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Sample records for enhances solution state

  1. Enhanced Conformational Sampling of N-glycans in Solution with Replica State Exchange Metadynamics.

    PubMed

    Galvelis, Raimondas; Re, Suyong; Sugita, Yuji

    2017-04-11

    Molecular dynamics (MD) simulation of a N-glycan in solution is challenging due to high- energy barriers of the glycosidic linkages, functional group rotational barriers, and numerous intra- and inter-molecular hydrogen bonds. In this study, we apply different enhanced conformational sampling approaches, namely, metadynamics (MTD), the replica-exchange MD (REMD), and the recently proposed replica state exchange MTD (RSE-MTD), to a N-glycan in solution and compare their conformational sampling efficiencies. MTD helps to cross the high- energy barrier along the ω angle by utilizing a bias potential, but it cannot enhance sampling of the other degrees of freedom. REMD ensures moderate-energy barrier crossings by exchanging temperatures between replicas, while it hardly crosses the barriers along ω. In contrast, RSE- MTD succeeds to cross the high-energy barrier along ω as well as to enhance sampling of the other degrees of freedom. We tested two RSE-MTD schemes: in one scheme, 64 replicas were simulated with the bias potential along ω at different temperatures, while simulations of 4 replicas were performed with the bias potentials for different CVs at 300 K. In both schemes, one unbiased replica at 300 K was included to compute conformational properties of the glycan. The conformational sampling of the former is better than the other enhanced sampling methods, while the latter shows reasonable performance without spending large computational resources. The latter scheme is likely to be useful when a N-glycan-attached protein is simulated.

  2. Carrier Transport Enhancement in Conjugated Polymers through Interfacial Self-Assembly of Solution-State Aggregates.

    PubMed

    Zhao, Kui; Khan, Hadayat Ullah; Li, Ruipeng; Hu, Hanlin; Amassian, Aram

    2016-08-03

    We demonstrate that local and long-range orders of poly(3-hexylthiophene) (P3HT) semicrystalline films can be synergistically improved by combining chemical functionalization of the substrate with solution-state disentanglement and preaggregation of P3HT in a θ solvent, leading to a very significant enhancement of the field effect carrier mobility. The preaggregation and surface functionalization effects combine to enhance the carrier mobility nearly 100-fold as compared with standard film preparation by spin-coating, and nearly 10-fold increase over the benefits of preaggregation alone. In situ quartz crystal microbalance with dissipation (QCM-D) experiments reveal enhanced deposition of preaggregates on surfaces modified with an alkyl-terminated self-assembled monolayer (SAM) in comparison to unaggregated polymer chains in the same conditions. Additional measurements reveal the combined preaggregation and surface functionalization significantly enhances local order of the conjugated polymer through planarization and extension of the conjugated backbone of the polymer which clearly translate to significant improvements of carrier transport at the semiconductor-dielectric interface in organic thin film transistors. This study points to opportunities in combining complementary routes, such as well-known preaggregation with substrate chemical functionalization, to enhance the polymer self-assembly and improve its interfacial order with benefits for transport properties.

  3. Innovative Solution to Video Enhancement

    NASA Technical Reports Server (NTRS)

    2001-01-01

    Through a licensing agreement, Intergraph Government Solutions adapted a technology originally developed at NASA's Marshall Space Flight Center for enhanced video imaging by developing its Video Analyst(TM) System. Marshall's scientists developed the Video Image Stabilization and Registration (VISAR) technology to help FBI agents analyze video footage of the deadly 1996 Olympic Summer Games bombing in Atlanta, Georgia. VISAR technology enhanced nighttime videotapes made with hand-held camcorders, revealing important details about the explosion. Intergraph's Video Analyst System is a simple, effective, and affordable tool for video enhancement and analysis. The benefits associated with the Video Analyst System include support of full-resolution digital video, frame-by-frame analysis, and the ability to store analog video in digital format. Up to 12 hours of digital video can be stored and maintained for reliable footage analysis. The system also includes state-of-the-art features such as stabilization, image enhancement, and convolution to help improve the visibility of subjects in the video without altering underlying footage. Adaptable to many uses, Intergraph#s Video Analyst System meets the stringent demands of the law enforcement industry in the areas of surveillance, crime scene footage, sting operations, and dash-mounted video cameras.

  4. Gate drain-overlapped-asymmetric gate dielectric-GAA-TFET: a solution for suppressed ambipolarity and enhanced ON state behavior

    NASA Astrophysics Data System (ADS)

    Madan, Jaya; Chaujar, Rishu

    2016-11-01

    The goal of this work is to overcome the major impediments of tunnel FET such as the inherent ambipolar current ( I AMB) and the lower ON current ( I ON). To suppress the I AMB, gate drain overlap (GDO) engineering scheme has been incorporated over the cylindrical gate all around TFET (GAA-TFET). However, to enhance the I ON, heterogate dielectrics (HD) are used in the gate oxide region. Results indicate that an appreciably reduced I AMB and significantly enhanced I ON has been obtained with the amalgamation of GDO and HD, respectively, onto GAA-TFET. Further, the effect of GDO length ( L ov) has also been studied. Quantitative analysis of ambipolarity factor " α" reveals that at large L ov, " α" improves. It is found that GDO degrades the high-frequency (HF) performance such as cutoff frequency ( f T) of the device, because of the enhanced parasitic capacitances. To surpass the deterioration at HF caused by GDO, the dielectric over GDO region has been altered, and it has been analyzed that by inserting a material of low-dielectric constant ( k = 1) and parasitic capacitances of the device reduces, resulting into enhancement in f T. Moreover, the low-k dielectric inserted over L ov reduces the I AMB supplementary, along with enhanced f T. Suppressed I AMB and enhanced f T of GDO-HD-GAA-TFET with low-k dielectric over L ov make it adequate for application in HF and digital circuitry.

  5. Reversible State Transition in Nanoconfined Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Zhao, Liang; Wang, Chunlei; Liu, Jian; Wen, Binghai; Tu, Yusong; Wang, Zuowei; Fang, Haiping

    2014-02-01

    Using molecular dynamics simulations, we find a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, which is not observed in macroscopic systems. The nanoscale confinement also leads to a significant increase of the critical aggregation concentration (CAC). A theoretical model based on Gibbs free energy calculation is developed to describe the simulation results. It indicates that the reversible state transition is attributed to the low free energy barrier (of order kBT) in between two energy minima corresponding to the dispersion and aggregation states, and the enhancement of the CAC results from the fact that at lower concentrations the number of solute molecules is not large enough to allow the formation of a stable cluster in the confined systems.

  6. Fullerene triplet states in solution

    NASA Astrophysics Data System (ADS)

    Ausman, Kevin Douglas

    Triplet state pre-equilibration by reversible energy transfer has been observed by transient-absorption spectroscopy in mixed toluene solutions of C70 and C60 and of C70 and C60(CH 3)2. The equilibrium constants governing the asymptotic partitioning of triplet energy in these mixtures were determined as a function of temperature. The enthalpies of these excited states were found from van't Hoff plots of the equilibrium constant data to be -0.1 +/- 0.2 and -3.4 +/- 0.3 kJ mol-1 for C60 and C60 (CH3)2 respectively relative to a C70 triplet energy exchange partner. The corresponding relative entropies are 5.8 +/- 0.5 and -4.0 +/- 1.0 kJ mol-1 K-1 respectively. Transient spectra from high temperature C70/C60(CH3)2 mixed samples revealed evidence of a third, unidentified transient absorber that exhibited different kinetics from the pre-equilibrated triplet pool. Triplet state transient difference spectra and intrinsic decay kinetics were measured and compared for C60 and several derivatives of C 60. These derivatives were C60H2, C60(CH 3)2, ortho-xylyl-C60, N,N'-dimethyl-1,2-ethylenediamine- C 60, C60C(COOCH2CH3)2, and C60O. The spectral locations of the main triplet-triplet absorption peak for these compounds correlates linearly with the observed intrinsic intersystem crossing rate constant. The triplet state persistence of C60 was measured in toluene solution as a function of both ground state concentration and solution temperature. The unimolecular intersystem crossing deactivation channel shows very little thermal activation, whereas the observed bimolecular self-quenching decay channel is found to be highly activated. At room temperature, the deduced exponential lifetime of the solvent-caged encounter complex between triplet and ground state molecules is three orders of magnitude shorter than that of the isolated monomer triplet state. This suggests that the self-quenching process is not a simple perturbation of an isolated molecule's intersystem crossing, but

  7. Transition state structures in solution

    SciTech Connect

    Bertran, J.; Lluch, J. M.; Gonzalez-Lafont, A.; Dillet, V.; Perez, V.

    1995-04-05

    In the present paper the location of transition state structures for reactions in solution has been studied. Continuum model calculations have been carried out on the Friedel-Crafts alkylation reaction and a proton transfer through a water molecule between two oxygen atoms in formic acid. In this model the separation between the chemical system and the solvent has been introduced. On the other hand, the discrete Monte Carlo methodology has also been used to simulate the solvent effect on dissociative electron transfer processes. In this model, the hypothesis of separability is not assumed. Finally, the validity of both approaches is discussed.

  8. Transition state structures in solution

    NASA Astrophysics Data System (ADS)

    Bertrán, J.; Lluch, J. M.; Gonzàlez-Lafont, A.; Dillet, V.; Pérez, V.

    1995-04-01

    In the present paper the location of transition state structures for reactions in solution has been studied. Continuum model calculations have been carried out on the Friedel-Crafts alkylation reaction and a proton transfer through a water molecule between two oxygen atoms in formic acid. In this model the separation between the chemical system and the solvent has been introduced. On the other hand, the discrete Monte Carlo methodology has also been used to simulate the solvent effect on dissociative electron transfer processes. In this model, the hypothesis of separability is not assumed. Finally, the validity of both approaches is discussed.

  9. Treatment of solutions with binary solutes using an admicellar enhanced CSTR: background solute effect.

    PubMed

    Lee, Chon-Lin; Lee, Jiu-Chang

    2002-04-01

    This study presents an admicellar enhanced continuous-flow stirred tank reactor (CSTR). Solutions containing single and binary aliphatic alcohols are introduced into this reactor for breakthrough experiments. Two phenomena occur during experiments with binary solutes: (a) a competitive effect caused by background solutes with relatively high hydrophobicity; (b) a co-solvent effect attributable to background solutes with relatively low hydrophobicity. The competition phenomenon and the corresponding mechanism involved are well demonstrated by directly monitoring the pre-adsolubilized solutes drawn out back to the solution while adsolubilizing other solutes with higher hydrophobicity. On the other hand, adsolubilization kinetics hindered by the background solute, which acts as a co-solvent, significantly alters the slopes of breakthrough curves of the target solute treated in the reactor.

  10. Effects of Electronic-State-Dependent Solute Polarizability: Application to Solute-Pump/Solvent-Probe Spectra.

    PubMed

    Sun, Xiang; Ladanyi, Branka M; Stratt, Richard M

    2015-07-23

    Experimental studies of solvation dynamics in liquids invariably ask how changing a solute from its electronic ground state to an electronically excited state affects a solution's dynamics. With traditional time-dependent-fluorescence experiments, that means looking for the dynamical consequences of the concomitant change in solute-solvent potential energy. But if one follows the shift in the dynamics through its effects on the macroscopic polarizability, as recent solute-pump/solvent-probe spectra do, there is another effect of the electronic excitation that should be considered: the jump in the solute's own polarizability. We examine the spectroscopic consequences of this solute polarizability change in the classic example of the solvation dye coumarin 153 dissolved in acetonitrile. After demonstrating that standard quantum chemical methods can be used to construct accurate multisite models for the polarizabilities of ground- and excited-state solvation dyes, we show via simulation that this polarizability change acts as a contrast agent, significantly enhancing the observable differences in optical-Kerr spectra between ground- and excited-state solutions. A comparison of our results with experimental solute-pump/solvent-probe spectra supports our interpretation and modeling of this spectroscopy. We predict, in particular, that solute-pump/solvent-probe spectra should be sensitive to changes in both the solvent dynamics near the solute and the electronic-state-dependence of the solute's own rotational dynamics.

  11. Perspectives on DNP-enhanced NMR spectroscopy in solutions

    NASA Astrophysics Data System (ADS)

    van Bentum, Jan; van Meerten, Bas; Sharma, Manvendra; Kentgens, Arno

    2016-03-01

    More than 60 years after the seminal work of Albert Overhauser on dynamic nuclear polarization by dynamic cross relaxation of coupled electron-nuclear spin systems, the quest for sensitivity enhancement in NMR spectroscopy is as pressing as ever. In this contribution we will review the status and perspectives for dynamic nuclear polarization in the liquid state. An appealing approach seems to be the use of supercritical solvents that may allow an extension of the Overhauser mechanism towards common high magnetic fields. A complementary approach is the use of solid state DNP on frozen solutions, followed by a rapid dissolution or in-situ melting step and NMR detection with substantially enhanced polarization levels in the liquid state. We will review recent developments in the field and discuss perspectives for the near future.

  12. Mechanism of alcohol-enhanced lucigenin chemiluminescence in alkaline solution.

    PubMed

    Chi, Quan; Chen, Wanying; He, Zhike

    2015-11-01

    The chemiluminescence (CL) of lucigenin (Luc(2+)) can be enhanced by different alcohols in alkaline solution. The effect of different fatty alcohols on the CL of lucigenin was related to the carbon chain length and the number of hydroxyl groups. Glycerol provides the greatest enhancement. UV/Vis absorption spectra and fluorescence spectra showed that N-methylacridone (NMA) was produced in the CL reaction in the presence of different alcohols. The peak of the CL spectrum was located at 470 nm in all cases, indicating that the luminophore was always the excited-state NMA. The quenching of lucigenin CL by superoxide dismutase (SOD) and the electron spin resonance (ESR) results with the spin trap of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) demonstrated that superoxide anions (O2 (•-)) were generated from dissolved oxygen in the CL reaction and that glycerol and dihydroxyacetone (DHA) can promote O2 (•-) production by the reduction of dissolved oxygen in alkaline solution. It was assumed that the enhancement provided by different alcohols was related to the solvent effect and reducing capacity. Glycerol and DHA can also reduce Luc(2+) into lucigenin cation radicals (Luc(•+) ), which react with O2 (•-) to produce CL, and glycerol can slowly transform into DHA, which is oxidized quickly in alkaline solution.

  13. Full analytical solution of Adapted Polarisation State Contrast Imaging.

    PubMed

    Upadhyay, Debajyoti; Mondal, Sugata; Lacot, Eric; Orlik, Xavier

    2011-12-05

    We have earlier proposed a 2-channel imaging technique: Adapted Polarisation State Contrast Imaging (APSCI), which noticeably enhances the polarimetric contrast between an object and its background using fully polarised incident state adapted to the scene, such that the polarimetric responses of those regions are located as far as possible on the Poincaré sphere. We address here the full analytical and graphical analysis of the ensemble of solutions of specific incident states, by introducing 3-Distance Eigen Space and explain the underlying physical structure of APSCI and the effect of noise over the measurements.

  14. Solvent suppression in DNP enhanced solid state NMR

    NASA Astrophysics Data System (ADS)

    Yarava, Jayasubba Reddy; Chaudhari, Sachin Rama; Rossini, Aaron J.; Lesage, Anne; Emsley, Lyndon

    2017-04-01

    We show how DNP enhanced solid-state NMR spectra can be dramatically simplified by suppression of solvent signals. This is achieved by (i) exploiting the paramagnetic relaxation enhancement of solvent signals relative to materials substrates, or (ii) by using short cross-polarization contact times to transfer hyperpolarization to only directly bonded carbon-13 nuclei in frozen solutions. The methods are evaluated for organic microcrystals, surfaces and frozen solutions. We show how this allows for the acquisition of high-resolution DNP enhanced proton-proton correlation experiments to measure inter-nuclear proximities in an organic solid.

  15. Corresponding-states laws for protein solutions.

    PubMed

    Katsonis, Panagiotis; Brandon, Simon; Vekilov, Peter G

    2006-09-07

    The solvent around protein molecules in solutions is structured and this structuring introduces a repulsion in the intermolecular interaction potential at intermediate separations. We use Monte Carlo simulations with isotropic, pair-additive systems interacting with such potentials. We test if the liquid-liquid and liquid-solid phase lines in model protein solutions can be predicted from universal curves and a pair of experimentally determined parameters, as done for atomic and colloid materials using several laws of corresponding states. As predictors, we test three properties at the critical point for liquid-liquid separation: temperature, as in the original van der Waals law, the second virial coefficient, and a modified second virial coefficient, all paired with the critical volume fraction. We find that the van der Waals law is best obeyed and appears more general than its original formulation: A single universal curve describes all tested nonconformal isotropic pair-additive systems. Published experimental data for the liquid-liquid equilibrium for several proteins at various conditions follow a single van der Waals curve. For the solid-liquid equilibrium, we find that no single system property serves as its predictor. We go beyond corresponding-states correlations and put forth semiempirical laws, which allow prediction of the critical temperature and volume fraction solely based on the range of attraction of the intermolecular interaction potential.

  16. All solution processed, nanowire enhanced ultraviolet photodetectors

    NASA Astrophysics Data System (ADS)

    Afal, Aysegul; Coskun, Sahin; Emrah Unalan, Husnu

    2013-01-01

    We report on the fabrication and characterization of transparent and fully solution processed, nanowire based ultraviolet (UV) photodetectors with high responsivity. For this purpose, UV sensitive zinc oxide (ZnO) nanowires were grown hydrothermally on transparent electrodes formed by spray coated network of silver (Ag) nanowires. Fabricated UV photodetectors showed short recovery time, around 4 s, with a decent on/off ratio of 2600. Effect of in-situ annealing and nanowire length was investigated. Our design provides a simple and cost effective approach for the fabrication of high performance UV photodetectors.

  17. Mechanism of connective drying of solutions of fish hydrolyzates in a foamed state

    NASA Astrophysics Data System (ADS)

    Buinov, A. A.; Ginzburg, A. S.; Syroedov, V. I.

    1982-07-01

    The results of experimental investigations of the kinetics of foam drying of fish hydrolyzates are presented. The dehydration mechanism is analyzed and the enhancement of the process with dehydration of solutions in a foamed state is explained.

  18. A comprehensive RFID solution to enhance inpatient medication safety.

    PubMed

    Peris-Lopez, Pedro; Orfila, Agustin; Mitrokotsa, Aikaterini; van der Lubbe, Jan C A

    2011-01-01

    Errors involving medication administration can be costly, both in financial and in human terms. Indeed, there is much potential for errors due to the complexity of the medication administration process. Nurses are often singled out as the only responsible of these errors because they are in charge of drug administration. Nevertheless, the interventions of every actor involved in the process and the system design itself contribute to errors (Wakefield et al. (1998). Proper inpatient medication safety systems can help to reduce such errors in hospitals. In this paper, we review in depth two recent proposals (Chien et al. (2010); Huang and Ku (2009)) that pursue the aforementioned objective. Unfortunately, they fail in their attempt mainly due to their security faults but interesting ideas can be drawn from both. These security faults refer to impersonation and replay attacks that could produce the generation of a forged proof stating that certain medication was administered to an inpatient when it was not. We propose a leading-edge solution to enhance inpatient medication safety based on RFID technology that overcomes these weaknesses. Our solution, named Inpatient Safety RFID system (IS-RFID), takes into account the Information Technology (IT) infrastructure of a hospital and covers every phase of the drug administration process. From a practical perspective, our system can be easily integrated within hospital IT infrastructures, has a moderate cost, is very ease to use and deals with security aspects as a key point.

  19. Ionic enhancement of silica surface nanowear in electrolyte solutions.

    PubMed

    Vakarelski, Ivan U; Teramoto, Naofumi; McNamee, Cathy E; Marston, Jeremy O; Higashitani, Ko

    2012-11-20

    The nanoscale wear and friction of silica and silicon nitride surfaces in aqueous electrolyte solutions were investigated by using sharp atomic force microscope (AFM) cantilever tips coated with silicon nitride. Measurements were carried out in aqueous solutions of varying pH and in monovalent and divalent cation chloride and nitrate solutions. The silica surface was shown to wear strongly in solutions of high pH (≈11.0), as expected, but the presence of simple cations, such as Cs(+) and Ca(2+), was shown to dramatically effect the wear depth and friction force for the silica surface. In the case of monovalent cations, their hydration enthalpies correlated well with the wear and friction. The weakest hydrated cation of Cs(+) showed the most significant enhancement of wear and friction. In the case of divalent cations, a complex dependence on the type of cation was found, where the type of anion was also seen to play an important role. The CaCl(2) solution showed the anomalous enhancement of wear depth and friction force, although the solution of Ca(NO(3))(2) did not. The present results obtained with an AFM tip were also compared with previous nanotribology studies of silica surfaces in electrolyte solutions, and possible molecular mechanisms as to why cations enhance the wear and friction were also discussed.

  20. Drag enhancement of aqueous electrolyte solutions in turbulent pipe flow.

    PubMed

    Doherty, Andrew P; Spedding, Peter L; Chen, John J J

    2010-04-22

    Detailed experimental results are presented for both laminar and turbulent flow of aqueous solutions in pipes of different diameters. Nonelectrolytes, such as sugar solutions followed the normal Moody pressure loss curves. Drag enhancement was demonstrated for turbulent flow of aqueous electrolyte solutions but not for laminar flow. The increased pressure drop for turbulent electrolyte flow was attributed to an electroviscous effect and a theory was developed to explain the drag enhancement. The increased pressure drop for the turbulent region of flow was shown to depend on the Debye length in the laminar sublayer on the pipe wall. Reasonable predictions of the increasing drag were obtained for both 1:1 and 2:1 electrolyte solutions.

  1. Fracture-Flow-Enhanced Solute Diffusion into Fractured Rock

    SciTech Connect

    Wu, Yu-Shu; Ye, Ming; Sudicky, E.A.

    2007-12-15

    We propose a new conceptual model of fracture-flow-enhanced matrix diffusion, which correlates with fracture-flow velocity, i.e., matrix diffusion enhancement induced by rapid fluid flow within fractures. According to the boundary-layer or film theory, fracture flow enhanced matrix diffusion may dominate mass-transfer processes at fracture-matrix interfaces, because rapid flow along fractures results in large velocity and concentration gradients at and near fracture-matrix interfaces, enhancing matrix diffusion at matrix surfaces. In this paper, we present a new formulation of the conceptual model for enhanced fracture-matrix diffusion, and its implementation is discussed using existing analytical solutions and numerical models. In addition, we use the enhanced matrix diffusion concept to analyze laboratory experimental results from nonreactive and reactive tracer breakthrough tests, in an effort to validate the new conceptual model.

  2. Plurality of inherent states in equiatomic solid solutions

    NASA Astrophysics Data System (ADS)

    Demkowicz, M. J.

    2017-03-01

    We show that single-crystal, equiatomic solid solutions of Lennard-Jones particles have a plurality of inherent states: mechanically stable configurations with identical lattice site occupancies, yet distinct potential-energy minima. External loading triggers transitions between inherent states via localized shear transformations. A plurality of inherent states and mechanically activated transitions between them make equiatomic solid solutions an unusual form of matter: one that is crystalline like single-component metals, yet exhibits localized shear transformations like metallic glasses.

  3. Trichloroethylene Volatilization Enhancement by the Addition of a Brine Solution

    NASA Astrophysics Data System (ADS)

    Irizarry, M. L.; Padilla, I. Y.

    2008-12-01

    Trichloroethylene (TCE) is one of the most widely detected organic contaminants at National Priority List (NPL) sites. In many sites, TCE is trapped as a dense non-aqueous phase liquid (DNAPL) in formations of low permeability, and serves as long-term source of contamination. Cost effective remediation technologies that can be applied to tight formations need to be developed. This study investigates the enhancement of TCE volatilization from unsaturated clayey soils by adding a NaCl brine solution. It is postulated that the overall effect of the brine solution causing structured water around soil particles, increased relative permeability, and increased fugacity into the vapor phase, is to enhance TCE volatilization. TCE removal through the soil vapor extraction (SVE) technique can then be enhanced. Preliminary experimental work involves the use of static and dynamic flux reactors, containing TCE, water and clay. NaCl brine solution is added at different concentrations to evaluate the effect on TCE concentrations and volatilization rates. In the static flux mode, vapor concentrations in the headspace of sealed reactors are measured after a two-day period. In the dynamic flux mode, air is swept through the headspace of the reactors and TCE vapor concentrations are measured over time. Plots relating static TCE vapor concentration to brine concentration are used to show the effect of brine concentrations on TCE fugacity. Temporal concentration distributions of TCE show the effect of brine on the rate of volatilization. Keywords: Trichloroethylene (TCE), Soil vapor extraction (SVE), clay

  4. Robustness enhancement of neurocontroller and state estimator

    NASA Technical Reports Server (NTRS)

    Troudet, Terry

    1993-01-01

    The feasibility of enhancing neurocontrol robustness, through training of the neurocontroller and state estimator in the presence of system uncertainties, is investigated on the example of a multivariable aircraft control problem. The performance and robustness of the newly trained neurocontroller are compared to those for an existing neurocontrol design scheme. The newly designed dynamic neurocontroller exhibits a better trade-off between phase and gain stability margins, and it is significantly more robust to degradations of the plant dynamics.

  5. Mechanism of Enhanced Dermal Permeation of 4-Cyanophenol and Methyl Paraben from Saturated Aqueous Solutions Containing Both Solutes

    PubMed Central

    Romonchuk, W.J.; Bunge, A.L.

    2010-01-01

    Dermal permeation through human epidermis and uptake into isolated human stratum corneum (SC) that was and was not delipidized were measured for 2 model compounds, 4-cyanophenol (CP) and methyl paraben (MP), from saturated aqueous solutions containing 1 or both compounds. Because the solutions were in equilibrium with the pure CP and MP, the thermodynamic activity of the compounds was constant. Compared with compounds that are known permeation enhancers, MP and CP would not normally be expected to act as enhancers. Nevertheless, when both compounds were present, the steady-state fluxes through the epidermis increased by factors of 5.2 and 2.6 for MP and CP, respectively. Within the variability of the measurements, this increase in MP flux is consistent with the 6.4-fold increase in the SC uptake, which occurs primarily into the nonlipid regions of the SC. In contrast, the 1.6-fold increase in CP uptake when MP is present is too small to explain the increase in CP flux. These results suggest that CP enhances the skin permeation of MP by primarily increasing the solubility of MP in the SC, especially in the nonlipid regions, while MP increases the skin permeation of CP by enhancing both the solubility and diffusivity of CP in the SC. PMID:20068385

  6. Enhanced Public Participation - A State's Perspective

    SciTech Connect

    Wingard, R.W.; Jenkins, S.E.

    2008-07-01

    An initiative was started in 2004 to enhance public participation across all of the environmental programs within South Carolina Department of Health and Environmental Control (SCDHEC). The initiative originated as a result of public meetings that created distrust of our Agency within the State's communities. The effort to enhance public participation focused on ways to involve the public more in decisions effecting their health and environment within their communities. Tools and techniques were created and are now used by SCDHEC and continuously evaluated in the process known as enhanced public participation. Enhanced public participation efforts are required for all significant permitting, environmental cleanup and corrective action activities affecting communities within South Carolina. We recognized that public participation is essential to the ability of the SCDHEC to provide outstanding customer service as well as to establish and maintain trust within the community. This paper will describe the development of the program and the results of the implementation of the enhanced public participation using examples of facilities that manage hazardous wastes, high-level radioactive wastes, low-level radioactive wastes as well as mixed waste. (authors)

  7. Geminate recombination kinetics of solute radical ions. Singlet excited state formation in cyclohexane solutions of biphenyl

    NASA Astrophysics Data System (ADS)

    Tagawa, S.; Washio, M.; Tabata, Y.; Kobayashi, H.

    Transient absorption spectra of the solute anion, cation and triplet state and the solute fluorescence in the pulse radiolysis of 0.1 mole 1 -1 biphenyl in cyclohexane were observed on a nanosecond timescale longer than 1 ns after a 20 ps pulse. The formation of the solute excited singlet state is mainly due to the geminate ion recombination reaction even in the high concentrated solutions. The decay of the solute ions obeys the reciprocal square root dependence on time longer than 10 ns from the end of a 10 ps pulse. The slope of this reciprocal square root plots agrees with the literature value on a longer timescale obtained by microwave absorption. The yield of free ions obtained from the intercept of the slope agrees also with the literature values obtained by the field clearing method. Ratio of the formation rate of the solute excited triplet state to the decay rate of the solute anion changes in a time range between 5 and 20 ns. It is very well correlated with a theoretical calculation of spin correlation decay of the germinate ion pairs by Brocklehurst, although the formation of the solute triplet state was observed even on a timescale shorter than 5 ns from the end of a 20 ps pulse, where loss of spin correlation is negligibly small.

  8. Exact solutions for matter-enhanced neutrino oscillations

    SciTech Connect

    Balantekin, A.B. ||

    1998-07-01

    The analogy between supersymmetric quantum mechanics and matter-enhanced neutrino oscillations is exploited to obtain exact solutions for a class of electron density profiles. This integrability condition is analogous to shape invariance in supersymmetric quantum mechanics. This method seems to be the most direct way to obtain the exact survival probabilities for a number of density profiles of interest, such as linear and exponential density profiles. The resulting neutrino amplitudes can also be utilized as comparison amplitudes for the uniform semiclassical treatment of neutrino propagation in arbitrary electron density profiles. {copyright} {ital 1998} {ital The American Physical Society}

  9. Contrast enhancing solution for use in confocal microscopy

    DOEpatents

    Tannous, Zeina; Torres, Abel; Gonzalez, Salvador

    2006-10-31

    A method of optically detecting a tumor during surgery. The method includes imaging at least one test point defined on the tumor using a first optical imaging system to provide a first tumor image. The method further includes excising a first predetermined layer of the tumor for forming an in-vivo defect area. A predetermined contrast enhancing solution is disposed on the in-vivo defect area, which is adapted to interact with at least one cell anomaly, such as basal cell carcinoma, located on the in-vivo defect area for optically enhancing the cell anomaly. Thereafter the defect area can be optically imaged to provide a clear and bright representation of the cell anomaly to aid a surgeon while surgically removing the cell anomaly.

  10. Two RFID-based solutions to enhance inpatient medication safety.

    PubMed

    Chien, Hung-Yu; Yang, Chia-Chuan; Wu, Tzong-Chen; Lee, Chin-Feng

    2011-06-01

    Owing to the low cost and convenience of identifying an object without physical contact, Radio Frequency Identification (RFID) systems provide innovative, promising and efficient applications in many domains. An RFID grouping protocol is a protocol that allows an off-line verifier to collect and verify the evidence of two or more tags simultaneously present. Recently, Huang and Ku (J. Med. Syst, 2009) proposed an efficient grouping protocol to enhance medication safety for inpatients based on low-cost tags. However, the Huang-Ku scheme is not secure; an attacker can easily make up fake grouping records to cheat the verifier. This weakness would seriously endanger the safety of inpatient medication safety. This paper will show the weaknesses, and then propose two RFID-based solutions to enhance medication safety for two different scenarios. The proposed schemes are practical, secure and efficient for medication applications.

  11. Enhanced removal of radioactive particles by fluorocarbon surfactant solutions

    SciTech Connect

    Kaiser, R.; Harling, O.K.

    1993-08-01

    The proposed research addressed the application of ESI`s particle removal process to the non-destructive decontamination of nuclear equipment. The cleaning medium used in this process is a solution of a high molecular weight fluorocarbon surfactant in an inert perfluorinated liquid which results in enhanced particle removal. The perfluorinated liquids of interest, which are recycled in the process, are nontoxic, nonflammable, and environmentally compatible, and do not present a hazard to the ozone layer. The information obtained in the Phase 1 program indicated that the proposed ESI process is technically effective and economically attractive. The fluorocarbon surfactant solutions used as working media in the ESI process survived exposure of up to 10 Mrad doses of gamma rays, and are considered sufficiently radiation resistant for the proposed process. Ultrasonic cleaning in perfluorinated surfactant solutions was found to be an effective method of removing radioactive iron (Fe 59) oxide particles from contaminated test pieces. Radioactive particles suspended in the process liquids could be quantitatively removed by filtration through a 0.1 um membrane filter. Projected economics indicate a pre-tax pay back time of 1 month for a commercial scale system.

  12. Fluctuation-enhanced electric conductivity in electrolyte solutions.

    PubMed

    Péraud, Jean-Philippe; Nonaka, Andrew J; Bell, John B; Donev, Aleksandar; Garcia, Alejandro L

    2017-09-26

    We analyze the effects of an externally applied electric field on thermal fluctuations for a binary electrolyte fluid. We show that the fluctuating Poisson-Nernst-Planck (PNP) equations for charged multispecies diffusion coupled with the fluctuating fluid momentum equation result in enhanced charge transport via a mechanism distinct from the well-known enhancement of mass transport that accompanies giant fluctuations. Although the mass and charge transport occurs by advection by thermal velocity fluctuations, it can macroscopically be represented as electrodiffusion with renormalized electric conductivity and a nonzero cation-anion diffusion coefficient. Specifically, we predict a nonzero cation-anion Maxwell-Stefan coefficient proportional to the square root of the salt concentration, a prediction that agrees quantitatively with experimental measurements. The renormalized or effective macroscopic equations are different from the starting PNP equations, which contain no cross-diffusion terms, even for rather dilute binary electrolytes. At the same time, for infinitely dilute solutions the renormalized electric conductivity and renormalized diffusion coefficients are consistent and the classical PNP equations with renormalized coefficients are recovered, demonstrating the self-consistency of the fluctuating hydrodynamics equations. Our calculations show that the fluctuating hydrodynamics approach recovers the electrophoretic and relaxation corrections obtained by Debye-Huckel-Onsager theory, while elucidating the physical origins of these corrections and generalizing straightforwardly to more complex multispecies electrolytes. Finally, we show that strong applied electric fields result in anisotropically enhanced "giant" velocity fluctuations and reduced fluctuations of salt concentration.

  13. Enhancement of flagellated bacterial motility in polymer solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Wenyu; Sha, Sha; Pelcovits, Robert; Tang, Jay

    2015-11-01

    Measurements of the swimming speed of many species of flagellated bacteria in polymer solutions have shown that with the addition of high molecular weight polymers, the speed initially increases as a function of the kinematic viscosity. It peaks at around 1.5-2 cP with typically 10-30% higher values than in cell media without added polymers (~ 1 cP). Past the peak, the average speed gradually decreases as the solution becomes more viscous. Swimming motility persists until solution viscosity reaches 5-10 cP. Models have been proposed to account for this behavior, and the magnitude of the peak becomes a crucial test of theoretical predictions. The status of the field is complicated in light of a recent report (Martinez et al., PNAS, 2014), stressing that low-molecular weight impurities account for the peaked speed-viscosity curves in some cases. We measured the swimming speed of a uni-flagellated bacterium, caulobacter crescentus, in solutions of a number of polymers of several different sizes. Our findings confirm the peaked speed-viscosity curve, only as the molecular weight of the flexible polymers used surpassed ~ 50,000 da. The threshold molecular weight required to augment swimming speed varies somewhat with the polymer species, but it generally corresponds to radius of gyration over tens of nanometers. This general feature is consistent with the model of Powers et al. (Physics of Fluid, 2009), predicting that nonlinear viscoelasticity of the fluid enhances swimming motility. Work Supported by the NSF Fluid Physics Program (Award number CBET 1438033).

  14. An Enhanced Artificial Bee Colony Algorithm with Solution Acceptance Rule and Probabilistic Multisearch.

    PubMed

    Yurtkuran, Alkın; Emel, Erdal

    2016-01-01

    The artificial bee colony (ABC) algorithm is a popular swarm based technique, which is inspired from the intelligent foraging behavior of honeybee swarms. This paper proposes a new variant of ABC algorithm, namely, enhanced ABC with solution acceptance rule and probabilistic multisearch (ABC-SA) to address global optimization problems. A new solution acceptance rule is proposed where, instead of greedy selection between old solution and new candidate solution, worse candidate solutions have a probability to be accepted. Additionally, the acceptance probability of worse candidates is nonlinearly decreased throughout the search process adaptively. Moreover, in order to improve the performance of the ABC and balance the intensification and diversification, a probabilistic multisearch strategy is presented. Three different search equations with distinctive characters are employed using predetermined search probabilities. By implementing a new solution acceptance rule and a probabilistic multisearch approach, the intensification and diversification performance of the ABC algorithm is improved. The proposed algorithm has been tested on well-known benchmark functions of varying dimensions by comparing against novel ABC variants, as well as several recent state-of-the-art algorithms. Computational results show that the proposed ABC-SA outperforms other ABC variants and is superior to state-of-the-art algorithms proposed in the literature.

  15. Enhanced semiconductor nanocrystal conductance via solution grown contacts.

    PubMed

    Sheldon, Matthew T; Trudeau, Paul-Emile; Mokari, Taleb; Wang, Lin-Wang; Alivisatos, A Paul

    2009-11-01

    We report a 100000-fold increase in the conductance of individual CdSe nanorods when they are electrically contacted via direct solution phase growth of Au tips on the nanorod ends. Ensemble UV-vis and X-ray photoelectron spectroscopies indicate this enhancement does not result from alloying of the nanorod. Rather, low temperature tunneling and high temperature (250-400 K) thermionic emission across the junction at the Au contact reveal a 75% lower interface barrier to conduction compared to a control sample. We correlate this barrier lowering with the electronic structure at the Au-CdSe interface. Our results emphasize the importance of a nanocrystal surface structure for robust device performance and the advantage of this contact method.

  16. Enhanced Semiconductor Nanocrystal Conductance via Solution Grown Contacts

    SciTech Connect

    Sheldon, Matthew T.; Trudeau, Paul-Emile; Mokari, Taleb; Wang, Lin-Wang; Alivisatos, A. Paul

    2009-08-19

    We report a 100,000-fold increase in the conductance of individual CdSe nanorods when they are electrically contacted via direct solution phase growth of Au tips on the nanorod ends. Ensemble UV-Vis and X-Ray photoelectron spectroscopy indicate this enhancement does not result from alloying of the nanorod. Rather, low temperature tunneling and high temperature (250-400 K) thermionic emission across the junction at the Au contact reveal a 75percent lower interface barrier to conduction compared to a control sample. We correlate this barrier lowering with the electronic structure at the Au-CdSe interface. Our results emphasize the importance of nanocrystal surface structure for robust device performance and the advantage of this contact method.

  17. Microbially-enhanced redox solution reoxidation for sweetening sour natural gas

    SciTech Connect

    Rai, C.

    1995-06-01

    About twenty five percent of natural gas produced in the United States is sour containing significant volumes of hydrogen sulfide and other contaminants. Liquid redox processes remove hydrogen sulfide from natural gas. Aqueous solution of chelated ferric ions oxidize the hydrogen sulfide to elemental sulfur. The reduced iron chelate is then oxidized by contact with air and recycled. This requires expensive equipment for regeneration, costly chemicals and the process is usually energy intensive. Recent studies show that the ferric ion regeneration rates are substantially enhanced in presence of acidophilic bacteria. The specific objectives of this project are to advance the technology and improve the economics of the commercial iron-based chelate processes utilizing biologically-enhanced reoxidation of the redox solutions used in these processes, such as LO-CAT II and SulFerox.

  18. Surface Defects Enhanced Visible Light Photocatalytic H2 Production for Zn-Cd-S Solid Solution.

    PubMed

    Zhang, Xiaoyan; Zhao, Zhao; Zhang, Wanwan; Zhang, Guoqiang; Qu, Dan; Miao, Xiang; Sun, Shaorui; Sun, Zaicheng

    2016-02-10

    In order to investigate the defect effect on photocatalytic performance of the visible light photocatalyst, Zn-Cd-S solid solution with surface defects is prepared in the hydrazine hydrate. X-ray photoelectron spectra and photoluminescence results confirm the existence of defects, such as sulfur vacancies, interstitial metal, and Zn and Cd in the low valence state on the top surface of solid solutions. The surface defects can be effectively removed by treating with sulfur vapor. The solid solution with surface defect exhibits a narrower band gap, wider light absorption range, and better photocatalytic perfomance. The optimized solid solution with defects exhibits 571 μmol h(-1) for 50 mg photocatalyst without loading Pt as cocatalyst under visible light irradiation, which is fourfold better than that of sulfur vapor treated samples. The wavelength dependence of photocatalytic activity discloses that the enhancement happens at each wavelength within the whole absorption range. The theoretical calculation shows that the surface defects induce the conduction band minimum and valence band maximum shift downward and upward, respectively. This constructs a type I junction between bulk and surface of solid solution, which promotes the migration of photogenerated charges toward the surface of nanostructure and leads to enhanced photocatalytic activity. Thus a new method to construct highly efficient visible light photocatalysts is opened.

  19. Matrix-enhanced secondary ion mass spectrometry: The Alchemist's solution?

    NASA Astrophysics Data System (ADS)

    Delcorte, Arnaud

    2006-07-01

    Because of the requirements of large molecule characterization and high-lateral resolution SIMS imaging, the possibility of improving molecular ion yields by the use of specific sample preparation procedures has recently generated a renewed interest in the static SIMS community. In comparison with polyatomic projectiles, however, signal enhancement by a matrix might appear to some as the alchemist's versus the scientist's solution to the current problems of organic SIMS. In this contribution, I would like to discuss critically the pros and cons of matrix-enhanced SIMS procedures, in the new framework that includes polyatomic ion bombardment. This discussion is based on a short review of the experimental and theoretical developments achieved in the last decade with respect to the three following approaches: (i) blending the analyte with a low-molecular weight organic matrix (MALDI-type preparation procedure); (ii) mixing alkali/noble metal salts with the analyte; (iii) evaporating a noble metal layer on the analyte sample surface (organic molecules, polymers).

  20. Exact Solutions of Relativistic Bound State Problem for Spinless Bosons

    NASA Astrophysics Data System (ADS)

    Aslanzadeh, M.; Rajabi, A. A.

    2017-01-01

    We investigated in detail the relativistic bound states of spin-zero bosons under the influence of Coulomb-plus-linear potentials with an arbitrary combination of scalar and vector couplings. Through an exact analytical solution of three-dimensional Klein-Gordon equation, closed form expressions were derived for energy eigenvalues and wave functions and some correlations between potential parameters were found. We also presented the relativistic description of bound states and nonrelativistic limit of the problem in some special cases.

  1. A theoretical framework for modeling dilution enhancement of non-reactive solutes in heterogeneous porous media.

    PubMed

    de Barros, F P J; Fiori, A; Boso, F; Bellin, A

    2015-01-01

    Spatial heterogeneity of the hydraulic properties of geological porous formations leads to erratically shaped solute clouds, thus increasing the edge area of the solute body and augmenting the dilution rate. In this study, we provide a theoretical framework to quantify dilution of a non-reactive solute within a steady state flow as affected by the spatial variability of the hydraulic conductivity. Embracing the Lagrangian concentration framework, we obtain explicit semi-analytical expressions for the dilution index as a function of the structural parameters of the random hydraulic conductivity field, under the assumptions of uniform-in-the-average flow, small injection source and weak-to-mild heterogeneity. Results show how the dilution enhancement of the solute cloud is strongly dependent on both the statistical anisotropy ratio and the heterogeneity level of the porous medium. The explicit semi-analytical solution also captures the temporal evolution of the dilution rate; for the early- and late-time limits, the proposed solution recovers previous results from the literature, while at intermediate times it reflects the increasing interplay between large-scale advection and local-scale dispersion. The performance of the theoretical framework is verified with high resolution numerical results and successfully tested against the Cape Cod field data.

  2. Sargassum as a natural solution to enhance dune plant growth.

    PubMed

    Williams, Amy; Feagin, Rusty

    2010-11-01

    Many beach management practices focus on creating an attractive environment for tourists, but can detrimentally affect long-term dune integrity. One such practice is mechanical beach raking in which the wrack line is removed from the beach front. In Texas, Sargassum fluitans and natans, types of brown alga, are the main components of wrack and may provide a subsidy to the ecosystem. In this study, we used greenhouse studies to test the hypothesis that the addition of sargassum can increase soil nutrients and produce increased growth in dune plants. We also conducted an analysis of the nutrients in the sargassum to determine the mechanisms responsible for any growth enhancement. Panicum amarum showed significant enhancement of growth with the addition of sargassum, and while Helianthus debilis, Ipomoea stolonifera, Sporobolus virginicus, and Uniola paniculata responded slightly differently to the specific treatments, none were impaired by the addition of sargassum. In general, plants seemed to respond well to unwashed sargassum and multiple additions of sargassum, indicating that plants may have adapted to capitalize on the subsidy in its natural state directly from the ocean. For coastal managers, the use of sargassum as a fertilizer could be a positive, natural, and efficient method of dealing with the accumulation of wrack on the beach.

  3. Sensitivity Enhancement in Static Solid-State NMR Experiments VIA Single and Multiple Quantum Dipolar Coherences

    PubMed Central

    Gopinath, T.; Veglia, Gianluigi

    2012-01-01

    We present a new method to enhance the sensitivity in static solid-state NMR for a gain in signal-to-noise ratio up to 40%. This sensitivity enhancement is different from the corresponding solution NMR sensitivity enhancement schemes and is achieved by combining single and multiple quantum dipolar coherences. While this new approach is demonstrated for the PISEMA (polarization inversion spin exchange at magic angle) experiment, it can be generalized to the other separated local field experiments for solid-state NMR spectroscopy. This method will have a direct impact on solid-state NMR spectroscopy of liquid crystals as well as membrane proteins aligned in lipid membranes. PMID:19351170

  4. Tau Aggregation Propensity Engrained in Its Solution State.

    PubMed

    Eschmann, Neil A; Do, Thanh D; LaPointe, Nichole E; Shea, Joan-Emma; Feinstein, Stuart C; Bowers, Michael T; Han, Songi

    2015-11-12

    A peptide fragment of the human tau protein which stacks to form neat cross β-sheet fibrils, resembling that found in pathological aggregation, (273)GKVQIINKKLDL(284) (here "R2/WT"), was modified with a spin-label at the N-terminus. With the resulting peptide, R2/G273C-SL, we probed events at time scales spanning seconds to hours after aggregation is initiated using transmission electron microscopy (TEM), thioflavin T (THT) fluorescence, ion mobility mass spectrometry (IMMS), electron paramagnetic resonance (EPR), and Overhauser dynamic nuclear polarization (ODNP) to determine if deliberate changes to its conformational states and population in solution influence downstream propensity to form fibrillar aggregates. We find varying solution conditions by adding the osmolyte urea or TMAO, or simply using different buffers (acetate buffer, phosphate buffer, or water), produces significant differences in early monomer/dimer populations and conformations. Crucially, these characteristics of the peptide in solution state before aggregation is initiated dictate the fibril formation propensity after aggregation. We conclude the driving forces that accelerate aggregation, when heparin is added, do not override the subtle intra- or interprotein interactions induced by the initial solvent conditions. In other words, the balance of protein-protein vs protein-solvent interactions present in the initial solution conditions is a critical driving force for fibril formation.

  5. Tau Aggregation Propensity Engrained in Its Solution State

    PubMed Central

    2016-01-01

    A peptide fragment of the human tau protein which stacks to form neat cross β-sheet fibrils, resembling that found in pathological aggregation, 273GKVQIINKKLDL284 (here “R2/WT”), was modified with a spin-label at the N-terminus. With the resulting peptide, R2/G273C-SL, we probed events at time scales spanning seconds to hours after aggregation is initiated using transmission electron microscopy (TEM), thioflavin T (THT) fluorescence, ion mobility mass spectrometry (IMMS), electron paramagnetic resonance (EPR), and Overhauser dynamic nuclear polarization (ODNP) to determine if deliberate changes to its conformational states and population in solution influence downstream propensity to form fibrillar aggregates. We find varying solution conditions by adding the osmolyte urea or TMAO, or simply using different buffers (acetate buffer, phosphate buffer, or water), produces significant differences in early monomer/dimer populations and conformations. Crucially, these characteristics of the peptide in solution state before aggregation is initiated dictate the fibril formation propensity after aggregation. We conclude the driving forces that accelerate aggregation, when heparin is added, do not override the subtle intra- or interprotein interactions induced by the initial solvent conditions. In other words, the balance of protein–protein vs protein–solvent interactions present in the initial solution conditions is a critical driving force for fibril formation. PMID:26484390

  6. Microbial enhancement of TCE and 1,2-DCA solute flux in UF-membrane bioreactors

    SciTech Connect

    Inguva, S.; Boensch, M.; Shreve, G.S.

    1998-09-01

    An ultrafiltration membrane process was used to remove and biograde chlorinated aliphatic hydrocarbons trichloroethylene (TCE) and 1,2-dichloroethane (1,2-DCA) from dilute aqueous streams. The effect of microbial biodegradative activity on TCE and 1,2-DCA solute flux in a polypropylene membrane was examined using microbial strains Pseudomonas cepacia PRI{sub 31} for the biodegradation of TCE and Xanthobacter autotrophicus GJ10 for the biodegradation of 1,2-DCA. Initial experiments were conducted in diaphragm cells in the absence of microorganisms to determine the diffusion coefficient of 1,2-DCA and TCE in the polypropylene ultrafiltration (UF) membranes. The diffusivities were 4.7 {times} 10{sup {minus}8} cm{sup 2}/s for 1,2-DCA and 1.41 {times} 10{sup {minus}7} cm{sup 2}/s for TCE. Subsequent experiments were conducted with microorganisms on the permeate side to examine the effect of microbial degradation of 1,2-DCA and TCE on the solute flux across the UF membrane. Experiments were conducted sequentially in batch and flow diaphragm cells and then in a hollow-fiber UF module to systematically examine the effect of microbial activity on the solute flux in each configuration and the ability of mathematical models to predict the microbial enhancement of solute flux. Microbial biodegradation of TCE and 1,2-DCA significantly enhanced the solute flux, and experimental results were correlated with steady- and nonsteady-state solute component balance models for the flow and batch diaphragm cells, respectively. Model and experimental results agree well. Implications for using membrane bioreactors to treat CAH contaminated groundwater and industrial effluents are discussed.

  7. 44 CFR 201.5 - Enhanced State Mitigation Plans.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 44 Emergency Management and Assistance 1 2012-10-01 2011-10-01 true Enhanced State Mitigation Plans. 201.5 Section 201.5 Emergency Management and Assistance FEDERAL EMERGENCY MANAGEMENT AGENCY, DEPARTMENT OF HOMELAND SECURITY DISASTER ASSISTANCE MITIGATION PLANNING § 201.5 Enhanced State Mitigation Plans. (a) A State with a FEMA approved...

  8. 44 CFR 201.5 - Enhanced State Mitigation Plans.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 44 Emergency Management and Assistance 1 2014-10-01 2014-10-01 false Enhanced State Mitigation Plans. 201.5 Section 201.5 Emergency Management and Assistance FEDERAL EMERGENCY MANAGEMENT AGENCY, DEPARTMENT OF HOMELAND SECURITY DISASTER ASSISTANCE MITIGATION PLANNING § 201.5 Enhanced State Mitigation Plans. (a) A State with a FEMA...

  9. 44 CFR 201.5 - Enhanced State Mitigation Plans.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 44 Emergency Management and Assistance 1 2013-10-01 2013-10-01 false Enhanced State Mitigation Plans. 201.5 Section 201.5 Emergency Management and Assistance FEDERAL EMERGENCY MANAGEMENT AGENCY, DEPARTMENT OF HOMELAND SECURITY DISASTER ASSISTANCE MITIGATION PLANNING § 201.5 Enhanced State Mitigation Plans. (a) A State with a FEMA...

  10. 44 CFR 201.5 - Enhanced State Mitigation Plans.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 44 Emergency Management and Assistance 1 2011-10-01 2011-10-01 false Enhanced State Mitigation Plans. 201.5 Section 201.5 Emergency Management and Assistance FEDERAL EMERGENCY MANAGEMENT AGENCY, DEPARTMENT OF HOMELAND SECURITY DISASTER ASSISTANCE MITIGATION PLANNING § 201.5 Enhanced State Mitigation Plans. (a) A State with a FEMA...

  11. Excited State Absorption Measurements In Some Scintillator Dye Solutions

    NASA Astrophysics Data System (ADS)

    Dharamsi, A., N.; Jong, Shawpin; Hassam, A. B.

    1986-11-01

    Time-resolved excited state triplet-triplet absorption spectra were measured for solutions of 2,5 diphenyloxazole (PPO) and 2,1 napthyl, 5 phenyloxazole (aNPO) in several solvents. Concentration quenching effects due to excimer formation in nonaromatic solvents were observed. A numerical analysis of the experimental results yielded the rate constants for intersystem crossing, triplet quenching by 02, triplet self quenching and the formation of excimers.

  12. Solid-State and Solution Characterization of Myricetin.

    PubMed

    Franklin, Stephen J; Myrdal, Paul B

    2015-12-01

    Myricetin (MYR) is a natural compound that has been investigated as a chemopreventative agent. MYR has been shown to suppresses ultraviolet B (UVB)-induced cyclooxygenase-2 (COX-2) protein expression and reduce the incidence of UVB-induced skin tumors in mice. Despite MYR's promise as a therapeutic agent, minimal information is available to guide the progression of formulations designed for future drug development. Here, data is presented describing the solid-state and solution characterization of MYR. Investigation into the solid-state properties of MYR identified four different crystal forms, two hydrates (MYR I and MYR II) and two metastable forms (MYR IA and MYR IIA). From solubility studies, it was evident that all forms are very insoluble (<5 μg/ml) in pure water. MYR I was found to be the most stable form at 23, 35, and 56°C. Stability determination indicated that MYR undergoes rapid apparent first-order degradation under basic pH conditions, and that degradation was influenced by buffer species. Apparent first-order degradation was also seen when MYR was introduced to an oxidizing solution. Improved stability was achieved after introducing 0.1% antioxidants to the solution. MYR was found to have good stability following exposure to ultraviolet radiation (UVR), which is a consideration for topical applications. Finally, a partitioning study indicated that MYR possess a log P of 2.94 which, along with its solid-state properties, contributes to its poor aqueous solubility. Both the solid-state properties and solution stability of MYR are important to consider when developing future formulations.

  13. Investigation on intermolecular interaction between two solutes where one solute occurs in two states

    NASA Astrophysics Data System (ADS)

    Kang, Xiaoyan; He, Anqi; Guo, Ran; Chen, Jing; Zhai, Yanjun; Xu, Yizhuang; Noda, Isao; Wu, Jinguang

    2016-11-01

    The spectral behavior of a pair of 2D asynchronous spectra generated by using the double asynchronous orthogonal sample design (DAOSD) approach on a chemical system is investigated. Two solutes (P and Q) are dissolved in the solution and intermolecular interaction between P and Q is characterized. In this particular system, P occurs in two exchangeable states when it is dissolved in the solutions. Results on mathematical analysis and computer simulation demonstrated that interference unrelated to the intermolecular interaction can be completely removed. Hence the resultant 2D asynchronous spectra generated by using the DAOSD approach can reflect intermolecular interaction reliably. Moreover, properties of cross peaks in different regions of the pair of asynchronous spectra are discussed. In our previous works, cross peaks generated by using the DAOSD and relevant techniques reflect variations on peak position, bandwidth or absorptivity of the characteristic peaks of solutes caused by intermolecular interaction. However, we find that cross peak can still be produced even if intermolecular interaction do not bring about any changes on the characteristic peaks of solutes. Mathematical analysis demonstrates that cross peaks are related to the variations of chemical systems caused by intermolecular interaction at a network level.

  14. Anharmonic densities of states: A general dynamics-based solution

    SciTech Connect

    Jellinek, Julius; Aleinikava, Darya

    2016-06-07

    Density of states is a fundamental physical characteristic that lies at the foundation of statistical mechanics and theoretical constructs that derive from them (e.g., kinetic rate theories, phase diagrams, and others). Even though most real physical systems are anharmonic, the vibrational density of states is customarily treated within the harmonic approximation, or with some partial, often limited, account for anharmonicity. The reason for this is that the problem of anharmonic densities of states stubbornly resisted a general and exact, yet convenient and straightforward in applications, solution. Here we formulate such a solution within both classical and quantum mechanics. It is based on actual dynamical behavior of systems as a function of energy and as observed, or monitored, on a chosen time scale, short or long. As a consequence, the resulting anharmonic densities of states are fully dynamically informed and, in general, time-dependent. As such, they lay the ground for formulation of new statistical mechanical frameworks that incorporate time and are ergodic, by construction, with respect to actual dynamical behavior of systems.

  15. Peculiarities of state diagrams of aqueous solutions of cryoprotective agents.

    PubMed

    Osetsky, Alexander I

    2009-10-01

    The phase transitions in aqueous solutions of glycerol and PEO-1500 within the temperature range of +30 to -150 degrees C have been studied using the methods of thermoplastic analysis and volumetric scanning tensodilatometry. We present the revealed phenomenon of cluster cyrystallization of these solutions as well as principles of describing this phenomenon using state diagrams, containing the intervals of concentration corresponding to the existence of amorphous and cryocolloid fractions. We note that for the cryocolloid fraction, a low temperature association of molecules of cryoprotective agents leads the formation of ice nanocrystals either close to or directly inside the aggregations. These fractions exist in cooled cryoprotective solutions near the vitrification temperatures of the liquid phase and may contribute to the initiation of damaging events in cryopreserved biological systems. Our data may be helpful in explaining the peculiarities observed during crystallization of cryoprotective solutions and may further contribute to a broader understanding of the principles of protection and protocol optimization of biological materials at temperatures approaching vitrification.

  16. Heat transfer enhancement accompanying Leidenfrost state suppression at ultrahigh temperatures.

    PubMed

    Shahriari, Arjang; Wurz, Jillian; Bahadur, Vaibhav

    2014-10-14

    The well-known Leidenfrost effect is the formation of a vapor layer between a liquid and an underlying hot surface. This insulating vapor layer severely degrades heat transfer and results in surface dryout. We measure the heat transfer enhancement and dryout prevention benefits accompanying electrostatic suppression of the Leidenfrost state. Interfacial electric fields in the vapor layer can attract liquid toward the surface and promote wetting. This principle can suppress dryout even at ultrahigh temperatures exceeding 500 °C, which is more than 8 times the Leidenfrost superheat for organic solvents. Robust Leidenfrost state suppression is observed for a variety of liquids, ranging from low electrical conductivity organic solvents to electrically conducting salt solutions. Elimination of the vapor layer increases heat dissipation capacity by more than 1 order of magnitude. Heat removal capacities exceeding 500 W/cm(2) are measured, which is 5 times the critical heat flux (CHF) of water on common engineering surfaces. Furthermore, the heat transfer rate can be electrically controlled by the applied voltage. The underlying science is explained via a multiphysics analytical model which captures the coupled electrostatic-fluid-thermal transport phenomena underlying electrostatic Leidenfrost state suppression. Overall, this work uncovers the physics underlying dryout prevention and demonstrates electrically tunable boiling heat transfer with ultralow power consumption.

  17. Formation of curcumin nanoparticles via solution-enhanced dispersion by supercritical CO2

    PubMed Central

    Zhao, Zheng; Xie, Maobin; Li, Yi; Chen, Aizheng; Li, Gang; Zhang, Jing; Hu, Huawen; Wang, Xinyu; Li, Shipu

    2015-01-01

    In order to enhance the bioavailability of poorly water-soluble curcumin, solution-enhanced dispersion by supercritical carbon dioxide (CO2) (SEDS) was employed to prepare curcumin nanoparticles for the first time. A 24 full factorial experiment was designed to determine optimal processing parameters and their influence on the size of the curcumin nanoparticles. Particle size was demonstrated to increase with increased temperature or flow rate of the solution, or with decreased precipitation pressure, under processing conditions with different parameters considered. The single effect of the concentration of the solution on particle size was not significant. Curcumin nanoparticles with a spherical shape and the smallest mean particle size of 325 nm were obtained when the following optimal processing conditions were adopted: P =20 MPa, T =35°C, flow rate of solution =0.5 mL·min−1, concentration of solution =0.5%. Fourier transform infrared (FTIR) spectroscopy measurement revealed that the chemical composition of curcumin basically remained unchanged. Nevertheless, X-ray powder diffraction (XRPD) and thermal analysis indicated that the crystalline state of the original curcumin decreased after the SEDS process. The solubility and dissolution rate of the curcumin nanoparticles were found to be higher than that of the original curcumin powder (approximately 1.4 μg/mL vs 0.2 μg/mL in 180 minutes). This study revealed that supercritical CO2 technologies had a great potential in fabricating nanoparticles and improving the bioavailability of poorly water-soluble drugs. PMID:25995627

  18. Gravastar solutions with continuous pressures and equation of state

    NASA Astrophysics Data System (ADS)

    DeBenedictis, A.; Horvat, D.; Ilijić, S.; Kloster, S.; Viswanathan, K. S.

    2006-04-01

    We study the gravitational vacuum star (gravastar) configuration as proposed by Cattoen et al (2005 Class. Quantum Grav. 22 4189) in a model where the interior de Sitter spacetime segment is continuously extended to the exterior Schwarzschild spacetime. The multilayered structure of Mazur and Mottola (2001 Preprint gr-qc/0109035, 2003 Proc. 6th Workshop on Quantum Field Theory Under the Influence of External Conditions (Oklahoma) (Princeton, NJ: Rinton), Preprint gr-qc/0405111 (2004 Proc. Natl Acad. Sci. 111 9545) is replaced by a continuous stress-energy tensor at the price of introducing anisotropy in the (fluid) model of the gravastar. Either with an ansatz for the equation of state connecting the radial pr and tangential pt pressure or with a calculated equation of state with non-homogeneous energy/fluid density, solutions are obtained which in all aspects satisfy the conditions expected for an anisotropic gravastar (Cattoen et al 2005 Class. Quantum Grav. 22 4189). Certain energy conditions have been shown to be obeyed and a polytropic equation of state has been derived. Stability of the solution with respect to possible axial perturbation is shown to hold.

  19. Steady-State Solution of a Flexible Wing

    NASA Technical Reports Server (NTRS)

    Karkehabadi, Reza; Chandra, Suresh; Krishnamurthy, Ramesh

    1997-01-01

    A fluid-structure interaction code, ENSAERO, has been used to compute the aerodynamic loads on a swept-tapered wing. The code has the capability of using Euler or Navier-Stokes equations. Both options have been used and compared in the present paper. In the calculation of the steady-state solution, we are interested in knowing how the flexibility of the wing influences the lift coefficients. If the results of a flexible wing are not affected by the flexibility of the wing significantly, one could consider the wing to be rigid and reduce the problem from fluid-structure interaction to a fluid problem.

  20. Perovskite enhanced solid state ZnO solar cells

    NASA Astrophysics Data System (ADS)

    Loh, L.; Briscoe, J.; Dunn, S.

    2013-12-01

    This paper will report on the design, fabrication and testing of a solid-state perovskite enhanced ZnO solar cell. The p-type perovskite material used is bismuth ferrite (BFO) which has an absorption range within the blue range of the visible light spectrum. The solid state solar cell, was sensitized with N719 dye and used a CuSCN hole conductor. A disadvantage of ZnO is its poor chemical stability in acidic and corrosive environments. As chemical solution techniques were used in depositing BFO, a buffer method using an aminosilane ((3-aminopropyltrimethoxysilane or H2N(CH2)3Si(OCH3)3)) coating was used to provide a protective coating on the ZnO nanorods before the BFO film was spin coated onto the ZnO nanorods. The photovoltaic performance of the solar cells were tested using a Keithley 2400 source meter under 100mW/cm2, AM 1.5G simulated sunlight, where improvements in Jsc and efficiency were observed. The BFO was able to harness more electrons and also acted as a buffer from electron recombination.

  1. Grating enhanced solid-state laser amplifiers

    DOEpatents

    Erlandson, Alvin C.; Britten, Jerald A.

    2010-11-09

    A novel method and apparatus for suppressing ASE and parasitic oscillation modes in a high average power laser is introduced. Such an invention, as disclosed herein, uses diffraction gratings to increase gain, stored energy density, and pumping efficiency of solid-state laser gain media, such as, but not limited to rods, disks and slabs. By coupling predetermined gratings to solid-state gain media, such as crystal or ceramic laser gain media, ASE and parasitic oscillation modes can be effectively suppressed.

  2. Enhancing physiologic simulations using supervised learning on coarse mesh solutions

    PubMed Central

    Kolandaivelu, Kumaran; O'Brien, Caroline C.; Shazly, Tarek; Edelman, Elazer R.; Kolachalama, Vijaya B.

    2015-01-01

    Computational modelling of physical and biochemical processes has emerged as a means of evaluating medical devices, offering new insights that explain current performance, inform future designs and even enable personalized use. Yet resource limitations force one to compromise with reduced order computational models and idealized assumptions that yield either qualitative descriptions or approximate, quantitative solutions to problems of interest. Considering endovascular drug delivery as an exemplary scenario, we used a supervised machine learning framework to process data generated from low fidelity coarse meshes and predict high fidelity solutions on refined mesh configurations. We considered two models simulating drug delivery to the arterial wall: (i) two-dimensional drug-coated balloons and (ii) three-dimensional drug-eluting stents. Simulations were performed on computational mesh configurations of increasing density. Supervised learners based on Gaussian process modelling were constructed from combinations of coarse mesh setting solutions of drug concentrations and nearest neighbourhood distance information as inputs, and higher fidelity mesh solutions as outputs. These learners were then used as computationally inexpensive surrogates to extend predictions using low fidelity information to higher levels of mesh refinement. The cross-validated, supervised learner-based predictions improved fidelity as compared with computational simulations performed at coarse level meshes—a result consistent across all outputs and computational models considered. Supervised learning on coarse mesh solutions can augment traditional physics-based modelling of complex physiologic phenomena. By obtaining efficient solutions at a fraction of the computational cost, this framework has the potential to transform how modelling approaches can be applied in the evaluation of medical technologies and their real-time administration in an increasingly personalized fashion. PMID:25652458

  3. Enhancing physiologic simulations using supervised learning on coarse mesh solutions.

    PubMed

    Kolandaivelu, Kumaran; O'Brien, Caroline C; Shazly, Tarek; Edelman, Elazer R; Kolachalama, Vijaya B

    2015-03-06

    Computational modelling of physical and biochemical processes has emerged as a means of evaluating medical devices, offering new insights that explain current performance, inform future designs and even enable personalized use. Yet resource limitations force one to compromise with reduced order computational models and idealized assumptions that yield either qualitative descriptions or approximate, quantitative solutions to problems of interest. Considering endovascular drug delivery as an exemplary scenario, we used a supervised machine learning framework to process data generated from low fidelity coarse meshes and predict high fidelity solutions on refined mesh configurations. We considered two models simulating drug delivery to the arterial wall: (i) two-dimensional drug-coated balloons and (ii) three-dimensional drug-eluting stents. Simulations were performed on computational mesh configurations of increasing density. Supervised learners based on Gaussian process modelling were constructed from combinations of coarse mesh setting solutions of drug concentrations and nearest neighbourhood distance information as inputs, and higher fidelity mesh solutions as outputs. These learners were then used as computationally inexpensive surrogates to extend predictions using low fidelity information to higher levels of mesh refinement. The cross-validated, supervised learner-based predictions improved fidelity as compared with computational simulations performed at coarse level meshes--a result consistent across all outputs and computational models considered. Supervised learning on coarse mesh solutions can augment traditional physics-based modelling of complex physiologic phenomena. By obtaining efficient solutions at a fraction of the computational cost, this framework has the potential to transform how modelling approaches can be applied in the evaluation of medical technologies and their real-time administration in an increasingly personalized fashion.

  4. Enhancing Application Layer Multicast Solutions by Wireless Underlay Support

    NASA Astrophysics Data System (ADS)

    Hübsch, Christian; Waldhorst, Oliver P.

    Application Layer Multicast (ALM) is an attractive solution to overcome the deployment problems of IP-Multicast. We show how to cope with the challenges of incorporating wireless devices into ALM protocols. As a first approach we extend the NICE protocol, significantly increasing its performance in scenarios with many devices connected through wireless LAN.

  5. Electronic states of graphene nanoribbons and analytical solutions

    PubMed Central

    Wakabayashi, Katsunori; Sasaki, Ken-ichi; Nakanishi, Takeshi; Enoki, Toshiaki

    2010-01-01

    Graphene is a one-atom-thick layer of graphite, where low-energy electronic states are described by the massless Dirac fermion. The orientation of the graphene edge determines the energy spectrum of π-electrons. For example, zigzag edges possess localized edge states with energies close to the Fermi level. In this review, we investigate nanoscale effects on the physical properties of graphene nanoribbons and clarify the role of edge boundaries. We also provide analytical solutions for electronic dispersion and the corresponding wavefunction in graphene nanoribbons with their detailed derivation using wave mechanics based on the tight-binding model. The energy band structures of armchair nanoribbons can be obtained by making the transverse wavenumber discrete, in accordance with the edge boundary condition, as in the case of carbon nanotubes. However, zigzag nanoribbons are not analogous to carbon nanotubes, because in zigzag nanoribbons the transverse wavenumber depends not only on the ribbon width but also on the longitudinal wavenumber. The quantization rule of electronic conductance as well as the magnetic instability of edge states due to the electron–electron interaction are briefly discussed. PMID:27877361

  6. TOPICAL REVIEW Electronic states of graphene nanoribbons and analytical solutions

    NASA Astrophysics Data System (ADS)

    Wakabayashi, Katsunori; Sasaki, Ken-ichi; Nakanishi, Takeshi; Enoki, Toshiaki

    2010-10-01

    Graphene is a one-atom-thick layer of graphite, where low-energy electronic states are described by the massless Dirac fermion. The orientation of the graphene edge determines the energy spectrum of π-electrons. For example, zigzag edges possess localized edge states with energies close to the Fermi level. In this review, we investigate nanoscale effects on the physical properties of graphene nanoribbons and clarify the role of edge boundaries. We also provide analytical solutions for electronic dispersion and the corresponding wavefunction in graphene nanoribbons with their detailed derivation using wave mechanics based on the tight-binding model. The energy band structures of armchair nanoribbons can be obtained by making the transverse wavenumber discrete, in accordance with the edge boundary condition, as in the case of carbon nanotubes. However, zigzag nanoribbons are not analogous to carbon nanotubes, because in zigzag nanoribbons the transverse wavenumber depends not only on the ribbon width but also on the longitudinal wavenumber. The quantization rule of electronic conductance as well as the magnetic instability of edge states due to the electron-electron interaction are briefly discussed.

  7. Ground state solutions for semilinear time-harmonic Maxwell equations

    NASA Astrophysics Data System (ADS)

    Tang, Xianhua; Qin, Dongdong

    2016-04-01

    This paper is concerned with the time-harmonic semilinear Maxwell equation: ∇ × (∇ × u) + λu = f(x, u) in Ω with the boundary condition ν × u = 0 on ∂Ω, where Ω ⊂ ℝ3 is a simply connected, smooth, bounded domain with connected boundary and ν : ∂Ω → ℝ3 is the exterior normal. Here ∇ × denotes the curl operator in ℝ3 and the boundary condition holds when Ω is surrounded by a perfect conductor. By using the generalized Nehari manifold method due to Szulkin and Weth [Handbook of Nonconvex Analysis and Applications (International Press, Somerville, 2010), pp. 597-632] and some new techniques, existence of ground state solutions for above equation is established under some generic conditions on f.

  8. Extended law of corresponding states for protein solutions

    NASA Astrophysics Data System (ADS)

    Platten, Florian; Valadez-Pérez, Néstor E.; Castañeda-Priego, Ramón; Egelhaaf, Stefan U.

    2015-05-01

    The so-called extended law of corresponding states, as proposed by Noro and Frenkel [J. Chem. Phys. 113, 2941 (2000)], involves a mapping of the phase behaviors of systems with short-range attractive interactions. While it has already extensively been applied to various model potentials, here we test its applicability to protein solutions with their complex interactions. We successfully map their experimentally determined metastable gas-liquid binodals, as available in the literature, to the binodals of short-range square-well fluids, as determined by previous as well as new Monte Carlo simulations. This is achieved by representing the binodals as a function of the temperature scaled with the critical temperature (or as a function of the reduced second virial coefficient) and the concentration scaled by the cube of an effective particle diameter, where the scalings take into account the attractive and repulsive contributions to the interaction potential, respectively. The scaled binodals of the protein solutions coincide with simulation data of the adhesive hard-sphere fluid. Furthermore, once the repulsive contributions are taken into account by the effective particle diameter, the temperature dependence of the reduced second virial coefficients follows a master curve that corresponds to a linear temperature dependence of the depth of the square-well potential. We moreover demonstrate that, based on this approach and cloud-point measurements only, second virial coefficients can be estimated, which we show to agree with values determined by light scattering or by Derjaguin-Landau-Verwey-Overbeek (DLVO)-based calculations.

  9. Steady state solutions to dynamically loaded periodic structures

    NASA Technical Reports Server (NTRS)

    Kalinowski, A. J.

    1980-01-01

    The general problem of solving for the steady state (time domain) dynamic response (i.e., NASTRAN rigid format-8) of a general elastic periodic structure subject to a phase difference loading of the type encountered in traveling wave propagation problems was studied. Two types of structural configurations were considered; in the first type, the structure has a repeating pattern over a span that is long enough to be considered, for all practical purposes, as infinite; in the second type, the structure has structural rotational symmetry in the circumferential direction. The theory and a corresponding set of DMAP instructions which permits the NASTRAN user to automatically alter the rigid format-8 sequence to solve the intended class of problems are presented. Final results are recovered as with any ordinary rigid format-8 solution, except that the results are only printed for the typical periodic segment of the structure. A simple demonstration problem having a known exact solution is used to illustrate the implementation of the procedure.

  10. Crystallization of probucol from solution and the glassy state.

    PubMed

    Kawakami, Kohsaku; Ohba, Chie

    2017-01-30

    Crystallization of probucol (PBL) from both solution and glassy solid state was investigated. In the crystallization study from solution, six solvents and three methods, i.e., evaporation, addition of a poor solvent, and cooling on ice, were used to obtain various crystal forms. In addition to common two crystal forms (forms I and II), two further forms (forms III and cyclohexane-solvate) were found in this study, and their thermodynamic relationships were determined. Forms I and II are likely to be enantiotropically related with thermodynamic transition temperature below 5°C. Isothermal crystallization studies revealed that PBL glass initially crystallized into form III between 25 and 50°C, and then transformed to form I. The isothermal crystallization appears to be a powerful option to find uncommon crystal forms. The crystallization of PBL was identified to be pressure controlled, thus the physical stability of PBL glass is higher than that of typical compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. NEXAFS Chemical State and Bond Lengths of p-Aminobenzoic Acid in Solution and Solid State

    NASA Astrophysics Data System (ADS)

    Stevens, J. S.; Gainar, A.; Suljoti, E.; Xiao, J.; Golnak, R.; Aziz, E. F.; Schroeder, S. L. M.

    2016-05-01

    Solid-state and solution pH-dependent NEXAFS studies allow direct observation of the electronic state of para-aminobenzoic acid (PABA) as a function of its chemical environment, revealing the chemical state and bonding of the chemical species. Variations in the ionization potential (IP) and 1s→π* resonances unequivocally identify the chemical species (neutral, cationic, or anionic) present and the varying local environment. Shifts in σ* shape resonances relative to the IP in the NEXAFS spectra vary with C-N bond length, and the important effect of minor alterations in bond length is confirmed with nitrogen FEFF calculations, leading to the possibility of bond length determination in solution.

  12. Enhanced consumption of salient solutions following pedunculopontine tegmental lesions

    PubMed Central

    MacLaren, Duncan AA; Markovic, Tamara; Daniels, Derek; Clark, Stewart D

    2014-01-01

    Rats with lesions of the pedunculopontine tegmental nucleus (PPTg) reliably overconsume high concentration sucrose solution. This effect is thought to be indicative of response-perseveration or loss of behavioral control in conditions of high excitement. While these theories have anatomical and behavioral support, they have never been explicitly tested. Here, we used a contact lickometer to examine the microstructure of drinking behavior to gain insight into the behavioral changes during overconsumption. Rats received either excitotoxic (ibotenic acid) damage to all PPTg neuronal subpopulations or selective depletion of the cholinergic neuronal sub-population (Dtx-UII lesions). We offered rats a variety of pleasant, neutral and aversive tastants to assess the generalizability and specificity of the overconsumption effect. Ibotenic lesioned rats consumed significantly more 20% sucrose than sham controls, and did so through licking significantly more times. However, the behavioral microstructure during overconsumption was unaffected by the lesion and showed no indications of response-perseveration. Furthermore, the overconsumption effect did not generalize to highly consumed saccharin. In contrast, while only consuming small amounts of quinine solution, ibotenic lesioned rats had significantly more licks and bursts for this tastant. Selective depletion of cholinergic PPTg neurons had no effect on consumption of any tastant. We then assessed whether it is the salience of the solution which determines overconsumption by ibotenic lesioned rats. While maintained on free-food, ibotenic lesioned rats had normal consumption of sucrose and hypertonic saline. After mild food deprivation ibotenic PPTg lesioned rats overconsumed 20% sucrose. Subsequently, after dietary induced sodium deficiency, lesioned rats consumed significantly more saline than controls. These results establish that it is the salience of the solution which is the determining factor leading to

  13. Security enhanced memory for quantum state.

    PubMed

    Mukai, Tetsuya

    2017-07-27

    Security enhancement is important in terms of both classical and quantum information. The recent development of a quantum storage device is noteworthy, and a coherence time of one second or longer has been demonstrated. On the other hand, although the encryption of a quantum bit or quantum memory has been proposed theoretically, no experiment has yet been carried out. Here we report the demonstration of a quantum memory with an encryption function that is realized by scrambling and retrieving the recorded quantum phase. We developed two independent Ramsey interferometers on an atomic ensemble trapped below a persistent supercurrent atom chip. By operating the two interferometers with random phases, the quantum phase recorded by a pulse of the first interferometer was modulated by the second interferometer pulse. The scrambled quantum phase was restored by employing another pulse of the second interferometer with a specific time delay. This technique paves way for improving the security of quantum information technology.

  14. Enzymatic treatment of spermatozoa with a trypsin solution, SpermSolute: improved motility and enhanced ATP concentration.

    PubMed

    Figenschau, Y; Bertheussen, K

    1999-10-01

    We have developed a solution, fully described in this report, that can be used in a pretreatment procedure to promote liquefaction and to enhance motility during preparation of spermatozoa. It was applied to native ejaculates prior to swim-up and, in parallel investigations, motility and adenosine triphosphate concentration were compared in treated and untreated samples, which revealed that the solution significantly improved both parameters. The solution, named SpermSolute, is based on a proteinase (trypsin), which previously has been shown to stimulate the activity of a glycolytic key-enzyme. We speculate that our findings reflect intracellular enzyme activation and we suggest that our formula can be used in sperm preparation to prevent cell aggregates and to promote liquefaction, in addition to promotion of motility.

  15. States leverage telepsychiatry solutions to ease ED crowding, accelerate care.

    PubMed

    2015-02-01

    Many states are having success turning to telepsychiatry-based solutions to connect mental health patients with needed care while also decompressing crowded EDs. Just one year into a statewide telepsychiatry initiative in North Carolina (NC-STeP), administrators say the approach has saved as much as $7 million, and hospital demand for the service is higher than anticipated. In Texas, mental health emergency centers (MHEC) that use telepsychiatry to connect patients in rural areas with needed psychiatric care are freeing up EDs to focus on medical care. In just 11 months, 91 North Carolina hospitals have at least started the process to engage in NC-STeP. Much of the savings from NC-STeP come from involuntary commitment orders being overturned as a result of the telepsychiatry consults, reducing the need for expensive inpatient care. Implementing NC-STeP has involved multiple hurdles including credentialing difficulties and technical/firewall challenges. The Texas model provides 24/7 availability of psychiatrists via telemedicine through a network of MHECs. In-person staff at the MHECs perform basic screening tests and blood draws so that medical clearance can be achieved without the need for an ED visit in most cases. Funding for the MHECs comes from the state, hospitals in the region, and local governmental authorities that reap savings or benefits from the initiative.

  16. Sensitivity Enhancement in Solution NMR: Emerging Ideas and New Frontiers

    PubMed Central

    Lee, Jung Ho; Okuno, Yusuke; Cavagnero, Silvia

    2014-01-01

    Modern NMR spectroscopy has reached an unprecedented level of sophistication in the determination of biomolecular structure and dynamics at atomic resolution in liquids. However, the sensitivity of this technique is still too low to solve a variety of cutting-edge biological problems in solution, especially those that involve viscous samples, very large biomolecules or aggregation-prone systems that need to be kept at low concentration. Despite the challenges, a variety of efforts have been carried out over the years to increase sensitivity of NMR spectroscopy in liquids. This review discusses basic concepts, recent developments and future opportunities in this exciting area of research. PMID:24656077

  17. Uniform Treatment of Solute-Solvent Dispersion in the Ground and Excited Electronic States of the Solute Based on a Solvation Model with State-Specific Polarizability.

    PubMed

    Marenich, Aleksandr V; Cramer, Christopher J; Truhlar, Donald G

    2013-08-13

    We present a new kind of treatment of the solute-solvent dispersion contribution to the free energy of solvation using a solvation model with state-specific polarizability (SMSSP). To evaluate the solute-solvent dispersion contribution, the SMSSP model utilizes only two descriptors, namely, the spherically averaged dipole polarizability of the solute molecule (either in its ground or excited electronic state) and the refractive index of the solvent. The model was parametrized over 643 ground-state solvation free energy data for 231 solutes in 14 nonpolar, non-hydrogen-bonding solvents. We show that the SMSSP model is applicable to solutes in both the ground and the excited electronic state. For example, in comparison to available experimental data, the model yields qualitatively accurate predictions of the solvatochromic shifts for a number of systems where solute-solvent dispersion is the dominant contributor to the shift.

  18. Water-enhanced solvation of organic solutes in ketone and ester solvents

    SciTech Connect

    Lee, J.H.; Brunt, V. van; King, C.J. . Dept. of Chemical Engineering Lawrence Berkeley Lab., CA )

    1994-05-01

    Previous research has shown that the solubilities of dicarboxylic acids in certain electron-donor solvents are substantially increased in the presence of water. Information on solubilities, liquid-liquid equilibria and maximum-boiling ternary azeotropes was screened so as to identify other systems where codissolved water appears to enhance solvation of organic solutes in solvents. Several carboxylic acids, an alcohol, diols, and phenols were selected for examination as solutes in ketone and ester solvents. Effects of water upon solute solubilities and volatilities were measured. Results showed that water-enhanced solvation is greatest for carboxylic acids. Solute activity coefficients decreased by factors of 2--3, 6--8, and 7--10 due to the presence of water for mono-, di and tricarboxylic acids, respectively. Activity coefficients decreased by a factor of about 1.5 for ethanol and 1,2-propanediol as solutes. Water-enhanced solvation of phenols is small, when existent.

  19. Analytical solution for enhanced recharge around a bedrock exposure caused by deep-aquifer dewatering through a variable thickness aquitard

    NASA Astrophysics Data System (ADS)

    Kompanizare, Mazda; Price, Jonathan S.

    2014-12-01

    In this study an analytical solution was developed to predict steady radially-symmetric percolation rates from an aquifer underlain by a variable thickness aquitard. The solutions consider an aquitard with constant thickness and with radial-symmetrically increasing thickness outward from the center. The solution was used to predict the percolation rate from a peat layer around a bedrock outcrop in the James Bay Lowland near the De Beers Victor diamond mine. In this case the marine sediment layer limited the direct connection between the peat layer and the bedrock as an aquitard. Our zero order solution with constant marine sediment thickness showed the best fit to the steady state water level data of June 2012. It was found that the enhanced recharge around bioherms (i.e., at rates greater than the regional average of 0.7 mm/day) will only occur in marine sediments less than 4.3 m thick, for extreme depressurization of 30 m.

  20. Enhanced electrodes for solid state gas sensors

    DOEpatents

    Garzon, Fernando H.; Brosha, Eric L.

    2001-01-01

    A solid state gas sensor generates an electrical potential between an equilibrium electrode and a second electrode indicative of a gas to be sensed. A solid electrolyte substrate has the second electrode mounted on a first portion of the electrolyte substrate and a composite equilibrium electrode including conterminous transition metal oxide and Pt components mounted on a second portion of the electrolyte substrate. The composite equilibrium electrode and the second electrode are electrically connected to generate an electrical potential indicative of the gas that is being sensed. In a particular embodiment of the present invention, the second electrode is a reference electrode that is exposed to a reference oxygen gas mixture so that the electrical potential is indicative of the oxygen in a gas stream.

  1. Enhanced Inflationary Trispectrum from a Non-Vacuum Initial State

    NASA Astrophysics Data System (ADS)

    Agullo, I.; Navarro-Salas, J.; Parker, L.

    2015-01-01

    We work out the primordial inflationary trispectrum for curvature perturbations in models with standard kinetic terms, when the initial quantum state is not necessarily the Bunch-Davies vacuum state. The presence of initial perturbations enhances the trispectrum amplitude for squeezed configurations, in parallel to the bispectrum enhancement. For those squeezed configurations the trispectrum acquires the so-called local form, with a scale dependent amplitude that can get values larger than the prediction of the so-called Maldacena consistency relation. The enhancement factor could be as large as 106, and could reach the sensitivity of forthcoming observations, even for single-field inflationary models.

  2. Solution-state polymer assemblies influence BCS class II drug dissolution and supersaturation maintenance.

    PubMed

    Dalsin, Molly C; Tale, Swapnil; Reineke, Theresa M

    2014-02-10

    Spray dried dispersions (SDDs), solid dispersions of polymer excipients and active pharmaceuticals, are important to the field of oral drug delivery for improving active stability, bioavailability, and efficacy. Herein, we examine the influence of solution-state polymer assemblies on amorphous spray-dried dispersion (SDD) performance with two BCS II model drugs, phenytoin and probucol. These drugs were spray dried with 4 model polymer excipients consisting of poly(ethylene-alt-propylene) (PEP), N,N,-dimethylacrylamide (DMA), or 2-methacrylamido glucopyranose (MAG): amphiphilic diblock ter- and copolymers, PEP-P(DMA-grad-MAG) and PEP-PDMA, and their respective hydrophilic analogues, P(DMA-grad-MAG) and PDMA. Selective and nonselective solvents for the hydrophilic block of the diblock ter- and copolymers were used to induce or repress solution-state assemblies prior to spray drying. Prespray dried solution-state assemblies of these four polymers were probed with dynamic light scattering (DLS) and showed differences in solution assembly size and structure (free polymer versus aggregates versus micelles). Solid-state structures of spray dried dispersions (SDDs) showed a single glass transition event implying a homogeneous mixture of drug/polymer. Crystallization temperatures and enthalpies indicated that the drugs interact mostly with the DMA-containing portions of the polymers. Scanning electron microscopy was used to determine SDD particle size and morphology for the various polymer-drug pairings. In vitro dissolution tests showed excellent performance for one system, spray-dried PEP-PDMA micelles with probucol. Dissolution structures were investigated through DLS to determine drug-polymer aggregates that lead to enhanced SDD performance. Forced aggregation of the polymer into regular micelle structures was found to be a critical factor to increase the dissolution rate and supersaturation maintenance of SDDs, and may be an attractive platform to exploit in excipient

  3. Realities and Choices: Helping States Enhance Family Economic Security.

    ERIC Educational Resources Information Center

    Venner, Sandra

    This document, which is designed to help state administrators and legislators formulate policies enhancing family economic security, summarizes research findings regarding barriers to economic self-sufficiency and policies used by various states to improve poor family's available work opportunities and economic security. Discussed in the…

  4. Incorporating convection into one-dimensional solute redistribution during crystal growth from the melt I. The steady-state solution

    NASA Astrophysics Data System (ADS)

    Yen, C. T.; Tiller, W. A.

    1992-03-01

    A one-dimensional mathematical analysis is made of the redistribution of solute which occurs during crystal growth from a convected melt. In this analysis, the important contribution from lateral melt convection to one-dimensional solute redistribution analysis is taken into consideration via an annihilation/creation term in the one-dimensional solute transport equation. Calculations of solute redistribution under steady-state conditions have been carried out analytically. It is found that this new solute redistribution model overcomes several weaknesses that occur when applying the Burton, Prim and Slichter solute segregation equation (1953) in real melt growth situations. It is also found that, with this correction, the diffusion coefficients for solute's in liquid silicon are now found to be in the same range as other liquid metal diffusion coefficients.

  5. Enhanced Communication Network Solution for Positive Train Control Implementation

    NASA Technical Reports Server (NTRS)

    Fatehi, M. T.; Simon, J.; Chang, W.; Chow, E. T.; Burleigh, S. C.

    2011-01-01

    The commuter and freight railroad industry is required to implement Positive Train Control (PTC) by 2015 (2012 for Metrolink), a challenging network communications problem. This paper will discuss present technologies developed by the National Aeronautics and Space Administration (NASA) to overcome comparable communication challenges encountered in deep space mission operations. PTC will be based on a new cellular wireless packet Internet Protocol (IP) network. However, ensuring reliability in such a network is difficult due to the "dead zones" and transient disruptions we commonly experience when we lose calls in commercial cellular networks. These disruptions make it difficult to meet PTC s stringent reliability (99.999%) and safety requirements, deployment deadlines, and budget. This paper proposes innovative solutions based on space-proven technologies that would help meet these challenges: (1) Delay Tolerant Networking (DTN) technology, designed for use in resource-constrained, embedded systems and currently in use on the International Space Station, enables reliable communication over networks in which timely data acknowledgments might not be possible due to transient link outages. (2) Policy-Based Management (PBM) provides dynamic management capabilities, allowing vital data to be exchanged selectively (with priority) by utilizing alternative communication resources. The resulting network may help railroads implement PTC faster, cheaper, and more reliably.

  6. Enhanced Communication Network Solution for Positive Train Control Implementation

    NASA Technical Reports Server (NTRS)

    Fatehi, M. T.; Simon, J.; Chang, W.; Chow, E. T.; Burleigh, S. C.

    2011-01-01

    The commuter and freight railroad industry is required to implement Positive Train Control (PTC) by 2015 (2012 for Metrolink), a challenging network communications problem. This paper will discuss present technologies developed by the National Aeronautics and Space Administration (NASA) to overcome comparable communication challenges encountered in deep space mission operations. PTC will be based on a new cellular wireless packet Internet Protocol (IP) network. However, ensuring reliability in such a network is difficult due to the "dead zones" and transient disruptions we commonly experience when we lose calls in commercial cellular networks. These disruptions make it difficult to meet PTC s stringent reliability (99.999%) and safety requirements, deployment deadlines, and budget. This paper proposes innovative solutions based on space-proven technologies that would help meet these challenges: (1) Delay Tolerant Networking (DTN) technology, designed for use in resource-constrained, embedded systems and currently in use on the International Space Station, enables reliable communication over networks in which timely data acknowledgments might not be possible due to transient link outages. (2) Policy-Based Management (PBM) provides dynamic management capabilities, allowing vital data to be exchanged selectively (with priority) by utilizing alternative communication resources. The resulting network may help railroads implement PTC faster, cheaper, and more reliably.

  7. Solid state lighting for the developing world: the only solution

    NASA Astrophysics Data System (ADS)

    Peon, Rudolfo; Doluweera, Ganesh; Platonova, Inna; Irvine-Halliday, Dave; Irvine-Halliday, Gregor

    2005-09-01

    Approximately two billion people, one third of humanity still has no access to electricity, and thus relies on fuel-based lighting, a dangerous alternative of last resort that is unhealthy, expensive, and offers very poor levels of illumination. This lack of light makes it difficult to perform most evening activities including studies by children and adults alike and therefore represents a significant barrier to human development. Over the past five years The Light Up The World Foundation (LUTW) has pioneered the use of the white light emitting diode (WLED) as an alternative home lighting solution, bringing clean, affordable light to thousands of non-electrified homes around the world. The information presented herein is intended to increase awareness of the enormous potential possessed by this emergent technology, "Solid State Lighting" (SSL), to improve the quality of life of millions of people around the world. The feasibility of its implementation is demonstrated with results from comprehensive field experience and laboratory research work. The mutual economic, social and environmental benefits for both stakeholders and SSL suppliers are discussed. Strategies conducive to the dissemination of this technology throughout the developing world are also presented.

  8. Solution-based metal enhanced fluorescence with gold and gold/silver core-shell nanorods

    NASA Astrophysics Data System (ADS)

    Ren, Zebin; Li, Xiaoyi; Guo, Jingxia; Wang, Ruibo; Wu, Yanni; Zhang, Mingdi; Li, Caixia; Han, Qingyan; Dong, Jun; Zheng, Hairong

    2015-12-01

    Metal enhanced fluorescence of Oxazine720 fluorophore with gold and gold/silver core-shell nanorods is investigated experimentally in aqueous solution system. Metallic nanorods are synthesized for providing proper localized surface plasmon resonance and necessary enhancement to the fluorophore molecule. The experimental observation shows that the fluorescence enhancement increases firstly and then decreases when the concentration of metallic nanorods increases, which is resulted by the competition between enhanced emission and inner-filtering effect. Further investigation with different amounts of metallic nanorods shows that the relationship between metal enhanced fluorescence and spectral correlation strongly depends on the concentration of metallic nanorods.

  9. Enhancing performance characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C [Santa Barbara, CA; Heeger, Alan J [Santa Barbara, CA; Moses, Daniel [Santa Barbara, CA; Peet, Jeffrey [Goleta, CA

    2013-09-25

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  10. Enhancing performing characteristics of organic semiconducting films by improved solution processing

    SciTech Connect

    Bazan, Guillermo C; Moses, Daniel; Peet, Jeffrey; Heeger, Alan J

    2014-05-13

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  11. Enhancing performance characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C; Mikhailovsky, Alexander; Moses, Daniel; Nguyen, Thuc-Quyen; Peet, Jeffrey; Soci, Cesare

    2012-11-27

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  12. Carbohydrate Electrolyte Solutions Enhance Endurance Capacity in Active Females

    PubMed Central

    Sun, Feng-Hua; Wong, Stephen Heung-Sang; Chen, Shi-Hui; Poon, Tsz-Chun

    2015-01-01

    The purpose of the present study was to investigate the effects of supplementation with a carbohydrate-electrolyte solution (CES) in active females during a prolonged session of submaximal running to exhaustion. Eight healthy active females volunteered to perform a session of open-ended running to exhaustion at 70% of their maximal oxygen consumption on a treadmill during the follicular phase of their menstrual cycle on two occasions. During each run, the subjects consumed either 3mL·kg−1 body mass of a 6% CES or a placebo drink (PL) every 20 min during exercise. The trials were administered in a randomized double-blind, cross-over design. During the run, the subjects ingested similar volumes of fluid in two trials (CES: 644 ± 75 mL vs. PL: 593 ± 66 mL, p > 0.05). The time to exhaustion was 16% longer during the CES trial (106.2 ± 9.4 min) than during the PL trial (91.6 ± 5.9 min) (p < 0.05). At 45 min during exercise, the plasma glucose concentration in the CES trial was higher than that in PL trial. No differences were observed in the plasma lactate level, respiratory exchange ratio, heart rate, perceived rate of exertion, sensation of thirst, or abdominal discomfort between the two trials (p > 0.05). The results of the present study confirm that CES supplementation improves the moderate intensity endurance capacity of active females during the follicular phases of the menstrual cycle. However, the exogenous oxidation of carbohydrate does not seem to explain the improved capacity after CES supplementation. PMID:25988766

  13. The nature of enhanced linear and nonlinear optical effects in fullerene solutions

    SciTech Connect

    Sheka, E. F. Razbirin, B. S. Starukhin, A. N.; Nelson, D. K.; Degunov, M. Yu.; Lyubovskaya, R. N.; Troshin, P. A.

    2009-05-15

    The 'blue' emission from fullerene C{sub 60} and its derivatives in frozen toluene solution is discovered and analyzed in the framework of the electromagnetic theory of enhanced optical effects. It is shown that the emission, combining enhanced spectra of Raman scattering and one-photon luminescence, is due to clustering of fullerene molecules in solution. Photoexcitation of charge-transfer excitons in clusters provides the polarization required for the enhancement. A direct relationship is established between the observed phenomenon and nonlinear optical properties of the medium. Empirical and computational tests are proposed to select matrices with various nonlinear optical properties.

  14. Unsteady-state transfer of impurities during crystal growth of sucrose in sugarcane solutions

    NASA Astrophysics Data System (ADS)

    Martins, P. M.; Ferreira, A.; Polanco, S.; Rocha, F.; Damas, A. M.; Rein, P.

    2009-07-01

    In this work, we present growth rate data of sucrose crystals in the presence of impurities that can be used by both sugar technologists and crystal growth scientists. Growth rate curves measured in a pilot-scale evaporative crystallizer suggest a period of slow growth that follows the seeding of crystals into supersaturated technical solutions. The observed trend was enhanced by adding typical sugarcane impurities such as starch, fructose or dextran to the industrial syrups. Maximum growth rates of sucrose resulted at intermediate rather than high supersaturation levels in the presence of the additives. The effects of the additives on the sucrose solubility and sucrose mass transfer in solution were taken into account to explain the observed crystal growth kinetics. A novel mechanism was identified of unsteady-state adsorption of impurities at the crystal surface and their gradual replacement by the crystallizing solute towards the equilibrium occupation of the active sites for growth. Specifically designed crystallization experiments at controlled supersaturation confirmed this mechanism by showing increasing crystal growth rates with time until reaching a steady-state value for a given supersaturation level and impurity content.

  15. Novel silver nanoparticle-enhanced fluorometric determination of trace tetracyclines in aqueous solutions.

    PubMed

    Wang, Ping; Wu, Tun-Hua; Zhang, Yong

    2016-01-01

    Metal-enhanced fluorescence (MEF) has exhibited promise for applications in fluorometric assays. The effects of silver nanoparticles (AgNP) on the fluorescence behaviours of tetracycline hydrochloride (TCH) and chlortetracycline hydrochloride (CTC) in aqueous solutions were investigated. The experimental results demonstrated that the fluorescence intensities of each tetracycline in water solutions were greatly enhanced by AgNP through the MEF effect. In addition, a novel silver nanoparticle-enhanced fluorometric method was established for the direct determination of TCH and CTC in aqueous solutions. Under optimum experimental conditions, the linear dynamic ranges for the determination of TCH and CTC in aqueous solutions varied from 0.10 to 6.0 mg L(-1) and 0.050 to 3.0 mg L(-1) with detection limits of 0.63 µg L(-1) and 0.19 µg L(-1), respectively, and with the relative standard deviation of less than 1.9% (n=9). The experimental recovery results for the determination of TCH and CTC in aqueous solutions ranged from 93-106% and 95-104%, respectively. Compared with the established method without the addition of AgNP, the limits of quantitation of the silver nanoparticle-enhanced fluorometric method were approximately 5-fold lower for TCH and 3-fold lower for CTC. Moreover, the newly established silver nanoparticle-enhanced fluorometric method was successfully applied to the direct determination of TCH and CTC in pharmaceutical preparations.

  16. Effect of solution saturation state and temperature on diopside dissolution

    PubMed Central

    Dixit, Suvasis; Carroll, Susan A

    2007-01-01

    Steady-state dissolution rates of diopside are measured as a function of solution saturation state using a titanium flow-through reactor at pH 7.5 and temperature ranging from 125 to 175°C. Diopside dissolved stoichiometrically under all experimental conditions and rates were not dependent on sample history. At each temperature, rates continuously decreased by two orders of magnitude as equilibrium was approached and did not exhibit a dissolution plateau of constant rates at high degrees of undersaturation. The variation of diopside dissolution rates with solution saturation can be described equally well with a ion exchange model based on transition state theory or pit nucleation model based on crystal growth/dissolution theory from 125 to 175°C. At 175°C, both models over predict dissolution rates by two orders of magnitude indicating that a secondary phase precipitated in the experiments. The ion exchange model assumes the formation of a Si-rich, Mg-deficient precursor complex. Lack of dependence of rates on steady-state aqueous calcium concentration supports the formation of such a complex, which is formed by exchange of protons for magnesium ions at the surface. Fit to the experimental data yields R a t e   ( m o l d i o p s i d e c m − 2 s − 1 ) = k × 10 − E a / 2.303 R T ( a H + 2 a M g 2 + ) n MathType@MTEF@5@5@+=feaafiart1ev1aaatCvAUfKttLearuWrP9MDH5MBPbIqV92AaeXatLxBI9gBaebbnrfifHhDYfgasaacH8akY=wiFfYdH8Gipec8Eeeu0xXdbba9frFj0=OqFfea0dXdd9vqai=hGuQ8kuc9pgc9s8qqaq=dirpe0xb9q8qiLsFr0=vr0=vr0dc8meaabaqaciaacaGaaeqabaqabeGadaaakeaaieaacqWFsbGucqWFHbqycqWF0baDcqWFLbqzcqqGGaaicqGGOaakcqWFTbqBcqWFVbWBcqWFSbaBcqWFGaaicqWFKbazcqWFPbqAcqWFVbWBcqWFWbaCcqWFZbWCcqWFPbqAcqWFKbazcqWFLbqzcqWFGaaicqWFJbWycqWFTbqBdaahaaWcbeqaaiabgkHiTiabikdaYaaakiab=bcaGiab=nhaZnaaCaaaleqabaGaeyOeI0IaeGymaedaaOGaeiykaKIaeyypa0Jaem4AaSMaey41aqRaeeymaeJaeeimaaZaaWbaaSqabeaacqGHsislcqWGfbqrdaWgaaadbaGaemyyaegabeaaliabc+caViabikdaYiabc6caUiabioda

  17. Evidence for Two New Solution States of Ubiquitin by IMS–MS Analysis

    PubMed Central

    2015-01-01

    Ion mobility spectrometry coupled with mass spectrometry (IMS–MS) is used to investigate the populations of different states for ubiquitin in water:methanol solutions. In these experiments, ubiquitin is electrosprayed from 20 water:methanol (100:0 to 5:95, pH = 2) solutions, ranging from native to denaturing conditions. With an increased percentage of methanol in solution, ubiquitin ions ([M + 7H]7+ to [M + 12H]12+) show substantial variations in both charge state distributions and ion mobility distributions. Analysis of these data provides evidence for the existence of five ubiquitin states in solution: the native N state, favored in solutions of 100:0 to 70:30 water:methanol for the +7 and +8 charge states; the more helical A state and a new closely related A′ state, favored in solutions of 70:30 to 5:95 water:methanol for the +9 to +12 charge states; the unfolded U state, populated in 40:60 to 5:95 water:methanol solutions for the +8 to +10 and +12 charge states; and a new low-abundance state termed the B state, observed for 100:0 to 70:30 water:methanol solutions in the +8 to +10 and +12 charge states. The relative abundances for different states in different solutions are determined. The analysis presented here provides insight into how solution structures evolve into anhydrous conformations and demonstrates the utility of IMS–MS methods as a means of characterizing populations of conformers for proteins in solution. PMID:24625065

  18. Relationships between the solution and solid-state properties of solution-cast low-k silica thin films.

    PubMed

    Chiang, Chao-Ching; Su, Chien-You; Yang, An-Chih; Wang, Ting-Yu; Lee, Wen-Ya; Hua, Chi-Chung; Kang, Dun-Yen

    2016-07-27

    This paper reports on the fabrication of low-k (amorphous) silica thin films cast from solutions without and with two different types of surfactants (TWEEN® 80 and Triton™ X-100) to elucidate the relationships between the structural/morphological features of the casting solutions and the physical properties of the resulting thin films. Cryogenic transmission microscopy (cryo-TEM), static/dynamic light scattering (SLS/DLS), and small-angle X-ray scattering (SAXS) revealed contrasting colloidal dispersion states and phase behavior among the three casting solutions. Casting solution with the Triton™ X-100 surfactant produced stable (>90 days) nanoparticles with good dispersion in solution (mean particle size ∼10 nm) as well as good mesopore volume (characterized by nitrogen physisorption) in powder and thin films of high mechanical strength (characterized by the nanoindentation test). The longer main chain and bulkier side units of the TWEEN® 80 surfactant led to stable micelle-nanoparticle coexisting dispersion, which resulted in the highest mesopore volume in powder and thin films with the lowest dielectric constant (∼3) among the samples in this study. The casting solution without the surfactant failed to produce a stabilized solution or thin films of acceptable uniformity. These findings demonstrate the possibility of fine-tuning low-k silica film properties by controlling the colloidal state of casting solutions.

  19. Controlling Molecular Ordering in Solution-State Conjugated Polymers

    SciTech Connect

    Zhu, Jiahua; Han, Youngkyu; Kumar, Rajeev; Hong, Kunlun; Bonnesen, Peter V.; Sumpter, Bobby G.; Smith, Gregory Scott; Ivanov, Ilia N.; Do, Changwoo

    2015-07-17

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in solution of conjugated polymers holds great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution, we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.

  20. Evidence of solute-solute interactions and cake enhanced concentration polarization during removal of pharmaceuticals from urban wastewater by nanofiltration.

    PubMed

    Azaïs, Antonin; Mendret, Julie; Petit, Eddy; Brosillon, Stephan

    2016-11-01

    The objective of this paper is to help understanding the distinctive influence of the matrix and of the flux decline (e.g. through the cake enhanced concentration polarization (CECP) phenomenon) on the removal mechanisms of four pharmaceutically active compounds (PhACs) from wastewater treatment plant (WWTP) effluent by nanofiltration (NF). PhACs which are commonly encountered in secondary treated effluent were spiked in various matrix (real and synthetic) to investigate the separate and synergetic effects of the organic and ionic environment on PhACs rejection by two commercial membranes (NF-90 and NF-270). With pure water, rejection of NF membranes is dependent on the type of PhACs and of the permeate flux variations. Then, it appeared that the rejection of PhACs by NF-90 was poorly influenced by the type of compounds, because of the prevalence of steric mechanisms, but rather influenced by permeate flux variations and thus to fouling. For this tight NF membrane, CECP impacts PhACs rejection at the start of filtration while after a dense cake is formed, it became enhanced. On the contrary, rejections of PhACs by the NF-270 were enhanced during the filtration of the real wastewater in comparison with spiked pure water. It appeared that for loose-NF membranes, PhACs rejection is mainly governed by solute-solute interactions (EfOM-compound association) or electrostatic membrane-solute interactions. Finally, it seems that calcium concentration of the effluent is a critical parameter for the rejection of PhACs as it alters both the availability of sites for PhACs association and the fouling layer density. Rejections of the NF-270 were negatively impacted in the presence of Ca(2+). Such a study has practical implications for further understanding of the fate of trace organic compounds during nanofiltration of wastewater for reuse applications.

  1. 44 CFR 201.5 - Enhanced State Mitigation Plans.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 44 Emergency Management and Assistance 1 2010-10-01 2010-10-01 false Enhanced State Mitigation Plans. 201.5 Section 201.5 Emergency Management and Assistance FEDERAL EMERGENCY MANAGEMENT AGENCY... initiatives (comprehensive, growth management, economic development, capital improvement, land development...

  2. Adsorption of fluoride from aqueous solution by enhanced chitosan/bentonite composite.

    PubMed

    Liu, Qian; Huang, Ruihua; Yang, Bingchao; Liu, Yanping

    2013-01-01

    In this work, enhanced chitosan/bentonite composite was prepared by treating chitosan/bentonite composite with concentrated hydrochloric acid (HCl). The adsorption of fluoride ions from aqueous solution onto the enhanced chitosan/bentonite composite was investigated. Adsorption studies were performed in a batch system, and the effects of various parameters, such as the pH value of the solution, adsorbent dosage and initial fluoride concentration, were evaluated. The optimum operating conditions for fluoride removal by the enhanced chitosan/bentonite composite were pH = 7 or so, and adsorbent dosage =1.2 g. Increasing initial fluoride concentration reduced the adsorption of fluoride onto the enhanced chitosan/bentonite composite. Furthermore, the presence of other co-anions weakened the adsorption of fluoride onto this adsorbent. The equilibrium adsorption isotherms were well described by both the Freundlich and Langmuir models. The maximum monolayer adsorption capacity was 2.95 mg/g at 293 K.

  3. Enabling Enhanced Company Operations (ECO): An Analysis of Tactical Communication Requirements and Solutions for a Marine Corps Company and Below

    DTIC Science & Technology

    2009-09-01

    OPTIMAL COMMUNICATION SOLUTION The optimal communication solution for enabling ECO is one that is designed to ensure interoperability. Current and...NAVAL POSTGRADUATE SCHOOL MONTEREY, CALIFORNIA THESIS ENABLING ENHANCED COMPANY OPERATIONS ( ECO ): AN ANALYSIS OF TACTICAL...AND SUBTITLE: Enabling Enhanced Company Operations ( ECO ): An Analysis of Tactical Communication Requirements and Solutions for a Marine Corps Company

  4. Post-processing of economic dispatch solutions for security enhancement based on approximate reasoning

    SciTech Connect

    Niimura, Takahide; Yokoyama, Ryuichi

    1996-05-01

    In this paper the authors present an approach to enhance the security of power systems by supplementing conventional economic dispatch solutions for less branch overload in case of contingencies. The supplementary control adjustment is determined by approximate reasoning based on qualitative rules and linguistic fuzzy sets. Fuzzy sets and reasoning procedure are defined for effective security enhancement of real power generation. Numerical examples prove that this approach efficiently produces more secure conditions against branch overload.

  5. Ultraviolet resonance Raman spectroscopy of explosives in solution and the solid state.

    PubMed

    Emmons, Erik D; Tripathi, Ashish; Guicheteau, Jason A; Fountain, Augustus W; Christesen, Steven D

    2013-05-23

    Resonance Raman cross sections of common explosives have been measured by use of excitation wavelengths in the deep-UV from 229 to 262 nm. These measurements were performed both in solution and in the native solid state for comparison. While measurements of UV Raman cross sections in solution with an internal standard are straightforward and commonly found in the literature, measurements on the solid phase are rare. This is due to the difficulty in preparing a solid sample in which the molecules of the internal standard and absorbing analyte/explosive experience the same laser intensity. This requires producing solid samples that are mixtures of strongly absorbing explosives and an internal standard transparent at the UV wavelengths used. For the solid-state measurements, it is necessary to use nanostructured mixtures of the explosive and the internal standard in order to avoid this bias due to the strong UV absorption of the explosive. In this study we used a facile spray-drying technique where the analyte of interest was codeposited with the nonresonant standard onto an aluminum-coated microscope slide. The generated resonance enhancement profiles and quantitative UV-vis absorption spectra were then used to plot the relative Raman return as a function of excitation wavelength and particle size.

  6. State Mindfulness During Meditation Predicts Enhanced Cognitive Reappraisal

    PubMed Central

    Hanley, Adam; Farb, Norman A.; Froeliger, Brett E.

    2013-01-01

    Putatively, mindfulness meditation involves generation of a state of “nonappraisal”, yet, little is known about how mindfulness may influence appraisal processes. We investigated whether the state and practice of mindfulness could enhance cognitive reappraisal. Participants (N = 44; M age = 24.44, SD = 4.00, range 19 – 38, 82.2% female) were randomized to either 1) mindfulness, 2) suppression, or 3) mind-wandering induction training conditions. Cognitive reappraisal was assessed with the Emotion Regulation Questionnaire (ERQ) prior to experimental induction, and state mindfulness was assessed immediately following induction using the Toronto Mindfulness Scale (TMS). Participants practiced their assigned strategy for one week and then were reassessed with the ERQ reappraisal subscale. Participants receiving mindfulness training reported significantly higher levels of state mindfulness than participants in the thought suppression and mind wandering conditions. Although brief mindfulness training did not lead to significantly greater increases in reappraisal than the other two conditions, state mindfulness during mindfulness meditation was prospectively associated with increases in reappraisal. Path analysis revealed that the indirect effect between mindfulness training and reappraisal was significant through state mindfulness. Degree of state mindfulness achieved during the act of mindfulness meditation significantly predicted increases in reappraisal over time, suggesting that mindfulness may promote emotion regulation by enhancing cognitive reappraisal. PMID:26085851

  7. State Mindfulness During Meditation Predicts Enhanced Cognitive Reappraisal.

    PubMed

    Garland, Eric L; Hanley, Adam; Farb, Norman A; Froeliger, Brett E

    2015-04-01

    Putatively, mindfulness meditation involves generation of a state of "nonappraisal", yet, little is known about how mindfulness may influence appraisal processes. We investigated whether the state and practice of mindfulness could enhance cognitive reappraisal. Participants (N = 44; M age = 24.44, SD = 4.00, range 19 - 38, 82.2% female) were randomized to either 1) mindfulness, 2) suppression, or 3) mind-wandering induction training conditions. Cognitive reappraisal was assessed with the Emotion Regulation Questionnaire (ERQ) prior to experimental induction, and state mindfulness was assessed immediately following induction using the Toronto Mindfulness Scale (TMS). Participants practiced their assigned strategy for one week and then were reassessed with the ERQ reappraisal subscale. Participants receiving mindfulness training reported significantly higher levels of state mindfulness than participants in the thought suppression and mind wandering conditions. Although brief mindfulness training did not lead to significantly greater increases in reappraisal than the other two conditions, state mindfulness during mindfulness meditation was prospectively associated with increases in reappraisal. Path analysis revealed that the indirect effect between mindfulness training and reappraisal was significant through state mindfulness. Degree of state mindfulness achieved during the act of mindfulness meditation significantly predicted increases in reappraisal over time, suggesting that mindfulness may promote emotion regulation by enhancing cognitive reappraisal.

  8. Considerable Enhancement of Emission Yields of [Au(CN)2(-)] Oligomers in Aqueous Solutions by Coexisting Cations.

    PubMed

    Wakabayashi, Ryo; Maeba, Junichi; Nozaki, Koichi; Iwamura, Munetaka

    2016-08-01

    The photophysical properties of [Au(CN)2(-)] oligomers in aqueous solutions were investigated as functions of coexisting cations as well as the viscosity and temperature of solutions. A solution of [Au(CN)2(-)] in the concentration range of 0.03-0.2 mol/dm(3) exhibited emission peaks at 460-480 nm because of the presence of oligomers larger than trimers. Although the emission yields (ϕem) of K[Au(CN)2] solutions were <1%, it considerably increased to 43% when 1.0 mol/dm(3) tetraethylammonium chloride (Et4NCl) was added. The lifetimes of the main emission bands were also significantly varied with additional salts, e.g., KCl, 15 ns; Et4NCl, 520 ns. The time-resolved emission measurements of [Au(CN)2(-)] in a water/glycerol mixture indicated that the lifetimes were almost directly proportional to the inverse of the viscosity of the solution. On the other hand, the intrinsic lifetimes of dimers and trimers with weak emission in shorter wavelength regions were very short and independent of the viscosity of the solutions and coexisting cations (dimer, ∼25 ps; trimer, ∼2 ns). These results indicated that the deactivation of the excited-state [Au(CN)2(-)]n oligomers (n ≥ 4) was dominated by the dissociation of the oligomers to a shorter species (dimer or trimer). The hydrophobic interactions between tetraalkylammonium cations and CN ligands remarkably stabilized the larger oligomers and suppressed the dissociation of the excited-state oligomers, which enhanced the emission yield of the oligomers. This work provides a new method of "exciplex tuning" by changing the environment of excited-state [Au(CN)2(-)]n oligomers.

  9. Ti(3+) Aqueous Solution: Hybridization and Electronic Relaxation Probed by State-Dependent Electron Spectroscopy.

    PubMed

    Seidel, Robert; Atak, Kaan; Thürmer, Stephan; Aziz, Emad F; Winter, Bernd

    2015-08-20

    The electronic structure of a Ti(3+) aqueous solution is studied by liquid-jet soft X-ray photoelectron (PE) spectroscopy. Measured valence and Ti 2p core-level binding energies, together with the Ti 2p resonant photoelectron (RPE) spectra and the derived partial electron-yield L-edge X-ray absorption (PEY-XA) spectra, reveal mixing between metal 3d and water orbitals. Specifically, ligand states with metal character are identified through the enhancement of signal intensities in the RPE spectra. An observed satellite 3d peak structure is assigned to several different metal-ligand states. Experimental energies and the delocalized nature of the respective orbitals are supported by ground-state electronic structure calculations. We also show that by choice of the detected Auger-electron-decay channel, from which different PEY-XA spectra are obtained, the experimental sensitivity to the interactions of the metal 3d electrons with the solvent can be varied. The effect of such a state-dependent electronic relaxation on the shape of the PEY-XA spectra is discussed in terms of different degrees of electron delocalization.

  10. Solid state and solution nitrate photochemistry: photochemical evolution of the solid state lattice.

    PubMed

    Asher, Sanford A; Tuschel, David D; Vargson, Todd A; Wang, Luling; Geib, Steven J

    2011-05-05

    We examined the deep UV 229 nm photochemistry of NaNO(3) in solution and in the solid state. In aqueous solution excitation within the deep UV NO(3)¯ strong π → π* transition causes the photochemical reaction NO(3)¯ → NO(2)¯ + O·. We used UV resonance Raman spectroscopy to examine the photon dose dependence of the NO(2)¯ band intensities and measure a photochemical quantum yield of 0.04 at pH 6.5. We also examined the response of solid NaNO(3) samples to 229 nm excitation and also observe formation of NO(2)¯. The quantum yield is much smaller at ∼10(-8). The solid state NaNO(3) photochemistry phenomena appear complex by showing a significant dependence on the UV excitation flux and dose. At low flux/dose conditions NO(2)¯ resonance Raman bands appear, accompanied by perturbed NO(3)¯ bands, indicating stress in the NaNO(3) lattice. Higher flux/dose conditions show less lattice perturbation but SEM shows surface eruptions that alleviate the stress induced by the photochemistry. Higher flux/dose measurements cause cratering and destruction of the NaNO(3) surface as the surface layers are converted to NO(2)¯. Modest laser excitation UV beams excavate surface layers in the solid NaNO(3) samples. At the lowest incident fluxes a pressure buildup competes with effusion to reach a steady state giving rise to perturbed NO(3)¯ bands. Increased fluxes result in pressures that cause the sample to erupt, relieving the pressure.

  11. Solution state structure determination of silicate oligomers by 29SI NMR spectroscopy and molecular modeling.

    PubMed

    Cho, Herman; Felmy, Andrew R; Craciun, Raluca; Keenum, J Patrick; Shah, Neil; Dixon, David A

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by (29)Si NMR homonuclear correlation experiments of (29)Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the (29)Si-(29)Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated cross-peaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stabilities of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  12. Solution State Structure Determination of Silicate Oligomers by 29Si NMR Spectroscopy and Molecular Modeling

    SciTech Connect

    Cho, Herman M.; Felmy, Andrew R.; Craciun, Raluca; Keenum, Johnathan P.; Shah, Neil K.; Dixon, David A.

    2006-02-22

    Evidence for nine new solution state silicate oligomers has been discovered by 29Si NMR homonuclear correlation experiments of 29Si-enriched samples. In addition to enhancing signal sensitivity, the isotopic enrichment increases the probability of the 29Si–29Si two-bond scalar couplings that are necessary for the observation of internuclear correlations in 2-D experiments. The proposed assignments are validated by comparisons of experimental and simulated crosspeaks obtained with high digital resolution. The internuclear connectivity indicated by the NMR data suggests that several of these oligomers can have multiple stereoisomers, including conformers and/or diastereomers. The stability of these oligomers and their possible stereoisomers have been investigated by electronic structure calculations.

  13. Osmotic Second Virial Coefficients of Aqueous Solutions from Two-Component Equations of State.

    PubMed

    Cerdeiriña, Claudio A; Widom, B

    2016-12-29

    Osmotic second virial coefficients in dilute aqueous solutions of small nonpolar solutes are calculated from three different two-component equations of state. The solutes are five noble gases, four diatomics, and six hydrocarbons in the range C1-C4. The equations of state are modified versions of the van der Waals, Redlich-Kwong, and Peng-Robinson equations, with an added hydrogen-bonding term for the solvent water. The parameters in the resulting equations of state are assigned so as to reproduce the experimental values and temperature dependence of the density, vapor pressure, and compressibility of the solvent, the gas-phase second virial coefficient of the pure solute, the solubility and partial molecular volume of the solute, and earlier estimates of the solutes' molecular radii. For all 15 solutes, the calculations are done for 298.15 K, whereas for CH4, C2H6, and C3H8 in particular, they are also done as functions of temperature over the full range 278.15-348.15 K. The calculated osmotic virial coefficients are compared with earlier calculations of these coefficients for these solutes and also with the results derived from earlier computer simulations of model aqueous solutions of methane. They are also compared with the experimental gas-phase second virial coefficients of the pure gaseous solutes to determine the effect the mediation of the solvent has on the resulting solute-solute interactions in the solution.

  14. Controlling Molecular Ordering in Solution-State Conjugated Polymers

    DOE PAGES

    Zhu, Jiahua; Han, Youngkyu; Kumar, Rajeev; ...

    2015-07-17

    Rationally encoding molecular interactions that can control the assembly structure and functional expression in solution of conjugated polymers holds great potential for enabling optimal organic optoelectronic and sensory materials. In this work, we show that thermally-controlled and surfactant-guided assembly of water-soluble conjugated polymers in aqueous solution is a simple and effective strategy to generate optoelectronic materials with desired molecular ordering. We have studied a conjugated polymer consisting of a hydrophobic thiophene backbone and hydrophilic, thermo-responsive ethylene oxide side groups, which shows a step-wise, multi-dimensional assembly in water. By incorporating the polymer into phase-segregated domains of an amphiphilic surfactant in solution,more » we demonstrate that both chain conformation and degree of molecular ordering of the conjugated polymer can be tuned in hexagonal, micellar and lamellar phases of the surfactant solution. The controlled molecular ordering in conjugated polymer assembly is demonstrated as a key factor determining the electronic interaction and optical function.« less

  15. Enhancing Pre-Service Elementary Teachers' Conceptual Understanding of Solution Chemistry with Conceptual Change Text

    ERIC Educational Resources Information Center

    Calik, Muammer; Ayas, Alipasa; Coll, Richard Kevin

    2007-01-01

    This paper reports on the use of a constructivist-based pedagogy to enhance understanding of some features of solution chemistry. Pre-service science teacher trainees' prior knowledge about the dissolution of salts and sugar in water were elicited by the use of a simple diagnostic tool. The test revealed widespread alternative conceptions. These…

  16. Enhancing Pre-Service Elementary Teachers' Conceptual Understanding of Solution Chemistry with Conceptual Change Text

    ERIC Educational Resources Information Center

    Calik, Muammer; Ayas, Alipasa; Coll, Richard Kevin

    2007-01-01

    This paper reports on the use of a constructivist-based pedagogy to enhance understanding of some features of solution chemistry. Pre-service science teacher trainees' prior knowledge about the dissolution of salts and sugar in water were elicited by the use of a simple diagnostic tool. The test revealed widespread alternative conceptions. These…

  17. WOWW: A Solution Orientated Approach to Enhance Classroom Relationships and Behaviour within a Primary Three Class

    ERIC Educational Resources Information Center

    Fernie, Lynne; Cubeddu, Daniela

    2016-01-01

    A Working on What Works (WOWW) approach was utilised over six sessions in a mainstream Scottish primary class to enhance classroom relationships and behaviours. The aim of the intervention was to manage everyday classroom problems within a natural classroom environment. WOWW incorporates positive psychology and implements a solution-focused…

  18. WOWW: A Solution Orientated Approach to Enhance Classroom Relationships and Behaviour within a Primary Three Class

    ERIC Educational Resources Information Center

    Fernie, Lynne; Cubeddu, Daniela

    2016-01-01

    A Working on What Works (WOWW) approach was utilised over six sessions in a mainstream Scottish primary class to enhance classroom relationships and behaviours. The aim of the intervention was to manage everyday classroom problems within a natural classroom environment. WOWW incorporates positive psychology and implements a solution-focused…

  19. Future Models of Higher Education in Scotland: Can Collaborative, Technology-Enhanced Learning Offer Solutions?

    ERIC Educational Resources Information Center

    Comrie, Andrew

    2011-01-01

    Purpose: This paper aims to discuss and provide examples of different collaborative models that are emerging and to argue that a technology-enhanced, socio-constructivist approach to future collaborative curriculum design and delivery enables partnership working and provides curriculum design solutions that supports delivery in different ways. The…

  20. Origin of hydrophobicity and enhanced water hydrogen bond strength near purely hydrophobic solutes

    PubMed Central

    Grdadolnik, Joze; Merzel, Franci; Avbelj, Franc

    2017-01-01

    Hydrophobicity plays an important role in numerous physicochemical processes from the process of dissolution in water to protein folding, but its origin at the fundamental level is still unclear. The classical view of hydrophobic hydration is that, in the presence of a hydrophobic solute, water forms transient microscopic “icebergs” arising from strengthened water hydrogen bonding, but there is no experimental evidence for enhanced hydrogen bonding and/or icebergs in such solutions. Here, we have used the redshifts and line shapes of the isotopically decoupled IR oxygen–deuterium (O-D) stretching mode of HDO water near small purely hydrophobic solutes (methane, ethane, krypton, and xenon) to study hydrophobicity at the most fundamental level. We present unequivocal and model-free experimental proof for the presence of strengthened water hydrogen bonds near four hydrophobic solutes, matching those in ice and clathrates. The water molecules involved in the enhanced hydrogen bonds display extensive structural ordering resembling that in clathrates. The number of ice-like hydrogen bonds is 10–15 per methane molecule. Ab initio molecular dynamics simulations have confirmed that water molecules in the vicinity of methane form stronger, more numerous, and more tetrahedrally oriented hydrogen bonds than those in bulk water and that their mobility is restricted. We show the absence of intercalating water molecules that cause the electrostatic screening (shielding) of hydrogen bonds in bulk water as the critical element for the enhanced hydrogen bonding around a hydrophobic solute. Our results confirm the classical view of hydrophobic hydration. PMID:28028244

  1. Is State-Mandated Redesign an Effective and Sustainable Solution?

    ERIC Educational Resources Information Center

    Young, Michelle D.

    2013-01-01

    There is a pervasive and ongoing perception that leadership preparation is a problem. Important questions remain about the intentions, capacity, and impact of state departments of education engaged in leadership preparation program redesign. In this essay, I take up several issues concerning this state policy work, including whether a one size…

  2. Is State-Mandated Redesign an Effective and Sustainable Solution?

    ERIC Educational Resources Information Center

    Young, Michelle D.

    2013-01-01

    There is a pervasive and ongoing perception that leadership preparation is a problem. Important questions remain about the intentions, capacity, and impact of state departments of education engaged in leadership preparation program redesign. In this essay, I take up several issues concerning this state policy work, including whether a one size…

  3. Concentrations of a triplet excited state are enhanced in illuminated ice.

    PubMed

    Chen, Zeyuan; Anastasio, Cort

    2017-01-25

    Photochemical reactions influence the fates and lifetimes of organic compounds in snow and ice, both through direct photoreactions and via photoproduced transient species such as hydroxyl radical (˙OH) and, perhaps, triplet excited states of organic compounds (i.e., triplets). While triplets can be important oxidants in atmospheric drops and surface waters, little is known of this class of oxidants in frozen samples. To investigate this, we examined the photoreaction of phenol with the triplet state of 3,4-dimethoxybenzaldehyde ((3)DMB*), a product from biomass combustion, in illuminated laboratory ices. Our results show that the rate of phenol loss due to (3)DMB* is, on average, increased by a factor of 95 ± 50 in ice compared to the equivalent liquid sample. We find that this experimentally measured freeze concentration factor, FEXP, is independent of total solute concentration and temperature, in contrast to what is expected from a liquid-like region whose composition follows freezing point depression. We also find that FEXP for triplets is independent of pH, although the rates of phenol loss increase with decreasing pH in both solution and ice. The enhancement in the rate of phenol loss in/on ice indicates that concentrations of triplet excited states are enhanced in ice relative to solution and suggests that this class of oxidants might be a significant sink for organics in snow and ice.

  4. [Effect of vitrification state of protective solutions on recovery of red blood cells after lyophilization preservation].

    PubMed

    Quan, Guo-Bo; Han, Ying; Liu, Xiu-Zhen; Liu, An; Jin, Peng; Cao, Wei

    2003-06-01

    To study effect of vitrification state of protective solutions on recovery of red blood cells after lyophilization, four protective solutions composed of isotonic buffers containing 7% DMSO (v/v) and 20%, 30%, 40% or 50% polyvinylpyrrolidone (PVP) (w/v) were adopted. Vitrification state of protective solutions was examined first when white ice crystal appeared in any protective solution during freezing or thawing, if the used solution was not a vitrification solution. Red blood cells were lyophilized in MINILYO45 freeze-dryer after washing, mixing with protective solutions and prefreezing. After lyophilization, the samples were quickly rehydrated by 37 degrees C rehydration solution. The results showed that in vitrification and devitrification experiments, white ice crystal appeared in solution of 20% PVP + 7% DMSO and 30% PVP + 7% DMSO during freezing and thawing; vitrification appeared in solution of 40% PVP + 7% DMSO during freezing, but devitrification appeared during thawing; vitrification appeared in solution of 50% PVP + 7% DMSO during freezing and thawing. After rehydration, the recoveries of red blood cells and hemoglobin in 40% PVP + 7% DMSO group were (81.36 +/- 14.94)% and (77.54 +/- 12.86)%, which were significantly higher than that in 20% PVP + 7% DMSO, 30% PVP + 7% DMSO and 50% PVP + 7% DMSO groups (P < 0.01). The concentration of free hemoglobin in 40% PVP + 7% DMSO group was also significantly lower than that in other three groups (P < 0.01). With increase of PVP concentration in protective solutions, vitrification state and protective effect of these solutions also increased; when concentration of PVP in protective solution was 40% though it was not a vitrification solution, the effect of lyophilization was the best; but when concentration of PVP further increased to 50%, though it was a vitrification solution, the effect decreased. It is concluded that excessive vitrification state could not benefit lyophilization of red blood cells.

  5. Utilizing transmembrane convection to enhance solute sampling and delivery by microdialysis: theory and in vitro validation

    PubMed Central

    Bungay, Peter M.; Wang, Tianli; Yang, Hua; Elmquist, William F.

    2009-01-01

    Microdialysis is a well-developed membrane-based tool relying on diffusion to sample diffusible constituents of complex media, such as biological tissue. The objective of this research is to expand the utility of microdialysis by combining transmembrane convection with diffusion to enhance solute exchange between microdialysis probes and the surrounding medium. We have developed a mathematical model to describe probe performance and performed validation experiments utilizing tracer solutes and commercially available probes with 100-kDa molecular weight cutoff membranes. Diffusive and fluid permeabilities of the probe membranes are evaluated for probes immersed in well-stirred bathing media in vitro. Transmembrane convection alters the solute extraction fraction, i.e., the fractional loss of a solute from the probe perfusate during delivery and the fractional gain by the perfusate during sampling. The extraction fraction change depends upon the magnitude and direction (inward or outward) of fluid movement across the membrane. However, for solutes with zero reflection coefficients, equality is maintained between these delivery and sampling extraction fractions. This equality is a prerequisite for probe calibration approaches that rely on analyte delivery from the perfusate. Thus, we have provided the theoretical and experimental basis for exploiting convection in a quantitative manner to enhance solute delivery and sampling in microdialysis applications. PMID:20161534

  6. NASA Water-Cycle Solutions Networks and Community of Practice Approaches to enhance Decision-making

    NASA Astrophysics Data System (ADS)

    Pozzi, W.; Ward, J.; Cox, E. L.; Lawford, R. G.; Matthews, D.; Houser, P.; Doherty, M.

    2009-12-01

    The Japanese Aerospace Exploration Agency (JAXA) has created the Asian Water Cycle Initiative regional network for South Asia and NASA has launched two networks to enhance the rapid transitioning of scientific achievements and NASA technology into operational use. All three networks meet a new type of scientific challenge by providing strong linkage among the scientific communities, the space agencies, and decision makers. We focus here on the two NASA-sponsored networks that carry out complementary approaches: WaterNet focused on large-scale national/international collaborations; North Olympic Peninsula Solution Network developed a local proof of concept project first, then began integration and collaboration at progressively larger scales, culminating with a national-level discourse via the National Association of Resource, Conservation and Development councils (NARC&DC). The ultimate goals of both groups were to bring NASA Science and Technology products to organizations/groups to improve decision making and to create collaborations and networks that would extend beyond the parent groups and expand and continue to be sustainable, after the original projects were completed. This paper provides a summary of lessons learned. The primary objective of the NOPSN is to bring NASA science and technology tools to watershed managers to improve the scientific basis of decision making in NASA national application areas of water management, agricultural efficiency, and ecological forecasting. To achieve this objective, the NOPSN team first developed and implemented a local proof-of-concept project for the Dungeness River, Washington, to improve water forecasting. The team then developed local and regional collaborations with water resource managers, stakeholder groups, and local, state, and federal agencies to identify environmental issues, challenges, and needs that could be addressed with NASA technology. Finally,through its partnership with NARC&D, it provided the NOPSN

  7. Enhancement of canonical sampling by virtual-state transitions

    NASA Astrophysics Data System (ADS)

    Higo, Junichi; Kasahara, Kota; Dasgupta, Bhaskar; Nakamura, Haruki

    2017-01-01

    A novel method was developed to enhance canonical sampling. A system is divided into virtually introduced sub-states, called "virtual states," which does not exist in reality. The configuration sampling is achieved by a standard canonical sampling method, the Metropolis Monte Carlo method, and confined in a virtual state for a while. In contrast, inter-virtual state motions are controlled by transition probabilities, which can be set arbitrarily. A simple recursive equation was introduced to determine the inter-virtual state transition probabilities, by which the sampling is enhanced considerably. We named this method "virtual-system coupled canonical Monte Carlo (VcMC) sampling." A simple method was proposed to reconstruct a canonical distribution function at a certain temperature from the resultant VcMC sampling data. Two systems, a one-dimensional double-well potential and a three-dimensional ligand-receptor binding/unbinding model, were examined. VcMC produced an accurate canonical distribution much more quickly than a conventional canonical Monte Carlo simulation does.

  8. Enhanced photovoltaic performance of organic/silicon nanowire hybrid solar cells by solution-evacuated method.

    PubMed

    Wang, Wei-Li; Zou, Xian-Shao; Zhang, Bin; Dong, Jun; Niu, Qiao-Li; Yin, Yi-An; Zhang, Yong

    2014-06-01

    A method has been developed to fabricate organic-inorganic hybrid heterojunction solar cells based on n-type silicon nanowire (SiNW) and poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) hybrid structures by evacuating the PEDOT:PSS solution with dip-dropping on the top of SiNWs before spin-coating (solution-evacuating). The coverage and contact interface between PEDOT:PSS and SiNW arrays can be dramatically enhanced by optimizing the solution-evacuated time. The maximum power conversion efficiency (PCE) reaches 9.22% for a solution-evacuated time of 2 min compared with 5.17% for the untreated pristine device. The improvement photovoltaic performance is mainly attributed to better organic coverage and contact with an n-type SiNW surface.

  9. Limits of Plasmonic Nanoparticle Enhancement in Solution-Processed Solar Cells

    NASA Astrophysics Data System (ADS)

    Arinze, Ebuka; Qiu, Botong; Nyirjesy, Gabrielle; Thon, Susanna

    Solution-processed solar cells are particularly suited to benefit from plasmonic absorption enhancement due to their transport-limited film thicknesses, and the favorable compatibility of material integration. To date, experimental demonstrations of device enhancements via plasmonic nanoparticle-based strategies have achieved photocurrents that still fall below the theoretical predicted limits. We critically evaluate the prospects for plasmonic enhancements in solution-processed thin-film solar cells. We develop an effective medium model for embedded plasmonic nanostructures in photovoltaic thin films, evaluate the model in the context of previous results achieved in the field, and use the model as a framework for identifying the most promising avenues to realizing plasmonic performance enhancements in practical photovoltaic devices. Our model results indicate that further plasmonic enhancement gains may be possible in organic photovoltaic cells. For achieving maximum photocurrent potential, we identify fine-tuning of the concentration of embedded plasmonic enhancers within the absorbing medium as the crucial factor in achieving a balance between useful scattering and detrimental parasitic absorption losses.

  10. Enhancement of phosphorescence and unimolecular behavior in the solid state by perfect insulation of platinum-acetylide polymers.

    PubMed

    Masai, Hiroshi; Terao, Jun; Makuta, Satoshi; Tachibana, Yasuhiro; Fujihara, Tetsuaki; Tsuji, Yasushi

    2014-10-22

    Controlling the thermal fluctuations and molecular environment of a phosphorescent polymer backbone is vital to enhancing its phosphorescence intensity in the solid state. Here, we demonstrate enhanced phosphorescence control through a systematic investigation of cyclodextrin-based insulated platinum-acetylide polymers with well-defined coverage areas. Modification of the coverage areas revealed two unprecedented effects of macrocyclic insulation on phosphorescence behavior. First, the insulation of particular areas suppresses the thermal relaxation processes of the triplet species because of the restriction of structural fluctuations. Cyclic insulation fixes a polymer chain and concomitantly enhances the phosphorescence intensity in both the solution and solid states. Second, complete three-dimensional insulation protects the polymer from interactions with other platinum and acetylide units, and even oxygen molecules. Notably, these polymers display identical phosphorescence behaviors in both the solution and solid states, essentially achieving "unimolecular phosphorescence."

  11. Normalization of bound-state solutions to the Breit equation

    SciTech Connect

    Malenfant, J.

    1989-03-15

    We derive the spin-(1/2), two-particle Breit equation from the Bethe-Salpeter equation with instantaneous interaction kernel, and solve for the relative time dependence of the resulting Bethe-Salpeter amplitude psi(x). As t..-->.. +- infinity, psi(x) increases exponentially in Dirac hole theory, but goes to zero in single-electron theory. Assuming single-electron theory, a normalization condition is derived for psi(r,0), the solution to the Breit equation, from the normalization for the Bethe-Salpeter amplitude.

  12. Solubility enhancement of simvastatin by arginine: thermodynamics, solute-solvent interactions, and spectral analysis.

    PubMed

    Meor Mohd Affandi, M M R; Tripathy, Minaketan; Shah, Syed Adnan Ali; Majeed, A B A

    2016-01-01

    We examined the solubility of simvastatin in water in 0.01 mol·dm(-3), 0.02 mol·dm(-3), 0.04 mol·dm(-3), 0.09 mol·dm(-3), 0.18 mol·dm(-3), 0.36 mol·dm(-3), and 0.73 mol·dm(-3) arginine (ARG) solutions. The investigated drug is termed the solute, whereas ARG the cosolute. Phase solubility studies illustrated a higher extent of solubility enhancement for simvastatin. The aforementioned system was subjected to conductometric and volumetric measurements at temperatures (T) of 298.15 K, 303.15 K, 308.15 K, and 313.15 K to illustrate the thermodynamics involved and related solute-solvent interactions. The conductance values were used to evaluate the limiting molar conductance and association constants. Thermodynamic parameters (ΔG (0), ΔH (0), ΔS (0), and E s) for the association process of the solute in the aqueous solutions of ARG were calculated. Limiting partial molar volumes and expansibilities were evaluated from the density values. These values are discussed in terms of the solute-solvent and solute-cosolute interactions. Further, these systems were analyzed using ultraviolet-visible analysis, Fourier-transform infrared spectroscopy, and (13)C, (1)H, and two-dimensional nuclear overhauser effect spectroscopy nuclear magnetic resonance to complement thermophysical explanation.

  13. Oxytocin knockout mice demonstrate enhanced intake of sweet and nonsweet carbohydrate solutions.

    PubMed

    Sclafani, Anthony; Rinaman, Linda; Vollmer, Regis R; Amico, Janet A

    2007-05-01

    Oxytocin knockout (OT KO) mice display enhanced intake of nutritive and nonnutritive sweet solutions (i.e., sucrose and saccharin) compared with wild-type (WT) mice of the same C57BL/6 background strain. The present study further investigated the differential behavioral response of OT KO and WT mice to sucrose solutions and also examined intake preferences of OT KO and WT mice for palatable but nonsweet isocaloric solutions of carbohydrate and fat. A progressive ratio operant licking procedure demonstrated that OT KO and WT mice display a similar motivational drive to consume 10% sucrose. A series of two-bottle intake tests revealed that OT KO mice consume significantly larger amounts of both sweet and nonsweet carbohydrate solutions (i.e., sucrose, Polycose, and cornstarch) compared with WT cohorts. Intake pattern analyses revealed that OT KO mice overconsume carbohydrate solutions by initiating more drinking bouts compared with WT mice; bout sizes did not differ between the genotypes. In contrast, OT KO and WT mice did not differ in their intake of Intralipid, a palatable soybean oil emulsion. These findings indicate that the absence of OT in mice does not affect their appetitive drive to consume palatable sucrose solutions. Instead, the absence of OT may increase daily intake of palatable sweet and nonsweet solutions of carbohydrate (but not fat) by selectively blunting or masking processes that contribute to postingestive satiety.

  14. Arbitrary Steady-State Solutions with the K-epsilon Model

    NASA Technical Reports Server (NTRS)

    Rumsey, Christopher L.; Pettersson Reif, B. A.; Gatski, Thomas B.

    2006-01-01

    Widely-used forms of the K-epsilon turbulence model are shown to yield arbitrary steady-state converged solutions that are highly dependent on numerical considerations such as initial conditions and solution procedure. These solutions contain pseudo-laminar regions of varying size. By applying a nullcline analysis to the equation set, it is possible to clearly demonstrate the reasons for the anomalous behavior. In summary, the degenerate solution acts as a stable fixed point under certain conditions, causing the numerical method to converge there. The analysis also suggests a methodology for preventing the anomalous behavior in steady-state computations.

  15. Counterterrorism in African Failed States: Challenges and Potential Solutions

    DTIC Science & Technology

    2006-04-01

    and generally accepted in the literature on state failure.4 For purposes of this anal - ysis, loss of government legitimacy, loss of public sector...the . . . fundamental problems—economic distress, ethnic and religious fissures , fragile governance, weak democracy, and rampant human rights abuses

  16. Thermoelectric effect enhanced by resonant states in graphene

    NASA Astrophysics Data System (ADS)

    Inglot, M.; Dyrdał, A.; Dugaev, V. K.; Barnaś, J.

    2015-03-01

    Thermoelectric effects in graphene are considered theoretically with particular attention paid to the role of resonant scattering on impurities. Using the T -matrix method we calculate the impurity resonant states and the momentum relaxation time due to scattering on impurities. The Boltzmann kinetic equation is used to determine the thermoelectric coefficients. It is shown that the resonant impurity states near the Fermi level give rise to a resonant enhancement of the Seebeck coefficient and figure of merit Z T . The Wiedemann-Franz ratio deviates from that known for ordinary metals, where this ratio is constant and equal to the Lorentz number. This deviation appears for small chemical potentials and in the vicinity of the resonant states. In the limit of a constant relaxation time, this ratio has been calculated analytically for μ =0 .

  17. Enhancement of femtosecond laser-induced nucleation of protein in a gel solution

    NASA Astrophysics Data System (ADS)

    Murai, Ryota; Yoshikawa, Hiroshi Y.; Takahashi, Yoshinori; Maruyama, Mihoko; Sugiyama, Shigeru; Sazaki, Gen; Adachi, Hiroaki; Takano, Kazufumi; Matsumura, Hiroyoshi; Murakami, Satoshi; Inoue, Tsuyoshi; Mori, Yusuke

    2010-01-01

    We found that the use of a gel solution with agarose enhanced femtosecond laser-induced nucleation and produced hen egg white lysozyme crystals at three to five times lower supersaturation than those by the femtosecond laser or agarose alone. The fast fluorescence imaging of the protein in the gel solution revealed that cavitation bubbles created high-concentration regions at the focal point, which could be the trigger for protein nucleation. The lower diffusions of protein molecules in agarose gel retained the high-concentration regions for a longer time, and facilitated the nucleation.

  18. Enhancement of the absorption of CO{sub 2} in alkaline buffer solutions: Joint action of two enhancers

    SciTech Connect

    Vazquez, G.; Chenlo, F.; Pereira, G.; Vazquez, P.

    1999-05-01

    The authors measured the absorption of CO{sub 2} in alkaline 0.5 M/0.5 M sodium carbonate/bicarbonate buffers containing either saccharose and sodium arsenite or saccharose and formaldehyde. Absorption enhancement increased upon increasing the concentration of either of the catalysts, but the joint action of the two was always less than the sum of their individual effects, the difference being a function of the acidities and concentrations of the catalysts and the pH of the carbonate/bicarbonate buffer solution

  19. Enhancing wastewater reuse by forward osmosis with self-diluted commercial fertilizers as draw solutes.

    PubMed

    Zou, Shiqiang; He, Zhen

    2016-08-01

    Using fertilizers as draw solutes in forward osmosis (FO) can accomplish wastewater reuse with elimination of recycling draw solute. In this study, three commercial fast-release all-purpose solid fertilizers (F1, F2 and F3) were examined as draw solutes in a submerged FO system for water extraction from either deionized (DI) water or the treated wastewater. Systematic optimizations were conducted to enhance water extraction performance, including operation modes, initial draw concentrations and in-situ chemical fouling control. In the mode of the active layer facing the feed (AL-F or FO), a maximum of 324 mL water was harvested using 1-M F1, which provided 41% of the water need for fertilizer dilution for irrigation. Among the three fertilizers, F1 containing a lower urea content was the most favored because of a higher water extraction and a lower reverse solute flux (RSF) of major nutrients. Using the treated wastewater as a feed solution resulted in a comparable water extraction performance (317 mL) to that of DI water in 72 h and a maximum water flux of 4.2 LMH. Phosphorus accumulation on the feed side was mainly due to the FO membrane solute rejection while total nitrogen and potassium accumulation was mainly due to RSF from the draw solute. Reducing recirculation intensity from 100 to 10 mL min(-1) did not obviously decrease water flux but significantly reduced the energy consumption from 1.86 to 0.02 kWh m(-3). These results have demonstrated the feasibility of using commercial solid fertilizers as draw solutes for extracting reusable water from wastewater, and challenges such as reverse solute flux will need to be further addressed.

  20. Enhancement of Electrical Conductivity of LiFePO4 by Controlled Solution Combustion Synthesis

    NASA Astrophysics Data System (ADS)

    Rajoba, S. J.; Jadhav, L. D.; Patil, P. S.; Tyagi, D. K.; Varma, S.; Wani, B. N.

    2017-03-01

    LiFePO4 has been synthesized by a solution combustion method at different oxidant-to-fuel ratios. At stoichiometric oxidant-to-fuel ratio (1:2), Fe2O3 formed in addition to LiFePO4 during combustion. Hence, reducing atmosphere was generated by increasing the ratio from stoichiometric to 1:4 and 1:8, named as 1-LFP, 2-LFP, and 4-LFP, respectively. Furthermore, as-prepared powders were calcined in inert atmosphere to avoid oxidation of LiFePO4 to Fe2O3 and Li3PO4, as confirmed by x-ray diffraction (XRD) and thermogravimetric and differential thermal analyses. The calcined powders were characterized by XRD analysis, Raman spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. X-ray photoelectron spectroscopy ascertained oxidation state of +2 and +5 for Fe and P, respectively. With increasing oxidant-to-fuel ratio, the binding energies of 2 p 3/2 and 2 p 1/2 levels of Fe shifted downwards and showed increased splitting. According to Raman spectroscopy results, the residual carbon is amorphous with sp 2 C-C bond. The conductivity of 1-LFP, 2-LFP, and 4-LFP measured at 313 K was 0.15 × 10-6 S/cm, 8.46 × 10-6 S/cm, and 1.21 × 10-3 S/cm, respectively. The enhanced conductivity of 4-LFP is due to presence of residual carbon and Fe2P.

  1. Enhancement of Electrical Conductivity of LiFePO4 by Controlled Solution Combustion Synthesis

    NASA Astrophysics Data System (ADS)

    Rajoba, S. J.; Jadhav, L. D.; Patil, P. S.; Tyagi, D. K.; Varma, S.; Wani, B. N.

    2016-12-01

    LiFePO4 has been synthesized by a solution combustion method at different oxidant-to-fuel ratios. At stoichiometric oxidant-to-fuel ratio (1:2), Fe2O3 formed in addition to LiFePO4 during combustion. Hence, reducing atmosphere was generated by increasing the ratio from stoichiometric to 1:4 and 1:8, named as 1-LFP, 2-LFP, and 4-LFP, respectively. Furthermore, as-prepared powders were calcined in inert atmosphere to avoid oxidation of LiFePO4 to Fe2O3 and Li3PO4, as confirmed by x-ray diffraction (XRD) and thermogravimetric and differential thermal analyses. The calcined powders were characterized by XRD analysis, Raman spectroscopy, scanning electron microscopy, and energy-dispersive x-ray spectroscopy. X-ray photoelectron spectroscopy ascertained oxidation state of +2 and +5 for Fe and P, respectively. With increasing oxidant-to-fuel ratio, the binding energies of 2p 3/2 and 2p 1/2 levels of Fe shifted downwards and showed increased splitting. According to Raman spectroscopy results, the residual carbon is amorphous with sp 2 C-C bond. The conductivity of 1-LFP, 2-LFP, and 4-LFP measured at 313 K was 0.15 × 10-6 S/cm, 8.46 × 10-6 S/cm, and 1.21 × 10-3 S/cm, respectively. The enhanced conductivity of 4-LFP is due to presence of residual carbon and Fe2P.

  2. Mechanism for the Enhanced Excited-State Lewis Acidity of Methyl Viologen.

    PubMed

    Hohenstein, Edward G

    2016-02-17

    Aqueous solutions of methyl viologen (MV(2+)) exhibit anomalous fluorescence behavior. Although it has long fluorescence lifetimes in polar solvents such as acetonitrile, MV(2+) has a short fluorescence lifetime in water. Recent experiments by Kohler and co-workers (Henrich et al. J. Phys. Chem. B 2015, 119, 2737-2748) have implicated an excited-state acid/base reaction as the source of the nonradiative decay pathway. While many chemical species exhibit enhanced Brønsted acidity in their excited state, MV(2+) is the first example of a species with enhanced Lewis acidity. Using a complete active space configuration interaction (CASCI) approach, excited-state molecular dynamics simulations of aqueous MV(2+) are performed in order to test the hypothesis that MV(2+) acts as a Lewis photoacid and to elucidate a mechanism for this behavior. These simulations show that the Lewis acidity of MV(2+) is indeed enhanced by photoexcitation. On its S1 excited state, MV(2+) reacts with water to generate a hydronium ion approximately 1.5 ps after excitation. After the hydronium ion is produced, the corresponding hydroxide ion adds to MV(2+) to form a covalently bound photoproduct and, subsequently, evolves toward a conical intersection.

  3. Yoga Enhances Positive Psychological States In Young Adult Musicians

    PubMed Central

    Butzer, Bethany; Ahmed, Khalique; Khalsa, Sat Bir S.

    2016-01-01

    Although yoga has been shown to be a viable technique for improving the performance of the mind and body, little attention has been directed to studying the relationship between yoga and the psychological states of flow and mindfulness. Musicians enrolled in a 2-month fellowship program in 2005, 2006 and 2007 were invited to participate in a yoga and meditation program. Fellows not participating in the yoga program were recruited separately as controls. All participants completed baseline and end-program questionnaires evaluating dispositional flow, mindfulness, confusion, and music performance anxiety. Compared to controls, yoga participants reported significant decreases in confusion and increases in dispositional flow. Yoga participants in the 2006 sample also reported significant increases in the mindfulness subscale of awareness. Correlational analyses revealed that increases in participants' dispositional flow and mindfulness scores were associated with decreases in confusion and music performance anxiety. This study demonstrates the commonalities between positive psychology and yoga, both of which are focused on enhancing human performance and promoting beneficial psychological states. The results suggest that yoga and meditation may enhance the states of flow and mindful awareness, and reduce confusion. PMID:26721471

  4. Enhancement of insect antifreeze protein activity by solutes of low molecular mass.

    PubMed

    Li, N; Andorfer, C A; Duman, J G

    1998-08-01

    Antifreeze proteins (AFPs) lower the non-equilibrium freezing point of water (in the presence of ice) below the melting point, thereby producing a difference between the freezing and melting points that has been termed thermal hysteresis. In general, the magnitude of the thermal hysteresis depends upon the specific activity and concentration of the AFP. This study describes several low-molecular-mass solutes that enhance the thermal hysteresis activity of an AFP from overwintering larvae of the beetle Dendroides canadensis. The most active of these is citrate, which increases the thermal hysteresis nearly sixfold from 1.2 degrees C in its absence to 6.8 degrees C. Solutes which increase activity approximately fourfold are succinate, malate, aspartate, glutamate and ammonium sulfate. Glycerol, sorbitol, alanine and ammonium bicarbonate increased thermal hysteresis approximately threefold. Interestingly, 0.5 mol l-1 sodium sulfate eliminated activity. Solute concentrations between 0.25 and 1 mol l-1 were generally required to elicit optimal thermal hysteresis activity. Glycerol is the only one of these enhancing solutes that is known to be present at these concentrations in overwintering D. canadensis, and therefore the physiological significance of most of these enhancers is unknown. The mechanism(s) of this enhancement is also unknown. The AFP used in this study (DAFP-4) is nearly identical to previously described D. canadensis AFPs. The mature protein consists of 71 amino acid residues arranged in six 12- or 13-mer repeats with a consensus sequence consisting of Cys-Thr-X3-Ser-X5-X6-Cys-X8-X9-Ala-X11-Thr-X1 3, where X3 and X11 tend to be charged residues, X5 tends to be Thr or Ser, X6 to be Asn or Asp, X9 to be Asn or Lys and X13 to be Ala in the 13-mers. DAFP-4 is shorter by one repeat than previously described D. canadensis AFPs.

  5. Low-cost Approaches for Flux-pinning Enhancements in YBCO Films Using Solution Processing

    SciTech Connect

    Sathyamurthy, Srivatsan; Leonard, Keith J; Bhuiyan, Md S; Aytug, Tolga; Kang, Sukill; Martin, Patrick M; Hunt, Rodney Dale; Paranthaman, Mariappan Parans

    2007-01-01

    Nanoparticles of several oxides have been synthesized using reverse micelle process. Microemulsions containing n-octane as the oil phase, cetyl trimethylammonium bromide and 1-butanol as surfactants, and an aqueous solution of metal nitrates and sodium hydroxide were used as the reaction medium. The nanoparticles obtained were characterized using differential thermal analysis, x-ray diffraction, and transmission electron microscopy. The application of these particles for flux-pinning enhancements has been studied.

  6. Power factor enhancement in solution-processed organic n-type thermoelectrics through molecular design.

    PubMed

    Russ, Boris; Robb, Maxwell J; Brunetti, Fulvio G; Miller, P Levi; Perry, Erin E; Patel, Shrayesh N; Ho, Victor; Chang, William B; Urban, Jeffrey J; Chabinyc, Michael L; Hawker, Craig J; Segalman, Rachel A

    2014-06-04

    A new class of high-performance n-type organic thermoelectric materials, self-doping perylene diimide derivatives with modified side chains, is reported. These materials achieve the highest n-type thermoelectric performance of solution-processed organic materials reported to date, with power factors as high as 1.4 μW/mK(2). These results demonstrate that molecular design is a promising strategy for enhancing organic thermoelectric performance.

  7. Enhancement of photonic density of states in finite graphene multilayers

    NASA Astrophysics Data System (ADS)

    DaSilva, Ashley M.; Chang, You-Chia; Norris, Ted; MacDonald, Allan H.

    2013-11-01

    We consider the optical properties of finite systems composed of a series of graphene sheets separated by thin dielectric layers. Because these systems respond as conductors to electric fields in the plane of the graphene sheets and as insulators to perpendicular electric fields, they can be expected to have properties similar to those of hyperbolic metamaterials. We show that under typical experimental conditions graphene/dielectric multilayers have enhanced Purcell factors, and enhanced photonic densities of states in both the terahertz (THz) and midinfrared (mid-IR) frequency range. These behaviors can be traced to the coupled plasmon modes of the multilayer graphene system. We show that these results can be obtained with just a few layers of graphene.

  8. Enhancing the fidelity of remote state preparation by partial measurements

    NASA Astrophysics Data System (ADS)

    Yang, Rui-Yuan; Liu, Jin-Ming

    2017-05-01

    Enhancing the fidelity of quantum state transmission in noisy environments is a significant subject in the field of quantum communication. In this paper, improving the fidelity of a deterministic remote state preparation (RSP) protocol under decoherence is investigated with the technique of weak measurement (WM) and weak measurement reversal (WMR). We first construct the quantum circuit of the deterministic remote preparation of a single-qubit state through an EPR state with the assistance of an auxiliary qubit. Then, we analytically derive the average fidelity of the deterministic RSP protocol under the influence of generalized amplitude damping noises acting on the EPR state. Our results show that when only qubit 2 undergoes the decoherence channel, the average fidelity of the RSP protocol subject to generalized amplitude damping noise is the same as that subject to amplitude damping noise. Moreover, we analyze the optimal average fidelity of the above RSP process by introducing WM and WMR. It is found that the application of WM and a subsequent reversal operation could lead to the remarkable improvement of the average fidelity for most values of the decoherence parameters.

  9. Solution-Processed CdS/Cu2S Superlattice Nanowire with Enhanced Thermoelectric Property.

    PubMed

    Xiong, Ze; Cai, Yu; Ren, Xiaodong; Cao, Bei; Liu, Jianjun; Huo, Ziyang; Tang, Jinyao

    2017-09-27

    Previously, the solution-based cation exchange reaction has been extensively studied for the synthesis of the complex heteroepitaxial nanocolloidals. Here, we demonstrated that the strain induced selective phase segregation technique can also be applied to large size nanowires in a well-studied CdS/Cu2S system, leading to the formation of superlattice nanowire structure with a simple solution-based cation exchange reaction. This structural evolution is driven by the distinct interface formation energy at different CdS facets as indicated by ab initio calculation. Because of the energy filtering effect, the superlattice nanowire shows an enhanced thermopower without significant decrease of the electrical conductivity. This study provides a promising low-cost solution process to produce superlattice nanostructures for practical thermoelectric applications.

  10. Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

    2016-09-01

    Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

  11. Physically-enhanced data visualisation: towards real time solution of Partial Differential Equations in 3D domains

    NASA Astrophysics Data System (ADS)

    Zlotnik, Sergio

    2017-04-01

    Information provided by visualisation environments can be largely increased if the data shown is combined with some relevant physical processes and the used is allowed to interact with those processes. This is particularly interesting in VR environments where the user has a deep interplay with the data. For example, a geological seismic line in a 3D "cave" shows information of the geological structure of the subsoil. The available information could be enhanced with the thermal state of the region under study, with water-flow patterns in porous rocks or with rock displacements under some stress conditions. The information added by the physical processes is usually the output of some numerical technique applied to solve a Partial Differential Equation (PDE) that describes the underlying physics. Many techniques are available to obtain numerical solutions of PDE (e.g. Finite Elements, Finite Volumes, Finite Differences, etc). Although, all these traditional techniques require very large computational resources (particularly in 3D), making them useless in a real time visualization environment -such as VR- because the time required to compute a solution is measured in minutes or even in hours. We present here a novel alternative for the resolution of PDE-based problems that is able to provide a 3D solutions for a very large family of problems in real time. That is, the solution is evaluated in a one thousands of a second, making the solver ideal to be embedded into VR environments. Based on Model Order Reduction ideas, the proposed technique divides the computational work in to a computationally intensive "offline" phase, that is run only once in a life time, and an "online" phase that allow the real time evaluation of any solution within a family of problems. Preliminary examples of real time solutions of complex PDE-based problems will be presented, including thermal problems, flow problems, wave problems and some simple coupled problems.

  12. Spurious States-Free Solution of the k dot p Hamiltonian for Heterostructures

    NASA Technical Reports Server (NTRS)

    Kolokolov, Konstantin I.; Li, Jian-Zhong; Ning, Cun-Zheng

    2003-01-01

    A method for eliminating spurious solution in the k dot p Hamiltonian has been proposed. Introduction of additional off-diagonal alpha k(exp 2) term converts spurious solution with large real wave vector to evanescent solution with large imaginary wave vector. This modification keeps the same effective masses at Gamma point and introduces negligible deviation from original nonparabolicity. A set of unphysical fast oscillation eigenfunctions in confined states of heterostructures are removed.

  13. Finite element solution of optimal control problems with state-control inequality constraints

    NASA Technical Reports Server (NTRS)

    Bless, Robert R.; Hodges, Dewey H.

    1992-01-01

    It is demonstrated that the weak Hamiltonian finite-element formulation is amenable to the solution of optimal control problems with inequality constraints which are functions of both state and control variables. Difficult problems can be treated on account of the ease with which algebraic equations can be generated before having to specify the problem. These equations yield very accurate solutions. Owing to the sparse structure of the resulting Jacobian, computer solutions can be obtained quickly when the sparsity is exploited.

  14. Finite element solution of optimal control problems with state-control inequality constraints

    NASA Technical Reports Server (NTRS)

    Bless, Robert R.; Hodges, Dewey H.

    1992-01-01

    It is demonstrated that the weak Hamiltonian finite-element formulation is amenable to the solution of optimal control problems with inequality constraints which are functions of both state and control variables. Difficult problems can be treated on account of the ease with which algebraic equations can be generated before having to specify the problem. These equations yield very accurate solutions. Owing to the sparse structure of the resulting Jacobian, computer solutions can be obtained quickly when the sparsity is exploited.

  15. VMCast: A VM-Assisted Stability Enhancing Solution for Tree-Based Overlay Multicast

    PubMed Central

    Gu, Weidong; Zhang, Xinchang; Gong, Bin; Zhang, Wei; Wang, Lu

    2015-01-01

    Tree-based overlay multicast is an effective group communication method for media streaming applications. However, a group member’s departure causes all of its descendants to be disconnected from the multicast tree for some time, which results in poor performance. The above problem is difficult to be addressed because overlay multicast tree is intrinsically instable. In this paper, we proposed a novel stability enhancing solution, VMCast, for tree-based overlay multicast. This solution uses two types of on-demand cloud virtual machines (VMs), i.e., multicast VMs (MVMs) and compensation VMs (CVMs). MVMs are used to disseminate the multicast data, whereas CVMs are used to offer streaming compensation. The used VMs in the same cloud datacenter constitute a VM cluster. Each VM cluster is responsible for a service domain (VMSD), and each group member belongs to a specific VMSD. The data source delivers the multicast data to MVMs through a reliable path, and MVMs further disseminate the data to group members along domain overlay multicast trees. The above approach structurally improves the stability of the overlay multicast tree. We further utilized CVM-based streaming compensation to enhance the stability of the data distribution in the VMSDs. VMCast can be used as an extension to existing tree-based overlay multicast solutions, to provide better services for media streaming applications. We applied VMCast to two application instances (i.e., HMTP and HCcast). The results show that it can obviously enhance the stability of the data distribution. PMID:26562152

  16. Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

    NASA Astrophysics Data System (ADS)

    Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

    2016-04-01

    Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

  17. Enhancement of dissolution rate through eutectic mixture and solid solution of posaconazole and benznidazole.

    PubMed

    Figueirêdo, Camila Bezerra Melo; Nadvorny, Daniela; de Medeiros Vieira, Amanda Carla Quintas; Soares Sobrinho, José Lamartine; Rolim Neto, Pedro José; Lee, Ping I; de La Roca Soares, Monica Felts

    2017-06-15

    Benznidazole (BNZ), the only commercialized antichagasic drug, and the antifungal compound posaconazole (PCZ) have shown synergistic action in the therapy of Chagas disease, however both active pharmaceutical ingredients (APIs) exhibit low aqueous solubility potentially limiting their bioavailability and therapeutic efficacy. In this paper, we report for the first time the formation of a eutectic mixture as well as an amorphous solid solution of PCZ and BNZ (at the same characteristic ratio of 80:20wt%), which provided enhanced solubility and dissolution rate for both APIs. This eutectic system was characterized by DSC and the melting points obtained were used for the construction of a phase diagram. The preservation of the characteristic PXRD patterns and the IR spectra of the parent APIs, and the visualization of a characteristic eutectic lamellar crystalline microstructure using Confocal Raman Microscopy confirm this system as a true eutectic mixture. The PXRD result also confirms the amorphous nature of the prepared solid solution. Theoretical chemical analyses indicate the predominance of π-stacking interactions in the amorphous solid solution, whereas an electrostatic interaction between the APIs is responsible for maintaining the alternating lamellar crystalline microstructure in the eutectic mixture. Both the eutectic mixture and the amorphous solid solution happen to have a characteristic PCZ to BNZ ratio similar to that of their pharmacological doses for treating Chagas disease, thus providing a unique therapeutic combination dose with enhanced apparent solubility and dissolution rate. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Engineered Injection and Extraction for Enhanced In-situ Remediation of Sorbing Solutes in Groundwater

    NASA Astrophysics Data System (ADS)

    Webber, B. D.; Neupauer, R. M.; Piscopo, A. N.; Mays, D. C.

    2012-12-01

    Groundwater remediation is becoming increasingly more important as the world's population grows and the necessity of access to clean drinking water persists. The majority of current groundwater treatment methods involve pumping the contaminated groundwater out of the soil and treating it above ground. Sorbed contaminants are difficult to remediate using this conventional pump-and-treat method, and often produce poor treatment results because sorbed contaminants are difficult to extract from the aquifer; therefore in-situ remediation research is of particular importance. One type of in-situ groundwater remediation involves a treatment solution of varying composition being injected into the polluted aquifer to react with the contaminant and degrade it to an acceptable byproduct. Increasing the amount of spreading between the contaminant and the treatment solution promotes an increase in contact area and more desired reactions. It has been previously determined that sequential injection and extraction using four wells for in-situ remediation can enhance the spreading of an aqueous contaminant and treatment solution and increase degradation through more reactions. In this work, we focus on sorbing contaminants and investigate the effectiveness of the injection and extraction methods on varying degrees of contaminant sorption. Tests were conducted in homogeneous and heterogeneous soil media, and with instantaneous and kinetic reaction. It was determined that engineered injection and extraction methods previously developed for aqueous contaminants also enhance in-situ remediation of sorbing solutes.

  19. Nonexistence of nonconstant steady-state solutions in a triangular cross-diffusion model

    NASA Astrophysics Data System (ADS)

    Lou, Yuan; Tao, Youshan; Winkler, Michael

    2017-05-01

    In this paper we study the Shigesada-Kawasaki-Teramoto model for two competing species with triangular cross-diffusion. We determine explicit parameter ranges within which the model exclusively possesses constant steady state solutions.

  20. Enhancing the Assistive Technology Workforce State by State. The TAP Bulletin.

    ERIC Educational Resources Information Center

    RESNA: Association for the Advancement of Rehabilitation Technology, Arlington, VA.

    This paper offers suggestions for state systems change activities to enhance the assistive technology (AT) workforce funded under the Technology-Related Assistance for Individuals with Disabilities Act of 1988. Nationally, the Rehabilitation Engineering and Assistive Technology Society of North America AT has begun to credential AT practitioners…

  1. Discontinuous steady-state analytical solutions of the Boussinesq equation and their numerical representation by MODFLOW.

    PubMed

    Zaidel, Jacob

    2013-01-01

    Known analytical solutions of groundwater flow equations are routinely used for verification of computer codes. However, these analytical solutions (e.g., the Dupuit solution for the steady-state unconfined unidirectional flow in a uniform aquifer with a flat bottom) represent smooth and continuous water table configurations, simulating which does not pose any significant problems for the numerical groundwater flow models, like MODFLOW. One of the most challenging numerical cases for MODFLOW arises from drying-rewetting problems often associated with abrupt changes in the elevations of impervious base of a thin unconfined aquifer. Numerical solutions of groundwater flow equations cannot be rigorously verified for such cases due to the lack of corresponding exact analytical solutions. Analytical solutions of the steady-state Boussinesq equation, associated with the discontinuous water table configurations over a stairway impervious base, are presented in this article. Conditions resulting in such configurations are analyzed and discussed. These solutions appear to be well suited for testing and verification of computer codes. Numerical solutions, obtained by the latest versions of MODFLOW (MODFLOW-2005 and MODFLOW-NWT), are compared with the presented discontinuous analytical solutions. It is shown that standard MODFLOW-2005 code (as well as MODFLOW-2000 and older versions) has significant convergence problems simulating such cases. The problems manifest themselves either in a total convergence failure or erroneous results. Alternatively, MODFLOW-NWT, providing a good match to the presented discontinuous analytical solutions, appears to be a more reliable and appropriate code for simulating abrupt changes in water table elevations.

  2. Charge-state enhancement for radioactive beam post-acceleration

    SciTech Connect

    Nolen, J.A.; Dooling, J.

    1995-08-01

    A critical question for an ISOL-type radioactive-beam facility, such as that being discussed by the North American Isospin Laboratory Committee, is the efficiency and q/m of the ion source for the radioactive species. ISOLDE at CERN demonstrated that high efficiency is obtained for a wide variety of species in the 1{sup +} charge state. These ion sources also generally have excellent transverse emittances and low energy spreads. One possibility is to use this proven technology plus an ionizer stage to increase the output of such sources to 2, 3, or 4{sup +} with high efficiency. We are currently investigating technical options for such charge-state enhancement. There is a proposal by a Heidelberg/ISOLDE collaboration to build a {open_quotes}charge-state breeder{close_quotes} as part of an experiment called REX-ISOLDE. This concept would deliver batches of radioactive ions with low duty cycle, optimized for relatively low-intensity secondary beams, on the order of 10{sup 6}/sec. We are independently doing simulations of an alternative approach, called the Electron-Beam Charge-State Amplifier (EBQA), which would yield DC beams with improved transverse emittance and would not have the intensity limitation of the batch transfer process. The cost and efficiency of the EBQA will have to be compared with those of a normally-conducting CW RFQ followed by ion stripping, as alternatives for the first stage of a secondary ion accelerator.

  3. Indolic uremic solutes enhance procoagulant activity of red blood cells through phosphatidylserine exposure and microparticle release.

    PubMed

    Gao, Chunyan; Ji, Shuting; Dong, Weijun; Qi, Yushan; Song, Wen; Cui, Debin; Shi, Jialan

    2015-10-28

    Increased accumulation of indolic uremic solutes in the blood of uremic patients contributes to the risk of thrombotic events. Red blood cells (RBCs), the most abundant blood cells in circulation, may be a privileged target of these solutes. However, the effect of uremic solutes indoxyl sulfate (IS) and indole-3-acetic acid (IAA) on procoagulant activity (PCA) of erythrocyte is unclear. Here, RBCs from healthy adults were treated with IS and IAA (mean and maximal concentrations reported in uremic patients). Phosphatidylserine (PS) exposure of RBCs and their microparticles (MPs) release were labeled with Alexa Fluor 488-lactadherin and detected by flow cytometer. Cytosolic Ca(2+) ([Ca(2+)]) with Fluo 3/AM was analyzed by flow cytometer. PCA was assessed by clotting time and purified coagulation complex assays. We found that PS exposure, MPs generation, and consequent PCA of RBCs at mean concentrations of IS and IAA enhanced and peaked in maximal uremic concentrations. Moreover, 128 nM lactadherin, a PS inhibitor, inhibited over 90% PCA of RBCs and RMPs. Eryptosis or damage, by indolic uremic solutes was due to, at least partially, the increase of cytosolic [Ca(2+)]. Our results suggest that RBC eryptosis in uremic solutes IS and IAA plays an important role in thrombus formation through releasing RMPs and exposing PS. Lactadherin acts as an efficient anticoagulant in this process.

  4. State-constrained booster trajectory solutions via finite elements and shooting

    NASA Technical Reports Server (NTRS)

    Bless, Robert R.; Hodges, Dewey H.; Seywald, Hans

    1993-01-01

    This paper presents an extension of a FEM formulation based on variational principles. A general formulation for handling internal boundary conditions and discontinuities in the state equations is presented, and the general formulation is modified for optimal control problems subject to state-variable inequality constraints. Solutions which only touch the state constraint and solutions which have a boundary arc of finite length are considered. Suitable shape and test functions are chosen for a FEM discretization. All element quadrature (equivalent to one-point Gaussian quadrature over each element) may be done in closed form. The final form of the algebraic equations is then derived. A simple state-constrained problem is solved. Then, for a practical application of the use of the FEM formulation, a launch vehicle subject to a dynamic pressure constraint (a first-order state inequality constraint) is solved. The results presented for the launch-vehicle trajectory have some interesting features, including a touch-point solution.

  5. State-constrained booster trajectory solutions via finite elements and shooting

    NASA Technical Reports Server (NTRS)

    Bless, Robert R.; Hodges, Dewey H.; Seywald, Hans

    1993-01-01

    This paper presents an extension of a FEM formulation based on variational principles. A general formulation for handling internal boundary conditions and discontinuities in the state equations is presented, and the general formulation is modified for optimal control problems subject to state-variable inequality constraints. Solutions which only touch the state constraint and solutions which have a boundary arc of finite length are considered. Suitable shape and test functions are chosen for a FEM discretization. All element quadrature (equivalent to one-point Gaussian quadrature over each element) may be done in closed form. The final form of the algebraic equations is then derived. A simple state-constrained problem is solved. Then, for a practical application of the use of the FEM formulation, a launch vehicle subject to a dynamic pressure constraint (a first-order state inequality constraint) is solved. The results presented for the launch-vehicle trajectory have some interesting features, including a touch-point solution.

  6. Protolytic dissociation of cyanophenols in ground and excited states in alcohol and water solutions

    NASA Astrophysics Data System (ADS)

    Szczepanik, Beata; Styrcz, Stanisław

    2011-08-01

    The effect of cyano substituents on acidity in ground and excited states of mono- and dicyanophenols was investigated. The equilibrium dissociation constants of 3,4-dicyanophenol in ground and lowest excited states in water solution and the change of these constants in the excited state during the transfer to the ground state for o-, m-, p-cyanophenol and 3,4-dicyanophenol in alcohol and water solutions were determined. It was shown that the cyano substitution increases the acidity of ortho-, meta- and dicyano-derivative in ground state in comparison to the phenol, which makes the anions of these derivatives appear in solutions from methanol to 1-butanol. In the excited state the acidity of investigated compounds changes significantly in comparison to the ground state. 3,4-Dicyanophenol is the strongest acid in the lowest excited singlet state, while p-cyanophenol is the weakest one in both alcohol and water solutions. The distribution of the electronic charge and dipole moments of all investigated cyanophenols in ground and excited states were determined on the basis of ab initio calculations using the GAMESS program.

  7. PROCESS OF SECURING PLUTONIUM IN NITRIC ACID SOLUTIONS IN ITS TRIVALENT OXIDATION STATE

    DOEpatents

    Thomas, J.R.

    1958-08-26

    >Various processes for the recovery of plutonium require that the plutonium be obtalned and maintained in the reduced or trivalent state in solution. Ferrous ions are commonly used as the reducing agent for this purpose, but it is difficult to maintain the plutonium in a reduced state in nitric acid solutions due to the oxidizing effects of the acid. It has been found that the addition of a stabilizing or holding reductant to such solution prevents reoxidation of the plutonium. Sulfamate ions have been found to be ideally suitable as such a stabilizer even in the presence of nitric acid.

  8. Efficient Steady-State Solution Techniques for Variably Saturated Groundwater Flow

    NASA Astrophysics Data System (ADS)

    Farthing, M. W.; Kees, C. E.; Coffey, T. S.; Kelley, C. T.; Miller, C. T.

    2002-12-01

    We consider the simulation of steady-state variably saturated groundwater flow using Richards' equation. The difficulties associated with solving Richards' equation numerically are well known. Most discretization approaches for Richards' equation lead to nonlinear systems that are large and difficult to solve. The solution of nonlinear systems for steady-state problems can be particularly challenging, since a good initial guess for the steady-state solution is often hard to obtain, and the resulting linear systems may be poorly scaled. Common approaches like modified Picard iteration or variations of Newton's method have their advantages but perform poorly with standard globalization techniques under certain conditions. Pseudo-transient continuation has been used in computational fluid dynamics for some time to obtain steady-state solutions for problems in which Newton's method with standard line-search strategies fails. It combines aspects of backward Euler time integration and Newton's method to select intermediate estimates of the steady-state solution. In this work, we examine the use of pseudo-transient continuation methods for Richards' equation. We evaluate their performance for steady-state problems in heterogeneous domains by comparing them with Newton's method using standard globalization techniques. We investigate the methods' performance with both direct and preconditioned Krylov iterative linear solvers. We then make recommendations for robust and efficient approaches to obtain steady-state solutions for Richards' equation under a variety of conditions.

  9. Solution of steady-state one-dimensional conservation laws by mathematical programming

    NASA Technical Reports Server (NTRS)

    Lavery, J. E.

    1989-01-01

    Solution techniques for a class of steady-state scalar conservation laws are developed analytically. Discretization by finite-volume formulas is employed to obtain an overdetermined system of algebraic equations, which are then perturbed nonsingularly (with perturbation coefficient = epsilon) and solved using the l(1) mathematical-programming algorithm of Seneta and Steiger (1984); this approach limits the matrix bandwidth to two, so that an explicit solution can be found efficiently. It is shown that, for small values of epsilon, the l(1) solutions exhibit sharp correctly located shocks and are nonoscillatory O(epsilon) approximations of the physically relevant solutions.

  10. Integrating matrix solution of the hybrid state vector equations for beam vibration

    NASA Technical Reports Server (NTRS)

    Lehman, L. L.

    1982-01-01

    A simple, versatile, and efficient computational technique has been developed for dynamic analysis of linear elastic beam and rod type of structures. Moreover, the method provides a rather general solution approach for two-point boundary value problems that are described by a single independent spatial variable. For structural problems, the method is implemented by a mixed state vector formulation of the differential equations, combined with an integrating matrix solution procedure. Highly accurate solutions are easily achieved with this approach. Example solutions are given for beam vibration problems including discontinuous stiffness and mass parameters, elastic restraint boundary conditions, concentrated inertia loading, and rigid body modes

  11. Efficiency of an enhanced linear optical Bell-state measurement scheme with realistic imperfections

    NASA Astrophysics Data System (ADS)

    Wein, Stephen; Heshami, Khabat; Fuchs, Christopher A.; Krovi, Hari; Dutton, Zachary; Tittel, Wolfgang; Simon, Christoph

    2016-09-01

    We compare the standard 50%-efficient single beam splitter method for Bell-state measurement to a proposed 75%-efficient auxiliary-photon-enhanced scheme [W. P. Grice, Phys. Rev. A 84, 042331 (2011), 10.1103/PhysRevA.84.042331] in light of realistic conditions. The two schemes are compared with consideration for high input state photon loss, auxiliary state photon loss, detector inefficiency and coupling loss, detector dark counts, and non-number-resolving detectors. We also analyze the two schemes when multiplexed arrays of non-number-resolving detectors are used. Furthermore, we explore the possibility of utilizing spontaneous parametric down-conversion as the auxiliary photon pair source required by the enhanced scheme. In these different cases, we determine the bounds on the detector parameters at which the enhanced scheme becomes superior to the standard scheme and describe the impact of the different imperfections on measurement success rate and discrimination fidelity. This is done using a combination of numeric and analytic techniques. For many of the cases discussed, the size of the Hilbert space and the number of measurement outcomes can be very large, which makes direct numerical solutions computationally costly. To alleviate this problem, all of our numerical computations are performed using pure states. This requires tracking the loss modes until measurement and treating dark counts as variations on measurement outcomes rather than modifications to the state itself. In addition, we provide approximate analytic expressions that illustrate the effect of different imperfections on the Bell-state analyzer quality.

  12. Near-infrared surface-enhanced fluorescence using silver nanoparticles in solution

    NASA Astrophysics Data System (ADS)

    Furtaw, Michael D.

    Fluorescence spectroscopy is a widely used detection technology in many research and clinical assays. Further improvement to assay sensitivity may enable earlier diagnosis of disease, novel biomarker discovery, and ultimately, improved outcomes of clinical care along with reduction in costs. Near-infrared, surface-enhanced fluorescence (NIR-SEF) is a promising approach to improve assay sensitivity via simultaneous increase in signal with a reduction in background. This dissertation describes research conducted with the overall goal to determine the extent to which fluorescence in solution may be enhanced by altering specific variables involved in the formation of plasmon-active nanostructures of dye-labeled protein and silver nanoparticles in solution, with the intent of providing a simple solution that may be readily adopted by current fluorescence users in the life science research community. First, it is shown that inner-filtering, re-absorption of the emitted photons, can red-shift the optimal fluorophore spectrum away from the resonant frequency of the plasmon-active nanostructure. It is also shown that, under certain conditions, the quality factor may be a better indicator of SEF than the commonly accepted overlap of the fluorophore spectrum with the plasmon resonance of the nanostructure. Next, it is determined that streptavidin is the best choice for carrier protein, among the most commonly used dye-labeled detection antibodies, to enable the largest fluorescence enhancement when labeled with IRDye 800CW and used in combination with silver nanoparticles in solution. It is shown that the relatively small and symmetric geometry of streptavidin enables substantial electromagnetic-field confinement when bound to silver nanoparticles, leading to strong and reproducible enhancement. The role of silver nanoparticle aggregation is demonstrated in a droplet-based microfluidic chip and further optimized in a standard microtiter-plate format. A NIR-SEF technology

  13. 1H relaxation enhancement induced by nanoparticles in solutions: Influence of magnetic properties and diffusion

    NASA Astrophysics Data System (ADS)

    Kruk, D.; Korpała, A.; Taheri, S. Mehdizadeh; Kozłowski, A.; Förster, S.; Rössler, E. A.

    2014-05-01

    Magnetic nanoparticles that induce nuclear relaxation are the most promising materials to enhance the sensitivity in Magnetic Resonance Imaging. In order to provide a comprehensive understanding of the magnetic field dependence of the relaxation enhancement in solutions, Nuclear Magnetic Resonance 1H spin-lattice relaxation for decalin and toluene solutions of various Fe2O3 nanoparticles was investigated. The relaxation experiments were performed in a frequency range of 10 kHz-20 MHz by applying Field Cycling method, and in the temperature range of 257-298 K, using nanoparticles differing in size and shape: spherical - 5 nm diameter, cubic - 6.5 nm diameter, and cubic - 9 nm diameter. The relaxation dispersion data were interpreted in terms of a theory of nuclear relaxation induced by magnetic crystals in solution. The approach was tested with respect to its applicability depending on the magnetic characteristics of the nanocrystals and the time-scale of translational diffusion of the solvent. The role of Curie relaxation and the contributions to the overall 1H spin-lattice relaxation associated with the electronic spin-lattice and spin-spin relaxation was thoroughly discussed. It was demonstrated that the approach leads to consistent results providing information on the magnetic (electronic) properties of the nanocrystals, i.e., effective electron spin and relaxation times. In addition, features of the 1H spin-lattice relaxation resulting from the electronic properties of the crystals and the solvent diffusion were explained.

  14. DNP-Enhanced MAS NMR of Bovine Serum Albumin Sediments and Solutions

    PubMed Central

    2015-01-01

    Protein sedimentation sans cryoprotection is a new approach to magic angle spinning (MAS) and dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) spectroscopy of proteins. It increases the sensitivity of the experiments by a factor of ∼4.5 in comparison to the conventional DNP sample preparation and circumvents intense background signals from the cryoprotectant. In this paper, we investigate sedimented samples and concentrated frozen solutions of natural abundance bovine serum albumin (BSA) in the absence of a glycerol-based cryoprotectant. We observe DNP signal enhancements of ε ∼ 66 at 140 GHz in a BSA pellet sedimented from an aqueous solution containing the biradical polarizing agent TOTAPOL and compare this with samples prepared using the conventional protocol (i.e., dissolution of BSA in a glycerol/water cryoprotecting mixture). The dependence of DNP parameters on the radical concentration points to the presence of an interaction between TOTAPOL and BSA, so much so that a frozen solution sans cryoprotectant still gives ε ∼ 50. We have studied the interaction of BSA with another biradical, SPIROPOL, that is more rigid than TOTAPOL and has been reported to give higher enhancements. SPIROPOL was also found to interact with BSA, and to give ε ∼ 26 close to its maximum achievable concentration. Under the same conditions, TOTAPOL gives ε ∼ 31, suggesting a lesser affinity of BSA for SPIROPOL with respect to TOTAPOL. Altogether, these results demonstrate that DNP is feasible in self-cryoprotecting samples. PMID:24460530

  15. DNP-enhanced MAS NMR of bovine serum albumin sediments and solutions.

    PubMed

    Ravera, Enrico; Corzilius, Björn; Michaelis, Vladimir K; Luchinat, Claudio; Griffin, Robert G; Bertini, Ivano

    2014-03-20

    Protein sedimentation sans cryoprotection is a new approach to magic angle spinning (MAS) and dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) spectroscopy of proteins. It increases the sensitivity of the experiments by a factor of ∼4.5 in comparison to the conventional DNP sample preparation and circumvents intense background signals from the cryoprotectant. In this paper, we investigate sedimented samples and concentrated frozen solutions of natural abundance bovine serum albumin (BSA) in the absence of a glycerol-based cryoprotectant. We observe DNP signal enhancements of ε ∼ 66 at 140 GHz in a BSA pellet sedimented from an aqueous solution containing the biradical polarizing agent TOTAPOL and compare this with samples prepared using the conventional protocol (i.e., dissolution of BSA in a glycerol/water cryoprotecting mixture). The dependence of DNP parameters on the radical concentration points to the presence of an interaction between TOTAPOL and BSA, so much so that a frozen solution sans cryoprotectant still gives ε ∼ 50. We have studied the interaction of BSA with another biradical, SPIROPOL, that is more rigid than TOTAPOL and has been reported to give higher enhancements. SPIROPOL was also found to interact with BSA, and to give ε ∼ 26 close to its maximum achievable concentration. Under the same conditions, TOTAPOL gives ε ∼ 31, suggesting a lesser affinity of BSA for SPIROPOL with respect to TOTAPOL. Altogether, these results demonstrate that DNP is feasible in self-cryoprotecting samples.

  16. Enhancement of Pool Boiling Heat Transfer to Lithium Bromide Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Furukawa, Masahiro; Kaji, Masuo; Suyama, Takayuki; Sekoguchi, Kotohiko

    An experimental study on enhancement of nucleate pool boiling heat tranfer by placing a sponge metal close to a plain heated surface was conducted in order to improve the heat transfer performance of the high temperature generator of absorption chiller/heater. The sponge metal has three dimensional porous mesh framework like sponge. Boiling curves of water under the atmospheric pressure were compared with those of lithium bromide aqueous solution of mass concentration 55 to 58%. Heat transfer characteristics were improved by 2 to3 times both for water and lithium bromide aqueous solution when the sponge metal was placed on the heated surface with and without cleareance. Three kinds of sponge metals were used for lithium bromide aqueous solution under the reduced pressure (24 kPa). At lower heat fluxes,#6 sponge metal which has the finest mesh and the lowest porosity shows excellent results. At high heat fluxes, however,it causes deterioration of heat transfer. Over the wide range of heat fluxes,# 4 sponge metal was found to be most suitable and the optimal clearence was determined as 0.5 mm. The sponge metal is of good practical use as a device to enhance the boiling, since no special manufacturing is required for placing it on the heated surface.

  17. Enhancement of pool boiling heat transfer to lithium bromide aqueous solution

    NASA Astrophysics Data System (ADS)

    Kaji, Masuo; Furukawa, Masahiro; Suyama, Takayuki; Sekoguchi, Kotohiko

    1995-04-01

    An experimental study on enhancement of nucleate pool boiling heat transfer by placing a sponge metal, which had a three-dimensional mesh structure like sponge, close to a plain smooth heat transfer surface was conducted to improve the heat transfer performance of the high temperature generator of absorption chiller/heaters. Boiling curves of water and lithium bromide aqueous solution of mass concentration of 55 to 58% at the atmospheric pressure were presented. Heat transfer characteristics were improved by two to three times both for water and lithium bromide aqueous solution when the sponge metal was attached with an appropriate clearance. Three kinds of sponge metals were tested for lithium bromide aqueous solution under a reduced pressure (24 kPa). The sponge metal #6, which had the finest mesh among the three sponge metals, brought about excellent results at lower heat fluxes, but it caused deterioration of heat transfer at higher heat fluxes. For the wide range of heat flux (5 x 10(exp 4) approximately 2 x 10(exp 5) W/m(exp 2), it was found that the sponge metal #4 with the middle fineness was the most suitable and the optimal clearance was in the range of 0.1 approximately 0.5 mm. The employment of sponge metals for enhancing boiling heat transfer is practically excellent, since no special manufacturing is required to mount them on the heated surface.

  18. [Fluorescence enhancement of flavoxate hydrochloride in alkali solution and its application in pharmaceutical analysis].

    PubMed

    Li, Wen-hong; Sun, Chong-mei; Wei, Yong-ju

    2015-10-01

    Fluorescence enhancement reaction of flavoxate hydrochloride (FX) in strong alkali solution was studied, the mechanism of the reaction was investigated, and a novel fluorimetric method for analysis of FX in drug sample was established. FX has no intrinsic fluorescence, but it can slowly produce fluorescence in strong alkali solution. Heating can promote the fluorescence enhancement reaction. In 3D fluorescence spectra of the decomposition product of FX, two fluorescence peaks, located respectively at excitation wavelengths λex/ emission wavelength λem =223/410 nm, and 302/410 nm, were observed. Using quinine sulfate as a reference, fluorescence quantum yield of the decomposition product was measured to be 0.50. The structural characteriza- tion and spectral analysis of the decomposition product reveal that ester bond hydrolysis reaction of FX is firstly occurred during heating process, forming 3-methylflavone-8-carboxylic acid (MFA), then a cleavage reaction of the γ-pyrone ring of MFA occurred, producing α, β-unsaturated ketone. This product includes adjacent hydroxyl benzoic acid group in its molecule, which can form intramolecular hydrogen bond under alkaline condition, so that increase the conjugate degree and enhance the rigidity of the molecule, and thereby cause fluorescence enhancement. Based on this fluorescence enhancement reaction, a fluorimetric method was proposed for the determination of FX. A linear calibration curve covered the concentration range 0.020 3-0.487 µg · mL. The regression equation was I(F) = 23.9 + 5357.3 c, with correlation coefficient r = 0.999 7 (n = 8), detection limit D = 1.1 ng · mL(-1). The method was applied to the analysis of FX tablets, with a spiked recovery rate of 100.2%. The reliability of the method was verified by a UV-spectrophotometric method.

  19. Novel cellulose-based amorphous solid dispersions enhance quercetin solution concentrations in vitro.

    PubMed

    Gilley, Andrew D; Arca, Hale Cigdem; Nichols, Brittany L B; Mosquera-Giraldo, Laura I; Taylor, Lynne S; Edgar, Kevin J; Neilson, Andrew P

    2017-02-10

    Quercetin (Q) is a bioactive flavonol with potential to benefit human health. However, Q bioavailability is relatively low, due to its poor aqueous solubility and extensive phase-II metabolism. Strategies to increase solution concentrations in the small intestinal lumen have the potential to substantially increase Q bioavailability, and by extension, efficacy. We aimed to achieve this by incorporating Q into amorphous solid dispersions (ASDs) with cellulose derivatives. Q was dispersed in matrices of cellulose esters including 6-carboxycellulose acetate butyrate (CCAB), hydroxypropylmethylcellulose acetate succinate (HPMCAS) and cellulose acetate suberate (CASub) to afford ASDs that provided stability against crystallization, and pH-triggered release. Blends of CASub and CCAB with the hydrophilic polyvinylpyrrolidone (PVP) further enhanced dissolution. The ASD 10% Q:20% PVP:70% CASub most significantly enhanced Q solution concentration under intestinal pH conditions, increasing area under the concentration/time curve (AUC) 18-fold compared to Q alone. This novel ASD method promises to enhance Q bioavailability in vivo.

  20. Theoretical Application of Irreversible (Nonequilibrium) Thermodynamic Principles to Enhance Solute Fluxes across Nanofabricated Hemodialysis Membranes

    PubMed Central

    Hedayat, Assem; Elmoselhi, Hamdi; Shoker, Ahmed

    2012-01-01

    Objective. Nanotechnology has the potential to improve hemodialysis membrane technology. Thus, a major objective is to understand how to enhance toxic solute fluxes across these membranes. The aim of this concept building study is to review the application of irreversible thermodynamic (IT) to solute fluxes. Methods. We expanded the application of the Nernst-Planck equation to include the Kedem-Katchalsky equation, pH, membrane thickness, pore size, and electric potential as variables. Results. (1) Reducing the membrane's thickness from 25 μm to 25 nm increased the flux of creatinine, β2-microglobulin, and tumor necrosis factor-α (TNF-α) by a thousand times but prevented completely albumin flux, (2) applying an electric potential of 50–400 mV across the membrane enhanced the flux of the respective molecules by 71.167 × 10−3, 38.7905 × 10−8, and 0.595 × 10−13 mol/s, and (3) changing the pH from 7.35 to 7.42 altered the fluxes minimally. Conclusions. The results supported an argument to investigate the application of IT to study forces of fluxes across membranes. Reducing the membrane's thickness—together with the application of an electrical potential—qualities achievable by nanotechnology, can enhance the removal of uremic toxins by many folds. However, changing the pH at a specific membrane thickness does not affect the flux significantly. PMID:23209903

  1. Comparison of water solubility enhancements of organic solutes by aquatic humic materials and commercial humic acids

    SciTech Connect

    Chiou, C.T.; Kile, D.E.; Brinton, T.I.; Malcolm, R.L.; Leenheer, J.A.; MacCarthy, P.

    1987-12-01

    Water solubility enhancements of 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (p,p'-DDT), 2,4,5,2',5'-pentachlorobiphenyl (2,4,5,2',5'-PCB), and 2,4,4'-trichlorobiphenyl (2,4,4'-PCB) by dissolved organic matter have been studied with the following samples: (1) acidic water samples from the Suwannee River, Georgia, and the Sopchoppy River, Florida; (2) a humic extract of a nearly neutral pH water from the Calcasieu River, Louisiana; (3) commercial humic acids from the Aldrich Chemical Co. and Fluka-Tridom Chemical Corp. The calculated partition coefficients on a dissolved organic carbon basis (K/sub doc/) for organic solutes with water samples and aquatic humic extracts from this and earlier studies indicate that the enhancement effect varies with the molecular composition of the aquatic humic materials, The K/sub doc/ values with water and aquatic humic samples are, however, far less than the observed K/sub doc/ values obtained with the two commercial samples, by factors of about 4-20. In view of this finding, one should be cautious in interpreting the effects of the dissolved organic matter on solubility enhancement of organic solutes on the basis of the use of commercial humic acids. 14 references, 3 figures, 2 tables.

  2. Novel chemiluminescent Western blot blocking and antibody incubation solution for enhanced antibody-antigen interaction and increased specificity.

    PubMed

    Schwartz, Kimberly; Bochkariov, Dmitry

    2017-07-13

    Western blotting is a ubiquitous tool used in protein and molecular biology research, providing information about the presence, size, relative abundance, and state of a protein in a mixture. First, the proteins in a sample are separated by size using SDS-PAGE then transferred onto a membrane for detection with a set of primary and secondary antibodies. High-quality Western data requires high signal-to-noise ratios, which depend upon reduction of nonspecific antibody interactions. Blocking is a critical step in the Western blot method as it prevents the antibodies from binding nonspecifically to the membrane and irrelevant proteins. A solution of nonfat dry milk (NFDM) in physiological buffer is commonly used for this purpose, but does not perform well with every type of antibody and is not optimal for low-abundance proteins. We present a novel blocking solution for chemiluminescent Western blots, AdvanBlock™-chemi, which outperforms NFDM in experiments with 20 unique antibodies by increasing signal-to-noise ratios and minimizing nonspecific binding. This solution enhances protein detection by Western blot and provides consistent results for detection of low abundant and modified proteins. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Stability of curcumin in different solvent and solution media: UV-visible and steady-state fluorescence spectral study.

    PubMed

    Mondal, Satyajit; Ghosh, Soumen; Moulik, Satya P

    2016-05-01

    In aqueous solution, curcumin is photodegradable (light sensitive), it is also self-degradable in the dark. In basic medium, the second process is enhanced. The dark process has been studied in water and also in a number of protic and aprotic solvents, and aqueous solutions of ionic liquids, pluronics, reverse micelles and salt. The kinetics of the process followed the first order rate law; a comparative as well as individual assessment of which has been made. The kinetics of curcumin self-degradation has been found to be fairly dependent on salt (NaCl) concentration. Curcumin molecules in solution may remain in the enol or keto-enol form. From the visible spectral analysis, an estimate of the proportions of these forms in aqueous ethanol medium has been made. The temperature effect on the visible and fluorescence spectra of curcumin has been also studied. The steady state fluorescence anisotropy of the photoactive curcumin has been evaluated in different solvent and solution media. The reversibility of the steady state fluorescence anisotropy of curcumin on heating and cooling conditions has been examined. The results herein presented are new and ought to be useful as the study of physicochemistry of curcumin has been gaining importance in the light of its biological importance.

  4. Outbreaks caused by sprouts, United States, 1998-2010: lessons learned and solutions needed.

    PubMed

    Dechet, Amy M; Herman, Karen M; Chen Parker, Cary; Taormina, Peter; Johanson, Joy; Tauxe, Robert V; Mahon, Barbara E

    2014-08-01

    After a series of outbreaks associated with sprouts in the mid-1990s, the U.S. Food and Drug Administration (FDA) published guidelines in 1999 for sprouts producers to reduce the risk of contamination. The recommendations included treating seeds with an antimicrobial agent such as calcium hypochlorite solution and testing spent irrigation water for pathogens. From 1998 through 2010, 33 outbreaks from seed and bean sprouts were documented in the United States, affecting 1330 reported persons. Twenty-eight outbreaks were caused by Salmonella, four by Shiga toxin-producing Escherichia coli, and one by Listeria. In 15 of the 18 outbreaks with information available, growers had not followed key FDA guidelines. In three outbreaks, however, the implicated sprouts were produced by firms that appeared to have implemented key FDA guidelines. Although seed chlorination, if consistently applied, reduces pathogen burden on sprouts, it does not eliminate the risk of human infection. Further seed and sprouts disinfection technologies, some recently developed, will be needed to enhance sprouts safety and reduce human disease. Improved seed production practices could also decrease pathogen burden but, because seeds are a globally distributed commodity, will require international cooperation.

  5. Flow-enhanced solution printing of all-polymer solar cells

    SciTech Connect

    Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A.; Gu, Kevin; Gu, Xiaodan; Tee, Benjamin C. K.; Pang, Changhyun; Yan, Hongping; Zhao, Dahui; Toney, Michael F.; Mannsfeld, Stefan C. B.; Bao, Zhenan

    2015-08-12

    Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a similar to 90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. However, we expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.

  6. Flow-enhanced solution printing of all-polymer solar cells

    PubMed Central

    Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A.; Gu, Kevin; Gu, Xiaodan; Tee, Benjamin C. K.; Pang, Changhyun; Yan, Hongping; Zhao, Dahui; Toney, Michael F.; Mannsfeld, Stefan C. B.; Bao, Zhenan

    2015-01-01

    Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility. PMID:26264528

  7. Flow-enhanced solution printing of all-polymer solar cells.

    PubMed

    Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; Shaw, Leo; Wang, Cheng; Park, Steve; Guo, Yikun; Reinspach, Julia A; Gu, Kevin; Gu, Xiaodan; Tee, Benjamin C K; Pang, Changhyun; Yan, Hongping; Zhao, Dahui; Toney, Michael F; Mannsfeld, Stefan C B; Bao, Zhenan

    2015-08-12

    Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a ∼90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.

  8. Quantum Dot Light Enhancement Substrate for OLED Solid-State Lighting

    SciTech Connect

    James Perkins; Matthew Stevenson; Gagan Mahan; Seth Coe-Sullivan; Peter Kazlas

    2011-01-21

    With DOE Award No. DE-EE00000628, QD Vision developed and demonstrated a cost-competitive solution for increasing the light extraction efficiency of OLEDs with efficient and stable color rendering index (CRI) for solid state lighting (SSL). Solution processable quantum dot (QD) films were integrated into OLED ITO-glass substrates to generate tunable white emission from blue emitting OLED) devices as well as outcouple light from the ITO film. This QD light-enhancement substrate (QD-LED) technology demonstrated a 60% increase in OLED forward light out-coupling, a value which increases to 76% when considering total increase in multi-directional light output. The objective for the first year was an 80% increase in light output. This project seeks to develop and demonstrate a cost-competitive solution for realizing increased extraction efficiency organic light emitting devices (OLEDs) with efficient and stable color rendering index (CRI) for SSL. Solution processible quantum dot (QD) films will be utilized to generate tunable white emission from blue emitting phosphorescent OLED (Ph-OLED) devices.

  9. Efficient Biologically Inspired Photocell Enhanced by Delocalized Quantum States

    NASA Astrophysics Data System (ADS)

    Creatore, C.; Parker, M. A.; Emmott, S.; Chin, A. W.

    2013-12-01

    Artificially implementing the biological light reactions responsible for the remarkably efficient photon-to-charge conversion in photosynthetic complexes represents a new direction for the future development of photovoltaic devices. Here, we develop such a paradigm and present a model photocell based on the nanoscale architecture and molecular elements of photosynthetic reaction centers. Quantum interference of photon absorption and emission induced by the dipole-dipole interaction between molecular excited states guarantees an enhanced light-to-current conversion and power generation for a wide range of electronic, thermal, and optical parameters for optimized dipolar geometries. This result opens a promising new route for designing artificial light-harvesting devices inspired by biological photosynthesis and quantum technologies.

  10. Simple solution to the Fresnel-Kirchoff diffraction integral for application to refraction-enhanced radiography.

    PubMed

    Koch, J A; Landen, O L; Suter, L J; Masse, L P

    2013-07-01

    We present a simple solution to the Fresnel-Kirchoff diffraction integral that is appropriate for x-ray radiography of strongly absorbing and phase-shifting objects in the geometrical optics regime, where phase contrast enhancements can be considered to be caused by refraction by a semi-opaque object. We demonstrate its accuracy by comparison to brute-force numerical ray trace and diffraction calculations of a representative simulated object, and show excellent agreement for spatial scales corresponding to Fresnel numbers greater than unity. The result represents a significant improvement over approximate formulas typically used in analysis of refraction-enhanced radiographs, particularly for radiography of transient phenomena in objects that strongly refract and show significant absorption.

  11. GPs with enhanced surgical skills: a questionable solution for remote surgical services

    PubMed Central

    Vinden, Christopher; Ott, Michael C.

    2015-01-01

    Summary The Canadian College of Family Physicians recently decided to recognize family physicians with enhanced surgical skills (ESS) and has proposed a 1-year curriculum of surgical training. The purpose of this initiative is to bring or enhance surgical services to remote and underserviced areas. We feel that this proposed curriculum is overly ambitious and unrealistic and that it is unlikely to produce surgeons, or a system, capable of delivering high-quality surgical services. The convergence of a new training curriculum for general surgeons, coupled with the current oversupply of surgeons, provide an alternate pathway to meet the needs of these communities. A long-term solution will also require alternate funding models, a sophisticated and coordinated national locum service and a national review of the population and infrastructure requirements necessary for both sustainable resident surgical services and surgical outreach services. PMID:26574827

  12. Proximity enhanced quantum spin Hall state in graphene

    SciTech Connect

    Kou, Liangzhi; Hu, Feiming; Yan, Binghai; Wehling, Tim; Felser, Claudia; Frauenheim, Thomas; Chen, Changfeng

    2015-02-23

    Graphene is the first model system of two-dimensional topological insulator (TI), also known as quantum spin Hall (QSH) insulator. The QSH effect in graphene, however, has eluded direct experimental detection because of its extremely small energy gap due to the weak spin–orbit coupling. Here we predict by ab initio calculations a giant (three orders of magnitude) proximity induced enhancement of the TI energy gap in the graphene layer that is sandwiched between thin slabs of Sb2Te3 (or MoTe2). This gap (1.5 meV) is accessible by existing experimental techniques, and it can be further enhanced by tuning the interlayer distance via compression. We reveal by a tight-binding study that the QSH state in graphene is driven by the Kane–Mele interaction in competition with Kekulé deformation and symmetry breaking. As a result, the present work identifies a new family of graphene-based TIs with an observable and controllable bulk energy gap in the graphene layer, thus opening a new avenue for direct verification and exploration of the long-sought QSH effect in graphene.

  13. Proximity enhanced quantum spin Hall state in graphene

    DOE PAGES

    Kou, Liangzhi; Hu, Feiming; Yan, Binghai; ...

    2015-02-23

    Graphene is the first model system of two-dimensional topological insulator (TI), also known as quantum spin Hall (QSH) insulator. The QSH effect in graphene, however, has eluded direct experimental detection because of its extremely small energy gap due to the weak spin–orbit coupling. Here we predict by ab initio calculations a giant (three orders of magnitude) proximity induced enhancement of the TI energy gap in the graphene layer that is sandwiched between thin slabs of Sb2Te3 (or MoTe2). This gap (1.5 meV) is accessible by existing experimental techniques, and it can be further enhanced by tuning the interlayer distance viamore » compression. We reveal by a tight-binding study that the QSH state in graphene is driven by the Kane–Mele interaction in competition with Kekulé deformation and symmetry breaking. As a result, the present work identifies a new family of graphene-based TIs with an observable and controllable bulk energy gap in the graphene layer, thus opening a new avenue for direct verification and exploration of the long-sought QSH effect in graphene.« less

  14. Emotional brain states carry over and enhance future memory formation.

    PubMed

    Tambini, Arielle; Rimmele, Ulrike; Phelps, Elizabeth A; Davachi, Lila

    2017-02-01

    Emotional arousal can produce lasting, vivid memories for emotional experiences, but little is known about whether emotion can prospectively enhance memory formation for temporally distant information. One mechanism that may support prospective memory enhancements is the carry-over of emotional brain states that influence subsequent neutral experiences. Here we found that neutral stimuli encountered by human subjects 9-33 min after exposure to emotionally arousing stimuli had greater levels of recollection during delayed memory testing compared to those studied before emotional and after neutral stimulus exposure. Moreover, multiple measures of emotion-related brain activity showed evidence of reinstatement during subsequent periods of neutral stimulus encoding. Both slow neural fluctuations (low-frequency connectivity) and transient, stimulus-evoked activity predictive of trial-by-trial memory formation present during emotional encoding were reinstated during subsequent neutral encoding. These results indicate that neural measures of an emotional experience can persist in time and bias how new, unrelated information is encoded and recollected.

  15. Sensitivity enhancement in static solid-state NMR experiments via single- and multiple-quantum dipolar coherences.

    PubMed

    Gopinath, T; Veglia, Gianluigi

    2009-04-29

    We present a new method for enhancing the sensitivity in static solid-state NMR experiments for a gain in signal-to-noise ratio of up to 40%. This sensitivity enhancement is different from the corresponding solution NMR sensitivity enhancement schemes and is achieved by combining single- and multiple-quantum dipolar coherences. While this new approach is demonstrated for the polarization inversion spin exchange at magic angle (PISEMA) experiment, it can be generalized to the other separated local field experiments for solid-state NMR spectroscopy. This method will have a direct impact on solid-state NMR spectroscopy of liquid crystals as well as of membrane proteins aligned in lipid membranes.

  16. Solute Enhanced Strain Hardening of Aluminum Alloys to Achieve Improved Combinations of Strength and Toughness

    NASA Astrophysics Data System (ADS)

    Hovanec, Christopher James

    2011-12-01

    The feasibility of achieving improved combinations of strength and toughness in aluminum alloy 2524 through solute enhanced strain hardening (SESH) has been explored in this study and shown to be viable. The effectiveness of SESH is directly dependent on the strain hardening rate (SHR) of the material being processed. Aluminum alloy 2524 naturally ages to the T4-temper after solution heat treating and quenching. The SHR of strain free and post cold rolled material as a function of natural aging time has been measured by means of simple compression. It has been determined that the SHR of AA2524 is more effective with solute in solution rather than clustered into GP zones. It has also been shown that the typical rapid formation of GP zones at room temperature (natural aging) is inhibited by moderate cold rolling strains (□CR ≥ 0.2) through dislocation aided vacancy annihilation. The practical limitations of quenching rate have been determined using hardness and eddy current electrical conductivity measurements. It has been shown that too slow of a quench rate results in solute being lost to both the formation of GP zones and embrittling precipitates during the quench, while too rapid of a quench rate results in mid-plane cracking of the work piece during the SESH processing. The mid-plane cracking was overcome by using an uphill quenching procedure to relieve residual stresses within the work piece. Aluminum alloy 2524 strengthened through SESH to a yield strength 11% greater than that in the T6-Temper exhibits: equivalent toughness, 5% greater UTS, 1% greater elongation, 7% greater R.A., and absorbs 15% more energy during tensile testing. At yield strengths comparable to published data for 2x24 alloys, the SESH 2524 exhibited up to a 60% increase in fracture toughness. The fractured surfaces of the SESH material exhibited transgranular dimpled rupture as opposed to the grain boundary ductile fracture (GBPF) observed in the artificially aged material.

  17. Singular perturbation solutions of steady-state Poisson-Nernst-Planck systems.

    PubMed

    Wang, Xiang-Sheng; He, Dongdong; Wylie, Jonathan J; Huang, Huaxiong

    2014-02-01

    We study the Poisson-Nernst-Planck (PNP) system with an arbitrary number of ion species with arbitrary valences in the absence of fixed charges. Assuming point charges and that the Debye length is small relative to the domain size, we derive an asymptotic formula for the steady-state solution by matching outer and boundary layer solutions. The case of two ionic species has been extensively studied, the uniqueness of the solution has been proved, and an explicit expression for the solution has been obtained. However, the case of three or more ions has received significantly less attention. Previous work has indicated that the solution may be nonunique and that even obtaining numerical solutions is a difficult task since one must solve complicated systems of nonlinear equations. By adopting a methodology that preserves the symmetries of the PNP system, we show that determining the outer solution effectively reduces to solving a single scalar transcendental equation. Due to the simple form of the transcendental equation, it can be solved numerically in a straightforward manner. Our methodology thus provides a standard procedure for solving the PNP system and we illustrate this by solving some practical examples. Despite the fact that for three ions, previous studies have indicated that multiple solutions may exist, we show that all except for one of these solutions are unphysical and thereby prove the existence and uniqueness for the three-ion case.

  18. Efficient steady-state solution techniques for variably saturated groundwater flow

    NASA Astrophysics Data System (ADS)

    Farthing, Matthew W.; Kees, Christopher E.; Coffey, Todd S.; Kelley, C. T.; Miller, Cass T.

    We consider the simulation of steady-state variably saturated groundwater flow using Richards' equation (RE). The difficulties associated with solving RE numerically are well known. Most discretization approaches for RE lead to nonlinear systems that are large and difficult to solve. The solution of nonlinear systems for steady-state problems can be particularly challenging, since a good initial guess for the steady-state solution is often hard to obtain, and the resulting linear systems may be poorly scaled. Common approaches like Picard iteration or variations of Newton's method have their advantages but perform poorly with standard globalization techniques under certain conditions. Pseudo-transient continuation has been used in computational fluid dynamics for some time to obtain steady-state solutions for problems in which Newton's method with standard line-search strategies fails. Here, we examine the use of pseudo-transient continuation as well as Newton's method combined with standard globalization techniques for steady-state problems in heterogeneous domains. We investigate the methods' performance with direct and preconditioned Krylov iterative linear solvers. We then make recommendations for robust and efficient approaches to obtain steady-state solutions for RE under a range of conditions.

  19. Infinite product expansion of the Fokker–Planck equation with steady-state solution

    PubMed Central

    Martin, R. J.; Craster, R. V.; Kearney, M. J.

    2015-01-01

    We present an analytical technique for solving Fokker–Planck equations that have a steady-state solution by representing the solution as an infinite product rather than, as usual, an infinite sum. This method has many advantages: automatically ensuring positivity of the resulting approximation, and by design exactly matching both the short- and long-term behaviour. The efficacy of the technique is demonstrated via comparisons with computations of typical examples. PMID:26346100

  20. Anti-periodic solutions of Liénard equations with state dependent impulses

    NASA Astrophysics Data System (ADS)

    Belley, J.-M.; Bondo, É.

    2016-10-01

    Subject to a priori bounds, Liénard equations with state dependent impulsive forcing are shown to admit a unique absolutely continuous anti-periodic solution with first derivative of bounded variation on finite intervals. The point-wise convergence of a sequence of iterates to the solution is obtained, along with a bound for the rate of convergence. The results are applied to Josephson's and van der Pol's equations.

  1. Approximate semi-analytical solutions for the steady-state expansion of a contactor plasma

    NASA Astrophysics Data System (ADS)

    Camporeale, E.; Hogan, E. A.; MacDonald, E. A.

    2015-04-01

    We study the steady-state expansion of a collisionless, electrostatic, quasi-neutral plasma plume into vacuum, with a fluid model. We analyze approximate semi-analytical solutions, that can be used in lieu of much more expensive numerical solutions. In particular, we focus on the earlier studies presented in Parks and Katz (1979 American Institute of Aeronautics, Astronautics Conf. vol 1), Korsun and Tverdokhlebova (1997 33rd Joint Prop. Conf. (Seattle, WA) AIAA-97-3065), and Ashkenazy and Fruchtman (2001 27th Int. Electric Propulsion Conf. (Pasadena, CA)). By calculating the error with respect to the numerical solution, we can judge the range of validity for each solution. Moreover, we introduce a generalization of earlier models that has a wider range of applicability, in terms of plasma injection profiles. We conclude by showing a straightforward way to extend the discussed solutions to the case of a plasma plume injected with non-null azimuthal velocity.

  2. f-state luminescence of lanthanide and actinide ions in solution

    SciTech Connect

    Beitz, J.V.

    1993-09-01

    Detailed studies of the luminescence of aquated Am{sup 3+} are presented in the context of prior lanthanide and actinide ion work. The luminescing state of aquated Am{sup 3+} is confirmed to be {sup 5}D{sub l} based on observed emission and excitation spectra. The luminescence lifetime of Am{sup 3+} in H{sub 2}O solution is (22 {plus_minus} 3) ns and (155 {plus_minus} 4) ns in D{sub 2}O solution at 295 K. Judd-Ofelt transition intensity theory qualitatively describes the observed Am{sup 3+} relative integrated fluorescence intensities. Recent luminescence studies on complexed trivalent f-element ions in solution are reviewed as to the similarities and differences between lanthanide ion 4f state and actinide ion 5f state properties.

  3. Isotope Labeling for Solution and Solid-State NMR Spectroscopy of Membrane Proteins

    PubMed Central

    Verardi, Raffaello; Traaseth, Nathaniel J.; Masterson, Larry R.; Vostrikov, Vitaly V.; Veglia, Gianluigi

    2013-01-01

    In this chapter, we summarize the isotopic labeling strategies used to obtain high-quality solution and solid-state NMR spectra of biological samples, with emphasis on integral membrane proteins (IMPs). While solution NMR is used to study IMPs under fast tumbling conditions, such as in the presence of detergent micelles or isotropic bicelles, solid-state NMR is used to study the structure and orientation of IMPs in lipid vesicles and bilayers. In spite of the tremendous progress in biomolecular NMR spectroscopy, the homogeneity and overall quality of the sample is still a substantial obstacle to overcome. Isotopic labeling is a major avenue to simplify overlapped spectra by either diluting the NMR active nuclei or allowing the resonances to be separated in multiple dimensions. In the following we will discuss isotopic labeling approaches that have been successfully used in the study of IMPs by solution and solid-state NMR spectroscopy. PMID:23076578

  4. Electro-enhanced removal of copper ions from aqueous solutions by capacitive deionization.

    PubMed

    Huang, Shu-Yun; Fan, Chen-Shiuan; Hou, Chia-Hung

    2014-08-15

    This study was performed to determine the feasibility of electrosorptive removal of copper ions from aqueous solutions using a capacitive deionization process. The electrosorptive potential of copper ions was determined using cyclic voltammetry measurements, and copper electrodeposition could be suppressed at a voltage less than 0.8 V. Importantly, the experimental results demonstrated a significant enhancement of electrosorption capability of copper ions using the activated carbon electrodes under electro-assistance, associated with electrical double-layer charging. At 0.8 V, the equilibrium electrosorption capacity was enhanced to 24.57 mg/g based on the Langmuir model, and the electrosorption constant rate was increased to 0.038 min(-1) simulated by a first-order kinetics model. Moreover, the activated carbon electrode showed great regeneration performance for the removal of low level copper ions. Additional experiments regarding electrosorption selectivity were performed in the presence of sodium chloride, natural organic matter, or dissolved silica. Copper ions that were preferentially electroadsorbed on the electrode surface can be effectively removed in a competitive environment. Therefore, the electrosorption process using activated carbon electrodes can be recommended to treat copper solutions at low concentrations for wastewater treatment and water purification.

  5. A simple solution for antibody signal enhancement in immunofluorescence and triple immunogold assays.

    PubMed

    Rosas-Arellano, Abraham; Villalobos-González, Juan B; Palma-Tirado, Lourdes; Beltrán, Felipe A; Cárabez-Trejo, Alfonso; Missirlis, Fanis; Castro, Maite A

    2016-10-01

    Immunolocalization techniques are standard in biomedical research. Tissue fixation with aldehydes and cell membrane permeabilization with detergents can distort the specific binding of antibodies to their high affinity epitopes. In immunofluorescence protocols, it is desirable to quench the sample's autofluorescence without reduction of the antibody-dependent signal. Here we show that adding glycine to the blocking buffer and diluting the antibodies in a phosphate saline solution containing glycine, Triton X-100, Tween20 and hydrogen peroxide increase the specific antibody signal in tissue immunofluorescence and immunogold electron microscopy. This defined antibody signal enhancer (ASE) solution gives similar results to the commercially available Pierce Immunostain Enhancer (PIE). Furthermore, prolonged tissue incubation in resin and fixative and application of ASE or PIE are described in an improved protocol for triple immunogold electron microscopy that is used to show co-localization of GABA-A ρ2 and dopamine D2 receptors in GFAP-positive astrocytes in the mouse striatum. The addition of glycine, Triton X-100, Tween20 and hydrogen peroxide during antibody incubation steps is recommended in immunohistochemistry methods.

  6. Analytical steady-state solutions for water-limited cropping systems using saline irrigation water

    NASA Astrophysics Data System (ADS)

    Skaggs, T. H.; Anderson, R. G.; Corwin, D. L.; Suarez, D. L.

    2014-12-01

    Due to the diminishing availability of good quality water for irrigation, it is increasingly important that irrigation and salinity management tools be able to target submaximal crop yields and support the use of marginal quality waters. In this work, we present a steady-state irrigated systems modeling framework that accounts for reduced plant water uptake due to root zone salinity. Two explicit, closed-form analytical solutions for the root zone solute concentration profile are obtained, corresponding to two alternative functional forms of the uptake reduction function. The solutions express a general relationship between irrigation water salinity, irrigation rate, crop salt tolerance, crop transpiration, and (using standard approximations) crop yield. Example applications are illustrated, including the calculation of irrigation requirements for obtaining targeted submaximal yields, and the generation of crop-water production functions for varying irrigation waters, irrigation rates, and crops. Model predictions are shown to be mostly consistent with existing models and available experimental data. Yet the new solutions possess advantages over available alternatives, including: (i) the solutions were derived from a complete physical-mathematical description of the system, rather than based on an ad hoc formulation; (ii) the analytical solutions are explicit and can be evaluated without iterative techniques; (iii) the solutions permit consideration of two common functional forms of salinity induced reductions in crop water uptake, rather than being tied to one particular representation; and (iv) the utilized modeling framework is compatible with leading transient-state numerical models.

  7. Billion-fold enhancement in sensitivity of nuclear magnetic resonance spectroscopy for magnesium ions in solution.

    PubMed

    Gottberg, Alexander; Stachura, Monika; Kowalska, Magdalena; Bissell, Mark L; Arcisauskaite, Vaida; Blaum, Klaus; Helmke, Alexander; Johnston, Karl; Kreim, Kim; Larsen, Flemming H; Neugart, Rainer; Neyens, Gerda; Garcia Ruiz, Ronald F; Szunyogh, Daniel; Thulstrup, Peter W; Yordanov, Deyan T; Hemmingsen, Lars

    2014-12-15

    β-nuclear magnetic resonance (NMR) spectroscopy is highly sensitive compared to conventional NMR spectroscopy, and may be applied for several elements across the periodic table. β-NMR has previously been successfully applied in the fields of nuclear and solid-state physics. In this work, β-NMR is applied, for the first time, to record an NMR spectrum for a species in solution. (31)Mg β-NMR spectra are measured for as few as 10(7) magnesium ions in ionic liquid (EMIM-Ac) within minutes, as a prototypical test case. Resonances are observed at 3882.9 and 3887.2 kHz in an external field of 0.3 T. The key achievement of the current work is to demonstrate that β-NMR is applicable for the analysis of species in solution, and thus represents a novel spectroscopic technique for use in general chemistry and potentially in biochemistry.

  8. Bound state solutions of the Schrödinger equation for modified Kratzer's molecular potential

    NASA Astrophysics Data System (ADS)

    Berkdemir, Cüneyt; Berkdemir, Ayşe; Han, Jiaguang

    2006-01-01

    We present the arbitrary angular momentum solutions of the Schrödinger equation for a diatomic molecule with the modified Kratzer potential De[( r - re)/ r] 2. The bound state energy eigenvalues and the corresponding eigenfunctions are obtained by the use of the Nikiforov-Uvarov (NU) method which is related to the solutions in terms of Jacobi polynomials. The bound states are calculated for various values of ℓ with n ⩽ 5 and applied to several diatomic molecules. All of these calculations present an effective and methodological procedure under the NU method to investigate the Kratzer's molecular systems.

  9. Periodic solution for state-dependent impulsive shunting inhibitory CNNs with time-varying delays.

    PubMed

    Şaylı, Mustafa; Yılmaz, Enes

    2015-08-01

    In this paper, we consider existence and global exponential stability of periodic solution for state-dependent impulsive shunting inhibitory cellular neural networks with time-varying delays. By means of B-equivalence method, we reduce these state-dependent impulsive neural networks system to an equivalent fix time impulsive neural networks system. Further, by using Mawhin's continuation theorem of coincide degree theory and employing a suitable Lyapunov function some new sufficient conditions for existence and global exponential stability of periodic solution are obtained. Previous results are improved and extended. Finally, we give an illustrative example with numerical simulations to demonstrate the effectiveness of our theoretical results.

  10. State of ions in electrolyte solutions in the ionic-plasma approximation

    SciTech Connect

    Baldanov, M.M.; Mokhosoev, M.V.

    1986-04-01

    This paper examines the state of ions in the framework of the concept of an ionic plasma. Results are presented of the evaluations of the equivalent conductivity of lithium chloride in aqueous solutions at 18 C. The Debye-Falkenhagne effect and the Wien effect are discussed. The proposed interpretation of the state of ions in electrolyte solutions gives a more natural and more systematic explanation for such factors as the Debye-Falkenhagen dispersion of the electrical conductivity, the Wien effect, and the activity coefficients of electrolytes.

  11. A solid state and solution NMR study of the tautomerism in hydroxyquinoline carboxylic acids.

    PubMed

    Gudat, Dietrich; Nycz, Jacek E; Polanski, Jaroslaw

    2008-01-01

    Some hydroxyquinoline carboxylic acids and their conjugate acids and bases were characterized by 13C and 15N NMR spectroscopy in solution and in the solid state. Differences in 13C and, in particular, 15N chemical shift patterns allow to distinguish between individual tautomers and confirm the presence of zwitterionic species in the solid state. Solution NMR spectra in dimethyl sulfoxide (DMSO) show effects resulting as a consequence of dynamic exchange and suggest the presence of an equilibrium mixture of hydroxyquinoline carboxylic acid and zwitterionic hydroxyquinolinium carboxylate tautomers.

  12. {sup 1}H relaxation enhancement induced by nanoparticles in solutions: Influence of magnetic properties and diffusion

    SciTech Connect

    Kruk, D.; Korpała, A.; Taheri, S. Mehdizadeh; Förster, S.; Kozłowski, A.; Rössler, E. A.

    2014-05-07

    Magnetic nanoparticles that induce nuclear relaxation are the most promising materials to enhance the sensitivity in Magnetic Resonance Imaging. In order to provide a comprehensive understanding of the magnetic field dependence of the relaxation enhancement in solutions, Nuclear Magnetic Resonance {sup 1}H spin-lattice relaxation for decalin and toluene solutions of various Fe{sub 2}O{sub 3} nanoparticles was investigated. The relaxation experiments were performed in a frequency range of 10 kHz–20 MHz by applying Field Cycling method, and in the temperature range of 257–298 K, using nanoparticles differing in size and shape: spherical – 5 nm diameter, cubic – 6.5 nm diameter, and cubic – 9 nm diameter. The relaxation dispersion data were interpreted in terms of a theory of nuclear relaxation induced by magnetic crystals in solution. The approach was tested with respect to its applicability depending on the magnetic characteristics of the nanocrystals and the time-scale of translational diffusion of the solvent. The role of Curie relaxation and the contributions to the overall {sup 1}H spin-lattice relaxation associated with the electronic spin-lattice and spin-spin relaxation was thoroughly discussed. It was demonstrated that the approach leads to consistent results providing information on the magnetic (electronic) properties of the nanocrystals, i.e., effective electron spin and relaxation times. In addition, features of the {sup 1}H spin-lattice relaxation resulting from the electronic properties of the crystals and the solvent diffusion were explained.

  13. Mechanisms of enhanced total organic carbon elimination from oxalic acid solutions by electro-peroxone process.

    PubMed

    Wang, Huijiao; Yuan, Shi; Zhan, Juhong; Wang, Yujue; Yu, Gang; Deng, Shubo; Huang, Jun; Wang, Bin

    2015-09-01

    Electro-peroxone (E-peroxone) is a novel electrocatalytic ozonation process that combines ozonation and electrolysis process to enhance pollutant degradation during water and wastewater treatment. This enhancement has been mainly attributed to several mechanisms that increase O3 transformation to ·OH in the E-peroxone system, e.g., electro-generation of H2O2 from O2 at a carbon-based cathode and its subsequent peroxone reaction with O3 to ·OH, electro-reduction of O3 to ·OH at the cathode, and O3 decomposition to ·OH at high local pH near the cathode. To get more insight how these mechanisms contribute respectively to the enhancement, this study investigated total organic carbon (TOC) elimination from oxalic acid (OA) solutions by the E-peroxone process. Results show that the E-peroxone process significantly increased TOC elimination rate by 10.2-12.5 times compared with the linear addition of the individual rates of corresponding ozonation and electrolysis process. Kinetic analyses reveal that the electrochemically-driven peroxone reaction is the most important mechanism for the enhanced TOC elimination rate, while the other mechanisms contribute minor to the enhancement by a factor of 1.6-2.5. The results indicate that proper selection of electrodes that can effectively produce H2O2 at the cathode is critical to maximize TOC elimination in the E-peroxone process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Analytical solution and simplified analysis of coupled parent-daughter steady-state transport with multirate mass transfer

    Treesearch

    R. Haggerty

    2013-01-01

    In this technical note, a steady-state analytical solution of concentrations of a parent solute reacting to a daughter solute, both of which are undergoing transport and multirate mass transfer, is presented. Although the governing equations are complicated, the resulting solution can be expressed in simple terms. A function of the ratio of concentrations, In (daughter...

  15. Model study of enhanced oil recovery by flooding with aqueous surfactant solution and comparison with theory.

    PubMed

    Fletcher, Paul D I; Savory, Luke D; Woods, Freya; Clarke, Andrew; Howe, Andrew M

    2015-03-17

    With the aim of elucidating the details of enhanced oil recovery by surfactant solution flooding, we have determined the detailed behavior of model systems consisting of a packed column of calcium carbonate particles as the porous rock, n-decane as the trapped oil, and aqueous solutions of the anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT). The AOT concentration was varied from zero to above the critical aggregation concentration (cac). The salt content of the aqueous solutions was varied to give systems of widely different, post-cac oil-water interfacial tensions. The systems were characterized in detail by measuring the permeability behavior of the packed columns, the adsorption isotherms of AOT from the water to the oil-water interface and to the water-calcium carbonate interface, and oil-water-calcium carbonate contact angles. Measurements of the percent oil recovery by pumping surfactant solutions into calcium carbonate-packed columns initially filled with oil were analyzed in terms of the characterization results. We show that the measured contact angles as a function of AOT concentration are in reasonable agreement with those calculated from values of the surface energy of the calcium carbonate-air surface plus the measured adsorption isotherms. Surfactant adsorption onto the calcium carbonate-water interface causes depletion of its aqueous-phase concentration, and we derive equations which enable the concentration of nonadsorbed surfactant within the packed column to be estimated from measured parameters. The percent oil recovery as a function of the surfactant concentration is determined solely by the oil-water-calcium carbonate contact angle for nonadsorbed surfactant concentrations less than the cac. For surfactant concentrations greater than the cac, additional oil removal occurs by a combination of solubilization and emulsification plus oil mobilization due to the low oil-water interfacial tension and a pumping pressure increase.

  16. Structural Analysis of Protein-RNA Complexes in Solution Using NMR Paramagnetic Relaxation Enhancements.

    PubMed

    Hennig, Janosch; Warner, Lisa R; Simon, Bernd; Geerlof, Arie; Mackereth, Cameron D; Sattler, Michael

    2015-01-01

    Biological activity in the cell is predominantly mediated by large multiprotein and protein-nucleic acid complexes that act together to ensure functional fidelity. Nuclear magnetic resonance (NMR) spectroscopy is the only method that can provide information for high-resolution three-dimensional structures and the conformational dynamics of these complexes in solution. Mapping of binding interfaces and molecular interactions along with the characterization of conformational dynamics is possible for very large protein complexes. In contrast, de novo structure determination by NMR becomes very time consuming and difficult for protein complexes larger than 30 kDa as data are noisy and sparse. Fortunately, high-resolution structures are often available for individual domains or subunits of a protein complex and thus sparse data can be used to define their arrangement and dynamics within the assembled complex. In these cases, NMR can therefore be efficiently combined with complementary solution techniques, such as small-angle X-ray or neutron scattering, to provide a comprehensive description of the structure and dynamics of protein complexes in solution. Particularly useful are NMR-derived paramagnetic relaxation enhancements (PREs), which provide long-range distance restraints (ca. 20Å) for structural analysis of large complexes and also report on conformational dynamics in solution. Here, we describe the use of PREs from sample production to structure calculation, focusing on protein-RNA complexes. On the basis of recent examples from our own research, we demonstrate the utility, present protocols, and discuss potential pitfalls when using PREs for studying the structure and dynamic features of protein-RNA complexes.

  17. Uniqueness of Positive Ground State Solutions of the Logarithmic Schrödinger Equation

    NASA Astrophysics Data System (ADS)

    Troy, William C.

    2016-12-01

    We prove the uniqueness of positive ground state solutions of the problem { {{d2u}/{dr2}} + {{n-1}/{r}}{du/dr}} + u ln(|u|) = 0}, {u(r) > 0 forall r ≥ 0}, and {(u(r),u'(r)) to (0, 0)} as {r to ∞}. This equation is derived from the logarithmic Schrödinger equation {iψt = {Δ} ψ + u ln (|u|2)}, and also from the classical equation {{{partial u}/{partial t}} = {Δ} u +u (|u|^{p-1}) -u}. For each {n ≥ 1}, a positive ground state solution is { u0(r) = exp (-{r^2/4} + {n/2}), 0 ≤ r < ∞}. We combine {u0(r)} with energy estimates and associated Ricatti equation estimates to prove that, for each {n in [1, 9 ]}, {u0(r)} is the only positive ground state. We also investigate the stability of {u0(r)}. Several open problems are stated.

  18. Solvating additives drive solution-mediated electrochemistry and enhance toroid growth in non-aqueous Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Aetukuri, Nagaphani B.; McCloskey, Bryan D.; García, Jeannette M.; Krupp, Leslie E.; Viswanathan, Venkatasubramanian; Luntz, Alan C.

    2015-01-01

    Given their high theoretical specific energy, lithium-oxygen batteries have received enormous attention as possible alternatives to current state-of-the-art rechargeable Li-ion batteries. However, the maximum discharge capacity in non-aqueous lithium-oxygen batteries is limited to a small fraction of its theoretical value due to the build-up of insulating lithium peroxide (Li2O2), the battery’s primary discharge product. The discharge capacity can be increased if Li2O2 forms as large toroidal particles rather than as a thin conformal layer. Here, we show that trace amounts of electrolyte additives, such as H2O, enhance the formation of Li2O2 toroids and result in significant improvements in capacity. Our experimental observations and a growth model show that the solvating properties of the additives prompt a solution-based mechanism that is responsible for the growth of Li2O2 toroids. We present a general formalism describing an additive’s tendency to trigger the solution process, providing a rational design route for electrolytes that afford larger lithium-oxygen battery capacities.

  19. Size evolution and surface characterization of solid-state nanopores in different aqueous solutions.

    PubMed

    Li, Qingtao; Zhao, Qing; Lu, Bo; Zhang, Hengbin; Liu, Song; Tang, Zhipeng; Qu, Lijia; Zhu, Rui; Zhang, Jingmin; You, Liping; Yang, Fuhua; Yu, Dapeng

    2012-03-07

    The stability and surface evolution of solid-state nanopores in aqueous solutions are extremely important since they would get immersed in solutions during DNA translocation experiment for DNA analyses. In this work, we systematically studied the size evolution of SiN nanopores in ethanol, deionized water and potassium chloride (KCl) solutions by careful surface characterization and composition analyses using a transmission electron microscope. Surprisingly, we found that nanopores closed up completely in ethanol in an hour and showed a 30% and 20% size decrease in deionized water and KCl solutions, respectively. Strong evidence of surface oxidation was found by composition analyses in the nanopore area. Nanopore size evolution was strongly dependent on initial pore size and solution pH value. In pH = 13 KCl solution, SiN nanopores were observed to increase in size instead of decrease. The results not only provide useful information for DNA detection based on solid-state nanopores, but can also guide design and application of other nanodevices exposed to electrolyte-solvent systems such as cell-on-a-chip devices and biosensors.

  20. Spatial and temporal variation of surface-enhanced Raman scattering at Ag nanowires in aqueous solution

    SciTech Connect

    Clayton, Daniel A.; McPherson, Tyler; Pan, Shanlin; Chen, Mingyang; Dixon, David A.; Hu, Dehong

    2012-12-13

    We present surface enhanced Raman spectroscopy (SERS) and Raman imaging of small organic molecules at well-defined nanostructures formed by single silver nanowires (NWs). We show that SERS can be obtained at single, crossed, and bundled Ag NWs for mercaptopyridine, adenine, cytosine, guanine, and thymine. Crossed wires and parallel Ag NWs have SERS enhancement factors much higher than single Ag NWs. New additional junctions formed by a silver nanoparticle and a single Ag NW, and bundled NWs provide SERS intensity higher than a single Ag NW. The SERS signal of single Ag NWs can be further enhanced by decorating the Ag NW surface with gold nanoparticles using electroless deposition. Single Ag NW Raman imaging with a 10 ms time resolution when compared with photoluminescence (PL) imaging results reveal a different dynamic response of SERS and PL under steady state laser excitation. Dynamic photoluminescence blinking activities are suppressed in the presence of the surface coating of Raman active molecules (e.g., mercaptopyridine) and the SERS signal is quite stable in a wide field excitation configuration. The Discrete Dipole Approximation (DDA) method was used to calculate the local field intensity that can be applied to help understand the enhanced PL and SERS at the junction of Ag NWs

  1. A solution state diode using semiconductor polymer nanorods with nanogap electrodes.

    PubMed

    Mutlu, Senol; Sonmez, Bedri Gurkan

    2012-06-22

    A solution state polymer diode, which uses regioregular poly(3-hexylthiophene-2,5-diyl) (P3HT):dichlorobenzene solution as the semiconductor between highly doped p-type silicon and aluminum electrodes has been built. Electrodes separated by a 40 nm gap enable intra-chain charge carrier transfer through the lengths of single polymer chains. This prevents chain to chain hopping and chain entanglements, increasing carrier mobility. The degradation with time and hysteresis effects of the diodes are measured. An optimal P3HT solution concentration of 6 mg ml(-1) is found. A current density of at least 300 mA cm(-2) is achieved, indicating at least a six-fold improvement in carrier mobility compared to previously fabricated solid state P3HT diodes.

  2. On the existence of sign changing bound state solutions of a quasilinear equation

    NASA Astrophysics Data System (ADS)

    Cortázar, Carmen; García-Huidobro, Marta; Yarur, Cecilia S.

    In this paper we establish the existence of bound state solutions having a prescribed number of sign changes for (P) Δmu+f(u)=0, x∈RN, N⩾m>1, where Δmu=∇ṡ(|∇u). Our result is new even for the case of the Laplacian (m=2).

  3. USING HIGH-RESOLUTION SOLUTION-STATE NMR SPECTROSCOPY TO INVESTIGATE PMDI REACTIONS WITH WOOD

    USDA-ARS?s Scientific Manuscript database

    Solution-state NMR spectroscopy provides a powerful tool for understanding the formation of chemical bonds between wood components and adhesives. Finely ground cell wall (CW) material fully dissolves in a solvent system containing dimethylsulfoxide (DMSO-d6) and N-methyl¬imidazole (NMI-d6), keeping ...

  4. C1 + α-strict solutions and wellposedness of abstract differential equations with state dependent delay

    NASA Astrophysics Data System (ADS)

    Hernandez, Eduardo; Pierri, Michelle; Wu, Jianhong

    2016-12-01

    We study the existence and uniqueness of C 1 + α-strict solutions for a general class of abstract differential equations with state dependent delay. We also study the local well-posedness of this type of problems on subspaces of C 1 + α ([ - p , 0 ] ; X). Some examples involving partial differential equations are presented.

  5. High-resolution solution-state NMR of unfractionated plant cell walls

    Treesearch

    John Ralph; Fachuang Lu; Hoon Kim; Dino Ress; Daniel J. Yelle; Kenneth E. Hammel; Sally A. Ralph; Bernadette Nanayakkara; Armin Wagner; Takuya Akiyama; Paul F. Schatz; Shawn D. Mansfield; Noritsugu Terashima; Wout Boerjan; Bjorn Sundberg; Mattias Hedenstrom

    2009-01-01

    Detailed structural studies on the plant cell wall have traditionally been difficult. NMR is one of the preeminent structural tools, but obtaining high-resolution solution-state spectra has typically required fractionation and isolation of components of interest. With recent methods for dissolution of, admittedly, finely divided plant cell wall material, the wall can...

  6. Efficient and Color-Tunable Oxyfluoride Solid Solution Phosphors for Solid-State White Lighting

    SciTech Connect

    Im, Won Bin; George, Nathan; Kurzman, Joshua; Brinkley, Stuart; Mikhailovsky, Alexander; Hu, Jerry; Chmelka, Bradley F.; DenBaars, Steven P.; Seshadri, Ram

    2012-09-06

    A solid solution strategy helps increase the efficiency of Ce{sup 3+} oxyfluoride phosphors for solid-state white lighting. The use of a phosphor-capping architecture provides additional light extraction. The accompanying image displays electroluminescence spectra from a 434-nm InGaN LED phosphor that has been capped with the oxyfluoride phosphor.

  7. Existence of ground state solutions to Dirac equations with vanishing potentials at infinity

    NASA Astrophysics Data System (ADS)

    Figueiredo, Giovany M.; Pimenta, Marcos T. O.

    2017-01-01

    In this work we study the existence of ground-state solutions of Dirac equations with potentials which are allowed to vanish at infinity. The approach is based on minimization of the energy functional over a generalized Nehari set. Some conditions on the potentials are given in order to overcome the lack of compactness.

  8. Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution.

    PubMed

    Lee, M H; Kim, J Y; Kim, W H; Jung, E C; Jee, K Y

    2008-12-01

    The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO(3) and HClO(4). The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III) approximately Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9M HCl medium was applied to IAEA reference soils where the activity concentrations of (239,240)Pu and (238)Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

  9. The equation of state for solutions of the sunflower oil+isomerhexane system

    NASA Astrophysics Data System (ADS)

    Safarov, M. M.; Abdukhamidova, Z.

    1995-11-01

    The article presents the results of an experimental investigation into the density of solutions of the sunflower oil+isomerhexane system (from 23 to 75%) at temperatures of from 293 to 450 K and pressures of from 0.101 to 98.1 MPa. An equation of state is obtained.

  10. alphaB-crystallin: a hybrid solid-state/solution-state NMR investigation reveals structural aspects of the heterogeneous oligomer.

    PubMed

    Jehle, Stefan; van Rossum, Barth; Stout, Joseph R; Noguchi, Satoshi M; Falber, Katja; Rehbein, Kristina; Oschkinat, Hartmut; Klevit, Rachel E; Rajagopal, Ponni

    2009-02-06

    Atomic-level structural information on alphaB-Crystallin (alphaB), a prominent member of the small heat-shock protein family, has been a challenge to obtain due its polydisperse oligomeric nature. We show that magic-angle spinning solid-state NMR can be used to obtain high-resolution information on an approximately 580-kDa human alphaB assembled from 175-residue 20-kDa subunits. An approximately 100-residue alpha-crystallin domain is common to all small heat-shock proteins, and solution-state NMR was performed on two different alpha-crystallin domain constructs isolated from alphaB. In vitro, the chaperone-like activities of full-length alphaB and the isolated alpha-crystallin domain are identical. Chemical shifts of the backbone and C(beta) resonances have been obtained for residues 64-162 (alpha-crystallin domain plus part of the C-terminus) in alphaB and the isolated alpha-crystallin domain by solid-state and solution-state NMR, respectively. Both sets of data strongly predict six beta-strands in the alpha-crystallin domain. A majority of residues in the alpha-crystallin domain have similar chemical shifts in both solid-state and solution-state, indicating similar structures for the domain in its isolated and oligomeric forms. Sites of intersubunit interaction are identified from chemical shift differences that cluster to specific regions of the alpha-crystallin domain. Multiple signals are observed for the resonances of M68 in the oligomer, identifying the region containing this residue as existing in heterogeneous environments within alphaB. Evidence for a novel dimerization motif in the human alpha-crystallin domain is obtained by a comparison of (i) solid-state and solution-state chemical shift data and (ii) (1)H-(15)N heteronuclear single quantum coherence spectra as a function of pH. The isolated alpha-crystallin domain undergoes a dimer-monomer transition over the pH range 7.5-6.8. This steep pH-dependent switch may be important for alphaB to function

  11. αB-Crystallin. A Hybrid Solid-State/Solution-State NMR Investigation Reveals Structural Aspects of the Heterogeneous Oligomer

    SciTech Connect

    Jehle, Stefan; van Rossum, Barth; Stout, Joseph R.; Noguchi, Satoshi M.; Falber, Katja; Rehbein, Kristina; Oschkinat, Hartmut; Klevit, Rachel E.; Rajagopal, Ponni

    2008-11-14

    Atomic-level structural information on αB-Crystallin (αB), a prominent member of the small heat-shock protein family, has been a challenge to obtain due its polydisperse oligomeric nature. We show that magic-angle spinning solid-state NMR can be used to obtain high-resolution information on an ~580-kDa human αB assembled from 175-residue 20-kDa subunits. An ~100-residue α-crystallin domain is common to all small heat-shock proteins, and solution-state NMR was performed on two different α- crystallin domain constructs isolated from αB. In vitro, the chaperone-like activities of full-length αB and the isolated α-crystallin domain are identical. Chemical shifts of the backbone and Cβ resonances have been obtained for residues 64–162 (α-crystallin domain plus part of the C-terminus) in αB and the isolated α-crystallin domain by solid-state and solution-state NMR, respectively. Both sets of data strongly predict six β-strands in the α-crystallin domain. A majority of residues in the α-crystallin domain have similar chemical shifts in both solid-state and solution-state, indicating similar structures for the domain in its isolated and oligomeric forms. Sites of intersubunit interaction are identified from chemical shift differences that cluster to specific regions of the α-crystallin domain. Multiple signals are observed for the resonances of M68 in the oligomer, identifying the region containing this residue as existing in heterogeneous environments within αB. Evidence for a novel dimerization motif in the human α-crystallin domain is obtained by a comparison of (i) solid-state and solution-state chemical shift data and (ii) 1H–15N heteronuclear single quantum coherence spectra as a function of pH. The isolated α-crystallin domain undergoes a dimer–monomer transition over the pH range 7.5–6.8. This steep pHdependent switch may be important for αB to function optimally (e.g., to preserve the filament integrity

  12. A fluorescent chemosensor for Zn(II). Exciplex formation in solution and the solid state.

    PubMed

    Bencini, Andrea; Berni, Emanuela; Bianchi, Antonio; Fornasari, Patrizia; Giorgi, Claudia; Lima, Joao C; Lodeiro, Carlos; Melo, Maria J; de Melo, J Seixas; Parola, Antonio Jorge; Pina, Fernando; Pina, Joao; Valtancoli, Barbara

    2004-07-21

    The macrocyclic phenanthrolinophane 2,9-[2,5,8-triaza-5-(N-anthracene-9-methylamino)ethyl]-[9]-1,10-phenanthrolinophane (L) bearing a pendant arm containing a coordinating amine and an anthracene group forms stable complexes with Zn(II), Cd(II) and Hg(II) in solution. Stability constants of these complexes were determined in 0.10 mol dm(-3) NMe(4)Cl H(2)O-MeCN (1:1, v/v) solution at 298.1 +/- 0.1 K by means of potentiometric (pH metric) titration. The fluorescence emission properties of these complexes were studied in this solvent. For the Zn(II) complex, steady-state and time-resolved fluorescence studies were performed in ethanol solution and in the solid state. In solution, intramolecular pi-stacking interaction between phenanthroline and anthracene in the ground state and exciplex emission in the excited state were observed. From the temperature dependence of the photostationary ratio (I(Exc)/I(M)), the activation energy for the exciplex formation (E(a)) and the binding energy of the exciplex (-DeltaH) were determined. The crystal structure of the [ZnLBr](ClO(4)).H(2)O compound was resolved, showing that in the solid state both intra- and inter-molecular pi-stacking interactions are present. Such interactions were also evidenced by UV-vis absorption and emission spectra in the solid state. The absorption spectrum of a thin film of the solid complex is red-shifted compared with the solution spectra, whereas its emission spectrum reveals the unique featureless exciplex band, blue shifted compared with the solution. In conjunction with X-ray data the solid-state data was interpreted as being due to a new exciplex where no pi-stacking (full overlap of the pi-electron cloud of the two chromophores - anthracene and phenanthroline) is observed. L is a fluorescent chemosensor able to signal Zn(II) in presence of Cd(II) and Hg(II), since the last two metal ions do not give rise either to the formation of pi-stacking complexes or to exciplex emission in solution.

  13. Optimal unambiguous state discrimination of two density matrices: Lower bound and class of exact solutions

    SciTech Connect

    Raynal, Philippe; Luetkenhaus, Norbert

    2005-08-15

    Recently the problem of unambiguous state discrimination of mixed quantum states has attracted much attention. So far, bounds on the optimum success probability have been derived [T. Rudolph, R. W. Spekkens, and P. S. Turner, Phys. Rev. A 68, 010301(R) (2003)]. For two mixed states they are given in terms of the fidelity. Here we give tighter bounds as well as necessary and sufficient conditions for two mixed states to reach these bounds. Moreover we construct the corresponding optimal measurement strategies. With this result, we provide analytical solutions for unambiguous discrimination of a class of generic mixed states. This goes beyond known results which are all reducible to some pure state case. Additionally, we show that examples exist where the bounds cannot be reached.

  14. Does State Aid Stimulate Public Library Expenditures? Evidence from Pennsylvania's Enhancement Aid Program

    ERIC Educational Resources Information Center

    Stine, William F.

    2006-01-01

    Pennsylvania public libraries began receiving increased allotments of state aid in 2000. In the first two years of enhancement aid, total state aid received by Pennsylvania libraries more than doubled. This reversed the trend of little growth in the years preceding 2000. The enhancement aid program also redesigned certain categories of state aid…

  15. Methanol-enhanced removal and metabolic conversion of formaldehyde by a black soybean from formaldehyde solutions.

    PubMed

    Tan, Hao; Xiong, Yun; Li, Kun-Zhi; Chen, Li-Mei

    2017-02-01

    Methanol regulation of some biochemical and physiological characteristics in plants has been documented in several references. This study showed that the pretreatment of methanol with an appropriate concentration could stimulate the HCHO uptake by black soybean (BS) plants. The process of methanol-stimulated HCHO uptake by BS plants was optimized using the Central Composite Design and response surface methodology for the three variables, methanol concentration, HCHO concentration, and treatment time. Under optimized conditions, the best stimulation effect of methanol on HCHO uptake was obtained. (13)C-NMR analysis indicated that the H(13)CHO metabolism produced H(13)COOH, [2-(13)C]Gly, and [3-(13)C]Ser in BS plant roots. Methanol pretreatment enhanced the metabolic conversion of H(13)CHO in BS plant roots, which consequently increased HCHO uptake by BS plants. Therefore, methanol pretreatment might be used to increase HCHO uptake by plants in the phytoremediation of HCHO-polluted solutions.

  16. Anomalously enhanced hydration of aqueous electrolyte solution in hydrophobic carbon nanotubes to maintain stability.

    PubMed

    Ohba, Tomonori

    2014-02-24

    An understanding of the structure and behavior of electrolyte solutions in nanoenvironements is crucial not only for a wide variety of applications, but also for the development of physical, chemical, and biological processes. We demonstrate the structure and stability of electrolyte in carbon nanotubes using hybrid reverse Monte Carlo simulations of X-ray diffraction patterns. Hydrogen bonds between water are adequately formed in carbon nanotubes, although some hydrogen bonds are restricted by the interfaces of carbon nanotubes. The hydrogen bonding network of water in electrolyte in the carbon nanotubes is further weakened. On the other hand, formation of the ion hydration shell is significantly enhanced in the electrolyte in the carbon nanotubes in comparison to ion hydration in bulk electrolyte. The significant hydrogen bond and hydration shell formation are a result of gaining stability in the hydrophobic nanoenvironment. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. One-step solution combustion synthesis of pure Ni nanopowders with enhanced coercivity: The fuel effect

    NASA Astrophysics Data System (ADS)

    Khort, Alexander; Podbolotov, Kirill; Serrano-García, Raquel; Gun'ko, Yurii K.

    2017-09-01

    In this paper, we report a new modified one-step combustion synthesis technique for production of Ni metal nanoparticles. The main unique feature of our approach is the use of microwave assisted foam preparation. Also, the effect of different types of fuels (urea, citric acid, glycine and hexamethylenetetramine) on the combustion process and characteristics of resultant solid products were investigated. It is observed that the combination of microwave assisted foam preparation and using of hexamethylenetetramine as a fuel allows producing pure ferromagnetic Ni metal nanoparticles with enhanced coercivity (78 Oe) and high value of saturation magnetization (52 emu/g) by one-step solution combustion synthesis under normal air atmosphere without any post-reduction processing.

  18. Dependence of fluorescent protein brightness on protein concentration in solution and enhancement of it

    PubMed Central

    Morikawa, Takamitsu J.; Fujita, Hideaki; Kitamura, Akira; Horio, Takashi; Yamamoto, Johtaro; Kinjo, Masataka; Sasaki, Akira; Machiyama, Hiroaki; Yoshizawa, Keiko; Ichimura, Taro; Imada, Katsumi; Nagai, Takeharu; Watanabe, Tomonobu M.

    2016-01-01

    Fluorescent proteins have been widely used in biology because of their compatibility and varied applications in living specimens. Fluorescent proteins are often undesirably sensitive to intracellular conditions such as pH and ion concentration, generating considerable issues at times. However, harnessing these intrinsic sensitivities can help develop functional probes. In this study, we found that the fluorescence of yellow fluorescent protein (YFP) depends on the protein concentration in the solution and that this dependence can be enhanced by adding a glycine residue in to the YFP; we applied this finding to construct an intracellular protein-crowding sensor. A Förster resonance energy transfer (FRET) pair, involving a cyan fluorescent protein (CFP) insensitive to protein concentration and a glycine-inserted YFP, works as a genetically encoded probe to evaluate intracellular crowding. By measuring the fluorescence of the present FRET probe, we were able to detect dynamic changes in protein crowding in living cells. PMID:26956628

  19. Developing technology-enhanced active learning for medical education: challenges, solutions, and future directions.

    PubMed

    McCoy, Lise; Pettit, Robin K; Lewis, Joy H; Bennett, Thomas; Carrasco, Noel; Brysacz, Stanley; Makin, Inder Raj S; Hutman, Ryan; Schwartz, Frederic N

    2015-04-01

    Growing up in an era of video games and Web-based applications has primed current medical students to expect rapid, interactive feedback. To address this need, the A.T. Still University-School of Osteopathic Medicine in Arizona (Mesa) has developed and integrated a variety of approaches using technology-enhanced active learning for medical education (TEAL-MEd) into its curriculum. Over the course of 3 years (2010-2013), the authors facilitated more than 80 implementations of games and virtual patient simulations into the education of 550 osteopathic medical students. The authors report on 4 key aspects of the TEAL-MEd initiative, including purpose, portfolio of tools, progress to date regarding challenges and solutions, and future directions. Lessons learned may be of benefit to medical educators at academic and clinical training sites who wish to implement TEAL-MEd activities.

  20. Microbially-Enhanced Redox Solution Reoxidation for Sour Natural Gas Sweetening

    SciTech Connect

    Kenneth Brezinsky

    2008-01-15

    The specific objective of this project are to advance the technology and improve the economics of the commercial iron-based chelate processes such as LO-CAT II and SulFerox process utilizing biologically enhanced reoxidation of the redox solutions used in these processes. The project is based on the use of chelated ferric iron as the catalyst for the production of elemental sulfur, and then oxidizing bacteria, such as Thiobacillus Ferrooxidans (ATCC 23270) as an oxidizer. The regeneration of Fe{sup 3+} - chelate is accomplished by the use of these same microbes under mild conditions at 25-30 C and at atmospheric pressure to minimize the chelate degradation process. The pH of the redox solution was observed to be a key process parameter. Other parameters such as temperature, total iron concentration, gas to liquid ratio and bacterial cell densities also influence the overall process. The second part of this project includes experimental data and a kinetic model of microbial H{sub 2}S removal from sour natural gas using thiobacillus species. In the experimental part, a series of experiments were conducted with a commercial chelated iron catalyst at pH ranges from 8.7 to 9.2 using a total iron concentration range from 925 ppm to 1050 ppm in the solution. Regeneration of the solution was carried out by passing air through the solution. Iron oxidizing bacteria were used at cell densities of 2.3 x 10{sup 7}cells/ml for optimum effective performance. In the modeling part, oxidation of Fe{sup 2+} ions by the iron oxidizing bacteria - Thiobacillus Ferrooxidans was studied for application to a continuous stirred tank reactor (CSTR). The factors that can directly affect the oxidation rate such as dilution rate, temperature, and pH were analyzed. The growth of the microorganism was assumed to follow Monod type of growth kinetics. Dilution rate had influence on the rate of oxidation of ferrous iron. Higher dilution rates caused washout of the biomass. The oxidation rate was

  1. Chitosan solution enhances both humoral and cell-mediated immune responses to subcutaneous vaccination.

    PubMed

    Zaharoff, David A; Rogers, Connie J; Hance, Kenneth W; Schlom, Jeffrey; Greiner, John W

    2007-03-01

    The development of safe, novel adjuvants is necessary to maximize the efficacy of new and/or available vaccines. Chitosan is a non-toxic, biocompatible, biodegradable, natural polysaccharide derived from the exoskeletons of crustaceans and insects. Chitosan's biodegradability, immunological activity and high viscosity make it an excellent candidate as a depot/adjuvant for parenteral vaccination. To this end, we explored chitosan solution as an adjuvant for subcutaneous vaccination of mice with a model protein antigen. We found that chitosan enhanced antigen-specific antibody titers over five-fold and antigen-specific splenic CD4+ proliferation over six-fold. Strong increases in antibody titers together with robust delayed-type hypersensitivity (DTH) responses revealed that chitosan induced both humoral and cell-mediated immune responses. When compared with traditional vaccine adjuvants, chitosan was equipotent to incomplete Freund's adjuvant (IFA) and superior to aluminum hydroxide. Mechanistic studies revealed that chitosan exhibited at least two characteristics that may allow it to function as an immune adjuvant. First, the viscous chitosan solution created an antigen depot. More specifically, less than 9% of a protein antigen, when delivered in saline, remained at the injection site after 8 h. However, more than 60% of a protein antigen delivered in chitosan remained at the injection site for 7 days. Second, chitosan induced a transient 67% cellular expansion in draining lymph nodes. The expansion peaked between 14 and 21 days after chitosan injection and diminished as the polysaccharide was degraded. These mechanistic studies, taken together with the enhancement of a vaccine response, demonstrate that chitosan is a promising and safe platform for parenteral vaccine delivery.

  2. Fabrication of high performance surface enhanced Raman scattering substrates by a solid-state ionics method.

    PubMed

    Xu, Dapeng; Dong, Zhanmin; Sun, Jia-Lin

    2012-03-30

    Silver nanostructures were prepared by a solid-state ionics method using fast ionic conductor RbAg(4)I(5) films under a direct current electric field (DCEF). The surface morphology of the silver nanostructures grown under different constant current fields was characterized by scanning electron microscopy (SEM). Rhodamine 6G (R6G) aqueous solutions were used as probe molecules to detect the Raman enhancement performance of the silver nanostructure substrates. The effect of external electric field current intensity on the surface morphology of the silver nanostructures during the preparation was studied in detail. The enhancement effect of the silver nanostructure surface enhanced Raman scattering (SERS) substrates with different surface morphologies toward R6G was determined. We found that disordered silver nanowires (DSNW), ordered silver nanowires (OSNW), densely arranged silver nanobamboo arrays (SNBA) and compactly arranged silver nanobud clusters (SNBC) were respectively obtained when the constant current intensity was 3 μA, 5 μA, 8 μA and 12 μA under the same vacuum evaporation plating conditions. The limiting concentrations of R6G for these SERS substrates were found to be 10(-7) mol l(-1), 10(-13) mol l(-1), 10(-13) mol l(-1) and 10(-16) mol l(-1), respectively.

  3. Enhanced fluorescence emission using bound states in continuum in a photonic crystal membrane

    NASA Astrophysics Data System (ADS)

    Romano, S.; Zito, G.; Managò, S.; Penzo, E.; Dhuey, S.; De Luca, A. C.; Cabrini, S.; Mocella, V.

    2017-05-01

    Metasurfaces are two-dimensional structures, arrays of scatterers with subwavelength separation or optically thin planar films, allowing light manipulation and enabling specific changes of optical properties, as for example beam-steering, anomalous refraction and optical-wavefront shaping. Due to the fabrication simplicity, the metasurfaces offer an alternative to 3-D metamaterials and providing a novel method for optical elements miniaturization. It has been demonstrated that a metasurface can support Bound States in Continuum (BIC), that are resonant states by zero width, due to the interaction between trapped electromagnetic. Experimentally, this involves very narrow coupled resonances, with a high Q-factor and an extremely large field intensity enhancement, up to 6 orders of magnitude larger than the intensity of the incident beam. Here, we demonstrate that the field enhancement in proximity of the surface can be applied to boost fluorescence emission of probe molecules dispersed on the surface of a photonic crystal membrane fabricated in silicon nitride. Our results provide new solutions for light manipulation at the nanoscale, especially for sensing and nonlinear optics applications.

  4. Enhanced copper surface protection in aqueous solutions containing short-chain alkanoic acid potassium salts.

    PubMed

    Abelev, Esta; Starosvetsky, David; Ein-Eli, Yair

    2007-10-23

    The ability of dissolved potassium monocarboxylate salts to produce surface passivation and to inhibit aqueous corrosion of copper was studied. The electrochemical measurements indicate that the inhibiting efficiency of these compounds, with a general formula Cn-1H2n-1COOK or CnK (n=3...12), is dependent on the hydrocarbon chain length. The inhibiting efficiency was higher for a longer hydrocarbon chain of n-alkanoic acid. The degree of copper protection was found to increase with an increase in n-alkanoic acid potassium salt concentration; the optimum concentration of potassium dodecanoate (C12K) in sulfate solutions was found to be 0.07 M. The protective layers formed at the copper surface subsequent to exposure in various n-alkanoic acid potassium salt solutions were characterized by contact angle measurements, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared reflection spectroscopy. Pronounced copper protection was attributed to the growth of a protective film on the copper surface, containing both copper oxides and copper carboxylate compounds. It is suggested that the organic molecules enhance copper protection by covering copper oxides with a thin and dense organic layer, which prevents water molecules or aggressive anions from interacting with the copper surface.

  5. Oral Mucosal Injection of a Local Anesthetic Solution Containing Epinephrine Enhances Muscle Relaxant Effects of Rocuronium

    PubMed Central

    Ninomiya, Asako; Terakawa, Yui; Matsuura, Nobuyuki; Ichinohe, Tatsuya; Kaneko, Yuzuru

    2012-01-01

    The purpose of this study was to examine how submucosal injection of a clinically relevant dose of a lidocaine hydrochloride solution containing epinephrine affects the muscle relaxant effects of rocuronium bromide. Sixteen patients scheduled for orthognathic surgery participated in this study. All patients were induced with fentanyl citrate, a target-controlled infusion of propofol and rocuronium bromide. Anesthesia was maintained by total intravenous anesthesia. After nasotracheal intubation, an infusion of rocuronium bromide was started at 7 µg/kg/min, and the infusion rate was then adjusted to maintain a train of four (TOF) ratio at 10 to 15%. The TOF ratio just prior to oral mucosal injection of a 1% lidocaine hydrochloride solution containing 10 µg/mL epinephrine (LE) was taken as the baseline. TOF ratio was observed for 20 minutes, with 1-minute intervals following the start of injection. Mean epinephrine dose was 85.6 ± 18.6 µg and mean infusion rate of rocuronium bromide was 6.3 ± 1.6 µg/kg/min. TOF ratio began to decrease 2 minutes after the injection of LE, reached the minimum value at 3.1 ± 3.6% 12 minutes after the injection, and then began to recover. We conclude that oral mucosal injection of LE enhances the muscle relaxant effects of rocuronium bromide. PMID:22428970

  6. Oral mucosal injection of a local anesthetic solution containing epinephrine enhances muscle relaxant effects of rocuronium.

    PubMed

    Ninomiya, Asako; Terakawa, Yui; Matsuura, Nobuyuki; Ichinohe, Tatsuya; Kaneko, Yuzuru

    2012-01-01

    The purpose of this study was to examine how submucosal injection of a clinically relevant dose of a lidocaine hydrochloride solution containing epinephrine affects the muscle relaxant effects of rocuronium bromide. Sixteen patients scheduled for orthognathic surgery participated in this study. All patients were induced with fentanyl citrate, a target-controlled infusion of propofol and rocuronium bromide. Anesthesia was maintained by total intravenous anesthesia. After nasotracheal intubation, an infusion of rocuronium bromide was started at 7 µg/kg/min, and the infusion rate was then adjusted to maintain a train of four (TOF) ratio at 10 to 15%. The TOF ratio just prior to oral mucosal injection of a 1% lidocaine hydrochloride solution containing 10 µg/mL epinephrine (LE) was taken as the baseline. TOF ratio was observed for 20 minutes, with 1-minute intervals following the start of injection. Mean epinephrine dose was 85.6 ± 18.6 µg and mean infusion rate of rocuronium bromide was 6.3 ± 1.6 µg/kg/min. TOF ratio began to decrease 2 minutes after the injection of LE, reached the minimum value at 3.1 ± 3.6% 12 minutes after the injection, and then began to recover. We conclude that oral mucosal injection of LE enhances the muscle relaxant effects of rocuronium bromide.

  7. On The Potential of Dynamic Nuclear Polarization Enhanced Diamonds in Solid-State and Dissolution (13) C NMR Spectroscopy.

    PubMed

    Bretschneider, Christian O; Akbey, Ümit; Aussenac, Fabien; Olsen, Greg L; Feintuch, Akiva; Oschkinat, Hartmut; Frydman, Lucio

    2016-09-05

    Dynamic nuclear polarization (DNP) is a versatile option to improve the sensitivity of NMR and MRI. This versatility has elicited interest for overcoming potential limitations of these techniques, including the achievement of solid-state polarization enhancement at ambient conditions, and the maximization of (13) C signal lifetimes for performing in vivo MRI scans. This study explores whether diamond's (13) C behavior in nano- and micro-particles could be used to achieve these ends. The characteristics of diamond's DNP enhancement were analyzed for different magnetic fields, grain sizes, and sample environments ranging from cryogenic to ambient temperatures, in both solution and solid-state experiments. It was found that (13) C NMR signals could be boosted by orders of magnitude in either low- or room-temperature solid-state DNP experiments by utilizing naturally occurring paramagnetic P1 substitutional nitrogen defects. We attribute this behavior to the unusually long electronic/nuclear spin-lattice relaxation times characteristic of diamond, coupled with a time-independent cross-effect-like polarization transfer mechanism facilitated by a matching of the nitrogen-related hyperfine coupling and the (13) C Zeeman splitting. The efficiency of this solid-state polarization process, however, is harder to exploit in dissolution DNP-enhanced MRI contexts. The prospects for utilizing polarized diamond approaching nanoscale dimensions for both solid and solution applications are briefly discussed.

  8. Zinc coordination to the bapbpy ligand in homogeneous solutions and at liposomes: zinc detection via fluorescence enhancement.

    PubMed

    Molenbroek, Elwin; Straathof, Natan; Dück, Sebastian; Rashid, Zahid; van Lenthe, Joop H; Lutz, Martin; Gandubert, Aurore; Klein Gebbink, Robertus J M; De Cola, Luisa; Bonnet, Sylvestre

    2013-02-28

    In this work, the complexation of the bapbpy ligand to zinc dichloride is described (bapbpy = 6,6′-bis(2-aminopyridyl)-2,2′-bipyridine). The water-soluble, colorless complex [Zn(bapbpy)Cl]Cl·2H2O (compound 2·H2O) was synthesized; its X-ray crystal structure shows a mononuclear, pentacoordinated geometry with one chloride ligand in apical position. Upon excitation of its lowest-energy absorption band (375 nm) compound 2 shows intense emission (Φ = 0.50) at 418 nm in aqueous solution, and an excited state lifetime of 5 ns at room temperature. Photophysical measurements, DFT, and TD-DFT calculations prove that emission arises from vibronically coupled Ligand-to-Ligand Charge Transfer singlet excited states, characterized by electron density flowing from the lone pairs of the non-coordinated NH bridges to the π* orbitals of the pyridine rings. Monofunctionalization of the ligand with one long alkyl chain was realized to afford ligand 3, which can be inserted into dimyristoylphosphatidylglycerol (DMPG) or dimyristoylphosphatidylcholine (DMPC) unilamellar vesicles. For negatively charged DMPG membranes the addition of a zinc salt to the vesicles leads to an enhancement of the fluorescence due to zinc coordination to the membrane-embedded tetrapyridyl ligand. No changes were observed for the zwitterionic DMPC lipids, where binding of the Zn ions does not take place. A modest binding constant was found (5 × 10(6) M(−1)) for the coordination of zinc cations to bapbpy-functionalized DMPG membranes, which allows for the detection of micromolar zinc concentrations in aqueous solution. The influence of chloride concentration and other transition metal ions on the zinc binding was evaluated, and the potential of liposome-supported metal chelators such as ligand 3 for zinc detection in biological media is discussed.

  9. Successful stabilization of graphene oxide in electrolyte solutions: enhancement of biofunctionalization and cellular uptake.

    PubMed

    Hong, Bong Jin; Compton, Owen C; An, Zhi; Eryazici, Ibrahim; Nguyen, SonBinh T

    2012-01-24

    Aqueous dispersions of graphene oxide are inherently unstable in the presence of electrolytes, which screen the electrostatic surface charge on these nanosheets and induce irreversible aggregation. Two complementary strategies, utilizing either electrostatic or steric stabilization, have been developed to enhance the stability of graphene oxide in electrolyte solutions, allowing it to stay dispersed in cell culture media and serum. The electrostatic stabilization approach entails further oxidation of graphene oxide to low C/O ratio (~1.1) and increases ionic tolerance of these nanosheets. The steric stabilization technique employs an amphiphilic block copolymer that serves as a noncovalently bound surfactant to minimize the aggregate-inducing nanosheet-nanosheet interactions. Both strategies can stabilize graphene oxide nanosheets with large dimensions (>300 nm) in biological media, allowing for an enhancement of >250% in the bioconjugation efficiency of streptavidin in comparison to untreated nanosheets. Notably, both strategies allow the stabilized nanosheets to be readily taken up by cells, demonstrating their excellent performance as potential drug-delivery vehicles.

  10. Enhanced cell surface polymer grafting in concentrated and nonreactive aqueous polymer solutions.

    PubMed

    Rossi, Nicholas A A; Constantinescu, Iren; Brooks, Donald E; Scott, Mark D; Kizhakkedathu, Jayachandran N

    2010-03-17

    Macromolecular cell surface modification techniques have shown tremendous utility in various biomedical applications. However, a major drawback concerns inefficient cell surface modification caused by the poor association of hydrophilic macromolecules with cell surfaces. Here, a novel, highly efficient, and universal strategy in which nonreactive "additive" macromolecules are used to modulate the grafting efficiency of cell surface reactive, hydrophilic macromolecules is described. Unprecedented enhanced cell surface modifications by up to 10-fold were observed when various concentrations of a suitable "additive" polymer was present with a constant and low concentration of a "reactive" macromolecule. The importance of this increased efficiency and the possible mechanisms involved are discussed. The cell compatible technique is demonstrated in the case of four different cell types--red blood cells (RBC), leukocytes, platelets, and Jurkat cells. A practical application of grafting macromolecules to cell surfaces in concentrated polymer solutions is demonstrated by the enhanced camouflage of RBC surface antigens for the development of RhD null RBC. In principle, the technique can be adapted to various macromolecular systems and cell types, with significant potential for biomedical applications such as live cell based technologies.

  11. An RFID solution for enhancing inpatient medication safety with real-time verifiable grouping-proof.

    PubMed

    Chen, Yu-Yi; Tsai, Meng-Lin

    2014-01-01

    The occurrence of a medication error can threaten patient safety. The medication administration process is complex and cumbersome, and nursing staffs are prone to error when they are tired. Proper Information Technology (IT) can assist the nurse in correct medication administration. We review a recent proposal regarding a leading-edge solution to enhance inpatient medication safety by using RFID technology. The proof mechanism is the kernel concept in their design and worth studying to develop a well-designed grouping-proof scheme. Other RFID grouping-proof protocols could be similarly applied in administering physician orders. We improve on the weaknesses of previous works and develop a reading-order independent RFID grouping-proof scheme in this paper. In our scheme, tags are queried and verified under the direct control of the authorized reader without connecting to the back-end database server. Immediate verification in our design makes this application more portable and efficient and critical security issues have been analyzed by the threat model. Our scheme is suitable for the safe drug administration scenario and the drug package scenario in a hospital environment to enhance inpatient medication safety. It automatically checks for correct drug unit-dose and appropriate inpatient treatments. Copyright © 2013. Published by Elsevier Ireland Ltd.

  12. Ovariectomy Enhances Mechanical Load-Induced Solute Transport around Osteocytes in Rat Cancellous Bone

    PubMed Central

    Ciani, Cesare; Sharma, Divya; Doty, Stephen B.; Fritton, Susannah P.

    2014-01-01

    To test if osteoporosis alters mechanical load-induced interstitial fluid flow in bone, this study examined the combined effect of estrogen deficiency and external loading on solute transport around osteocytes. An in vivo tracer, FITC-labeled bovine serum albumin, was injected into anaesthetized ovariectomized and control female Sprague Dawley rats before the right tibia was subjected to a controlled, physiological, non-invasive sinusoidal load to mimic walking. Tracer movement through the lacunar-canalicular system surrounding osteocytes was quantified in cortical and cancellous bone from the proximal tibia using confocal microscopy, with the non-loaded tibia serving as internal control. Overall, the application of mechanical loading increased the percentage of osteocyte lacunae labeled with injected tracer, and ovariectomy further enhanced movement of tracer. An analysis of separate regions demonstrated that ovariectomy enhanced in vivo transport of the injected tracer in the cancellous bone of the tibial epiphysis and metaphysis but not in the cortical bone of the metaphysis. These findings show that bone changes due to reduced estrogen levels alter convectional transport around osteocytes in cancellous bone and demonstrate a functional difference of interstitial fluid flow around osteocytes in estrogen-deficient rats undergoing the same physical activity as controls. The altered interstitial fluid flow around osteocytes is likely related to nanostructural matrix-mineral level differences recently demonstrated at the lacunar-canalicular surface of estrogen-deficient rats, which could affect the transmission of mechanical loads to the osteocyte. PMID:24316418

  13. Successful Stabilization of Graphene Oxide in Electrolyte Solutions: Enhancement of Bio-functionalization and Cellular Uptake

    PubMed Central

    Hong, Bong Jin; Compton, Owen C.; An, Zhi; Eryzazici, Ibrahim; Nguyen, SonBinh T.

    2013-01-01

    Aqueous dispersions of graphene oxide are inherently unstable in the presence of electrolytes, which screen the electrostatic surface charge on these nanosheets and induce irreversible aggregation. Two complementary strategies, utilizing either electrostatic or steric stabilization, have been developed to enhance the stability of graphene oxide in electrolyte solutions, allowing it to stay dispersed in cell culture media and serum. The electrostatic stabilization approach entails further oxidation of graphene oxide to low C/O ratio (~1.03) and increases ionic tolerance of these nanosheets. The steric stabilization technique employs an amphiphilic block copolymer that serves as a non-covalently bound surfactant to minimize the aggregate-induced nanosheets-nanosheet interactions. Both strategies can stabilize graphene oxide nanosheets with large dimensions (>300 nm) in biological media, allowing for an enhancement of >250% in the bioconjugation efficiency of streptavidin in comparison to untreated nanosheets. Notably, both strategies allow the stabilized nanosheets to be readily uptake by cells, demonstrating their excellent performance as potential drug delivery vehicles. PMID:22017285

  14. Steady-state protein focusing in carrier ampholyte based isoelectric focusing: Part I-Analytical solution.

    PubMed

    Shim, Jaesool; Yoo, Kisoo; Dutta, Prashanta

    2017-03-01

    The determination of an analytical solution to find the steady-state protein concentration distribution in IEF is very challenging due to the nonlinear coupling between mass and charge conservation equations. In this study, approximate analytical solutions are obtained for steady-state protein distribution in carrier ampholyte based IEF. Similar to the work of Svensson, the final concentration profile for proteins is assumed to be Gaussian, but appropriate expressions are presented in order to obtain the effective electric field and pH gradient in the focused protein band region. Analytical results are found from iterative solutions of a system of coupled algebraic equations using only several iterations for IEF separation of three plasma proteins: albumin, cardiac troponin I, and hemoglobin. The analytical results are compared with numerically predicted results for IEF, showing excellent agreement. Analytically obtained electric field and ionic conductivity distributions show significant deviation from their nominal values, which is essential in finding the protein focusing behavior at isoelectric points. These analytical solutions can be used to determine steady-state protein concentration distribution for experiment design of IEF considering any number of proteins and ampholytes. Moreover, the model presented herein can be used to find the conductivity, electric field, and pH field. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Combining solid-state and solution-state 31P NMR to study in vivo phosphorus metabolism.

    PubMed Central

    Cholli, A L; Yamane, T; Jelinski, L W

    1985-01-01

    Otherwise unavailable information concerning the distribution of phosphorylated compounds in biological systems is obtained by a combined solid-state/solution-state NMR approach, illustrated here for oocytes from Rana pipiens. General methodology is developed, and further extensions are proposed. The following conclusions pertain to the specific system under examination. (i) Nucleoside phosphates can be observed by magic-angle sample spinning of the lyophilized material. (ii) The solid-state NMR technique of dipolar decoupling provides no additional resolution of the phospholipid and phosphoprotein components of the yolk. However, cellular death produces sufficient pH changes to cause the phospholipid and protein phosphate peaks to become resolvable. The concentration of nucleoside phosphates also decreases. (iii) The phospholipid and phosphoprotein components are shown by computer simulation to be present in a ratio of 40:60, respectively. (iv) The amounts of inorganic phosphate, nucleoside phosphates, and sugar phosphates are determined by solution-state NMR observation of the perchloric acid extract of the oocytes. PMID:3871524

  16. Structure impact of two galactomannan fractions on their viscosity properties in dilute solution, unperturbed state and gel state.

    PubMed

    Gillet, Sébastien; Aguedo, Mario; Petrut, Raul; Olive, Gilles; Anastas, Paul; Blecker, Christophe; Richel, Aurore

    2017-03-01

    Two fractions of carob galactomannans (GM25 and GM80) were extracted at respectively 25°C and 80°C from crude locust bean gum. Those fractions having slightly different chemical structures, previously characterized, were studied for their viscosity properties over a wide range of concentrations: diluted solution, unperturbed state and gel state. For each of the physical properties, links to the chemical fine structure could be established, expanding knowledge on the topic: in dilute solution, GM25 is more soluble in water while GM80 seems to tend to self-association due to its structure as highlighted by intrinsic viscosity measurements ([η]GM25=9.96dLg(-1) and [η]GM80=4.04dLg(-1)). In unperturbed state, initial viscosities η0 were more important for GM80 fractions at 1% and 2% due to greater hyperentanglements (η0(GM80,1%)=9.9Pas; η0(GM80,2%)=832.0; Pa.s η0(GM25,1%)=3.1Pas; η0(GM25,2%)=45.1Pas). In gel state, hydrogels obtained from GM80 were also stronger (hardness GM80 (2%)=0.51N and hardness GM25 (2%)=0.11N), suggesting a much more important number of junction areas within the gel network. The findings discussed herein demonstrate the potential for new applications.

  17. Multiplicity results for sign changing bound state solutions of a semilinear equation

    NASA Astrophysics Data System (ADS)

    Cortázar, Carmen; García-Huidobro, Marta; Herreros, Pilar

    2015-12-01

    In this paper we give conditions on $f$ so that problem $$ \\Delta u +f(u)=0,\\quad x\\in \\mathbb{R}^N, N\\ge 2, $$ has at least two radial bound state solutions with any prescribed number of zeros, and such that $u(0)$ belongs to a specific subinterval of $(0,\\infty)$. This property will allow us to give conditions on $f$ so that this problem has at least any given number of radial solutions having a prescribed number of zeros.

  18. On the steady-state solutions of a nonlinear photonic lattice model

    SciTech Connect

    Liu, Chungen E-mail: tjftp@mail.nankai.edu.cn; Ren, Qiang E-mail: tjftp@mail.nankai.edu.cn

    2015-03-15

    In this paper, we consider the steady-state solutions of the following equation related with nonlinear photonic lattice model Δu=(Pu)/(1+|u|{sup 2}+|v|{sup 2}) +λu, Δv=(Qv)/(1+|u|{sup 2}+|v|{sup 2}) +λv, where u, v are real-value function defined on R/(τ{sub 1}Z) × R/(τ{sub 2}Z). The existence and non-existence of non-constant semi-trivial (with only one component zero) solutions are considered.

  19. A multi-level solution algorithm for steady-state Markov chains

    NASA Technical Reports Server (NTRS)

    Horton, Graham; Leutenegger, Scott T.

    1993-01-01

    A new iterative algorithm, the multi-level algorithm, for the numerical solution of steady state Markov chains is presented. The method utilizes a set of recursively coarsened representations of the original system to achieve accelerated convergence. It is motivated by multigrid methods, which are widely used for fast solution of partial differential equations. Initial results of numerical experiments are reported, showing significant reductions in computation time, often an order of magnitude or more, relative to the Gauss-Seidel and optimal SOR algorithms for a variety of test problems. The multi-level method is compared and contrasted with the iterative aggregation-disaggregation algorithm of Takahashi.

  20. A hybrid multigrid technique for computing steady-state solutions to supersonic flows

    NASA Technical Reports Server (NTRS)

    Sanders, Richard

    1992-01-01

    Recently, Li and Sanders have introduced a class of finite difference schemes to approximate generally discontinuous solutions to hyperbolic systems of conservation laws. These equations have the form together with relevant boundary conditions. When modelling hypersonic spacecraft reentry, the differential equations above are frequently given by the compressible Euler equations coupled with a nonequilibrium chemistry model. For these applications, steady state solutions are often sought. Many tens (to hundreds) of super computer hours can be devoted to a single three space dimensional simulation. The primary difficulty is the inability to rapidly and reliably capture the steady state. In these notes, we demonstrate that a particular variant from the schemes presented can be combined with a particular multigrid approach to capture steady state solutions to the compressible Euler equations in one space dimension. We show that the rate of convergence to steady state coming from this multigrid implementation is vastly superior to the traditional approach of artificial time relaxation. Moreover, we demonstrate virtual grid independence. That is, the rate of convergence does not depend on the degree of spatial grid refinement.

  1. Co‐existence of Distinct Supramolecular Assemblies in Solution and in the Solid State

    PubMed Central

    Reddy, G. N. Manjunatha; Huqi, Aida; Iuga, Dinu; Sakurai, Satoshi; Marsh, Andrew; Davis, Jeffery T.; Masiero, Stefano

    2016-01-01

    Abstract The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G‐quartet‐based assemblies are formed in chloroform depending on the nature of the cation, anion and the salt concentration, as characterized by circular dichroism and time course diffusion‐ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G‐quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon‐like assemblies as revealed by fast magic‐angle spinning (MAS) NMR spectroscopy. Distinct N−H⋅⋅⋅N and N−H⋅⋅⋅O intermolecular hydrogen bonding interactions drive quartet and ribbon‐like self‐assembly resulting in markedly different 2D 1H solid‐state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible–further demonstrating the changes that occur in the self‐assembly process of a lipophilic nucleoside upon a solid‐state to solution‐state transition and vice versa. A systematic study for complexation with different cations (K+, Sr2+) and anions (picrate, ethanoate and iodide) emphasizes that the existence of a stable solution or solid‐state structure may not reflect the stability of the same supramolecular entity in another phase. PMID:27897351

  2. Helping States enhance health care quality through technical assistance.

    PubMed

    Martinez-Vidal, Enrique; Gauthier, Anne K; DiVincenzo, Allison

    2010-01-01

    For the money spent on health care in the United States, far better quality of care should be expected. The Commonwealth Fund and AcademyHealth have created the State Quality Improvement Institute to assist states in implementing sustainable quality improvement strategies. Lessons have emerged about the role of states in advancing fundamental and systemic changes in the way care is delivered, as well as how providers are organized and compensated. The experiences of states participating in the institute may offer insights for other states seeking to achieve similar goals.

  3. Color-selective photocurrent enhancement in coupled J-aggregate/nanowires formed in solution.

    PubMed

    Walker, Brian J; Dorn, August; Bulović, Vladimir; Bawendi, Moungi G

    2011-07-13

    J-aggregates are ordered clusters of coherently coupled molecular dyes, (1) and they have been used as light sensitizers in film photography due to their intense absorptions. Hybrid structures containing J-aggregates may also have applications in devices that require spectral specificity, such as color imaging or optical signaling. (2) However the use of J-aggregates in optoelectronic devices has posed a long-standing challenge (3, 4) due to the difficulty of controlling aggregate formation and the low charge carrier mobility of many J-aggregates in solid state. In this paper, we demonstrate a modular method to assemble three different cyanine J-aggregates onto CdSe nanowires, resulting in a photodetector that is color-sensitized in three specific, narrow absorption bands. Both the J-aggregate and nanowire device components are fabricated from solution and the sensitizing wavelength is switched from blue to red to green, using only solution-phase exchange of the J-aggregates on the same underlying device.

  4. The potential for solubilizing agents to enhance the remediation of hydrophobic organic solutes in soil-water suspensions. [Quarterly report

    SciTech Connect

    Laha, S.; Liu, Z.; Edwards, D.; Luthy, R.G.

    1991-02-01

    This paper discusses the feasibility for use of surfactant solubilizing agents to enhance the solubility and the rate of microbial degradation of hydrophobic organic solutes in soil-water suspensions. Hydrophobic organic contaminants are strongly sorbed to soil or sediment material, and as a consequence the rate of microbial degradation may depend greatly on the desorption of the sorbed-phase contaminant and the accessibility of the contaminant to soil microorganisms. Chemical solubilizing agents may enhance the rate of hydrophobic organic solute degradation by increasing the rate of solute desorption from soil and the extent of solute partitioning to the aqueous phase. The presentation will review on-going research on: surfactant solubilization of polycyclic aromatic hydrocarbon (PAH) compounds in clean water, and in soil-water suspensions; and experiments to assess if the addition of surfactant to soil-water suspension results in faster rate of mineralization of PAH compounds in soil.

  5. The potential for solubilizing agents to enhance the remediation of hydrophobic organic solutes in soil-water suspensions

    SciTech Connect

    Laha, S.; Liu, Z.; Edwards, D.; Luthy, R.G.

    1991-02-01

    This paper discusses the feasibility for use of surfactant solubilizing agents to enhance the solubility and the rate of microbial degradation of hydrophobic organic solutes in soil-water suspensions. Hydrophobic organic contaminants are strongly sorbed to soil or sediment material, and as a consequence the rate of microbial degradation may depend greatly on the desorption of the sorbed-phase contaminant and the accessibility of the contaminant to soil microorganisms. Chemical solubilizing agents may enhance the rate of hydrophobic organic solute degradation by increasing the rate of solute desorption from soil and the extent of solute partitioning to the aqueous phase. The presentation will review on-going research on: surfactant solubilization of polycyclic aromatic hydrocarbon (PAH) compounds in clean water, and in soil-water suspensions; and experiments to assess if the addition of surfactant to soil-water suspension results in faster rate of mineralization of PAH compounds in soil.

  6. On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions.

    PubMed

    Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch; Ziegelbauer, Joseph M; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

    2017-02-08

    We demonstrate herein that Mn(3+) and not Mn(2+), as commonly accepted, is the dominant dissolved manganese cation in LiPF6-based electrolyte solutions of Li-ion batteries with lithium manganate spinel positive and graphite negative electrodes chemistry. The Mn(3+) fractions in solution, derived from a combined analysis of electron paramagnetic resonance and inductively coupled plasma spectroscopy data, are ∼80% for either fully discharged (3.0 V hold) or fully charged (4.2 V hold) cells, and ∼60% for galvanostatically cycled cells. These findings agree with the average oxidation state of dissolved Mn ions determined from X-ray absorption near-edge spectroscopy data, as verified through a speciation diagram analysis. We also show that the fractions of Mn(3+) in the aprotic nonaqueous electrolyte solution are constant over the duration of our experiments and that disproportionation of Mn(3+) occurs at a very slow rate.

  7. State space truncation with quantified errors for accurate solutions to discrete Chemical Master Equation

    PubMed Central

    Cao, Youfang; Terebus, Anna; Liang, Jie

    2016-01-01

    The discrete chemical master equation (dCME) provides a general framework for studying stochasticity in mesoscopic reaction networks. Since its direct solution rapidly becomes intractable due to the increasing size of the state space, truncation of the state space is necessary for solving most dCMEs. It is therefore important to assess the consequences of state space truncations so errors can be quantified and minimized. Here we describe a novel method for state space truncation. By partitioning a reaction network into multiple molecular equivalence groups (MEG), we truncate the state space by limiting the total molecular copy numbers in each MEG. We further describe a theoretical framework for analysis of the truncation error in the steady state probability landscape using reflecting boundaries. By aggregating the state space based on the usage of a MEG and constructing an aggregated Markov process, we show that the truncation error of a MEG can be asymptotically bounded by the probability of states on the reflecting boundary of the MEG. Furthermore, truncating states of an arbitrary MEG will not undermine the estimated error of truncating any other MEGs. We then provide an overall error estimate for networks with multiple MEGs. To rapidly determine the appropriate size of an arbitrary MEG, we also introduce an a priori method to estimate the upper bound of its truncation error. This a priori estimate can be rapidly computed from reaction rates of the network, without the need of costly trial solutions of the dCME. As examples, we show results of applying our methods to the four stochastic networks of 1) the birth and death model, 2) the single gene expression model, 3) the genetic toggle switch model, and 4) the phage lambda bistable epigenetic switch model. We demonstrate how truncation errors and steady state probability landscapes can be computed using different sizes of the MEG(s) and how the results validate out theories. Overall, the novel state space

  8. State Space Truncation with Quantified Errors for Accurate Solutions to Discrete Chemical Master Equation.

    PubMed

    Cao, Youfang; Terebus, Anna; Liang, Jie

    2016-04-01

    The discrete chemical master equation (dCME) provides a general framework for studying stochasticity in mesoscopic reaction networks. Since its direct solution rapidly becomes intractable due to the increasing size of the state space, truncation of the state space is necessary for solving most dCMEs. It is therefore important to assess the consequences of state space truncations so errors can be quantified and minimized. Here we describe a novel method for state space truncation. By partitioning a reaction network into multiple molecular equivalence groups (MEGs), we truncate the state space by limiting the total molecular copy numbers in each MEG. We further describe a theoretical framework for analysis of the truncation error in the steady-state probability landscape using reflecting boundaries. By aggregating the state space based on the usage of a MEG and constructing an aggregated Markov process, we show that the truncation error of a MEG can be asymptotically bounded by the probability of states on the reflecting boundary of the MEG. Furthermore, truncating states of an arbitrary MEG will not undermine the estimated error of truncating any other MEGs. We then provide an overall error estimate for networks with multiple MEGs. To rapidly determine the appropriate size of an arbitrary MEG, we also introduce an a priori method to estimate the upper bound of its truncation error. This a priori estimate can be rapidly computed from reaction rates of the network, without the need of costly trial solutions of the dCME. As examples, we show results of applying our methods to the four stochastic networks of (1) the birth and death model, (2) the single gene expression model, (3) the genetic toggle switch model, and (4) the phage lambda bistable epigenetic switch model. We demonstrate how truncation errors and steady-state probability landscapes can be computed using different sizes of the MEG(s) and how the results validate our theories. Overall, the novel state space

  9. Relating dynamic brain states to dynamic machine states: Human and machine solutions to the speech recognition problem.

    PubMed

    Wingfield, Cai; Su, Li; Liu, Xunying; Zhang, Chao; Woodland, Phil; Thwaites, Andrew; Fonteneau, Elisabeth; Marslen-Wilson, William D

    2017-09-01

    There is widespread interest in the relationship between the neurobiological systems supporting human cognition and emerging computational systems capable of emulating these capacities. Human speech comprehension, poorly understood as a neurobiological process, is an important case in point. Automatic Speech Recognition (ASR) systems with near-human levels of performance are now available, which provide a computationally explicit solution for the recognition of words in continuous speech. This research aims to bridge the gap between speech recognition processes in humans and machines, using novel multivariate techniques to compare incremental 'machine states', generated as the ASR analysis progresses over time, to the incremental 'brain states', measured using combined electro- and magneto-encephalography (EMEG), generated as the same inputs are heard by human listeners. This direct comparison of dynamic human and machine internal states, as they respond to the same incrementally delivered sensory input, revealed a significant correspondence between neural response patterns in human superior temporal cortex and the structural properties of ASR-derived phonetic models. Spatially coherent patches in human temporal cortex responded selectively to individual phonetic features defined on the basis of machine-extracted regularities in the speech to lexicon mapping process. These results demonstrate the feasibility of relating human and ASR solutions to the problem of speech recognition, and suggest the potential for further studies relating complex neural computations in human speech comprehension to the rapidly evolving ASR systems that address the same problem domain.

  10. Residence time distributions for hydrologic systems: Mechanistic foundations and steady-state analytical solutions

    NASA Astrophysics Data System (ADS)

    Leray, Sarah; Engdahl, Nicholas B.; Massoudieh, Arash; Bresciani, Etienne; McCallum, James

    2016-12-01

    This review presents the physical mechanisms generating residence time distributions (RTDs) in hydrologic systems with a focus on steady-state analytical solutions. Steady-state approximations of the RTD in hydrologic systems have seen widespread use over the last half-century because they provide a convenient, simplified modeling framework for a wide range of problems. The concept of an RTD is useful anytime that characterization of the timescales of flow and transport in hydrologic systems is important, which includes topics like water quality, water resource management, contaminant transport, and ecosystem preservation. Analytical solutions are often adopted as a model of the RTD and a broad spectrum of models from many disciplines has been applied. Although these solutions are typically reduced in dimensionality and limited in complexity, their ease of use makes them preferred tools, specifically for the interpretation of tracer data. Our review begins with the mechanistic basis for the governing equations, highlighting the physics for generating a RTD, and a catalog of analytical solutions follows. This catalog explains the geometry, boundary conditions and physical aspects of the hydrologic systems, as well as the sampling conditions, that altogether give rise to specific RTDs. The similarities between models are noted, as are the appropriate conditions for their applicability. The presentation of simple solutions is followed by a presentation of more complicated analytical models for RTDs, including serial and parallel combinations, lagged systems, and non-Fickian models. The conditions for the appropriate use of analytical solutions are discussed, and we close with some thoughts on potential applications, alternative approaches, and future directions for modeling hydrologic residence time.

  11. Co-existence of Distinct Supramolecular Assemblies in Solution and in the Solid State.

    PubMed

    Reddy, G N Manjunatha; Huqi, Aida; Iuga, Dinu; Sakurai, Satoshi; Marsh, Andrew; Davis, Jeffery T; Masiero, Stefano; Brown, Steven P

    2017-02-16

    The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G-quartet-based assemblies are formed in chloroform depending on the nature of the cation, anion and the salt concentration, as characterized by circular dichroism and time course diffusion-ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G-quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon-like assemblies as revealed by fast magic-angle spinning (MAS) NMR spectroscopy. Distinct N-H⋅⋅⋅N and N-H⋅⋅⋅O intermolecular hydrogen bonding interactions drive quartet and ribbon-like self-assembly resulting in markedly different 2D (1) H solid-state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible-further demonstrating the changes that occur in the self-assembly process of a lipophilic nucleoside upon a solid-state to solution-state transition and vice versa. A systematic study for complexation with different cations (K(+) , Sr(2+) ) and anions (picrate, ethanoate and iodide) emphasizes that the existence of a stable solution or solid-state structure may not reflect the stability of the same supramolecular entity in another phase. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Stochastic quasi-steady state approximations for asymptotic solutions of the chemical master equation.

    PubMed

    Alarcón, Tomás

    2014-05-14

    In this paper, we propose two methods to carry out the quasi-steady state approximation in stochastic models of enzyme catalytic regulation, based on WKB asymptotics of the chemical master equation or of the corresponding partial differential equation for the generating function. The first of the methods we propose involves the development of multiscale generalisation of a WKB approximation of the solution of the master equation, where the separation of time scales is made explicit which allows us to apply the quasi-steady state approximation in a straightforward manner. To the lowest order, the multi-scale WKB method provides a quasi-steady state, Gaussian approximation of the probability distribution. The second method is based on the Hamilton-Jacobi representation of the stochastic process where, as predicted by large deviation theory, the solution of the partial differential equation for the corresponding characteristic function is given in terms of an effective action functional. The optimal transition paths between two states are then given by those paths that maximise the effective action. Such paths are the solutions of the Hamilton equations for the Hamiltonian associated to the effective action functional. The quasi-steady state approximation is applied to the Hamilton equations thus providing an approximation to the optimal transition paths and the transition time between two states. Using this approximation we predict that, unlike the mean-field quasi-steady approximation result, the rate of enzyme catalysis depends explicitly on the initial number of enzyme molecules. The accuracy and validity of our approximated results as well as that of our predictions regarding the behaviour of the stochastic enzyme catalytic models are verified by direct simulation of the stochastic model using Gillespie stochastic simulation algorithm.

  13. Stochastic quasi-steady state approximations for asymptotic solutions of the chemical master equation

    SciTech Connect

    Alarcón, Tomás

    2014-05-14

    In this paper, we propose two methods to carry out the quasi-steady state approximation in stochastic models of enzyme catalytic regulation, based on WKB asymptotics of the chemical master equation or of the corresponding partial differential equation for the generating function. The first of the methods we propose involves the development of multiscale generalisation of a WKB approximation of the solution of the master equation, where the separation of time scales is made explicit which allows us to apply the quasi-steady state approximation in a straightforward manner. To the lowest order, the multi-scale WKB method provides a quasi-steady state, Gaussian approximation of the probability distribution. The second method is based on the Hamilton-Jacobi representation of the stochastic process where, as predicted by large deviation theory, the solution of the partial differential equation for the corresponding characteristic function is given in terms of an effective action functional. The optimal transition paths between two states are then given by those paths that maximise the effective action. Such paths are the solutions of the Hamilton equations for the Hamiltonian associated to the effective action functional. The quasi-steady state approximation is applied to the Hamilton equations thus providing an approximation to the optimal transition paths and the transition time between two states. Using this approximation we predict that, unlike the mean-field quasi-steady approximation result, the rate of enzyme catalysis depends explicitly on the initial number of enzyme molecules. The accuracy and validity of our approximated results as well as that of our predictions regarding the behaviour of the stochastic enzyme catalytic models are verified by direct simulation of the stochastic model using Gillespie stochastic simulation algorithm.

  14. Optical limiting and excited-state absorption in fullerene solutions and doped glasses

    SciTech Connect

    McBranch, D.; Smilowitz, L.; Klimov, V.

    1995-09-01

    We report the ground state and excited state optical absorption spectra in the visible and near infrared for several substituted fullerenes and higher fullerenes in toluene solutions. Based on these measurements, broadband predictions of the optical limiting performance of these molecules can be deduced. These predictions are then tested at 532 to 700 nm in intensity-dependent transmission measurements. We observe optical limiting in all fullerenes measured; higher fullerenes show the greatest potential for limiting in the near infrared (650-1000 nm), while substituted C{sub 60} shows optimal limiting in the visible (450-700 nm). We observe dramatically reduced limiting for solid forms of C{sub 60} (thin films and C{sub 60}-doped porous glasses), indicating that efficient optical limiting in fullerenes requires true molecular solutions.

  15. Stability of periodic steady-state solutions to a non-isentropic Euler-Maxwell system

    NASA Astrophysics Data System (ADS)

    Liu, Cunming; Peng, Yue-Jun

    2017-10-01

    This paper is concerned with a stability problem in a periodic domain for a non-isentropic Euler-Maxwell system without temperature diffusion term. This system is used to describe the dynamics of electrons in magnetized plasmas when the ion density is a given smooth function which can be large. When the initial data are close to the steady states of the system, we show the global existence of smooth solutions which converge toward the steady states as the time tends to infinity. We make a change of unknown variables and choose a non-diagonal symmetrizer of the full Euler equations to get the dissipation estimates. We also adopt an induction argument on the order of derivatives of solutions in energy estimates to get the stability result.

  16. Interaction between triethanolamine and singlet or triplet excited state of xanthene dyes in aqueous solution

    NASA Astrophysics Data System (ADS)

    Li, Shuang; Zhang, Huiyu; Lu, Rong; Yu, Anchi

    2017-09-01

    Triethanolamine (TEOA) has been often used as a hole-scavenger in dye-sensitized semiconductor photocatalytic systems. However, the femtosecond time-resolved kinetics of the interaction between a sensitized dye and TEOA has not been reported in literatures. Herein, we selected four commonly used xanthene dyes, such as fluorescein, dibromofluorescein, eosin Y, and erythrosine B, and studied their ultrafast fluorescence quenching dynamics in the presence of TEOA in aqueous solution, respectively, by using both femtosecond transient absorption and time-resolved fluorescence measurements. We obtained the electron transfer rate from TEOA to each photoexcited xanthene dye in 2.0 M TEOA solution. We also obtained the intersystem crossing rate of each xanthene dye in aqueous solution with fluorescence quantum yield and lifetime measurements. Finally we found that TEOA mainly interacts with the singlet excited-state of fluorescein, dibromofluorescein, and eosin Y, and that TEOA can interact with both the singlet and triplet excited-states of erythrosine B in high concentration of TEOA aqueous solution.

  17. Adiabatic generation of arbitrary coherent superpositions of two quantum states: Exact and approximate solutions

    NASA Astrophysics Data System (ADS)

    Zlatanov, Kaloyan N.; Vitanov, Nikolay V.

    2017-07-01

    The common objective of the application of adiabatic techniques in the field of quantum control is to transfer a quantum system from one discrete energy state to another. These techniques feature both high efficiency and insensitivity to variations in the experimental parameters, e.g., variations in the driving field amplitude, duration, frequency, and shape, as well as fluctuations in the environment. Here we explore the potential of adiabatic techniques for creating arbitrary predefined coherent superpositions of two quantum states. We show that an equally weighted coherent superposition can be created by temporal variation of the ratio between the Rabi frequency Ω (t ) and the detuning Δ (t ) from 0 to ∞ (case 1) or vice versa (case 2), as it is readily deduced from the explicit adiabatic solution for the Bloch vector. We infer important differences between cases 1 and 2 in the composition of the created coherent superposition: The latter depends on the dynamical phase of the process in case 2, while it does not depend on this phase in case 1. Furthermore, an arbitrary coherent superposition of unequal weights can be created by using asymptotic ratios of Ω (t )/Δ (t ) different from 0 and ∞ . We supplement the general adiabatic solution with analytic solutions for three exactly soluble models: two trigonometric models and the hyperbolic Demkov-Kunike model. They allow us not only to demonstrate the general predictions in specific cases but also to derive the nonadiabatic corrections to the adiabatic solutions.

  18. The optimal solution of a non-convex state-dependent LQR problem and its applications.

    PubMed

    Xu, Xudan; Zhu, J Jim; Zhang, Ping

    2014-01-01

    This paper studies a Non-convex State-dependent Linear Quadratic Regulator (NSLQR) problem, in which the control penalty weighting matrix [Formula: see text] in the performance index is state-dependent. A necessary and sufficient condition for the optimal solution is established with a rigorous proof by Euler-Lagrange Equation. It is found that the optimal solution of the NSLQR problem can be obtained by solving a Pseudo-Differential-Riccati-Equation (PDRE) simultaneously with the closed-loop system equation. A Comparison Theorem for the PDRE is given to facilitate solution methods for the PDRE. A linear time-variant system is employed as an example in simulation to verify the proposed optimal solution. As a non-trivial application, a goal pursuit process in psychology is modeled as a NSLQR problem and two typical goal pursuit behaviors found in human and animals are reproduced using different control weighting [Formula: see text]. It is found that these two behaviors save control energy and cause less stress over Conventional Control Behavior typified by the LQR control with a constant control weighting [Formula: see text], in situations where only the goal discrepancy at the terminal time is of concern, such as in Marathon races and target hitting missions.

  19. The Optimal Solution of a Non-Convex State-Dependent LQR Problem and Its Applications

    PubMed Central

    Xu, Xudan; Zhu, J. Jim; Zhang, Ping

    2014-01-01

    This paper studies a Non-convex State-dependent Linear Quadratic Regulator (NSLQR) problem, in which the control penalty weighting matrix in the performance index is state-dependent. A necessary and sufficient condition for the optimal solution is established with a rigorous proof by Euler-Lagrange Equation. It is found that the optimal solution of the NSLQR problem can be obtained by solving a Pseudo-Differential-Riccati-Equation (PDRE) simultaneously with the closed-loop system equation. A Comparison Theorem for the PDRE is given to facilitate solution methods for the PDRE. A linear time-variant system is employed as an example in simulation to verify the proposed optimal solution. As a non-trivial application, a goal pursuit process in psychology is modeled as a NSLQR problem and two typical goal pursuit behaviors found in human and animals are reproduced using different control weighting . It is found that these two behaviors save control energy and cause less stress over Conventional Control Behavior typified by the LQR control with a constant control weighting , in situations where only the goal discrepancy at the terminal time is of concern, such as in Marathon races and target hitting missions. PMID:24747417

  20. Efficiency enhancement in solution processed organic and organic-inorganic perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Xiao, Zhengguo

    Solution processed thin film photovoltaic devices are one of the most promising renewable energy sources. Organic solar cells have been intensively studied due to their advantages of light-weight, flexibility and low-cost materials and manufacturing. The organic-inorganic hybrid perovskite materials have recently shown great potential application in solar cells. The PCE increased dramatically from 3.8% in 2009 to a certified efficiency of 20.1% in 2014. In this dissertation, we focus on the efficiency enhancement for solution processed organic and organic-inorganic solar cells. In Chapter 2, I demonstrated that the crystallinity of the ferroelectric polymer P(VDF-TrFE) at the organic active layer/ electrode interface plays a critical role in the efficiency enhancement of organic solar cells. Then, The ferroelectric P(VDF-TrFE) nanocrystals was synthesized and successfully applied in the low band gap polymers. A high efficiency of 6.8% was achieved in the PCDTBT:PCBM system. Another small polar molecule, TPACA, was also applied to increase the efficiency of organic solar cells. In Chapter 3, I developed a universal approach of solvent fluxing to fabricate graded bulk heterojunction (BHJ) polymer:fullerene films to increase the device efficiency. The solvent fluxing process can extract part of the fullerene inside the BHJ film to the top surface to form graded BHJ. The PCE of the devices after solvent fluxing is increased by 15%--50% compared with the control devices without solvent fluxing. In Chapter 5, a two-step spin coating approach was developed to fabricate the continuous and compact organolead trihalide perovskite (OTP) films. The average PCE of methylammonium lead iodide (MAPbI3) perovskite devices reached 14.5% and 85% of the devices had efficiency above 14%. In Chapter 6, I discovered that the solvent annealing can be used to increase the grain size and crystallinity of the perovskite films. The highest device efficiency reached 15.6%, and device

  1. Approaches to the solution of coupled multiexponential transient-state rate kinetic equations: A critical review.

    PubMed

    Fisher, Harvey F

    2016-08-01

    The transient-state kinetic approach has failed to reach its full potential despite its advantage over the steady-state approach in its ability to observe mechanistic events directly and in real time. This failure has been due in part to the lack of any rigorously derived and readily applicable body of theory corresponding to that which currently characterizes the steady-state approach. In order to clarify the causes of this discrepancy and to suggest a route to its solution we examine the capabilities and limitations of the various forms of transient-state kinetic approaches to the mathematical resolution of enzymatic reaction mechanisms currently available. We document a lack of validity inherent in their basic assumptions and suggest the need for a potentially more rigorous analytic approach.

  2. On the efficient and reliable numerical solution of rate-and-state friction problems

    NASA Astrophysics Data System (ADS)

    Pipping, Elias; Kornhuber, Ralf; Rosenau, Matthias; Oncken, Onno

    2016-03-01

    We present a mathematically consistent numerical algorithm for the simulation of earthquake rupture with rate-and-state friction. Its main features are adaptive time stepping, a novel algebraic solution algorithm involving nonlinear multigrid and a fixed point iteration for the rate-and-state decoupling. The algorithm is applied to a laboratory scale subduction zone which allows us to compare our simulations with experimental results. Using physical parameters from the experiment, we find a good fit of recurrence time of slip events as well as their rupture width and peak slip. Computations in 3-D confirm efficiency and robustness of our algorithm.

  3. Bifurcating steady-state solutions of the dissipative quasi-geostrophic equation in Lagrangian formulation

    NASA Astrophysics Data System (ADS)

    Chen, Zhi-Min

    2016-10-01

    It is shown that the non-homogeneous dissipative quasi-geostrophic equation ∂θ∂t+uṡ∇θ+κ(-Δ)αθ=sin⁡x2,   u=(-∂x2, ∂x1)(-Δ)-β/2θ with α =0 and β >1 losses stability at a critical value {κc}>0 and this instability gives rise to a circle of steady-state solutions.

  4. Characterization of nonderivatized plant cell walls using high-resolution solution-state NMR spectroscopy

    Treesearch

    Daniel J. Yelle; John Ralph; Charles R. Frihart

    2008-01-01

    A recently described plant cell wall dissolution system has been modified to use perdeuterated solvents to allow direct in-NMR-tube dissolution and high-resolution solution-state NMR of the whole cell wall without derivatization. Finely ground cell wall material dissolves in a solvent system containing dimethylsulfoxide-d6 and 1-methylimidazole-d6 in a ratio of 4:1 (v/...

  5. The solution and solid state stability and excipient compatibility of parthenolide in feverfew.

    PubMed

    Jin, Ping; Madieh, Shadi; Augsburger, Larry L

    2007-12-14

    The objectives of this research were to evaluate the stability of parthenolide in feverfew solution state and powdered feverfew (solid state), and explore the compatibility between commonly used excipients and parthenolide in feverfew. Feverfew extract solution was diluted with different pH buffers to study the solution stability of parthenolide in feverfew. Powdered feverfew extract was stored under 40 degrees C/0% approximately 75% relative humidities (RH) or 31% RH/5~50 degrees C to study the influence of temperature and relative humidity on the stability of parthenolide in feverfew solid state. Binary mixtures of feverfew powered extract and different excipients were stored at 50 degrees C/ 75% RH for excipient compatibility evaluation. The degradation of parthenolide in feverfew solution appears to fit a typical first-order reaction. Parthenolide is comparatively stable when the environmental pH is in the range of 5 to 7, becoming unstable when pH is less than 3 or more than 7. Parthenolide degradation in feverfew in the solid state does not fit any obvious reaction model. Moisture content and temperature both play important roles affecting the degradation rate. After 6 months of storage, parthenolide in feverfew remains constant at 5 degrees C/31% RH. However, approximately 40% parthenolide in feverfew can be degraded if stored at 50 degrees C/31% RH. When the moisture changed from 0% to 75% RH, the degradation of parthenolide in feverfew increased from 18% to 32% after 6-month storage under 40 degrees C. Parthenolide in feverfew exhibits good compatibility with commonly used excipients under stressed conditions in a 3-week screening study.

  6. Analytical Solution of Steady State Equations for Chemical Reaction Networks with Bilinear Rate Laws

    PubMed Central

    Halász, Ádám M.; Lai, Hong-Jian; McCabe, Meghan M.; Radhakrishnan, Krishnan; Edwards, Jeremy S.

    2014-01-01

    True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher dimensional space. We show that the linearized version of the steady state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1. PMID:24334389

  7. Optimal unambiguous state discrimination of two density matrices: A second class of exact solutions

    SciTech Connect

    Raynal, Philippe; Luetkenhaus, Norbert

    2007-11-15

    We consider the unambiguous state discrimination (USD) of two mixed quantum states. We study the rank and the spectrum of the elements of an optimal USD measurement. This naturally leads to a partial fourth reduction theorem. This theorem shows that either the failure probability equals its overall lower bound given in terms of the fidelity or a two-dimensional subspace can be split off from the original Hilbert space. We then use this partial reduction theorem to derive the optimal solution for any two equally probable geometrically uniform states {rho}{sub 0} and {rho}{sub 1}=U{rho}{sub 0}U{sup {dagger}}, U{sup 2}=1, in a four-dimensional Hilbert space. This represents a second class of analytical solutions for USD problems that cannot be reduced to some pure state cases. We apply our result to answer two questions that are relevant in implementations of the Bennett and Brassard 1984 quantum key distribution protocol using weak coherent states.

  8. Analytical solution of steady-state equations for chemical reaction networks with bilinear rate laws.

    PubMed

    Halász, Adám M; Lai, Hong-Jian; McCabe Pryor, Meghan; Radhakrishnan, Krishnan; Edwards, Jeremy S

    2013-01-01

    True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady-state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here, we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher-dimensional space. We show that the linearized version of the steady-state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1.

  9. Transformation of photophysical properties from solution to solid state in alkoxy-cyano-diphenylacetylene molecules.

    PubMed

    Karunakaran, Venugopal; Prabhu, Deepak D; Das, Suresh; Varughese, Sunil

    2015-07-28

    Detailed photophysical properties of cyano and mono (MA)/bis alkoxy (DA) substituted diphenylacetylene moieties with different alkyl chain lengths (methyl (1), octyl (8) and dodecyl (12)) were investigated in solution and the solid state in an effort to determine the effect of self-aggregation on these properties. The solvated molecules showed a minimal bathochromic shift with an increase of solvent polarity in their absorption spectra, whereas a significant shift was observed in the emission spectra. This could be attributed to the relatively low change in dipole moment between ground and Franck-Condon excited states and luminescence arising from the intramolecular charge transfer state with a dipole moment significantly higher than that of the ground state. In solid state the emission quantum yields of these materials were significantly higher than in solution. For DA1, polymorphic materials with distinct photophysical properties were obtained. The DA1 materials obtained by fast precipitation (DA1) showed broad fluorescence with peaks at 398, 467 and 535 nm upon excitation at different wavelengths. Detailed analysis of absorption, emission and excitation spectra and lifetime experiments indicated that these peaks could be attributed to the monomer, J- and H-type aggregates respectively. Whereas the crystals obtained by slow crystallization (DA1C) showed only one emission peak at around 396 nm attributed to the monomer. This is supported by the single crystal X-ray structure which consists of a monomer molecule having minimal interaction with nearest neighbour molecules.

  10. Two-Photon Excitation of Conjugated Molecules in Solution: Spectroscopy and Excited-State Dynamics

    NASA Astrophysics Data System (ADS)

    Elles, Christopher G.; Houk, Amanda L.; de Wergifosse, Marc; Krylov, Anna

    2017-06-01

    We examine the two-photon absorption (2PA) spectroscopy and ultrafast excited-state dynamics of several conjugated molecules in solution. By controlling the relative wavelength and polarization of the two photons, the 2PA measurements provide a more sensitive means of probing the electronic structure of a molecule compared with traditional linear absorption spectra. We compare experimental spectra of trans-stilbene, cis-stilbene, and phenanthrene in solution with the calculated spectra of the isolated molecules using EOM-EE-CCSD. The calculated spectra show good agreement with the low-energy region of the experimental spectra (below 6 eV) after suppressing transitions with strong Rydberg character and accounting for solvent and method-dependent shifts of the valence transitions. We also monitor the excited state dynamics following two-photon excitation to high-lying valence states of trans-stilbene up to 6.5 eV. The initially excited states rapidly relax to the lowest singlet excited state and then follow the same reaction path as observed following direct one-photon excitation to the lowest absorption band at 4.0 eV.

  11. Probing the excited state relaxation dynamics of pyrimidine nucleosides in chloroform solution.

    PubMed

    Röttger, Katharina; Marroux, Hugo J B; Böhnke, Hendrik; Morris, David T J; Voice, Angus T; Temps, Friedrich; Roberts, Gareth M; Orr-Ewing, Andrew J

    2016-12-16

    Ultrafast transient electronic and vibrational absorption spectroscopy (TEAS and TVAS) of 2'-deoxy-cytidine (dC) and 2'-deoxy-thymidine (dT) dissolved in chloroform examines their excited-state dynamics and the recovery of ground electronic state molecules following absorption of ultraviolet light. The chloroform serves as a weakly interacting solvent, allowing comparisons to be drawn with prior experimental studies of the photodynamics of these nucleosides in the gas phase and in polar solvents such as water. The pyrimidine base nucleosides have some propensity to dimerize in aprotic solvents, but the monomer photochemistry can be resolved clearly and is the focus of this study. UV absorption at a wavelength of 260 nm excites a (1)ππ* ← S0 transition, but prompt crossing of a significant fraction (50% in dC, 17% in dT) of the (1)ππ* population into a nearby (1)nπ* state is too fast for the experiments to resolve. The remaining flux on the (1)ππ* state leaves the vertical Franck-Condon region and encounters a conical intersection with the ground electronic state of ethylenic twist character. In dC, the (1)ππ* state decays to the ground state with a time constant of 1.1 ± 0.1 ps. The lifetime of the (1)nπ* state is much longer in the canonical forms of both molecules: recovery of the ground state population from these states occurs with time constants of 18.6 ± 1.1 ps in amino-oxo dC and ∼114 ps in dT, indicating potential energy barriers to the (1)nπ*/S0 conical intersections. The small fraction of the imino-oxo tautomer of dC present in solution has a longer-lived (1)nπ* state with a lifetime for ground state recovery of 193 ± 55 ps. No evidence is found for photo-induced tautomerization of amino-oxo dC to the imino-oxo form, or for population of low lying triplet states of this nucleoside. In contrast, ∼8% of the UV-excited dT molecules access the long-lived T1 ((3)ππ*) state through the (1)nπ* state. The primary influence of the solvent

  12. Steady-state electrodiffusion. Scaling, exact solution for ions of one charge, and the phase plane.

    PubMed Central

    Leuchtag, H R; Swihart, J C

    1977-01-01

    This is the first of two papers dealing with electrodiffusion theory (the Nernst-Planck equation coupled with Gauss's law) and its application to the current-voltage behavior of squid axon. New developments in the exact analysis of the steady-state electrodiffusion problem presented here include (a) a scale transformation that connects a given solution to an infinity of other solutions, suggesting the po-sibility of direct comparison of electrical data for membranes with different thicknesses and other properties; (b) a first-integral relation between the electric field and ion densities more general than analogous relations previously reported, and (c) an exact solution for the homovalent system, i.e., a membrane system permeated by various ion species of the same charge. The latter is a generalization of the known one-ion solution. The properties of the homovalent solution are investigated analytically and graphically. In particular we study the phase-plane curves, which reduce to the parabolas discussed by K. S. Cole in the special case in which the current-density parameter (a linear combination of the ionic current densities) is zero. PMID:831855

  13. Molecular Environment Modulates Conformational Differences between Crystal and Solution States of Human β-Defensin 2.

    PubMed

    Li, Jianguo; Hu, Zhongqiao; Beuerman, Roger; Verma, Chandra

    2017-04-06

    Human β-defensin 2 is a cysteine-rich antimicrobial peptide. In the crystal state, the N-terminal segment (residues 1-11) exhibits a helical conformation. However, a truncated form, with four amino acids removed from the N-terminus, adopts nonhelical conformations in solution, as shown by NMR. To explore the molecular origins of these different conformations, we performed Hamiltonian replica exchange molecular dynamics simulations of the peptide in solution and in the crystal state. It is found that backbone hydration and specific protein-protein interactions are key parameters that determine the peptide conformation. The helical conformation in the crystal state mainly arises from reduced hydration as well as a salt bridge between the peptide and a symmetry-related neighboring monomer in the crystal. When the extent of hydration is reduced and the salt bridge is reintroduced artificially, the peptide is successfully folded back to the helical conformation in solution. The findings not only shed light on the development of accurate force field parameters for protein molecules but also provide practical guidance in the design of functional proteins and peptides.

  14. Understanding the solution phase chemistry and solid state thermodynamic behavior of pharmaceutical cocrystals

    NASA Astrophysics Data System (ADS)

    Maheshwari, Chinmay

    Cocrystals have drawn a lot of research interest in the last decade due to their potential to favorably alter the physicochemical and biopharmaceutical properties of active pharmaceutical ingredients. This dissertation focuses on the thermodynamic stability and solubility of pharmaceutical cocrystals. Specifically, the objectives are to; (i) investigate the influence of coformer properties such as solubility and ionization characteristics on cocrystal solubility and stability as a function of pH, (ii) to measure the thermodynamic solubility of metastable cocrystals, and study the solubility differences measured by kinetic and equilibrium methods, (iii) investigate the role of surfactants on the solubility and synthesis of cocrystals, (iv) investigate the solid state phase transformation of reactants to cocrystals and the factors that influence the reaction kinetics and, (v) provide models that enable the prediction of cocrystal formation by calculating the free energy of formation for a solid to solid transformation of reactants to cocrystals. Cocrystal solubilities were measured directly when cocrystals were thermodynamically stable, while solubilities were calculated from eutectic concentration measurements when cocrystals were of higher solubility than its components. Cocrystal solubility was highly dependent on coformer solubilities for gabapentin-lactam and lamotrigine cocrystals. It was found that melting point is not a good indicator of cocrystal solubility as solute-solvent interactions quantified by the activity coefficient play a huge role in the observed solubility. Similar to salts, cocrystals also exhibit pHmax, however the salts and cocrystals have different dependencies on the parameters that govern the value of pHmax. It is also shown that cocrystals could provide solubility advantage over salts as lamotrigine-nicotinamide cocrystal hydrate has about 6 fold higher solubility relative to lamotrigine-saccharin salt. In the case of mixtures of solid

  15. Multiple solutions of steady-state Poisson-Nernst-Planck equations with steric effects

    NASA Astrophysics Data System (ADS)

    Lin, Tai-Chia; Eisenberg, Bob

    2015-07-01

    Experiments measuring currents through single protein channels show unstable currents. Channels switch between ‘open’ or ‘closed’ states in a spontaneous stochastic process called gating. Currents are either (nearly) zero or at a definite level, characteristic of each type of protein, independent of time, once the channel is open. The steady state Poisson-Nernst-Planck equations with steric effects (PNP-steric equations) describe steady current through the open channel quite well, in a wide variety of conditions. Here we study the existence of multiple solutions of steady state PNP-steric equations to see if they themselves, without modification or augmentation, can describe two levels of current. We prove that there are two steady state solutions of PNP-steric equations for (a) three types of ion species (two types of cations and one type of anion) with a positive constant permanent charge, and (b) four types of ion species (two types of cations and their counter-ions) with a constant permanent charge but no sign condition. The excess currents (due to steric effects) associated with these two steady state solutions are derived and expressed as two distinct formulas. Our results indicate that PNP-steric equations may become a useful model to study spontaneous gating of ion channels. Spontaneous gating is thought to involve small structural changes in the channel protein that perhaps produce large changes in the profiles of free energy that determine ion flow. Gating is known to be modulated by external structures. Both can be included in future extensions of our present analysis.

  16. Thixotropic solutions enhance viral-mediated gene transfer to airway epithelia.

    PubMed

    Seiler, Michael P; Luner, Paul; Moninger, Thomas O; Karp, Philip H; Keshavjee, Shaf; Zabner, Joseph

    2002-08-01

    Adenovirus-mediated gene transfer to airway epithelia is inefficient in part because its receptor is absent on the apical surface of the airways. Targeting adenovirus to other receptors, increasing the viral concentration, and even prolonging the incubation time with adenovirus vectors can partially overcome the lack of receptors and facilitate gene transfer. Unfortunately, mucociliary clearance would prevent prolonged incubation time in vivo. Thixotropic solutions (TS) are gels that upon a vigorous shearing force reversibly become liquid. We hypothesized that formulating recombinant adenoviruses in TS would decrease virus clearance and thus enhance gene transfer to the airway epithelia. We found that clearance of virus-sized fluorescent beads by human airway epithelia in vitro and by monkey trachea in vivo were markedly decreased when the beads were formulated in TS compared with phosphate-buffered saline (PBS). Adenovirus formulated in TS significantly increased adenovirus-mediated gene transfer of a reporter gene in human airway epithelia in vitro and in murine airway epithelia in vivo. Furthermore, an adenovirus encoding the cystic fibrosis transmembrane regulator (CFTR) gene (AdCFTR) formulated in TS was more efficient in correcting the chloride transport defect in cystic fibrosis airway epithelia than AdCFTR formulated in PBS. These data indicate a novel strategy to augment the efficiency of gene transfer to the airways that may be applicable to a number of different gene transfer vectors and could be of value in gene transfer to cystic fibrosis (CF) airway epithelia in vivo.

  17. Phthalate degradation by glow discharge plasma enhanced with pyrite in aqueous solution.

    PubMed

    Shen, Chensi; Wu, Shaoshuai; Chen, Hui; Rashid, Sadia; Wen, Yuezhong

    2016-09-01

    In order to prevent health risk from potential exposures to phthalates, a glow discharge plasma (GDP) process was applied for phthalate degradation in aqueous solution. The results revealed that the phthalate derivatives 4-hydroxyphthalic acid, 4-methylphthalic acid and 4-tert-butylphthalic anhydride could be degraded efficiently in GDP process (498 V, 0.2 A) with high removal efficiencies of over 99% in 60 minutes. Additionally, pyrite as a promising heterogeneous iron source in the Fenton reaction was found to be favorable for GDP process. The phthalate degradation reaction could be significantly enhanced by the continuous formation of •OH and the inhibition of the quenching reaction in the pyrite Fenton system due to the constant dissolution of Fe(II) from pyrite surface. Meanwhile, the initial pH value showed little impact on the degradation of phthalates and the energy efficiency of GDP system for phthalate degradation ranged between 0.280 × 10(-9) and 1.210 × 10(-9) mol/J, which is similar to the GDP system with phenol, bisphenol A and methyl tert-butyl ether as the substrates. Further, the X-ray diffraction and scanning electron microscopy with energy dispersive X-ray spectroscopy analyses indicated that the pyrite was relatively stable in GDP system and there was no obvious polymeric compound formed on the catalyst surface. Overall, this GDP process offers high removal efficiency, simple technology, considerable energy efficiency and the applicability to salt-containing phthalate wastewater.

  18. Contribution of various components to the enhanced accuracy of GIPSY/OASIS II PPP solutions

    NASA Astrophysics Data System (ADS)

    Hayal, Adem G.; Ugur Sanli, D.

    2016-04-01

    The accuracy of GIPSY PPP has now been revised following the substantial improvements in JPL analysis strategies and product quality after the year 2007. The accuracy improvement in GIPSY solutions was due mainly to the rigorous analysis procedures adopted in computing the satellite orbits in JPL, incorporating single receiver ambiguity resolution among GIPSY modules, and applying a new 2nd order ionosphere modeling. The 2010 positioning accuracy model, which accounts for the procedures prior to 2007 enhancements, was refined in 2015 using a global set of International GNSS Service (IGS) stations and v. 6.3 of GIPSY/OASIS II software. This was just after the reprocessing of JPL final orbit products with second order ionospheric corrections (Oct/Nov 2014).The improvement in regard to precise satellite orbits was previously shared with research community by the NASA. However, comparative contribution of single receiver ambiguity resolution and 2nd order ionosphere correction into the accuracy model has not been assessed yet. Here we perform the so-called assessment and find that contribution of single receiver ambiguity resolution is comparatively greater than that of the 2nd order ionosphere modeling for our particular global sampling.

  19. Iridium-Tin oxide solid-solution nanocatalysts with enhanced activity and stability for oxygen evolution

    NASA Astrophysics Data System (ADS)

    Li, Guangfu; Yu, Hongmei; Yang, Donglei; Chi, Jun; Wang, Xunying; Sun, Shucheng; Shao, Zhigang; Yi, Baolian

    2016-09-01

    Addressing major challenges from the material cost, efficiency and stability, it is highly desirable to develop high-performance catalysts for oxygen evolution reaction (OER). Herein we explore a facile surfactant-assisted approach for fabricating Irsbnd Sn (Ir/Sn = 0.6/0.4, by mol.) nano-oxide catalysts with good morphology control. Direct proofs from XRD and X-ray photoelectron spectra indicate hydrophilic triblock polymer (TBP, like Pluronic® F108) surfactant can boost the formation of stable solid-solution structure. With the TBP hydrophilic and block-length increase, the fabricated Irsbnd Sn oxides undergoing the rod-to-sphere transition obtain the relatively lower crystallization, decreased crystallite size, Ir-enriched surface and incremental available active sites, all of which can bolster the OER activity and stability. Meanwhile, it is observed that the coupled Ir oxidative etching takes a crucial role in determining the material structure and performance. Compared with commercial Ir black, half-cell tests confirm F108-assistant catalysts with over 40 wt% Ir loading reduction show 2-fold activity enhancement as well as significant stability improvement. The lowest cell voltage using 0.88 mg cm-2 Ir loading is only 1.621 V at 1000 mA cm-2 and 80 °C with a concomitant energy efficiency of 75.8% which is beyond the DOE 2017 efficiency target of 74%.

  20. Plasma Creatine Kinetics After Ingestion of Microencapsulated Creatine Monohydrate with Enhanced Stability in Aqueous Solutions.

    PubMed

    Hone, Michelle; Kent, Robert M; Scotto di Palumbo, Alessandro; Bleiel, Sinead B; De Vito, Giuseppe; Egan, Brendan

    2017-07-04

    Creatine monohydrate represents one of the largest sports supplement markets. Enhancing creatine (CRE) stability in aqueous solutions, such as with microencapsulation, represents innovation potential. Ten physically active male volunteers were randomly assigned in a double-blind design to either placebo (PLA) (3-g maltodextrin; n = 5) or microencapsulated CRE (3-g creatine monohydrate; n = 5) conditions. Experimental conditions involved ingestion of the samples in a 70-mL ready-to-drink format. CRE was delivered in a novel microencapsulation matrix material consisting entirely of hydrolyzed milk protein. Three hours after ingestion, plasma creatine concentrations were unchanged during PLA, and averaged ∼45 μM. During CRE, plasma creatine concentration peaked after 30 min at 101.6 ± 14.9 μM (p < 0.05), representing a 2.3-fold increase over PLA. Thereafter, plasma creatine concentration gradually trended downwards but remained significantly elevated (∼50% above resting levels) 3 hr after ingestion. These results demonstrate that the microencapsulated form of creatine monohydrate reported herein remains bioavailable when delivered in aqueous conditions, and has potential utility in ready-to-drink formulations for creatine supplementation.

  1. Enhancing a phase measurement by sequentially probing a solid-state system

    NASA Astrophysics Data System (ADS)

    Knott, P. A.; Munro, W. J.; Dunningham, J. A.

    2016-05-01

    In a recent paper, Liu et al. [Nat. Commun. 6:6726 (2015)] claim to perform the first room temperature entanglement-enhanced phase measurement in a solid-state system. We argue here that this claim is incorrect: their measurement is not enhanced because of the entanglement in their system, but instead the enhancement comes from the fact that the phase shift is applied twice to their state.

  2. Successfully Demonstrating an Integrated Roofing and BIPV Solution for an Historic Building Renovation at the United States Air Force Academy

    DTIC Science & Technology

    2011-05-01

    Successfully Demonstrating an Integrated Roofing and BIPV Solution for an Historic Building Renovation at the United States Air Force Academy...COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE Successfully Demonstrating an Integrated Roofing and BIPV Solution for an Historic...ANSI Std Z39-18 Successfully Demonstrating an Integrated Roofing and BIPV Solution for an Historic Building Renovation at the United States Air Force

  3. Navigating the information technology highway: computer solutions to reduce errors and enhance patient safety.

    PubMed

    Koshy, Ranie

    2005-10-01

    Standardized, seamless, integrated information technology in the health-care environment used with other industry tools can markedly decrease preventable errors or adverse events and increase patient safety. According to an Institute of Medicine (IOM) report released in 1999, preventable errors have caused between 44,000 and 98,000 deaths per year. Following the report, President Bill Clinton requested that the Agency of Healthcare Research and Quality, a government agency, look into the issue and fund, at the local or state level, processes that can reduce errors. Funding subsequently was made available for research that utilizes best practice tools in clinical practice to increase patient safety. The Joint Commission on Accreditation of Healthcare Organization has placed a great deal of emphasis on strategies to reduce patient identification errors. Fragmented systems tout the individual as well as enhanced safety applications. These applications, however, are related to prevention in specific conditions and in specific health-care settings. Systems are not integrated with common reference data and common terminology aggregated at a regional or national level to provide access to patient safety risks for timely interventions before errors and adverse events occur. Standardized integrated patient care information systems are not available either on a regional or on a national level. This article examines tangible options to increase patient safety through improved state-of-the-art tools that can be incorporated into the health-care system to prevent errors.

  4. SedNMR: on the edge between solution and solid-state NMR.

    PubMed

    Bertini, Ivano; Luchinat, Claudio; Parigi, Giacomo; Ravera, Enrico

    2013-09-17

    Solid-state NMR (SS-NMR) of proteins requires that those molecules be immobilized, usually by crystallization, freezing, or lyophilization. However, self-crowding can also slow molecular rotation sufficiently to prevent the nuclear interactions from averaging. To achieve self-crowding, researchers can use a centrifugal field to create a concentration gradient or use regular ultracentrifugation to produce highly concentrated, gel-like solutions. Thus sedimented solute NMR (SedNMR) provides a simple method to prepare biological samples for SS-NMR experiments with minimal perturbation. This method may also give researchers a way to investigate species that are not otherwise accessible by NMR. We induce the sedimentation in one of two ways: (1) by the extreme centrifugal force exerted during magic angle spinning (MAS-induced sedimentation or in situ) or (2) by an ultracentrifuge (UC-induced sedimentation or ex situ). Sedimentation is particularly useful in situations where it is difficult to obtain protein crystals. Furthermore, because the proteins remain in a largely hydrated state, the sedimented samples may provide SS-NMR spectra that have better resolution than the spectra from frozen solutions or lyophilized powders. If sedimentation is induced in situ, the same protein sample can be used for both solution and SS-NMR studies. Finally, we show that in situ SedNMR can be used to detect the NMR signals of large molecular adducts that have binding constants that are too weak to allow for the selective isolation and crystallization of the complexed species. We can selectively induce sedimentation for the heaviest molecular species. Because the complexed molecules are subtracted from the bulk solution, the reaction proceeds further toward the formation of complexes.

  5. Conformation Types of Ubiquitin [M+8H]8+ Ions from Water:Methanol Solutions: Evidence for the N and A States in Aqueous Solution

    PubMed Central

    Shi, Huilin; Pierson, Nicholas A.; Valentine, Stephen J.; Clemmer, David E.

    2012-01-01

    Ion mobility and mass spectrometry measurements are used to examine the gas-phase populations of [M+8H]8+ ubiquitin ions formed upon electrospraying 20 different solutions: from 100:0 to 5:95 water:methanol that are maintained at pH = 2.0. Over this range of solution conditions, mobility distributions for the +8 charge state show substantial variations. Here we develop a model that treats the combined measurements as one data set. By varying the relative abundances of a discrete set of conformation types, it is possible to represent distributions obtained from any solution. For solutions that favor the well-known A-state ubiquitin, it is possible to represent the gas-phase distributions with seven conformation types. Aqueous conditions that favor the native structure require four more structural types to represent the distribution. This analysis provides the first direct evidence for trace amounts of the A state under native conditions. The method of analysis presented here should help illuminate how solution populations evolve into new gas-phase structures as solvent is removed. Evidence for trace quantities of previously unknown states under native solution conditions may provide insight about the relationship of dynamics to protein function as well as misfolding and aggregation phenomena. PMID:22315998

  6. Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR

    PubMed Central

    2015-01-01

    We show how dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy can be used to characterize polymorphs and solvates of organic solids. We applied DNP to three polymorphs and one hydrated form of the asthma drug molecule theophylline. For some forms of theophylline, sample grinding and impregnation with the radical-containing solution, which are necessary to prepare the samples for DNP, were found to induce polymorphic transitions or desolvation between some forms. We present protocols for sample preparation for solid-state magic-angle spinning (MAS) DNP experiments that avoid the polymorphic phase transitions in theophylline. These protocols include cryogrinding, grinding under inert atmosphere, and the appropriate choice of the impregnating liquid. By applying these procedures, we subsequently demonstrate that two-dimensional correlation experiments, such as 1H–13C and 1H–15N HETCOR or 13C–13C INADEQUATE, can be obtained at natural isotopic abundance in reasonable times, thus enabling more advanced structural characterization of polymorphs. PMID:26393368

  7. Polymorphs of Theophylline Characterized by DNP Enhanced Solid-State NMR.

    PubMed

    Pinon, Arthur C; Rossini, Aaron J; Widdifield, Cory M; Gajan, David; Emsley, Lyndon

    2015-11-02

    We show how dynamic nuclear polarization (DNP) enhanced solid-state NMR spectroscopy can be used to characterize polymorphs and solvates of organic solids. We applied DNP to three polymorphs and one hydrated form of the asthma drug molecule theophylline. For some forms of theophylline, sample grinding and impregnation with the radical-containing solution, which are necessary to prepare the samples for DNP, were found to induce polymorphic transitions or desolvation between some forms. We present protocols for sample preparation for solid-state magic-angle spinning (MAS) DNP experiments that avoid the polymorphic phase transitions in theophylline. These protocols include cryogrinding, grinding under inert atmosphere, and the appropriate choice of the impregnating liquid. By applying these procedures, we subsequently demonstrate that two-dimensional correlation experiments, such as (1)H-(13)C and (1)H-(15)N HETCOR or (13)C-(13)C INADEQUATE, can be obtained at natural isotopic abundance in reasonable times, thus enabling more advanced structural characterization of polymorphs.

  8. Steady-state solutions of a diffusive energy-balance climate model and their stability

    NASA Technical Reports Server (NTRS)

    Ghil, M.

    1975-01-01

    A diffusive energy-balance climate model, governed by a nonlinear parabolic partial differential equation, was studied. Three positive steady-state solutions of this equation are found; they correspond to three possible climates of our planet: an interglacial (nearly identical to the present climate), a glacial, and a completely ice-covered earth. Models similar to the main one are considered, and the number of their steady states was determined. All the models have albedo continuously varying with latitude and temperature, and entirely diffusive horizontal heat transfer. The stability under small perturbations of the main model's climates was investigated. A stability criterion is derived, and its application shows that the present climate and the deep freeze are stable, whereas the model's glacial is unstable. The dependence was examined of the number of steady states and of their stability on the average solar radiation.

  9. A modified two-state empirical valence bond model for proton transport in aqueous solutions

    SciTech Connect

    Mabuchi, Takuya; Fukushima, Akinori; Tokumasu, Takashi

    2015-07-07

    A detailed analysis of the proton solvation structure and transport properties in aqueous solutions is performed using classical molecular dynamics simulations. A refined two-state empirical valence bond (aTS-EVB) method, which is based on the EVB model of Walbran and Kornyshev and the anharmonic water force field, is developed in order to describe efficiently excess proton transport via the Grotthuss mechanism. The new aTS-EVB model clearly satisfies the requirement for simpler and faster calculation, because of the simplicity of the two-state EVB algorithm, while providing a better description of diffusive dynamics of the excess proton and water in comparison with the previous two-state EVB models, which significantly improves agreement with the available experimental data. The results of activation energies for the excess proton and water calculated between 300 and 340 K (the temperature range used in this study) are also found to be in good agreement with the corresponding experimental data.

  10. Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state.

    PubMed

    Silver, Mark A; Cary, Samantha K; Johnson, Jason A; Baumbach, Ryan E; Arico, Alexandra A; Luckey, Morgan; Urban, Matthew; Wang, Jamie C; Polinski, Matthew J; Chemey, Alexander; Liu, Guokui; Chen, Kuan-Wen; Van Cleve, Shelley M; Marsh, Matthew L; Eaton, Teresa M; van de Burgt, Lambertus J; Gray, Ashley L; Hobart, David E; Hanson, Kenneth; Maron, Laurent; Gendron, Frédéric; Autschbach, Jochen; Speldrich, Manfred; Kögerler, Paul; Yang, Ping; Braley, Jenifer; Albrecht-Schmitt, Thomas E

    2016-08-26

    Berkelium is positioned at a crucial location in the actinide series between the inherently stable half-filled 5f(7) configuration of curium and the abrupt transition in chemical behavior created by the onset of a metastable divalent state that starts at californium. However, the mere 320-day half-life of berkelium's only available isotope, (249)Bk, has hindered in-depth studies of the element's coordination chemistry. Herein, we report the synthesis and detailed solid-state and solution-phase characterization of a berkelium coordination complex, Bk(III)tris(dipicolinate), as well as a chemically distinct Bk(III) borate material for comparison. We demonstrate that berkelium's complexation is analogous to that of californium. However, from a range of spectroscopic techniques and quantum mechanical calculations, it is clear that spin-orbit coupling contributes significantly to berkelium's multiconfigurational ground state.

  11. Final Report - Montana State University - Microbial Activity and Precipitation at Solution-Solution Mixing Zones in Porous Media

    SciTech Connect

    Gerlach, Robin

    2014-10-31

    Background. The use of biological and chemical processes that degrade or immobilize contaminants in subsurface environments is a cornerstone of remediation technology. The enhancement of biological and chemical processes in situ, involves the transport, displacement, distribution and mixing of one or more reactive agents. Biological and chemical reactions all require diffusive transport of solutes to reaction sites at the molecular scale and accordingly, the success of processes at the meter-scale and larger is dictated by the success of phenomena that occur at the micron-scale. However, current understanding of scaling effects on the mixing and delivery of nutrients in biogeochemically dynamic porous media systems is limited, despite the limitations this imposes on the efficiency and effectiveness of the remediation challenges at hand. Objectives. We therefore proposed to experimentally characterize and computationally describe the growth, evolution, and distribution of microbial activity and mineral formation as well as changes in transport processes in porous media that receive two or more reactive amendments. The model system chosen for this project was based on a method for immobilizing 90Sr, which involves stimulating microbial urea hydrolysis with ensuing mineral precipitation (CaCO3), and co-precipitation of Sr. Studies at different laboratory scales were used to visualize and quantitatively describe the spatial relationships between amendment transport and consumption that stimulate the production of biomass and mineral phases that subsequently modify the permeability and heterogeneity of porous media. Biomass growth, activity, and mass deposition in mixing zones was investigated using two-dimensional micro-model flow cells as well as flow cells that could be analyzed using synchrotron-based x-ray tomography. Larger-scale flow-cell experiments were conducted where the spatial distribution of media properties, flow, segregation of biological activity and

  12. Solid-State and Solution Metallophilic Aggregation of a Cationic [Pt(NCN)L](+) Cyclometalated Complex.

    PubMed

    Sivchik, Vasily V; Grachova, Elena V; Melnikov, Alexei S; Smirnov, Sergey N; Ivanov, Alexander Yu; Hirva, Pipsa; Tunik, Sergey P; Koshevoy, Igor O

    2016-04-04

    The noncovalent intermolecular interactions (π-π stacking, metallophilic bonding) of the cyclometalated complexes [Pt(NCN)L](+)X(-) (NCN = dipyridylbenzene, L = pyridine (1), acetonitrile (2)) are determined by the steric properties of the ancillary ligands L in the solid state and in solution, while the nature of the counterion X(-) (X(-) = PF6(-), ClO4(-), CF3SO3(-)) affects the molecular arrangement of 2·X in the crystal medium. According to the variable-temperature X-ray diffraction measurements, the extensive Pt···Pt interactions and π-stacking in 2·X are significantly temperature-dependent. The variable concentration (1)H and diffusion coefficients NMR measurements reveal that 2·X exists in the monomeric form in dilute solutions at 298 K, while upon increase in concentration [Pt(NCN)(NCMe)](+) cations undergo the formation of the ground-state oligomeric aggregates with an average aggregation number of ∼3. The photoluminescent characteristics of 1 and 2·X are largely determined by the intermolecular aggregation. For the discrete molecules the emission properties are assigned to metal perturbed IL charge transfer mixed with some MLCT contribution. In the case of oligomers 2·X the luminescence is significantly red-shifted with respect to 1 and originates mainly from the (3)MMLCT excited states. The emission energies depend on the structural arrangement in the crystal and on the complex concentration in solution, variation of which allows for the modulation of the emission color from greenish to deep red. In the solid state the lability of the ligands L leads to vapor-induced reversible transformation 1 ↔ 2 that is accompanied by the molecular reorganization and, consequently, dramatic change of the photophysical properties. Time-dependent density functional theory calculations adequately support the models proposed for the rationalization of the experimental observations.

  13. High-density P300 enhancers control cell state transitions.

    PubMed

    Witte, Steven; Bradley, Allan; Enright, Anton J; Muljo, Stefan A

    2015-11-06

    Transcriptional enhancers are frequently bound by a set of transcription factors that collaborate to activate lineage-specific gene expression. Recently, it was appreciated that a subset of enhancers comprise extended clusters dubbed stretch- or super-enhancers (SEs). These SEs are located near key cell identity genes, and enriched for non-coding genetic variations associated with disease. Previously, SEs have been defined as having the highest density of Med1, Brd4 or H3K27ac by ChIP-seq. The histone acetyltransferase P300 has been used as a marker of enhancers, but little is known about its binding to SEs. We establish that P300 marks a similar SE repertoire in embryonic stem cells as previously reported using Med1 and H3K27ac. We also exemplify a role for SEs in mouse T helper cell fate decision. Similarly, upon activation of macrophages by bacterial endotoxin, we found that many SE-associated genes encode inflammatory proteins that are strongly up-regulated. These SEs arise from small, low-density enhancers in unstimulated macrophages. We also identified expression quantitative trait loci (eQTL) in human monocytes that lie within such SEs. In macrophages and Th17 cells, inflammatory SEs can be perturbed either genetically or pharmacologically thus revealing new avenues to target inflammation. Our findings support the notion that P300-marked SEs can help identify key nodes of transcriptional control during cell fate decisions. The SE landscape changes drastically during cell differentiation and cell activation. As these processes are crucial in immune responses, SEs may be useful in revealing novel targets for treating inflammatory diseases.

  14. Cosmic ray heating in cool core clusters I: diversity of steady state solutions

    NASA Astrophysics Data System (ADS)

    Jacob, Svenja; Pfrommer, Christoph

    2017-01-01

    The absence of large cooling flows in cool core clusters appears to require self-regulated energy feedback by active galactic nuclei (AGNs) but the exact heating mechanism has not yet been identified. Here, we analyse whether a combination of cosmic ray (CR) heating and thermal conduction can offset radiative cooling. To this end, we compile a large sample of 39 cool core clusters and determine steady state solutions of the hydrodynamic equations that are coupled to the CR energy equation. We find solutions that match the observed density and temperature profiles for all our clusters well. Radiative cooling is balanced by CR heating in the cluster centres and by thermal conduction on larger scales, thus demonstrating the relevance of both heating mechanisms. Our mass deposition rates vary by three orders of magnitude and are linearly correlated to the observed star formation rates. Clusters with large mass deposition rates show larger cooling radii and require a larger radial extent of the CR injection function. Interestingly, our sample shows a continuous sequence in cooling properties: clusters hosting radio mini halos are characterised by the largest cooling radii, star formation and mass deposition rates in our sample and thus signal the presence of a higher cooling activity. The steady state solutions support the structural differences between clusters hosting a radio mini halo and those that do not.

  15. The finite state projection algorithm for the solution of the chemical master equation

    NASA Astrophysics Data System (ADS)

    Munsky, Brian; Khammash, Mustafa

    2006-01-01

    This article introduces the finite state projection (FSP) method for use in the stochastic analysis of chemically reacting systems. One can describe the chemical populations of such systems with probability density vectors that evolve according to a set of linear ordinary differential equations known as the chemical master equation (CME). Unlike Monte Carlo methods such as the stochastic simulation algorithm (SSA) or τ leaping, the FSP directly solves or approximates the solution of the CME. If the CME describes a system that has a finite number of distinct population vectors, the FSP method provides an exact analytical solution. When an infinite or extremely large number of population variations is possible, the state space can be truncated, and the FSP method provides a certificate of accuracy for how closely the truncated space approximation matches the true solution. The proposed FSP algorithm systematically increases the projection space in order to meet prespecified tolerance in the total probability density error. For any system in which a sufficiently accurate FSP exists, the FSP algorithm is shown to converge in a finite number of steps. The FSP is utilized to solve two examples taken from the field of systems biology, and comparisons are made between the FSP, the SSA, and τ leaping algorithms. In both examples, the FSP outperforms the SSA in terms of accuracy as well as computational efficiency. Furthermore, due to very small molecular counts in these particular examples, the FSP also performs far more effectively than τ leaping methods.

  16. Cosmic ray heating in cool core clusters - I. Diversity of steady state solutions

    NASA Astrophysics Data System (ADS)

    Jacob, Svenja; Pfrommer, Christoph

    2017-05-01

    The absence of large cooling flows in cool core clusters appears to require self-regulated energy feedback by active galactic nuclei but the exact heating mechanism has not yet been identified. Here, we analyse whether a combination of cosmic ray (CR) heating and thermal conduction can offset radiative cooling. To this end, we compile a large sample of 39 cool core clusters and determine steady state solutions of the hydrodynamic equations that are coupled to the CR energy equation. We find solutions that match the observed density and temperature profiles for all our clusters well. Radiative cooling is balanced by CR heating in the cluster centres and by thermal conduction on larger scales, thus demonstrating the relevance of both heating mechanisms. Our mass deposition rates vary by three orders of magnitude and are linearly correlated to the observed star formation rates. Clusters with large mass deposition rates show larger cooling radii and require a larger radial extent of the CR injection function. Interestingly, our sample shows a continuous sequence in cooling properties: clusters hosting radio mini haloes are characterized by the largest cooling radii, star formation and mass deposition rates in our sample and thus signal the presence of a higher cooling activity. The steady state solutions support the structural differences between clusters hosting a radio mini halo and those that do not.

  17. Ruthenium complexes of substituted hydrazine: new solution- and solid-state binding modes.

    PubMed

    Dabb, Serin L; Messerle, Barbara A; Otting, Gottfried; Wagler, Jörg; Willis, Anthony

    2008-01-01

    The methylhydrazine complex [Ru(NH(2)NHMe)(PyP)(2)]Cl(BPh(4)) (PyP=1-[2-(diphenylphosphino)ethyl]pyrazole) was synthesised by addition of methylhydrazine to the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(BPh(4))(2). The methylhydrazine ligand of the ruthenium complex has two different binding modes: side-on (eta(2)-) when the complex is in the solid state and end-on (eta(1)-) when the complex is in solution. The solid-state structure of [Ru(PyP)(2)(NH(2)NHMe)]Cl(BPh(4)) was determined by X-ray crystallography. 2D NMR spectroscopic experiments with (15)N at natural abundance confirmed that in solution the methylhydrazine is bound to the metal centre by only the -NH(2) group and the ruthenium complex retains an octahedral conformation. Hydrazine complexes [RuCl(PyP)(2)(eta(1)-NH(2)NRR')]OSO(2)CF(3) (in which R=H, R'=Ph, R=R'=Me and NRR'=NC(5)H(10)) were formed in situ by the addition of phenylhydrazine, 1,1-dimethylhydrazine and N-aminopiperidine, respectively, to a solution of the bimetallic complex [Ru(mu-Cl)(PyP)(2)](2)(OSO(2)CF(3))(2) in dichloromethane. These substituted hydrazine complexes of ruthenium were shown to exist in an equilibrium mixture with the bimetallic starting material.

  18. California Enhanced Monitoring; State Implementation Plan (SIP) Revision

    EPA Pesticide Factsheets

    is proposing to approve a SIP revision submitted by the State of California on November 10, 1993 concerning the establishment of a Photochemical Assessment Monitoring System (PAMS) network in six ozone nonattainment areas within California.

  19. Drop coating deposition Raman spectroscopy of proteinogenic amino acids compared with their solution and crystalline state

    NASA Astrophysics Data System (ADS)

    Pazderka, Tomáš; Kopecký, Vladimír

    2017-10-01

    The Raman spectra of 20 proteinogenic amino acids were recorded in the solution, glass phase (as drop coating deposition Raman (DCDR) samples) and crystalline forms in the wide spectral range of 200-3200 cm- 1. The most apparent spectral differences between the Raman spectra of the crystalline forms, glass phases and aqueous solutions of amino acids were briefly discussed and described in the frame of published works. The possible density dependencies of spectral bands were noted. In some cases, a strong influence of the sample density, as well as of the organization of the water envelope, was observed. The most apparent changes were observed for Ser and Thr. Nevertheless, for the majority of amino acids, the DCDR sample form is an intermediate between the solution and crystalline forms. In contrast, aromatic amino acids have only a small sensitivity to the form of the sample. Our reference set of Raman spectra is useful for revealing discrepancies between the SERS and solid/solution spectra of amino acids. We also found that some previously published Raman spectra of polycrystalline samples resemble glassy state rather than crystalline spectra. Therefore, this reference set of spectra will find application in every branch of Raman spectroscopy where the spectra of biomolecules are collected from coatings.

  20. Drop coating deposition Raman spectroscopy of proteinogenic amino acids compared with their solution and crystalline state.

    PubMed

    Pazderka, Tomáš; Kopecký, Vladimír

    2017-10-05

    The Raman spectra of 20 proteinogenic amino acids were recorded in the solution, glass phase (as drop coating deposition Raman (DCDR) samples) and crystalline forms in the wide spectral range of 200-3200cm(-1). The most apparent spectral differences between the Raman spectra of the crystalline forms, glass phases and aqueous solutions of amino acids were briefly discussed and described in the frame of published works. The possible density dependencies of spectral bands were noted. In some cases, a strong influence of the sample density, as well as of the organization of the water envelope, was observed. The most apparent changes were observed for Ser and Thr. Nevertheless, for the majority of amino acids, the DCDR sample form is an intermediate between the solution and crystalline forms. In contrast, aromatic amino acids have only a small sensitivity to the form of the sample. Our reference set of Raman spectra is useful for revealing discrepancies between the SERS and solid/solution spectra of amino acids. We also found that some previously published Raman spectra of polycrystalline samples resemble glassy state rather than crystalline spectra. Therefore, this reference set of spectra will find application in every branch of Raman spectroscopy where the spectra of biomolecules are collected from coatings. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Hydrodynamics of steady state phloem transport with radial leakage of solute

    PubMed Central

    Cabrita, Paulo; Thorpe, Michael; Huber, Gregor

    2013-01-01

    Long-distance phloem transport occurs under a pressure gradient generated by the osmotic exchange of water associated with solute exchange in source and sink regions. But these exchanges also occur along the pathway, and yet their physiological role has almost been ignored in mathematical models of phloem transport. Here we present a steady state model for transport phloem which allows solute leakage, based on the Navier-Stokes and convection-diffusion equations which describe fluid motion rigorously. Sieve tube membrane permeability Ps for passive solute exchange (and correspondingly, membrane reflection coefficient) influenced model results strongly, and had to lie in the bottom range of the values reported for plant cells for the results to be realistic. This smaller permeability reflects the efficient specialization of sieve tube elements, minimizing any diffusive solute loss favored by the large concentration difference across the sieve tube membrane. We also found there can be a specific reflection coefficient for which pressure profiles and sap velocities can both be similar to those predicted by the Hagen-Poiseuille equation for a completely impermeable tube. PMID:24409189

  2. Creation of Novel Solid-Solution Alloy Nanoparticles on the Basis of Density-of-States Engineering by Interelement Fusion.

    PubMed

    Kobayashi, Hirokazu; Kusada, Kohei; Kitagawa, Hiroshi

    2015-06-16

    Currently 118 known elements are represented in the periodic table. Of these 118 elements, only about 80 elements are stable, nonradioactive, and widely available for our society. From the viewpoint of the "elements strategy", we need to make full use of the 80 elements to bring out their latent ability and create innovative materials. Furthermore, there is a strong demand that the use of rare or toxic elements be reduced or replaced while their important properties are retained. Advanced science and technology could create higher-performance materials even while replacing or reducing minor or harmful elements through the combination of more abundant elements. The properties of elements are correlated directly with their electronic states. In a solid, the magnitude of the density of states (DOS) at the Fermi level affects the physical and chemical properties. In the present age, more attention has been paid to improving the properties of materials by means of alloying elements. In particular, the solid-solution-type alloy is advantageous because the properties can be continuously controlled by tuning the compositions and/or combinations of the constituent elements. However, the majority of bulk alloys are of the phase-separated type under ambient conditions, where constituent elements are immiscible with each other. To overcome the challenge of the bulk-phase metallurgical aspects, we have focused on the nanosize effect and developed methods involving "nonequilibrium synthesis" or "a process of hydrogen absorption/desorption". We propose a new concept of "density-of-states engineering" for the design of materials having the most desirable and suitable properties by means of "interelement fusion". In this Account, we describe novel solid-solution alloys of Pd-Pt, Ag-Rh, and Pd-Ru systems in which the constituent elements are immiscible in the bulk state. The homogeneous solid-solution alloys of Pd and Pt were created from Pd core/Pt shell nanoparticles using a

  3. Photoluminescence Enhancement of CuInS2 Quantum Dots in Solution Coupled to Plasmonic Gold Nanocup Array.

    PubMed

    Peer, Akshit; Hu, Zhongjian; Singh, Ajay; Hollingsworth, Jennifer A; Biswas, Rana; Htoon, Han

    2017-09-01

    A strong plasmonic enhancement of photoluminescence (PL) decay rate in quantum dots (QDs) coupled to an array of gold-coated nanocups is demonstrated. CuInS2 QDs that emit at a wavelength that overlaps with the extraordinary optical transmission (EOT) of the gold nanocup array are placed in the cups as solutions. Time-resolved PL reveals that the decay rate of the QDs in the plasmonically coupled system can be enhanced by more than an order of magnitude. Using finite-difference time-domain (FDTD) simulations, it is shown that this enhancement in PL decay rate results from an enhancement factor of ≈100 in electric field intensity provided by the plasmonic mode of the nanocup array, which is also responsible for the EOT. The simulated Purcell factor approaches 86 at the bottom of the nanocup and is ≈3-15 averaged over the nanocup cavity height, agreeing with the experimental enhancement result. This demonstration of solution-based coupling between QDs and gold nanocups opens up new possibilities for applications that would benefit from a solution environment such as biosensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Photoluminescence Enhancement of CuInS2 Quantum Dots in Solution Coupled to Plasmonic Gold Nanocup Array

    DOE PAGES

    Peer, Akshit; Hu, Zhongjian; Singh, Ajay; ...

    2017-07-05

    A strong plasmonic enhancement of photoluminescence (PL) decay rate in quantum dots (QDs) coupled to an array of gold-coated nanocups is demonstrated. CuInS2 QDs that emit at a wavelength that overlaps with the extraordinary optical transmission (EOT) of the gold nanocup array are placed in the cups as solutions. Time-resolved PL reveals that the decay rate of the QDs in the plasmonically coupled system can be enhanced by more than an order of magnitude. Using finite-difference time-domain (FDTD) simulations, it is shown that this enhancement in PL decay rate results from an enhancement factor of ≈100 in electric field intensitymore » provided by the plasmonic mode of the nanocup array, which is also responsible for the EOT. The simulated Purcell factor approaches 86 at the bottom of the nanocup and is ≈3–15 averaged over the nanocup cavity height, agreeing with the experimental enhancement result. In conclusion, this demonstration of solution-based coupling between QDs and gold nanocups opens up new possibilities for applications that would benefit from a solution environment such as biosensing.« less

  5. Preparation of visible-light-excited luminescence enhancement solutions for time-resolved luminescence detection of europium biolabel.

    PubMed

    Zhang, Hui; Tian, Lu; Zhang, Ruoyu; Ye, Zhiqiang; Yuan, Jingli

    2012-10-07

    Dissociation enhanced lanthanide fluoroimmunoassay (DELFIA) technique based on EDTA-Eu(3+) derivative biolabels is the most widely used time-resolved luminescence bioassay technique for clinical diagnosis, but its major drawback is that the conventional luminescence enhancement solution of EDTA-Eu(3+) requires UV excitation (<360 nm). In this work, three new visible-light-excited luminescence enhancement solutions are developed and their luminescence response behaviors to EDTA-Eu(3+) are systematically investigated. The new solutions were prepared by co-dissolving a newly synthesized tetradentate β-diketone, 1,2-bis[8'-(1'',1'',1'',2'',2'',3'',3''-heptafluoro-4'',6''-hexanedion-6''-yl)-naphth-2'-yl]-benzene (BHHNB), and one of three derivatives of triazine, 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine (DPBT), 2-(N,N-diethylanilin-4-yl)-4,6-bis(3-methylpyrazol-1-yl)-1,3,5-triazine (MPBT) or 2-(N,N-diethylanilin-4-yl)-4,6-bis(pyrazol-1-yl)-1,3,5-triazine (BPT), in a weakly acidic aqueous buffer at pH 3.2 containing 0.1% Triton X-100. These solutions showed sensitive and rapid luminescence responses to non-luminescent EDTA-Eu(3+) by the formation of the ternary Eu(3+) complexes, BHHNB-Eu(3+)-DPBT, BHHNB-Eu(3+)-MPBT and BHHNB-Eu(3+)-BPT. These complexes have long luminescence lifetimes (>500 μs) and a wide excitation wavelength range from UV to visible light with the excitation peaks at 390, 400 and 420 nm, respectively, which enabled the solutions to be used as visible-light-excited luminescence enhancement solutions for the highly sensitive time-resolved luminescence detection of EDTA-Eu(3+).

  6. Soil and soil solution chemistry under red spruce stands across the northeastern united states

    USGS Publications Warehouse

    David, M.B.; Lawrence, G.B.

    1996-01-01

    Red spruce ecosystems in the northeastern United States are of interest because this species is undergoing regional decline. Their underlying soils have been examined closely at only a few sites, and information available on red spruce soils throughout this region is limited.This study was conducted to examine soil and soil solution chemistry at red spruce sites in the northeastern US that encompass the range of soil conditions in which red spruce grow. Soils and soil solutions from Oa and B horizons were obtained over a 2-year period from 12 undisturbed red spruce forests (elevations of 80-975 m) in New York, Vermont, New Hampshire, and Maine. All sites had extremely acid Spodosols (Oa soil pH range 2.56 to 3.11 in 0.01 M CaCl2), with generally low concentrations of base cations and high concentrations of Al on soil exchange sites. There was considerable range in exchange chemistry across the sites, however, with exchangeable Ca in Oa horizons ranging from 2.1 to 21.6 cmolckg-1 and exchangeable Al from 3.6 to 18.3 cmolckg-1. Solution chemistry had high concentrations of DOC in the Oa horizons (1160-15200 ??mol L-1), with higher concentrations in the fall than in the spring, which was probably a reflection of fresh litter inputs. Despite high concentrations of DOC in all solutions, inorganic Al was found in some Oa solutions at concentrations as high as 26 ??mol L-1. Ratios of Ca2+ to inorganic Al concentraturns were less than 1.0 in the Oa horizon of one site, and were well below 1.0 in B horizons of all sites. That soil chemistry was related to soil solution chemistry was demonstrated by solution Al concentrations in the forest floor having significant relationships with pyrophosphate extractable Al, although it was not related in the B horizon. Soil exchangeable Ca/Al ratios in the Oa horizon explained 75% of the variation in solution Ca2+/inorganic Al ratios when mean values were used for each site. Our studies have expanded the range of soil chemical

  7. Characterization of Swollen States of Polyelectrolyte Brushes in Salt Solution by Neutron Reflectivity

    NASA Astrophysics Data System (ADS)

    Kobayashi, Motoyasu; Mitamura, Koji; Terada, Masami; Yamada, Norifumi L.; Takahara, Atsushi

    2011-01-01

    Cationic and zwitterionic polyelectrolyte brushes on quartz substrate were synthesized by surface-initiated atom transfer radical polymerization of 2-(methacryloyloxy)-ethyltrimethylammonium chloride (MTAC) and 2-(methacryloyloxy)ethyl phosphorylcholine (MPC). The effects of ionic strength on brush structure are investigated by neutron reflectivity (NR) in NaCl deuterium oxide (D2O) solutions. We observed that poly(MTAC) chains were drastically shrunk at concentrations above 0.1 M NaCl/D2O, which may be the change in charge-screening effect against ions on poly(MTAC). On the other hand, effect of salt concentration on a swollen state of poly(MPC) brush was negligible, even at the high concentration (5.0 M) close to saturation. The behaviour of poly(MPC) in salt aqueous solution is completely different from that of poly(MTAC), which may arise from the unique interaction properties, neutral nature, and hydrated water structure of phosphorylcholine units.

  8. Refractive index and equation of state of a shock-compressed aqueous solution of zinc chloride

    NASA Astrophysics Data System (ADS)

    Wise, J. L.

    1983-06-01

    Velocity interferometers measurements have yielded refractive index and Hugoniot equation-of-state data for a 9.1-molar aqueous solution of zinc chloride which was shock-compressed to initial stresses ranging from 2.2 to 24.1 GPa in a series of plate-impact experiments. The Hugoniot data are accurately described by a linear variation of shock velocity with particle velocity. The optical data verify sustained solution transparency over the investigated range of shock stresses, and provide a calibration of the correction which must be applied to interferometer measurements to account for the stress-induced change in refractive index of the material. Refractive index data derived from the measured particle velocity corrections exhibit a departure from predictions based on the Gladstone-Dale relation.

  9. The transverse magnetic field effect on steady-state solutions of the Bursian diode

    SciTech Connect

    Pramanik, Sourav; Chakrabarti, Nikhil

    2015-04-15

    A study of steady-states of a planar vacuum diode driven by a cold electron beam (the Bursian diode) under an external transverse magnetic field is presented. The regime of no electrons turned around by a magnetic field only is under the consideration. The emitter electric field is evaluated as a characteristic function for the existence of solutions depending on the diode length, the applied voltage, and the magnetic field strength. At certain conditions, it is shown that a region of non-unique solutions exists in the Bursian diode when the magnetic field is absent. An expression for the maximum current transmitted through the diode is derived. The external magnetic field is put forth to control fast electronic switches based on the Bursian diode.

  10. Fully tuneable, Purcell-enhanced solid-state quantum emitters

    SciTech Connect

    Petruzzella, M. Xia, T.; Pagliano, F.; Birindelli, S.; Zobenica, Z.; Fiore, A.; Midolo, L.; Li, L. H.; Linfield, E. H.

    2015-10-05

    We report the full energy control over a semiconductor cavity-emitter system, consisting of single Stark-tunable quantum dots embedded in mechanically reconfigurable photonic crystal membranes. A reversible wavelength tuning of the emitter over 7.5 nm as well as an 8.5 nm mode shift are realized on the same device. Harnessing these two electrical tuning mechanisms, a single exciton transition is brought on resonance with the cavity mode at several wavelengths, demonstrating a ten-fold enhancement of its spontaneous emission. These results open the way to bring several cavity-enhanced emitters mutually into resonance and therefore represent a key step towards scalable quantum photonic circuits featuring multiple sources of indistinguishable single photons.

  11. Enhanced lithographic resolution using longitudinal polarization state of light

    NASA Astrophysics Data System (ADS)

    Van, My-Phung; Ushakova, Katsiaryna; Bastiaansen, Cees W. M.; Pereira, Silvania F.; Urbach, H. Paul; Broer, Dirk J.

    2015-10-01

    Laser direct-writing is an important technique for the fabrication of complex patterns. There is a continuous need for structures with increasingly small features, i.e., enhanced resolution. Focused radially polarized light is known to exhibit a narrow longitudinal polarization component. Here, a proof-of-concept is shown of enhanced resolution through polarization-selectivity by the selective recording of the longitudinal polarization component in a polarization-selective homeotropic and smectic B photoresist. The full-width-at-half-maximum (FWHM) of the fabricated spots in the polarization-selective resist is up to 56% smaller compared to the FWHM of the same spot in a photoresist that is not polarization-selective, which supports simulations that predict a theoretical maximum reduction of 62%.

  12. The behavior of Gliclazide in solution and in the solid state: a case of organic compound presenting a solid-solution structure.

    PubMed

    Santa María, Dolores; Claramunt, Rosa M; Alkorta, Ibon; Elguero, José

    2009-06-01

    The structure of the hypoglycemic agent Gliclazide has been studied by (1)H, (13)C, and (15)N NMR in solution (CDCl(3) and DMSO-d(6)) and in the solid state. In the solid state, the compound crystallizes as an EZ isomer without dynamic properties. In CDCl(3) solution, the structure is still EZ but with a slow nitrogen inversion about the pyrrolidine nitrogen: two invertomers have been observed and characterized. In DMSO-d(6), the rate is faster and only averaged signals were observed. GIAO calculated absolute shieldings were used to confirm the nature of the observed species. In the solid state, Gliclazide presents the phenomenon of solid-solution with two disordered conformations present in the crystal at a 90:10 ratio.

  13. Enhanced recovery pathways in pancreatic surgery: State of the art

    PubMed Central

    Pecorelli, Nicolò; Nobile, Sara; Partelli, Stefano; Cardinali, Luca; Crippa, Stefano; Balzano, Gianpaolo; Beretta, Luigi; Falconi, Massimo

    2016-01-01

    Pancreatic surgery is being offered to an increasing number of patients every year. Although postoperative outcomes have significantly improved in the last decades, even in high-volume centers patients still experience significant postoperative morbidity and full recovery after surgery takes longer than we think. In recent years, enhanced recovery pathways incorporating a large number of evidence-based perioperative interventions have proved to be beneficial in terms of improved postoperative outcomes, and accelerated patient recovery in the context of gastrointestinal, genitourinary and orthopedic surgery. The role of these pathways for pancreatic surgery is still unclear as high-quality randomized controlled trials are lacking. To date, non-randomized studies have shown that care pathways for pancreaticoduodenectomy and distal pancreatectomy are safe with no difference in postoperative morbidity, leading to early discharge and no increase in hospital readmissions. Hospital costs are reduced due to better organization of care and resource utilization. However, further research is needed to clarify the effect of enhanced recovery pathways on patient recovery and post-discharge outcomes following pancreatic resection. Future studies should be prospective and follow recent recommendations for the design and reporting of enhanced recovery pathways. PMID:27605881

  14. Unified semiclassical theory for the two-state system: Analytical solutions for scattering matrices

    NASA Astrophysics Data System (ADS)

    Zhu, Chaoyuan

    1996-09-01

    Unified semiclassical theory is established for general two-state system by employing an exactly analytical quantum solution [C. Zhu, J. Phys. A29, 1293 (1996)] for the Nikitin exponential-potential model which contains the two-state curve crossing and noncrossing cases as a whole. Analytical solutions for scattering matrices are found for both three- and two-channel cases within the time-independent treatment. This is made possible by introducing a very important parameter d(R0)=√)/[V22(R0)-V11(R0)]2 (V11(R), V22(R) and V12(R) are diabatic potentials and coupling, R0 is real part of complex crossing point between two adiabatic potentials) which represents a type of nonadiabatic transition for the two-state system. For instance, d=∞ represents the Landau-Zener type and d=√ represents Rosen-Zener type. Since d(R0) runs from unity to infinity, this parameter provides a quantitative description of nonadiabatic transition. The idea used here is the parameter comparison method which makes a unique link between the model and general potential system at the complex crossing point. This method is testified not only by numerical examples, but also by agreement of the present semiclassical formulas with all existing semiclassical formulas.

  15. Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR) Methodology

    PubMed Central

    Wen, Jia-Long; Sun, Shao-Long; Xue, Bai-Liang; Sun, Run-Cang

    2013-01-01

    The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA), nitrobenzene oxidation (NBO), and derivatization followed by reductive cleavage (DFRC). Recent advances in nuclear magnetic resonance (NMR) technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ), as well as their applications are reviewed. PMID:28809313

  16. Acid-base state of the preterm infant and the formulation of intravenous feeding solutions.

    PubMed

    MacMahon, P; Mayne, P D; Blair, M; Pope, C; Kovar, I Z

    1990-04-01

    An acidic intravenous source of phosphorus (Addiphos) was compared with dipotassium hydrogen phosphate in 25 preterm infants to study acid-base state. Eight infants were given either Addiphos or dipotassium hydrogen phosphate alternately for 48 hour periods and similar amounts of calcium and phosphorus were delivered. There were no significant differences in calcium and phosphorus intake, calcium and phosphate plasma concentrations, or acid-base state between study periods on the two solutions. Seventeen infants were given the two solutions alternately for 72 hour periods; Addiphos was used to increase the amounts of calcium and phosphorus being delivered. Calcium and phosphorus intake was decreased on dipotassium hydrogen phosphate, but Addiphos significantly increased calcium and phosphorus intake and plasma calcium and phosphate concentrations. It also lowered the pH of the urine and raised the titratable acidity. Acid-base state, however, was not significantly different. It is therefore possible to increase intake of calcium and phosphorus in preterm infants without causing a significant metabolic acidosis.

  17. Acid-base state of the preterm infant and the formulation of intravenous feeding solutions.

    PubMed Central

    MacMahon, P; Mayne, P D; Blair, M; Pope, C; Kovar, I Z

    1990-01-01

    An acidic intravenous source of phosphorus (Addiphos) was compared with dipotassium hydrogen phosphate in 25 preterm infants to study acid-base state. Eight infants were given either Addiphos or dipotassium hydrogen phosphate alternately for 48 hour periods and similar amounts of calcium and phosphorus were delivered. There were no significant differences in calcium and phosphorus intake, calcium and phosphate plasma concentrations, or acid-base state between study periods on the two solutions. Seventeen infants were given the two solutions alternately for 72 hour periods; Addiphos was used to increase the amounts of calcium and phosphorus being delivered. Calcium and phosphorus intake was decreased on dipotassium hydrogen phosphate, but Addiphos significantly increased calcium and phosphorus intake and plasma calcium and phosphate concentrations. It also lowered the pH of the urine and raised the titratable acidity. Acid-base state, however, was not significantly different. It is therefore possible to increase intake of calcium and phosphorus in preterm infants without causing a significant metabolic acidosis. PMID:2110804

  18. Simple solutions of fireball hydrodynamics for rotating and expanding triaxial ellipsoids and final state observables

    NASA Astrophysics Data System (ADS)

    Nagy, M. I.; Csörgő, T.

    2016-12-01

    We present a class of analytic solutions of nonrelativistic fireball hydrodynamics for a fairly general class of equation of state. The presented solution describes the expansion of a triaxial ellipsoid that rotates around one of its principal axes. We calculate the hadronic final state observables such as single-particle spectra, directed, elliptic, and third flows, as well as two-particle Bose-Einstein (also named HBT) correlations and corresponding radius parameters, utilizing simple analytic formulas. The final tilt angle of the fireball, an important observable quantity, is shown to be not independent of its exact definition: one gets different tilt angles from the geometrical anisotropies, from the single-particle spectra, and from HBT measurements. Taken together, the tilt angle in the momentum space and in the relative momentum or HBT variable may be sufficient for the determination of the magnitude of the rotation of the fireball. We argue that observing this rotation and its dependence on collision energy could characterize the softest point of the equation of state. Thus determining the rotation may be a powerful tool for the experimental search for the critical point in the phase diagram of strongly interacting matter.

  19. [Enhancement of luminol-dependent chemiluminescence in an aqueous NaCl/H2O2 solution by argon].

    PubMed

    Voeĭkov, V L; Khimich, M V

    2002-01-01

    It was found that the bubbling of argon through NaCl/H2O2 aqueous solutions results in the development of intense sustained luminol-dependent chemiluminescence. Bubbling of nitrogen and air through similar solutions does not result in such effect. The relationship between argon-supported chemiluminescence and initial concentrations of NaCl and H2O2 is characterized by threshold effects. In NaCl/H2O2 solutions blown with argon, hypochlorite was found, indicating that argon intensifies the reaction of chloride oxidation with H2O2. It is suggested that the enhancement of this reaction in aqueous solutions saturated with argon is related to specific changes in the properties of water, which is a highly nonequilibrium system. Possible consequences of relatively high concentrations of argon in the atmosphere for the chemical processes that occur in aqueous systems and, in particular, living systems are discussed.

  20. Enhanced Internet firewall design using stateful filters final report

    SciTech Connect

    Hutchins, J.A.; Simons, R.W.

    1997-08-01

    The current state-of-the-art in firewall design provides a lot of security for company networks, but normally at the expense of performance and/or functionality. Sandia researched a new approach to firewall design which incorporates a highly stateful approach, allowing much more flexibility for protocol checking and manipulation while retaining performance. A prototype system was built and multiple protocol policy modules implemented to test the concept. The resulting system, though implemented on a low-power workstation, performed almost at the same performance as Sandia`s current firewall.

  1. The physical state of nafcillin sodium in frozen aqueous solutions and freeze-dried powders.

    PubMed

    Milton, N; Nail, S L

    1996-10-01

    The purpose of this study was to develop a better understanding of the physical chemistry of freeze drying of lyotropic liquid crystals using nafcillin sodium as a model solute. Solutions and freeze-dried powders of nafcillin sodium were studied by polarized light microscopy, differential scanning calorimetry, x-ray powder diffraction, and water vapor adsorption. Differential scanning calorimetry thermograms of nafcillin sodium solutions contain a melting endotherm at approximately -5.5 degrees C and, depending on the concentration and heating rate, a crystallization exotherm immediately after this endotherm followed by the melting endotherm of ice. When the sample is annealed at -4 degrees C, both the endotherm and exotherm are eliminated, and a new endotherm appears at approximately -1 degree C on the shoulder of the ice-melting endotherm. The data are interpreted as melting of a liquid crystalline phase, followed by crystallization. X-ray powder diffractograms of unannealed freeze-dried nafcillin sodium are consistent with a lamellar liquid crystal. Diffractograms of annealed freeze-dried nafcillin sodium indicate crystalline material which is a different crystal form than the monohydrate starting material. Moisture adsorption isotherms of the freeze-dried annealed (crystalline) and unannealed (liquid crystalline) nafcillin sodium show different affinities for moisture compared to the crystalline starting material. Solid-state stability data demonstrate that the freeze-dried liquid crystalline form of nafcillin sodium is much less stable than the freeze-dried crystal-line material. The literature recognizes two types of solute behavior on freezing, where the solute either crystallizes from the freeze concentrate or remains amorphous. Lyotropic liquid crystal formation during freezing represents a separate category of freezing behavior, the physical chemistry of which is worthy of further investigation.

  2. Steady-state axisymmetric nonlinear magnetohydrodynamic solutions with various boundary conditions

    NASA Astrophysics Data System (ADS)

    Wang, Lile; Lou, Yu-Qing

    2014-04-01

    Axisymmetric magnetohydrodynamics (MHD) can be invoked for describing astrophysical magnetized flows and formulated to model stellar magnetospheres including main-sequence stars (e.g. the Sun), compact stellar objects [e.g. magnetic white dwarfs (MWDs), radio pulsars, anomalous X-ray pulsars, magnetars, isolated neutron stars, etc.] and planets as a major step forward towards a full three-dimensional model construction. Using powerful and reliable numerical solvers based on two distinct finite-difference method and finite-element method schemes of algorithm, we examine axisymmetric steady-state or stationary MHD models in Throumoulopoulos & Tasso, finding that their separable semi-analytic non-linear solutions are actually not unique given their specific selection of several free functionals and chosen boundary conditions. Similar situations of multiple non-linear solutions with the same boundary conditions actually also happen to force-free magnetic field models of Low & Lou. The multiplicity of non-linear steady MHD solutions gives rise to differences in the total energies contained in the magnetic fields and flow velocity fields as well as in the asymptotic behaviours approaching infinity, which may in turn explain why numerical solvers tend to converge to a non-linear solution with a lower energy than the corresponding separable semi-analytic one. By properly adjusting model parameters, we invoke semi-analytic and numerical solutions to describe different kinds of scenarios, including nearly parallel case and the situation in which the misalignment between the plasma flow and magnetic field is considerable. We propose that these MHD models are capable of describing the magnetospheres of MWDs as examples of applications with moderate conditions (including magnetic field) where the typical values of several important parameters are consistent with observations. Physical parameters can also be estimated based on such MHD models directly. We discuss the challenges

  3. Anatomy of topological surface states: Exact solutions from destructive interference on frustrated lattices

    NASA Astrophysics Data System (ADS)

    Kunst, Flore K.; Trescher, Maximilian; Bergholtz, Emil J.

    2017-08-01

    The hallmark of topological phases is their robust boundary signature whose intriguing properties—such as the one-way transport on the chiral edge of a Chern insulator and the sudden disappearance of surface states forming open Fermi arcs on the surfaces of Weyl semimetals—are impossible to realize on the surface alone. Yet, despite the glaring simplicity of noninteracting topological bulk Hamiltonians and their concomitant energy spectrum, the detailed study of the corresponding surface states has essentially been restricted to numerical simulation. In this work, however, we show that exact analytical solutions of both topological and trivial surface states can be obtained for generic tight-binding models on a large class of geometrically frustrated lattices in any dimension without the need for fine-tuning of hopping amplitudes. Our solutions derive from local constraints tantamount to destructive interference between neighboring layer lattices perpendicular to the surface and provide microscopic insights into the structure of the surface states that enable analytical calculation of many desired properties including correlation functions, surface dispersion, Berry curvature, and the system size dependent gap closing, which necessarily occurs when the spatial localization switches surface. This further provides a deepened understanding of the bulk-boundary correspondence. We illustrate our general findings on a large number of examples in two and three spatial dimensions. Notably, we derive exact chiral Chern insulator edge states on the spin-orbit-coupled kagome lattice, and Fermi arcs relevant for recently synthesized slabs of pyrochlore-based Eu2Ir2O7 and Nd2Ir2O7 , which realize an all-in-all-out spin configuration, as well as for spin-ice-like two-in-two-out and one-in-three-out configurations, which are both relevant for Pr2Ir2O7 . Remarkably, each of the pyrochlore examples exhibit clearly resolved Fermi arcs although only the one

  4. Structural investigations of aroylhydrazones derived from nicotinic acid hydrazide in solid state and in solution

    NASA Astrophysics Data System (ADS)

    Galić, Nives; Brođanac, Ivan; Kontrec, Darko; Miljanić, Snežana

    2013-04-01

    Structural forms of aroylhydrazones derived from nicotinic acid hydrazide have been studied in the solid state by FT-IR spectroscopy and in solution by NMR, UV-Vis and ATR spectroscopy. The studied compounds were N'-benzylidene-3-pyridinecarbohydrazide (1), N'-(2,4-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N'-(5-chloro-2-hydroxyphenylmethylidene)-3-pyridinecarbohydrazide (3), and N'-(3,5-dichloro-2-hydroxymethoxyphenylmethylidene)-3-pyridinecarbohydrazide (4). The compound 1 adopted the most stable ketoamine form (form I, sbnd COsbnd NHsbnd Ndbnd Csbnd ) in the solid state as well as in various organic solvents. In mixtures of organic solvents with water the UV-Vis and ATR spectra implied intermolecular hydrogen bonding of 1 with water molecules. The presence of both tautomeric forms I and II (form II, sbnd COHdbnd Nsbnd Ndbnd Csbnd ) was proposed for the solid substance and highly concentrated solutions of 2, whereas form I was detected as the predominant one in diluted solutions. For compounds 3 and 4 a coexistence of forms I and III (form III, sbnd COsbnd NHsbnd NHsbnd Cdbnd Csbnd COsbnd ) was noticed in the solid state and in polar protic organic solvents. The conversion to form III was induced by increasing the water content in the solvent mixtures. This process was the most pronounced for compound 4. When exposed to daylight, an appearance of a new band was observed during time in the UV-Vis spectrum of 4 in organic solvent/water 1/1 mixtures, which implied that tautomeric interconversion was most likely followed by E/Z isomerisation.

  5. Excited-state intramolecular proton transfer (ESIPT) emission of hydroxyphenylimidazopyridine: computational study on enhanced and polymorph-dependent luminescence in the solid state.

    PubMed

    Shigemitsu, Yasuhiro; Mutai, Toshiki; Houjou, Hirohiko; Araki, Koji

    2012-12-13

    Although 2-(2'-hydroxyphenyl)imidazo[1,2-a]pyridine (HPIP) is only weakly fluorescent in solution, two of its crystal polymorphs in which molecules are packed as stacked pairs and in nearly coplanar conformation exhibit bright excited-state intramolecular proton transfer (ESIPT) luminescence of different colors (blue-green and yellow). In order to clarify the enhanced and polymorph-dependent luminescence of HPIP in the solid state, the potential energy surfaces (PESs) of HPIP in the ground (S(0)) and excited (S(1)) states were analyzed computationally by means of ab initio quantum chemical calculations. The calculations reproduced the experimental photophysical properties of HPIP in solution, indicating that the coplanar keto form in the first excited (S(1)) state smoothly approaches the S(0)/S(1) conical intersection (CI) coupled with the twisting motion of the central C-C bond. The S(1)-S(0) energy gap of the keto form became sufficiently small at the torsion angle of 60°, and the corresponding CI point was found at 90°. Since a minor role of the proximity effect was indicated experimentally and theoretically, the observed emission enhancement of the HPIP crystals was ascribed to the following two factors: (1) suppression of efficient radiationless decay via the CI by fixing the torsion angle at the nearly coplanar conformation of the molecules in the crystals and (2) inhibition of excimer formation resulting from the lower excited level of the S(1)-keto state compared to the S(0)-S(1) excitation energy in the enol form. However, the fluorescence color difference between the two crystal polymorphs having slightly different torsion angles was not successfully reproduced, even at the MS-CASPT2 level of theory.

  6. Elastic modulus and equilibrium swelling of networks crosslinked by end-linking oligodimethylsiloxane at solution state

    NASA Astrophysics Data System (ADS)

    Urayama, Kenji; Kawamura, Takanobu; Kohjiya, Shinzo

    1996-09-01

    We have investigated the degree of equilibrium swelling and the elastic modulus of networks prepared by end-linking oligo(dimethylsiloxane)s (ODMS) in solution as a function of polymer concentration at crosslinking. The molecular weight of ODMS is so low that entanglement couplings are not formed in uncrosslinked state. It has been found from the preparation concentration dependence of elastic modulus in preparation state that trapped entanglements are formed by the introduction of crosslinks, and those considerably contribute to elastic modulus, even if the prepolymers are not entangled in uncrosslinked state. The experimental results for preparation concentration dependence of the degree of equilibrium swelling and the elastic modulus of equilibrium swollen networks are compared with the theoretical predictions by the two theories, i.e., the affine model and the c* theorem. It has been clearly shown that the affine model describes well the experimental results, while the discrepancies between the experimental results and the predictions by the c* theorem are considerable. These results strongly suggest that preparation concentration should be regarded as a reference state, and the displacement of crosslinks moves affinely on swelling, while the complete disinterpenetration of network chains in equilibrium swollen state, which is a postulate of the c* theorem, does not occur.

  7. On the uniqueness of sign changing bound state solutions of a semilinear equation

    NASA Astrophysics Data System (ADS)

    Cortázar, Carmen; García-Huidobro, Marta; Yarur, Cecilia S.

    2011-07-01

    We establish the uniqueness of the higher radial bound state solutions of $$ \\Delta u +f(u)=0,\\quad x\\in \\RR^n. \\leqno(P) $$ We assume that the nonlinearity $f\\in C(-\\infty,\\infty)$ is an odd function satisfying some convexity and growth conditions, and either has one zero at $b>0$, is non positive and not identically 0 in $(0,b)$, and is differentiable and positive $[b,\\infty)$, or is positive and differentiable in $[0,\\infty)$.

  8. Existence of ground state solutions to a generalized quasilinear Schrödinger-Maxwell system

    NASA Astrophysics Data System (ADS)

    Zhu, Xiaoli; Li, Fuyi; Liang, Zhanping

    2016-10-01

    In this paper, a class of generalized quasilinear Schrödinger-Maxwell systems is considered. Via the mountain pass theorem, we conclude the existence of positive ground state solutions when the potential may vanish at infinity and the nonlinear term has a quasicritical growth. During this process, we use the Coulomb energy studied by Ruiz [Arch. Ration. Mech. Anal. 198(1), 349-368 (2010)] and establish a convergency theorem to overcome the lack of compactness caused by the potential which may vanish at infinity.

  9. Self-regulating genes. Exact steady state solution by using Poisson representation

    NASA Astrophysics Data System (ADS)

    Sugár, István; Simon, István

    2014-09-01

    Systems biology studies the structure and behavior of complex gene regulatory networks. One of its aims is to develop a quantitative understanding of the modular components that constitute such networks. The self-regulating gene is a type of auto regulatory genetic modules which appears in over 40% of known transcription factors in E. coli. In this work, using the technique of Poisson Representation, we are able to provide exact steady state solutions for this feedback model. By using the methods of synthetic biology (P.E.M. Purnick and Weiss, R., Nature Reviews, Molecular Cell Biology, 2009, 10: 410-422) one can build the system itself from modules like this.

  10. Analytical solutions for transient and steady state beam loading in arbitrary traveling wave accelerating structures

    SciTech Connect

    Lunin, A.; Yakovlev, V.; Grudiev, A.; /CERN

    2011-05-02

    Analytical solutions are derived for both transient and steady state gradient distributions in the traveling wave (TW) accelerating structures with arbitrary variation of parameters over the structure length. The results of the unloaded and beam loaded cases are presented. Finally, the exact analytical shape of the rf pulse waveform was found in order to apply the transient beam loading compensation scheme during the structure filling time. The obtained theoretical formulas were cross-checked by direct numerical simulations on the CLIC main linac accelerating structure and demonstrated a good agreement. The proposed methods provide a fast and reliable tool for the initial stage of the TW structure analysis.

  11. Synthesis of dental enamel-like hydroxyapatite through solution mediated solid-state conversion.

    PubMed

    Zhang, Junling; Jiang, Dongliang; Zhang, Jingxian; Lin, Qingling; Huang, Zhengren

    2010-03-02

    An ordered dental enamel-like structure of hydroxyapatite (HAp) was achieved through a solution mediated solid-state conversion process with organic phosphate surfactant and gelatin as the mediating agent. Transmission electron microscopy (TEM) tests demonstrated uniform sizes in the obtained apatite nanorods which arranged in parallel to each other along the c-axis and formed organized microarchitectural units over 10 microm in size. The sizes of the synthetic hydroxyapatite nanorods were similar to that observed in enamel from human teeth. The formation and regulation of the orientation and size of HAp nanorods might lead to a better understanding of the biomineralization process for the preparation of high performance biomaterials.

  12. Characterizing RNA Dynamics at Atomic Resolution Using Solution-state NMR Spectroscopy

    PubMed Central

    Bothe, Jameson R.; Nikolova, Evgenia N.; Eichhorn, Catherine D.; Chugh, Jeetender; Hansen, Alexandar L.; Al-Hashimi, Hashim M.

    2012-01-01

    Many recently discovered non-coding RNAs do not fold into a single native conformation, but rather, sample many different conformations along their free energy landscape to carry out their biological function. Unprecedented insights into the RNA dynamic structure landscape are provided by solution-state NMR techniques that measure the structural, kinetic, and thermodynamic characteristics of motions spanning picosecond to second timescales at atomic resolution. From these studies a basic description of the RNA dynamic structure landscape is emerging, bringing new insights into how RNA structures change to carry out their function as well as applications in RNA-targeted drug discovery and RNA bioengineering. PMID:22036746

  13. A Solution Space for a System of Null-State Partial Differential Equations: Part 3

    NASA Astrophysics Data System (ADS)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the third of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations (PDEs) in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE κ ). The system comprises 2 N null-state equations and three conformal Ward identities that govern CFT correlation functions of 2 N one-leg boundary operators. In the first two articles (Flores and Kleban, in Commun Math Phys, arXiv:1212.2301, 2012; Commun Math Phys, arXiv:1404.0035, 2014), we use methods of analysis and linear algebra to prove that dim , with C N the Nth Catalan number. Extending these results, we prove in this article that dim and entirely consists of (real-valued) solutions constructed with the CFT Coulomb gas (contour integral) formalism. In order to prove this claim, we show that a certain set of C N such solutions is linearly independent. Because the formulas for these solutions are complicated, we prove linear independence indirectly. We use the linear injective map of Lemma 15 in Flores and Kleban (Commun Math Phys, arXiv:1212.2301, 2012) to send each solution of the mentioned set to a vector in , whose components we find as inner products of elements in a Temperley-Lieb algebra. We gather these vectors together as columns of a symmetric matrix, with the form of a meander matrix. If the determinant of this matrix does not vanish, then the set of C N Coulomb gas solutions is linearly independent. And if this determinant does vanish, then we construct an alternative set of C N Coulomb gas solutions and follow a similar procedure to show that this set is linearly independent. The latter situation is closely related to CFT minimal models. We emphasize that, although the system of PDEs arises in CFT in away that is typically non-rigorous, our treatment of this system here and in Flores and Kleban (Commun Math Phys, arXiv:1212.2301, 2012; Commun Math Phys, arXiv:1404

  14. Enhanced photocatalytic performance of BiVO4 in aqueous AgNO3 solution under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Kai; Wu, Tsunghsueh; Huang, Chang-Wei; Lai, Chi-Yung; Wu, Mei-Yao; Lin, Yang-Wei

    2017-03-01

    Monoclinic-phase bismuth vanadate (BiVO4) with a 2.468 eV band gap exhibited enhanced synergic photodegradation activity toward methylene blue (MB) when combined with silver ions (Ag+) in an aqueous solution under visible light irradiation. The mass ratio of AgNO3 to BiVO4 and the calcination temperature were discovered to considerably affect the degradation activity of BiVO4/Ag+. Superior photocatalytic performance was obtained when BiVO4 was mixed with 0.01%(w/v) AgNO3 solution, and complete degradation of MB was achieved after 25 min visible light irradiation, outperforming BiVO4 or AgNO3 solution alone. The enhanced photodegradation was investigated using systematic luminescence measurements, electrochemical impedance spectroscopy, and scavenger addition, after which a photocatalytic mechanism for MB degradation under visible light irradiation was identified that involved oxygen radicals and holes. This study also discovered the two dominating processes involved in enhancing the electron-hole separation efficiency and reducing their recombination rate, namely photoreduction of Ag+ and the formation of a BiVO4/Ag heterojunction. The synergic effect between BiVO4 and Ag+ was discovered to be unique. BiVO4/Ag+ was successfully used to degrade two other dyes and disinfect Escherichia Coli. A unique fluorescent technique using BiVO4 and a R6G solution to detect Ag+ ions in water was discovered.

  15. Surface corrosion enhancement of passive films on NiTi shape memory alloy in different solutions.

    PubMed

    Jinlong, Lv; Tongxiang, Liang; Chen, Wang; Limin, Dong

    2016-06-01

    The corrosion behaviors of NiTi shape memory alloy in NaCl solution, H2SO4 solution and borate buffer solution were investigated. It was found that TiO2 in passive film improved the corrosion resistance of NiTi shape memory. However, low corrosion resistance of passive film was observed in low pH value acidic solution due to TiO2 dissolution. Moreover, the corrosion resistance of NiTi shape memory alloy decreased with the increasing of passivated potential in the three solutions. The donor density in passive film increased with the increasing of passivated potential. Different solutions affect the semiconductor characteristics of the passive film. The reducing in the corrosion resistance was attributed to the more donor concentrations in passive film and thinner thickness of the passive film. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Evaluation of alkaline electrolyzed water to replace traditional phosphate enhancement solutions: Effects on water holding capacity, tenderness, and sensory characteristics.

    PubMed

    Rigdon, Macc; Hung, Yen-Con; Stelzleni, Alexander M

    2017-01-01

    Sixty-four pork loins were randomly assigned to one of four treatments to evaluate the use of alkaline electrolyzed reduced water as a replacement for traditional enhancement solutions. Treatments included: alkaline electrolyzed reduced water (EOH; pH≈11.5), EOH plus 2.5% potassium-lactate (EOK), industry standard (IS; 0.35% sodium tri-polyphosphate, 0.14% sodium chloride, 2.5% potassium-lactate), and no enhancement (CON). After enhancement (targeting 110%) and rest period, chops were cut (2.54-cm) to test treatment effects on water holding capacity, Warner-Bratzler shear force (WBSF), and sensory attributes. Despite its alkaline nature EOH chops exuded more water (P<0.05) than EOK, IS, or CON chops. Control chops were similar (P>0.05) to EOK, however CON and EOK both lost more moisture (P<0.05) than IS. The use of alkaline electrolyzed reduced water did not improve WBSF or sensory characteristics compared to IS treated chops. As a stand-alone enhancement solution alkaline electrolyzed reduced water was not a suitable replacement for industry standard solutions.

  17. Hartree-Fock solutions for spin polarized states in low dimensional

    NASA Astrophysics Data System (ADS)

    Giuliani, G. F.; Marinescu, D. C.

    2000-03-01

    In the Hartree-Fock (HF) approximation, a two dimensional electron gas is known to exhibit a number of magnetic instabilities both in the absence as well as in the presence of a quantizing magnetic field. The situation is even more interesting in layered structures (e.g. bilayers and semiconducting superlattices) where the HF phase diagram is richer. Here HF states with non uniform magnetization have been predicted to occur and be actually physically realized under suitable conditions.(D.C. Marinescu, G. F. Giuliani, and J.J. Quinn, submitted) Although the HF approximation for the electron gas problem has been known for quite some time, there have been no detailed studies of the self-consistent solutions corresponding to non uniform states in these systems. Results of such a study are discussed in the present paper for a number of electronic systems in this class.

  18. Diode-pumped all-solid state lasers: solutions for scientific, biomedical, and industrial applications

    NASA Astrophysics Data System (ADS)

    Agnesi, Antoniangelo; Reali, Giancarlo C.

    1998-07-01

    Referring to the work carried out in our laboratory, we review low-medium power diode pumped all solid state laser systems for scientific, bio-medical and industrial applications. Side- and end-pumping are discussed and compared for such a laser systems. End-pumped scheme is mainly exploited in this report. Coupling solutions and cavity design are described emphasizing energy deposition and extraction optimization, thermal lens effects, beam quality control and longitudinal mode control. Both cw- and quasi-cw-pumped lasers are considered, operating either in continuous wave, passive Q-switching, and mode-locking regimes. Intracavity and extracavity harmonic generation, optical parametric generation and short pulse generation are among the aims of these all-solid-state sources: some result of these applications are reported.

  19. Adiabatic triplet state tautomerization of p-hydroxyacetophenone in aqueous solution.

    PubMed

    Klíčová, Ĺubica; Šebej, Peter; Šolomek, Tomáš; Hellrung, Bruno; Slavíček, Petr; Klán, Petr; Heger, Dominik; Wirz, Jakob

    2012-03-22

    The primary photophysical processes of p-hydroxyacetophenone (HA) and the ensuing proton transfer reactions in aqueous solution were investigated by picosecond pump-probe spectroscopy and nanosecond laser flash photolysis. Previous studies have led to mutually inconsistent conclusions. The combined data allow us to rationalize the excited-state proton transfer processes of HA in terms of a comprehensive, well-established reaction scheme. Following fast and quantitative ISC to the triplet state, (3)HA*, adiabatic proton transfer through solvent water simultaneously forms both the anion, (3)A(-)*, and the quinoid triplet enol tautomer, (3)Q*. The latter subsequently equilibrates with its anion (3)A(-)*. Ionization and tautomerization are likely to compete with the desired release reactions of p-hydroxyphenacyl photoremovable protecting groups. © 2012 American Chemical Society

  20. Synthesis of silver particles on copper substrates using ethanol-based solution for surface-enhanced Raman spectroscopy

    SciTech Connect

    Chen, Li Zhang, Zuojun; Chen, Gang; Zhou, Hui; Lai, Chunhong

    2014-03-15

    The displacement reaction of AgNO{sub 3} and copper metal is an effective and economical way to fabricate Ag-Cu surface enhanced Raman scattering (SERS) substrates. Aqueous solutions of AgNO{sub 3} are usually used for substrate preparation. In this work, a new method for Ag-Cu SERS substrate preparation is proposed, which uses an ethanol solution rather than an aqueous AgNO{sub 3} solution. Analysis of the surface morphologies of sample substrates by field emission scanning electron microscopy (FESEM) showed that the silver nanoparticles prepared by this new method were more regular than those prepared in the traditional aqueous solution. The SERS spectra of Rhodamine 6G (R6G) adsorbed on these Ag-Cu substrates were then investigated and compared. It was found that the Ag-Cu substrates prepared by this method provide significant improvements in Raman signal sensitivity and large-area uniformity. The enhancement factor of this new substrate is about 330 times higher than that prepared using an aqueous AgNO{sub 3} solution under identical experimental conditions. It was also found that 70% of the original sensitivity of the substrate remains after 15 days of exposure to air.

  1. Current state of the art for enhancing urine biomarker discovery

    PubMed Central

    Harpole, Michael; Davis, Justin; Espina, Virginia

    2016-01-01

    Urine is a highly desirable biospecimen for biomarker analysis because it can be collected recurrently by non-invasive techniques, in relatively large volumes. Urine contains cellular elements, biochemicals, and proteins derived from glomerular filtration of plasma, renal tubule excretion, and urogenital tract secretions that reflect, at a given time point, an individual's metabolic and pathophysiologic state. High-resolution mass spectrometry, coupled with state of the art fractionation systems are revealing the plethora of diagnostic/prognostic proteomic information existing within urinary exosomes, glycoproteins, and proteins. Affinity capture pre-processing techniques such as combinatorial peptide ligand libraries and biomarker harvesting hydrogel nanoparticles are enabling measurement/identification of previously undetectable urinary proteins. Future challenges in the urinary proteomics field include a) defining either single or multiple, universally applicable data normalization methods for comparing results within and between individual patients/data sets, and b) defining expected urinary protein levels in healthy individuals. PMID:27232439

  2. All-Solution-Based Aggregation Control in Solid-State Photon Upconverting Organic Model Composites.

    PubMed

    Goudarzi, Hossein; Keivanidis, Panagiotis E

    2017-01-11

    Hitherto, great strides have been made in the development of organic systems that exhibit triplet-triplet annihilation-induced photon-energy upconversion (TTA-UC). Yet, the exact role of intermolecular states in solid-state TTA-UC composites remains elusive. Here we perform a comprehensive spectroscopic study in a series of solution-processable solid-state TTA-UC organic composites with increasing segregated phase content for elucidating the impact of aggregate formation in their TTA-UC properties. Six different states of aggregation are reached in composites of the 9,10-diphenylanthracene (DPA) blue emitter mixed with the (2,3,7,8,12,13,17,18-octaethylporphyrinato)platinum(II) sensitizer (PtOEP) in a fixed nominal ratio (2 wt % PtOEP). Fine-tuning of the PtOEP and DPA phase segregation in these composites is achieved with a low-temperature solution-processing protocol when three different solvents of increasing boiling point are alternatively used and when the binary DPA:PtOEP system is dispersed in the optically inert polystyrene (PS) matrix (PS:DPA:PtOEP). Time-gated (in the nanosecond and microsecond time scales) photoluminescence measurements identify the upper level of PtOEP segregation at which the PtOEP aggregate-based networks favor PtOEP triplet exciton migration toward the PtOEP:DPA interfaces and triplet energy transfer to the DPA triplet manifold. The maximum DPA TTA-UC luminescence intensity is ensured when the bimolecular annihilation constant of PtOEP remains close to γTTA-PtOEP = 1.1 × 10(-13) cm(3) s(-1). Beyond this PtOEP segregation level, the DPA TTA-UC luminescence intensity decreases because of losses caused by the generation of PtOEP delayed fluorescence and DPA phosphorescence in the nanosecond and microsecond time scales, respectively.

  3. Implicit unified gas-kinetic scheme for steady state solutions in all flow regimes

    NASA Astrophysics Data System (ADS)

    Zhu, Yajun; Zhong, Chengwen; Xu, Kun

    2016-06-01

    This paper presents an implicit unified gas-kinetic scheme (UGKS) for non-equilibrium steady state flow computation. The UGKS is a direct modeling method for flow simulation in all regimes with the updates of both macroscopic flow variables and microscopic gas distribution function. By solving the macroscopic equations implicitly, a predicted equilibrium state can be obtained first through iterations. With the newly predicted equilibrium state, the evolution equation of the gas distribution function and the corresponding collision term can be discretized in a fully implicit way for fast convergence through iterations as well. The lower-upper symmetric Gauss-Seidel (LU-SGS) factorization method is implemented to solve both macroscopic and microscopic equations, which improves the efficiency of the scheme. Since the UGKS is a direct modeling method and its physical solution depends on the mesh resolution and the local time step, a physical time step needs to be fixed before using an implicit iterative technique with a pseudo-time marching step. Therefore, the physical time step in the current implicit scheme is determined by the same way as that in the explicit UGKS for capturing the physical solution in all flow regimes, but the convergence to a steady state speeds up through the adoption of a numerical time step with large CFL number. Many numerical test cases in different flow regimes from low speed to hypersonic ones, such as the Couette flow, cavity flow, and the flow passing over a cylinder, are computed to validate the current implicit method. The overall efficiency of the implicit UGKS can be improved by one or two orders of magnitude in comparison with the explicit one.

  4. Enhanced repertoire of brain dynamical states during the psychedelic experience.

    PubMed

    Tagliazucchi, Enzo; Carhart-Harris, Robin; Leech, Robert; Nutt, David; Chialvo, Dante R

    2014-11-01

    The study of rapid changes in brain dynamics and functional connectivity (FC) is of increasing interest in neuroimaging. Brain states departing from normal waking consciousness are expected to be accompanied by alterations in the aforementioned dynamics. In particular, the psychedelic experience produced by psilocybin (a substance found in "magic mushrooms") is characterized by unconstrained cognition and profound alterations in the perception of time, space and selfhood. Considering the spontaneous and subjective manifestation of these effects, we hypothesize that neural correlates of the psychedelic experience can be found in the dynamics and variability of spontaneous brain activity fluctuations and connectivity, measurable with functional Magnetic Resonance Imaging (fMRI). Fifteen healthy subjects were scanned before, during and after intravenous infusion of psilocybin and an inert placebo. Blood-Oxygen Level Dependent (BOLD) temporal variability was assessed computing the variance and total spectral power, resulting in increased signal variability bilaterally in the hippocampi and anterior cingulate cortex. Changes in BOLD signal spectral behavior (including spectral scaling exponents) affected exclusively higher brain systems such as the default mode, executive control, and dorsal attention networks. A novel framework enabled us to track different connectivity states explored by the brain during rest. This approach revealed a wider repertoire of connectivity states post-psilocybin than during control conditions. Together, the present results provide a comprehensive account of the effects of psilocybin on dynamical behavior in the human brain at a macroscopic level and may have implications for our understanding of the unconstrained, hyper-associative quality of consciousness in the psychedelic state. Copyright © 2014 Wiley Periodicals, Inc.

  5. Photofragmentation, state interaction, and energetics of Rydberg and ion-pair states: Resonance enhanced multiphoton ionization of HI

    SciTech Connect

    Hróðmarsson, Helgi Rafn; Wang, Huasheng; Kvaran, Ágúst

    2014-06-28

    Mass resolved resonance enhanced multiphoton ionization data for hydrogen iodide (HI), for two-photon resonance excitation to Rydberg and ion-pair states in the 69 600–72 400 cm{sup −1} region were recorded and analyzed. Spectral perturbations due to homogeneous and heterogeneous interactions between Rydberg and ion-pair states, showing as deformations in line-positions, line-intensities, and line-widths, were focused on. Parameters relevant to photodissociation processes, state interaction strengths and spectroscopic parameters for deperturbed states were derived. Overall interaction and dynamical schemes to describe the observations are proposed.

  6. Critical field enhancement of asymptotic optical bound states in the continuum

    PubMed Central

    Yoon, Jae Woong; Song, Seok Ho; Magnusson, Robert

    2015-01-01

    We study spectral singularities and critical field enhancement factors associated with embedded photonic bound states in subwavelength periodic Si films. Ultrahigh-Q resonances supporting field enhancement factor exceeding 108 are obtained in the spectral vicinity of exact embedded eigenvalues in spite of deep surface modulation and vertical asymmetry of the given structure. Treating relations between the partial resonance Q and field enhancement factors with an analytical coupled-mode model, we derive a general strategy to maximize the field enhancement associated with these photonic bound states in the presence of material dissipation. The analytical expression for the field enhancement quantitatively agrees with rigorous numerical calculations. Therefore, our results provide a general knowledge for designing practical resonance elements based on optical bound states in the continuum in various applications. PMID:26673548

  7. Steady state analytical solutions for pumping in a fully bounded rectangular aquifer

    NASA Astrophysics Data System (ADS)

    Lu, Chunhui; Xin, Pei; Li, Ling; Luo, Jian

    2015-10-01

    Using the Schwartz-Christoffel conformal mapping method together with the complex variable techniques, we derive steady state analytical solutions for pumping in a rectangular aquifer with four different combinations of impermeable and constant-head boundaries. These four scenarios include: (1) one constant-head boundary and three impermeable boundaries, (2) two pairs of orthogonal impermeable and constant-head boundaries, (3) three constant-head boundaries and one impermeable boundary, and (4) four constant-head boundaries. For these scenarios, the impermeable and constant-head boundaries can be combined after applying the mapping functions, and hence only three image wells exist in the transformed plane, despite an infinite number of image wells in the real plane. The closed-form solutions reflect the advantage of the conformal mapping method, though the method is applicable for the aspect ratio of the rectangle between 1/10.9 and 10.9/1 due to the limitation in the numerical computation of the conformal transformation from a half plane onto an elongated region (i.e., so-called "crowding" phenomenon). By contrast, for an additional scenario with two parallel constant-head boundaries and two parallel impermeable boundaries, an infinite series of image wells is necessary to express the solution, since it is impossible to combine these two kinds of boundaries through the conformal transformation. The usefulness of the results derived is demonstrated by an application to pumping in a finite coastal aquifer.

  8. Carbon-dot organic surface modifier analysis by solution-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Philippidis, Aggelos; Spyros, Apostolos; Anglos, Demetrios; Bourlinos, Athanasios B.; Zbořil, Radek; Giannelis, Emmanuel P.

    2013-07-01

    Carbon dots (C-dots) represent a new class of carbon-based materials that were discovered recently and have drawn the interest of the scientific community, particularly because of their attractive optical properties and their potential as fluorescent sensors. Investigation of the chemical structure of C-dots is extremely important for correlating the surface modifier composition with C-dot optical properties and allow for structure-properties fine tuning. In this article, we report the structural analysis of the surface modifiers of three different types of C-dot nanoparticles (Cwax, Cws, and Csalt) by use of 1D- and 2D-high-resolution NMR spectroscopy in solution. We unambiguously verify that the structure of the modifier chains remains chemically unchanged during the passivation procedure, and confirm the covalent attachment of the modifiers to the nanoparticle core, which contributes no signal to the solution-state NMR spectra. To our knowledge, this is the first study confirming the full structural assignment of C-dot organic surface modifiers by use of solution NMR spectroscopy.

  9. Structures in solid state and solution of dimethoxy curcuminoids: regioselective bromination and chlorination

    PubMed Central

    2013-01-01

    Background Several papers described the structure of curcumin and some other derivatives in solid and in solution. In the crystal structure of curcumin, the enol H atom is located symmetrically between both oxygen atoms of the enolone fragment with an O···O distance of 2.455 Å, which is characteristic for symmetrical H-bonds. In the solution, the geometry of the enolone fragment is attributed to the inherent disorder of the local environment, which solvates one of the basic sites better than the other, stabilizing one tautomer over the other. In this paper, how the position of methoxy groups in dimethoxy curcuminoids influence the conformation of molecules and how the halogen atoms change it when they are bonded at α-position in keto-enol part of molecules is described. Results Six isomers of dimethoxy curcuminoids were prepared. Conformations in solid state, which were determined by X-ray single crystallography and 1H MAS and 13C CPMAS NMR measurements, depend on the position of methoxy groups in curcuminoid molecules. In solution, a fast equilibrium between both keto-enol forms exists. A theoretical calculation finding shows that the position of methoxy groups changes the energy of HOMO and LUMO. An efficient protocol for the highly regioselective bromination and chlorination leading to α-halogenated product has been developed. All α-halogenated compounds are present mainly in cis keto-enol form. Conclusions The structures in solid state of dimethoxy curcuminoids depend on the position of methoxy groups. The NMR data of crystalline solid samples of 3,4-diOCH3 derivative, XRD measurements and X-ray structures lead us to the conclusion that polymorphism exists in solids. The same conclusion can be done for 3,5-diOCH3 derivative. In solution, dimethoxy curcuminoids are present in the forms that can be described as the coexistence of two equivalent tautomers being in fast equilibrium. The position of methoxy groups has a small influence on the enolic hydrogen

  10. Vibrational and electronic spectroscopy of the retro-carotenoid rhodoxanthin in avian plumage, solid-state films, and solution.

    PubMed

    Berg, Christopher J; LaFountain, Amy M; Prum, Richard O; Frank, Harry A; Tauber, Michael J

    2013-11-15

    Rhodoxanthin is one of few retro-carotenoids in nature. These chromophores are defined by a pattern of single and double bond alternation that is reversed relative to most carotenoids. Rhodoxanthin is found in the plumage of several families of birds, including fruit doves (Ptilinopus, Columbidae) and the red cotingas (Phoenicircus, Cotingidae). The coloration associated with the rhodoxanthin-containing plumage of these fruit dove and cotinga species ranges from brilliant red to magenta or purple. In the present study, rhodoxanthin is characterized in situ by UV-Vis reflectance and resonance Raman spectroscopy to gain insights into the mechanisms of color-tuning. The spectra are compared with those of the isolated pigment in solution and in thin solid films. Key vibrational signatures are identified for three isomers of rhodoxanthin, primarily in the fingerprint region. Electronic structure (DFT) calculations are employed to describe the normal modes of vibration, and determine characteristic modes of retro-carotenoids. These results are discussed in the context of various mechanisms that change the electronic absorption, including structural distortion of the chromophore or enhanced delocalization of π-electrons in the ground-state. From the spectroscopic evidence, we suggest that the shift in absorption is likely a consequence of perturbations that primarily affect the excited state of the chromophore.

  11. Michigan State University. Strategy without Deep Pockets: Enhancing Institutional Capacity from Within. Exemplars.

    ERIC Educational Resources Information Center

    Wegner, Gregory

    This paper describes the solution developed by Michigan State University to increase the institutions capacity for strategic innovation while respecting the Universitys limited financial means. One element of Michigan States strategy has been to send cross-institutional teams to participate in the Knight Collaboratives Wharton-IRHE (Institute for…

  12. Multiple Multidentate Halogen Bonding in Solution, in the Solid State, and in the (Calculated) Gas Phase.

    PubMed

    Jungbauer, Stefan H; Schindler, Severin; Herdtweck, Eberhardt; Keller, Sandro; Huber, Stefan M

    2015-09-21

    The binding properties of neutral halogen-bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X-ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X-ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas-phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors.

  13. Bound state solutions of Dirac equation with radial exponential-type potentials

    NASA Astrophysics Data System (ADS)

    Peña, J. J.; Morales, J.; García-Ravelo, J.

    2017-04-01

    In this work, a direct approach for obtaining analytical bound state solutions of the Dirac equation for radial exponential-type potentials with spin and pseudospin symmetry conditions within the frame of the Green and Aldrich approximation to the centrifugal term is presented. The proposal is based on the relation existing between the Dirac equation and the exactly solvable Schrödinger equation for a class of multi-parameter exponential-type potential. The usefulness of the present approach is exemplified by considering some known specific exponential-type potentials which are obtained as particular cases from our proposal. That is, instead of solving the Dirac equation for a special exponential potential, by means of a specialized method, the energy spectra and wave functions are derived directly from the proposed approach. Beyond the applications considered in this work, our proposition could be used as an alternative way in the search of bound state solutions of the Dirac equation for other potentials as well as it can be easily adapted to other approximations to the centrifugal term.

  14. Spin-symmetric solution of an interacting quantum dot attached to superconducting leads: Andreev states and the 0- π transition

    NASA Astrophysics Data System (ADS)

    Janiš, Václav; Pokorný, Vladislav; Žonda, Martin

    2016-09-01

    Behavior of Andreev gap states in a quantum dot with Coulomb repulsion symmetrically attached to superconducting leads is studied via the perturbation expansion in the interaction strength. We find the exact asymptotic form of the spin-symmetric solution for the Andreev states continuously approaching the Fermi level. We thereby derive a critical interaction at which the Andreev states at zero temperature merge at the Fermi energy, being the upper bound for the 0-π transition. We show that the spin-symmetric solution becomes degenerate beyond this interaction, in the π phase, and the Andreev states do not split unless the degeneracy is lifted. We further demonstrate that the degeneracy of the spin-symmetric state extends also into the 0 phase in which the solutions with zero and non-zero frequencies of the Andreev states may coexist.

  15. Enhancing Science Teaching through Performing Marbling Art Using Basic Solutions and Base Indicators

    ERIC Educational Resources Information Center

    Çil, Emine; Çelik, Kevser; Maçin, Tuba; Demirbas, Gülay; Gökçimen, Özlem

    2014-01-01

    Basic solutions are an indispensable part of our daily life. Basic solutions are commonly used in industries such as the textile industry, oil refineries, the fertilizer industry, and pharmaceutical products. Most cleaning agents, such as soap, detergent, and bleach, and some of our foods, such as chocolate and eggs, include bases. Bases are the…

  16. Enhancing Science Teaching through Performing Marbling Art Using Basic Solutions and Base Indicators

    ERIC Educational Resources Information Center

    Çil, Emine; Çelik, Kevser; Maçin, Tuba; Demirbas, Gülay; Gökçimen, Özlem

    2014-01-01

    Basic solutions are an indispensable part of our daily life. Basic solutions are commonly used in industries such as the textile industry, oil refineries, the fertilizer industry, and pharmaceutical products. Most cleaning agents, such as soap, detergent, and bleach, and some of our foods, such as chocolate and eggs, include bases. Bases are the…

  17. Advances in numerical solutions to integral equations in liquid state theory

    NASA Astrophysics Data System (ADS)

    Howard, Jesse J.

    Solvent effects play a vital role in the accurate description of the free energy profile for solution phase chemical and structural processes. The inclusion of solvent effects in any meaningful theoretical model however, has proven to be a formidable task. Generally, methods involving Poisson-Boltzmann (PB) theory and molecular dynamic (MD) simulations are used, but they either fail to accurately describe the solvent effects or require an exhaustive computation effort to overcome sampling problems. An alternative to these methods are the integral equations (IEs) of liquid state theory which have become more widely applicable due to recent advancements in the theory of interaction site fluids and the numerical methods to solve the equations. In this work a new numerical method is developed based on a Newton-type scheme coupled with Picard/MDIIS routines. To extend the range of these numerical methods to large-scale data systems, the size of the Jacobian is reduced using basis functions, and the Newton steps are calculated using a GMRes solver. The method is then applied to calculate solutions to the 3D reference interaction site model (RISM) IEs of statistical mechanics, which are derived from first principles, for a solute model of a pair of parallel graphene plates at various separations in pure water. The 3D IEs are then extended to electrostatic models using an exact treatment of the long-range Coulomb interactions for negatively charged walls and DNA duplexes in aqueous electrolyte solutions to calculate the density profiles and solution thermodynamics. It is found that the 3D-IEs provide a qualitative description of the density distributions of the solvent species when compared to MD results, but at a much reduced computational effort in comparison to MD simulations. The thermodynamics of the solvated systems are also qualitatively reproduced by the IE results. The findings of this work show the IEs to be a valuable tool for the study and prediction of

  18. Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T.

    PubMed

    Brownbill, Nick J; Gajan, David; Lesage, Anne; Emsley, Lyndon; Blanc, Frédéric

    2017-02-23

    We report (17)O dynamic nuclear polarisation (DNP) enhanced solid-state NMR experiments at 18.8 T. Several formulations were investigated on the Mg(OH)2 compound. A signal enhancement factor of 17 could be obtained when the solid particles were incorporated into a glassy o-terphenyl matrix doped with BDPA using the Overhauser polarisation transfer scheme whilst the cross effect mechanism enabled by TEKPol yielded a slightly lower enhancement but more time efficient data acquisition.

  19. Bound state solution of Dirac equation for Hulthen plus trigonometric Rosen Morse non-central potential using Romanovski polynomial

    SciTech Connect

    Suparmi, A. Cari, C.; Angraini, L. M.

    2014-09-30

    The bound state solutions of Dirac equation for Hulthen and trigonometric Rosen Morse non-central potential are obtained using finite Romanovski polynomials. The approximate relativistic energy spectrum and the radial wave functions which are given in terms of Romanovski polynomials are obtained from solution of radial Dirac equation. The angular wave functions and the orbital quantum number are found from angular Dirac equation solution. In non-relativistic limit, the relativistic energy spectrum reduces into non-relativistic energy.

  20. Enhanced Water Splitting Efficiency Through Selective Surface State Removal.

    PubMed

    Zandi, Omid; Hamann, Thomas W

    2014-05-01

    Hematite (α-Fe2O3) thin film electrodes prepared by atomic layer deposition (ALD) were employed to photocatalytically oxidize water under 1 sun illumination. It was shown that annealing at 800 °C substantially improves the water oxidation efficiency of the ultrathin film hematite electrodes. The effect of high temperature treatment is shown to remove one of two surface states identified, which reduces recombination and Fermi level pinning. Further modification with Co-Pi water oxidation catalyst resulted in unprecedented photocurrent onset potential of ∼0.6 V versus reversible hydrogen electrode (RHE; slightly positive of the flat band potential).

  1. Solid-State Recorders Enhance Scientific Data Collection

    NASA Technical Reports Server (NTRS)

    2010-01-01

    Under Small Business Innovation Research (SBIR) contracts with Goddard Space Flight Center, SEAKR Engineering Inc., of Centennial, Colorado, crafted a solid-state recorder (SSR) to replace the tape recorder onboard a Spartan satellite carrying NASA's Inflatable Antenna Experiment. Work for that mission and others has helped SEAKR become the world leader in SSR technology for spacecraft. The company has delivered more than 100 systems, more than 85 of which have launched onboard NASA, military, and commercial spacecraft including imaging satellites that provide much of the high-resolution imagery for online mapping services like Google Earth.

  2. Unexpectedly Enhanced Solubility of Aromatic Amino Acids and Peptides in an Aqueous Solution of Divalent Transition-Metal Cations

    NASA Astrophysics Data System (ADS)

    Shi, Guosheng; Dang, Yaru; Pan, Tingting; Liu, Xing; Liu, Hui; Li, Shaoxian; Zhang, Lijuan; Zhao, Hongwei; Li, Shaoping; Han, Jiaguang; Tai, Renzhong; Zhu, Yiming; Li, Jichen; Ji, Qing; Mole, R. A.; Yu, Dehong; Fang, Haiping

    2016-12-01

    We experimentally observed considerable solubility of tryptophan (Trp) in a CuCl2 aqueous solution, which could reach 2-5 times the solubility of Trp in pure water. Theoretical studies show that the strong cation-π interaction between Cu2 + and the aromatic ring in Trp modifies the electronic distribution of the aromatic ring to enhance significantly the water affinity of Trp. Similar solubility enhancement has also been observed for other divalent transition-metal cations (e.g., Zn2 + and Ni2 + ), another aromatic amino acid (phenylalanine), and three aromatic peptides (Trp-Phe, Phe-Phe, and Trp-Ala-Phe).

  3. Dynamic characterization of hydrophobic and hydrophilic solutes in oleic-acid enhanced transdermal delivery using two-photon fluorescence microscopy

    SciTech Connect

    Tseng, Te-Yu; Yang, Chiu-Sheng; Chen, Yang-Fang; Tsai, Tsung-Hua; Dong, Chen-Yuan

    2014-10-20

    In this letter, we propose an efficient methodology of investigating dynamic properties of sulforhodamine B and rhodamine B hexyl ester molecules transporting across ex-vivo human stratum corneum with and without oleic acid enhancement. Three-dimensional, time-lapse fluorescence images of the stratum corneum can be obtained using two-photon fluorescence microscopy. Furthermore, temporal quantifications of transport enhancements in diffusion parameters can be achieved with the use of Fick's second law. Dynamic characterization of solutes transporting across the stratum corneum is an effective method for understanding transient phenomena in transdermal delivery of probe molecules, leading to improved delivery strategies of molecular species for therapeutic purposes.

  4. Dynamic characterization of hydrophobic and hydrophilic solutes in oleic-acid enhanced transdermal delivery using two-photon fluorescence microscopy

    NASA Astrophysics Data System (ADS)

    Tseng, Te-Yu; Yang, Chiu-Sheng; Tsai, Tsung-Hua; Chen, Yang-Fang; Dong, Chen-Yuan

    2014-10-01

    In this letter, we propose an efficient methodology of investigating dynamic properties of sulforhodamine B and rhodamine B hexyl ester molecules transporting across ex-vivo human stratum corneum with and without oleic acid enhancement. Three-dimensional, time-lapse fluorescence images of the stratum corneum can be obtained using two-photon fluorescence microscopy. Furthermore, temporal quantifications of transport enhancements in diffusion parameters can be achieved with the use of Fick's second law. Dynamic characterization of solutes transporting across the stratum corneum is an effective method for understanding transient phenomena in transdermal delivery of probe molecules, leading to improved delivery strategies of molecular species for therapeutic purposes.

  5. STATE-SPACE SOLUTIONS TO THE DYNAMIC MAGNETOENCEPHALOGRAPHY INVERSE PROBLEM USING HIGH PERFORMANCE COMPUTING.

    PubMed

    Long, Christopher J; Purdon, Patrick L; Temereanca, Simona; Desai, Neil U; Hämäläinen, Matti S; Brown, Emery N

    2011-06-01

    Determining the magnitude and location of neural sources within the brain that are responsible for generating magnetoencephalography (MEG) signals measured on the surface of the head is a challenging problem in functional neuroimaging. The number of potential sources within the brain exceeds by an order of magnitude the number of recording sites. As a consequence, the estimates for the magnitude and location of the neural sources will be ill-conditioned because of the underdetermined nature of the problem. One well-known technique designed to address this imbalance is the minimum norm estimator (MNE). This approach imposes an L(2) regularization constraint that serves to stabilize and condition the source parameter estimates. However, these classes of regularizer are static in time and do not consider the temporal constraints inherent to the biophysics of the MEG experiment. In this paper we propose a dynamic state-space model that accounts for both spatial and temporal correlations within and across candidate intra-cortical sources. In our model, the observation model is derived from the steady-state solution to Maxwell's equations while the latent model representing neural dynamics is given by a random walk process. We show that the Kalman filter (KF) and the Kalman smoother [also known as the fixed-interval smoother (FIS)] may be used to solve the ensuing high-dimensional state-estimation problem. Using a well-known relationship between Bayesian estimation and Kalman filtering, we show that the MNE estimates carry a significant zero bias. Calculating these high-dimensional state estimates is a computationally challenging task that requires High Performance Computing (HPC) resources. To this end, we employ the NSF Teragrid Supercomputing Network to compute the source estimates. We demonstrate improvement in performance of the state-space algorithm relative to MNE in analyses of simulated and actual somatosensory MEG experiments. Our findings establish the

  6. Enhanced Solid-State Biogas Production from Lignocellulosic Biomass by Organosolv Pretreatment

    PubMed Central

    Mirmohamadsadeghi, Safoora; Zamani, Akram; Horváth, Ilona Sárvári

    2014-01-01

    Organosolv pretreatment was used to improve solid-state anaerobic digestion (SSAD) for methane production from three different lignocellulosic substrates (hardwood elm, softwood pine, and agricultural waste rice straw). Pretreatments were conducted at 150 and 180°C for 30 and 60 min using 75% ethanol solution as an organic solvent with addition of sulfuric acid as a catalyst. The statistical analyses showed that pretreatment temperature was the significant factor affecting methane production. Optimum temperature was 180°C for elmwood while it was 150°C for both pinewood and rice straw. Maximum methane production was 152.7, 93.7, and 71.4 liter per kg carbohydrates (CH), which showed up to 32, 73, and 84% enhancement for rice straw, elmwood, and pinewood, respectively, compared to those from the untreated substrates. An inverse relationship between the total methane yield and the lignin content of the substrates was observed. Kinetic analysis of the methane production showed that the process followed a first-order model for all untreated and pretreated lignocelluloses. PMID:25243134

  7. Enhanced third harmonic generation using the surface states of light in periodic photonic structures

    NASA Astrophysics Data System (ADS)

    Zaytsev, Kirill I.; Gorelik, Vladimir S.; Katyba, Gleb M.; Yurchenko, Stanislav O.

    2014-10-01

    Third harmonic generation enhancement in periodic photonic structures was experimentally observed and theoretically interpreted. Nonlinear optical effects in opal globular photonic crystals (PC) have been studied under the femtosecond laser pumping. Strong dependence of the third harmonic generation efficiency on the ratio between the central pumping wavelength and the spectral location of the PC band gaps was found. Numerical simulations based on the finite difference time-domain technique for the solution of the Maxwell's equations were applied for investigations of the observed phenomenon origin. The simulation results have shown that the origin of the efficient nonlinear conversion is related with the surface state of electromagnetic field in PC. Interacting with the PC surface the light wavefront distorts coherently, and the effect of structure light focusing appears. Coherent wavefront distortion leads to the strong optical field localization, hence the light intensity within the certain PC regions increases. In case of the band gap pumping dramatic light redistribution appears; very sharp peaks of light intensity emerge in the region of the quartz globules, which leads to the high-efficient PC pumping.

  8. Exact solution of the hydrodynamical Riemann problem with nonzero tangential velocities and the ultrarelativistic equation of state.

    PubMed

    Mach, Patryk; Pietka, Małgorzata

    2010-04-01

    We give a solution of the Riemann problem in relativistic hydrodynamics in the case of ultrarelativistic equation of state and nonvanishing components of the velocity tangent to the initial discontinuity. Simplicity of the ultrarelativistic equation of state (the pressure being directly proportional to the energy density) allows us to express this solution in analytical terms. The result can be used both to construct and test numerical schemes for relativistic Euler equations in (3+1) dimensions.

  9. Enhancements and limits in drug membrane transport using supersaturated solutions of poorly water soluble drugs.

    PubMed

    Raina, Shweta A; Zhang, Geoff G Z; Alonzo, David E; Wu, Jianwei; Zhu, Donghua; Catron, Nathaniel D; Gao, Yi; Taylor, Lynne S

    2014-09-01

    Amorphous solid dispersions (ASDs) give rise to supersaturated solutions (solution concentration greater than equilibrium crystalline solubility). We have recently found that supersaturating dosage forms can exhibit the phenomenon of liquid-liquid phase separation (LLPS). Thus, the high supersaturation generated by dissolving ASDs can lead to a two-phase system wherein one phase is an initially nanodimensioned and drug-rich phase and the other is a drug-lean continuous aqueous phase. Herein, the membrane transport of supersaturated solutions, at concentrations above and below the LLPS concentration has been evaluated using a side-by-side diffusion cell. Measurements of solution concentration with time in the receiver cell yield the flux, which reflects the solute thermodynamic activity in the donor cell. As the nominal concentration of solute in the donor cell increases, a linear increase in flux was observed up to the concentration where LLPS occurred. Thereafter, the flux remained essentially constant. Both nifedipine and felodipine solutions exhibit such behavior as long as crystallization is absent. This suggests that there is an upper limit in passive membrane transport that is dictated by the LLPS concentration. These results have several important implications for drug delivery, especially for poorly soluble compounds requiring enabling formulation technologies.

  10. Aqueous solutions: state of the art in ab initio molecular dynamics.

    PubMed

    Hassanali, Ali A; Cuny, Jérôme; Verdolino, Vincenzo; Parrinello, Michele

    2014-03-13

    The simulation of liquids by ab initio molecular dynamics (AIMD) has been a subject of intense activity over the last two decades. The significant increase in computational resources as well as the development of new and efficient algorithms has elevated this method to the status of a standard quantum mechanical tool that is used by both experimentalists and theoreticians. As AIMD computes the electronic structure from first principles, it is free of ad hoc parametrizations and has thus been applied to a large variety of physical and chemical problems. In particular, AIMD has provided microscopic insight into the structural and dynamical properties of aqueous solutions which are often challenging to probe experimentally. In this review, after a brief theoretical description of the Born-Oppenheimer and Car-Parrinello molecular dynamics formalisms, we show how AIMD has enhanced our understanding of the properties of liquid water and its constituent ions: the proton and the hydroxide ion. Thereafter, a broad overview of the application of AIMD to other aqueous systems, such as solvated organic molecules and inorganic ions, is presented. We also briefly describe the latest theoretical developments made in AIMD, such as methods for enhanced sampling and the inclusion of nuclear quantum effects.

  11. Concentration dependence of nitroxyl spin probes in liposomal solution: electron spin resonance and overhauser-enhanced magnetic resonance studies.

    PubMed

    Meenakumari, V; Utsumi, Hideo; Jawahar, A; Franklin Benial, A Milton

    2016-12-21

    In this work, the detailed studies of electron spin resonance (ESR) and overhauser-enhanced magnetic resonance imaging (OMRI) were carried out for permeable nitroxyl spin probe, MC-PROXYL as a function of agent concentration in liposomal solution. In order to compare the impermeable nature of nitroxyl radical, the study was also carried out only at 2 mM concentration of carboxy-PROXYL. The ESR parameters were estimated using L-band and 300 MHz ESR spectrometers. The line width broadening was measured as a function of agent concentration in liposomal solution. The estimated rotational correlation time is proportional to the agent concentration, which indicates that less mobile nature of nitroxyl spin probe in liposomal solution. The partition parameter and permeability values indicate that the diffusion of nitroxyl spin probe distribution into the lipid phase is maximum at 2 mM concentration of MC-PROXYL. The dynamic nuclear polarization (DNP) parameters such as DNP factor, longitudinal relaxivity, saturation parameter, leakage factor and coupling factor were estimated for 2 mM MC-PROXYL in 400 mM liposomal dispersion. The spin lattice relaxation time was shortened in liposomal solution, which leads to the high relaxivity. Reduction in coupling factor is due to less interaction between the electron and nuclear spins, which causes the reduction in enhancement. The leakage factor increases with increasing agent concentration. The increase in DNP enhancement was significant up to 2 mM in liposomal solution. These results paves the way for choosing optimum agent concentration and OMRI scan parameters used in intra and extra membrane water by loading the liposome vesicles with a lipid permeable nitroxyl spin probes in OMRI experiments.

  12. Fractional Factorial Design Study on the Performance of GAC-Enhanced Electrocoagulation Process Involved in Color Removal from Dye Solutions

    PubMed Central

    Secula, Marius Sebastian; Cretescu, Igor; Cagnon, Benoit; Manea, Liliana Rozemarie; Stan, Corneliu Sergiu; Breaban, Iuliana Gabriela

    2013-01-01

    The aim of this study was to determine the effects of main factors and interactions on the color removal performance from dye solutions using the electrocoagulation process enhanced by adsorption on Granular Activated Carbon (GAC). In this study, a mathematical approach was conducted using a two-level fractional factorial design (FFD) for a given dye solution. Three textile dyes: Acid Blue 74, Basic Red 1, and Reactive Black 5 were used. Experimental factors used and their respective levels were: current density (2.73 or 27.32 A/m2), initial pH of aqueous dye solution (3 or 9), electrocoagulation time (20 or 180 min), GAC dose (0.1 or 0.5 g/L), support electrolyte (2 or 50 mM), initial dye concentration (0.05 or 0.25 g/L) and current type (Direct Current—DC or Alternative Pulsed Current—APC). GAC-enhanced electrocoagulation performance was analyzed statistically in terms of removal efficiency, electrical energy, and electrode material consumptions, using modeling polynomial equations. The statistical significance of GAC dose level on the performance of GAC enhanced electrocoagulation and the experimental conditions that favor the process operation of electrocoagulation in APC regime were determined. The local optimal experimental conditions were established using a multi-objective desirability function method. PMID:28811405

  13. Calculation of the solvent and solute enhancement factors in BCC metals assuming a hypothetical structure with fourteen first nearest neighbors.

    PubMed

    Pelleg, Joshua; Segel, V

    2009-04-08

    In this paper the solute and solvent enhancement factors in a hypothetical body centered cubic (b.c.c) structure having fourteen first nearest neighbors are calculated by using a statistical model for diffusion in dilute alloys. Inherent to the model is the assumption of the equality of the first and second nearest neighbor jump distances, since in the b.c.c structure the difference between these distances, respectively, is only ∼13.5%. The number of parameters required for fitting to evaluate the enhancement factors (b and B) is substantially reduced in comparison to existing models and therefore fewer experiments are necessary. Correlation effects are implicit in the calculated values of b and B. The results of the fitting provide values for the frequency ratios, the additional energies required to form a vacancy in the vicinity of a solute and for the binding energies between solute pairs, i.e., between the reference and tracer solute. Values of b and B in several dilute alloys were calculated at different temperatures. In general there is a good agreement between experimental and calculated values of b and B in the alloys tested. The equations for b and B can be used for temperatures where no experimental data exist.

  14. Surface Tension Gradient Driven Spreading on Aqueous Mucin Solutions: A Possible Route to Enhanced Pulmonary Drug Delivery

    PubMed Central

    Koch, Kevin; Dew, Beautia; Corcoran, Timothy E.; Przybycien, Todd M.; Tilton, Robert D.; Garoff, Stephen

    2011-01-01

    Surface tension gradient driven, or “Marangoni,” flow can be used to move exogenous fluid, either surfactant dispersions or drug carrying formulations, through the lung. In this paper, we investigate the spreading of aqueous solutions of water-soluble surfactants over entangled, aqueous mucin solutions that mimic the airway surface liquid of the lung. We measure the movement of the formulation by incorporating dyes into the formulation while we measure surface flows of the mucin solution subphase using tracer particles. Surface tension forces and/or Marangoni stresses initiate a convective spreading flow over this rheologically complex subphase. As expected, when the concentration of surfactant is reduced until its surface tension is above that of the mucin solution, the convective spreading does not occur. The convective spreading front moves ahead of the drop containing the formulation. Convective spreading ends with the solution confined to a well-defined static area which must be governed by a surface tension balance. Further motion of the spread solution progresses by much slower diffusive processes. Spreading behaviors are qualitatively similar for formulations based on anionic, cationic, or nonionic surfactants, containing either hydrophilic or hydrophobic dyes, on mucin as well as on other entangled aqueous polymer solution subphases. This independence of qualitative spreading behaviors from the chemistry of the surfactant and subphase indicates that there is little chemical interaction between the formulation and the subphase during the spreading process. The spreading and final solution distributions are controlled by capillary and hydrodynamic phenomena and not by specific chemical interactions among the components of the system. It is suggested that capillary forces and Marangoni flows driven by soluble surfactants may thereby enhance the uniformity of drug delivery to diseased lungs. PMID:21250745

  15. A Solution Space for a System of Null-State Partial Differential Equations: Part 1

    NASA Astrophysics Data System (ADS)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the first of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations (PDEs) in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE). In CFT, these are null-state equations and conformal Ward identities. They govern partition functions for the continuum limit of a statistical cluster or loop-gas model, such as percolation, or more generally the Potts models and O( n) models, at the statistical mechanical critical point. (SLE partition functions also satisfy these equations.) For such a lattice model in a polygon with its 2 N sides exhibiting a free/fixed side-alternating boundary condition , this partition function is proportional to the CFT correlation function where the w i are the vertices of and where is a one-leg corner operator. (Partition functions for "crossing events" in which clusters join the fixed sides of in some specified connectivity are linear combinations of such correlation functions.) When conformally mapped onto the upper half-plane, methods of CFT show that this correlation function satisfies the system of PDEs that we consider. In this first article, we use methods of analysis to prove that the dimension of this solution space is no more than C N , the Nth Catalan number. While our motivations are based in CFT, our proofs are completely rigorous. This proof is contained entirely within this article, except for the proof of Lemma 14, which constitutes the second article (Flores and Kleban, in Commun Math Phys, arXiv:1404.0035, 2014). In the third article (Flores and Kleban, in Commun Math Phys, arXiv:1303.7182, 2013), we use the results of this article to prove that the solution space of this system of PDEs has dimension C N and is spanned by solutions constructed with the CFT Coulomb gas (contour integral) formalism. In the fourth article (Flores and Kleban, in Commun Math Phys, arXiv:1405

  16. Thiophene functionalized silicon-containing aggregation-induced emission enhancement materials: applications as fluorescent probes for the detection of nitroaromatic explosives in aqueous-based solutions.

    PubMed

    Wang, Xuefeng; Bian, Jiangyan; Xu, Lichao; Wang, Hua; Feng, Shengyu

    2015-12-28

    Two novel aggregation-induced emission enhancement (AIEE) molecules, namely, 3,4-diphenyl-2,5-di(2-thienyl)phenyltrimethylsilane (DPTB-TMS) and bis[3,4-diphenyl- 2,5-di(2-thienyl)phenyl]methylphenylsilane (DPTB-TMS) were designed and synthesized. The optical properties of the two silanes were completely opposite to the traditional luminescent materials. Unlike the aggregation caused quenching, they all emit faint fluorescence in the dispersed state, while emission intensity increased sharply in aggregate states. Fluorescence spectra showed that the two compounds exhibited AIEE properties and that is due to the weak π-π stacking caused by the restriction of intramolecular rotations of dye segments, particularly the -SiMe3 and thienyl groups in the aggregate state. As fluorescent (FL) probes, the fluorescence quenching behavior was further investigated. Thanks to the richer-electron thiophene groups, both compounds showed good performance in detecting nitroaromatics, especially picric acid (PA). The two AIEE FL probes exhibited better quenching efficiency in aqueous-based than in organic-based solutions. For DPTB-MPS, the addition of 80 μM nitrobenzene, 60 μM m-nitrobenzene and 40 μM PA resulted in about 50% quenching in aqueous solutions. The quenching mechanism would be electron transfer from silanes to nitroaromatics. This work provides a basis for designing organic-silanes with "abnormal" but useful optical properties and FL probes with AIEE properties for the detection of nitroaromatics.

  17. Component Analysis of Multipurpose Contact Lens Solutions To Enhance Activity against Pseudomonas aeruginosa and Staphylococcus aureus

    PubMed Central

    Lin, Leo; Kim, Janie; Chen, Hope; Kowalski, Regis

    2016-01-01

    More than 125 million people wear contact lenses worldwide, and contact lens use is the single greatest risk factor for developing microbial keratitis. We tested the antibacterial activity of multipurpose contact lens solutions and their individual component preservatives against the two most common pathogens causing bacterial keratitis, Pseudomonas aeruginosa and Staphylococcus aureus. The in vitro antibacterial activity of five multipurpose contact lens solutions (Opti-Free GP, Boston Simplus, Boston Advance, Menicare GP, and Lobob) was assayed by the standard broth dilution method. Synergy between the preservative components found in the top performing solutions was assayed using checkerboard and time-kill assays. The ISO 14729 criteria and the standard broth dilution method were used to define an optimized contact lens solution formulation against a clinical panel of drug-susceptible and drug-resistant P. aeruginosa and S. aureus strains. Preservatives with the biguanide function group, chlorhexidine and polyaminopropylbiguanide (PAPB), had the best antistaphylococcal activity, while EDTA was the best antipseudomonal preservative. The combination of chlorhexidine and EDTA had excellent synergy against P. aeruginosa. A solution formulation containing chlorhexidine (30 ppm), PAPB (5 ppm), and EDTA (5,000 ppm) had three to seven times more antipseudomonal activity than anything available to consumers today. A multipurpose contact lens solution containing a combination of chlorhexidine, PAPB, and EDTA could help to reduce the incidence of microbial keratitis for contact lens users worldwide. PMID:27139484

  18. Prospects for enhanced oil recovery in the United States

    SciTech Connect

    Claridge, E.L.

    1982-08-01

    It appears that only one third of the crude oil discovered in the United States will be recovered by primary and secondary recovery methods. The application of tertiary recovery methods is not proceeding at a rate sufficient to prevent the abandonment of about 250 billion barrels at a rate of about 10 billion barrels per year, which has begun and will continue unless significant steps are taken, either to make tertiary recovery more immediately attractive or to ''moth-ball'' the oil fields and their leases and operating unit agreements until economic conditions are made more favorable. The current status and prospects of each major process are examined. The reasons why thermal recovery is the principal process at present, but is unable to expand much, why CO/sub 2/ flooding is about to begin on a large scale but not in many places where it would be applicable, and why chemical flooding has lost promise even though it is needed for most of the fields nearing abandonment, are discussed. It appears likely that no more than 15 billion barrels will be recovered by EOR processes by 2000 A.D.

  19. Electron-enhanced Raman scattering: a history of its discovery and spectroscopic applications to solution and interfacial chemistry.

    PubMed

    Yui, Hiroharu

    2010-06-01

    Raman scattering spectroscopy can be used to distinguish highly similar molecules and obtain useful information on local physical and chemical environments at their functional group levels. However, obtaining a high-quality Raman spectrum requires high-power excitation and a long acquisition time owing to the inherently small Raman scattering cross section, which is problematic in the analyses of living cells and real-time environmental monitoring. Herein, a new Raman enhancement technique, electron-enhanced Raman scattering (EERS), is described in which artificially generated electrons affect the polarizability of target molecular systems and enhance their inherent Raman cross sections. The EERS technique stands in contrast to the well-known SERS technique, which requires roughened metal surfaces. The history of EERS and its spectroscopic applications to aqueous solutions are presented.

  20. The steady state solutions of radiatively driven stellar winds for a non-Sobolev, pure absorption model

    NASA Technical Reports Server (NTRS)

    Poe, C. H.; Owocki, S. P.; Castor, J. I.

    1990-01-01

    The steady state solution topology for absorption line-driven flows is investigated for the condition that the Sobolev approximation is not used to compute the line force. The solution topology near the sonic point is of the nodal type with two positive slope solutions. The shallower of these slopes applies to reasonable lower boundary conditions and realistic ion thermal speed v(th) and to the Sobolev limit of zero of the usual Castor, Abbott, and Klein model. At finite v(th), this solution consists of a family of very similar solutions converging on the sonic point. It is concluded that a non-Sobolev, absorption line-driven flow with a realistic values of v(th) has no uniquely defined steady state. To the extent that a pure absorption model of the outflow of stellar winds is applicable, radiatively driven winds should be intrinsically variable.

  1. GEL-STATE NMR OF BALL-MILLED WHOLE CELL WALLS IN DMSO-d6 USING 2D SOLUTION-STATE NMR SPECTROSCOPY

    USDA-ARS?s Scientific Manuscript database

    Plant cell walls were used for obtaining 2D solution-state NMR spectra without actual solubilization or structural modification. Ball-milled whole cell walls were swelled directly in the NMR tube with DMSO-d6 where they formed a gel. There are relatively few gel-state NMR studies. Most have involved...

  2. Solution of steady-state, two-dimensional conservation laws by mathematical programming

    NASA Technical Reports Server (NTRS)

    Lavery, John E.

    1991-01-01

    A truly two-dimensional algorithm is created for solving the steady-state two-dimensional conservation-law problem. An overdetermined system of algebraic equations is obtained through discretization by finite-volume formulas. These equations are perturbed nonsingularly and are solved by an efficient geometrically oriented l(1) procedure. The basic algorithm and the theory for the linear case f(u) = u are presented, and computational results for the nonlinear case f(u) = sq u are also analyzed. It is noted that the l(1) procedure captures boundary shocks as well as oblige and zigzag interior shocks in bands that are one cell wide, and the solution values are accurate up to the edge of the shock.

  3. Analysis of lasers as a solution to efficiency droop in solid-state lighting

    SciTech Connect

    Chow, Weng W.; Crawford, Mary H.

    2015-10-06

    This letter analyzes the proposal to mitigate the efficiency droop in solid-state light emitters by replacing InGaN light-emitting diodes (LEDs) with lasers. The argument in favor of this approach is that carrier-population clamping after the onset of lasing limits carrier loss to that at threshold, while stimulated emission continues to grow with injection current. A fully quantized (carriers and light) theory that is applicable to LEDs and lasers (above and below threshold) is used to obtain a quantitative evaluation. The results confirm the potential advantage of higher laser output power and efficiency above lasing threshold, while also indicating disadvantages including low efficiency prior to lasing onset, sensitivity of lasing threshold to temperature, and the effects of catastrophic laser failure. As a result, a solution to some of these concerns is suggested that takes advantage of recent developments in nanolasers.

  4. Analysis of lasers as a solution to efficiency droop in solid-state lighting

    DOE PAGES

    Chow, Weng W.; Crawford, Mary H.

    2015-10-06

    This letter analyzes the proposal to mitigate the efficiency droop in solid-state light emitters by replacing InGaN light-emitting diodes (LEDs) with lasers. The argument in favor of this approach is that carrier-population clamping after the onset of lasing limits carrier loss to that at threshold, while stimulated emission continues to grow with injection current. A fully quantized (carriers and light) theory that is applicable to LEDs and lasers (above and below threshold) is used to obtain a quantitative evaluation. The results confirm the potential advantage of higher laser output power and efficiency above lasing threshold, while also indicating disadvantages includingmore » low efficiency prior to lasing onset, sensitivity of lasing threshold to temperature, and the effects of catastrophic laser failure. As a result, a solution to some of these concerns is suggested that takes advantage of recent developments in nanolasers.« less

  5. Vibrationally quantum-state-specific reaction dynamics of H atom abstraction by CN radical in solution.

    PubMed

    Greaves, Stuart J; Rose, Rebecca A; Oliver, Thomas A A; Glowacki, David R; Ashfold, Michael N R; Harvey, Jeremy N; Clark, Ian P; Greetham, Gregory M; Parker, Anthony W; Towrie, Michael; Orr-Ewing, Andrew J

    2011-03-18

    Solvent collisions can often mask initial disposition of energy to the products of solution-phase chemical reactions. Here, we show with transient infrared absorption spectra obtained with picosecond time resolution that the nascent HCN products of reaction of CN radicals with cyclohexane in chlorinated organic solvents exhibit preferential excitation of one quantum of the C-H stretching mode and up to two quanta of the bending mode. On time scales of approximately 100 to 300 picoseconds, the HCN products undergo relaxation to the vibrational ground state by coupling to the solvent bath. Comparison with reactions of CN radicals with alkanes in the gas phase, known to produce HCN with greater C-H stretch and bending mode excitation (up to two and approximately six quanta, respectively), indicates partial damping of the nascent product vibrational motion by the solvent. The transient infrared spectra therefore probe solvent-induced modifications to the reaction free energy surface and chemical dynamics.

  6. Investigating the Mechanisms of Amylolysis of Starch Granules by Solution-State NMR

    PubMed Central

    2015-01-01

    Starch is a prominent component of the human diet and is hydrolyzed by α-amylase post-ingestion. Probing the mechanism of this process has proven challenging, due to the intrinsic heterogeneity of individual starch granules. By means of solution-state NMR, we demonstrate that flexible polysaccharide chains protruding from the solvent-exposed surfaces of waxy rice starch granules are highly mobile and that during hydrothermal treatment, when the granules swell, the number of flexible residues on the exposed surfaces increases by a factor of 15. Moreover, we show that these flexible chains are the primary substrates for α-amylase, being cleaved in the initial stages of hydrolysis. These findings allow us to conclude that the quantity of flexible α-glucan chains protruding from the granule surface will greatly influence the rate of energy acquisition from digestion of starch. PMID:25815624

  7. Determining the Photoisomerization Quantum Yield of Photoswitchable Molecules in Solution and in the Solid State

    PubMed Central

    Stranius, K.; Börjesson, K.

    2017-01-01

    Photoswitchable molecules are able to isomerize between two metastable forms through light stimuli. Originally being studied by photochemists, this type of molecule has now found a wide range of applications within physics, chemistry and biology. The extensive usage of photochromic molecules is due to the two isomers having fundamentally different physical and chemical properties. The most important attribute of a photoswitch is the photoisomerization quantum yield, which defines the efficiency of the photoisomerization event. Here we show how to determine the photoisomerization quantum yield in the solid state and in solution when taking thermal processes into account. The described method together with provided software allows for rapid and accurate determination of the isomerization process for this important class of molecules. PMID:28117426

  8. Determining the Photoisomerization Quantum Yield of Photoswitchable Molecules in Solution and in the Solid State

    NASA Astrophysics Data System (ADS)

    Stranius, K.; Börjesson, K.

    2017-01-01

    Photoswitchable molecules are able to isomerize between two metastable forms through light stimuli. Originally being studied by photochemists, this type of molecule has now found a wide range of applications within physics, chemistry and biology. The extensive usage of photochromic molecules is due to the two isomers having fundamentally different physical and chemical properties. The most important attribute of a photoswitch is the photoisomerization quantum yield, which defines the efficiency of the photoisomerization event. Here we show how to determine the photoisomerization quantum yield in the solid state and in solution when taking thermal processes into account. The described method together with provided software allows for rapid and accurate determination of the isomerization process for this important class of molecules.

  9. Photon emission via surface state at the gold/acetonitrile solution interface

    SciTech Connect

    Uosaki, Kohei; Murakoshi, Kei; Kita, Hideaki )

    1991-01-24

    The emission of light caused by an electron-transfer reaction at a gold electrode in acetonitrile solution containing one of three redox species (benzophenone, trans-stilbene, and benzonitrile) with different redox potentials was studied. The high-energy threshold of the spectrum decreases linearly as the potential of the gold electrode becomes more negative. The peak position with respect to the high-energy threshold of the spectrum varies with electrode potential and is not affected by the redox potential of the electron injection species at the same electrode potential. The emission efficiency also depends on the potential. From these results, the authors proposed that the emission is due to a charge-transfer reaction inverse photoemission (CTRIP) process that takes place via a surface state.

  10. Analysis of lasers as a solution to efficiency droop in solid-state lighting

    NASA Astrophysics Data System (ADS)

    Chow, W. W.; Crawford, M. H.

    2015-10-01

    This letter analyzes the proposal to mitigate the efficiency droop in solid-state light emitters by replacing InGaN light-emitting diodes (LEDs) with lasers. The argument in favor of this approach is that carrier-population clamping after the onset of lasing limits carrier loss to that at threshold, while stimulated emission continues to grow with injection current. A fully quantized (carriers and light) theory that is applicable to LEDs and lasers (above and below threshold) is used to obtain a quantitative evaluation. The results confirm the potential advantage of higher laser output power and efficiency above lasing threshold, while also indicating disadvantages including low efficiency prior to lasing onset, sensitivity of lasing threshold to temperature, and the effects of catastrophic laser failure. A solution to some of these concerns is suggested that takes advantage of recent developments in nanolasers.

  11. Exact solution to the steady-state dynamics of a periodically modulated resonator

    NASA Astrophysics Data System (ADS)

    Minkov, Momchil; Shi, Yu; Fan, Shanhui

    2017-07-01

    We provide an analytic solution to the coupled-mode equations describing the steady-state of a single periodically modulated optical resonator driven by a monochromatic input. The phenomenology of this system was qualitatively understood only in the adiabatic limit, i.e., for low modulation speed. However, both in and out of this regime, we find highly non-trivial effects for specific parameters of the modulation. For example, we show complete suppression of the transmission even with zero detuning between the input and the static resonator frequency. We also demonstrate the possibility for complete, lossless frequency conversion of the input into the sideband frequencies, as well as for optimizing the transmitted signal towards a given target temporal waveform. The analytic results are validated by first-principle simulations.

  12. Structure-forming properties of 3-furylpropenoic acid derivatives in solution and in the solid state

    NASA Astrophysics Data System (ADS)

    Kiss, J. T.; Felföldi, K.; Paksi, Z.; Pálinkó, I.

    2003-06-01

    Measurements by infrared (FT-IR) spectroscopy in the solid state as well as in solution and molecular modeling calculations revealed that the major structure forming force (short range ordering) between 2-phenyl-3(2'-furyl)propenoic acid stereoisomers was the CO⋯H-O intermolecular hydrogen bonding between the carboxylic groups. For the E isomer no other secondary intermolecular interaction could be measured nor calculated. Molecular modeling showed that long-range ordering was possible between the hydrogen-bonded dimers of the Z isomer via (phenyl)C-H⋯(furyl)O close contacts. The methyl esters also had short-range ordering through (phenyl)C-H⋯(carbonyl)O interaction, while only the Z isomer offered the possibility of long-range order. Chain-like structures were formed via (phenyl)C-H⋯(furyl)O hydrogen bonds.

  13. Kinetic properties of tetrameric glycogen phosphorylase b in solution and in the crystalline state.

    PubMed Central

    Leonidas, D. D.; Oikonomakos, N. G.; Papageorgiou, A. C.; Sotiroudis, T. G.

    1992-01-01

    R-state monoclinic P2(1) crystals of phosphorylase have been shown to be catalytically active in the presence of an oligosaccharide primer and glucose-1-phosphate in 0.9 M ammonium sulfate, 10 mM beta-glycerophosphate, 0.5 mM EDTA, and 1 mM dithiothreitol, the medium in which the crystals are grown or equilibrated for crystallographic studies (Barford, D. & Johnson, L.N., 1989, Nature 360, 609-616; Barford, D., Hu, S.-H., & Johnson, L.N., 1991, J. Mol. Biol. 218, 233-260). Kinetic data suggest that the activity of crystalline tetrameric phosphorylase is similar to that determined in solution for the enzyme tetramer. However, large differences were found in the maximal velocities for both oligosaccharide or glucose-1-phosphate substrates between the soluble dimeric and crystalline tetrameric enzyme. PMID:1304391

  14. Dynamics of liquid state chemical reactions: Vibrational energy relaxation of molecular iodine in liquid solution

    NASA Astrophysics Data System (ADS)

    Brooks, C. L., III; Balk, M. W.; Adelman, S. A.

    1983-07-01

    The dynamics of vibrational energy relaxation of highly excited molecular iodine in three monatomic solvents is studied via stochastic classical trajectory simulations based on the molecular timescale generalized Langevin equation (MTGLE) of motion for liquid state chemical reactions [S. A. Adelman, J. Chem. Phys. 73, 3145 (1980)]. Also presented for comparison purposes are parallel studies based on a matrix Langevin equation of motion characterized by friction coefficients which depend on the instantaneous I2 internuclear separation R. The qualitative features of the energy relaxation may be interpreted as effects arising from modifications of the solute dynamics due to molecular timescale correlations between its motion and that of its solvation shells. Such dynamical solvent effects are realistically described by the MTGLE equation of motion but not by the Langevin equation. Thus, for example, the marked slowdown of the rate of I2 energy relaxtion in simple solvents when the I2 vibrational quantum number drops below a solvent-dependent critical value, earlier predicted by Nesbitt and Hynes, is predicted by MTGLE dynamics but not by Langevin dynamics. Finally, practical algorithms for numerically constructing the MTGLE and Langevin equations for specific solute-solvent systems are presented.

  15. FTIR assessment of poly(ethylene oxide) irradiated in solid state, melt and aqeuous solution

    NASA Astrophysics Data System (ADS)

    Pucić, Irina; Jurkin, Tanja

    2012-09-01

    FTIR spectroscopy was used to study poly(ethylene oxide), PEO, irradiated in solid and molten aggregate states and as aqueous solutions of various concentrations. The changes in shape and width of -C-O-C- complex absorption intensities at around 1112 cm-1 were the most prominent. On irradiation of solid samples in contact with air shrinking of -C-O-C- complex and increase in its absorption intensities indicated predominant degradation. Crosslinking prevailed on irradiation of molten PEO and of its aqueous solutions in nitrogen atmosphere and manifested itself as widening of -C-O-C- absorption and decrease of corresponding intensities. Partial or complete merging of CH2 wagging vibrations at 1342 cm-1 and 1360 cm-1 that are characteristic of crystalline PEO into a single absorption at around 1350 cm-1 indicated amorphization what was observed for samples that had reduced degree of crystallinity determined by differential scanning calorimetry. DSC could not discriminate between degradation and crosslinking while the changes in width and shape of -C-O-C- complex were independent of the changes in crystallinity. Comparison of FTIR spectra of the same PEO samples obtained as thin film and as KBr pellets revealed that pellet preparation results in a number of spectral artefacts.

  16. A globally convergent algorithm for the solution of the steady-state semiconductor device equations

    NASA Astrophysics Data System (ADS)

    Korman, Can E.; Mayergoyz, Isaak D.

    1990-08-01

    An iterative method for solving the discretized steady-state semiconductor device equations is presented. This method uses Gummel's block iteration technique to decouple the nonlinear Poisson and electron-hole current continuity equations. However, the main feature of this method is that it takes advantage of the diagonal nonlinearity of the discretized equations, and solves each equation iteratively by using the nonlinear Jacobi method. Using the fact that the diagonal nonlinearities are monotonically increasing functions, it is shown that this method has two important advantages. First, it has global convergence, i.e., convergence is guaranteed for any initial guess. Second, the solution of simultaneous algebraic equations is avoided by updating the value of the electrostatic and quasi-Fermi potentials at each mesh point by means of explicit formulae. This allows the implementation of this method on computers with small random access memories, such as personal computers, and also makes it very attractive to use on parallel processor machines. Furthermore, for serial computations, this method is generalized to the faster nonlinear successive overrelaxation method which has global convergence as well. The iterative solution of the nonlinear Poisson equation is formulated with energy- and position-dependent interface traps. It is shown that the iterative method is globally convergent for arbitrary distributions of interface traps. This is an important step in analyzing hot-electron effects in metal-oxide-silicon field-effect transistors (MOSFETs). Various numerical results on two- and three-dimensional MOSFET geometries are presented as well.

  17. State of the Art in LP-WAN Solutions for Industrial IoT Services

    PubMed Central

    Sanchez-Iborra, Ramon; Cano, Maria-Dolores

    2016-01-01

    The emergence of low-cost connected devices is enabling a new wave of sensorization services. These services can be highly leveraged in industrial applications. However, the technologies employed so far for managing this kind of system do not fully cover the strict requirements of industrial networks, especially those regarding energy efficiency. In this article a novel paradigm, called Low-Power Wide Area Networking (LP-WAN), is explored. By means of a cellular-type architecture, LP-WAN–based solutions aim at fulfilling the reliability and efficiency challenges posed by long-term industrial networks. Thus, the most prominent LP-WAN solutions are reviewed, identifying and discussing the pros and cons of each of them. The focus is also on examining the current deployment state of these platforms in Spain. Although LP-WAN systems are at early stages of development, they represent a promising alternative for boosting future industrial IIoT (Industrial Internet of Things) networks and services. PMID:27196909

  18. State of the Art in LP-WAN Solutions for Industrial IoT Services.

    PubMed

    Sanchez-Iborra, Ramon; Cano, Maria-Dolores

    2016-05-17

    The emergence of low-cost connected devices is enabling a new wave of sensorization services. These services can be highly leveraged in industrial applications. However, the technologies employed so far for managing this kind of system do not fully cover the strict requirements of industrial networks, especially those regarding energy efficiency. In this article a novel paradigm, called Low-Power Wide Area Networking (LP-WAN), is explored. By means of a cellular-type architecture, LP-WAN-based solutions aim at fulfilling the reliability and efficiency challenges posed by long-term industrial networks. Thus, the most prominent LP-WAN solutions are reviewed, identifying and discussing the pros and cons of each of them. The focus is also on examining the current deployment state of these platforms in Spain. Although LP-WAN systems are at early stages of development, they represent a promising alternative for boosting future industrial IIoT (Industrial Internet of Things) networks and services.

  19. Fabrication and Performance of All-Solid-State Chloride Sensors in Synthetic Concrete Pore Solutions

    PubMed Central

    Gao, Xiaojian; Zhang, Jian; Yang, Yingzi; Deng, Hongwei

    2010-01-01

    One type of all-solid-state chloride sensor was fabricated using a MnO2 electrode and a Ag/AgCl electrode. The potentiometric response of the sensor to chloride in synthetic concrete pore solutions was systematically studied, and the polarization performance was also evaluated. The results show a good linear relationship between the potential reading of the sensor and the logarithm of chloride activity (concentration ranges from 0.05 to 5.0 M), and the potential value remains stable with increasing immersion time. The existence of K+, Ca2+, Na+ and SO42− ions have little influence on the potentiometric response of the sensor to chloride, but the pH has a significant influence on the potential value of the sensor at low chloride concentration. The potential reading of the sensor increases linearly with the solution temperature over the range from 5 to 45 °C. Meanwhile, an excellent polarization behavior is proven by galvanostatic and potentiodynamic tests. All of the results reveal that the developed sensor has a great potential for monitoring chloride ions in concrete environments. PMID:22163467

  20. State of the art and recent development of embedded network solutions research

    NASA Astrophysics Data System (ADS)

    Gillet, Michel; Balandin, Sergey

    2008-04-01

    Recently we could observe a huge change in the mobile industry when the original idea of mobile phone was transformed into the new concept of mobile multimedia devices capable to perform multiple complex tasks and integrating a number of functionalities. As a consequence it resulted in significant increase of the device integration time and cost and complicated deployment of the new technologies. The device integrators are forced to favor modularity everywhere where it is possible in design of new devices, which results in a new trend towards networked architectures for the mobile devices. However, moving towards networked architectures specifically designed to overcome limitations brought by the mobile devices is a time consuming task. It requires fresh mind analysis of many solutions applied in other contexts, since some of the constraints and requirements are unique in comparison with e.g. SoC, NoC, which are the most known embedded network solutions, and of course they are significantly different comparing to the wide area networks. The main differentiating factors are: strongly constrained power consumption by the battery life time; and a need for modular architecture to allow reuse of the existing components or modules. The paper provides an overview of the state of art in the embedded networks research and describes general background for our studies, key assumptions, restrictions and limitations that we faced at the beginning of development of the embedded networks architecture for mobile devices.

  1. Conflicts between sandhill cranes and farmers in the western United States: evolving issues and solutions

    USGS Publications Warehouse

    Austin, Jane E.

    2012-01-01

    The main conflicts between Sandhill Cranes (Grus canadensis) and farmers in western United States occur in the Rocky Mountain region during migration and wintering periods. Most crop damage by cranes occurs in mature wheat (Triticum aestivum) and barley (Hordeum vulgare), young shoots of alfalfa (Medicago sativa) and cereal grains, chilies (Capsicum annuum), and silage corn (Zea mays). Damage is related to proximity of crop fields to roost sites and timing of crane concentrations relative to crop maturity or vulnerability. The evolution of conflicts between farmers and cranes and current solutions are described for two areas of the Rocky Mountains used by staging, migrating, or wintering cranes: Grays Lake, Idaho, and the Middle Rio Grande Valley, New Mexico. In both areas, conflicts with growing crane populations were aggravated by losses of wetlands and cropland, proximity of crops to roosts and other wetland areas, changing crop types and practices, and increasing urbanization. At Grays Lake, fall-staging cranes damaged barley fields near an important breeding refuge as well as fields 15-50 km away. In the Middle Rio Grande Valley, migrating and wintering cranes damaged young alfalfa fields, chilies, and silage corn. Solutions in both areas have been addressed through cooperative efforts among federal and state agencies, that manage wetlands and croplands to increase food availability and carrying capacity on public lands, provide hazing programs for private landowners, and strategically target crane hunting to problem areas. Sustaining the success of these programs will be challenging. Areas important to Sandhill Cranes in the western United Sates experience continued loss of habitat and food resources due to urbanization, changes in agricultural crops and practices, and water-use conflicts, which threaten the abilities of both public and private landowners to manage wetlands and croplands for cranes. Conservation of habitats and water resources are important

  2. Excited state intramolecular charge transfer reaction in nonaqueous electrolyte solutions: Temperature dependence

    NASA Astrophysics Data System (ADS)

    Pradhan, Tuhin; Gazi, Harun Al Rasid; Biswas, Ranjit

    2009-08-01

    Temperature dependence of the excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in ethyl acetate (EA), acetonitrile (ACN), and ethanol at several concentrations of lithium perchlorate (LiClO4) has been investigated by using the steady state and time resolved fluorescence spectroscopic techniques. The temperature range considered is 267-343 K. The temperature dependent spectral peak shifts and reaction driving force (-ΔGr) in electrolyte solutions of these solvents can be explained qualitatively in terms of interaction between the reactant molecule and ion-atmosphere. Time resolved studies indicate that the decay kinetics of P4C is biexponential, regardless of solvents, LiClO4 concentrations, and temperatures considered. Except at higher electrolyte concentrations in EA, reaction rates in solutions follow the Arrhenius-type temperature dependence where the estimated activation energy exhibits substantial electrolyte concentration dependence. The average of the experimentally measured activation energies in these three neat solvents is found to be in very good agreement with the predicted value based on data in room temperature solvents. While the rate constant in EA shows a electrolyte concentration induced parabolic dependence on reaction driving force (-ΔGr), the former in ethanol and ACN increases only linearly with the increase in driving force (-ΔGr). The data presented here also indicate that the step-wise increase in solvent reorganization energy via sequential addition of electrolyte induces the ICT reaction in weakly polar solvents to crossover from the Marcus inverted region to the normal region.

  3. Excited state intramolecular charge transfer reaction in nonaqueous electrolyte solutions: temperature dependence.

    PubMed

    Pradhan, Tuhin; Gazi, Harun Al Rasid; Biswas, Ranjit

    2009-08-07

    Temperature dependence of the excited state intramolecular charge transfer reaction of 4-(1-azetidinyl)benzonitrile (P4C) in ethyl acetate (EA), acetonitrile (ACN), and ethanol at several concentrations of lithium perchlorate (LiClO(4)) has been investigated by using the steady state and time resolved fluorescence spectroscopic techniques. The temperature range considered is 267-343 K. The temperature dependent spectral peak shifts and reaction driving force (-DeltaG(r)) in electrolyte solutions of these solvents can be explained qualitatively in terms of interaction between the reactant molecule and ion-atmosphere. Time resolved studies indicate that the decay kinetics of P4C is biexponential, regardless of solvents, LiClO(4) concentrations, and temperatures considered. Except at higher electrolyte concentrations in EA, reaction rates in solutions follow the Arrhenius-type temperature dependence where the estimated activation energy exhibits substantial electrolyte concentration dependence. The average of the experimentally measured activation energies in these three neat solvents is found to be in very good agreement with the predicted value based on data in room temperature solvents. While the rate constant in EA shows a electrolyte concentration induced parabolic dependence on reaction driving force (-DeltaG(r)), the former in ethanol and ACN increases only linearly with the increase in driving force (-DeltaG(r)). The data presented here also indicate that the step-wise increase in solvent reorganization energy via sequential addition of electrolyte induces the ICT reaction in weakly polar solvents to crossover from the Marcus inverted region to the normal region.

  4. Limitations and Extensions of the Lock-and-Key Principle: Differences between Gas State, Solution and Solid State Structures

    PubMed Central

    Schneider, Hans-Jörg

    2015-01-01

    The lock-and-key concept is discussed with respect to necessary extensions. Formation of supramolecular complexes depends not only, and often not even primarily on an optimal geometric fit between host and guest. Induced fit and allosteric interactions have long been known as important modifications. Different binding mechanisms, the medium used and pH effects can exert a major influence on the affinity. Stereoelectronic effects due to lone pair orientation can lead to variation of binding constants by orders of magnitude. Hydrophobic interactions due to high-energy water inside cavities modify the mechanical lock-and-key picture. That optimal affinities are observed if the cavity is only partially filled by the ligand can be in conflict with the lock-and-key principle. In crystals other forces than those between host and guest often dominate, leading to differences between solid state and solution structures. This is exemplified in particular with calixarene complexes, which by X-ray analysis more often than other hosts show guest molecules outside their cavity. In view of this the particular problems with the identification of weak interactions in crystals is discussed. PMID:25815592

  5. A strategy for selecting the pH of protein solutions to enhance crystallization.

    PubMed

    Zhang, Chen Yan; Wu, Zi Qing; Yin, Da Chuan; Zhou, Bo Ru; Guo, Yun Zhu; Lu, Hui Meng; Zhou, Ren Bin; Shang, Peng

    2013-07-01

    The pH of a solution is an important parameter in crystallization that needs to be controlled in order to ensure success. The actual pH of the crystallization droplet is determined by the combined contribution of the buffers in the screening and protein solutions, although the contribution of the latter to the pH is often ignored. In this study, the effects of the buffer and protein solution pH values on the results of screening are systematically investigated. It was found that these parameters significantly affected the results and thus the following strategy for the selection of appropriate pH values is proposed: (i) when screening with only one protein solution, the pH should be as low, as high or as divergent from the pI as possible for a basic, acidic or neutral protein, respectively, within its stable pH range; (ii) when screening with two protein solutions, the pH values should be well separated from one another; and (iii) when multiple pH values are utilized, an even distribution of pH values is the best approach to increase the success rate of crystallization.

  6. A strategy for selecting the pH of protein solutions to enhance crystallization

    PubMed Central

    Zhang, Chen-Yan; Wu, Zi-Qing; Yin, Da-Chuan; Zhou, Bo-Ru; Guo, Yun-Zhu; Lu, Hui-Meng; Zhou, Ren-Bin; Shang, Peng

    2013-01-01

    The pH of a solution is an important parameter in crystallization that needs to be controlled in order to ensure success. The actual pH of the crystallization droplet is determined by the combined contribution of the buffers in the screening and protein solutions, although the contribution of the latter to the pH is often ignored. In this study, the effects of the buffer and protein solution pH values on the results of screening are systematically investigated. It was found that these parameters significantly affected the results and thus the following strategy for the selection of appropriate pH values is proposed: (i) when screening with only one protein solution, the pH should be as low, as high or as divergent from the pI as possible for a basic, acidic or neutral protein, respectively, within its stable pH range; (ii) when screening with two protein solutions, the pH values should be well separated from one another; and (iii) when multiple pH values are utilized, an even distribution of pH values is the best approach to increase the success rate of crystallization. PMID:23832217

  7. Enhancement of sub-daily positioning solutions for surface deformation monitoring at Deception volcano (South Shetland Islands, Antarctica)

    NASA Astrophysics Data System (ADS)

    Prates, G.; Berrocoso, M.; Fernández-Ros, A.; García, A.

    2013-02-01

    Deception Island is one of the most visited places in Antarctica. There are biological, geological, and archeological features that are major attractions within Port Foster, its horse shoe-shaped natural inner bay, and two scientific bases that are occupied during austral summers. Deception Island is an active volcano, however, and needs to be monitored in order to reduce risk to people on the island. Surface deformation in response to fluid pressure is one of the main volcanic activities to observe. Automated data acquisition and processing using the global navigation satellite systems allow measurements of surface deformation in near real time. Nevertheless, the positioning repeatability in sub-daily solutions is affected by geophysical influences such as ocean tidal loading, among others. Such periodic influences must be accurately modeled to achieve similar repeatability as daily solutions that average them. However, a single solution each 24 h will average out the deformation suffered during that period, and the position update waiting time can be a limitation for near real-time purposes. Throughout the last five austral summer campaigns in Deception, using simultaneous wireless communications between benchmarks, a processing strategy was developed to achieve millimeter-level half-hourly positioning solutions that have similar repeatability as those given by 24-h solutions. For these half-hourly solutions, a tidal analysis was performed to assess any mismodeling of ocean tide loading, and a discrete Kalman filter was designed and implemented to enhance the sub-daily positioning repeatability. With these solutions, the volcano-dynamic activity resulting in localized surface deformation for the last five austral summer campaigns is addressed. Although based on only three carefully located benchmarks, it is shown that Deception has been shortening and subsiding during these last 4 years. The method's accuracy in baselines up to a few hundred kilometers assures

  8. Resonance-Enhanced Excited-State Raman Spectroscopy of Conjugated Thiophene Derivatives: Combining Experiment with Theory

    NASA Astrophysics Data System (ADS)

    Barclay, Matthew S.; Quincy, Timothy J.; Caricato, Marco; Elles, Christopher G.

    2017-06-01

    Resonance-enhanced Femtosecond Stimulated Raman Spectroscopy (FSRS) is an ultrafast experimental method that allows for the study of excited-state structural behaviors, as well as the characterization of higher electronically excited states accessible through the resonant conditions of the observed vibrations. However, interpretation of the experiment is difficult without an accurate vibrational assignment of the resonance-enhanced spectra. We therefore utilize simulations of off-resonant excited-state Raman spectra, in which we employ a numerical derivative of the analytical excited-state polarizabilities along the normal mode displacements, in order to identify and interpret the resonance-enhanced vibrations observed in experiment. We present results for a benchmark series of conjugated organic thiophene derivatives, wherein we have computed the off-resonant excited-state Raman spectra for each molecule and matched it with its resonance-enhanced experimental spectrum. This comparison allows us to successfully identify the vibrational displacements of the observed FSRS bands, as well as validate the accuracy of the theoretical results through an experimental benchmark. The agreement between the experimental and computed results demonstrates that we are able to predict qualitatively accurate excited-state Raman spectra for these conjugated thiophenes, allowing for a more thorough interpretation of excited-state Raman signals at relatively low computational cost.

  9. Analytical solutions for surfactant-enhanced remediation of nonaqueous phase liquids

    NASA Astrophysics Data System (ADS)

    Laforce, Tara; Johns, Russell T.

    2005-10-01

    Benchmark compositional solutions are presented for the remediation of aquifers contaminated with nonaqueous phase liquids (NAPLs) by injection of surfactant-water mixtures. The method of characteristics (MOC) is used to find one-dimensional analytical solutions to the Riemann problem where three partially miscible phases are flowing in a Winsor type III microemulsion. In partially miscible flow, two or three phases form when the components (constituents) are mixed in some but not all proportions. Three relative permeability models are examined, and MOC solutions are found. Fine-grid numerical simulations match the MOC results. The composition routes and contaminant recoveries can differ significantly depending on the relative permeability model used. The results for each model are optimized to determine the minimum surfactant volume required for complete contaminant recovery. Unlike two-phase partially miscible flow, the presence of three flowing phases makes it impossible to reach miscibility between the injected and resident fluids, regardless of surfactant concentration.

  10. Optimization of an absolute sensitivity in a glassy matrix during DNP-enhanced multidimensional solid-state NMR experiments.

    PubMed

    Takahashi, Hiroki; Fernández-de-Alba, Carlos; Lee, Daniel; Maurel, Vincent; Gambarelli, Serge; Bardet, Michel; Hediger, Sabine; Barra, Anne-Laure; De Paëpe, Gaël

    2014-02-01

    Thanks to instrumental and theoretical development, notably the access to high-power and high-frequency microwave sources, high-field dynamic nuclear polarization (DNP) on solid-state NMR currently appears as a promising solution to enhance nuclear magnetization in many different types of systems. In magic-angle-spinning DNP experiments, systems of interest are usually dissolved or suspended in glass-forming matrices doped with polarizing agents and measured at low temperature (down to ∼100K). In this work, we discuss the influence of sample conditions (radical concentration, sample temperature, etc.) on DNP enhancements and various nuclear relaxation times which affect the absolute sensitivity of DNP spectra, especially in multidimensional experiments. Furthermore, DNP-enhanced solid-state NMR experiments performed at 9.4 T are complemented by high-field CW EPR measurements performed at the same magnetic field. Microwave absorption by the DNP glassy matrix is observed even below the glass transition temperature caused by softening of the glass. Shortening of electron relaxation times due to glass softening and its impact in terms of DNP sensitivity is discussed. Copyright © 2014. Published by Elsevier Inc.

  11. Enhanced Conformational Sampling Using Replica Exchange with Concurrent Solute Scaling and Hamiltonian Biasing Realized in One Dimension

    PubMed Central

    2015-01-01

    Replica exchange (REX) is a powerful computational tool for overcoming the quasi-ergodic sampling problem of complex molecular systems. Recently, several multidimensional extensions of this method have been developed to realize exchanges in both temperature and biasing potential space or the use of multiple biasing potentials to improve sampling efficiency. However, increased computational cost due to the multidimensionality of exchanges becomes challenging for use on complex systems under explicit solvent conditions. In this study, we develop a one-dimensional (1D) REX algorithm to concurrently combine the advantages of overall enhanced sampling from Hamiltonian solute scaling and the specific enhancement of collective variables using Hamiltonian biasing potentials. In the present Hamiltonian replica exchange method, termed HREST-BP, Hamiltonian solute scaling is applied to the solute subsystem, and its interactions with the environment to enhance overall conformational transitions and biasing potentials are added along selected collective variables associated with specific conformational transitions, thereby balancing the sampling of different hierarchical degrees of freedom. The two enhanced sampling approaches are implemented concurrently allowing for the use of a small number of replicas (e.g., 6 to 8) in 1D, thus greatly reducing the computational cost in complex system simulations. The present method is applied to conformational sampling of two nitrogen-linked glycans (N-glycans) found on the HIV gp120 envelope protein. Considering the general importance of the conformational sampling problem, HREST-BP represents an efficient procedure for the study of complex saccharides, and, more generally, the method is anticipated to be of general utility for the conformational sampling in a wide range of macromolecular systems. PMID:26082676

  12. Unprecedented synthesis of 1,3-dimethylcyclobutadiene in the solid state and aqueous solution.

    PubMed

    Legrand, Yves-Marie; Gilles, Arnaud; Petit, Eddy; van der Lee, Arie; Barboiu, Mihail

    2011-08-29

    Cyclobutadiene (CBD), the smallest cyclic hydrocarbon bearing conjugated double bonds, has long intrigued chemists because of its chemical characteristics. The question of whether the molecule could be prepared at all has been answered, but the parent compound and its unperturbed derivatives have eluded crystallographic characterization or synthesis "in water". Different approaches have been used to generate and to trap cyclobutadiene in a variety of confined environments: a) an Ar matrix at cryogenic temperatures, b) a hemicarcerand cage enabling the characterization by NMR spectroscopy in solution, and c) a crystalline guanidinium-sulfonate-calixarene G(4)C matrix that is stable enough to allow photoreactions in the solid state. In the latter case, the 4,6-dimethyl-α-pyrone precursor, Me(2)1, has been immobilized in a guanidinium-sulfonate-calixarene G(4)C crystalline network through a combination of non-covalent interactions. UV irradiation of the crystals transforms the entrapped Me(2)1 into a 4,6-dimethyl-Dewar-β-lactone intermediate, Me(2)2, and rectangular-bent 1,3-dimethylcyclobutadiene, Me(2)CBD(R), which are sufficiently stable under the confined conditions at 175 K to allow a conventional structure determination by X-ray diffraction. Further irradiation drives the reaction towards Me(2)3&Me(2)CBD(S)/CO(2) (63.7 %) and Me(2)CBD(R) (37.3 %) superposed crystalline architectures and the amplification of Me(2)CBD(R). The crystallographic models are supported by additional FTIR and Raman experiments in the solid state and by (1)H NMR spectroscopy and ESI mass spectrometry experiments in aqueous solution. Amazingly, the 4,6-dimethyl-Dewar-β-lactone, Me(2)2, the cyclobutadiene-carboxyl zwitterion, Me(2)3, and 1,3-dimethylcyclobutadiene, Me(2)CBD, were obtained by ultraviolet irradiation of an aqueous solution of G(4)C{Me(2)1}. 1,3-Dimethylcyclobutadiene is stable in water at room temperature for several weeks and even up to 50 °C as demonstrated by

  13. Solution and Solid-State Studies of DNA-Programmable Nanoparticle Single Crystals

    NASA Astrophysics Data System (ADS)

    Auyeung, Evelyn

    This thesis lays the foundation for three main areas that have significantly advanced the field of DNA-programmable nanoparticle assembly: (1) the synthesis of nanoparticle superlattices with novel lattice symmetries (2) post-assembly characterization and applications of superlattices that have been transferred from solution to the solid state and (3) the realization of a slow-cooling strategy for synthesizing faceted nanoparticle single crystals. Together, these advances mark a turning point in the evolution of DNA-programmable assembly from a simple proof-of-concept demonstrated in 1996 to a powerful materials development strategy that has inspired many ongoing investigations in fields including catalysis, plasmonics, and electronics. Chapter 1 begins with an overview of controlled crystallization and its importance across fields including chemistry and materials science. This followed by a description of DNA-programmable assembly and a discussion on its advantages as an assembly strategy. Chapter 2 describes a powerful strategy for synthesizing nanoparticle superlattices using a coreless nanoparticle consisting purely of spherically-oriented oligonucleotides. This "three dimensional spacer approach" allows for the synthesis of nanoparticle superlattices with exotic structures, including one with no mineral equivalent. While DNA is a versatile ligand for nanoparticle assembly, the resulting superlattices are only stable in solution. Chapter 3 addresses these limitations and presents a method for transitioning these materials from solution to the solid state through silica encapsulation. This encapsulation process has transformed the ability to interrogate these materials using electron microscopy, and it has enabled all the studies in subsequent chapters of this thesis. In Chapter 4, a slow-cooling crystallization technique is described that allows for the synthesis of single crystalline microcrystals with well-defined facets from DNA-nanoparticle building blocks

  14. Enhancement of sub-daily positioning solutions for surface deformation surveillance at El Hierro volcano (Canary Islands, Spain)

    NASA Astrophysics Data System (ADS)

    Prates, G.; García, A.; Fernández-Ros, A.; Marrero, J. M.; Ortiz, R.; Berrocoso, M.

    2013-06-01

    El Hierro Island in the Canary Archipelago recently experienced a submerged eruption a few kilometers off its southern shore, detected 2011 October 10 on the island's south-rift alignment. The seismic activity suddenly increased around mid 2011 July, and ground deformation was then detected on the only geodetic benchmark that is continuously observed by global navigation satellite systems techniques and provides public data access. Based on that information, several other global navigation satellite system signal receivers were deployed on the island to provide continuous observation. For data collected by these receivers, a processing strategy was applied to achieve millimeter-level half-hourly positioning solutions. Position updates every 24 h are satisfactory to determine tectonic-plates' velocities. Updates near 1 s or less are required to characterize seismic waves. In between, minute-level updates are well suited for monitoring active volcano's inflation or deflation, providing an optimal time resolution of the local ground deformation. In half-hourly positioning solutions, the heterogeneous satellites' distribution in their orbital planes gives different constraints during satellite-constellation revolution, which can bias the solutions. Also, several geophysical influences can bias the solutions, including those related to gravitational movements. These influences have mostly semi-diurnal periodicities and may be considered Gaussian colored noise on the position's time series. Daily solutions that average out these influences can be applied in active volcanoes, but they can impose some limitations because they average the daily deformation, and the update waiting time is not suitable when near real-time surveillance is mandatory. These semi-diurnal biases do need to be removed or minimized to achieve millimeter-level sub-daily positioning solutions, however, and to do so, a discrete Kalman filter was applied to enhance the half-hourly positioning solutions

  15. A Solution Space for a System of Null-State Partial Differential Equations: Part 4

    NASA Astrophysics Data System (ADS)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the last of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE). The system comprises 2 N null-state equations and three conformal Ward identities that govern CFT correlation functions of 2 N one-leg boundary operators. In the first two articles (Flores and Kleban in Commun Math Phys, 2012; Flores and Kleban, in Commun Math Phys, 2014), we use methods of analysis and linear algebra to prove that dim , with C N the Nth Catalan number. Using these results in the third article (Flores and Kleban, in Commun Math Phys, 2013), we prove that dim and is spanned by (real-valued) solutions constructed with the Coulomb gas (contour integral) formalism of CFT. In this article, we use these results to prove some facts concerning the solution space . First, we show that each of its elements equals a sum of at most two distinct Frobenius series in powers of the difference between two adjacent points (unless is odd, in which case a logarithmic term may appear). This establishes an important element in the operator product expansion for one-leg boundary operators, assumed in CFT. We also identify particular elements of , which we call connectivity weights, and exploit their special properties to conjecture a formula for the probability that the curves of a multiple-SLE process join in a particular connectivity. This leads to new formulas for crossing probabilities of critical lattice models inside polygons with a free/fixed side-alternating boundary condition, which we derive in Flores et al. (Partition functions and crossing probabilities for critical systems inside polygons, in preparation). Finally, we propose a reason for why the exceptional speeds [certain values that appeared in the analysis of the Coulomb gas solutions in Flores and Kleban (Commun Math Phys, 2013)] and

  16. Temperature-dependent vibrational spectra of zinc(II) bis-(N,N'-diethyldithiocarbamate) in solid state and solution

    NASA Astrophysics Data System (ADS)

    Trendafilova, N.; Kellner, R.

    The IR spectra of zinc(II) bis-(N,N'-diethyldithiocarbamate) in the solid state (at 20, 80 and 120°C) as well as in solution (20°C) have been recorded and discussed as to the changes in the zinc coordination sphere that may occur upon heating and dissolution. The decreased number of bands in the high-temperature and in the solution specta as compared with the room temperature solid state spectra has been explained by removal of the intermolecular contacts upon dissolution or thermal averaging in the high temperature solid state.

  17. An exact solution for the steady state phase distribution in an array of oscillators coupled on a hexagonal lattice

    NASA Technical Reports Server (NTRS)

    Pogorzelski, Ronald J.

    2004-01-01

    When electronic oscillators are coupled to nearest neighbors to form an array on a hexagonal lattice, the planar phase distributions desired for excitation of a phased array antenna are not steady state solutions of the governing non-linear equations describing the system. Thus the steady state phase distribution deviates from planar. It is shown to be possible to obtain an exact solution for the steady state phase distribution and thus determine the deviation from the desired planar distribution as a function of beam steering angle.

  18. The Impact of Enhanced Summer Thaw, Hillslope Disturbances, and Late Season Rainfall on Solute Fluxes from High Arctic Headwater Catchments

    NASA Astrophysics Data System (ADS)

    Lafreniere, M. J.; Lamoureux, S. F.

    2011-12-01

    This study examines variations in the composition and total seasonal fluxes of dissolved solutes in several small High Arctic headwater catchments at the Cape Bounty Arctic Watershed Observatory (CBAWO), Melville Island, Nunavut (74°54'N, 109°35'W) over multiple snowmelt seasons (2007, 2008, 2009) with contrasting climate and permafrost active layer conditions. Climate warming in the High Arctic will affect a number processes that will alter the hydrological and biogeochemical exports from the landscape. Climate change is projected to alter precipitation regimes, resulting in increases in both winter and summer precipitation in the High Arctic, thereby altering hydrological regimes. Warming will result in thickening of the seasonal active layer, which will alter hydrological flow paths and water and solute sources. Additionally, active layer thickening and permafrost warming is also project to enhance the development of thermokarst features, including hillslope disturbances, such as active layer detachment slides and retrogressive thaw slumps. This research compares the flux of inorganic and organic solutes emanating from a group of catchments that were subject to a range hillslope disturbances, or active layer detachment slides (ALDs), at the end of summer 2007. One of the catchments, Goose, was not subject to any disturbance, while active layer slides covered between 6% and 46% of the catchment area in the disturbed catchments. It was hypothesised that solute fluxes would increase primarily with increasing extent and degree of disturbance. This however, was not observed. Rather, comparing five sites with varying degrees of disturbance in 2009 illustrates that on a specific area and specific volume of runoff basis, solute fluxes were unrelated to disturbance extent. Comparing two catchments that were monitored from 2007 (pre-disturbance) through to 2009 (2 yrs post disturbance), shows that both catchments were subject to solute flux increases, however the solute

  19. Electronic solution spectra for uranium and neptunium in oxidation states (III) to (VI) in anhydrous hydrogen fluoride

    SciTech Connect

    Baluka, M.; Edelstein, N.; O'Donnell, T. A.

    1981-10-01

    In this paper, spectra have been recorded for solutions in anhydrous hydrogen fluoride (AHF) of uranium and neptunium in oxidation states III to VI. The spectra for U(III), Np(III), and Np(IV) in AHF are very similar to those in acidified aqueous solution, but that for U(IV) suggests that the cationic species is UF22+. The AHF spectra for the elements in oxidation states V and VI are not comparable with those of the formally analogous aqueous solutions, where the elements exist as well-defined dioxo cations. Nonetheless, the AHF spectra can be related to spectra in the gas phase, in the solid state or in nonaqueous solvents for each element in its appropriate oxidation state.

  20. Proton-transfer mediated quenching of pyrene/indole charge-transfer states in isooctane solutions.

    PubMed

    Altamirano, Marcela S; Bohorquez, María del Valle; Previtali, Carlos M; Chesta, Carlos A

    2008-01-31

    The fluorescence quenching of pyrene (Py) by a series of N-methyl and N-H substituted indoles was studied in isooctane at 298 K. The fluorescence quenching rate constants were evaluated by mean of steady-state and time-resolved measurements. In all cases, the quenching process involves a charge-transfer (CT) mechanism. The I(o)/I and tau(o)/tau Stern-Volmer plots obtained for the N-H indoles show a very unusual upward deviation with increasing concentration of the quenchers. This behavior is attributed to the self-quenching of the CT intermediates by the free indoles in solution. The efficiency of quenching of the polyaromatic by the N-H indoles increases abruptly in the presence of small amount of added pyridine (or propanol). A detailed analysis of the experimental data obtained in the presence of pyridine provides unambiguous evidence that the self-quenching process involves proton transfer from the CT states to indoles.

  1. A physical theory of the living state: application to water and solute distribution.

    PubMed

    Ling, G N

    1988-06-01

    This review begins with a summary of the disproof of the membrane-pump theory and the alternative theory of the living cell, the association-induction (AI) hypothesis. Being alive in the AI hypothesis represents the maintenance of a high (negative) energy-low entropy state in which the two major components K+ and water of the living cell are closely associated with the third major component of the living cells, proteins. K+ is adsorbed singly on beta- and gamma- carboxyl groups and the bulk of cell water in multilayers on the exposed NHCO groups of fully extended polypeptide chains of cell proteins. These adsorptions account for both the constancy of cell K+ and cell water per unit of cell proteins. ATP plays a key role in the maintenance of the cooperatively linked protein-ion-water assembly at the living state by its adsorption on key protein site and exercises the controlling influence through its strong inductive effects. Water polarized in multilayers demonstrates size-dependent exclusion of solutes, e.g., large (hydrated) Na+ is excluded from water in living cells or model systems while smaller urea that fits into the dynamic water structure is not excluded. The confirmation of the polarized multilayer theory of cell water by nuclear magnetic resonance (NMR), dielectric, neutron scattering, and other studies not only reverses the conventional belief of the existence of the cell water as normal liquid water; it also gives a new definition to colloids.

  2. Modeling of dielectric properties of aqueous salt solutions with an equation of state.

    PubMed

    Maribo-Mogensen, Bjørn; Kontogeorgis, Georgios M; Thomsen, Kaj

    2013-09-12

    The static permittivity is the most important physical property for thermodynamic models that account for the electrostatic interactions between ions. The measured static permittivity in mixtures containing electrolytes is reduced due to kinetic depolarization and reorientation of the dipoles in the electrical field surrounding ions. Kinetic depolarization may explain 25-75% of the observed decrease in the permittivity of solutions containing salts, but since this is a dynamic property, this effect should not be included in the thermodynamic modeling of electrolytes. Kinetic depolarization has, however, been ignored in relation to thermodynamic modeling, and authors have either neglected the effect of salts on permittivity or used empirical correlations fitted to the measured static permittivity, leading to an overestimation of the reduction in the thermodynamic static permittivity. We present a new methodology for obtaining the static permittivity over wide ranges of temperatures, pressures, and compositions for use within an equation of state for mixed solvents containing salts. The static permittivity is calculated from a new extension of the framework developed by Onsager, Kirkwood, and Fröhlich to associating mixtures. Wertheim's association model as formulated in the statistical associating fluid theory is used to account for hydrogen-bonding molecules and ion-solvent association. Finally, we compare the Debye-Hückel Helmholtz energy obtained using an empirical model with the new physical model and show that the empirical models may introduce unphysical behavior in the equation of state.

  3. Molecular dynamics of excited state intramolecular proton transfer: 3-hydroxyflavone in solution

    SciTech Connect

    Bellucci, Michael A.; Coker, David F.

    2012-05-21

    The ultrafast enol-keto photoisomerization in the lowest singlet excited state of 3-hydroxyflavone is investigated using classical molecular dynamics in conjunction with empirical valence bond (EVB) potentials for the description of intramolecular interactions, and a molecular mechanics and variable partial charge model, dependent on transferring proton position, for the description of solute-solvent interactions. A parallel multi-level genetic program was used to accurately fit the EVB potential energy surfaces to high level ab initio data. We have studied the excited state intramolecular proton transfer (ESIPT) reaction in three different solvent environments: methylcyclohexane, acetonitrile, and methanol. The effects of the environment on the proton transfer time and the underlying mechanisms responsible for the varied time scales of the ESIPT reaction rates are analyzed. We find that simulations with our EVB potential energy surfaces accurately reproduce experimentally determined reaction rates, fluorescence spectra, and vibrational frequency spectra in all three solvents. Furthermore, we find that the ultrafast ESIPT process results from a combination of ballistic transfer, and intramolecular vibrational redistribution, which leads to the excitation of a set of low frequency promoting vibrational modes. From this set of promoting modes, we find that an O-O in plane bend and a C-H out of plane bend are present in all three solvents, indicating that they are fundamental to the ultrafast proton transfer. Analysis of the slow proton transfer trajectories reveals a solvent mediated proton transfer mechanism, which is diffusion limited.

  4. Supramolecular stabilization of metastable tautomers in solution and the solid state.

    PubMed

    Juribašić, Marina; Bregović, Nikola; Stilinović, Vladimir; Tomišić, Vladislav; Cindrić, Marina; Sket, Primož; Plavec, Janez; Rubčić, Mirta; Užarević, Krunoslav

    2014-12-22

    This work presents a successful application of a recently reported supramolecular strategy for stabilization of metastable tautomers in cocrystals to monocomponent, non-heterocyclic, tautomeric solids. Quantum-chemical computations and solution studies show that the investigated Schiff base molecule, derived from 3-methoxysalicylaldehyde and 2-amino-3-hydroxypyridine (ap), is far more stable as the enol tautomer. In the solid state, however, in all three obtained polymorphic forms it exists solely as the keto tautomer, in each case stabilized by an unexpected hydrogen-bonding pattern. Computations have shown that hydrogen bonding of the investigated Schiff base with suitable molecules shifts the tautomeric equilibrium to the less stable keto form. The extremes to which supramolecular stabilization can lead are demonstrated by the two polymorphs of molecular complexes of the Schiff base with ap. The molecules of both constituents of molecular complexes are present as metastable tautomers (keto anion and protonated pyridine, respectively), which stabilize each other through a very strong hydrogen bond. All the obtained solid forms proved stable in various solid-state and solvent-mediated methods used to establish their relative thermodynamic stabilities and possible interconversion conditions.

  5. Solution and Solid State Nuclear Magnetic Resonance Spectroscopic Characterization of Efavirenz.

    PubMed

    Sousa, Eduardo Gomes Rodrigues de; Carvalho, Erika Martins de; San Gil, Rosane Aguiar da Silva; Santos, Tereza Cristina Dos; Borré, Leandro Bandeira; Santos-Filho, Osvaldo Andrade; Ellena, Javier

    2016-09-01

    Samples of efavirenz (EFZ) were evaluated to investigate the influence of the micronization process on EFZ stability. A combination of X-ray diffraction, thermal analysis, FTIR, observations of isotropic chemical shifts of (1)H in distinct solvents, their temperature dependence and spin-lattice relaxation time constants (T1), solution (1D and 2D) (13)C nuclear magnetic resonance (NMR), and solid-state (13)C NMR (CPMAS NMR) provides valuable structural information and structural elucidation of micronized EFZ and heptane-recrystallized polymorphs (EFZ/HEPT). This study revealed that the micronization process did not affect the EFZ crystalline structure. It was observed that the structure of EFZ/HEPT is in the same form as that obtained from ethyl acetate/hexane, as shown in the literature. A comparison of the solid-state NMR spectra revealed discrepancies regarding the assignments of some carbons published in the literature that have been resolved. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  6. Functional and shunt states of bacteriorhodopsin resolved by 250 GHz dynamic nuclear polarization–enhanced solid-state NMR

    PubMed Central

    Bajaj, Vikram S.; Mak-Jurkauskas, Melody L.; Belenky, Marina; Herzfeld, Judith; Griffin, Robert G.

    2009-01-01

    Observation and structural studies of reaction intermediates of proteins are challenging because of the mixtures of states usually present at low concentrations. Here, we use a 250 GHz gyrotron (cyclotron resonance maser) and cryogenic temperatures to perform high-frequency dynamic nuclear polarization (DNP) NMR experiments that enhance sensitivity in magic-angle spinning NMR spectra of cryo-trapped photocycle intermediates of bacteriorhodopsin (bR) by a factor of ≈90. Multidimensional spectroscopy of U-13C,15N-labeled samples resolved coexisting states and allowed chemical shift assignments in the retinylidene chromophore for several intermediates not observed previously. The correlation spectra reveal unexpected heterogeneity in dark-adapted bR, distortion in the K state, and, most importantly, 4 discrete L substates. Thermal relaxation of the mixture of L's showed that 3 of these substates revert to bR568 and that only the 1 substate with both the strongest counterion and a fully relaxed 13-cis bond is functional. These definitive observations of functional and shunt states in the bR photocycle provide a preview of the mechanistic insights that will be accessible in membrane proteins via sensitivity-enhanced DNP NMR. These observations would have not been possible absent the signal enhancement available from DNP. PMID:19474298

  7. Functional and shunt states of bacteriorhodopsin resolved by 250 GHz dynamic nuclear polarization-enhanced solid-state NMR.

    PubMed

    Bajaj, Vikram S; Mak-Jurkauskas, Melody L; Belenky, Marina; Herzfeld, Judith; Griffin, Robert G

    2009-06-09

    Observation and structural studies of reaction intermediates of proteins are challenging because of the mixtures of states usually present at low concentrations. Here, we use a 250 GHz gyrotron (cyclotron resonance maser) and cryogenic temperatures to perform high-frequency dynamic nuclear polarization (DNP) NMR experiments that enhance sensitivity in magic-angle spinning NMR spectra of cryo-trapped photocycle intermediates of bacteriorhodopsin (bR) by a factor of approximately 90. Multidimensional spectroscopy of U-(13)C,(15)N-labeled samples resolved coexisting states and allowed chemical shift assignments in the retinylidene chromophore for several intermediates not observed previously. The correlation spectra reveal unexpected heterogeneity in dark-adapted bR, distortion in the K state, and, most importantly, 4 discrete L substates. Thermal relaxation of the mixture of L's showed that 3 of these substates revert to bR(568) and that only the 1 substate with both the strongest counterion and a fully relaxed 13-cis bond is functional. These definitive observations of functional and shunt states in the bR photocycle provide a preview of the mechanistic insights that will be accessible in membrane proteins via sensitivity-enhanced DNP NMR. These observations would have not been possible absent the signal enhancement available from DNP.

  8. Surface modification of activated carbon for enhanced adsorption of perfluoroalkyl acids from aqueous solutions.

    PubMed

    Zhi, Yue; Liu, Jinxia

    2016-02-01

    The objective of the research was to examine the effect of increasing carbon surface basicity on uptake of perfluorooctane sulfonic (PFOS) and carboxylic acids (PFOA) by activated carbon. Granular activated carbons made from coal, coconut shell, wood, and phenolic-polymer-based activated carbon fibers were modified through high-temperature and ammonia gas treatments to facilitate systematical evaluation of the impact of basicity of different origins. Comparison of adsorption isotherms and adsorption distribution coefficients showed that the ammonia gas treatment was more effective than the high-temperature treatment in enhancing surface basicity. The resultant higher point of zero charges and total basicity (measured by total HCl uptake) correlated with improved adsorption affinity for PFOS and PFOA. The effectiveness of surface modification to enhance adsorption varied with carbon raw material. Wood-based carbons and activated carbon fibers showed enhancement by one to three orders of magnitudes while other materials could experience reduction in adsorption towards either PFOS or PFOA.

  9. Observation of a Zundel-like transition state during proton transfer in aqueous hydroxide solutions

    PubMed Central

    Roberts, Sean T.; Petersen, Poul B.; Ramasesha, Krupa; Tokmakoff, Andrei; Ufimtsev, Ivan S.; Martinez, Todd J.

    2009-01-01

    It is generally accepted that the anomalous diffusion of the aqueous hydroxide ion results from its ability to accept a proton from a neighboring water molecule; yet, many questions exist concerning the mechanism for this process. What is the solvation structure of the hydroxide ion? In what way do water hydrogen bond dynamics influence the transfer of a proton to the ion? We present the results of femtosecond pump-probe and 2D infrared experiments that probe the O-H stretching vibration of a solution of dilute HOD dissolved in NaOD/D2O. Upon the addition of NaOD, measured pump-probe transients and 2D IR spectra show a new feature that decays with a 110-fs time scale. The calculation of 2D IR spectra from an empirical valence bond molecular dynamics simulation of a single NaOH molecule in a bath of H2O indicates that this fast feature is due to an overtone transition of Zundel-like H3O2− states, wherein a proton is significantly shared between a water molecule and the hydroxide ion. Given the frequency of vibration of shared protons, the observations indicate the shared proton state persists for 2–3 vibrational periods before the proton localizes on a hydroxide. Calculations based on the EVB-MD model argue that the collective electric field in the proton transfer direction is the appropriate coordinate to describe the creation and relaxation of these Zundel-like transition states. PMID:19666493

  10. A comparison of water solubility enhancements of organic solutes by aquatic humic materials and commercial humic acids

    USGS Publications Warehouse

    Chlou, C.T.; Kile, D.E.; Brinton, T.I.; Malcolm, R.L.; Leenheer, J.A.; MacCarthy, P.

    1987-01-01

    Water solubility enhancements of 1,1-bis(p-chloro-phenyl)-2,2,2-trichloroethane (p,p???-DDT), 2,4,5,2???,5???-pentachlorobiphenyl (2,4,5,2???,5???-PCB), and 2,4,4???-tri-chlorobiphenyl (2,4,4???-PCB) by dissolved organic matter have been studied with the following samples: (1) acidic water samples from the Suwannee River, Georgia, and the Sopchoppy River, Florida; (2) a humic extract of a nearly neutral pH water from the Calcasieu River, Louisiana; (3) commercial humic acids from the Aldrich Chemical Co. and Fluka-Tridom Chemical Corp. The calculated partition coefficients on a dissolved organic carbon basis (Kdoc) for organic solutes with water samples and aquatic humic extracts from this and earlier studies indicate that the enhancement effect varies with the molecular composition of the aquatic humic materials. The Kdoc values with water and aquatic humic samples are, however, far less than the observed Kdoc values obtained with the two commercial samples, by factors of about 4-20. In view of this finding, one should be cautious in interpreting the effects of the dissolved organic matter on solubility enhancement of organic solutes on the basis of the use of commercial humic acids.

  11. Sensitive marker bands for the detection of spin states of heme in surface-enhanced resonance Raman scattering spectra of metmyoglobin.

    PubMed

    Kitahama, Yasutaka; Egashira, Masatoshi; Suzuki, Toshiaki; Tanabe, Ichiro; Ozaki, Yukihiro

    2014-12-21

    Surface-enhanced resonance Raman scattering (SERRS) spectra of myoglobin (Mb) with various ligands were measured. In the resonance Raman scattering (RRS) spectra, peaks at around 1610 and 1640 cm(-1) have so far been used to discriminate between the heme iron in a high or low spin state. In the SERRS spectra, however, the spin state cannot be distinguished by the corresponding peaks. Alternatively, the intensity ratio of the SERRS peak at 1560 cm(-1) to that at 1620 cm(-1) was applied to detect the spin states sensitively (1.5 × 10(5) times compared with the RRS); namely, a high ratio was obtained from met-Mb in the high spin state at pH ≤ 7 except for in a strong acid solution. The different marker bands between the SERRS and RRS spectra may be due to the enhancement order from the surface selection rule.

  12. Inclusion of Paracetamol into β-cyclodextrin nanocavities in solution and in the solid state

    NASA Astrophysics Data System (ADS)

    El-Kemary, Maged; Sobhy, Saffaa; El-Daly, Samy; Abdel-Shafi, Ayman

    2011-09-01

    We report on steady-state UV-visible absorption and emission characteristics of Paracetamol, drug used as antipyretic agent, in water and within cyclodextrins (CDs): β-CD, 2-hydroxypropyl- β-CD (HP- β-CD) and 2,6-dimethyl- β-CD (Me- β-CD). The results reveal that Paracetamol forms a 1:1 inclusion complex with CD. Upon encapsulation, the emission intensity enhances, indicating a confinement effect of the nanocages on the photophysical behavior of the drug. Due to its methyl groups, the Me- β-CD shows the largest effect for the drug. The observed binding constant showing the following trend: Me- β-CD > HP- β-CD > β-CD. The less complexing effectiveness of HP- β-CD is due to the steric effect of the hydroxypropyl-substituents, which can hamper the inclusion of the guest molecules. The solid state inclusion complex was prepared by co-precipitation method and its characterization was investigated by Fourier transform infrared spectroscopy, 1H NMR and X-ray diffractometry. These approaches indicated that Paracetamol was able to form an inclusion complex with CDs, and the inclusion compounds exhibited different spectroscopic features and properties from Paracetamol.

  13. Chelation-enhanced fluorescence detection of metal and nonmetal ions in aqueous solution

    NASA Astrophysics Data System (ADS)

    Czarnik, Anthony W.

    1992-04-01

    Our group has previously described large chelation-enhanced fluorescence (CHEF) effects upon the binding of metal ions, phosphates, and carboxylates to conjugate probes, providing large, readily measurable signals to these molecular recognition events. In understanding the structural requirements for CHEF, it is now possible to use the vast body of information on selective binding by azacrowns and cryptands in the synthesis of selective fluorescence probes. For example, a conjugate probe that allows for the selective, simultaneous assay of Zn(II) and Cd(II) ions has been synthesized and is described. In the homologous series of anthrylazamacrocycles that demonstrate chelation-enhanced fluorescence (CHEF) upon Zn(II) or Cd(II) binding in water, the pentacyclen derivative uniquely complexes Cd(II) with perturbation of the emission spectrum. The binding of anions such as phosphate and citrate give rise to fluorescence enhancements as large as six-fold; an observed pH dependence on the magnitude of fluorescence enhancements upon phosphate binding points to intracomplex protonation of the benzylic nitrogen by the HPO42- ion as the origin of this CHEF effect. Anthrylpolyamine conjugate probes yield large (up to 80-fold) changes in fluorescence upon binding to biological polyanions (e.g., DNA, heparin, and polyglutamate) at 1 M concentrations. These fluorescence changes have been used as the basis for a fluorometric assay of heparinase activity; the enzymatic hydrolysis of ATP can also be monitored conveniently using anthrylpolyamine fluoroionophores.

  14. Reasons why current speech-enhancement algorithms do not improve speech intelligibility and suggested solutions.

    PubMed

    Loizou, Philipos C; Kim, Gibak

    2011-01-01

    Existing speech enhancement algorithms can improve speech quality but not speech intelligibility, and the reasons for that are unclear. In the present paper, we present a theoretical framework that can be used to analyze potential factors that can influence the intelligibility of processed speech. More specifically, this framework focuses on the fine-grain analysis of the distortions introduced by speech enhancement algorithms. It is hypothesized that if these distortions are properly controlled, then large gains in intelligibility can be achieved. To test this hypothesis, intelligibility tests are conducted with human listeners in which we present processed speech with controlled speech distortions. The aim of these tests is to assess the perceptual effect of the various distortions that can be introduced by speech enhancement algorithms on speech intelligibility. Results with three different enhancement algorithms indicated that certain distortions are more detrimental to speech intelligibility degradation than others. When these distortions were properly controlled, however, large gains in intelligibility were obtained by human listeners, even by spectral-subtractive algorithms which are known to degrade speech quality and intelligibility.

  15. State of hydrophobic and hydrophilic ionic liquids in aqueous solutions: are the ions fully dissociated?

    PubMed

    Yee, Patrick; Shah, Jindal K; Maginn, Edward J

    2013-10-17

    Molecular dynamics simulations were performed for aqueous solutions of five ionic liquids (ILs): 1-ethyl-3-methylimidazolium ([C2mim]) bis(trifluoromethanesulfonyl) imide ([NTf2]), 1-n-butyl-3-methylimidazolium ([C4mim]) [NTf2], 1-n-hexyl-3-methylimidazolium ([C6mim]) [NTf2], [C2mim] ethylsulfate ([C2H5SO4]), and [C2mim] chloride (Cl) to determine whether the ions of these ILs are associated at relatively high dilutions and whether the association is governed by hydrophobicity/hydrophilicity of the ILs. The adaptive biasing force technique was applied to calculate the potential of mean force (PMF) for each IL ion pair. For all of the ILs, the PMF is characterized by two distinct contact minima in which the ions have different relative conformations. The hydrophobic ILs bearing the anion [NTf2](-) exist predominantly in the associative state; the strength of the association of these ILs increases with increase in the alkyl chain length. The most hydrophilic IL [C2mim] Cl was determined to be almost fully dissociated at the concentration examined in the study. [C2mim] [C2H5SO4] showed hydration behavior that was intermediate between that exhibited by the ILs in which the anion is substituted with either Cl(-) or [NTf2](-) paired with [C2mim](+). Association constants for these ILs were also computed. Radial distribution functions calculated by constraining the ions at the contact minima showed that hydration of the anion plays the dominant role in determining the microscopic behavior of these ILs in aqueous solutions.

  16. Solute retention and the states of water in polyethylene glycol and poly(vinyl alcohol) gels.

    PubMed

    Baba, Takayuki; Sakamoto, Ryosaku; Shibukawa, Masami; Oguma, Koichi

    2004-06-18

    The states of water sorbed in a cross-linked polyethylene glycol (PEG) gel, TSKgel Ether-250, and cross-linked poly(vinyl alcohol) (PVA) gels of different pore sizes, TSKgel Toyopearl HW-40S, 50S, 55S and 75S, were investigated by means of differential scanning calorimetry (DSC). It was found that there were three types of water in these hydrogels, non-freezing water, freezable bound water and free water. The amount of water that functions as the stationary phase in the column packed with the each gel was also estimated by a liquid chromatographic method. The estimated amount of the stationary phase water is in good agreement with the sum of the amount of non-freezing water and that of freezable bound water for HW-40S, 50S and 55S, while it agrees with the amount of only non-freezing water for HW-75S and Ether-250. This means that the stationary phase water consists of non-freezing water and freezable bound water for HW-40S, 50S and 55S, while only non-freezing water functions as the stationary phase in HW-75S and Ether-250 gels. This result can be attributed to the difference in the structure of the gels; the PVA gels containing PVA at relatively high concentrations, HW-40S, 50S and 55S, have a homogeneous gel phase, whereas HW-75S and Ether-250 have a heterogeneous gel phase consisting hydrated polymer domains and macropores with relatively hydrophobic surface. The freezable bound water in Toyopearl HW-40S, 50S and 55S can be regarded as a component of a homogeneous PVA solution phase, while that in HW-75S and Ether-250 may be water isolated in small pores of the hydrophobic domains. The results obtained by the investigation on the retention selectivity of these hydrogels in aqueous solutions supported our postulated view on the structures of the hydrogels.

  17. Solution and solid state properties of a set of procaine and procainamide derivatives.

    PubMed

    Olivera, María Eugenia; Ramírez Rigo, María Veronica; Chattah, Ana Karina; Levstein, Patricia Rebeca; Baschini, Miria; Manzo, Ruben Hilario

    2003-04-01

    A set of potential Class III antiarrhythmic agents of structure p-HOOC-R-CO-NH-C(6)H(4)-CO-X-C(2)H(5)-N(C(2)H(5))(2) were isolated as crystalline solids of the amide and ester derivatives, I: succinylprocainamide (X=-NH-, R=-C(2)H(4)-); II: succinylprocaine (X=-O-, R=-C(2)H(4)-); III: maleylprocainamide (X=-NH-, R=-C(2)H(2)-) and IV: maleylprocaine (X=-O-, R=-C(2)H(2)-). Although compounds I-IV exhibit similar solution properties (i.e. acid-base speciation, with zwitterionic (+-) to neutral (00) form ratios higher than 10(4)), aqueous solubility of -NH- derivatives is significantly higher than that of -O- derivatives and also, solvent effects on solubility (i.e. the change of water by ethanol) is clearly different in both series. Solution and solid-state properties of I-IV were characterized to account for the observed differences. Results indicate that procainamide derivatives I and III crystallizes as (+-)(s) but procaine derivatives II and IV as (00)(s). Besides, I is anhydrous but II-IV are hydrates. Aqueous solubility and solvent effect on solubility are controlled by the intrinsic solubility of the species (+-) in I and III and (00) in II and IV. The rise of hydrophilicity of species (00) due to the structural change from -O- to -NH- would determine the change in the structure of the precipitating crystals from (00)(s) to (+-)(s). Solid structure (zwitterionic or neutral), as well as composition (anhydrous or hydrated) may be recognized as the main factors in determining the rank of aqueous solubility of the set: (+-)>(+-.H(2)O)>(00.H(2)O).

  18. Enhanced removal of Hg(II) from acidic aqueous solution using thiol-functionalized biomass.

    PubMed

    Chai, Liyuan; Wang, Qingwei; Li, Qingzhu; Yang, Zhihui; Wang, Yunyan

    2010-01-01

    Spent grain, the low-cost and abundant biomass produced in the brewing industry, was functionalized with thiol groups to be used as an adsorbent for Hg(II) removal from acidic aqueous solution. The adsorbents were characterized by the energy-dispersive X-ray analysis (EDAX) and Fourier transform infrared (FTIR) spectroscopy. Optimum pH for Hg(II) adsorption onto the thiol-functionalized spent grain (TFSG) was 2.0. The equilibrium and kinetics of the adsorption of Hg(II) onto TFSG from acidic aqueous solution were investigated. From the Langmuir isotherm model the maximum adsorption capacity of TFSG for Hg(II) was found to be 221.73 mg g(-1), which was higher than that of most various adsorbents reported in literature. Moreover, the adsorption of Hg(II) onto TFSG followed pseudo-second-order kinetic model.

  19. Origin of stress and enhanced carrier transport in solution-cast organic semiconductor films

    NASA Astrophysics Data System (ADS)

    Cour, Ishviene; Chinta, Priya V.; Schlepütz, Christian M.; Yang, Yongsoo; Clarke, Roy; Pindak, Ron; Headrick, Randall L.

    2013-09-01

    Molecular packing in laterally directed solution deposition is a strong function of variables such as printing speed, substrate temperature, and solution concentration. Knowledge of the ordering mechanisms impacts on the development of new processes and materials for improved electronic devices. Here, we present real-time synchrotron x-ray scattering results combined with optical video microscopy, revealing the stages of ordering during the deposition of organic thin films via hollow capillary writing. Limited long range ordering is observed during the initial crystallization, but it gradually develops over 3-4 s for a range of deposition conditions. Buckling of thin films is typically observed for deposition above room temperature. We infer that compressive stress originates from thermal transients related to solvent evaporation on timescales similar to the development of long range ordering. Under optimized conditions, elimination of cracks and other structural defects significantly improves the average charge carrier mobility in organic field-effect transistors.

  20. Evidence of enhanced radius of Hoyle rotational state in12C inelastic scattering

    NASA Astrophysics Data System (ADS)

    Ito, M.

    2017-06-01

    Nuclear radius of three α rotational state in12C with a life time of 10-21 second, which has been expected to have much more extended radius than the ground12C nucleus, is speculated from systematic analysis of the differential cross section of the α +12C inelastic scattering. Present analysis predicts about 0.6 ∼ 1.0 fm enhancement in the matter radius of the three α rotational state in comparison to the normal radius of the ground state. The spatial extension of the three α rotational state is comparable to the extended radius observed in the neutron halo phenomena.

  1. Enhanced two-photon absorption and fluorescence upconversion in Thioflavin T micelle-type aggregates in glycerol/water solution

    NASA Astrophysics Data System (ADS)

    Donnelly, Julie; Vesga, Yuly; Hernandez, Florencio E.

    2016-09-01

    In this article, we report the systematic characterization of the two-photon absorption of ThT in different mixtures of glycerol/water solution. The relationships of TPA peak position and amplitude revealed a dependence on particle size suggesting that the curious trend observed in TPA with changing glycerol content can be attributed to the presence of micelle-type aggregates. Consequently, the relatively strong TPA cross-section (δTPA = 300 GM) obtained in 8.75% glycerol/water solutions could be attributed to the immobilization of dye molecules and the strong coupling of the molecular transition dipoles in micelle-type aggregates. This enhancement of TPA, in addition to the already reported significant fluorescence quantum yield of ThT attached to brain tissue, is expected to boost the application of this compound for in vitro and perhaps in vivo high resolution multiphoton bioimaging of amyloids in brain tissue.

  2. YbCu2Si2-LaCu2Si2 Solid Solutions with Enhanced Thermoelectric Power Factors

    NASA Astrophysics Data System (ADS)

    Lehr, Gloria J.; Morelli, Donald T.; Jin, Hyungyu; Heremans, Joseph P.

    2015-06-01

    Cryogenic Peltier coolers are ideal for cooling infrared sensors on satellites. To make these thermoelectric devices a realistic option for this application, the efficiency of thermoelectric materials at cryogenic temperatures must be substantially enhanced. Intermediate valence Yb-based compounds have large peaks in the Seebeck coefficient at low temperatures; to optimize these materials this must be understood. We created solid solutions between the intermediate valence compound YbCu2Si2 and an isostructural compound LaCu2Si2 to manipulate the temperature at which the Seebeck coefficient peaks and to maximize zT by reduction of lattice thermal conductivity. An enormous power factor of 110 μW/cm K2 at 100 K and a maximum zT of 0.14 at 125 K were achieved for one of these solid solutions.

  3. Perfusion enhances solute transfer into the shell of hollow fiber membrane bioreactors for bone tissue engineering.

    PubMed

    De Napoli, Ilaria Ester; Catapano, Gerardo

    2010-06-01

    Preparation of tissue engineered (TE) 3D constructs to repair large bone defects is limited by the difficult supply of nutrients and oxygen to cells in the innermost regions of constructs cultured in bioreactors. Poor oxygenation negatively affects cell viability and function. Bioreactor design optimization may help relieve these limitations. Bioreactors in which cells are cultured outside bundles of hollow fiber membranes (HFMBs) are structurally similar to natural bone. HFMB operation in pure diffusion has been reported to suffice for fibroblasts, but is deemed insufficient for bone cells. In this paper, the effect of perfusion flows in the cell compartment on solute transfer was investigated in HFMBs differing in design and operating conditions. HFMBs were designed and operated using values of non-dimensional groups that ensured solutes transfer towards the cell compartment mainly by diffusion; in the presence of low to high Starling flows; in the presence of pulsatile radial flows obtained by periodically stopping the solution flow leaving the bioreactor using a pinch valve. Distribution of matter in cell-free HFMBs was evaluated with tracer experiments in an optimized apparatus. Effectiveness of solute transfer to cell compartment was assessed based on the bioreactor response in terms of the shell volume actively involved in mass transfer (V(MTA)) according to transport models developed specifically for the purpose. V(MTA) increased with increasing Starling flows. In the pulsatile radial flow mode, tracer concentration in the shell increased 3 times faster than at high Starling flows. This suggests that controlled perfusion flows in HFMBs might enable the engineering of large TE bone constructs.

  4. Solution-based characterization of surface-enhanced Raman response of single scattering centers

    SciTech Connect

    Laurence, T A; Talley, C; Schwartzberg, A; Braun, G; Moskovits, M; Reich, N; Huser, T

    2008-03-06

    We demonstrate the rapid optical characterization of large numbers of individual metal nanoparticles freely diffusing in colloidal solution by confocal laser spectroscopy. We find that hollow gold nanospheres and solid silver nanoparticles linked with a bifunctional ligand, both designed nanostructures, exhibit significantly higher monodispersity in their Rayleigh and Raman scattering response than randomly aggregated gold and silver nanoparticles. We show that measurements of rotational diffusion timescales allow sizing of particles significantly more reliably than can be obtained using translational diffusion timescales.

  5. Enhanced catalytic performance of Pd catalyst for formic acid electrooxidation in ionic liquid aqueous solution

    NASA Astrophysics Data System (ADS)

    Feng, Yuan-Yuan; Yin, Qian-Ying; Lu, Guo-Ping; Yang, Hai-Fang; Zhu, Xiao; Kong, De-Sheng; You, Jin-Mao

    2014-12-01

    A protic ionic liquid (IL), n-butylammonium nitrate (N4NO3), is prepared and employed as the electrolyte for formic acid electrooxidation reaction (FAOR) on Pd catalysts. The oxidation peak potential of FAOR in the IL solution shows about a 200 mV negative shift as compared with those in traditional H2SO4/HClO4 electrolytes, suggesting that FAOR can be more easily carried out on Pd catalysts in IL media. The catalytic properties of Pd toward FAOR are not only dependent on the concentration of IL, as a consequence of the varied electronic conductivity of the IL solution, but also on the high potential limit of the cyclic voltammograms. When the Pd catalyst is cycled up to 1.0 V (vs. SCE), which induces a significant oxidation of Pd, it shows ca. 4.0 times higher activity than that not subjected to the Pd oxidation (up to 0.6 V). The Pd oxides, which are more easily formed in IL solution than in traditional H2SO4/HClO4 electrolytes, may play a crucial role in increasing the catalytic activities of Pd toward FAOR. Our work would shed new light on the mechanism of FAOR and highlight the potential applications of IL as green and environment-friendly electrolytes in fuel cells and other technologies.

  6. Accelerometer based solution for precision livestock farming: geolocation enhancement and animal activity identification

    NASA Astrophysics Data System (ADS)

    Terrasson, G.; Llaria, A.; Marra, A.; Voaden, S.

    2016-07-01

    The rapid evolution of electronics and communication technologies in the last years has contributed to the expansion of Precision Livestock Farming applications. In this context, animal geolocation systems applied to extensive farming are interesting for farmers to optimize their daily work organization. Nevertheless, the deployment of these solutions implies several technical challenges which must be resolved, mainly the energy consumption and the suitability of the communication protocols. A recently developed solution that deals with these technical challenges is the e-Pasto platform, which is composed of low power geolocation devices embedded into collars that offer an energetic autonomy of at least seven months, completed with a visualization user interface. The autonomy is assured employing a duty-cycle operation that results in one geolocation position measurement per hour. This work studies the employ of accelerometers to overcome this limitation assuring, at the same time, the required autonomy for the geolocation device. The authors also propose an algorithm that processes the acceleration data in order to identify the steps of an individual. The whole solution (step identification and geolocation) has been validated by means of several experimental tests.

  7. Enhanced TiO2 photocatalytic degradation of bisphenol E by beta-cyclodextrin in suspended solutions.

    PubMed

    Wang, Guanghui; Wu, Feng; Zhang, Xu; Luo, Mingdao; Deng, Nansheng

    2006-05-20

    Enhancement of beta-cyclodextrin (beta-CD) on TiO(2) photocatalytic degradation of bisphenol E (BPE, bis(4-hydroxyphenyl)ethane) was investigated under a 250 W metal halide lamp (lambda> or =365 nm) in this work. In the system of photocatalytic degradation of BPE, the photodegradation rate of BPE in aqueous solutions containing beta-CD and TiO(2) was obviously faster than that in aqueous solutions containing only TiO(2). After 40 min of irradiation, beta-CD could increase the photodegradation efficiency by about 26% for 10 mg l(-1) BPE in the UV-vis/TiO(2) system and the photodegradation of 2.5-20.0 mg l(-1) BPE in aqueous solutions was found to follow pseudo-first-order law and the adsorption constant and the reaction rate constant of BPE in the system containing beta-CD and TiO(2) are obviously higher than those in the system containing only TiO(2), the influence factors on photodegradation of BPE were studied and described in details, such as beta-CD concentration, pH, BPE initial concentration and gas medium. The formation of CO(2) as a result of mineralization of BPE was observed during the photodegradation process. After 120 min of irradiation, the mineralization efficiency of BPE reached 61% in the presence of beta-CD, whereas mineralization efficiency was only 23% in the absence of beta-CD. The enhancement of photodegradation of BPE could be dependent on the enhancement of adsorption of BPE on TiO(2) surface and moderate inclusion-depth of BPE in the beta-CD cavity.

  8. Solution and Solid State Chemistry of Dimolybdenum Fluoroacetates with Ethylenediamine Derivatives

    NASA Astrophysics Data System (ADS)

    Snowden, Kevin Joseph

    Reactions of Mo_2 (O_2 CCF_3)_4, Mo_2O _2CCHF_2)_4, and Mo _2(O_2 CCH_2 F)_4 with the diamines (N,N-dimethylethylene-diamine (udmed), N,N^'-dimethylethylenediamine (sdmed), and N,N,N^',N ^',-tetramethylethylenediamine (tmed)) have been studied. Mo_2(O_2 CCF_3) _4 reacts with udmed in ethanol or acetonitrile to form crystalline (Mo_2(O_2 CCF_3)_3(udmed)_2 ) -(O_2{CCF}_3 ). A single-crystal x-ray study of the orange blades indicate that the complex exists as an ion pair, in which the udmed ligands bind as axial-equatorial chelates to each of the metals. The structure contains hydrogen bonds between the Mo_2 (rm O_2{CCF}_3)_3(udmed) ^+ cation and the free CF_3 {CO}_2^- anion. The compound crystallizes in the monoclinc space group I2/a. The solution reactions of Mo_2( rm O_2{CCF}_3)_4 with udmed, sdmed, and tmed have been studied at -20^circC in ethanol/CD_3CN by ^ {19}F NMR spectroscopy, with Mo _2: diamine ratios up to 1: 8. Udmed displaces on average up to three bridging CF_3{CO}_2 groups from the Mo _2(rm O_2 {CF}_3) _4 core. Sdmed displaces all bridging CF _3{CO}_2 groups. Tmed forms products which on average have two bridging and two free CF_3{CO }_2 groups. The course of these reactions and possible structures of the products are discussed based on spectra and chemical observations. The complex Mo_2(rm O_2 {CCH}_2rm F)_4 reacts with udmed in ethanol to produce crystalline (Mo _2(rm O_2{CCH} _2rm F)_3(udmed)_2 ) -(O_2{CCH}_2 rm F). Solid-state IR establish and single -crystal x-ray studies of the chunky orange crystals show that this compound is much like the trifluoroacetate analogue. The compound crystallizes in monoclinic space group P2 _1/c. The solution reaction reactions of Mo _2(rm O_2{CCHF}_2) _4 with udmed, sdmed, and tmed have been studied at -20^circ C in ethanol/CD_3CN by ^{19}F NMR spectroscopy, with Mo _2: diamine ratios up to 1: 8. Udmed produces appreciable amount of nonbridging and free CHF _2{CO}_2 groups. Sdmed readily displaces all bridging

  9. Dentin wettability enhancement for three irrigating solutions and their effect on push out bond strength of gutta percha / AH Plus

    PubMed Central

    El Gendy, Abeer-Abdel-Hakim; El Ashry, Salma-Hassan

    2015-01-01

    Background The aim of this study was to investigate the effect of wettability enhancement for 17% EDTA, 2.5% sodium hypochlorite and 7% maleic acid solutions on push out bond strength of gutta percha /AH Plus to root dentin. Material and Methods One hundred and eight extracted single rooted human lower premolars were instrumented up to Protaper Universal F5 then irrigated with 3ml of 2.5% NaOCl after each file. Irrigants were prepared and a pilot study for determination of Tween 80 concentration yielding the lowest surface tension value in every solution was conducted. Samples were randomly divided into a control group and two experimental groups (17% EDTA and 7% Maleate), further split into eight subgroups (n=12), according to Tween 80 implementation sequence. Roots were obturated using gutta percha and AH plus by lateral condensation. Bond strength was measured by push out test. Mode of failure was then evaluated quantitatively by stereomicroscopy. Data were statistically analyzed using one way ANOVA followed by Tukey-Kramer for multiple comparisons. Results Control group showed the lowest values. Maleic acid subgroups showed significantly higher overall values than EDTA subgroups (P<0.05). Protocols implementing surfactant containing NaOCl showed significantly lower values than plain counterparts. Failure pattern was predominantly cohesive for plain regimens and the ones implementing Tween 80 in maleic acid solutions with plain NaOCl. Conclusions Tween 80 addition to demineralizing irrigants increased the bond strength values. Surfactant containing NaOCl solutions yielded lower bond strength than plain ones. Key words:Wettability enhancement for three irrigants vs. corresponding gutta percha/AH Plus bonding. PMID:26155339

  10. University teaching hospital and private clinic collaboration to enhance veterinary educational opportunities at Mississippi State University.

    PubMed

    Tyner, C Lee; Harkness, John; Hoblet, Kent; Zumwalt, Lauren; Templeton, Karen; McLaughlin, Ron

    2014-01-01

    The College of Veterinary Medicine at Mississippi State University established a not-for-profit corporation (MSU-CVM-COS) to develop and manage private specialty clinics that would enhance teaching and student learning, increase caseload, and generate revenue. The corporation currently operates the Animal Emergency and Referral Center (AERC) and the Veterinary Specialty Center (VSC) as affiliates of Mississippi State University. These privately managed facilities provide access to advanced medical equipment, enhance clinical service and teaching, and promote the College's One Health initiative.

  11. Excited state properties of 7-hydroxy-4-methylcoumarin in the gas phase and in solution. A theoretical study.

    PubMed

    Georgieva, I; Trendafilova, N; Aquino, A; Lischka, H

    2005-12-29

    TDDFT/B3LYP and RI-CC2 calculations with different basis sets have been performed for vertical and adiabatic excitations and emission properties of the lowest singlet states for the neutral (enol and keto), protonated and deprotonated forms of 7-hydroxy-4-methylcoumarin (7H4MC) in the gas phase and in solution. The effect of 7H4MC-solvent (water) interactions on the lowest excited and fluorescence states were computed using the Polarizable Continuum Method (PCM), 7H4MC-water clusters and a combination of both approaches. The calculations revealed that in aqueous solution the pi pi* energy is the lowest one for excitation and fluorescence transitions of all forms of 7H4MC studied. The calculated excitation and fluorescence energies in aqueous solution are in good agreement with experiment. It was found that, depending on the polarity of the medium, the solvent shifts vary, leading to a change in the character of the lowest excitation and fluorescence transition. The dipole-moment and electron-density changes of the excited states relative to the ground state correlate with the solvation effect on the singlet excited states and on transition energies, respectively. The calculations show that, in contrast to the ground state, the keto form has a lower energy in the pi pi* state as compared to enol, demonstrating from this point of view the energetic possibility of proton transfer from the enol to the keto form in the excited state.

  12. Enhanced in vivo visualization of the microcirculation by topical application of fructose solution confirmed with correlation mapping optical coherence tomography

    NASA Astrophysics Data System (ADS)

    Enfield, Joey; McGrath, James; Daly, Susan M.; Leahy, Martin

    2016-08-01

    Changes within the microcirculation can provide an early indication of the onset of a plethora of ailments. Various techniques have thus been developed that enable the study of microcirculatory irregularities. Correlation mapping optical coherence tomography (cmOCT) is a recently proposed technique, which enables mapping of vasculature networks at the capillary level in a noninvasive and noncontact manner. This technique is an extension of conventional optical coherence tomography (OCT) and is therefore likewise limited in the penetration depth of ballistic photons in biological media. Optical clearing has previously been demonstrated to enhance the penetration depth and the imaging capabilities of OCT. In order to enhance the achievable maximum imaging depth, we propose the use of optical clearing in conjunction with the cmOCT technique. We demonstrate in vivo a 13% increase in OCT penetration depth by topical application of a high-concentration fructose solution, thereby enabling the visualization of vessel features at deeper depths within the tissue.

  13. Marshak Lectureship Talk: Women in Physics in the Baltic States Region: Problems and Solutions

    NASA Astrophysics Data System (ADS)

    Satkovskiene, Dalia

    2008-03-01

    In this contribution the gender equality problem in physics will be discussed on the basis of the results obtained implementing the project ``Baltic States Network: Women in Sciences and High Technology'' (BASNET) initiated by Lithuanian women physicists and financed by European Commission. The main goal of BASNET project was creation of the regional Strategy how to deal with women in sciences problem in the Baltic States. It has some stages and the contribution follows them. The first one was in depth sociological study aiming to find out disincentives and barriers women scientists face in their career and work at science and higher education institutions. Analysis of results revealed wide range of problems concerned with science organization, management and financing common for both counterparts. However it also proved the existence of women discrimination in sciences. As main factors influencing women under-representation in Physics was found: the stereotypes existing in the society where physics is assigned to the masculine area of activity; failings of the science management system, where highest positions are distributed not using the institutionalized objective criteria but by voting, where the correctness of majority solutions is anticipated implicitly. In physics where male scientists are the majority (they also usually compose executive boards, committees etc.) results of such a procedures often are unfavorable for women. The same reasons also influence women ``visibility'' in physicist's community and as the consequence possibility to receive needed recourses for their research as well as appropriate presentation of results obtained. The study revealed also the conservatism of scientific community- reluctance to face existing in the scientific society problems and to start solving them. On the basis of the results obtained as well practice of other countries the common strategy of solving women in physics (sciences) in the Baltic States region was

  14. A Solution Space for a System of Null-State Partial Differential Equations: Part 2

    NASA Astrophysics Data System (ADS)

    Flores, Steven M.; Kleban, Peter

    2015-01-01

    This article is the second of four that completely and rigorously characterize a solution space for a homogeneous system of 2 N + 3 linear partial differential equations in 2 N variables that arises in conformal field theory (CFT) and multiple Schramm-Löwner evolution (SLE). The system comprises 2 N null-state equations and three conformal Ward identities which govern CFT correlation functions of 2 N one-leg boundary operators. In the first article (Flores and Kleban, Commun Math Phys, arXiv:1212.2301, 2012), we use methods of analysis and linear algebra to prove that dim , with C N the Nth Catalan number. The analysis of that article is complete except for the proof of a lemma that it invokes. The purpose of this article is to provide that proof. The lemma states that if every interval among ( x 2, x 3), ( x 3, x 4),…,( x 2 N-1, x 2 N ) is a two-leg interval of (defined in Flores and Kleban, Commun Math Phys, arXiv:1212.2301, 2012), then F vanishes. Proving this lemma by contradiction, we show that the existence of such a nonzero function implies the existence of a non-vanishing CFT two-point function involving primary operators with different conformal weights, an impossibility. This proof (which is rigorous in spite of our occasional reference to CFT) involves two different types of estimates, those that give the asymptotic behavior of F as the length of one interval vanishes, and those that give this behavior as the lengths of two intervals vanish simultaneously. We derive these estimates by using Green functions to rewrite certain null-state PDEs as integral equations, combining other null-state PDEs to obtain Schauder interior estimates, and then repeatedly integrating the integral equations with these estimates until we obtain optimal bounds. Estimates in which two interval lengths vanish simultaneously divide into two cases: two adjacent intervals and two non-adjacent intervals. The analysis of the latter case is similar to that for one vanishing

  15. A diagonal algorithm for the method of pseudocompressibility. [for steady-state solution to incompressible Navier-Stokes equation

    NASA Technical Reports Server (NTRS)

    Rogers, S. E.; Kwak, D.; Chang, J. L. C.

    1986-01-01

    The method of pseudocompressibility has been shown to be an efficient method for obtaining a steady-state solution to the incompressible Navier-Stokes equations. Recent improvements to this method include the use of a diagonal scheme for the inversion of the equations at each iteration. The necessary transformations have been derived for the pseudocompressibility equations in generalized coordinates. The diagonal algorithm reduces the computing time necessary to obtain a steady-state solution by a factor of nearly three. Implicit viscous terms are maintained in the equations, and it has become possible to use fourth-order implicit dissipation. The steady-state solution is unchanged by the approximations resulting from the diagonalization of the equations. Computed results for flow over a two-dimensional backward-facing step and a three-dimensional cylinder mounted normal to a flat plate are presented for both the old and new algorithms. The accuracy and computing efficiency of these algorithms are compared.

  16. Higher-order vector discrete rogue-wave states in the coupled Ablowitz-Ladik equations: Exact solutions and stability.

    PubMed

    Wen, Xiao-Yong; Yan, Zhenya; Malomed, Boris A

    2016-12-01

    An integrable system of two-component nonlinear Ablowitz-Ladik equations is used to construct complex rogue-wave (RW) solutions in an explicit form. First, the modulational instability of continuous waves is studied in the system. Then, new higher-order discrete two-component RW solutions of the system are found by means of a newly derived discrete version of a generalized Darboux transformation. Finally, the perturbed evolution of these RW states is explored in terms of systematic simulations, which demonstrates that tightly and loosely bound RWs are, respectively, nearly stable and strongly unstable solutions.

  17. Higher-order vector discrete rogue-wave states in the coupled Ablowitz-Ladik equations: Exact solutions and stability

    NASA Astrophysics Data System (ADS)

    Wen, Xiao-Yong; Yan, Zhenya; Malomed, Boris A.

    2016-12-01

    An integrable system of two-component nonlinear Ablowitz-Ladik equations is used to construct complex rogue-wave (RW) solutions in an explicit form. First, the modulational instability of continuous waves is studied in the system. Then, new higher-order discrete two-component RW solutions of the system are found by means of a newly derived discrete version of a generalized Darboux transformation. Finally, the perturbed evolution of these RW states is explored in terms of systematic simulations, which demonstrates that tightly and loosely bound RWs are, respectively, nearly stable and strongly unstable solutions.

  18. Changes in caffeine states enhance return of fear in spider phobia.

    PubMed

    Mystkowski, Jayson L; Mineka, Susan; Vernon, Laura L; Zinbarg, Richard E

    2003-04-01

    Treatment of phobias is sometimes followed by a return of fear. Animal and human research has shown that changes in external and internal contexts between the time of treatment and follow-up tests often enhance return of fear. The present study examined whether shifts in caffeine (C) state would enhance return of fear. Participants who were highly afraid of spiders (n = 43) were treated in 1-session exposure-based therapy and tested for follow-up 1 week later. Participants were randomly assigned to 1 of 4 groups and received either placebo (P) or C at treatment and follow-up sessions: CC, PP, CP, and PC. Results demonstrated state-dependent learning. Participants experiencing incongruent drug states during treatment and follow-up (CP and PC) exhibited greater return of fear than those experiencing congruent drug states (CC and PP).

  19. Pool boiling of enhanced heat transfer surfaces in refrigerant-oil mixtures and aqueous calcium sulfate solutions

    SciTech Connect

    Curcio, L.A.; Somerscales, E.F.

    1994-08-01

    Pool boiling data of structured surfaces in R113/3GS oil mixtures show a general decrease in heat transfer with oil concentration, degradation in performance of all surfaces at 10% oil, no change in enhancement of the structured surfaces over plain surface, and restoration of performance of the enhanced surfaces upon cleaning in denatured alcohol. Fouling data of structured surfaces in pool boiling of sat. aq. CaSO{sub 4} solution show that effects of fouling (wall superheat changes, deposit weight) are more pronounced at 80 kW/m{sup 2} than at 10 kW/m{sup 2} heat flux; precipitation fouling show an effect within the first 2 h exposure. High flux surfaces have lower deposition weight than other surfaces; thus the deposition rate may depend strongly on wall superheat. The numerous nucleation sites of the enhanced surfaces provide more turbulent motion near the boiling surface than for the plain surface; thus the removal rate should be greater for an enhanced surface, although no removal of a deposit was ever observed.

  20. High-Rate Deposition of Ferrite Films in Aqueous Solution by Light-Enhanced Ferrite Plating

    NASA Astrophysics Data System (ADS)

    Itoh, Tomoyuki; Hori, Seiichiro; Abe, Masanori; Tamaura, Yutaka

    1990-08-01

    By irradiating the substrate surface with a Xe-lamp at 450 W/cm2, the deposition rate of Fe3O4 film in ferrite plating was increased by a factor of 10 (from ˜ 30 nm/min to ˜ 320 nm/min). The high deposition rate in light-enhanced ferrite plating cannot be simply ascribed to the increase of thermal energy.

  1. New steady-state models for water-limited cropping systems using saline irrigation waters: Analytical solutions and applications

    NASA Astrophysics Data System (ADS)

    Skaggs, T. H.; Anderson, R. G.; Corwin, D. L.; Suarez, D. L.

    2014-12-01

    Due to the diminishing availability of good quality water for irrigation, it is increasingly important that irrigation and salinity management tools be able to target submaximal crop yields and support the use of marginal quality waters. In this work, we present a steady-state irrigated systems modeling framework that accounts for reduced plant water uptake due to root zone salinity. Two new explicit, closed-form analytical solutions for the root zone solute concentration profile are obtained, corresponding to two alternative functional forms of the uptake reduction function. The solutions express a general relationship between irrigation water salinity, irrigation rate, crop salt tolerance, crop transpiration, and (using standard approximations) crop yield. Example applications are illustrated, including the calculation of irrigation requirements for obtaining targeted submaximal yields, and the generation of crop-water production functions for varying irrigation waters, irrigation rates, and crops. Model predictions are shown to be mostly consistent with existing models and available experimental data. Yet the new solutions possess clear advantages over available alternatives, including: (i) the new solutions were derived from a complete physical-mathematical description of the system, rather than based on an ad hoc formulation; (ii) the new analytical solutions are explicit and can be evaluated without iterative techniques; (iii) the solutions permit consideration of two common functional forms of salinity induced reductions in crop water uptake, rather than being tied to one particular representation; and (iv) the utilized modeling framework is compatible with leading transient-state numerical models.

  2. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with (pyrazol-1-yl)acetic acid.

    PubMed

    Chen, Xiao-Yan; Goff, George S; Scott, Brian L; Janicke, Michael T; Runde, Wolfgang

    2013-03-18

    As a precursor of carboxyl-functionalized task-specific ionic liquids (TSILs) for f-element separations, (pyrazol-1-yl)acetic acid (L) can be deprotonated as a functionalized pyrazolate anion to coordinate with hard metal cations. However, the coordination chemistry of L with f-elements remains unexplored. We reacted L with lanthanides in aqueous solution at pH = 5 and synthesized four lanthanide complexes of general formula [Ln(L)3(H2O)2]·nH2O (1, Ln = La, n = 2; 2, Ln = Ce, n = 2; 3, Ln = Pr, n = 2; 4, Ln = Nd, n = 1). All complexes were characterized by single crystal X-ray diffraction analysis revealing one-dimensional chain formations. Two distinct crystallographic structures are governed by the different coordination modes of carboxylate groups in L: terminal bidentate and bridging tridentate (1-3); terminal bidentate, bridging bidentate, and tridentate coordination in 4. Comparison of the solid state UV-vis-NIR diffuse reflectance spectra with solution state UV-vis-NIR spectra suggests a different species in solution and solid state. The different coordination in solid state and solution was verified by distinctive (13)C NMR signals of the carboxylate groups in the solid state NMR.

  3. Solid-Solution Alloying of Immiscible Ru and Cu with Enhanced CO Oxidation Activity.

    PubMed

    Huang, Bo; Kobayashi, Hirokazu; Yamamoto, Tomokazu; Matsumura, Syo; Nishida, Yoshihide; Sato, Katsutoshi; Nagaoka, Katsutoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Kitagawa, Hiroshi

    2017-03-24

    We report on novel solid-solution alloy nanoparticles (NPs) of Ru and Cu that are completely immiscible even above melting point in bulk phase. Powder X-ray diffraction, scanning transmission electron microscopy, and energy-dispersive X-ray measurements demonstrated that Ru and Cu atoms were homogeneously distributed in the alloy NPs. Ru0.5Cu0.5 NPs demonstrated higher CO oxidation activity than fcc-Ru NPs, which are known as one of the best monometallic CO oxidation catalysts.

  4. Resistive switching behavior and multiple transmittance states in solution-processed tungsten oxide.

    PubMed

    Wu, Wei-Ting; Wu, Jih-Jen; Chen, Jen-Sue

    2011-07-01

    In this work, a tungsten oxide (WO(x)) film is prepared using a thiourea-assisted solution process. We demonstrate a device composed of fluorine doped tin oxide (FTO)-glass/WO(x)/electrolyte/indium-tin oxide (ITO)-glass stacking electrochromic (EC) structure and Al electrodes that are locally patterned and interposed between the WO(x) film and electrolyte, which form an Al(top electrode)/WO(x)/FTO(bottom electrode) resistance random access memory (RRAM) unit. According to transmission electron microscopy and X-ray photoelectron spectroscopy analyses, the WO(x) film contains nanosize pores and metallic-tungsten nanoclusters which are scattered within the tungsten oxide layer and concentrated along the interface between the Al electrode and WO(x) film. With application of voltage to the ITO electrode, multiple transmittance states are achieved for the EC unit due to the different quantity of intercalated Li ions in the WO(x) film. As for the Al/WO(x)/FTO RRAM unit, a bipolar nonvolatile resistive switching behavior is attained by applying voltage on the Al top electrode, showing electrical bistability with an ON/OFF current ratio up to 1 × 10(4).

  5. Two-lane traffic-flow model with an exact steady-state solution.

    PubMed

    Kanai, Masahiro

    2010-12-01

    We propose a stochastic cellular-automaton model for two-lane traffic flow based on the misanthrope process in one dimension. The misanthrope process is a stochastic process allowing for an exact steady-state solution; hence, we have an exact flow-density diagram for two-lane traffic. In addition, we introduce two parameters that indicate, respectively, driver's driving-lane preference and passing-lane priority. Due to the additional parameters, the model shows a deviation of the density ratio for driving-lane use and a biased lane efficiency in flow. Then, a mean-field approach explicitly describes the asymmetric flow by the hop rates, the driving-lane preference, and the passing-lane priority. Meanwhile, the simulation results are in good agreement with an observational data, and we thus estimate these parameters. We conclude that the proposed model successfully produces two-lane traffic flow particularly with the driving-lane preference and the passing-lane priority.

  6. Photosensitized degradation of acetaminophen in natural organic matter solutions: The role of triplet states and oxygen.

    PubMed

    Li, Yanyun; Pan, Yanheng; Lian, Lushi; Yan, Shuwen; Song, Weihua; Yang, Xin

    2017-02-01

    The photolysis of acetaminophen, a widely used pharmaceutical, in simulated natural organic matter solutions was investigated. The triplet states of natural organic matter ((3)NOM*) were found to play the dominant role in its photodegradation, while the contributions from hydroxyl radicals and singlet oxygen were negligible. Dissolved oxygen (DO) plays a dual role. From anaerobic to microaerobic (0.5 mg/L DO) conditions, the degradation rate of acetaminophen increased by 4-fold. That suggests the involvement of DO in reactions with the degradation intermediates. With increasing oxygen levels to saturated conditions (26 mg/L DO), the degradation rate became slower, mainly due to DO's quenching effect on (3)NOM*. Superoxide radical (O2(-)) did not react with acetaminophen directly, but possibly quenched the intermediates to reverse the degradation process. The main photochemical pathways were shown to involve phenoxyl radical and N-radical cations, finally yielding hydroxylated derivatives, dimers and nitrosophenol. A reaction mechanism involving (3)NOM*, oxygen and O2(-) is proposed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Self-assembly solid-state enhanced red emission of quinolinemalononitrile: optical waveguides and stimuli response.

    PubMed

    Shi, Chuanxing; Guo, Zhiqian; Yan, Yongli; Zhu, Shiqin; Xie, Yongshu; Zhao, Yong Sheng; Zhu, Weihong; Tian, He

    2013-01-01

    The fluorescence of luminescent emitters is often quenched in the solid state, because of the typical aggregation-caused quenching (ACQ) effect, which is a thorny obstacle to high-performance organic optoelectronic materials. The exploration of solid-state enhanced long wavelength, red-emitting chromophores, especially possessing one-dimensional (1D) assembly features, is of great importance. Interestingly, an excellent solid-state enhanced red emission system (denoted as ED) based on quinolinemalononitrile has been developed via the delicate modification of the conventional ACQ dicyanomethylene-4H-pyran (DCM) derivative (denoted as BD) through crystal engineering. ED exhibits extraordinary self-assembly property in a variety of solvents, even realizing the "waving ribbons" with a length of 6 mm and a diameter of 10 μm. Crystal analysis shows that the CH···π and CH···N supramolecular interactions of ED contribute to the twisted self-assembly solid-state enhanced emission phenomenon. However, for BD, strong face-to-face stacking leads to fluorescence quenching in the solid state. Because of such easy assembly and strong solid-state emission properties, application for optical waveguides of ED is realized with a low optical loss. Stimuli-responsive behavior is also elaborated with color change between orange and red by grinding/fuming or pressing/heating.

  8. Flow-enhanced solution printing of all-polymer solar cells

    DOE PAGES

    Diao, Ying; Zhou, Yan; Kurosawa, Tadanori; ...

    2015-08-12

    Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a similar to 90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhancedmore » all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. However, we expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.« less

  9. Hydrologic and biogeochemical controls of river subsurface solutes under agriculturally enhanced ground water flow

    USGS Publications Warehouse

    Wildman, R.A.; Domagalski, J.L.; Hering, J.G.

    2009-01-01

    The relative influences of hydrologic processes and biogeochemistry on the transport and retention of minor solutes were compared in the riverbed of the lower Merced River (California, USA). The subsurface of this reach receives ground water discharge and surface water infiltration due to an altered hydraulic setting resulting from agricultural irrigation. Filtered ground water samples were collected from 30 drive point locations in March, June, and October 2004. Hydrologic processes, described previously, were verified by observations of bromine concentrations; manganese was used to indicate redox conditions. The separate responses of the minor solutes strontium, barium, uranium, and phosphorus to these influences were examined. Correlation and principal component analyses indicate that hydrologic processes dominate the distribution of trace elements in the ground water. Redox conditions appear to be independent of hydrologic processes and account for most of the remaining data variability. With some variability, major processes are consistent in two sampling transects separated by 100 m. Copyright ?? 2009 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

  10. Characterization of Protein-Protein Interfaces in Large Complexes by Solid-State NMR Solvent Paramagnetic Relaxation Enhancements.

    PubMed

    Öster, Carl; Kosol, Simone; Hartlmüller, Christoph; Lamley, Jonathan M; Iuga, Dinu; Oss, Andres; Org, Mai-Liis; Vanatalu, Kalju; Samoson, Ago; Madl, Tobias; Lewandowski, Józef R

    2017-09-06

    Solid-state NMR is becoming a viable alternative for obtaining information about structures and dynamics of large biomolecular complexes, including ones that are not accessible to other high-resolution biophysical techniques. In this context, methods for probing protein-protein interfaces at atomic resolution are highly desirable. Solvent paramagnetic relaxation enhancements (sPREs) proved to be a powerful method for probing protein-protein interfaces in large complexes in solution but have not been employed toward this goal in the solid state. We demonstrate that (1)H and (15)N relaxation-based sPREs provide a powerful tool for characterizing intermolecular interactions in large assemblies in the solid state. We present approaches for measuring sPREs in practically the entire range of magic angle spinning frequencies used for biomolecular studies and discuss their benefits and limitations. We validate the approach on crystalline GB1, with our experimental results in good agreement with theoretical predictions. Finally, we use sPREs to characterize protein-protein interfaces in the GB1 complex with immunoglobulin G (IgG). Our results suggest the potential existence of an additional binding site and provide new insights into GB1:IgG complex structure that amend and revise the current model available from studies with IgG fragments. We demonstrate sPREs as a practical, widely applicable, robust, and very sensitive technique for determining intermolecular interaction interfaces in large biomolecular complexes in the solid state.

  11. Characterization of Protein–Protein Interfaces in Large Complexes by Solid-State NMR Solvent Paramagnetic Relaxation Enhancements

    PubMed Central

    2017-01-01

    Solid-state NMR is becoming a viable alternative for obtaining information about structures and dynamics of large biomolecular complexes, including ones that are not accessible to other high-resolution biophysical techniques. In this context, methods for probing protein–protein interfaces at atomic resolution are highly desirable. Solvent paramagnetic relaxation enhancements (sPREs) proved to be a powerful method for probing protein–protein interfaces in large complexes in solution but have not been employed toward this goal in the solid state. We demonstrate that 1H and 15N relaxation-based sPREs provide a powerful tool for characterizing intermolecular interactions in large assemblies in the solid state. We present approaches for measuring sPREs in practically the entire range of magic angle spinning frequencies used for biomolecular studies and discuss their benefits and limitations. We validate the approach on crystalline GB1, with our experimental results in good agreement with theoretical predictions. Finally, we use sPREs to characterize protein–protein interfaces in the GB1 complex with immunoglobulin G (IgG). Our results suggest the potential existence of an additional binding site and provide new insights into GB1:IgG complex structure that amend and revise the current model available from studies with IgG fragments. We demonstrate sPREs as a practical, widely applicable, robust, and very sensitive technique for determining intermolecular interaction interfaces in large biomolecular complexes in the solid state. PMID:28780861

  12. Comparative analysis of zaleplon complexation with cyclodextrins and hydrophilic polymers in solution and in solid state.

    PubMed

    Jablan, Jasna; Szalontai, Gábor; Jug, Mario

    2012-12-01

    The aim of this work was to investigate the potential synergistic effect of water-soluble polymers (hypromellose, HPMC and polyvinylpyrrolidone, PVP) on zaleplon (ZAL) complexation with parent β-cyclodextrin (βCD) and its randomly methylated derivative (RAMEB) in solution and in solid state. The addition of HPMC to the complexation medium improved ZAL complexation and solubilization with RAMEB (K(ZAL/RAMEB)=156±5M(-1) and K(ZAL/RAMEB/HPMC)=189±8M(-1); p<0.01), while such effect was not observed for βCD (K(ZAL/βCD)=112±2M(-1) and K(ZAL/βCD/HPMC)=119±8M(-1); p>0.05). Although PVP increased the ZAL aqueous solubility from 0.22 to 0.27mg/mL, it did not show any synergistic effects on ZAL solubilization with the cyclodextrins tested. Binary and ternary systems of ZAL with βCD, RAMEB and HPMC were prepared by spray-drying. Differential scanning calorimetry, X-ray powder diffraction and scanning electron microscopy demonstrated a partial ZAL amorphization in spray-dried binary and ternary systems with βCD, while the drug was completely amorphous in all samples with RAMEB. Furthermore, inclusion complex formation in all systems prepared was confirmed by solid-state NMR spectroscopy. The in vitro dissolution rate followed the rank order ZAL/RAMEB/HPMC>ZAL/RAMEB=ZAL/βCD/HPMC>ZAL/βCD≫ZAL, clearly demonstrating the superior performance of RAMEB on ZAL complexation in the solid state and its synergistic effect with HPMC on drug solubility. Surprisingly, when loaded into tablets made with insoluble microcrystalline cellulose, RAMEB complexes had no positive effect on drug dissolution, because HPMC and RAMEB acted as a binders inside the tablets, prolonging their disintegration. Oppositely, the formulation with mannitol, a soluble excipient, containing a ternary RAMEB system, released the complete drug-dose in only 5min, clearly demonstrating its suitability for the development of immediate-release oral formulation of ZAL.

  13. Branched truxene and triindole compounds and their solid-state luminescent enhancement

    NASA Astrophysics Data System (ADS)

    Du, Xianchao; Yuan, Mao-Sen; Xu, Fan; Wang, Hui; Wang, Qin; Wang, Wenji; Wang, Dong-En; Wang, Jinyi

    2016-07-01

    C3-symmetric truxene and triindole have been widely used to design the branched optoelectronic molecules. However, most of them exhibit high luminous efficiency in the solution and quenched luminescence in the solid state. Here, we respectively chose alkylated truxene and triindole as the central core, 2-methylphenyl as the peripheral functional groups to synthesize three branched compounds. Their photophysical properties have been explored combining with the theoretical calculation. The three compounds exhibit good solubility and high solid-state fluorescence quantum yields. The absorption and emission peaks of triindole compound exhibit apparent red-shift in comparison with those of truxene compounds, which indicates triindole more highly electron delocalization than truxene. The single-crystal structure shows that alkylation of the central core and branched steric bulkiness of these molecules effectively reduce the intermolecular π ⋯ π stacking and avoid the non-radiative transition of these molecules from excited state to ground state in the solid state.

  14. Enhanced active liposomal loading of a poorly soluble ionizable drug using supersaturated drug solutions.

    PubMed

    Modi, Sweta; Xiang, Tian-Xiang; Anderson, Bradley D

    2012-09-10

    Nanoparticulate drug carriers such as liposomal drug delivery systems are of considerable interest in cancer therapy because of their ability to passively accumulate in solid tumors. For liposomes to have practical utility for antitumor therapy in patients, however, optimization of drug loading, retention, and release kinetics are necessary. Active loading is the preferred method for optimizing loading of ionizable drugs in liposomes as measured by drug-to-lipid ratios, but the extremely low aqueous solubilities of many anticancer drug candidates may limit the external driving force, thus slowing liposomal uptake during active loading. This report demonstrates the advantages of maintaining drug supersaturation during active loading. A novel method was developed for creating and maintaining supersaturation of a poorly soluble camptothecin analogue, AR-67 (7-t-butyldimethylsilyl-10-hydroxycamptothecin), using a low concentration of a cyclodextrin (sulfobutylether-β-cyclodextrin) to inhibit crystallization over a 48 h period. Active loading into liposomes containing high concentrations of entrapped sodium or calcium acetate was monitored using drug solutions at varying degrees of supersaturation. Liposomal uptake rates increased linearly with the degree of supersaturation of drug in the external loading solution. A mathematical model was developed to predict the rate and extent of drug loading versus time, taking into account the chemical equilibria inside and outside of the vesicles and the transport kinetics of various permeable species across the lipid bilayer and the dialysis membrane. Intraliposomal sink conditions were maintained by the high internal pH caused by the efflux of acetic acid and exchange with AR-67, which undergoes lactone ring-opening, ionization, and membrane binding in the interior of the vesicles. The highest drug to lipid ratio achieved was 0.17 from a supersaturated solution at a total drug concentration of 0.6 mg/ml. The rate and extent of

  15. Ground-state charge transfer as a mechanism for surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Lippitsch, Max E.

    1984-03-01

    A model is presented for the contribution of ground-state charge transfer between a metal and adsorbate to surface-enhanced Raman scattering (SERS). It is shown that this contribution can be understood using the vibronic theory for calculating Raman intensities. The enhancement is due to vibronic coupling of the molecular ground state to the metal states, the coupling mechanism being a modulation of the ground-state charge-transfer energy by the molecular vibrations. An analysis of the coupling operator gives the selection rules for this process, which turn out to be dependent on the overall symmetry of the adsorbate-metal system, even if the charge transfer is small enough for the symmetry of the adsorbate to remain the same as that of the free molecule. It is shown that the model can yield predictions on the properties of SERS, e.g., specificity to adsorption geometry, appearance of forbidden bands, dependence on the applied potential, and dependence on the excitation wavelength. The predictions are in good agreement with experimental results. It is also deduced from this model that in many cases atomic-scale roughness is a prerequisite for the observation of SERS. A result on the magnitude of the enhancement can only be given in a crude approximation. Although in most cases an additional electromagnetic enhancement seems to be necessary to give an observable signal, this charge-transfer mechanism should be important in many SERS systems.

  16. Thermal lens spectrometry in aqueous solutions of Brij 35: investigation of micelle effects on the time-resolved and steady-state signals.

    PubMed

    Arnaud, N; Georges, J

    2001-04-01

    This work investigates the effect of micelles on the time-resolved and steady-state thermal lens signals in aqueous solutions. The temperature gradient produced subsequently to non-radiative relaxation of the sample induces migration of micelles towards the colder region of the irradiated area along with an opposite flow of solute molecules. This phenomenon, known as the Soret effect, produces an additional probe beam signal with a rise time that is much longer than the thermal time constant and depends on the surfactant and solute concentrations. Extrapolation of the mass-diffusion constant at zero solute concentration allowed the determination of diffusion coefficients that are close to those derived by other methods for Brij 35 micelles in water. It is also shown that the surfactant has only a small effect on the thermal lens signal and that the enhancement produced by micelles with respect to pure water originates mainly firom the Soret effect. It follows that interpretation of experimental data without discriminating both components of the probe beam signal can lead to erroneous values of dn/dT.

  17. Matching Solid-State to Solution-Phase Photoluminescence for Near-Unity Down-Conversion Efficiency Using Giant Quantum Dots.

    PubMed

    Hanson, Christina J; Buck, Matthew R; Acharya, Krishna; Torres, Joseph A; Kundu, Janardan; Ma, Xuedan; Bouquin, Sarah; Hamilton, Christopher E; Htoon, Han; Hollingsworth, Jennifer A

    2015-06-24

    Efficient, stable, and narrowband red-emitting fluorophores are needed as down-conversion materials for next-generation solid-state lighting that is both efficient and of high color quality. Semiconductor quantum dots (QDs) are nearly ideal color-shifting phosphors, but solution-phase efficiencies have not traditionally extended to the solid-state, with losses from both intrinsic and environmental effects. Here, we assess the impacts of temperature and flux on QD phosphor performance. By controlling QD core/shell structure, we realize near-unity down-conversion efficiency and enhanced operational stability. Furthermore, we show that a simple modification of the phosphor-coated light-emitting diode device-incorporation of a thin spacer layer-can afford reduced thermal or photon-flux quenching at high driving currents (>200 mA).

  18. THE VAPOUR PRESSURES OF AQUEOUS SOLUTIONS WITH SPECIAL REFERENCE TO THE PROBLEM OF THE STATE OF WATER IN BIOLOGICAL FLUIDS.

    PubMed

    Grollman, A

    1931-05-20

    DATA FOR THE DEPRESSION OF VAPOUR PRESSURE ARE PRESENTED FOR THE FOLLOWING AQUEOUS SOLUTIONS: NaCl (0.03 to 0.1 molar), KCl (0.03 to 0.1 molar), urea (0.05 to 0.5 molar), sucrose (0.05 to 0.10 molar), lactic and succinic acids, creatine, CaCl(2) (0.05 molar), and mixtures of these substances with one another and with certain other solutions (gelatin, gum acacia, sea water, LiCl, etc.). The relation of the depression of vapour pressure of a mixed solution to that of solutions of the individual constituents was investigated in order to ascertain to what extent such studies may be used for the determination of the degree of hydration, or of the state of water, in solutions. Organic substances (urea, sucrose, etc.) showed anomalous results which were markedly affected and unpredictable in mixed solutions. They are, therefore, unsuited for the study of water binding. In the case of solutions of inorganic substances-LiCl and CaCl(2)-the principle of the additive nature of colligative properties is also only approximately true-except perhaps in very dilute solutions. The limitations of the colligative method for determining the degree of hydration have been defined in accord with the above findings. Studies of the vapour pressures of mixtures of gelatin or gum acacia with NaCl or KCl demonstrated that hydration in gelatin is relatively small at pH = 7 and undetectable in gum acacia solutions. The view, therefore, that hydrophilic colloids are strongly hydrated has not been substantiated. The passage from the sol to the gel state also was not accompanied in gelatin or in blood by any appreciable change in the degree of hydration of the hydrophilic colloids present in these substances.

  19. THE VAPOUR PRESSURES OF AQUEOUS SOLUTIONS WITH SPECIAL REFERENCE TO THE PROBLEM OF THE STATE OF WATER IN BIOLOGICAL FLUIDS

    PubMed Central

    Grollman, Arthur

    1931-01-01

    Data for the depression of vapour pressure are presented for the following aqueous solutions: NaCl (0.03 to 0.1 molar), KCl (0.03 to 0.1 molar), urea (0.05 to 0.5 molar), sucrose (0.05 to 0.10 molar), lactic and succinic acids, creatine, CaCl2 (0.05 molar), and mixtures of these substances with one another and with certain other solutions (gelatin, gum acacia, sea water, LiCl, etc.). The relation of the depression of vapour pressure of a mixed solution to that of solutions of the individual constituents was investigated in order to ascertain to what extent such studies may be used for the determination of the degree of hydration, or of the state of water, in solutions. Organic substances (urea, sucrose, etc.) showed anomalous results which were markedly affected and unpredictable in mixed solutions. They are, therefore, unsuited for the study of water binding. In the case of solutions of inorganic substances—LiCl and CaCl2—the principle of the additive nature of colligative properties is also only approximately true—except perhaps in very dilute solutions. The limitations of the colligative method for determining the degree of hydration have been defined in accord with the above findings. Studies of the vapour pressures of mixtures of gelatin or gum acacia with NaCl or KCl demonstrated that hydration in gelatin is relatively small at pH = 7 and undetectable in gum acacia solutions. The view, therefore, that hydrophilic colloids are strongly hydrated has not been substantiated. The passage from the sol to the gel state also was not accompanied in gelatin or in blood by any appreciable change in the degree of hydration of the hydrophilic colloids present in these substances. PMID:19872614

  20. Enhancement of Vibronic and Ground-State Vibrational Coherences in 2D Spectra of Photosynthetic Complexes

    PubMed Central

    Chenu, Aurélia; Christensson, Niklas; Kauffmann, Harald F.; Mančal, Tomáš

    2013-01-01

    A vibronic-exciton model is applied to investigate the recently proposed mechanism of enhancement of coherent oscillations due to mixing of electronic and nuclear degrees of freedom. We study a dimer system to elucidate the role of resonance coupling, site energies, vibrational frequency and energy disorder in the enhancement of vibronic-exciton and ground-state vibrational coherences, and to identify regimes where this enhancement is significant. For a heterodimer representing two coupled bachteriochloropylls of the FMO complex, long-lived vibronic coherences are found to be generated only when the frequency of the mode is in the vicinity of the electronic energy difference. Although the vibronic-exciton coherences exhibit a larger initial amplitude compared to the ground-state vibrational coherences, we conclude that, due to the dephasing of the former, both type of coherences have a similar magnitude at longer population time. PMID:23778355