diffusion measurements for poly(ethylene oxide) (PEO) suggested that kappa-carrageenan formed thick aggregates that decreased hindrance to PEO diffusion by decreasing the solute kappa-carrageenan concentration in the voids of the aggregated chains, and that iota-carrageenan formed fine aggregates that decreased the solute iota-carrageenan concentration less. DPEO in a mixed solution of kappa-carrageenan and iota-carrageenan suggested two possibilities for the microscopic network structure: an interpenetrating network structure, or micro-phase separation. Copyright © 2016. Published by Elsevier Ltd.

Lump and rogue waves for the variable-coefficient Kadomtsev-Petviashvili equation in a fluid

NASA Astrophysics Data System (ADS)

Jia, Xiao-Yue; Tian, Bo; Du, Zhong; Sun, Yan; Liu, Lei

2018-04-01

Under investigation in this paper is the variable-coefficient Kadomtsev-Petviashvili equation, which describes the long waves with small amplitude and slow dependence on the transverse coordinate in a single-layer shallow fluid. Employing the bilinear form and symbolic computation, we obtain the lump, mixed lump-stripe soliton and mixed rogue wave-stripe soliton solutions. Discussions indicate that the variable coefficients are related to both the lump soliton’s velocity and amplitude. Mixed lump-stripe soliton solutions display two different properties, fusion and fission. Mixed rogue wave-stripe soliton solutions show that a rogue wave arises from one of the stripe solitons and disappears into the other. When the time approaches 0, rogue wave’s energy reaches the maximum. Interactions between a lump soliton and one-stripe soliton, and between a rogue wave and a pair of stripe solitons, are shown graphically.

Apparatus and method for continuous production of materials

DOEpatents

Chang, Chih-hung; Jin, Hyungdae

2014-08-12

Embodiments of a continuous-flow injection reactor and a method for continuous material synthesis are disclosed. The reactor includes a mixing zone unit and a residence time unit removably coupled to the mixing zone unit. The mixing zone unit includes at least one top inlet, a side inlet, and a bottom outlet. An injection tube, or plurality of injection tubes, is inserted through the top inlet and extends past the side inlet while terminating above the bottom outlet. A first reactant solution flows in through the side inlet, and a second reactant solution flows in through the injection tube(s). With reference to nanoparticle synthesis, the reactant solutions combine in a mixing zone and form nucleated nanoparticles. The nucleated nanoparticles flow through the residence time unit. The residence time unit may be a single conduit, or it may include an outer housing and a plurality of inner tubes within the outer housing.

Dynamics of lumps and dark-dark solitons in the multi-component long-wave-short-wave resonance interaction system.

PubMed

Rao, Jiguang; Porsezian, Kuppuswamy; He, Jingsong; Kanna, Thambithurai

2018-01-01

General semi-rational solutions of an integrable multi-component (2+1)-dimensional long-wave-short-wave resonance interaction system comprising multiple short waves and a single long wave are obtained by employing the bilinear method. These solutions describe the interactions between various types of solutions, including line rogue waves, lumps, breathers and dark solitons. We only focus on the dynamical behaviours of the interactions between lumps and dark solitons in this paper. Our detailed study reveals two different types of excitation phenomena: fusion and fission. It is shown that the fundamental (simplest) semi-rational solutions can exhibit fission of a dark soliton into a lump and a dark soliton or fusion of one lump and one dark soliton into a dark soliton. The non-fundamental semi-rational solutions are further classified into three subclasses: higher-order, multi- and mixed-type semi-rational solutions. The higher-order semi-rational solutions show the process of annihilation (production) of two or more lumps into (from) one dark soliton. The multi-semi-rational solutions describe N ( N ≥2) lumps annihilating into or producing from N -dark solitons. The mixed-type semi-rational solutions are a hybrid of higher-order semi-rational solutions and multi-semi-rational solutions. For the mixed-type semi-rational solutions, we demonstrate an interesting dynamical behaviour that is characterized by partial suppression or creation of lumps from the dark solitons.

Dynamics of lumps and dark-dark solitons in the multi-component long-wave-short-wave resonance interaction system

NASA Astrophysics Data System (ADS)

Rao, Jiguang; Porsezian, Kuppuswamy; He, Jingsong; Kanna, Thambithurai

2018-01-01

General semi-rational solutions of an integrable multi-component (2+1)-dimensional long-wave-short-wave resonance interaction system comprising multiple short waves and a single long wave are obtained by employing the bilinear method. These solutions describe the interactions between various types of solutions, including line rogue waves, lumps, breathers and dark solitons. We only focus on the dynamical behaviours of the interactions between lumps and dark solitons in this paper. Our detailed study reveals two different types of excitation phenomena: fusion and fission. It is shown that the fundamental (simplest) semi-rational solutions can exhibit fission of a dark soliton into a lump and a dark soliton or fusion of one lump and one dark soliton into a dark soliton. The non-fundamental semi-rational solutions are further classified into three subclasses: higher-order, multi- and mixed-type semi-rational solutions. The higher-order semi-rational solutions show the process of annihilation (production) of two or more lumps into (from) one dark soliton. The multi-semi-rational solutions describe N(N≥2) lumps annihilating into or producing from N-dark solitons. The mixed-type semi-rational solutions are a hybrid of higher-order semi-rational solutions and multi-semi-rational solutions. For the mixed-type semi-rational solutions, we demonstrate an interesting dynamical behaviour that is characterized by partial suppression or creation of lumps from the dark solitons.

The effect of sludge water treatment plant residuals on the properties of compressed brick

NASA Astrophysics Data System (ADS)

Shamsudin, Shamrul-Mar; Shahidan, S.; Azmi, M. A. M.; Ghaffar, S. A.; Ghani, M. B. Abdul; Saiful Bahari, N. A. A.; Zuki, S. S. M.

2017-11-01

The focus of this study is on the production of compressed bricks which contains sludge water treatment plant (SWTP) residuals obtained from SAJ. The main objective of this study is to utilise and incorporate discarded material (SWTP) in the form of residual solution to produce compressed bricks. This serves as one of the recycling efforts to conserve the environment. This study determined the optimum mix based on a mix ratio of 1:2:4 (cement: sand: soil) in the production of compressed bricks where 5 different mixes were investigated i. e. 0%, 5%, 10%, 20%, and 30% of water treatment plant residue solution. The production of the compressed bricks is in accordance with the Malaysian Standard MS 7.6: 1972 and British Standard BS 3921: 1985 - Compressive Strength & Water Absorption. After being moulded and air dried, the cured bricks were subjected to compression tests and water absorption tests. Based on the tests conducted, it was found that 20% of water treatment plant residue solution which is equivalent to 50% of soil content replacement with a mix composition of [10: cement] [20: sand] [20: soil] [20: water treatment plant residue solution] is the optimum mix. It was also observed that the bricks containing SWTP residuals were lighter in weight compared to the control specimens

Evaporation of NaCl solution from porous media with mixed wettability

NASA Astrophysics Data System (ADS)

Bergstad, Mina; Shokri, Nima

2016-05-01

Evaporation of saline water from porous media is ubiquitous in many processes including soil salinization, crop production, and CO2 sequestration in deep saline acquirer. It is controlled by the transport properties of porous media, atmospheric conditions, and properties of the evaporating saline solution. In the present study, the effects of mixed wettability conditions on the general dynamics of water evaporation from porous media saturated with NaCl solution were investigated. To do so, we conducted a comprehensive series of evaporation experiments using sand mixtures containing different fractions of hydrophobic grains saturated with NaCl solutions. Our results showed that increasing fraction of hydrophobic grains in the mixed wettability sand pack had minor impact on the evaporative mass losses due to the presence of salt whose precipitation patterns were significantly influenced by the mixed wettability condition. Through macroscale and microscale investigations, we found formation of patchy efflorescence in the case of mixed wettability sand pack as opposed to crusty efflorescence in the case of completely hydrophilic porous media. Furthermore, the presence of salty water and hydrophobic grains in the sand pack significantly influenced the general dynamics and morphology of the receding drying front. Our results extend the understanding of the saline water evaporation from porous media with direct applications to various hydrological and engineering processes.

Mixing Single Scattering Properties in Vector Radiative Transfer for Deterministic and Stochastic Solutions

NASA Astrophysics Data System (ADS)

Mukherjee, L.; Zhai, P.; Hu, Y.; Winker, D. M.

2016-12-01

Among the primary factors, which determine the polarized radiation, field of a turbid medium are the single scattering properties of the medium. When multiple types of scatterers are present, the single scattering properties of the scatterers need to be properly mixed in order to find the solutions to the vector radiative transfer theory (VRT). The VRT solvers can be divided into two types: deterministic and stochastic. The deterministic solver can only accept one set of single scattering property in its smallest discretized spatial volume. When the medium contains more than one kind of scatterer, their single scattering properties are averaged, and then used as input for the deterministic solver. The stochastic solver, can work with different kinds of scatterers explicitly. In this work, two different mixing schemes are studied using the Successive Order of Scattering (SOS) method and Monte Carlo (MC) methods. One scheme is used for deterministic and the other is used for the stochastic Monte Carlo method. It is found that the solutions from the two VRT solvers using two different mixing schemes agree with each other extremely well. This confirms the equivalence to the two mixing schemes and also provides a benchmark for the VRT solution for the medium studied.

Rapid colorimetric assay for gentamicin injection.

PubMed

Tarbutton, P

1987-01-01

A rapid colorimetric method for determining gentamicin concentration in commercial preparations of gentamicin sulfate injection was developed. Methods currently available for measuring gentamicin concentration via its colored complex with cupric ions in alkaline solution were modified to reduce the time required for a single analysis. The alkaline copper tartrate (ACT) reagent solution was prepared such that each milliliter contained 100 mumol cupric sulfate, 210 mumol potassium sodium tartrate, and 1.25 mmol sodium hydroxide. The assay involves mixing 0.3 mL gentamicin sulfate injection 40 mg/mL (of gentamicin), 1.0 mL ACT reagent, and 0.7 mL water; the absorbance of the resulting solution at 560 nm was used to calculate the gentamicin concentration in the sample. For injections containing 10 mg/mL of gentamicin, the amount of the injection was increased to 0.5 mL and water decreased to 0.5 mL. The concentration of gentamicin in samples representing 11 lots of gentamicin sulfate injection 40 mg/mL and 8 lots of gentamicin sulfate injection 10 mg/mL was determined. The specificity, reproducibility, and accuracy of the assay were assessed. The colored complex was stable for at least two hours. Gentamicin concentration ranged from 93.7 to 108% and from 95 to 109% of the stated label value of the 40 mg/mL and the 10 mg/mL injections, respectively. No components of the preservative system present in the injections interfered with the assay. Since other aminoglycosides produced a colored complex, the assay is not specific for gentamicin. The assay was accurate and reproducible over the range of 4-20 mg of gentamicin. This rapid and accurate assay can be easily applied in the hospital pharmacy setting.

The vesicle-to-micelle transition of phosphatidylcholine vesicles induced by nonionic detergents: effects of sodium chloride, sucrose and urea.

PubMed

Walter, A; Kuehl, G; Barnes, K; VanderWaerdt, G

2000-11-23

The vesicle-to-micelle transition of egg phosphatidylcholine LUVs induced by octylglucoside was studied in buffers with 0-4 M sodium chloride, sucrose or urea. We used both light scattering and fluorescent probes to follow the lipid-detergent complexes in these buffers. The vesicle-to-micelle transition process was fundamentally the same in each solute. However, the detergent-to-lipid ratio required for micelle formation shifted in ways that depended on the aqueous solute. The partitioning of octylglucoside between the vesicles and the aqueous phase was primarily determined by the change in its critical micelle concentration (cmc) induced by each solute. Specifically, the cmc decreased in high salt and sucrose buffers but increased in high concentrations of urea. Cmc for two additional nonionic detergents, decyl- and dodecyl-maltoside, and three zwittergents (3-12, 3-14 and 3-16) were determined as a function of concentration for each of the solutes. In all cases NaCl and sucrose decreased the solubility of the detergents, whereas urea increased their solubilities. The effects clearly depended on acyl chain length in urea-containing solutions, but this dependence was less clear with increasing NaCl and sucrose concentrations. The contributions of these solutes to solubility and to interfacial interactions in the bilayers, pure and mixed micelles are considered.

Investigation of Phase Mixing in Amorphous Solid Dispersions of AMG 517 in HPMC-AS Using DSC, Solid-State NMR, and Solution Calorimetry.

PubMed

Calahan, Julie L; Azali, Stephanie C; Munson, Eric J; Nagapudi, Karthik

2015-11-02

Intimate phase mixing between the drug and the polymer is considered a prerequisite to achieve good physical stability for amorphous solid dispersions. In this article, spray dried amorphous dispersions (ASDs) of AMG 517 and HPMC-as were studied by differential scanning calorimetry (DSC), solid-state NMR (SSNMR), and solution calorimetry. DSC analysis showed a weakly asymmetric (ΔTg ≈ 13.5) system with a single glass transition for blends of different compositions indicating phase mixing. The Tg-composition data was modeled using the BKCV equation to accommodate the observed negative deviation from ideality. Proton spin-lattice relaxation times in the laboratory and rotating frames ((1)H T1 and T1ρ), as measured by SSNMR, were consistent with the observation that the components of the dispersion were in intimate contact over a 10-20 nm length scale. Based on the heat of mixing calculated from solution calorimetry and the entropy of mixing calculated from the Flory-Huggins theory, the free energy of mixing was calculated. The free energy of mixing was found to be positive for all ASDs, indicating that the drug and polymer are thermodynamically predisposed to phase separation at 25 °C. This suggests that miscibility measured by DSC and SSNMR is achieved kinetically as the result of intimate mixing between drug and polymer during the spray drying process. This kinetic phase mixing is responsible for the physical stability of the ASD.

Monte Carlo exploration of Mikheyev-Smirnov-Wolfenstein solutions to the solar neutrino problem

NASA Technical Reports Server (NTRS)

Shi, X.; Schramm, D. N.; Bahcall, J. N.

1992-01-01

The paper explores the impact of astrophysical uncertainties on the Mikheyev-Smirnov-Wolfenstein (MSW) solution by calculating the allowed MSW solutions for 1000 different solar models with a Monte Carlo selection of solar model input parameters, assuming a full three-family MSW mixing. Applications are made to the chlorine, gallium, Kamiokande, and Borexino experiments. The initial GALLEX result limits the mixing parameters to the upper diagonal and the vertical regions of the MSW triangle. The expected event rates in the Borexino experiment are also calculated, assuming the MSW solutions implied by GALLEX.

Computations of Drop Collision and Coalescence

NASA Technical Reports Server (NTRS)

Tryggvason, Gretar; Juric, Damir; Nas, Selman; Mortazavi, Saeed

1996-01-01

Computations of drops collisions, coalescence, and other problems involving drops are presented. The computations are made possible by a finite difference/front tracking technique that allows direct solutions of the Navier-Stokes equations for a multi-fluid system with complex, unsteady internal boundaries. This method has been used to examine the various collision modes for binary collisions of drops of equal size, mixing of two drops of unequal size, behavior of a suspension of drops in linear and parabolic shear flows, and the thermal migration of several drops. The key results from these simulations are reviewed. Extensions of the method to phase change problems and preliminary results for boiling are also shown.

Polymeric microcapsules with switchable mechanical properties for self-healing concrete: synthesis, characterisation and proof of concept

NASA Astrophysics Data System (ADS)

Kanellopoulos, A.; Giannaros, P.; Palmer, D.; Kerr, A.; Al-Tabbaa, A.

2017-04-01

Microcapsules, with sodium silicate solution as core, were produced using complex coacervation in a double, oil-in-water-in oil, emulsion system. The shell material was a gelatin-acacia gum crosslinked coacervate and the produced microcapsules had diameters ranging from 300 to 700 μm. The shell material designed with switchable mechanical properties. When it is hydrated exhibits soft and ‘rubbery’ behaviour and, when dried, transitions to a stiff and ‘glassy’ material. The microcapsules survived drying and rehydrating cycles and preserved their structural integrity when exposed to highly alkaline solutions that mimic the pH environment of concrete. Microscopy revealed that the shell thickness of the microcapsules varies across their perimeter from 5 to 20 μm. Thermal analysis showed that the produced microcapsules were very stable up to 190 °C. Proof of concept investigation has demonstrated that the microcapsules successfully survive and function when exposed to a cement-based matrix. Observations showed that the microcapsules survive mixing with cement and rupture successfully upon crack formation releasing the encapsulated sodium silicate solution.

Multi-Objective Programming for Lot-Sizing with Quantity Discount

NASA Astrophysics Data System (ADS)

Kang, He-Yau; Lee, Amy H. I.; Lai, Chun-Mei; Kang, Mei-Sung

2011-11-01

Multi-objective programming (MOP) is one of the popular methods for decision making in a complex environment. In a MOP, decision makers try to optimize two or more objectives simultaneously under various constraints. A complete optimal solution seldom exists, and a Pareto-optimal solution is usually used. Some methods, such as the weighting method which assigns priorities to the objectives and sets aspiration levels for the objectives, are used to derive a compromise solution. The ɛ-constraint method is a modified weight method. One of the objective functions is optimized while the other objective functions are treated as constraints and are incorporated in the constraint part of the model. This research considers a stochastic lot-sizing problem with multi-suppliers and quantity discounts. The model is transformed into a mixed integer programming (MIP) model next based on the ɛ-constraint method. An illustrative example is used to illustrate the practicality of the proposed model. The results demonstrate that the model is an effective and accurate tool for determining the replenishment of a manufacturer from multiple suppliers for multi-periods.

Competitive adsorption of dopamine and rhodamine 6G on the surface of graphene oxide.

PubMed

Ren, Hui; Kulkarni, Dhaval D; Kodiyath, Rajesh; Xu, Weinan; Choi, Ikjun; Tsukruk, Vladimir V

2014-02-26

Competitive adsorption-desorption behavior of popular fluorescent labeling and bioanalyte molecules, Rhodamine 6G (R6G) and dopamine (DA), on a chemically heterogeneous graphene oxide (GO) surface is discussed in this study. Individually, R6G and DA compounds were found to adsorb rapidly on the surface of graphene oxide as they followed the traditional Langmuir adsorption behavior. FTIR analysis suggested that both R6G and DA molecules predominantly adsorb on the hydrophilic oxidized regions of the GO surface. Thus, when R6G and DA compounds were adsorbed from mixed solution, competitive adsorption was observed around the oxygen-containing groups of GO sheets, which resulted in partial desorption of R6G molecules from the surface of GO into the solution. The desorbed R6G molecules can be monitored by fluorescence change in solution and was dependent on the DA concentration. We suggest that the efficient competitive adsorption of different strongly bound bioanalytes onto GO-dye complex can be used for the development of sensitive and selective colorimetric biosensors.

Temperature control in a 30 stage, 5-cm Centrifugal Contactor Pilot Plant

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

Jack D. Law; Troy G. Garn; David H. Meikrantz

2009-09-01

Temperature profile testing was performed using a 30 stage 5-cm centrifugal contactor pilot plant. These tests were performed to evaluate the ability to control process temperature by adjusting feed solution temperatures. This would eliminate the need for complex jacketed heat exchanger installation on the centrifugal contactors. Thermocouples were installed on the inlet and outlets of each stage, as well as directly in the mixing zone of several of the contactor stages. Lamp oil, a commercially available alkane mixture of C14 to C18 chains, and tap water adjusted to pH 2 with nitric acid were the solution feeds for the temperaturemore » profile testing. Temperature data profiles for an array of total throughputs and contactor rpm values for both single-phase and two-phase systems were collected with selected profiles. The total throughput ranged from 0.5-1.4 L/min with rotor speeds from 3500-4000 rpm. Inlet solution temperatures ranging from ambient up to 50 °C were tested. Results of the two-phase temperature profile testing are detailed« less

Simple and Precise Quantification of Iron Catalyst Content in Carbon Nanotubes Using UV/Visible Spectroscopy.

PubMed

Agustina, Elsye; Goak, Jeungchoon; Lee, Suntae; Seo, Youngho; Park, Jun-Young; Lee, Naesung

2015-10-01

Iron catalysts have been used widely for the mass production of carbon nanotubes (CNTs) with high yield. In this study, UV/visible spectroscopy was used to determine the Fe catalyst content in CNTs using a colorimetric technique. Fe ions in solution form red-orange complexes with 1,10-phenanthroline, producing an absorption peak at λ=510 nm, the intensity of which is proportional to the solution Fe concentration. A series of standard Fe solutions were formulated to establish the relationship between optical absorbance and Fe concentration. Many Fe catalysts were microscopically observed to be encased by graphitic layers, thus preventing their extraction. Fe catalyst dissolution from CNTs was investigated with various single and mixed acids, and Fe concentration was found to be highest with CNTs being held at reflux in HClO4/HNO3 and H2SO4/HNO3 mixtures. This novel colorimetric method to measure Fe concentrations by UV/Vis spectroscopy was validated by inductively coupled plasma optical emission spectroscopy, indicating its reliability and applicability to asses Fe content in CNTs.

FERMI: a digital Front End and Readout MIcrosystem for high resolution calorimetry

NASA Astrophysics Data System (ADS)

Alexanian, H.; Appelquist, G.; Bailly, P.; Benetta, R.; Berglund, S.; Bezamat, J.; Blouzon, F.; Bohm, C.; Breveglieri, L.; Brigati, S.; Cattaneo, P. W.; Dadda, L.; David, J.; Engström, M.; Genat, J. F.; Givoletti, M.; Goggi, V. G.; Gong, S.; Grieco, G. M.; Hansen, M.; Hentzell, H.; Holmberg, T.; Höglund, I.; Inkinen, S. J.; Kerek, A.; Landi, C.; Ledortz, O.; Lippi, M.; Lofstedt, B.; Lund-Jensen, B.; Maloberti, F.; Mutz, S.; Nayman, P.; Piuri, V.; Polesello, G.; Sami, M.; Savoy-Navarro, A.; Schwemling, P.; Stefanelli, R.; Sundblad, R.; Svensson, C.; Torelli, G.; Vanuxem, J. P.; Yamdagni, N.; Yuan, J.; Ödmark, A.; Fermi Collaboration

1995-02-01

We present a digital solution for the front-end electronics of high resolution calorimeters at future colliders. It is based on analogue signal compression, high speed {A}/{D} converters, a fully programmable pipeline and a digital signal processing (DSP) chain with local intelligence and system supervision. This digital solution is aimed at providing maximal front-end processing power by performing waveform analysis using DSP methods. For the system integration of the multichannel device a multi-chip, silicon-on-silicon multi-chip module (MCM) has been adopted. This solution allows a high level of integration of complex analogue and digital functions, with excellent flexibility in mixing technologies for the different functional blocks. This type of multichip integration provides a high degree of reliability and programmability at both the function and the system level, with the additional possibility of customising the microsystem to detector-specific requirements. For enhanced reliability in high radiation environments, fault tolerance strategies, i.e. redundancy, reconfigurability, majority voting and coding for error detection and correction, are integrated into the design.

Cysteine as a green corrosion inhibitor for Cu37Zn brass in neutral and weakly alkaline sulphate solutions.

PubMed

Radovanović, Milan B; Petrović, Marija B; Simonović, Ana T; Milić, Snežana M; Antonijević, Milan M

2013-07-01

The aim of this study was to investigate electrochemical properties of brass in neutral and weakly alkaline solutions in the presence of cysteine as a nontoxic and ecological corrosion inhibitor. Potentiodynamic measurements, open circuit potential measurements, as well as chronoamperometric measurements were the methods used during investigation of the inhibitory effect of cysteine on the corrosion behaviour of brass. Potentiodynamic measurements showed that cysteine behaves as a mixed-type inhibitor in the investigated media. Based on polarization curves for brass in a weakly alkaline solution of sodium sulphate at varying cysteine concentrations, an interaction occurs between Cu(+) ions and the inhibitor, resulting in the formation of a protective complex on the electrode surface. The results of chronoamperometric measurements confirm the results obtained by potentiodynamic measurements. Optical microphotography of the brass surface also confirms the formation of a protective film in the presence of a 1 × 10(-4) mol/dm(3) cysteine. Adsorption of cysteine on the brass surface proceeds according to the Langmuir adsorption isotherm.

Complexation of phospholipids and cholesterol by triterpenic saponins in bulk and in monolayers.

PubMed

Wojciechowski, Kamil; Orczyk, Marta; Gutberlet, Thomas; Geue, Thomas

2016-02-01

The interactions between three triterpene saponins: α-hederin, hederacoside C and ammonium glycyrrhizate with model lipids: cholesterol and dipalmitoylphosphatidylcholine (DPPC) are described. The oleanolic acid-type saponins (α-hederin and hederacoside C) were shown to form 1:1 complexes with lipids in bulk, characterized by stability constants in the range (4.0±0.2)·10(3)-(5.0±0.4)·10(4) M(-1). The complexes with cholesterol are generally stronger than those with DPPC. On the contrary, ammonium glycyrrhizate does not form complexes with any of the lipids in solution. The saponin-lipid interactions were also studied in a confined environment of Langmuir monolayers of DPPC and DPPC/cholesterol with the saponins present in the subphase. A combined monolayer relaxation, surface dilational rheology, fluorescence microscopy and neutron reflectivity (NR) study showed that all three saponins are able to penetrate pure DPPC and mixed DPPC/cholesterol monolayers. Overall, the effect of the saponins on the model lipid monolayers does not fully correlate with the lipid-saponin complex formation in the homogeneous solution. The best correlation was found for α-hederin, for which even the preference for cholesterol over DPPC observed in bulk is well reflected in the monolayer studies and the literature data on its membranolytic activity. Similarly, the lack of interaction of ammonium glycyrrhizate with both lipids is evident equally in bulk and monolayer experiments, as well as in its weak membranolytic activity. The combined bulk and monolayer results are discussed in view of the role of confinement in modulating the saponin-lipid interactions and possible mechanism of membranolytic activity of saponins. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of Ferrite Nickel Nano-particles and Its Role as a p-Dopant in the Improvement of Hole Injection of an Organic Light-Emitting Diode

NASA Astrophysics Data System (ADS)

Noori, Maryam; Jafari, Mohammad Reza; Hosseini, Sayed Mohsen; Shahedi, Zahra

2017-07-01

We fabricated an organometallic complex based on zinc ions using zinc complex as a fluorescent in organic light-emitting diodes (OLEDs). Also, the nano-particles of ferrite nickel were produced in a simple aqueous system prepared by mixing Ni (NO3)2, Fe (NO3)3 and deionized water solutions. The synthesized zinc bis (8-hydroxyquinoline) (Znq2) complex and NiFe2O4 nano-particles were characterized by using x-ray diffraction (XRD), ultraviolet-visible (UV-Vis), Fourier transform infrared spectroscopy (FT-IR) as well as photoluminescence spectroscopy analysis. Their energy level was also determined by some cyclic voltammetry (CV) measurements. The maximum green photoluminescence was observed at 565 nm. The nano-particles of ferrite nickel were utilized in preparation of OLEDs by blending of the magnetic nano-particles with PEDOT:PSS and Zn-complex solutions. The electrical and optical performance of prepared OLEDs with/without doped nano-particle was studied. The samples were configured into two structures: (1) Indium Tin Oxide (ITO)/ poly(3,4-ethylenedi-oxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/Znq2/(2-4-biphenylyl)-5-phenyl-oxadiazole (PBD)/aluminum (Al) and (2) ITO/PEDOT:PSS:NiFe2O4(NPs)/Znq2/PBD/Al. Obtained results showed that the current density and electroluminescence efficiency were increased and the turn-on voltage decreased (about 3 V) by using nano-particles into a PEDOT:PSS layer (Hole transport layer). Also, the electroluminescence efficiency was decreased by incorporating magnetic nano-particles into a Zn-complex layer (emissive layer). It was found that utilizing NiFe2O4 nano-particles caused an increase of hole-injection layer conductivity effectively and a decrease of the turn-on voltage.

Generic evolution of mixing in heterogeneous media

NASA Astrophysics Data System (ADS)

De Dreuzy, J.; Carrera, J.; Dentz, M.; Le Borgne, T.

2011-12-01

Mixing in heterogeneous media results from the competition bewteen flow fluctuations and local scale diffusion. Flow fluctuations quickly create concentration contrasts and thus heterogeneity of the concentration field, which is slowly homogenized by local scale diffusion. Mixing first deviates from Gaussian mixing, which represents the potential mixing induced by spreading before approaching it. This deviation fundamentally expresses the evolution of the interaction between spreading and local scale diffusion. We characterize it by the ratio γ of the non-Gaussian to the Gaussian mixing states. We define the Gaussian mixing state as the integrated squared concentration of the Gaussian plume that has the same longitudinal dispersion as the real plume. The non-Gaussian mixing state is the difference between the overall mixing state defined as the integrated squared concentration and the Gaussian mixing state. The main advantage of this definition is to use the full knowledge previously acquired on dispersion for characterizing mixing even when the solute concentration field is highly non Gaussian. Using high precision numerical simulations, we show that γ quickly increases, peaks and slowly decreases. γ can be derived from two scales characterizing spreading and local mixing, at least for large flux-weighted solute injection conditions into classically log-normal Gaussian correlated permeability fields. The spreading scale is directly related to the longitudinal dispersion. The local mixing scale is the largest scale over which solute concentrations can be considered locally uniform. More generally, beyond the characteristics of its maximum, γ turns out to have a highly generic scaling form. Its fast increase and slow decrease depend neither on the heterogeneity level, nor on the ratio of diffusion to advection, nor on the injection conditions. They might even not depend on the particularities of the flow fields as the same generic features also prevail for Taylor dispersion. This generic characterization of mixing can offer new ways to set up transport equations that honor not only advection and spreading (dispersion), but also mixing.

Effects of ionic concentration gradient on electroosmotic flow mixing in a microchannel.

PubMed

Peng, Ran; Li, Dongqing

2015-02-15

Effects of ionic concentration gradient on electroosmotic flow (EOF) mixing of one stream of a high concentration electrolyte solution with a stream of a low concentration electrolyte solution in a microchannel are investigated numerically. The concentration field, flow field and electric field are strongly coupled via concentration dependent zeta potential, dielectric constant and electric conductivity. The results show that the electric field and the flow velocity are non-uniform when the concentration dependence of these parameters is taken into consideration. It is also found that when the ionic concentration of the electrolyte solution is higher than 1M, the electrolyte solution essentially cannot enter the channel due to the extremely low electroosmotic flow mobility. The effects of the concentration dependence of zeta potential, dielectric constant and electric conductivity on electroosmotic flow mixing are studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Advanced scatter search approach and its application in a sequencing problem of mixed-model assembly lines in a case company

NASA Astrophysics Data System (ADS)

Liu, Qiong; Wang, Wen-xi; Zhu, Ke-ren; Zhang, Chao-yong; Rao, Yun-qing

2014-11-01

Mixed-model assembly line sequencing is significant in reducing the production time and overall cost of production. To improve production efficiency, a mathematical model aiming simultaneously to minimize overtime, idle time and total set-up costs is developed. To obtain high-quality and stable solutions, an advanced scatter search approach is proposed. In the proposed algorithm, a new diversification generation method based on a genetic algorithm is presented to generate a set of potentially diverse and high-quality initial solutions. Many methods, including reference set update, subset generation, solution combination and improvement methods, are designed to maintain the diversification of populations and to obtain high-quality ideal solutions. The proposed model and algorithm are applied and validated in a case company. The results indicate that the proposed advanced scatter search approach is significant for mixed-model assembly line sequencing in this company.

Alkali-activated complex binders from class C fly ash and Ca-containing admixtures.

PubMed

Guo, Xiaolu; Shi, Huisheng; Chen, Liming; Dick, Warren A

2010-01-15

Processes that maximize utilization of industrial solid wastes are greatly needed. Sodium hydroxide and sodium silicate solution were used to create alkali-activated complex binders (AACBs) from class C fly ash (CFA) and other Ca-containing admixtures including Portland cement (PC), flue gas desulfurization gypsum (FGDG), and water treatment residual (WTR). Specimens made only from CFA (CFA100), or the same fly ash mixed with 40 wt% PC (CFA60-PC40), with 10 wt% FGDG (CFA90-FGDG10), or with 10 wt% WTR (CFA90-WTR10) had better mechanical performance compared to binders using other mix ratios. The maximum compressive strength of specimens reached 80.0 MPa. Geopolymeric gel, sodium polysilicate zeolite, and hydrated products coexist when AACB reactions occur. Ca from CFA, PC, and WTR precipitated as Ca(OH)(2), bonded in geopolymers to obtain charge balance, or reacted with dissolved silicate and aluminate species to form calcium silicate hydrate (C-S-H) gel. However, Ca from FGDG probably reacted with dissolved silicate and aluminate species to form ettringite. Utilization of CFA and Ca-containing admixtures in AACB is feasible. These binders may be widely utilized in various applications such as in building materials and for solidification/stabilization of other wastes, thus making the wastes more environmentally benign.

Modelling removal mechanisms of Pb, Cu, Zn and Cd in acidic groundwater during the neutralization by ambient surface and ground waters

USGS Publications Warehouse

Paulson, Anthony J.; Balistrieri, Laurie S.

1999-01-01

Removal of Pb, Cu, Zn, and Cd during neutralization of acid rock drainage is examined using model simulations of field conditions and laboratory experiments involving mixing of natural drainage and surface waters or groundwaters. The simulations consider sorption onto hydrous Fe and Al oxides and particulate organic carbon, mineral precipitation, and organic and inorganic solution complexation of metals for two physical systems where newly formed oxides and particulate organic matter are either transported or retained along the chemical pathway. The calculations indicate that metal removal is a strong function of the physical system. Relative to direct discharge of ARD into streams, lower metal removals are observed where ARD enters streamwaters during the latter stages of neutralization by ambient groundwater after most of the Fe has precipitated and been retained in the soils. The mixing experiments, which represent the field simulations, also demonstrated the importance of dissolved metal to particle Fe ratios in controlling dissolved metal removal along the chemical pathway. Finally, model calculations indicate that hydrous Fe oxides and particulate organic carbon are more important than hydrous Al oxides in removing metals and that both inorganic and organic complexation must be considered when modeling metal removal from aquatic systems that are impacted by sulfide oxidation.

Laboratory simulations of the atmospheric mixed-layer in flow over complex topography

EPA Science Inventory

A laboratory study of the influence of complex terrain on the interface between a well-mixed boundary layer and an elevated stratified layer was conducted in the towing-tank facility of the U.S. Environmental Protection Agency. The height of the mixed layer in the daytime boundar...

An ignored variable: solution preparation temperature in protein crystallization

PubMed Central

Chen, Rui-Qing; Lu, Qin-Qin; Cheng, Qing-Di; Ao, Liang-Bo; Zhang, Chen-Yan; Hou, Hai; Liu, Yong-Ming; Li, Da-Wei; Yin, Da-Chuan

2015-01-01

Protein crystallization is affected by many parameters, among which certain parameters have not been well controlled. The temperature at which the protein and precipitant solutions are mixed (i.e., the ambient temperature during mixing) is such a parameter that is typically not well controlled and is often ignored. In this paper, we show that this temperature can influence protein crystallization. The experimental results showed that both higher and lower mixing temperatures can enhance the success of crystallization, which follows a parabolic curve with an increasing ambient temperature. This work illustrates that the crystallization solution preparation temperature is also an important parameter for protein crystallization. Uncontrolled or poorly controlled room temperature may yield poor reproducibility in protein crystallization. PMID:25597864

Strongly Stratified Turbulence Wakes and Mixing Produced by Fractal Wakes

NASA Astrophysics Data System (ADS)

Dimitrieva, Natalia; Redondo, Jose Manuel; Chashechkin, Yuli; Fraunie, Philippe; Velascos, David

2017-04-01

This paper describes Shliering and Shadowgraph experiments of the wake induced mixing produced by tranversing a vertical or horizontal fractal grid through the interfase between two miscible fluids at low Atwood and Reynolds numbers. This is a configuration design to models the mixing across isopycnals in stably-stratified flows in many environmental relevant situations (either in the atmosphere or in the ocean. The initial unstable stratification is characterized by a reduced gravity: g' = gΔρ ρ where g is gravity, Δρ being the initial density step and ρ the reference density. Here the Atwood number is A = g' _ 2 g . The topology of the fractal wake within the strong stratification, and the internal wave field produces both a turbulent cascade and a wave cascade, with frecuen parametric resonances, the envelope of the mixing front is found to follow a complex non steady 3rd order polinomial function with a maximum at about 4-5 Brunt-Vaisalla non-dimensional time scales: t/N δ = c1(t/N) + c2g Δρ ρ (t/N)2 -c3(t/N)3. Conductivity probes and Shliering and Shadowgraph visual techniques, including CIV with (Laser induced fluorescence and digitization of the light attenuation across the tank) are used in order to investigate the density gradients and the three-dimensionality of the expanding and contracting wake. Fractal analysis is also used in order to estimate the fastest and slowest growing wavelengths. The large scale structures are observed to increase in wave-length as the mixing progresses, and the processes involved in this increase in scale are also examined.Measurements of the pointwise and horizontally averaged concentrations confirm the picture obtained from past flow visualization studies. They show that the fluid passes through the mixing region with relatively small amounts of molecular mixing,and the molecular effects only dominate on longer time scales when the small scales have penetrated through the large scale structures. The Non-stationary dynamicss and structure of stratified fluid flows around a wedge were also studied based of the fundamental equations set using numerical modeling. Due to breaking of naturally existing background diffusion flux of stratifying agent by an impermeable surface of the wedge a complex multi-level vortex system of compensatory fluid motions is formed around the obstacle. The flow is characterized by a wide range of values of internal scales that are absent in a homogeneous liquid. Numerical solution of the fundamental system with the boundary conditions is constructed using a solver such as stratifiedFoam developed within the frame of the open source computational package OpenFOAM using the finite volume method. The computations were performed in parallel using computing resources of the Scientific Research Supercomputer Complex of MSU (SRCC MSU) and the technological platform UniHUB. The evolution of the flow pattern of the wedge by stratified flow has been demonstrated. The complex structure of the fields of physical quantities and their gradients has been shown. Observed in experiment are multiple flow components, including upstream disturbances, internal waves and the downstream wake with submerged transient vortices well reproduced. Structural elements of flow differ in size and laws of variation in space and time. Rich fine flow structure visualized in vicinity and far from the obstacle. The global efficiency of the mixing process is measured and compared with previous estimates of mixing efficiency.

Nitric oxide production by visible light irradiation of aqueous solution of nitrosyl ruthenium complexes.

PubMed

Sauaia, Marília Gama; de Lima, Renata Galvão; Tedesco, Antonio Claudio; da Silva, Roberto Santana

2005-12-26

[Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](PF(6))(5) (L is NH(3), py, or 4-acpy) was prepared with good yields in a straightforward way by mixing an equimolar ratio of cis-[Ru(NO(2))(bpy)(2)(NO)](PF(6))(2), sodium azide (NaN(3)), and trans-[RuL(NH(3))(4)(pz)] (PF(6))(2) in acetone. These binuclear compounds display nu(NO) at ca. 1945 cm(-)(1), indicating that the nitrosyl group exhibits a sufficiently high degree of nitrosonium ion (NO(+)). The electronic spectrum of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex in aqueous solution displays the bands in the ultraviolet and visible regions typical of intraligand and metal-to-ligand charge transfers, respectively. Cyclic voltammograms of the binuclear complexes in acetonitrile give evidence of three one-electron redox processes consisting of one oxidation due to the Ru(2+/3+) redox couple and two reductions concerning the nitrosyl ligand. Flash photolysis of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex is capable of releasing nitric oxide (NO) upon irradiation at 355 and 532 nm. NO production was detected and quantified by an amperometric technique with a selective electrode (NOmeter). The irradiation at 532 nm leads to NO release as a consequence of a photoinduced electron transfer. All species exhibit similar photochemical behavior, a feature that makes their study extremely important for their future application in the upgrade of photodynamic therapy in living organisms.

Frictionless Contact of Multilayered Composite Half Planes Containing Layers With Complex Eigenvalues

NASA Technical Reports Server (NTRS)

Zhang, Wang; Binienda, Wieslaw K.; Pindera, Marek-Jerzy

1997-01-01

A previously developed local-global stiffness matrix methodology for the response of a composite half plane, arbitrarily layered with isotropic, orthotropic or monoclinic plies, to indentation by a rigid parabolic punch is further extended to accommodate the presence of layers with complex eigenvalues (e.g., honeycomb or piezoelectric layers). First, a generalized plane deformation solution for the displacement field in an orthotropic layer or half plane characterized by complex eigenvalues is obtained using Fourier transforms. A local stiffness matrix in the transform domain is subsequently constructed for this class of layers and half planes, which is then assembled into a global stiffness matrix for the entire multilayered half plane by enforcing continuity conditions along the interfaces. Application of the mixed boundary condition on the top surface of the half plane indented by a rigid punch results in an integral equation for the unknown pressure in the contact region. The integral possesses a divergent kernel which is decomposed into Cauchy-type and regular parts using the asymptotic properties of the local stiffness matrix and a relationship between Fourier and finite Hilbert transform of the contact pressure. The solution of the resulting singular integral equation is obtained using a collocation technique based on the properties of orthogonal polynomials developed by Erdogan and Gupta. Examples are presented that illustrate the important influence of low transverse properties of layers with complex eigenvalues, such as those exhibited by honeycomb, on the load versus contact length response and contact pressure distributions for half planes containing typical composite materials.

Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solutions

NASA Astrophysics Data System (ADS)

Schliesser, Jacob M.; Huang, Baiyu; Sahu, Sulata K.; Asplund, Megan; Navrotsky, Alexandra; Woodfield, Brian F.

2018-03-01

We have measured the heat capacities of several well-characterized bulk and nanophase Fe3O4-Co3O4 and Fe3O4-Mn3O4 spinel solid solution samples from which magnetic properties of transitions and third-law entropies have been determined. The magnetic transitions show several features common to effects of particle and magnetic domain sizes. From the standard molar entropies, excess entropies of mixing have been generated for these solid solutions and compared with configurational entropies determined previously by assuming appropriate cation and valence distributions. The vibrational and magnetic excess entropies for bulk materials are comparable in magnitude to the respective configurational entropies indicating that excess entropies of mixing must be included when analyzing entropies of mixing. The excess entropies for nanophase materials are even larger than the configurational entropies. Changes in valence, cation distribution, bonding and microstructure between the mixing ions are the likely sources of the positive excess entropies of mixing.

Discrete bivariate population balance modelling of heteroaggregation processes.

PubMed

Rollié, Sascha; Briesen, Heiko; Sundmacher, Kai

2009-08-15

Heteroaggregation in binary particle mixtures was simulated with a discrete population balance model in terms of two internal coordinates describing the particle properties. The considered particle species are of different size and zeta-potential. Property space is reduced with a semi-heuristic approach to enable an efficient solution. Aggregation rates are based on deterministic models for Brownian motion and stability, under consideration of DLVO interaction potentials. A charge-balance kernel is presented, relating the electrostatic surface potential to the property space by a simple charge balance. Parameter sensitivity with respect to the fractal dimension, aggregate size, hydrodynamic correction, ionic strength and absolute particle concentration was assessed. Results were compared to simulations with the literature kernel based on geometric coverage effects for clusters with heterogeneous surface properties. In both cases electrostatic phenomena, which dominate the aggregation process, show identical trends: impeded cluster-cluster aggregation at low particle mixing ratio (1:1), restabilisation at high mixing ratios (100:1) and formation of complex clusters for intermediate ratios (10:1). The particle mixing ratio controls the surface coverage extent of the larger particle species. Simulation results are compared to experimental flow cytometric data and show very satisfactory agreement.

Trialkylphosphine-stabilized copper(I) gallium(III) phenylchalcogenolate complexes: crystal structures and generation of ternary semiconductors by thermolysis.

PubMed

Kluge, Oliver; Krautscheid, Harald

2012-06-18

A series of organometallic trialkylphosphine-stabilized copper gallium phenylchalcogenolate complexes [(R(3)P)(m)Cu(n)Me(2-x)Ga(EPh)(n+x+1)] (R = Me, Et, (i)Pr, (t)Bu; E = S, Se, Te; x = 0, 1) has been prepared and structurally characterized by X-ray diffraction. From their molecular structures three groups of compounds can be distinguished: ionic compounds, ring systems, and cage structures. All these complexes contain one gallium atom bound to one or two methyl groups, whereas the number of copper atoms, and therefore the nuclearity of the complexes, is variable and depends mainly on size and amount of phosphine ligand used in synthesis. The Ga-E bonds are relatively rigid, in contrast to flexible Cu-E bonds. The lengths of the latter are controlled by the coordination number and steric influences. The Ga-E bond lengths depend systematically on the number of methyl groups bound to the gallium atom, with somewhat shorter bonds in monomethyl compounds compared to dimethyl compounds. Quantum chemical computations reproduce this trend and show furthermore that the rotation of one phenyl group around the Ga-E bond is a low energy process with two distinct minima, corresponding to two different conformations found experimentally. Mixtures of different types of chalcogen atoms on molecular scale are possible, and then ligand exchange reactions in solution lead to mixed site occupation. In thermogravimetric studies the complexes were converted into the ternary semiconductors CuGaE(2). The thermolysis reaction is completed at temperatures between 250 and 400 °C, typically with lower temperatures for the heavier chalcogens. Because of significant release of Me(3)Ga during the thermolysis process, and especially in case of copper excess in the precursor complexes, binary copper chalcogenides are obtained as additional thermolysis products. Quaternary semiconductors can be obtained from mixed chalcogen precursors.

Electrochemistry of mixed-metal bimetallic complexes containing the pentacyanoferrate(II) or pentaammineruthenium(II) metal center

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

Moore, K.J.; Lee, L.; Mabbott, G.A.

1983-03-30

The electrochemistry of a series of mixed-metal bimetallic complexes of the type B/sub 5/MLM'B'/sub 5/, where B/sub 5/M = (CNN)/sub 5/Fe/sup II/ or (NH/sub 3/)/sub 5/Ru/sup II/, L = pyrazine, 4,4'-bipyridine, or 4-cyanopyridine, M'B'/sub 5/ = Rh/sup III/(NH/sub 3/)/sub 5/ or Co/sup III/(CN)/sub 5/, is reported. The bimetallic complexes all have metal-to-ligand charge-transfer (MLCT) bands associated with the M-B unit (d/sub ..pi../M ..-->.. p/sub ..pi../*L). The effect of the remote metal center, M'B'/sub 5/, is to function as a Lewis acid, shifting the MLCT maximum to lower energy and shifting the M/sup III///sup II/ reduction potential more positive with respectmore » to free B/sub 5/ML. The remote metal influence is attenuated by longer bridging ligands and by reduced ..pi..-overlap. A comparison of the electrochemical data of the mixed-valence Fe(II)/Fe(III) and Ru(II)/Ru(III) complexes to the mixed-metal Fe(II)/Co(III) and Ru(II)/Rh(III) complexes has enabled a quantitative measure of the stabilization due to electron delocalization in the mixed-valence complexes. The results show that electron delocalization is greater for the ruthenium complexes than for the iron complexes, is a small contributor to the total stabilization of the mixed-valence state, and even in ruthenium drops off rapidly as the length of the bridge increases.« less

Mixed convection flow of nanofluid in a square enclosure with an intruded rectangular fin

NASA Astrophysics Data System (ADS)

Cong, Ran; Zhou, Xuanyu; De Souza Machado, Bruno; Das, Prodip K.

2016-07-01

Mixed convection flow in enclosures has been a subject of interest for many years due to their ever increasing applications in solar collectors, electronic cooling, lubrication technologies, food processing, and nuclear reactors. In comparison, little effort has been given to the problem of mixed convection in enclosures filled with nanofluids, while the addition of nanoparticles in a fluid base to alter specific material properties is considered a feasible solution for many heat transfer problems. Mixed convection of nanofluids is a challenging problem as the addition of nanoparticles changes the fluid's thermo-physical properties as well as due to the complex interactions among inertia, viscous, and buoyancy forces. In this study, a two-dimensional steady-state numerical model has been developed to investigate mixed convection flow of nanofluids in a square enclosure with an intruded rectangular fin and to optimize the fin geometry for maximizing the heat transfer using the Constructal design. The model has been developed using ANSYS-FLUENT for various fin geometries. Flow fields, temperature fields, and heat transfer rates are examined for different values of Rayleigh and Reynolds numbers for several geometries of the fin with the aim of maximizing the heat transfer from the fin to the surrounding flow. Outcome of this study provides important insight into the heat transfer behavior of nanofluids, which will help in developing novel geometries with enhanced and controlled heat transfer for solar collectors and electronic devices.

Mixed convection flow of nanofluid in a square enclosure with an intruded rectangular fin

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

Cong, Ran; Zhou, Xuanyu; De Souza Machado, Bruno

Mixed convection flow in enclosures has been a subject of interest for many years due to their ever increasing applications in solar collectors, electronic cooling, lubrication technologies, food processing, and nuclear reactors. In comparison, little effort has been given to the problem of mixed convection in enclosures filled with nanofluids, while the addition of nanoparticles in a fluid base to alter specific material properties is considered a feasible solution for many heat transfer problems. Mixed convection of nanofluids is a challenging problem as the addition of nanoparticles changes the fluid’s thermo-physical properties as well as due to the complex interactionsmore » among inertia, viscous, and buoyancy forces. In this study, a two-dimensional steady-state numerical model has been developed to investigate mixed convection flow of nanofluids in a square enclosure with an intruded rectangular fin and to optimize the fin geometry for maximizing the heat transfer using the Constructal design. The model has been developed using ANSYS-FLUENT for various fin geometries. Flow fields, temperature fields, and heat transfer rates are examined for different values of Rayleigh and Reynolds numbers for several geometries of the fin with the aim of maximizing the heat transfer from the fin to the surrounding flow. Outcome of this study provides important insight into the heat transfer behavior of nanofluids, which will help in developing novel geometries with enhanced and controlled heat transfer for solar collectors and electronic devices.« less

Generalised syntheses of ordered mesoporous oxides: the atrane route

NASA Astrophysics Data System (ADS)

Cabrera, Saúl; El Haskouri, Jamal; Guillem, Carmen; Latorre, Julio; Beltrán-Porter, Aurelio; Beltrán-Porter, Daniel; Marcos, M. Dolores; Amorós *, Pedro

2000-06-01

A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant-inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructured intermediates and the final mesoporous materials are chemically homogeneous. The final ordered mesoporous materials are thermally stable and show unimodal porosity, as well as homogeneous microstructure and texture. Examples of materials synthesised on account of the versatility of this new method, including siliceous, non siliceous and mixed oxides, are presented and discussed.

Adsorption of Polycyclic aromatic hydrocarbons (fluoranthene and anthracenemethanol) by functional graphene oxide and removal by pH and temperature-sensitive coagulation.

PubMed

Zhang, Caili; Wu, Lin; Cai, Dongqing; Zhang, Caiyun; Wang, Ning; Zhang, Jing; Wu, Zhengyan

2013-06-12

A new kind of functional graphene oxide with fine stability in water was fabricated by mixing graphene oxide (GO) and brilliant blue (BB) with a certain weight ratio. The adsorption performance of this mixture of BB and GO (BBGO) to polycyclic aromatic hydrocarbons (anthracenemethanol (AC) and fluoranthene (FL)) was investigated, and the results indicated BBGO possessed adsorption capacity of 1.676 mmol/g and removal efficiency of 72.7% as to AC and adsorption capacity of 2.212 mmol/g and removal efficiency of 93.2% as to FL. After adsorption, pH and temperature-sensitive coagulation (PTC) method was used to remove the AC/BBGO or FL/BBGO complex and proved to be an effective approach to flocculate the AC/BBGO or FL/BBGO complex into large flocs, which tended to be removed from the aqueous solution.

Ice Melting to Release Reactants in Solution Syntheses.

PubMed

Wei, Hehe; Huang, Kai; Zhang, Le; Ge, Binghui; Wang, Dong; Lang, Jialiang; Ma, Jingyuan; Wang, Da; Zhang, Shuai; Li, Qunyang; Zhang, Ruoyu; Hussain, Naveed; Lei, Ming; Liu, Li-Min; Wu, Hui

2018-03-19

Aqueous solution syntheses are mostly based on mixing two solutions with different reactants. It is shown that freezing one solution and melting it in another solution provides a new interesting strategy to mix chemicals and to significantly change the reaction kinetics and thermodynamics. For example, a precursor solution containing a certain concentration of AgNO 3 was frozen and dropped into a reductive NaBH 4 solution at about 0 °C. The ultra-slow release of reactants was successfully achieved. An ice-melting process can be used to synthesize atomically dispersed metals, including cobalt, nickel, copper, rhodium, ruthenium, palladium, silver, osmium, iridium, platinum, and gold, which can be easily extended to other solution syntheses (such as precipitation, hydrolysis, and displacement reactions) and provide a generalized method to redesign the interphase reaction kinetics and ion diffusion in wet chemistry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

C-H...Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu{sup I}Cu{sup II} coordination polymers

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

Shi Ling; Yang Ping; School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510631

Two mixed-valence Cu{sup I}Cu{sup II} coordination polymers [Cu{sup I}Cu{sup II}(qdiol)ClL]{sub n} (qdiol{sup 2-}=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl{sub 2}, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu{sup II}, qdiol{sup 2-} and L are identical in both complexes. But the Cu{sup I} ions are two- and three-coordinated, and the Cl{sup -} ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H...Cl hydrogen bonding pattern of bpy and phen. The temperaturemore » variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting. - Graphical Abstract: Subtly different C-H...Cl bonding nature leads to diverse coordination modes and supramolecular networks, as well as physical properties of two Cu{sup I}Cu{sup II} coordination polymers with similar compositions. Highlights: > Two new Cu(I)-Cu(II) mixed-valence coordination polymers are obtained. > Environments of Cu(I) and Cl are different caused by C-H...Cl H-bonding. > Supramolecular networks are hence diverse. > Magnetic and semiconducting properties are influenced by the structures.« less

Evaluation of effectiveness of various irrigating solutions on removal of calcium hydroxide mixed with 2% chlorhexidine gel and detection of orange-brown precipitate after removal.

PubMed

Arslan, Hakan; Gok, Tuba; Saygili, Gokhan; Altintop, Hülya; Akçay, Merve; Çapar, Ismail Davut

2014-11-01

The aims of the present study were to evaluate the effect of various irrigating solutions on the removal of calcium hydroxide mixed with 2% chlorhexidine gel from an artificial groove created in a root canal and the generation of orange-brown precipitate in the remaining calcium hydroxide mixed with 2% chlorhexidine gel after irrigation with the various irrigating solutions. The root canals of 48 mandibular premolars were prepared using ProTaper Universal Rotary instruments (Dentsply Maillefer, Ballaigues, Switzerland) up to size F4. The roots were split longitudinally, and a standardized groove was prepared in the apical part of 1 segment. The root halves were reassembled, and calcium hydroxide mixed with 2% chlorhexidine gel medicament was placed into the grooves. The roots were randomly divided into 4 experimental groups specified by the irrigation solution used: 1% NaOCl, 17% EDTA, 7% maleic acid, and 10% citric acid (n = 12). The amount of remaining medicament was evaluated under a stereomicroscope using a 4-grade scoring system. After irrigation, the specimens were also evaluated for the presence/absence of orange-brown precipitate. The effects of the different irrigation solutions on medicament removal were statistically evaluated using the Kruskal-Wallis and Mann-Whitney U tests with Bonferroni correction at a 95% confidence level (P = .0083). Solutions of 7% maleic acid and 10% citric acid were superior to solutions of 1% NaOCl and 17% EDTA in removing calcium hydroxide mixed with 2% chlorhexidine gel (P < .0083). There were no significant differences among the other groups (P > .0083). Orange-brown precipitate was observed in all specimens of the NaOCl group but in no specimens in the other groups. Irrigation solutions of 7% maleic acid and 10% citric acid were more effective in the removal of calcium hydroxide mixed with 2% chlorhexidine gel than those of 1% NaOCl and 17% EDTA. Orange-brown precipitate was found in all specimens of the NaOCl-irrigated groups. However, the precipitate was not observed in specimens in the groups irrigated with 17% EDTA, 7% maleic acid, and 10% citric acid. Copyright © 2014 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Typological diversity of tall buildings and complexes in relation to their functional structure

NASA Astrophysics Data System (ADS)

Generalov, Viktor P.; Generalova, Elena M.; Kalinkina, Nadezhda A.; Zhdanova, Irina V.

2018-03-01

The paper focuses on peculiarities of tall buildings and complexes, their typology and its formation in relation to their functional structure. The research is based on the analysis of tall buildings and complexes and identifies the following main functional elements of their formation: residential, administrative (office), hotel elements. The paper also considers the following services as «disseminated» in the space-planning structure: shops, medicine, entertainment, kids and sports facilities, etc., their location in the structure of the total bulk of the building and their impact on typological diversity. Research results include suggestions to add such concepts as «single-function tall buildings» and «mixed-use tall buildings and complexes» into the classification of tall buildings. In addition, if a single-function building or complex performs serving functions, it is proposed to add such concepts as «a residential tall building (complex) with provision of services», «an administrative (public) tall building (complex) with provision of services» into the classification of tall buildings. For mixed-use buildings and complexes the following terms are suggested: «a mixed-use tall building with provision of services», «a mixed-use tall complex with provision of services».

Study of complex formation of 5,5'-(2 E, 2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) (HYT) macrocyclic ligand with Cd2+ cation in non-aqueous solution by spectroscopic and conductometric methods

NASA Astrophysics Data System (ADS)

Mallaekeh, Hassan; Shams, Alireza; Shaker, Mohammad; Bahramzadeh, Ehsan; Arefi, Donya

2014-12-01

In this paper the complexation reaction of the 5,5'-(2 E,2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) ligand (HYT) with Cd2+ education was studied in some binary mixtures of methanol (MeOH), n-propanol (PrOH) and dimethyl-formamide (DMF) at different temperatures using the conductometry and spectrophotometry. The stability constants of the complex was determined using a GENPLOT computer program. The conductance data and absorbance-mole ratio plots show that in all solvent systems, the stoichiometry of the complex formed between (HYT) and Cd2+ cation is 1: 1. The obtained results show that the stability of (HYT)-Cd complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (Δ G ∘, Δ H ∘, and Δ S ∘) for formation of (HYT)-Cd complex were obtained from temperature dependence of the stability constant using the van't Hoff plots. The results show that in most cases, the complex are enthalpy destabilized but entropy stabilized and the complex formation is affected by pH, time, temperature and the nature of the solvent.

Establishment of primary mixed cell cultures from spontaneous canine mammary tumors: Characterization of classic and new cancer-associated molecules

PubMed Central

Gentile, Luciana B.; Nagamine, Marcia K.; Biondi, Luiz R.; Sanches, Daniel S.; Toyota, Fábio; Giovani, Tatiane M.; de Jesus, Isis P.; da Fonseca, Ivone I. M.; Queiroz-Hazarbassanov, Nicolle; Diaz, Bruno L.; Salles Gomes, Cristina de O. Massoco

2017-01-01

There are many factors which make canine cancer like cancer in humans. The occurrence of spontaneous mammary tumors in pet dogs, tumor genetics, molecular targets and exposure to the same environmental risk factors are among these factors. Therefore, the study of canine cancer can provide useful information to the oncology field. This study aimed to establish and characterize a panel of primary mixed cell cultures obtained from spontaneous canine mammary tumors. Eight established cell cultures obtained from one normal mammary gland, one complex adenoma, one mixed adenoma, two complex carcinomas and two mixed carcinomas were analyzed. The gene expression levels of classic molecular cancer players such as fibroblast growth factor receptor (FGFR) 2, breast cancer (BRCA) 1, BRCA2 and estrogen receptor (ESR) 1 were evaluated. For the first time, three orphan nuclear receptors, estrogen-related receptors (ERRs) α, β and γ were studied in canine mammary cancer. The highest expression level of ERRα was observed in complex carcinoma-derived cell culture, while the highest levels of ERRβ and γ were observed in cells derived from a mixed carcinoma. Meanwhile, complex carcinomas presented the highest levels of expression of ESR1, BRCA1 and FGFR2 among all samples. BRCA2 was found exclusively in complex adenoma. The transcription factor GATA3 had its highest levels in mixed carcinoma samples and its lowest levels in complex adenoma. Proliferation assays were also performed to evaluate the mixed cell cultures response to ER ligands, genistein and DES, both in normoxia and hypoxic conditions. Our results demonstrate that morphological and functional studies of primary mixed cell cultures derived from spontaneous canine mammary tumors are possible and provide valuable tool for the study of various stages of mammary cancer development. PMID:28945747

Evolution of scalar and velocity dynamics in planar shock-turbulence interaction

NASA Astrophysics Data System (ADS)

Boukharfane, R.; Bouali, Z.; Mura, A.

2018-01-01

Due to the short residence time of air in supersonic combustors, achieving efficient mixing in compressible turbulent reactive flows is crucial for the design of supersonic ramjet (Scramjet) engines. In this respect, improving the understanding of shock-scalar mixing interactions is of fundamental importance for such supersonic combustion applications. In these compressible flows, the interaction between the turbulence and the shock wave is reciprocal, and the coupling between them is very strong. A basic understanding of the physics of such complex interactions has already been obtained through the analysis of relevant simplified flow configurations, including propagation of the shock wave in density-stratified media, shock-wave-mixing-layer interaction, and shock-wave-vortex interaction. Amplification of velocity fluctuations and substantial changes in turbulence characteristic length scales are the most well-known outcomes of shock-turbulence interaction, which may also deeply influence scalar mixing between fuel and oxidizer. The effects of the shock wave on the turbulence have been widely characterized through the use of so-called amplification factors, and similar quantities are introduced herein to characterize the influence of the shock wave on scalar mixing. One of the primary goals of the present study is indeed to extend previous analyses to the case of shock-scalar mixing interaction, which is directly relevant to supersonic combustion applications. It is expected that the shock wave will affect the scalar dissipation rate (SDR) dynamics. Special emphasis is placed on the modification of the so-called turbulence-scalar interaction as a leading-order contribution to the production of mean SDR, i.e., a quantity that defines the mixing rate and efficiency. To the best of the authors' knowledge, this issue has never been addressed in detail in the literature, and the objective of the present study is to scrutinize this influence. The turbulent mixing of a passive (i.e., chemically inert) scalar in the presence of a shock wave is thus investigated using high-resolution numerical simulations. The starting point of the analysis relies on the transport equations of the variance of the mixture fraction, i.e., a fuel inlet tracer that quantifies the mixing between fuel and oxidizer. The influence of the shock wave is investigated for three distinct values of the shock Mach number M, and the obtained results are compared to reference solutions featuring no shock wave. The computed solutions show that the shock wave significantly modifies the scalar field topology. The larger the value of M, the stronger is the amplification of the alignment of the scalar gradient with the most compressive principal direction of the strain-rate tensor, which signifies the enhancement of scalar mixing with the shock Mach number.

Mixing at double-Tee junctions with unequal pipe sizes in water distribution systems

EPA Science Inventory

Pipe flow mixing with various solute concentrations and flow rates at pipe junctions is investigated. The degree of mixing affects the spread of contaminants in a water distribution system. Many studies have been conducted on the mixing at the cross junctions. Yet a few have focu...

Auxiliary principle technique and iterative algorithm for a perturbed system of generalized multi-valued mixed quasi-equilibrium-like problems.

PubMed

Rahaman, Mijanur; Pang, Chin-Tzong; Ishtyak, Mohd; Ahmad, Rais

2017-01-01

In this article, we introduce a perturbed system of generalized mixed quasi-equilibrium-like problems involving multi-valued mappings in Hilbert spaces. To calculate the approximate solutions of the perturbed system of generalized multi-valued mixed quasi-equilibrium-like problems, firstly we develop a perturbed system of auxiliary generalized multi-valued mixed quasi-equilibrium-like problems, and then by using the celebrated Fan-KKM technique, we establish the existence and uniqueness of solutions of the perturbed system of auxiliary generalized multi-valued mixed quasi-equilibrium-like problems. By deploying an auxiliary principle technique and an existence result, we formulate an iterative algorithm for solving the perturbed system of generalized multi-valued mixed quasi-equilibrium-like problems. Lastly, we study the strong convergence analysis of the proposed iterative sequences under monotonicity and some mild conditions. These results are new and generalize some known results in this field.

Pore-scale and continuum simulations of solute transport micromodel benchmark experiments

DOE PAGES

Oostrom, M.; Mehmani, Y.; Romero-Gomez, P.; ...

2014-06-18

Four sets of nonreactive solute transport experiments were conducted with micromodels. Three experiments with one variable, i.e., flow velocity, grain diameter, pore-aspect ratio, and flow-focusing heterogeneity were in each set. The data sets were offered to pore-scale modeling groups to test their numerical simulators. Each set consisted of two learning experiments, for which our results were made available, and one challenge experiment, for which only the experimental description and base input parameters were provided. The experimental results showed a nonlinear dependence of the transverse dispersion coefficient on the Peclet number, a negligible effect of the pore-aspect ratio on transverse mixing,more » and considerably enhanced mixing due to flow focusing. Five pore-scale models and one continuum-scale model were used to simulate the experiments. Of the pore-scale models, two used a pore-network (PN) method, two others are based on a lattice Boltzmann (LB) approach, and one used a computational fluid dynamics (CFD) technique. Furthermore, we used the learning experiments, by the PN models, to modify the standard perfect mixing approach in pore bodies into approaches to simulate the observed incomplete mixing. The LB and CFD models used the learning experiments to appropriately discretize the spatial grid representations. For the continuum modeling, the required dispersivity input values were estimated based on published nonlinear relations between transverse dispersion coefficients and Peclet number. Comparisons between experimental and numerical results for the four challenge experiments show that all pore-scale models were all able to satisfactorily simulate the experiments. The continuum model underestimated the required dispersivity values, resulting in reduced dispersion. The PN models were able to complete the simulations in a few minutes, whereas the direct models, which account for the micromodel geometry and underlying flow and transport physics, needed up to several days on supercomputers to resolve the more complex problems.« less

Solution of the nonlinear mixed Volterra-Fredholm integral equations by hybrid of block-pulse functions and Bernoulli polynomials.

PubMed

Mashayekhi, S; Razzaghi, M; Tripak, O

2014-01-01

A new numerical method for solving the nonlinear mixed Volterra-Fredholm integral equations is presented. This method is based upon hybrid functions approximation. The properties of hybrid functions consisting of block-pulse functions and Bernoulli polynomials are presented. The operational matrices of integration and product are given. These matrices are then utilized to reduce the nonlinear mixed Volterra-Fredholm integral equations to the solution of algebraic equations. Illustrative examples are included to demonstrate the validity and applicability of the technique.

Solution of the Nonlinear Mixed Volterra-Fredholm Integral Equations by Hybrid of Block-Pulse Functions and Bernoulli Polynomials

PubMed Central

Mashayekhi, S.; Razzaghi, M.; Tripak, O.

2014-01-01

A new numerical method for solving the nonlinear mixed Volterra-Fredholm integral equations is presented. This method is based upon hybrid functions approximation. The properties of hybrid functions consisting of block-pulse functions and Bernoulli polynomials are presented. The operational matrices of integration and product are given. These matrices are then utilized to reduce the nonlinear mixed Volterra-Fredholm integral equations to the solution of algebraic equations. Illustrative examples are included to demonstrate the validity and applicability of the technique. PMID:24523638

Facile fabrication of high-quality Ag/PS coaxial nanocables based on the mixed mode of soft/hard templates

PubMed Central

Wan, Mimi; Zhao, Wenbo; Peng, Fang; Wang, Qi; Xu, Ping; Mao, Chun; Shen, Jian

2016-01-01

A new kind of high-quality Ag/PS coaxial nanocables can be facilely synthesized by using soft/hard templates method. In order to effectively introduce Ag sources into porous polystyrene (PS) nanotubes which were trapped in porous anodic aluminum oxide (AAO) hard template, Pluronic F127 (F127) was used as guiding agent, soft template and reductant. Meanwhile, ethylene glycol solution was also used as solvent and co-reducing agent to assist in the formation of silver nanowires. The influences of concentration of F127 and reducing reaction time on the formation of Ag/PS coaxial nanocables were discussed. Results indicated that the high-quality Ag/PS coaxial nanocables can be obtained by the mixed mode of soft/hard templates under optimized conditions. This strategy is expected to be extended to design more metal/polymer coaxial nanocables for the benefit of creation of complex and functional nanoarchitectures and components. PMID:27477888

Analysis and generation of groundwater concentration time series

NASA Astrophysics Data System (ADS)

Crăciun, Maria; Vamoş, Călin; Suciu, Nicolae

2018-01-01

Concentration time series are provided by simulated concentrations of a nonreactive solute transported in groundwater, integrated over the transverse direction of a two-dimensional computational domain and recorded at the plume center of mass. The analysis of a statistical ensemble of time series reveals subtle features that are not captured by the first two moments which characterize the approximate Gaussian distribution of the two-dimensional concentration fields. The concentration time series exhibit a complex preasymptotic behavior driven by a nonstationary trend and correlated fluctuations with time-variable amplitude. Time series with almost the same statistics are generated by successively adding to a time-dependent trend a sum of linear regression terms, accounting for correlations between fluctuations around the trend and their increments in time, and terms of an amplitude modulated autoregressive noise of order one with time-varying parameter. The algorithm generalizes mixing models used in probability density function approaches. The well-known interaction by exchange with the mean mixing model is a special case consisting of a linear regression with constant coefficients.

Adsorption of Heavy Metal Ions from Aqueous Solutions by Bentonite Nanocomposites.

PubMed

Ma, Jing; Su, Guojun; Zhang, Xueping; Huang, Wen

2016-08-01

A series of bentonite nanocomposites have been synthesized by modifying bentonite with hexadecyltrimethylammonium bromide (CTMAB) and the common complexing agents, complexone (ethylene diamine tetraacetic acid, EDTA) or mercaptocomplexant (2-Mercaptobenzothiazole, MBT). These adsorbents are used to remove heavy metal ions (Cu(2+), Zn(2+), Mn(2+),Co(2+)). The Bent-CTMAB-MBT adsorbed metal ions are higher than Bent-CTMAB-EDTA under the same ion concentration in AAS. Compared with the single ion system, the adsorption of the mixed ion system of Cu(2+), Zn(2+), Mn(2+), Co(2+) had decreased differently. In the mixed system, the adsorption of Mn(2+) is significantly lower, but the adsorption of Cu(2+) was highest. The adsorption sequence of these four metal ions was Cu(2+) > Zn(2+) > Co(2+) > Mn(2+), and the selective adsorption was closely related to the hydration energy of heavy metal ions. We could remove more metal ions in different stages with the adsorption sequence.

Enthalpy of Mixing in Al–Tb Liquid

DOE PAGES

Zhou, Shihuai; Tackes, Carl; Napolitano, Ralph

2017-06-21

The liquid-phase enthalpy of mixing for Al$-$Tb alloys is measured for 3, 5, 8, 10, and 20 at% Tb at selected temperatures in the range from 1364 to 1439 K. Methods include isothermal solution calorimetry and isoperibolic electromagnetic levitation drop calorimetry. Mixing enthalpy is determined relative to the unmixed pure (Al and Tb) components. The required formation enthalpy for the Al3Tb phase is computed from first-principles calculations. Finally, based on our measurements, three different semi-empirical solution models are offered for the excess free energy of the liquid, including regular, subregular, and associate model formulations. These models are also compared withmore » the Miedema model prediction of mixing enthalpy.« less

A detailed study of ice nucleation by feldspar minerals

NASA Astrophysics Data System (ADS)

Whale, T. F.; Murray, B. J.; Wilson, T. W.; Carpenter, M. A.; Harrison, A.; Holden, M. A.; Vergara Temprado, J.; Morris, J.; O'Sullivan, D.

2015-12-01

Immersion mode heterogeneous ice nucleation plays a crucial role in controlling the composition of mixed phase clouds, which contain both supercooled liquid water and ice particles. The amount of ice in mixed phase clouds can affect cloud particle size, lifetime and extent and so affects radiative properties and precipitation. Feldspar minerals are probably the most important minerals for ice nucleation in mixed phase clouds because they nucleate ice more efficiently than other components of atmospheric mineral dust (Atkinson et al. 2013). The feldspar class of minerals is complex, containing numerous chemical compositions, several crystal polymorphs and wide variations in microscopic structure. Here we present the results of a study into ice nucleation by a wide range of different feldspars. We found that, in general, alkali feldspars nucleate ice more efficiently than plagioclase feldspars. However, we also found that particular alkali feldspars nucleate ice relatively inefficiently, suggesting that chemical composition is not the only important factor that dictates the ice nucleation efficiency of feldspar minerals. Ice nucleation by feldspar is described well by the singular model and is probably site specific in nature. The alkali feldspars that do not nucleate ice efficiently possess relatively homogenous structure on the micrometre scale suggesting that the important sites for nucleation are related to surface topography. Ice nucleation active site densities for the majority of tested alkali feldspars are similar to those found by Atkinson et al (2013), meaning that the validity of global aerosol modelling conducted in that study is not affected. Additionally, we have found that ice nucleation by feldspars is strongly influenced, both positively and negatively, by the solute content of droplets. Most other nucleants we have tested are unaffected by solutes. This provides insight into the mechanism of ice nucleation by feldspars and could be of importance when modelling ice nucleation in mixed phase clouds. Atkinson, J. D., Murray, B. J., Woodhouse, M. T., Carslaw, K. S., Whale, T. F., Baustian, K. J., Dobbie, S., O'Sullivan, D., and Malkin, T. L.: The importance of feldspar for ice nucleation by mineral dust in mixed-phase clouds, Nature, 10.1038/nature12278, (2013).

Plasma synthesis of lithium based intercalation powders for solid polymer electrolyte batteries

DOEpatents

Kong, Peter C [Idaho Falls, ID; Pink, Robert J [Pocatello, ID; Nelson, Lee O [Idaho Falls, ID

2005-01-04

The invention relates to a process for preparing lithium intercalation compounds by plasma reaction comprising the steps of: forming a feed solution by mixing lithium nitrate or lithium hydroxide or lithium oxide and the required metal nitrate or metal hydroxide or metal oxide and between 10-50% alcohol by weight; mixing the feed solution with O.sub.2 gas wherein the O.sub.2 gas atomizes the feed solution into fine reactant droplets, inserting the atomized feed solution into a plasma reactor to form an intercalation powder; and if desired, heating the resulting powder to from a very pure single phase product.

Active mixing of complex fluids at the microscale

DOE PAGES

Ober, Thomas J.; Foresti, Daniele; Lewis, Jennifer A.

2015-09-22

Mixing of complex fluids at low Reynolds number is fundamental for a broad range of applications, including materials assembly, microfluidics, and biomedical devices. Of these materials, yield stress fluids (and gels) pose the most significant challenges, especially when they must be mixed in low volumes over short timescales. New scaling relationships between mixer dimensions and operating conditions are derived and experimentally verified to create a framework for designing active microfluidic mixers that can efficiently homogenize a wide range of complex fluids. As a result, active mixing printheads are then designed and implemented for multimaterial 3D printing of viscoelastic inks withmore » programmable control of local composition.« less

Active mixing of complex fluids at the microscale

PubMed Central

Ober, Thomas J.; Foresti, Daniele; Lewis, Jennifer A.

2015-01-01

Mixing of complex fluids at low Reynolds number is fundamental for a broad range of applications, including materials assembly, microfluidics, and biomedical devices. Of these materials, yield stress fluids (and gels) pose the most significant challenges, especially when they must be mixed in low volumes over short timescales. New scaling relationships between mixer dimensions and operating conditions are derived and experimentally verified to create a framework for designing active microfluidic mixers that can efficiently homogenize a wide range of complex fluids. Active mixing printheads are then designed and implemented for multimaterial 3D printing of viscoelastic inks with programmable control of local composition. PMID:26396254

Quantifying uncertainty in stable isotope mixing models

DOE PAGES

Davis, Paul; Syme, James; Heikoop, Jeffrey; ...

2015-05-19

Mixing models are powerful tools for identifying biogeochemical sources and determining mixing fractions in a sample. However, identification of actual source contributors is often not simple, and source compositions typically vary or even overlap, significantly increasing model uncertainty in calculated mixing fractions. This study compares three probabilistic methods, SIAR [ Parnell et al., 2010] a pure Monte Carlo technique (PMC), and Stable Isotope Reference Source (SIRS) mixing model, a new technique that estimates mixing in systems with more than three sources and/or uncertain source compositions. In this paper, we use nitrate stable isotope examples (δ 15N and δ 18O) butmore » all methods tested are applicable to other tracers. In Phase I of a three-phase blind test, we compared methods for a set of six-source nitrate problems. PMC was unable to find solutions for two of the target water samples. The Bayesian method, SIAR, experienced anchoring problems, and SIRS calculated mixing fractions that most closely approximated the known mixing fractions. For that reason, SIRS was the only approach used in the next phase of testing. In Phase II, the problem was broadened where any subset of the six sources could be a possible solution to the mixing problem. Results showed a high rate of Type I errors where solutions included sources that were not contributing to the sample. In Phase III some sources were eliminated based on assumed site knowledge and assumed nitrate concentrations, substantially reduced mixing fraction uncertainties and lowered the Type I error rate. These results demonstrate that valuable insights into stable isotope mixing problems result from probabilistic mixing model approaches like SIRS. The results also emphasize the importance of identifying a minimal set of potential sources and quantifying uncertainties in source isotopic composition as well as demonstrating the value of additional information in reducing the uncertainty in calculated mixing fractions.« less

Travelling Fronts and Entire Solutionsof the Fisher-KPP Equation in N

NASA Astrophysics Data System (ADS)

Hamel, François; Nadirashvili, Nikolaï

This paper is devoted to time-global solutions of the Fisher-KPP equation in N: where f is a C2 concave function on [0,1] such that f(0)=f(1)=0 and f>0 on (0,1). It is well known that this equation admits a finite-dimensional manifold of planar travelling-fronts solutions. By considering the mixing of any density of travelling fronts, we prove the existence of an infinite-dimensional manifold of solutions. In particular, there are infinite-dimensional manifolds of (nonplanar) travelling fronts and radial solutions. Furthermore, up to an additional assumption, a given solution u can be represented in terms of such a mixing of travelling fronts.

Density fluctuations in aqueous solution of ionic liquid with lower critical solution temperature: Mixture of tetrabutylphosphonium trifluoroacetate and water

NASA Astrophysics Data System (ADS)

Nitta, Ayako; Morita, Takeshi; Saita, Shohei; Kohno, Yuki; Ohno, Hiroyuki; Nishikawa, Keiko

2015-05-01

Aqueous solutions of tetrabutylphosphonium trifluoroacetate ([P4444]CF3COO) exhibit a LCST-type phase transition with the critical point near 0.025 in mole fraction of [P4444]CF3COO at T = 302 K. The phase behavior of [P4444]CF3COO-water mixtures was investigated by evaluating their density fluctuations, which provide quantitative descriptions of the mixing states of the solutions. The concentration dependence of the density fluctuations was investigated at 293 and 301 K for the mixtures without distinguishing the components and for the individual components ([P4444]CF3COO and water). A drastic change in the mixing state was observed for the solution when the critical point was approached.

Applications of Analytical Self-Similar Solutions of Reynolds-Averaged Models for Instability-Induced Turbulent Mixing

NASA Astrophysics Data System (ADS)

Hartland, Tucker; Schilling, Oleg

2017-11-01

Analytical self-similar solutions to several families of single- and two-scale, eddy viscosity and Reynolds stress turbulence models are presented for Rayleigh-Taylor, Richtmyer-Meshkov, and Kelvin-Helmholtz instability-induced turbulent mixing. The use of algebraic relationships between model coefficients and physical observables (e.g., experimental growth rates) following from the self-similar solutions to calibrate a member of a given family of turbulence models is shown. It is demonstrated numerically that the algebraic relations accurately predict the value and variation of physical outputs of a Reynolds-averaged simulation in flow regimes that are consistent with the simplifying assumptions used to derive the solutions. The use of experimental and numerical simulation data on Reynolds stress anisotropy ratios to calibrate a Reynolds stress model is briefly illustrated. The implications of the analytical solutions for future Reynolds-averaged modeling of hydrodynamic instability-induced mixing are briefly discussed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

An outer approximation method for the road network design problem

PubMed Central

2018-01-01

Best investment in the road infrastructure or the network design is perceived as a fundamental and benchmark problem in transportation. Given a set of candidate road projects with associated costs, finding the best subset with respect to a limited budget is known as a bilevel Discrete Network Design Problem (DNDP) of NP-hard computationally complexity. We engage with the complexity with a hybrid exact-heuristic methodology based on a two-stage relaxation as follows: (i) the bilevel feature is relaxed to a single-level problem by taking the network performance function of the upper level into the user equilibrium traffic assignment problem (UE-TAP) in the lower level as a constraint. It results in a mixed-integer nonlinear programming (MINLP) problem which is then solved using the Outer Approximation (OA) algorithm (ii) we further relax the multi-commodity UE-TAP to a single-commodity MILP problem, that is, the multiple OD pairs are aggregated to a single OD pair. This methodology has two main advantages: (i) the method is proven to be highly efficient to solve the DNDP for a large-sized network of Winnipeg, Canada. The results suggest that within a limited number of iterations (as termination criterion), global optimum solutions are quickly reached in most of the cases; otherwise, good solutions (close to global optimum solutions) are found in early iterations. Comparative analysis of the networks of Gao and Sioux-Falls shows that for such a non-exact method the global optimum solutions are found in fewer iterations than those found in some analytically exact algorithms in the literature. (ii) Integration of the objective function among the constraints provides a commensurate capability to tackle the multi-objective (or multi-criteria) DNDP as well. PMID:29590111

An outer approximation method for the road network design problem.

PubMed

Asadi Bagloee, Saeed; Sarvi, Majid

2018-01-01

Best investment in the road infrastructure or the network design is perceived as a fundamental and benchmark problem in transportation. Given a set of candidate road projects with associated costs, finding the best subset with respect to a limited budget is known as a bilevel Discrete Network Design Problem (DNDP) of NP-hard computationally complexity. We engage with the complexity with a hybrid exact-heuristic methodology based on a two-stage relaxation as follows: (i) the bilevel feature is relaxed to a single-level problem by taking the network performance function of the upper level into the user equilibrium traffic assignment problem (UE-TAP) in the lower level as a constraint. It results in a mixed-integer nonlinear programming (MINLP) problem which is then solved using the Outer Approximation (OA) algorithm (ii) we further relax the multi-commodity UE-TAP to a single-commodity MILP problem, that is, the multiple OD pairs are aggregated to a single OD pair. This methodology has two main advantages: (i) the method is proven to be highly efficient to solve the DNDP for a large-sized network of Winnipeg, Canada. The results suggest that within a limited number of iterations (as termination criterion), global optimum solutions are quickly reached in most of the cases; otherwise, good solutions (close to global optimum solutions) are found in early iterations. Comparative analysis of the networks of Gao and Sioux-Falls shows that for such a non-exact method the global optimum solutions are found in fewer iterations than those found in some analytically exact algorithms in the literature. (ii) Integration of the objective function among the constraints provides a commensurate capability to tackle the multi-objective (or multi-criteria) DNDP as well.

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy.

PubMed

Slenkamp, Karla M; Lynch, Michael S; Van Kuiken, Benjamin E; Brookes, Jennifer F; Bannan, Caitlin C; Daifuku, Stephanie L; Khalil, Munira

2014-02-28

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O and formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm(-1). The mixed-mode anharmonicities range from 2 to 14 cm(-1). In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm(-1). This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

Let Your Ions Shine.

ERIC Educational Resources Information Center

Koubek, Edward

1985-01-01

Outlines a demonstration involving weak acids and bases in aqueous solutions. A standard conductivity demonstration with a solution of acetic acid yields a barely glowing light bulb; a similar result occurs with ammonia solution. However, the bulb glows brightly when the solutions are mixed. (DH)

Nonlinear oscillations and waves in multi-species cold plasmas

NASA Astrophysics Data System (ADS)

Verma, Prabal Singh

2016-12-01

The spatio-temporal evolution of nonlinear oscillations in multi-species plasma is revisited to provide more insight into the physics of phase mixing by constructing two sets of nonlinear solutions up to the second order. The first solution exhibits perfect oscillations in the linear regime and phase mixing appears only nonlinearly in the second order as a response to the ponderomotive forces. This response can be both direct and indirect. The indirect contribution of the ponderomotive forces appears through self-consistently generated low frequency fields. Furthermore, the direct and indirect contributions of the ponderomotive forces on the phase mixing process is explored and it is found that the indirect contribution is negligible in an electron-ion plasma and it disappears in the case of electron-positron plasma, yet represents an equal contribution in the electron-positron-ion plasma. However, the second solution does not exhibit any phase mixing due to the absence of ponderomotive forces but results in an undistorted nonlinear traveling wave. These investigations have relevance for laboratory/astrophysical multi-species plasma.

Mixed lump-kink and rogue wave-kink solutions for a (3 + 1) -dimensional B-type Kadomtsev-Petviashvili equation in fluid mechanics

NASA Astrophysics Data System (ADS)

Hu, Cong-Cong; Tian, Bo; Wu, Xiao-Yu; Yuan, Yu-Qiang; Du, Zhong

2018-02-01

Under investigation is a (3 + 1) -dimensional B-type Kadomtsev-Petviashvili equation, which describes the weakly dispersive waves in a fluid. Via the Hirota method and symbolic computation, we obtain the mixed lump-kink and mixed rogue wave-kink solutions. Through the mixed lump-kink solutions, we observe three different phenomena between a lump and one kink. For the fusion phenomenon, a lump and a kink are merged with the lump's energy transferring into the kink gradually, until the lump merges into the kink completely. Fission phenomenon displays that a lump separates from a kink. The last phenomenon shows that a lump travels together with a kink with their amplitudes unchanged. In addition, we graphically study the interaction between a rogue wave and a pair of the kinks. It can be observed that the rogue wave arises from one kink and disappears into the other kink. At certain time, the amplitude of the rogue wave reaches the maximum.

Aggregation study in mixture surfactant system TX-100+SDS in heavy water solutions by SANS method

NASA Astrophysics Data System (ADS)

Rajewska, A.; Islamov, A. Kh.; Bakeeva, R. F.

2018-03-01

The mixing of amphiphiles in water may lead to the formation of mixed micelles which often present new properties with respect to the pure component solutions [1,2]. The mixture system of classic surfactants SDS (sodium dodecyl sulfate)+TX-100(p-(1,1,3,3- tetramethyl) poly(oxyethylene) (anionic + non-ionic) in heavy water solutions was investigated at temperatures 30°, 50°, 70°C for compositions 1:1, 2:1, 3:1 by the small-angle neutron scattering(SANS) method on spectrometer (‘YuMO’) at the IBR-2 pulsed neutron source at FLNP, JINR in Dubna (Russia). Measurements have covered Q range from 8x10-3 to 0.4 Å-1. From the measured dependence of the scattered intensity on the scattering angle, we derived the size, shape of micelles, aggregation number at various compositions and temperatures. The size of mixed micelle is a weak function of the mixing ratio between the two components.

The MHOST finite element program: 3-D inelastic analysis methods for hot section components. Volume 1: Theoretical manual

NASA Technical Reports Server (NTRS)

Nakazawa, Shohei

1991-01-01

Formulations and algorithms implemented in the MHOST finite element program are discussed. The code uses a novel concept of the mixed iterative solution technique for the efficient 3-D computations of turbine engine hot section components. The general framework of variational formulation and solution algorithms are discussed which were derived from the mixed three field Hu-Washizu principle. This formulation enables the use of nodal interpolation for coordinates, displacements, strains, and stresses. Algorithmic description of the mixed iterative method includes variations for the quasi static, transient dynamic and buckling analyses. The global-local analysis procedure referred to as the subelement refinement is developed in the framework of the mixed iterative solution, of which the detail is presented. The numerically integrated isoparametric elements implemented in the framework is discussed. Methods to filter certain parts of strain and project the element discontinuous quantities to the nodes are developed for a family of linear elements. Integration algorithms are described for linear and nonlinear equations included in MHOST program.

Visual compatibility of defibrotide with selected drugs during simulated Y-site administration.

PubMed

Correard, Florian; Savry, Amandine; Gauthier-Villano, Laurence; Pisano, Pascale; Pourroy, Bertrand

2014-08-01

The visual compatibility of a solution of defibrotide (the only drug recommended for treatment and prophylaxis of hepatic venoocclusive disease) with solutions of various drugs commonly administered in bone marrow transplant procedures was studied. Solutions of 43 drug products in concentrations typically used in clinical practice were evaluated in 1:1 mixtures with defibrotide solution in glass tubes kept at room temperature. The evaluated products included antiinfectious, corticoid, sedative, analgesic, and cardiovascular agents widely used for hematopoietic stem cell transplantation and other marrow transplant procedures; in most cases, test solutions were prepared via dilution in or reconstitution with sterile water, 0.9% sodium chloride injection, or 5% dextrose injection. The mixtures were visually observed immediately after manual mixing and at specified time points (60, 150, and 240 minutes). Visual compatibility was defined as the absence of color change, haze, fibers, particles, gas generation, and precipitate formation. The effect of mixing order on visual compatibility was ascertained. Of the 43 tested drug solutions, 36 were found to be visually compatible with the defibrotide solution over the entire four-hour study period. Solutions of 7 drugs (amikacin, furosemide, midazolam, mycophenolate mofetil, nicardipine, tobramycin, and vancomycin) were visually incompatible with defibrotide solution. In some cases, evidence of incompatibility was observed intermittently or was dependent on mixing order. Defibrotide solution was found to be visually compatible with solutions of 36 i.v. products that are likely to be coadministered with the drug in a bone marrow transplant unit. Seven drug solutions were visually incompatible with defibrotide solution. Copyright © 2014 by the American Society of Health-System Pharmacists, Inc. All rights reserved.

[Leaching Remediation of Copper and Lead Contaminated Lou Soil by Saponin Under Different Conditions].

PubMed

Deng, Hong-xia; Yang, Ya-li; Li, Zhen; Xu, Yan; Li, Rong-hua; Meng, Zhao-fu; Yang, Ya-ti

2015-04-01

In order to investigate the leaching remediation effect of the eco-friendly biosurfactant saponin for Cu and Pb in contaminated Lou soil, batch tests method was used to study the leaching effect of saponin solution on single Cu, Pb contaminated Lou soil and mixed Cu and Pb contaminated Lou soil under different conditions such as reaction time, mass concentration of saponin, pH, concentration of background electrolyte and leaching times. The results showed that the maximum leaching removal effect of Cu and Pb in contaminated Lou soil was achieved by complexation of the heavy metals with saponin micelle, when the mass concentration of saponin solution was 50 g x L(-1), pH was 5.0, the reaction time was 240 min, and there was no background electrolyte. In single and mixed contaminated Lou soil, the leaching percentages of Cu were 29.02% and 25.09% after a single leaching with 50 g x L(-1) saponin under optimal condition, while the single leaching percentages of Pb were 31.56% and 28.03%, respectively. The result indicated the removal efficiency of Pb was more significant than that of Cu. After 4 times of leaching, the cumulative leaching percentages of Cu reached 58.92% and 53.11%, while the cumulative leaching percentages of Pb reached 77.69% and 65.32% for single and mixed contaminated Lou soil, respectively. The fractionation results of heavy metals in soil before and after a single leaching showed that the contents of adsorbed and exchangeable Cu and Pb increased in the contaminated soil, while the carbonate-bound, organic bound and sulfide residual Cu and Pb in the contaminated Lou soil could be effectively removed by saponin.

Fully Passive Wireless Acquisition of Neuropotentials

NASA Astrophysics Data System (ADS)

Schwerdt, Helen N.

The ability to monitor electrophysiological signals from the sentient brain is requisite to decipher its enormously complex workings and initiate remedial solutions for the vast amount of neurologically-based disorders. Despite immense advancements in creating a variety of instruments to record signals from the brain, the translation of such neurorecording instrumentation to real clinical domains places heavy demands on their safety and reliability, both of which are not entirely portrayed by presently existing implantable recording solutions. In an attempt to lower these barriers, alternative wireless radar backscattering techniques are proposed to render the technical burdens of the implant chip to entirely passive neurorecording processes that transpire in the absence of formal integrated power sources or powering schemes along with any active circuitry. These radar-like wireless backscattering mechanisms are used to conceive of fully passive neurorecording operations of an implantable microsystem. The fully passive device potentially manifests inherent advantages over current wireless implantable and wired recording systems: negligible heat dissipation to reduce risks of brain tissue damage and minimal circuitry for long term reliability as a chronic implant. Fully passive neurorecording operations are realized via intrinsic nonlinear mixing properties of the varactor diode. These mixing and recording operations are directly activated by wirelessly interrogating the fully passive device with a microwave carrier signal. This fundamental carrier signal, acquired by the implant antenna, mixes through the varactor diode along with the internal targeted neuropotential brain signals to produce higher frequency harmonics containing the targeted neuropotential signals. These harmonics are backscattered wirelessly to the external interrogator that retrieves and recovers the original neuropotential brain signal. The passive approach removes the need for internal power sources and may alleviate heat trauma and reliability issues that limit practical implementation of existing implantable neurorecorders.

Determination of a flame retardant hydrolysis product in human urine by SPE and LC-MS. Comparison of molecularly imprinted solid-phase extraction with a mixed-mode anion exchanger.

PubMed

Möller, Kristina; Crescenzi, Carlo; Nilsson, Ulrika

2004-01-01

Diphenyl phosphate is a hydrolysis product and possible metabolite of the flame retardant and plasticiser additive triphenyl phosphate. A molecularly imprinted polymer solid-phase extraction (MISPE) method for extracting diphenyl phosphate from aqueous solutions has been developed and compared with SPE using a commercially available mixed-mode anion exchanger. The imprinted polymer was prepared using 2-vinylpyridine (2-Vpy) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linker, and a structural analogue of the analyte as the template molecule. The imprinted polymer was evaluated for use as a SPE sorbent, in tests with both aqueous standards and spiked urine samples, by comparing recovery and breakthrough data obtained using the imprinted form of the polymer and a non-imprinted form (NIP). Extraction from aqueous solutions resulted in more than 80% recovery. Adsorption by the molecularly imprinted polymer (MIP) was non-selective, but selectivity was achieved by selective desorption in the wash steps. Diphenyl phosphate could also be selectively extracted from urine samples, although the urine matrix reduced the capacity of the MISPE cartridges. Recoveries from urine extraction were higher than 70%. It was important to control pH during sample loading. The MISPE method was found to yield a less complex LC-ESI-MS chromatogram of the urine extracts compared with the mixed-mode anion-exchanger method. An LC-ESI-MS method using a Hypercarb LC column with a graphitised carbon stationary phase was also evaluated for organophosphate diesters. LC-ESI-MS using negative-ion detection in selected ion monitoring (SIM) mode was shown to be linear for diphenyl phosphate in the range 0.08-20 ng microL(-1).

Experimental and numerical analysis of parallel reactant flow and transverse mixing with mineral precipitation in homogeneous and heterogeneous porous media

DOE PAGES

Fox, Don T.; Guo, Luanjing; Fujita, Yoshiko; ...

2015-12-17

Formation of mineral precipitates in the mixing interface between two reactant solutions flowing in parallel in porous media is governed by reactant mixing by diffusion and dispersion and is coupled to changes in porosity/permeability due to precipitation. The spatial and temporal distribution of mixing-dependent precipitation of barium sulfate in porous media was investigated with side-by-side injection of barium chloride and sodium sulfate solutions in thin rectangular flow cells packed with quartz sand. The results for homogeneous sand beds were compared to beds with higher or lower permeability inclusions positioned in the path of the mixing zone. In the homogeneous andmore » high permeability inclusion experiments, BaSO 4 precipitate (barite) formed in a narrow deposit along the length and in the center of the solution–solution mixing zone even though dispersion was enhanced within, and downstream of, the high permeability inclusion. In the low permeability inclusion experiment, the deflected BaSO 4 precipitation zone broadened around one side and downstream of the inclusion and was observed to migrate laterally toward the sulfate solution. A continuum-scale fully coupled reactive transport model that simultaneously solves the nonlinear governing equations for fluid flow, transport of reactants and geochemical reactions was used to simulate the experiments and provide insight into mechanisms underlying the experimental observations. Lastly, migration of the precipitation zone in the low permeability inclusion experiment could be explained by the coupling effects among fluid flow, reactant transport and localized mineral precipitation reaction.« less

THRSTER: A THRee-STream Ejector Ramjet Analysis and Design Tool

NASA Technical Reports Server (NTRS)

Chue, R. S.; Sabean, J.; Tyll, J.; Bakos, R. J.

2000-01-01

An engineering tool for analyzing ejectors in rocket based combined cycle (RBCC) engines has been developed. A key technology for multi-cycle RBCC propulsion systems is the ejector which functions as the compression stage of the ejector ramjet cycle. The THRee STream Ejector Ramjet analysis tool was developed to analyze the complex aerothermodynamic and combustion processes that occur in this device. The formulated model consists of three quasi-one-dimensional streams, one each for the ejector primary flow, the secondary flow, and the mixed region. The model space marches through the mixer, combustor, and nozzle to evaluate the solution along the engine. In its present form, the model is intended for an analysis mode in which the diffusion rates of the primary and secondary into the mixed stream are stipulated. The model offers the ability to analyze the highly two-dimensional ejector flowfield while still benefits from the simplicity and speed of an engineering tool. To validate the developed code, wall static pressure measurements from the Penn-State and NASA-ART RBCC experiments were used to compare with the results generated by the code. The calculated solutions were generally found to have satisfactory agreement with the pressure measurements along the engines, although further modeling effort may be required when a strong shock train is formed at the rocket exhaust. The range of parameters in which the code would generate valid results are presented and discussed.

THRSTER: A Three-Stream Ejector Ramjet Analysis and Design Tool

NASA Technical Reports Server (NTRS)

Chue, R. S.; Sabean, J.; Tyll, J.; Bakos, R. J.; Komar, D. R. (Technical Monitor)

2000-01-01

An engineering tool for analyzing ejectors in rocket based combined cycle (RBCC) engines has been developed. A key technology for multi-cycle RBCC propulsion systems is the ejector which functions as the compression stage of the ejector ramjet cycle. The THRee STream Ejector Ramjet analysis tool was developed to analyze the complex aerothermodynamic and combustion processes that occur in this device. The formulated model consists of three quasi-one-dimensional streams, one each for the ejector primary flow, the secondary flow, and the mixed region. The model space marches through the mixer, combustor, and nozzle to evaluate the solution along the engine. In its present form, the model is intended for an analysis mode in which the diffusion rates of the primary and secondary into the mixed stream are stipulated. The model offers the ability to analyze the highly two-dimensional ejector flowfield while still benefits from the simplicity and speed of an engineering tool. To validate the developed code, wall static pressure measurements from the Penn-State and NASA-ART RBCC experiments were used to compare with the results generated by the code. The calculated solutions were generally found to have satisfactory agreement with the pressure measurements along the engines, although further modeling effort may be required when a strong shock train is formed at the rocket exhaust. The range of parameters in which the code would generate valid results are presented and discussed.

Rapid three-dimensional microfluidic mixer for high viscosity solutions to unravel earlier folding kinetics of G-quadruplex under molecular crowding conditions.

PubMed

Liu, Chao; Li, Ying; Li, Yiwei; Chen, Peng; Feng, Xiaojun; Du, Wei; Liu, Bi-Feng

2016-01-01

Rapid mixing of highly viscous solutions is a great challenge, which helps to analyze the reaction kinetics in viscous liquid phase, particularly to discover the folding kinetics of macromolecules under molecular crowding conditions mimicking the conditions inside cells. Here, we demonstrated a novel microfluidic mixer based on Dean flows with three-dimensional (3D) microchannel configuration for fast mixing of high-viscosity fluids. The main structure contained three consecutive subunits, each consisting of a "U"-type channel followed by a chamber with different width and height. Thus, the two solutions injected from the two inlets would undergo a mixing in the first "U"-type channel due to the Dean flow effect, and simultaneous vortices expansions in both horizontal and vertical directions in the following chamber. Numerical simulations and experimental characterizations confirmed that the micromixer could achieve a mixing time of 122.4μs for solutions with viscosities about 33.6 times that of pure water. It was the fastest micromixer for high viscosity solutions compared with previous reports. With this highly efficient 3D microfluidic mixer, we further characterized the early folding kinetics of human telomere G-quadruplex under molecular crowding conditions, and unravelled a new folding process within 550μs. Copyright © 2015 Elsevier B.V. All rights reserved.

Student Characteristics, Prior Experiences, and the Perception of Mixed Methods as an Innovation

ERIC Educational Resources Information Center

Brown, Sydney E.

2014-01-01

There are persistent challenges to teaching mixed methods and innovative solutions are sought in order to address the needs of an increasingly diverse global audience seeking mixed methods instruction. This mixed methods study was conducted to gain insights to course design by more fully understanding the relationships among graduate student…

Constrained minimization problems for the reproduction number in meta-population models.

PubMed

Poghotanyan, Gayane; Feng, Zhilan; Glasser, John W; Hill, Andrew N

2018-02-14

The basic reproduction number ([Formula: see text]) can be considerably higher in an SIR model with heterogeneous mixing compared to that from a corresponding model with homogeneous mixing. For example, in the case of measles, mumps and rubella in San Diego, CA, Glasser et al. (Lancet Infect Dis 16(5):599-605, 2016. https://doi.org/10.1016/S1473-3099(16)00004-9 ), reported an increase of 70% in [Formula: see text] when heterogeneity was accounted for. Meta-population models with simple heterogeneous mixing functions, e.g., proportionate mixing, have been employed to identify optimal vaccination strategies using an approach based on the gradient of the effective reproduction number ([Formula: see text]), which consists of partial derivatives of [Formula: see text] with respect to the proportions immune [Formula: see text] in sub-groups i (Feng et al. in J Theor Biol 386:177-187, 2015.  https://doi.org/10.1016/j.jtbi.2015.09.006 ; Math Biosci 287:93-104, 2017.  https://doi.org/10.1016/j.mbs.2016.09.013 ). These papers consider cases in which an optimal vaccination strategy exists. However, in general, the optimal solution identified using the gradient may not be feasible for some parameter values (i.e., vaccination coverages outside the unit interval). In this paper, we derive the analytic conditions under which the optimal solution is feasible. Explicit expressions for the optimal solutions in the case of [Formula: see text] sub-populations are obtained, and the bounds for optimal solutions are derived for [Formula: see text] sub-populations. This is done for general mixing functions and examples of proportionate and preferential mixing are presented. Of special significance is the result that for general mixing schemes, both [Formula: see text] and [Formula: see text] are bounded below and above by their corresponding expressions when mixing is proportionate and isolated, respectively.

Coupled charge migration and fluid mixing in reactive fronts

NASA Astrophysics Data System (ADS)

Ghosh, Uddipta; Bandopadhyay, Aditya; Jougnot, Damien; Le Borgne, Tanguy; Meheust, Yves

2017-04-01

Quantifying fluid mixing in subsurface environments and its consequence on biogeochemical reactions is of paramount importance owing to its role in processes such as contaminant migration, aquifer remediation, CO2 sequestration or clogging processes, to name a few (Dentz et al. 2011). The presence of strong velocity gradients in porous media is expected to lead to enhanced diffusive mixing and augmented reaction rates (Le Borgne et al. 2014). Accurate in situ imaging of subsurface reactive solute transport and mixing remains to date a challenging proposition: the opacity of the medium prevents optical imaging and field methods based on tracer tests do not provide spatial information. Recently developed geophysical methods based on the temporal monitoring of electrical conductivity and polarization have shown promises for mapping and monitoring biogeochemical reactions in the subsurface although it remains challenging to decipher the multiple sources of electrical signals (e.g. Knight et al. 2010). In this work, we explore the coupling between fluid mixing, reaction and charge migration in porous media to evaluate the potential of mapping reaction rates from electrical measurements. To this end, we develop a new theoretical framework based on a lamellar mixing model (Le Borgne et al. 2013) to quantify changes in electrical mobility induced by chemical reactions across mixing fronts. Electrical conductivity and induced polarization are strongly dependent on the concentration of ionic species, which in turn depend on the local reaction rates. Hence, our results suggest that variation in real and complex electrical conductivity may be quantitatively related to the mixing and reaction dynamics. Thus, the presented theory provides a novel upscaling framework for quantifying the coupling between mixing, reaction and charge migration in heterogeneous porous media flows. References: Dentz. et al., Mixing, spreading and reaction in heterogeneous media: A brief review J. Contam. Hydrol. 120-121, 1 (2011). Le Borgne et al. Impact of Fluid Deformation on Mixing-Induced Chemical Reactions in heterogeneous Flows, Geophys. Res. Lett. 41, 7898 (2014). Knight, et al., Geophysics at the interface: Response of geophysical properties to solid-fluid, fluid-fluid, and solid-solid interfaces. Rev. Geophys. 48, (2010). Le Borgne et al. (2013) Stretching, coalescence and mixing in porous media, Phys. Rev. Lett., 110, 204501

Reliability and Validity in Hospital Case-Mix Measurement

PubMed Central

Pettengill, Julian; Vertrees, James

1982-01-01

There is widespread interest in the development of a measure of hospital output. This paper describes the problem of measuring the expected cost of the mix of inpatient cases treated in a hospital (hospital case-mix) and a general approach to its solution. The solution is based on a set of homogenous groups of patients, defined by a patient classification system, and a set of estimated relative cost weights corresponding to the patient categories. This approach is applied to develop a summary measure of the expected relative costliness of the mix of Medicare patients treated in 5,576 participating hospitals. The Medicare case-mix index is evaluated by estimating a hospital average cost function. This provides a direct test of the hypothesis that the relationship between Medicare case-mix and Medicare cost per case is proportional. The cost function analysis also provides a means of simulating the effects of classification error on our estimate of this relationship. Our results indicate that this general approach to measuring hospital case-mix provides a valid and robust measure of the expected cost of a hospital's case-mix. PMID:10309909

Soliton interactions and complexes for coupled nonlinear Schrödinger equations.

PubMed

Jiang, Yan; Tian, Bo; Liu, Wen-Jun; Sun, Kun; Li, Min; Wang, Pan

2012-03-01

Under investigation in this paper are the coupled nonlinear Schrödinger (CNLS) equations, which can be used to govern the optical-soliton propagation and interaction in such optical media as the multimode fibers, fiber arrays, and birefringent fibers. By taking the 3-CNLS equations as an example for the N-CNLS ones (N≥3), we derive the analytic mixed-type two- and three-soliton solutions in more general forms than those obtained in the previous studies with the Hirota method and symbolic computation. With the choice of parameters for those soliton solutions, soliton interactions and complexes are investigated through the asymptotic and graphic analysis. Soliton interactions and complexes with the bound dark solitons in a mode or two modes are observed, including that (i) the two bright solitons display the breatherlike structures while the two dark ones stay parallel, (ii) the two bright and dark solitons all stay parallel, and (iii) the states of the bound solitons change from the breatherlike structures to the parallel one even with the distance between those solitons smaller than that before the interaction with the regular one soliton. Asymptotic analysis is also used to investigate the elastic and inelastic interactions between the bound solitons and the regular one soliton. Furthermore, some discussions are extended to the N-CNLS equations (N>3). Our results might be helpful in such applications as the soliton switch, optical computing, and soliton amplification in the nonlinear optics.

Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution

PubMed Central

Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J.; Golovanov, Alexander P.

2016-01-01

The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (SosCat) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of SosCat, while SosCat also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos. PMID:27412770

Mixed-Valence Molecular Unit for Quantum Cellular Automata: Beyond the Born-Oppenheimer Paradigm through the Symmetry-Assisted Vibronic Approach.

PubMed

Clemente-Juan, Juan Modesto; Palii, Andrew; Coronado, Eugenio; Tsukerblat, Boris

2016-08-09

In this article, we focus on the electron-vibrational problem of the tetrameric mixed-valence (MV) complexes proposed for implementation as four-dot molecular quantum cellular automata (mQCA).1 Although the adiabatic approximation explored in ref 2 is an appropriate tool for the qualitative analysis of the basic characteristics of mQCA, like vibronic trapping of the electrons encoding binary information and cell-cell response, it loses its accuracy providing moderate vibronic coupling and fails in the description of the discrete pattern of the vibronic levels. Therefore, a precise solution of the quantum-mechanical vibronic problem is of primary importance for the evaluation of the shapes of the electron transfer optical absorption bands and quantitative analysis of the main parameters of tetrameric quantum cells. Here, we go beyond the Born-Oppenheimer paradigm and present a solution of the quantum-mechanical pseudo Jahn-Teller (JT) vibronic problem in bielectronic MV species (exemplified by the tetra-ruthenium complexes) based on the recently developed symmetry-assisted approach.3,4 The mathematical approach to the vibronic eigenproblem takes into consideration the point symmetry basis, and therefore, the total matrix of the JT Hamiltonian is blocked to the maximum extent. The submatrices correspond to the irreducible representations (irreps) of the point group. With this tool, we also extend the theory of the mQCA cell beyond the limit of prevailing Coulomb repulsion in the electronic pair (adopted in ref 2), and therefore, the general pseudo-JT problems for spin-singlet ((1)B1g, 2(1)A1g, (1)B2g, (1)Eu) ⊗ (b1g + eu) and spin-triplet states ((3)A2g, (3)B1g, 2(3)Eu) ⊗ (b1g + eu) in a square-planar bielectronic system are solved. The obtained symmetry-adapted electron-vibrational functions are employed for the calculation of the profiles (shape functions) of the charge transfer absorption bands in the tetrameric MV complexes and for the discussion of the magnetic properties.

Solute-Filled Syringe For Formulating Intravenous Solution

NASA Technical Reports Server (NTRS)

Owens, Jim; Bindokas, AL; Dudar, Tom; Finley, Mike; Scharf, Mike

1993-01-01

Prefilled syringe contains premeasured amount of solute in powder or concentrate form used to deliver solute to sterile interior of large-volume parenteral (LVP) bag. Predetermined amount of sterile water also added to LVP bag through sterilizing filter, and mixed with contents of syringe, yielding sterile intravenous solution of specified concentration.

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

PubMed

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-09-30

This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

Exploring the intermolecular interactions acting in solvent-modified MEKC by Molecular Dynamics and NMR: The effect of n-butanol on the separation of diclofenac and its impurities.

PubMed

Caprini, Claudia; Pasquini, Benedetta; Melani, Fabrizio; Del Bubba, Massimo; Giuffrida, Alessandro; Calleri, Enrica; Orlandini, Serena; Furlanetto, Sandra

2018-02-05

An integrated approach involving CE experiments, Molecular Dynamics (MD) simulations and two-dimensional NOE spectroscopy (2D-NOESY) experiments was employed to elucidate the intermolecular interactions and the separation mechanisms involved in a solvent-modified MEKC method for the simultaneous determination of diclofenac sodium and its impurities. The CE findings indicated that the addition of n-butanol (nBuOH) to the SDS micellar solution played a primary role for controlling the partitioning into the mixed micelles and the migration of the analytes and that the presence of nBuOH as cosurfactant was compulsory for achieving the complete separation of the compounds. The different capacity factors of the analytes were calculated and a change in solute association with the mixed micelle when changing the SDS/nBuOH molar ratio was highlighted. The optimal SDS/nBuOH molar ratio for the electrophoretic separation was 1:8. On the other hand, both MD simulations and NMR experiments indicated that the most favorable molar ratio for the formation of mixed SDS/nBuOH micelles was 1:2. These results suggested that probably there is an excess of nBuOH in the background electrolyte, both as free molecules and in form of aggregates, which is able to interact with the analytes, and thus may compete with mixed micelles for the considered compounds. The calculated values of gain in potential energy of the analytes when included in mixed micelles were in agreement with the observed migration order of the compounds. The role of methyl-β-cyclodextrin (MβCyD) in the background electrolyte was also investigated, since the addition of this CyD to the solvent-modified MEKC system was found to be useful to reduce the analysis time. MD simulations and 2D-NOESY spectra highlighted the formation of inclusion complexes with MβCyD not only with the analytes, but also with SDS. MβCyD may lower the availability of both SDS and nBuOH for forming micelles and mostly may compete with the mixed micelle as a second pseudostationary phase. Copyright © 2017 Elsevier B.V. All rights reserved.

Cognitive Task Complexity Effects on L2 Writing Performance: An Application of Mixed-Methods Approaches

ERIC Educational Resources Information Center

Abdi Tabari, Mahmoud; Ivey, Toni A.

2015-01-01

This paper provides a methodological review of previous research on cognitive task complexity, since the term emerged in 1995, and investigates why much research was more quantitative rather than qualitative. Moreover, it sheds light onto the studies which used the mixed-methods approach and determines which version of the mixed-methods designs…

SCM Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership

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

Foster, T.

This report summarizes experimental work performed by SIMCO Technologies Inc. (SIMCO) as part of the Cementitious Barriers Partnership (CBP) project. The test series followed an experimental program dedicated to the study of ordinary Portland cement (OPC) hydrated cement pastes exposed to aggressive solutions. In the present study, the scope is extended to hydrated cement pastes incorporating supplementary cementitious materials (SCM) such as fly ash and ground granulated blast furnace slag (GGBFS). Also, the range of aggressive contact solutions was expanded. The experimental program aimed at testing aggressive contact solutions that more closely mimic the chemical composition of saltstone pore solution.more » Five different solutions, some of which incorporated high levels of carbonate and nitrate, were placed in contact with four different hydrated cement paste mixes. In all solutions, 150 mmol/L of SO 4 2– (14 400 ppm) were present. The solutions included different pH conditions and different sodium content. Two paste mixes were equivalent to Vault 1/4 and Vault 2 concrete mixes used at SRS in storage structures. Two additional paste mixes, cast at the same water-to-cement ratio and using the same cements but without SCMs, were also tested. The damage evolution in samples was monitored using ultrasonic pulse velocity (UPV) and mass measurements. After three and twelve months of exposure conditions, samples were taken out of solution containers and analyzed to perform migration tests and porosity measurements. Globally, results were in line with the previous study and confirmed that high pH may limit the formation of some deleterious phases like gypsum. In this case, ettringite may form but is not necessarily associated with damage. However, the high concentration of sodium may be associated with the formation of an AFm-like mineral called U-phase. The most significant evidences of damage were all associated with the Vault 2 paste analog. This material proved very sensitive to high pH. All measurement techniques used to monitor and evaluate damage to samples indicated significant alterations to this mix when immersed in contact solutions containing sodium hydroxide. It was hypothesized that the low cement content, combined with high silica content coming from silica fume, fly ash and GGBFS led to the presence unreacted silica. It is possible that the pozzolanic reaction of these SCMs could not be activated due to the low alkali content, a direct consequence of low cement content. In this scenario, the material end up having a lot of silica available to react upon contact with sodium hydroxide, possibly forming a gel that may be similar to the gel formed in alkali-silica reactions. This scenario needs further experimental confirmation, but it may well explain the poor behavior of mix PV2 in presence of NaOH.« less

Impact of cationic surfactant on the self-assembly of sodium caseinate.

PubMed

Vinceković, Marko; Curlin, Marija; Jurašin, Darija

2014-08-27

The impact of a cationic surfactant, dodecylammonium chloride (DDACl), on the self-assembly of sodium caseinate (SC) has been investigated by light scattering, zeta potential, and rheological measurements as well as by microscopy (transmission electron and confocal laser scanning microscopy). In SC dilute solutions concentration-dependent self-assembly proceeds through the formation of spherical associates and their aggregation into elongated structures composed of connected spheres. DDACl interacts with SC via its hydrophilic and hydrophobic groups, inducing changes in SC self-assembled structures. These changes strongly depend on the surfactant aggregation states (monomeric or micellar) as well as concentration ratio of both components, leading to the formation of soluble and insoluble complexes of nano- to microdimensions. DDACl monomers interact with SC self-assembled entities in a different way compared to their micelles. Surfactant monomers form soluble complexes (similar to surfactant mixed micelles) at lower SC concentration but insoluble gelatinous complexes at higher SC concentration. At surfactant micellar concentration soluble complexes with casein chains wrapped around surfactant micelles are formed. This study suggests that the use of proper cationic surfactant concentration will allow modification and control of structural changes of SC self-assembled entities.

Communication: Correct charge transfer in CT complexes from the Becke'05 density functional

NASA Astrophysics Data System (ADS)

Becke, Axel D.; Dale, Stephen G.; Johnson, Erin R.

2018-06-01

It has been known for over twenty years that density functionals of the generalized-gradient approximation (GGA) type and exact-exchange-GGA hybrids with low exact-exchange mixing fraction yield enormous errors in the properties of charge-transfer (CT) complexes. Manifestations of this error have also plagued computations of CT excitation energies. GGAs transfer far too much charge in CT complexes. This error has therefore come to be called "delocalization" error. It remains, to this day, a vexing unsolved problem in density-functional theory (DFT). Here we report that a 100% exact-exchange-based density functional known as Becke'05 or "B05" [A. D. Becke, J. Chem. Phys. 119, 2972 (2003); 122, 064101 (2005)] predicts excellent charge transfers in classic CT complexes involving the electron donors NH3, C2H4, HCN, and C2H2 and electron acceptors F2 and Cl2. Our approach is variational, as in our recent "B05min" dipole moments paper [Dale et al., J. Chem. Phys. 147, 154103 (2017)]. Therefore B05 is not only an accurate DFT for thermochemistry but is promising as a solution to the delocalization problem as well.

Datasets for Ostrava PMF paper

EPA Pesticide Factsheets

These data support a published journal paper described as follows:A 14-week investigation during a warm and cold seasons was conducted to improve understanding of airpollution sources that might be impacting air quality in Ostrava, the Czech Republic. Fine particulatematter (PM2.5) samples were collected in consecutive 12-h day and night increments during spring andfall 2012 sampling campaigns. Sampling sites were strategically located to evaluate conditions in closeproximity of a large steel works industrial complex, as well as away from direct influence of theindustrial complex. These samples were analyzed for metals and other elements, organic and elemental(black) carbon, and polycyclic aromatic hydrocarbons (PAHs). The PM2.5 samples were supplementedwith pollutant gases and meteorological parameters. We applied the EPA PMF v5.1 model with uncertainty estimate features to the Ostrava data set. Using the model's bootstrapping procedure and other considerations, six factors were determined to provide the optimum solution. Each model run consisted of 100 iterations to ensure that the solution represents a global minimum. The resulting factors were identified as representing coal (power plants), mixed Cl, crustal, industrial 1 (alkali metals and PAHs), industrial 2 (transition metals), and home heat/transportation. The home heating source is thought to be largely domestic boilers burning low quality fuels such as lignite, wood, and domestic waste.Transportation-r

Sustainable aggregate production planning in the chemical process industry - A benchmark problem and dataset.

PubMed

Brandenburg, Marcus; Hahn, Gerd J

2018-06-01

Process industries typically involve complex manufacturing operations and thus require adequate decision support for aggregate production planning (APP). The need for powerful and efficient approaches to solve complex APP problems persists. Problem-specific solution approaches are advantageous compared to standardized approaches that are designed to provide basic decision support for a broad range of planning problems but inadequate to optimize under consideration of specific settings. This in turn calls for methods to compare different approaches regarding their computational performance and solution quality. In this paper, we present a benchmarking problem for APP in the chemical process industry. The presented problem focuses on (i) sustainable operations planning involving multiple alternative production modes/routings with specific production-related carbon emission and the social dimension of varying operating rates and (ii) integrated campaign planning with production mix/volume on the operational level. The mutual trade-offs between economic, environmental and social factors can be considered as externalized factors (production-related carbon emission and overtime working hours) as well as internalized ones (resulting costs). We provide data for all problem parameters in addition to a detailed verbal problem statement. We refer to Hahn and Brandenburg [1] for a first numerical analysis based on and for future research perspectives arising from this benchmarking problem.

Self-assembled carrageenan/protamine polyelectrolyte nanoplexes-Investigation of critical parameters governing their formation and characteristics.

PubMed

Dul, Maria; Paluch, Krzysztof J; Kelly, Hazel; Healy, Anne Marie; Sasse, Astrid; Tajber, Lidia

2015-06-05

The aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT. Copyright © 2015 Elsevier Ltd. All rights reserved.

The investigations of changes in mineral-organic and carbon-phosphate ratios in the mixed saliva by synchrotron infrared spectroscopy

NASA Astrophysics Data System (ADS)

Seredin, Pavel; Goloshchapov, Dmitry; Kashkarov, Vladimir; Ippolitov, Yuri; Bambery, Keith

The objective of this study was to investigate the efficiency of the saturation of mixed saliva by mineral complexes and groups necessary for the remineralisation of tooth enamel using exogenous and endogenous methods of caries prevention. Using IR spectroscopy and high-intensity synchrotron radiation, changes in the composition of the human mixed saliva were identified when exogenous and endogenous methods of caries prevention are employed. Based on the calculations of mineral/organic and carbon/phosphate ratios, changes in the composition of the human mixed saliva depending on a certain type of prevention were identified. It is shown that the use of a toothpaste (exogenous prevention) alone based on a multi-mineral complex including calcium glycerophosphate provides only a short-term effect of saturating the oral cavity with mineral complexes and groups. Rinsing of the oral cavity with water following the preventive use of a toothpaste completely removes the effect of the saturation of the mixed saliva with mineral groups and complexes. The use of tablets of a multi-mineral complex with calcium glycerophosphate (endogenous prevention) in combination with exogenous prevention causes an average increase of ∼10% in the content of mineral groups and complexes in the mixed saliva and allows long-term saturation of the oral fluid by them. This method outperforms the exogenous one owing to a long-term effect of optimal concentrations of endogenous and biologically available derivatives of phosphates on the enamel surface.

Information entropy to measure the spatial and temporal complexity of solute transport in heterogeneous porous media

NASA Astrophysics Data System (ADS)

Li, Weiyao; Huang, Guanhua; Xiong, Yunwu

2016-04-01

The complexity of the spatial structure of porous media, randomness of groundwater recharge and discharge (rainfall, runoff, etc.) has led to groundwater movement complexity, physical and chemical interaction between groundwater and porous media cause solute transport in the medium more complicated. An appropriate method to describe the complexity of features is essential when study on solute transport and conversion in porous media. Information entropy could measure uncertainty and disorder, therefore we attempted to investigate complexity, explore the contact between the information entropy and complexity of solute transport in heterogeneous porous media using information entropy theory. Based on Markov theory, two-dimensional stochastic field of hydraulic conductivity (K) was generated by transition probability. Flow and solute transport model were established under four conditions (instantaneous point source, continuous point source, instantaneous line source and continuous line source). The spatial and temporal complexity of solute transport process was characterized and evaluated using spatial moment and information entropy. Results indicated that the entropy increased as the increase of complexity of solute transport process. For the point source, the one-dimensional entropy of solute concentration increased at first and then decreased along X and Y directions. As time increased, entropy peak value basically unchanged, peak position migrated along the flow direction (X direction) and approximately coincided with the centroid position. With the increase of time, spatial variability and complexity of solute concentration increase, which result in the increases of the second-order spatial moment and the two-dimensional entropy. Information entropy of line source was higher than point source. Solute entropy obtained from continuous input was higher than instantaneous input. Due to the increase of average length of lithoface, media continuity increased, flow and solute transport complexity weakened, and the corresponding information entropy also decreased. Longitudinal macro dispersivity declined slightly at early time then rose. Solute spatial and temporal distribution had significant impacts on the information entropy. Information entropy could reflect the change of solute distribution. Information entropy appears a tool to characterize the spatial and temporal complexity of solute migration and provides a reference for future research.

Forward osmosis for oily wastewater reclamation: Multi-charged oxalic acid complexes as draw solutes.

PubMed

Ge, Qingchun; Amy, Gary Lee; Chung, Tai-Shung

2017-10-01

Forward osmosis (FO) has demonstrated its merits in hybrid FO seawater desalination. However, FO may have a potential for other applications if suitable draw solutes are available. In this study, a series of novel draw solutes based on oxalic acid (OA)-transitional metal complexes are presented. Influential factors of FO performance have been systematically investigated by varying the transitional metals, cations of the complex draw solutes as well as the experimental conditions. Compared to NaCl and other recently synthesized draw solutes, the OA complexes show superior FO performance in terms of high water fluxes up to 27.5 and 89.1 LMH under the respective FO and PRO (pressure retarded osmosis) modes, both with negligible reverse solute fluxes. The features of octahedral geometry, abundant hydrophilic groups and ionic species are crucial for the OA complexes as appropriate draw solutes with satisfactory FO performance. Among the synthesized OA complexes, the ammonium salt of chromic complex (NH 4 -Cr-OA) outperforms others due to the presence of more ionic species in its complex system. NH 4 -Cr-OA also performs better than the typical NaCl draw solute in FO oily wastewater treatment with higher water recovery and negligible reverse fluxes. Dilute solutions of OA complexes have been reconcentrated through membrane distillation (MD) and reused to new round of FO processes. The OA complexes have demonstrated their suitability and superiority as a novel class of draw solutes for the FO process in this study. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optimal design and dispatch of a system of diesel generators, photovoltaics and batteries for remote locations

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

Scioletti, Michael S.; Newman, Alexandra M.; Goodman, Johanna K.

Renewable energy technologies, specifically, solar photovoltaic cells, combined with battery storage and diesel generators, form a hybrid system capable of independently powering remote locations, i.e., those isolated from larger grids. If sized correctly, hybrid systems reduce fuel consumption compared to diesel generator-only alternatives. We present an optimization model for establishing a hybrid power design and dispatch strategy for remote locations, such as a military forward operating base, that models the acquisition of different power technologies as integer variables and their operation using nonlinear expressions. Our cost-minimizing, nonconvex, mixed-integer, nonlinear program contains a detailed battery model. Due to its complexities, wemore » present linearizations, which include exact and convex under-estimation techniques, and a heuristic, which determines an initial feasible solution to serve as a “warm start” for the solver. We determine, in a few hours at most, solutions within 5% of optimality for a candidate set of technologies; these solutions closely resemble those from the nonlinear model. Lastly, our instances contain real data spanning a yearly horizon at hour fidelity and demonstrate that a hybrid system could reduce fuel consumption by as much as 50% compared to a generator-only solution.« less

Optimal design and dispatch of a system of diesel generators, photovoltaics and batteries for remote locations

DOE PAGES

Scioletti, Michael S.; Newman, Alexandra M.; Goodman, Johanna K.; ...

2017-05-08

Renewable energy technologies, specifically, solar photovoltaic cells, combined with battery storage and diesel generators, form a hybrid system capable of independently powering remote locations, i.e., those isolated from larger grids. If sized correctly, hybrid systems reduce fuel consumption compared to diesel generator-only alternatives. We present an optimization model for establishing a hybrid power design and dispatch strategy for remote locations, such as a military forward operating base, that models the acquisition of different power technologies as integer variables and their operation using nonlinear expressions. Our cost-minimizing, nonconvex, mixed-integer, nonlinear program contains a detailed battery model. Due to its complexities, wemore » present linearizations, which include exact and convex under-estimation techniques, and a heuristic, which determines an initial feasible solution to serve as a “warm start” for the solver. We determine, in a few hours at most, solutions within 5% of optimality for a candidate set of technologies; these solutions closely resemble those from the nonlinear model. Lastly, our instances contain real data spanning a yearly horizon at hour fidelity and demonstrate that a hybrid system could reduce fuel consumption by as much as 50% compared to a generator-only solution.« less

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

Extraction of Lithium from Brine Solution by Hydrolysis of Activated Aluminum Powder

NASA Astrophysics Data System (ADS)

Li, Yanhong; Chen, Xingyu; Liu, Xuheng; Zhao, Zhongwei; Liu, Chongwu

2018-05-01

Activated aluminum powder has been used to extract lithium from Mg-Li mixed solution via a hydrolysis-adsorption reaction. First, activated aluminum powder was prepared under the optimal conditions of NaCl addition of 70%, ball-milling time of 3 h, and ball-to-powder mass ratio of 20:1. Then, the activated aluminum powder was added into the Mg-Li mixed solution to extract lithium. X-ray diffraction analysis indicated that Li+ was adsorbed by freshly formed Al(OH)3 in the form of LADH-Cl [LiCl·2Al(OH)3·mH2O]. Under the optimal conditions of reaction time of 3 h, Al/Li molar ratio of 4:1 for activated aluminum powder addition, and reaction temperature of 70°C, lithium precipitation exceeded 90% while magnesium precipitation was controlled at 13%. These results indicate that activated aluminum powder can efficiently extract lithium from Mg-Li mixed solution via a hydrolysis-adsorption reaction.

Biochemical and technological studies on the production of isolated guar protein.

PubMed

Khalil, M M

2001-02-01

Guar seeds contain 32% crude protein. Therefore, attempts were made to prepare protein isolates from guar seed flour (GSF) by extraction in different media (distilled water, salt solution, alkali solution alone or in combination) followed by a precipitation at acid pH. From the four technologies adopted, mixed salt-alkali solution was found to be the most satisfactory for extraction of protein from GSF. The highest amount of product was obtained in the mixed technology along with the highest amount of protein (87.5%). Protein isolates were also nutritionally evaluated following well-established rat bioassay procedures in a comparative study with casein as standard. The protein isolates are rich in lysine but poor in sulphur-containing amino acids such as methionine and cysteine. Protein isolates obtained by mixed salt-alkali solution showed high water and oil absorption as well as good emulsifying and foaming stability. The results indicate that protein isolates can be used as a supplementary source of protein in different food industries.

Impact of computerized order entry and pre-mixed dialysis solutions for continuous veno-venous hemodiafiltration on selection of therapy for acute renal failure.

PubMed

Saadulla, Lawand; Reeves, W Brian; Irey, Brittany; Ghahramani, Nasrollah

2012-02-01

To investigate the impacts of availability of pre-mixed solutions and computerized order entry on nephrologists' choice of the initial mode of renal replacement therapy in acute renal failure. We studied 898 patients with acute renal failure in 3 consecutive eras: era 1 (custom-mixed solution; n = 309), era 2 (pre-mixed commercial solution; n = 324), and era 3 (post-computerized order entry; n = 265). The proportion of patients treated with renal replacement therapy and the time from consult to initiation of continuous renal replacement therapy was similar in the 3 eras. Following introduction of the pre-mixed solution, the proportion of patients treated with continuous renal replacement therapy increased (20% vs. 33%; p < 0.05), it was initiated at a lower serum creatinine (353 ± 123 μmol/L vs. 300 ± 80 μmol/L; p < 0.05) and in older patients (53 ± 12 vs. 61 ± 14 years; p < 0.05). There was a progressive increase in the use of continuous veno-venous hemodialysis (18% vs. 79% vs. 100%; p < 0.05) and in the total prescribed flow rate (1,382 ± 546 vs. 2,324 ± 737 vs. 2,900 ± 305 mL/hr 3; p < 0.05). There was no significant impact on mortality. The availability of a pre-mixed solution increases the likelihood of initiating continuous renal replacement therapy in acute renal failure, initiating it at a lower creatinine and for older patients, use of continuous veno-venous hemodialysis and higher prescribed continuous renal replacement therapy dose. Computerized order entry implementation is associated with an additional increase in the use of continuous veno-venous hemodialysis, higher total prescribed dialysis dose, and use of CRRT among an increasing number of patients not on mechanical ventilation. The effect of these changes on patient survival is not significant.

The enhancement and suppression of immersion mode heterogeneous ice-nucleation by solutes.

PubMed

Whale, Thomas F; Holden, Mark A; Wilson, Theodore W; O'Sullivan, Daniel; Murray, Benjamin J

2018-05-07

Heterogeneous nucleation of ice from aqueous solutions is an important yet poorly understood process in multiple fields, not least the atmospheric sciences where it impacts the formation and properties of clouds. In the atmosphere ice-nucleating particles are usually, if not always, mixed with soluble material. However, the impact of this soluble material on ice nucleation is poorly understood. In the atmospheric community the current paradigm for freezing under mixed phase cloud conditions is that dilute solutions will not influence heterogeneous freezing. By testing combinations of nucleators and solute molecules we have demonstrated that 0.015 M solutions (predicted melting point depression <0.1 °C) of several ammonium salts can cause suspended particles of feldspars and quartz to nucleate ice up to around 3 °C warmer than they do in pure water. In contrast, dilute solutions of certain alkali metal halides can dramatically depress freezing points for the same nucleators. At 0.015 M, solutes can enhance or deactivate the ice-nucleating ability of a microcline feldspar across a range of more than 10 °C, which corresponds to a change in active site density of more than a factor of 10 5 . This concentration was chosen for a survey across multiple solutes-nucleant combinations since it had a minimal colligative impact on freezing and is relevant for activating cloud droplets. Other nucleators, for instance a silica gel, are unaffected by these 'solute effects', to within experimental uncertainty. This split in response to the presence of solutes indicates that different mechanisms of ice nucleation occur on the different nucleators or that surface modification of relevance to ice nucleation proceeds in different ways for different nucleators. These solute effects on immersion mode ice nucleation may be of importance in the atmosphere as sea salt and ammonium sulphate are common cloud condensation nuclei (CCN) for cloud droplets and are internally mixed with ice-nucleating particles in mixed-phase clouds. In addition, we propose a pathway dependence where activation of CCN at low temperatures might lead to enhanced ice formation relative to pathways where CCN activation occurs at higher temperatures prior to cooling to nucleation temperature.

Source of solutes to the coastal sabkha of Abu Dhabi

USGS Publications Warehouse

Wood, W.W.; Sanford, W.E.; Al Habshi, A.R.S.

2002-01-01

An ascending-brine model is proposed to address the observed isotope geochemistry, solute composition, and solute and water fluxes in the coastal sabkha of the Emirate of Abu Dhabi. Mass-balance measurements document that >95% of the solutes are derived from ascending continental brines; minor amounts are derived from rainfall and from groundwater entering from upgradient areas. Nearly 100% of the annual water loss is from evaporation and not lateral discharge. Direct rainfall on the sabkha and subsequent recharge to the underlying aquifer account for ~ 90% of the annual water input to the system; the remaining 10% comes from both lateral and ascending groundwater flow. Thus, the water and solutes in this system are from different sources. Solute concentrations of conservative (i.e., nonreactive) elements in the coastal, sabkha-covered aquifer are consistent with the fluid pore volumes of ascending brine calculated from hydrologic properties. Calcium to sulfate ratios and sulfur isotopes are consistent with this source of solute from the underlying Tertiary formations. Recharging rainwater dissolves halite and other soluble minerals on the surface, causing the solution to become more dense and sink to the bottom of the aquifer where it vertically mixes with less dense ascending brines. Solutes are returned to the surface by capillary forces and recycled or lost from the system by eolian or fluvial processes. Thus, the system becomes vertically mixed, consistent with the presence of tritium throughout the aquifer; but there is essentially no horizontal mixing of seawater with groundwater. The observed seawater solutes in the supratidal zone come from interstitial seawater trapped by the rapid progradation of the sediments into the Arabian Gulf and are not refluxed or laterally mixed. The ascending-brine model contrasts significantly with both the seawater-flooding and evaporative-pumping models previously proposed as a source of solutes to the coastal sabkha of the Emirate of Abu Dhabi. Use of these earlier models leads to incorrect conclusions and raises serious questions about their applicability in the evaluation of sabkhat in the geologic record.

Stability of Adrenaline in Irrigating Solution for Intraocular Surgery.

PubMed

Shibata, Yuuka; Kimura, Yasuhiro; Taogoshi, Takanori; Matsuo, Hiroaki; Kihira, Kenji

2016-01-01

Intraocular irrigating solution containing 1 µg/mL adrenaline is widely used during cataract surgery to maintain pupil dilation. Prepared intraocular irrigating solutions are recommended for use within 6 h. After the irrigating solution is admistered for dilution, the adrenaline may become oxidized, and this may result in a decrease in its biological activity. However, the stability of adrenaline in intraocular irrigating solution is not fully understood. The aim of this study was to evaluate the stability of adrenaline in clinically used irrigating solutions of varying pH. Six hours after mixing, the adrenaline percentages remaining were 90.6%±3.7 (pH 7.2), 91.1%±2.2 (pH 7.5), and 65.2%±2.8 (pH 8.0) of the initial concentration. One hour after mixing, the percentages remaining were 97.6%±2.0 (pH 7.2), 97.4%±2.7 (pH 7.5), and 95.6%±3.3 (pH 8.0). The degradation was especially remarkable and time dependent in the solution at pH 8.0. These results indicate that the concentration of adrenaline is decreased after preparation. Moreover, we investigated the influence of sodium bisulfite on adrenaline stability in irrigating solution. The percentage adrenaline remaining at 6 h after mixing in irrigating solution (pH 8.0) containing sodium bisulfite at 0.5 µg/mL (concentration in irrigating solution) or at 500 µg/mL (concentration in the undiluted adrenaline preparation) were 57.5 and 97.3%, respectively. Therefore, the low concentration of sodium bisulfite in the irrigating solution may be a cause of the adrenaline loss. In conclusion, intraocular irrigation solution with adrenaline should be prepared just prior to its use in surgery.

Influence of gold species (AuCl4(-) and AuCl2(-)) on self-assembly of PS-b-P2VP in solutions and morphology of composite thin films fabricated at the air/liquid interfaces.

PubMed

Zhao, Xingjuan; Wang, Qian; Zhang, Xiaokai; Lee, Yong-Ill; Liu, Hong-Guo

2016-01-21

Composite thin films doped with Au species were fabricated at an air/liquid interface via a series of steps, including the mass transfer of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) across the liquid/liquid interface between a DMF/CHCl3 solution and an aqueous solution containing either AuCl4(-) or AuCl2(-), self-assembly of PS-b-P2VP in a mixed DMF-water solution, and adsorption and further self-organization of the formed aggregates at the air/liquid interface. This is a new approach for fabricating composite polymer films and can be completed within a very short time. AuCl4(-) and AuCl2(-) ions were found to significantly influence the self-assembly behavior of the block copolymer and the morphologies of the composite films, leading to the formation of nanowire arrays and a foam structure at the air/liquid interface, respectively, which originated from rod-like micelles and microcapsules that had formed in the respective solutions. The effect of the metal complex was analyzed based on the packing parameters of the amphiphilic polymer molecules in different microenvironments and the interactions between the pyridine groups and the metal chloride anions. In addition, these composite thin films exhibited stable and durable performance as heterogeneous catalysts for the hydrogenation of nitroaromatics in aqueous solutions.

Spectrophotometric study of the thorium-morin mixed-color system

USGS Publications Warehouse

Fletcher, M.H.; Milkey, R.G.

1956-01-01

A spectrophotometric study was made of the thoriummorin reaction to evaluate the suitability of morin as a reagent for the determination of trace amounts of thorium. At pH 2, the equilibrium constant for the reaction is 1 ?? 106, and a single complex having a thorium-morin ratio of 1 to 2 is formed. The complex shows maximum absorbance at a wave length of 410 m??, and its absorbance obeys Beer's law. The absorbance readings are highly reproducible, and the sensitivity is relatively high, an absorbance difference of 0.001 being equivalent to 0.007 ?? of ThO2 per sq. cm. The effects of acid, alcohol, and morin concentration, time, temperature, and age of the morin reagent as well as the behavior of morin with zirconium(IV), iron(III), aluminum(III), ytterbium(III), yttrium(III), uranium(VI), praseodymium(III), lead(II), lanthanum(III), and calcium(II) ions are discussed. A method is presented for the determination of thorium in pure solutions. Appropriate separations for the isolation of thorium may extend the usefulness of the method and permit the determination of trace amounts of thorium in complex materials.

Phase formation and UV luminescence of Gd{sup 3+} doped perovskite-type YScO{sub 3}

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

Shimizu, Yuhei; Ueda, Kazushige, E-mail: kueda@che.kyutech.ac.jp

Synthesis of pure and Gd{sup 3+}doped perovskite-type YScO{sub 3} was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd{sup 3+} doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phasemore » at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO{sub 3} formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO{sub 3}. Because Gd{sup 3+} ions were also dissolved into the single C-type phase in Gd{sup 3+} doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase. - Graphical abstract: A pure perovskite-type YScO{sub 3} phase was successfully synthesized by a polymerized complex (PC) method. The perovskite-type YScO{sub 3} was generated through a solid solution of C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} with drastic change of morphology. The PC method enabled a preparation of the single phase of the perovskite-type YScO{sub 3} at lower temperature and in shorter heating time. Gd{sup 3+} doped perovskite-type YScO{sub 3} was found to show a strong sharp UV emission at 314 nm. - Highlights: • Pure YScO{sub 3} phase was successfully synthesized by polymerized complex (PC) method. • Pure perovskite-type YScO{sub 3} phase was generated from pure C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} one. • YScO{sub 3} was obtained at lower temperature and in shorter heating time by PC method. • Perovskite-type YScO{sub 3}:Gd{sup 3+} was found to show strong sharp UV emission at 314 nm.« less

Rayleigh-Taylor and Richtmyer-Meshkov instability induced flow, turbulence, and mixing. II

NASA Astrophysics Data System (ADS)

Zhou, Ye

2017-12-01

Rayleigh-Taylor (RT) and Richtmyer-Meshkov(RM) instabilities are well-known pathways towards turbulent mixing layers, in many cases characterized by significant mass and species exchange across the mixing layers (Zhou, 2017. Physics Reports, 720-722, 1-136). Mathematically, the pathway to turbulent mixing requires that the initial interface be multimodal, to permit cross-mode coupling leading to turbulence. Practically speaking, it is difficult to experimentally produce a non-multi-mode initial interface. Numerous methods and approaches have been developed to describe the late, multimodal, turbulent stages of RT and RM mixing layers. This paper first presents the initial condition dependence of RT mixing layers, and introduces parameters that are used to evaluate the level of "mixedness" and "mixed mass" within the layers, as well as the dependence on density differences, as well as the characteristic anisotropy of this acceleration-driven flow, emphasizing some of the key differences between the two-dimensional and three-dimensional RT mixing layers. Next, the RM mixing layers are discussed, and differences with the RT mixing layer are elucidated, including the RM mixing layers dependence on the Mach number of the initiating shock. Another key feature of the RM induced flows is its response to a reshock event, as frequently seen in shock-tube experiments as well as inertial confinement events. A number of approaches to modeling the evolution of these mixing layers are then described, in order of increasing complexity. These include simple buoyancy-drag models, Reynolds-averaged Navier-Stokes models of increased complexity, including K- ε, K-L, and K- L- a models, up to full Reynolds-stress models with more than one length-scale. Multifield models and multiphase models have also been implemented. Additional complexities to these flows are examined as well as modifications to the models to understand the effects of these complexities. These complexities include the presence of magnetic fields, compressibility, rotation, stratification and additional instabilities. The complications induced by the presence of converging geometries are also considered. Finally, the unique problems of astrophysical and high-energy-density applications, and efforts to model these are discussed.

Integrated copper-containing wastewater treatment using xanthate process.

PubMed

Chang, Yi-Kuo; Chang, Juu-En; Lin, Tzong-Tzeng; Hsu, Yu-Ming

2002-09-02

Although, the xanthate process has been shown to be an effective method for heavy metal removal from contaminated water, a heavy metal contaminated residual sludge is produced by the treatment process and the metal-xanthate sludge must be handled in accordance with the Taiwan EPA's waste disposal requirements. This work employed potassium ethyl xanthate (KEX) to remove copper ions from wastewater. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) were used to determine the leaching potential and stability characteristics of the residual copper xanthate (Cu-EX) complexes. Results from metal removal experiments showed that KEX was suitable for the treatment of copper-containing wastewater over a wide copper concentration range (50, 100, 500, and 1000 mg/l) to the level that meets the Taiwan EPA's effluent regulations (3mg/l). The TCLP results of the residual Cu-EX complexes could meet the current regulations and thus the Cu-EX complexes could be treated as a non-hazardous material. Besides, the results of SDLT indicated that the complexes exhibited an excellent performance for stabilizing metals under acidic conditions, even slight chemical changes of the complexes occurred during extraction. The xanthate process, mixing KEX with copper-bearing solution to form Cu-EX precipitates, offered a comprehensive strategy for solving both copper-containing wastewater problems and subsequent sludge disposal requirements.

Electron localization in a mixed-valence diniobium benzene complex

DOE PAGES

Gianetti, Thomas L.; Nocton, Grégory; Minasian, Stefan G.; ...

2014-11-11

Reaction of the neutral diniobium benzene complex {[Nb(BDI)N tBu] 2(μ-C 6H 6)} (BDI = N,N'-diisopropylbenzene-β-diketiminate) with Ag[B(C 6F 5) 4] results in a single electron oxidation to produce a cationic diniobium arene complex, {[Nb(BDI)N tBu] 2(μ-C 6H 6)}{B(C 6F 5) 4}. Investigation of the solid state and solution phase structure using single-crystal X-ray diffraction, cyclic voltammetry, magnetic susceptibility, and multinuclear NMR spectroscopy indicates that the oxidation results in an asymmetric molecule with two chemically inequivalent Nb atoms. Further characterization using density functional theory (DFT) calculations, UV-visible, Nb L 3,2-edge X-ray absorption near-edge structure (XANES), and EPR spectroscopies supports assignment ofmore » a diniobium complex, in which one Nb atom carries a single unpaired electron that is not largely delocalized on the second Nb atom. During the oxidative transformation, one electron is removed from the δ-bonding HOMO, which causes a destabilization of the molecule and formation of an asymmetric product. Subsequent reactivity studies indicate that the oxidized product allows access to metal-based chemistry with substrates that did not exhibit reactivity with the starting neutral complex.« less

Problem of the thermodynamic status of the mixed-layer minerals

USGS Publications Warehouse

Zen, E.-A.

1962-01-01

Minerals that show mixed layering, particularly with the component layers in random sequence, pose problems because they may behave thermodynamically as single phases or as polyphase aggregates. Two operational criteria are proposed for their distinction. The first scheme requires two samples of mixed-layer material which differ only in the proportions of the layers. If each of these two samples are allowed to equilibrate with the same suitably chosen monitoring solution, then the intensive parameters of the solution will be invariant if the mixed-layer sample is a polyphase aggregate, but not otherwise. The second scheme makes use of the fact that portions of many titration curves of clay minerals show constancy of the chemical activities of the components in the equilibrating solutions, suggesting phase separation. If such phase separation occurs for a mixed-layer material, then, knowing the number of independent components in the system, it should be possible to decide on the number of phases the mixed-layer material represents. Knowledge of the phase status of mixed-layer material is essential to the study of the equilibrium relations of mineral assemblages involving such material, because a given mixed-layer mineral will be plotted and treated differently on a phase diagram, depending on whether it is a single phase or a polyphase aggregate. Extension of the titration technique to minerals other than the mixed-layer type is possible. In particular, this method may be used to determine if cryptoperthites and peristerites are polyphase aggregates. In general, for any high-order phase separation, the method may be used to decide just at what point in this continuous process the system must be regarded operationally as a polyphase aggregate. ?? 1962.

The Effect of Combined Magnetic Geometries on Thermally Driven Winds. II. Dipolar, Quadrupolar, and Octupolar Topologies

NASA Astrophysics Data System (ADS)

Finley, Adam J.; Matt, Sean P.

2018-02-01

During the lifetime of Sun-like or low-mass stars a significant amount of angular momentum is removed through magnetized stellar winds. This process is often assumed to be governed by the dipolar component of the magnetic field. However, observed magnetic fields can host strong quadrupolar and/or octupolar components, which may influence the resulting spin-down torque on the star. In Paper I, we used the MHD code PLUTO to compute steady-state solutions for stellar winds containing a mixture of dipole and quadrupole geometries. We showed the combined winds to be more complex than a simple sum of winds with these individual components. This work follows the same method as Paper I, including the octupole geometry, which not only increases the field complexity but also, more fundamentally, looks for the first time at combining the same symmetry family of fields, with the field polarity of the dipole and octupole geometries reversing over the equator (unlike the symmetric quadrupole). We show, as in Paper I, that the lowest-order component typically dominates the spin-down torque. Specifically, the dipole component is the most significant in governing the spin-down torque for mixed geometries and under most conditions for real stars. We present a general torque formulation that includes the effects of complex, mixed fields, which predicts the torque for all the simulations to within 20% precision, and the majority to within ≈5%. This can be used as an input for rotational evolution calculations in cases where the individual magnetic components are known.

Controlling the surface‐mediated release of DNA using ‘mixed multilayers’

PubMed Central

Appadoo, Visham; Carter, Matthew C. D.

2016-01-01

Abstract We report the design of erodible ‘mixed multilayer’ coatings fabricated using plasmid DNA and combinations of both hydrolytically degradable and charge‐shifting cationic polymer building blocks. Films fabricated layer‐by‐layer using combinations of a model poly(β‐amino ester) (polymer 1) and a model charge‐shifting polymer (polymer 2) exhibited DNA release profiles that were substantially different than those assembled using DNA and either polymer 1 or polymer 2 alone. In addition, the order in which layers of these two cationic polymers were deposited during assembly had a profound impact on DNA release profiles when these materials were incubated in physiological buffer. Mixed multilayers ∼225 nm thick fabricated by depositing layers of polymer 1/DNA onto films composed of polymer 2/DNA released DNA into solution over ∼60 days, with multi‐phase release profiles intermediate to and exhibiting some general features of polymer 1/DNA or polymer 2/DNA films (e.g., a period of rapid release, followed by a more extended phase). In sharp contrast, ‘inverted’ mixed multilayers fabricated by depositing layers of polymer 2/DNA onto films composed of polymer 1/DNA exhibited release profiles that were almost completely linear over ∼60‐80 days. These and other results are consistent with substantial interdiffusion and commingling (or mixing) among the individual components of these compound materials. Our results reveal this mixing to lead to new, unanticipated, and useful release profiles and provide guidance for the design of polymer‐based coatings for the local, surface‐mediated delivery of DNA from the surfaces of topologically complex interventional devices, such as intravascular stents, with predictable long‐term release profiles. PMID:27981243

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

Mayberry, J.; Stelle, S.; O`Brien, M.

The Mixed Waste Integrated Program Logic Diagram was developed to provide technical alternative for mixed wastes projects for the Office of Technology Development`s Mixed Waste Integrated Program (MWIP). Technical solutions in the areas of characterization, treatment, and disposal were matched to a select number of US Department of Energy (DOE) treatability groups represented by waste streams found in the Mixed Waste Inventory Report (MWIR).

Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations.

PubMed

Hänninen, Mikko M; Välivaara, Juha; Mota, Antonio J; Colacio, Enrique; Lloret, Francesc; Sillanpää, Reijo

2013-02-18

A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.

Stimuli-Responsive Reagent System for Enabling Microfluidic Immunoassays with Biomarker Purification and Enrichment

PubMed Central

2015-01-01

Immunoassays have been translated into microfluidic device formats, but significant challenges relating to upstream sample processing still limit their applications. Here, stimuli-responsive polymer–antibody conjugates are utilized in a microfluidic immunoassay to enable rapid biomarker purification and enrichment as well as sensitive detection. The conjugates were constructed by covalently grafting poly(N-isopropylacrylamide) (PNIPAAm), a thermally responsive polymer, to the lysine residues of anti-prostate specific antigen (PSA) Immunoglobulin G (IgG) using carbodiimide chemistry via the polymer end-carboxylate. The antibody-PNIPAAm (capture) conjugates and antibody-alkaline phosphatase (detection) conjugates formed sandwich immunocomplexes via PSA binding in 50% human plasma. The complexes were loaded into a recirculating poly(dimethylsiloxane) microreactor, equipped with micropumps and transverse flow features, for subsequent separation, enrichment, and quantification. The immunocomplexes were captured by heating the solution to 39 °C, mixed over the transverse features for 2 min, and washed with warm buffer. In one approach, the assay utilized immunocomplex solution that was contained in an 80 nL microreactor, which was loaded with solution at room temperature and subsequently heated to 39 °C. The assay took 25 min and resulted in 37 pM PSA limit of detection (LOD), which is comparable to a plate ELISA employing the same antibody pair. In another approach, the microreactor was preheated to 39 °C, and immunocomplex solution was flowed through the reactor, mixed, and washed. When the specimen volume was increased to 7.5 μL by repeating the capture process three times, the higher specimen volume led to immunocomplex enrichment within the microreactor. The resulting assay LOD was 0.5 pM, which is 2 orders of magnitude lower than the plate ELISA. Both approaches generate antigen specific signal over a clinically significant range. The sample processing capabilities and subsequent utility in a biomarker assay demonstrate the opportunity for stimuli-responsive polymer–protein conjugates in novel diagnostic technologies. PMID:25405605

Milk whey proteins and xanthan gum interactions in solution and at the air-water interface: a rheokinetic study.

PubMed

Perez, Adrián A; Sánchez, Cecilio Carrera; Patino, Juan M Rodríguez; Rubiolo, Amelia C; Santiago, Liliana G

2010-11-01

In this contribution, we present experimental information about the effect of xanthan gum (XG) on the adsorption behaviour of two milk whey protein samples (MWP), beta-lactoglobulin (beta-LG) and whey protein concentrate (WPC), at the air-water interface. The MWP concentration studied corresponded to the protein bulk concentration which is able to saturate the air-water interface (1.0 wt%). Temperature, pH and ionic strength of aqueous systems were kept constant at 20 degrees C, pH 7 and 0.05 M, respectively, while the XG bulk concentration varied in the range 0.00-0.25 wt%. Biopolymer interactions in solution were analyzed by extrinsic fluorescence spectroscopy using 1-anilino-8-naphtalene sulphonic acid (ANS) as a protein fluorescence probe. Interfacial biopolymer interactions were evaluated by dynamic tensiometry and surface dilatational rheology. Adsorption behaviour was discussed from a rheokinetic point of view in terms of molecular diffusion, penetration and conformational rearrangement of adsorbed protein residues at the air-water interface. Differences in the interaction magnitude, both in solution and at the interface vicinity, and in the adsorption rheokinetic parameters were observed in MWP/XG mixed systems depending on the protein type (beta-LG or WPC) and biopolymer relative concentration. beta-LG adsorption in XG presence could be promoted by mechanisms based on biopolymer segregative interactions and thermodynamic incompatibility in the interface vicinity, resulting in better surface and viscoelastic properties. The same mechanism could be responsible of WPC interfacial adsorption in the presence of XG. The interfacial functionality of WPC was improved by the synergistic interactions with XG, although WPC chemical complexity might complicate the elucidation of molecular events that govern adsorption dynamics of WPC/XG mixed systems at the air-water interface. Copyright (c) 2010 Elsevier B.V. All rights reserved.