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Sample records for complex mg-ni-la-co-h phases

  1. Griffiths Phases on Complex Networks

    NASA Astrophysics Data System (ADS)

    Muñoz, Miguel A.; Juhász, Róbert; Castellano, Claudio; Ódor, Géza

    2010-09-01

    Quenched disorder is known to play a relevant role in dynamical processes and phase transitions. Its effects on the dynamics of complex networks have hardly been studied. Aimed at filling this gap, we analyze the contact process, i.e., the simplest propagation model, with quenched disorder on complex networks. We find Griffiths phases and other rare-region effects, leading rather generically to anomalously slow (algebraic, logarithmic, …) relaxation, on Erdős-Rényi networks. Similar effects are predicted to exist for other topologies with a finite percolation threshold. More surprisingly, we find that Griffiths phases can also emerge in the absence of quenched disorder, as a consequence of topological heterogeneity in networks with finite topological dimension. These results have a broad spectrum of implications for propagation phenomena and other dynamical processes on networks.

  2. Phase distribution in complex geometry conduits

    SciTech Connect

    Lahey, R.T. Jr.; Lopez de Bertodano, M.; Jones, O.C. Jr.

    1992-12-31

    Some of the most important and challenging problems in two-phase flow today have to do with the understanding and prediction of multidimensional phenomena, in particular, lateral phase distribution in both simple and complex geometry conduits. A prior review paper summarized the state-of-the-art in the understanding of phase distribution phenomena, and the ability to perform mechanistic multidimensional predictions. The purpose of this paper is to update that review, with particular emphasis on complex geometry conduit predictive capabilities.

  3. Simulating Complex Modulated Phases Through Spin Models

    NASA Astrophysics Data System (ADS)

    Selinger, Jonathan V.; Lopatina, Lena M.; Geng, Jun; Selinger, Robin L. B.

    2009-03-01

    We extend the computational approach for studying striped phases on curved surfaces, presented in the previous talk, to two new problems involving complex modulated phases. First, we simulate a smectic liquid crystal on an arbitrary mesh by mapping the director field onto a vector spin and the density wave onto an Ising spin. We can thereby determine how the smectic phase responds to any geometrical constraints, including hybrid boundary conditions, patterned substrates, and disordered substrates. This method may provide a useful tool for designing ferroelectric liquid crystal cells. Second, we explore a model of vector spins on a flat two-dimensional (2D) lattice with long-range antiferromagnetic interactions. This model generates modulated phases with surprisingly complex structures, including 1D stripes and 2D periodic cells, which are independent of the underlying lattice. We speculate on the physical significance of these structures.

  4. Solid-phase preparation of protein complexes.

    PubMed

    Pengo, Paolo; Veggiani, Gianluca; Rattanamanee, Kwanchai; Gallotta, Andrea; Beneduce, Luca; Fassina, Giorgio

    2010-01-01

    Protein-protein conjugation is usually achieved by solution phase methods requiring concentrated protein solution and post-synthetic purification steps. In this report we describe a novel continuous-flow solid-phase approach enabling the assembly of protein complexes minimizing the amount of material needed and allowing the repeated use of the same solid phase. The method exploits an immunoaffinity matrix as solid support; the matrix reversibly binds the first of the complex components while the other components are sequentially introduced, thus allowing the complex to grow while immobilized. The tethering technique employed relies on the use of the very mild synthetic conditions and fast association rates allowed by the avidin-biotin system. At the end of the assembly, the immobilized complexes can be removed from the solid support and recovered by lowering the pH of the medium. Under the conditions used for the sequential complexation and recovery, the solid phase was not damaged or irreversibly modified and could be reused without loss of binding capacity. The method was specifically designed to prepare protein complexes to be used in immunometric methods of analysis, where the immunoreactivity of each component needs to be preserved. The approach was successfully exploited for the preparation of two different immunoaffinity reagents with immunoreactivity mimicking native squamous cell carcinoma antigen-immunoglobulin M (SCCA-IgM) and alphafetoprotein-immunoglobulin M (AFP-IgM) immune complexes, which were characterized by dedicated sandwich enzyme-linked immunosorbent assay (ELISA) and immunoblot. Besides the specific application described in the paper, the method is sufficiently general to be used for the preparation of a broad range of protein assemblies. PMID:21038355

  5. Phase equilibria for complex fluid mixtures

    SciTech Connect

    Prausnitz, J.M.

    1983-04-01

    After defining complex mixtures, attention is given to the canonical procedure used for the thermodynamics of fluid mixtures: first, we establish a suitable, idealized reference system and then we establish a perturbation (or excess function) which corrects the idealized system for real behavior. For complex mixtures containing identified components (e.g. alcohols, ketones, water) discussion is directed at possible techniques for extending to complex mixtures our conventional experience with reference systems and perturbations for simple mixtures. Possible extensions include generalization of the quasi-chemical approximation (local compositions) and superposition of chemical equilibria (association and solvation) on a physical equation of state. For complex mixtures containing unidentified components (e.g. coal-derived fluids), a possible experimental method is suggested for characterization; conventional procedures can then be used to calculate phase equilibria using the concept of pseudocomponents whose properties are given by the characterization data. Finally, as an alternative to the pseudocomponent method, a brief introduction is given to phase-equilibrium calculations using continuous thermodynamics.

  6. Thermoelectric Properties of Complex Zintl Phases

    NASA Astrophysics Data System (ADS)

    Snyder, G. Jeffrey

    2008-03-01

    Complex Zintl phases make ideal thermoelectric materials because they can exhibit the necessary ``electron-crystal, phonon-glass'' properties required for high thermoelectric efficiency. Complex crystal structures can lead to high thermoelectric figure of merit (zT) by having extraordinarily low lattice thermal conductivity. A recent example is the discovery that Yb14MnSb11, a complex Zintl compound, has twice the zT as the SiGe based material currently in use at NASA. The high temperature (300K - 1300K) electronic properties of Yb14MnSb11 can be understood using models for heavily doped semiconductors. The free hole concentration, confirmed by Hall effect measurements, is set by the electron counting rules of Zintl and the valence of the transition metal (Mn^+2). Substitution of nonmagnetic Zn^+2 for the magnetic Mn^+2 reduces the spin-disorder scattering and leads to increased zT (10%). The reduction of spin-disorder scattering is consistent with the picture of Yb14MnSb11 as an underscreened Kondo lattice as derived from low temperature measurements. The hole concentration can be reduced by the substitution of Al^+3 for Mn^+2, which leads to an increase in the Seebeck coefficient and electrical resistivity consistent with models for degenerate semiconductors. This leads to further improvements (about 25%) in zT and a reduction in the temperature where the zT peaks. The peak in zT is due to the onset of minority carrier conduction and can be correlated with reduction in Seebeck coefficient, increase in electrical conductivity and increase in thermal conductivity due to bipolar thermal conduction.

  7. Phase Behavior of Complex Superprotonic Solid Acids

    NASA Astrophysics Data System (ADS)

    Panithipongwut, Chatr

    Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4) 2-RbHSO4 system, Rb3H(SeO4)2-Cs 3H(SeO4)2 solid solution system, and Cs6 (H2SO4)3(H1.5PO4) 4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems. Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO 4 and the previously unknown compound Rb5H3(SO 4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3m of Cs5H 3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity. The compounds Rb3H(SeO4)2 and Cs 3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member. The compound Cs6(H2

  8. Complex phase behavior induced by repulsive interactions

    PubMed

    Velasco; Mederos; Navascues; Hemmer; Stell

    2000-07-01

    For a solid in which the interactions have a hard core plus a simple soft repulsive tail we show, using a perturbation theory, that the possible stable crystalline structures give rise to a rich phase behavior. We find two concomitant critical points each corresponding to phase transitions separating bcc and fcc structures, respectively, and the occurrence of a transition between fcc and bcc phases without change in density. This novel phenomenology may be relevant to the behavior of some metallic systems, colloids, and to water. PMID:10991174

  9. Complexities of One-Component Phase Diagrams

    ERIC Educational Resources Information Center

    Ciccioli, Andrea; Glasser, Leslie

    2011-01-01

    For most materials, the solid at and near the triple-point temperature is denser than the liquid with which it is in equilibrium. However, for water and certain other materials, the densities of the phases are reversed, with the solid being less dense. The profound consequences for the appearance of the "pVT" diagram of one-component materials…

  10. Dual-phase evolution in complex adaptive systems

    PubMed Central

    Paperin, Greg; Green, David G.; Sadedin, Suzanne

    2011-01-01

    Understanding the origins of complexity is a key challenge in many sciences. Although networks are known to underlie most systems, showing how they contribute to well-known phenomena remains an issue. Here, we show that recurrent phase transitions in network connectivity underlie emergent phenomena in many systems. We identify properties that are typical of systems in different connectivity phases, as well as characteristics commonly associated with the phase transitions. We synthesize these common features into a common framework, which we term dual-phase evolution (DPE). Using this framework, we review the literature from several disciplines to show that recurrent connectivity phase transitions underlie the complex properties of many biological, physical and human systems. We argue that the DPE framework helps to explain many complex phenomena, including perpetual novelty, modularity, scale-free networks and criticality. Our review concludes with a discussion of the way DPE relates to other frameworks, in particular, self-organized criticality and the adaptive cycle. PMID:21247947

  11. Chirality-selected phase behaviour in ionic polypeptide complexes

    SciTech Connect

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, III, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-14

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

  12. Chirality-selected phase behaviour in ionic polypeptide complexes

    DOE PAGESBeta

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, III, Charles F.; Margossian, Khatcher O.; et al

    2015-01-14

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

  13. Chirality-selected phase behaviour in ionic polypeptide complexes

    PubMed Central

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-01

    Polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation. PMID:25586861

  14. Chirality-selected phase behaviour in ionic polypeptide complexes

    NASA Astrophysics Data System (ADS)

    Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; Kade, Matthew J.; Priftis, Dimitrios; Black, Katie A.; Wong, Derek; Klein, Ryan A.; Pierce, Charles F.; Margossian, Khatcher O.; Whitmer, Jonathan K.; Qin, Jian; de Pablo, Juan J.; Tirrell, Matthew

    2015-01-01

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

  15. Phase sensitivity of complex cells in primary visual cortex.

    PubMed

    Hietanen, M A; Cloherty, S L; van Kleef, J P; Wang, C; Dreher, B; Ibbotson, M R

    2013-05-01

    Neurons in the primary visual cortex are often classified as either simple or complex based on the linearity (or otherwise) of their response to spatial luminance contrast. In practice, classification is typically based on Fourier analysis of a cell's response to an optimal drifting sine-wave grating. Simple cells are generally considered to be linear and produce responses modulated at the fundamental frequency of the stimulus grating. In contrast, complex cells exhibit significant nonlinearities that reduce the response at the fundamental frequency. Cells can therefore be easily and objectively classified based on the relative modulation of their responses - the ratio of the phase-sensitive response at the fundamental frequency of the stimulus (F₁) to the phase-invariant sustained response (F₀). Cells are classified as simple if F₁/F₀>1 and complex if F₁/F₀<1. This classification is broadly consistent with criteria based on the spatial organisation of cells' receptive fields and is accordingly presumed to reflect disparate functional roles of simple and complex cells in coding visual information. However, Fourier analysis of spiking responses is sensitive to the number of spikes available - F₁/F₀ increases as the number of spikes is reduced, even for phase-invariant complex cells. Moreover, many complex cells encountered in the laboratory exhibit some phase sensitivity, evident as modulation of their responses at the fundamental frequency. There currently exists no objective quantitative means of assessing the significance or otherwise of these modulations. Here we derive a statistical basis for objectively assessing whether the modulation of neuronal responses is reliable, thereby adding a level of statistical certainty to measures of phase sensitivity. We apply our statistical analysis to neuronal responses to moving sine-wave gratings recorded from 367 cells in cat primary visual cortex. We find that approximately 60% of complex cells exhibit

  16. Molecular Complexation and Phase Diagrams of Urea/PEG Mixtures

    NASA Astrophysics Data System (ADS)

    Fu, Guoepeng; Kyu, Thein

    2014-03-01

    Polyethylene glycol (PEG) and urea complexation has been known to form a stable crystal due to molecular complexation. The effect of molecular weight of PEG on the phase diagrams of its blends with urea has been explored. In the case of high molecular weight PEG8k/urea, the observed phase diagram is azeotrope, accompanied by eutectoid reactions in the submerged phases such as induced stable ``alpha'' phase crystals and metastable ``beta'' phase crystals. The metastable crystal can transform to stable crystal under a certain thermal annealing condition. However, the phase diagram of PEG1k/urea is of coexistence loop, whereas PEG400/urea exhibits eutectic character. Subsequently, the change of azeotrope to eutectic behavior with PEG molecular weight is analyzed in the context of the combined Flory-Huggins theory of liquid-liquid demixing and phase field theory of crystal solidification. Of particular interest is that only a very small urea amount (2 wt%) is needed to form a stable inclusion crystal via complexation with PEG. Potential application in lithium battery is discussed based on AC impedance spectroscopy and cyclic voltammetry. Supported by NSF-DMR 1161070.

  17. Phase Transitions in Nanostructured Polyelectrolyte-Surfactant Complexes

    NASA Astrophysics Data System (ADS)

    Leonard, Michael; Strey, Helmut

    2001-03-01

    When a water-soluble polyelectrolyte is combined with an oppositely-charged surfactant solution at a stoichiometric charge ratio, self-assembly into highly-ordered, water-insoluble structures occurs. We have prepared such complexes with poly(sodium acrylate)-co-acrylamide, alginic acid, and chitosan, combined with cationic and anionic surfactants. The phases exhibited by these complexes in aqueous solution are highly sensitive to such factors as osmotic pressure, salt type, ionic strength, and polyelectrolyte charge density. In this study, we have used small angle X-ray scattering to examine osmotic stress-induced structural phase transitions in these complexes under these various environmental conditions. The morphological consequences of combining polyelectrolytes with swollen, emulsion-bound surfactant micelles were also investigated. Results of this work, as well as the potential to use these complexes as nanoporous, biocompatible materials, will be discussed.

  18. Phase-retrieval ghost imaging of complex-valued objects

    SciTech Connect

    Gong Wenlin; Han Shensheng

    2010-08-15

    An imaging approach, based on ghost imaging, is reported to recover a pure-phase object or a complex-valued object. Our analytical results, which are backed up by numerical simulations, demonstrate that both the complex-valued object and its amplitude-dependent part can be separately and nonlocally reconstructed using this approach. Both effects influencing the quality of reconstructed images and methods to further improve the imaging quality are also discussed.

  19. Complexes of in-phase two-dimensional laser solitons

    SciTech Connect

    Rosanov, N N; Fedorov, S V; Shatsev, A N

    2008-01-31

    The structure and motion of complexes of in-phase weakly coupled fundamental solitons in a wide-aperture class A laser with saturable absorption are analysed. The symmetry of the field distribution and its relation to the motion of the complex are studied. Due to the absence of wavefront dislocations in such complexes, the transverse radiation intensity and phase distributions are the symmetry objects, which simplifies analysis compared to the case when wavefront dislocations are present. Four types of the motion of soliton complexes are demonstrated: a motionless complex in the presence of two mirror symmetry axes; linear motion of the complex when only one mirror symmetry axis exists; rotation around a motionless centre of inertia in the absence of the mirror symmetry axis and in the presence of symmetry with respect to rotation through the angle 2{pi}/M (M is an integer); and curvilinear (circular) motion of the centre of inertia and simultaneous rotation of the complex around the instantaneous position of the centre of inertia in the absence of symmetry elements. (nonlinear optical phenomena)

  20. Chirality-selected phase behavior in ionic polypeptide complexes

    NASA Astrophysics Data System (ADS)

    Tirrell, Matthew

    2015-03-01

    We demonstrate that chirality determines the phase state of polyelectrolyte complexes formed from mixing dilute solutions of oppositely charged polypeptides. In these systems, the physical state of the resultant complex is determined by the combination of electrostatic and hydrogen bonding interactions. The formation of fluid complexes occurs when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with a β-sheet structure on mixing. Analogous behavior occurs in micellar cores formed from polypeptide block copolymers with polyethylene oxide, where microphase separation into discrete, self-assembled aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in systems based on polyelectrolyte complexation. Its role in these systems gives insight into polyelectrolyte complex phase behavior more broadly. This work was supported by the U.S. Department of Energy Office of Science Program in Basic Energy Sciences, Materials Sciences and Engineering Division.

  1. Phase effects in masking by harmonic complexes: Speech recognition

    PubMed Central

    Deroche, Mickael L. D.; Culling, John F.; Chatterjee, Monita

    2013-01-01

    Harmonic complexes that generate highly modulated temporal envelopes on the basilar membrane (BM) mask a tone less effectively than complexes that generate relatively flat temporal envelopes, because the non-linear active gain of the BM selectively amplifies a low-level tone in the dips of a modulated masker envelope. The present study examines a similar effect in speech recognition. Speech reception thresholds (SRTs) were measured for a voice masked by harmonic complexes with partials in sine phase (SP) or in random phase (RP). The masker’s fundamental frequency (F0) was 50, 100 or 200 Hz. SRTs were considerably lower for SP than for RP maskers at 50-Hz F0, but the two converged at 100-Hz F0, while at 200-Hz F0, SRTs were a little higher for SP than RP maskers. The results were similar whether the target voice was male or female and whether the masker’s spectral profile was flat or speech-shaped. Although listening in the masker dips has been shown to play a large role for artificial stimuli such as Schroeder-phase complexes at high levels, it contributes weakly to speech recognition in the presence of harmonic maskers with different crest factors at more moderate sound levels (65 dB SPL). PMID:24076425

  2. Using Neural Networks to Describe Complex Phase Transformation Behavior

    SciTech Connect

    Vitek, J.M.; David, S.A.

    1999-05-24

    Final microstructures can often be the end result of a complex sequence of phase transformations. Fundamental analyses may be used to model various stages of the overall behavior but they are often impractical or cumbersome when considering multicomponent systems covering a wide range of compositions. Neural network analysis may be a useful alternative method of identifying and describing phase transformation beavior. A neural network model for ferrite prediction in stainless steel welds is described. It is shown that the neural network analysis provides valuable information that accounts for alloying element interactions. It is suggested that neural network analysis may be extremely useful for analysis when more fundamental approaches are unavailable or overly burdensome.

  3. Complex PTSD and phased treatment in refugees: a debate piece

    PubMed Central

    ter Heide, F. Jackie June; Mooren, Trudy M.; Kleber, Rolf J.

    2016-01-01

    Background Asylum seekers and refugees have been claimed to be at increased risk of developing complex posttraumatic stress disorder (complex PTSD). Consequently, it has been recommended that refugees be treated with present-centred or phased treatment rather than stand-alone trauma-focused treatment. This recommendation has contributed to a clinical practice of delaying or waiving trauma-focused treatment in refugees with PTSD. Objective The aim of this debate piece is to defend two theses: (1) that complex trauma leads to complex PTSD in a minority of refugees only and (2) that trauma-focused treatment should be offered to all refugees who seek treatment for PTSD. Methods The first thesis is defended by comparing data on the prevalence of complex PTSD in refugees to those in other trauma-exposed populations, using studies derived from a systematic review. The second thesis is defended using conclusions of systematic reviews and a meta-analysis of the efficacy of psychotherapeutic treatment in refugees. Results Research shows that refugees are more likely to meet a regular PTSD diagnosis or no diagnosis than a complex PTSD diagnosis and that prevalence of complex PTSD in refugees is relatively low compared to that in survivors of childhood trauma. Effect sizes for trauma-focused treatment in refugees, especially narrative exposure therapy (NET) and culturally adapted cognitive-behaviour therapy (CA-CBT), have consistently been found to be high. Conclusions Complex PTSD in refugees should not be assumed to be present on the basis of complex traumatic experiences but should be carefully diagnosed using a validated interview. In line with treatment guidelines for PTSD, a course of trauma-focused treatment should be offered to all refugees seeking treatment for PTSD, including asylum seekers. PMID:26886486

  4. Luttinger liquid with complex forward scattering: Robustness and Berry phase

    NASA Astrophysics Data System (ADS)

    Dóra, Balázs; Moessner, Roderich

    2016-02-01

    Luttinger liquids (LLs) are one-dimensional systems with well-understood instabilities due to Umklapp or backscattering. We study a generalization of the Luttinger model, which incorporates a time reversal symmetry breaking interaction producing a complex forward scattering amplitude (g2 process). The resulting low energy state is still a LL and belongs to the family of interacting Schulz-Shastry models. Remarkably, it becomes increasingly robust against additional perturbations—for purely imaginary g2, both Umklapp and local backscattering are always irrelevant. Changing the phase of the interaction generates a nontrivial Berry phase, with a universal geometric phase difference between ground and a one boson excited state depending only on the LL parameter.

  5. Enlightening intracellular complexity of living cells with quantitative phase microscopy

    NASA Astrophysics Data System (ADS)

    Martinez Torres, C.; Laperrousaz, B.; Berguiga, L.; Boyer Provera, E.; Elezgaray, J.; Nicolini, F. E.; Maguer-Satta, V.; Arneodo, A.; Argoul, F.

    2016-03-01

    The internal distribution of refractive indices (RIs) of a living cell is much more complex than usually admitted in multi-shell models. The reconstruction of RI maps from single phase images has rarely been achieved for several reasons: (i) we still have very little knowledge of the impact of internal macromolecular complexes on the local RI and (ii) phase changes produced by light propagation through the sample are mixed with diffraction effects by internal cell bodies. We propose the implementation a 2D wavelet-based contour chain detection method to distinguish internal boundaries thanks to their greatest optical path difference gradients. These contour chains correspond to the highest image phase contrast and follow the local RI inhomogeneities linked to the intracellular structural intricacy. Their statistics and spatial distribution are morphological indicators for distinguishing cells of different origins and to follow their transformation in pathologic situations. We use this method to compare non adherent blood cells from primary and laboratory culture origins, in healthy and pathological situations (chronic myelogenous leukaemia). In a second part of this presentation, we concentrate on the temporal dynamics of the phase contour chains and we discuss the spectral decomposition of their dynamics in both health and disease.

  6. Electrical switching to probe complex phases in a frustrated manganite

    NASA Astrophysics Data System (ADS)

    Asthana, Saket; Fujiwara, Kohei; Tanaka, Hidekazu

    2014-06-01

    Electrical switching was used to investigate complex phases induced by Cr-substitution in (Pr1/3Sm2/3)2/3Sr1/3MnO3. This system was expected to transform from a Type I (Mn4+/Mn3+≈3/7) to Type II (Mn4+/Mn3+≈1) manganite at critical Cr content, satisfying a virtual Mn4+/Mn3+ ratio close to unity. The phase diagram of (Pr1/3Sm2/3)2/3Sr1/3Mn0.8Cr0.2O3 including charge/spin ordered/disordered phases was probed by electrical switching. The ferromagnetic insulating phase at <~100 K, located next to the charge-ordered antiferromagnetic phase, exhibited a sudden rise in conductivity upon electric-field biasing. This resulted from the melting of charge ordering, and demonstrated the presence of a crossover regime of two coexisting magnetic orderings.

  7. Nucleic Acid-Peptide Complex Phase Controlled by DNA Hybridization

    NASA Astrophysics Data System (ADS)

    Vieregg, Jeffrey; Lueckheide, Michael; Leon, Lorraine; Marciel, Amanda; Tirrell, Matthew

    When polyanions and polycations are mixed, counterion release drives formation of polymer-rich complexes that can either be solid (precipitates) or liquid (coacervates) depending on the properties of the polyelectrolytes. These complexes are important in many fields, from encapsulation of industrial polymers to membrane-free segregation of biomolecules such as nucleic acids and proteins. Condensation of long double-stranded DNA has been studied for several decades, but comparatively little attention has been paid to the polyelectrolyte behavior of oligonucleotides. We report here studies of DNA oligonucleotides (10 - 88 nt) complexed with polylysine (10 - 100 aa). Unexpectedly, we find that the phase of the resulting complexes is controlled by the hybridization state of the nucleic acid, with double-stranded DNA forming precipitates and single-stranded DNA forming coacervates. Stability increases with polyelectrolyte length and decreases with solution salt concentration, with complexes of the longer double-stranded polymers undergoing precipitate/coacervate/soluble transitions as ionic strength is increased. Mixing coacervates formed by complementary single-stranded oligonucleotides results in precipitate formation, raising the possibility of stimulus-responsive material design.

  8. Complex quantum network geometries: Evolution and phase transitions

    NASA Astrophysics Data System (ADS)

    Bianconi, Ginestra; Rahmede, Christoph; Wu, Zhihao

    2015-08-01

    Networks are topological and geometric structures used to describe systems as different as the Internet, the brain, or the quantum structure of space-time. Here we define complex quantum network geometries, describing the underlying structure of growing simplicial 2-complexes, i.e., simplicial complexes formed by triangles. These networks are geometric networks with energies of the links that grow according to a nonequilibrium dynamics. The evolution in time of the geometric networks is a classical evolution describing a given path of a path integral defining the evolution of quantum network states. The quantum network states are characterized by quantum occupation numbers that can be mapped, respectively, to the nodes, links, and triangles incident to each link of the network. We call the geometric networks describing the evolution of quantum network states the quantum geometric networks. The quantum geometric networks have many properties common to complex networks, including small-world property, high clustering coefficient, high modularity, and scale-free degree distribution. Moreover, they can be distinguished between the Fermi-Dirac network and the Bose-Einstein network obeying, respectively, the Fermi-Dirac and Bose-Einstein statistics. We show that these networks can undergo structural phase transitions where the geometrical properties of the networks change drastically. Finally, we comment on the relation between quantum complex network geometries, spin networks, and triangulations.

  9. Generalizing the Boltzmann equation in complex phase space.

    PubMed

    Zadehgol, Abed

    2016-08-01

    In this work, a generalized form of the BGK-Boltzmann equation is proposed, where the velocity, position, and time can be represented by real or complex variables. The real representation leads to the conventional BGK-Boltzmann equation, which can recover the continuity and Navier-Stokes equations. We show that the complex representation yields a different set of equations, and it can also recover the conservation and Navier-Stokes equations, at low Mach numbers, provided that the imaginary component of the macroscopic mass can be neglected. We briefly review the Constant Speed Kinetic Model (CSKM), which was introduced in Zadehgol and Ashrafizaadeh [J. Comp. Phys. 274, 803 (2014)JCTPAH0021-999110.1016/j.jcp.2014.06.053] and Zadehgol [Phys. Rev. E 91, 063311 (2015)PLEEE81539-375510.1103/PhysRevE.91.063311]. The CSKM is then used as a basis to show that the complex-valued equilibrium distribution function of the present model can be identified with a simple singularity in the complex phase space. The virtual particles, in the present work, are concentrated on virtual "branes" which surround the computational nodes. Employing the Cauchy integral formula, it is shown that certain variations of the "branes," in the complex phase space, do not affect the local kinetic states. This property of the new model, which is referred to as the "apparent jumps" in the present work, is used to construct new models. The theoretical findings have been tested by simulating three benchmark flows. The results of the present simulations are in excellent agreement with the previous results reported by others. PMID:27627421

  10. Phase-separation models for swimming enhancement in complex fluids

    NASA Astrophysics Data System (ADS)

    Man, Yi; Lauga, Eric

    2015-08-01

    Swimming cells often have to self-propel through fluids displaying non-Newtonian rheology. While past theoretical work seems to indicate that stresses arising from complex fluids should systematically hinder low-Reynolds number locomotion, experimental observations suggest that locomotion enhancement is possible. In this paper we propose a physical mechanism for locomotion enhancement of microscopic swimmers in a complex fluid. It is based on the fact that microstructured fluids will generically phase-separate near surfaces, leading to the presence of low-viscosity layers, which promote slip and decrease viscous friction near the surface of the swimmer. We use two models to address the consequence of this phase separation: a nonzero apparent slip length for the fluid and then an explicit modeling of the change of viscosity in a thin layer near the swimmer. Considering two canonical setups for low-Reynolds number locomotion, namely the waving locomotion of a two-dimensional sheet and that of a three-dimensional filament, we show that phase-separation systematically increases the locomotion speeds, possibly by orders of magnitude. We close by confronting our predictions with recent experimental results.

  11. Phase-separation models for swimming enhancement in complex fluids.

    PubMed

    Man, Yi; Lauga, Eric

    2015-08-01

    Swimming cells often have to self-propel through fluids displaying non-Newtonian rheology. While past theoretical work seems to indicate that stresses arising from complex fluids should systematically hinder low-Reynolds number locomotion, experimental observations suggest that locomotion enhancement is possible. In this paper we propose a physical mechanism for locomotion enhancement of microscopic swimmers in a complex fluid. It is based on the fact that microstructured fluids will generically phase-separate near surfaces, leading to the presence of low-viscosity layers, which promote slip and decrease viscous friction near the surface of the swimmer. We use two models to address the consequence of this phase separation: a nonzero apparent slip length for the fluid and then an explicit modeling of the change of viscosity in a thin layer near the swimmer. Considering two canonical setups for low-Reynolds number locomotion, namely the waving locomotion of a two-dimensional sheet and that of a three-dimensional filament, we show that phase-separation systematically increases the locomotion speeds, possibly by orders of magnitude. We close by confronting our predictions with recent experimental results. PMID:26382500

  12. Quantum trajectories in complex phase space: multidimensional barrier transmission.

    PubMed

    Wyatt, Robert E; Rowland, Brad A

    2007-07-28

    The quantum Hamilton-Jacobi equation for the action function is approximately solved by propagating individual Lagrangian quantum trajectories in complex-valued phase space. Equations of motion for these trajectories are derived through use of the derivative propagation method (DPM), which leads to a hierarchy of coupled differential equations for the action function and its spatial derivatives along each trajectory. In this study, complex-valued classical trajectories (second order DPM), along which is transported quantum phase information, are used to study low energy barrier transmission for a model two-dimensional system involving either an Eckart or Gaussian barrier along the reaction coordinate coupled to a harmonic oscillator. The arrival time for trajectories to reach the transmitted (product) region is studied. Trajectories launched from an "equal arrival time surface," defined as an isochrone, all reach the real-valued subspace in the transmitted region at the same time. The Rutherford-type diffraction of trajectories around poles in the complex extended Eckart potential energy surface is described. For thin barriers, these poles are close to the real axis and present problems for computing the transmitted density. In contrast, for the Gaussian barrier or the thick Eckart barrier where the poles are further from the real axis, smooth transmitted densities are obtained. Results obtained using higher-order quantum trajectories (third order DPM) are described for both thick and thin barriers, and some issues that arise for thin barriers are examined. PMID:17672677

  13. Phase shifting and the beating of complex waves

    NASA Astrophysics Data System (ADS)

    Keeports, David

    2011-03-01

    At the introductory level, the demonstration and analysis of sound beating is usually limited to the superposition of two purely sinusoidal waves with equal amplitudes and very similar frequencies. Under such conditions, an observer hears the periodic variation of the loudness of a sound with an unchanging timbre. On the other hand, when complex waves with very similar frequencies are superimposed, each harmonic beats with a frequency proportional to the frequency of the harmonic. Consequently, the resulting sound exhibits a subtle variation of timbre with time. This article extends the normal introductory discussion of beating and explains why electronic phase shifters, devices familiar to many musicians, can produce the sound of beating complex waves.

  14. Nonlinearity compensation and complex-to-phase conversion of complex incoherent digital holograms for optical reconstruction.

    PubMed

    Liu, Jung-Ping; Wang, Sheng-Yen; Tsang, P W M; Poon, Ting-Chung

    2016-06-27

    Incoherent digital holography (IDH) can be realized by optical scanning holography or self-interference incoherent holography. Although IDH can exhibit high quality reconstruction due to its inherently speckle-free property, direct display of an incoherent hologram is a challenge because of its amplitude nonlinearity and the demand of complex modulation. In this paper we propose to compensate the amplitude nonlinearity at the object plane, and use bidirectional error-diffusion method to convert the complex-type incoherent Fresnel hologram to a phase-only Fresnel hologram for display. A spatial light modulator is used to reconstruct the phase-only hologram optically to demonstrate the validity of our proposed method. PMID:27410610

  15. Modelling of phase diagrams of nanoalloys with complex metallic phases: application to Ni-Sn.

    PubMed

    Kroupa, A; Káňa, T; Buršík, J; Zemanová, A; Šob, M

    2015-11-14

    A method for modelling of size-dependent phase diagrams was developed by combining the semiempirical CALPHAD method and ab initio calculations of surface stresses for intermetallic phases. A novel approach was devised for the calculation of surface energy, free of systematic errors from the selection of different parameters of the software (e.g. number of the k-points) and for handling layered structures and off-stoichiometric slabs. Our approach allows the determination of complex size-dependent phase diagrams of systems with intermetallic phases, which was not possible up to now. The method was verified for the modelling of the phase diagram of the Ni-Sn system and basic comparison with rare experimental results was shown. There is reasonable agreement between the calculated and experimental results. The modelling of size-dependent phase diagrams of real systems allows the prediction of phase equilibria existing in nanosystems and possible changes in material properties. There is a need for such knowledge and the existence of reliable data for simpler systems is crucial for further application of this approach. This should motivate future experimental work. PMID:25824490

  16. Complex network analysis of phase dynamics underlying oil-water two-phase flows.

    PubMed

    Gao, Zhong-Ke; Zhang, Shan-Shan; Cai, Qing; Yang, Yu-Xuan; Jin, Ning-De

    2016-01-01

    Characterizing the complicated flow behaviors arising from high water cut and low velocity oil-water flows is an important problem of significant challenge. We design a high-speed cycle motivation conductance sensor and carry out experiments for measuring the local flow information from different oil-in-water flow patterns. We first use multivariate time-frequency analysis to probe the typical features of three flow patterns from the perspective of energy and frequency. Then we infer complex networks from multi-channel measurements in terms of phase lag index, aiming to uncovering the phase dynamics governing the transition and evolution of different oil-in-water flow patterns. In particular, we employ spectral radius and weighted clustering coefficient entropy to characterize the derived unweighted and weighted networks and the results indicate that our approach yields quantitative insights into the phase dynamics underlying the high water cut and low velocity oil-water flows. PMID:27306101

  17. Complex network analysis of phase dynamics underlying oil-water two-phase flows

    PubMed Central

    Gao, Zhong-Ke; Zhang, Shan-Shan; Cai, Qing; Yang, Yu-Xuan; Jin, Ning-De

    2016-01-01

    Characterizing the complicated flow behaviors arising from high water cut and low velocity oil-water flows is an important problem of significant challenge. We design a high-speed cycle motivation conductance sensor and carry out experiments for measuring the local flow information from different oil-in-water flow patterns. We first use multivariate time-frequency analysis to probe the typical features of three flow patterns from the perspective of energy and frequency. Then we infer complex networks from multi-channel measurements in terms of phase lag index, aiming to uncovering the phase dynamics governing the transition and evolution of different oil-in-water flow patterns. In particular, we employ spectral radius and weighted clustering coefficient entropy to characterize the derived unweighted and weighted networks and the results indicate that our approach yields quantitative insights into the phase dynamics underlying the high water cut and low velocity oil-water flows. PMID:27306101

  18. Complex network analysis of phase dynamics underlying oil-water two-phase flows

    NASA Astrophysics Data System (ADS)

    Gao, Zhong-Ke; Zhang, Shan-Shan; Cai, Qing; Yang, Yu-Xuan; Jin, Ning-De

    2016-06-01

    Characterizing the complicated flow behaviors arising from high water cut and low velocity oil-water flows is an important problem of significant challenge. We design a high-speed cycle motivation conductance sensor and carry out experiments for measuring the local flow information from different oil-in-water flow patterns. We first use multivariate time-frequency analysis to probe the typical features of three flow patterns from the perspective of energy and frequency. Then we infer complex networks from multi-channel measurements in terms of phase lag index, aiming to uncovering the phase dynamics governing the transition and evolution of different oil-in-water flow patterns. In particular, we employ spectral radius and weighted clustering coefficient entropy to characterize the derived unweighted and weighted networks and the results indicate that our approach yields quantitative insights into the phase dynamics underlying the high water cut and low velocity oil-water flows.

  19. Strain rate behaviour of multi-phase and complex-phase steels for automotive applications

    NASA Astrophysics Data System (ADS)

    Cadoni, E.; Singh, N. K.; Singha, M. K.; Gupta, N. K.

    2012-08-01

    A combined study on the mechanical behaviour of multi-phase 800 high yield strength steel (MP800HY) and complex-phase 800 steel (CP800) is carried out under tensile loads in the strain rate range from 0.001s-1 to 750s-1. Quasi-static (0.001s-1) tests are performed on electromechanical machine, whereas, medium (5s-1 and 25s-1) and high strain rate (250s-1, 500s-1 and 750s-1) experiments are conducted on hydro-pneumatic machine (HPM) and modified Hopkinson bar (MHB) setup respectively. The thermal softening behaviors of the materials are investigated at quasi-static condition and the materials' m-parameters of the existing Johnson-Cook model are imposed in authors' previous work. Thereafter, the predicted flow stress by Johnson-Cook model has been compared with the experimental results.

  20. A phased approach to enable hybrid simulation of complex structures

    NASA Astrophysics Data System (ADS)

    Spencer, Billie F.; Chang, Chia-Ming; Frankie, Thomas M.; Kuchma, Daniel A.; Silva, Pedro F.; Abdelnaby, Adel E.

    2014-08-01

    Hybrid simulation has been shown to be a cost-effective approach for assessing the seismic performance of structures. In hybrid simulation, critical parts of a structure are physically tested, while the remaining portions of the system are concurrently simulated computationally, typically using a finite element model. This combination is realized through a numerical time-integration scheme, which allows for investigation of full system-level responses of a structure in a cost-effective manner. However, conducting hybrid simulation of complex structures within large-scale testing facilities presents significant challenges. For example, the chosen modeling scheme may create numerical inaccuracies or even result in unstable simulations; the displacement and force capacity of the experimental system can be exceeded; and a hybrid test may be terminated due to poor communication between modules (e.g., loading controllers, data acquisition systems, simulation coordinator). These problems can cause the simulation to stop suddenly, and in some cases can even result in damage to the experimental specimens; the end result can be failure of the entire experiment. This study proposes a phased approach to hybrid simulation that can validate all of the hybrid simulation components and ensure the integrity large-scale hybrid simulation. In this approach, a series of hybrid simulations employing numerical components and small-scale experimental components are examined to establish this preparedness for the large-scale experiment. This validation program is incorporated into an existing, mature hybrid simulation framework, which is currently utilized in the Multi-Axial Full-Scale Sub-Structuring Testing and Simulation (MUST-SIM) facility of the George E. Brown Network for Earthquake Engineering Simulation (NEES) equipment site at the University of Illinois at Urbana-Champaign. A hybrid simulation of a four-span curved bridge is presented as an example, in which three piers are

  1. Phase Transitions in the Quadratic Contact Process on Complex Networks

    NASA Astrophysics Data System (ADS)

    Varghese, Chris; Durrett, Rick

    2013-03-01

    The quadratic contact process (QCP) is a natural extension of the well studied linear contact process where a single infected (1) individual can infect a susceptible (0) neighbor and infected individuals are allowed to recover (1 --> 0). In the QCP, a combination of two 1's is required to effect a 0 --> 1 change. We extend the study of the QCP, which so far has been limited to lattices, to complex networks as a model for the change in a population via sexual reproduction and death. We define two versions of the QCP - vertex centered (VQCP) and edge centered (EQCP) with birth events 1 - 0 - 1 --> 1 - 1 - 1 and 1 - 1 - 0 --> 1 - 1 - 1 respectively, where ` -' represents an edge. We investigate the effects of network topology by considering the QCP on regular, Erdős-Rényi and power law random graphs. We perform mean field calculations as well as simulations to find the steady state fraction of occupied vertices as a function of the birth rate. We find that on the homogeneous graphs (regular and Erdős-Rényi) there is a discontinuous phase transition with a region of bistability, whereas on the heavy tailed power law graph, the transition is continuous. The critical birth rate is found to be positive in the former but zero in the latter.

  2. Complex interfaces in "phase-change" contrast agents.

    PubMed

    Capece, Sabrina; Domenici, Fabio; Brasili, Francesco; Oddo, Letizia; Cerroni, Barbara; Bedini, Angelico; Bordi, Federico; Chiessi, Ester; Paradossi, Gaio

    2016-03-28

    In this paper we report on the study of the interface of hybrid shell droplets encapsulating decafluoropentane (DFP), which exhibit interesting potentialities for ultrasound (US) imaging. The fabrication of the droplets is based on the deposition of a dextran methacrylate layer onto the surface of surfactants. The droplets have been stabilized against coalescence by UV curing, introducing crosslinks in the polymer layer and transforming the shell into an elastomeric membrane with a thickness of about 300 nm with viscoelastic behaviour. US irradiation induces the evaporation of the DFP core of the droplets transforming the particles into microbubbles (MBs). The presence of a robust crosslinked polymer shell introduces an unusual stability of the droplets also during the core phase transition and allows the recovery of the initial droplet state after a few minutes from switching off US. The interfacial tension of the droplets has been investigated by two approaches, the pendant drop method and an indirect method, based on the determination of the liquid ↔ gas transition point of DFP confined in the droplet core. The re-condensation process has been followed by capturing images of single MBs by confocal microscopy. The time evolution of MB relaxation to droplets was analysed in terms of a modified Church model to account for the structural complexity of the MB shell, i.e. a crosslinked polymer layer over a layer of surfactants. In this way the microrheology parameters of the shell were determined. In a previous paper (Chem. Commun., 2013, 49, 5763-5765) we showed that these systems could be used as ultrasound contrast agents (UCAs). In this work we substantiate this view assessing some key features offered by the viscoelastic nature of the droplet shell. PMID:26931337

  3. Carbonate Complexation of Mn2+ in Aqueous Phase

    PubMed Central

    Dasgupta, Jyotishman; Tyryshkin, Alexei M.; Kozlov, Yuri N.; Klimov, Vyacheslav V.; Dismukes, G. Charles

    2008-01-01

    The chemical speciation of Mn2+ within cells is critical for its transport, availability and redox properties. Herein we investigate the redox behavior and complexation equilibria of Mn2+ in aqueous solutions of bicarbonate by voltametry and electron paramagnetic resonance (EPR) spectroscopy, and discuss the implications for the uptake of Mn2+ by mangano-cluster enzymes like photosystem II (PSII). Both the electrochemical reduction of Mn2+ to Mn0 at an Hg electrode and EPR (in the absence of a polarizing electrode), revealed formation of 1:1 and 1:2 Mn-(bi)carbonate complexes as a function of Mn2+ and bicarbonate concentrations. Pulsed EPR spectroscopy, including ENDOR, ESEEM and 2D-HYSCORE, were used to probe the hyperfine couplings to 1H and 13C nuclei of the ligand(s) bound to Mn2+. For the 1:2 complex the complete 13C hyperfine tensor for one of the (bi)carbonate ligands was determined and it was established that this ligand coordinates to Mn2+ in bidentate mode with 13C-Mn distance of 2.85 ± 0.1 Å. The second (bi)carbonate ligand in the 1:2 complex coordinates possibly in monodentate mode, which is structurally less defined, and its 13C signal is broad and unobservable. 1H ENDOR reveals that 1-2 water ligands are lost upon binding of one bicarbonate ion in the 1:1 complex while 3-4 water ligands are lost upon forming the 1:2 complex. Thus, we deduce that the dominant species above 0.1 M bicarbonate concentration is the 1:2 complex, [Mn(CO3)(HCO3)(OH2)3]-. PMID:16526753

  4. Aqueous Gemini Surfactant Self-Assembly into Complex Lyotropic Phases

    NASA Astrophysics Data System (ADS)

    Mahanthappa, Mahesh; Sorenson, Gregory

    2012-02-01

    In spite of the potentially wide-ranging applications of aqueous bicontinuous lyotropic liquid crystals (LLCs), the discovery of amphiphiles that reliably form these non-constant mean curvature morphologies over large phase windows remains largely serendipitous. Recent work has established that cationic gemini surfactants exhibit a pronounced tendency to form bicontinuous cubic (e.g. gyroid) phases as compared to their parent single-tail amphiphiles. The universality of this phenomenon in other surfactant systems remains untested. In this paper, we will report the aqueous LLC phase behavior of a new class of anionic gemini surfactants derived from long chain carboxylic acids. Our studies show that these new surfactants favor the formation of non-constant mean curvature gyroid and primitive (``Plumber's Nightmare'') structures over amphiphile concentration windows up to 20 wt% wide. Based on these observations, we will discuss insights gained into the delicate force balance governing the self-assembly of these surfactants into aqueous bicontinuous LLCs.

  5. Accurate thermodynamic properties of gas phase hydrogen bonded complexes.

    PubMed

    Hansen, Anne S; Maroun, Zeina; Mackeprang, Kasper; Frandsen, Benjamin N; Kjaergaard, Henrik G

    2016-08-24

    We have measured the infrared spectra of ethanol·dimethylamine and methanol·dimethylamine complexes in the 299-374 K temperature range, and have determined the enthalpy of complex formation (ΔH) to be -31.1 ± 2 and -29.5 ± 2 kJ mol(-1), respectively. The corresponding values of the Gibbs free energy (ΔG) are determined from the experimental integrated absorbance and a calculated oscillator strength of the OH-stretching vibrational transition to be 4.1 ± 0.3 and 3.9 ± 0.3 kJ mol(-1) at 302 and 300 K, respectively. The entropy, ΔS is determined from the values of ΔH and ΔG to be -117 ± 7 and -111 ± 10 J (mol K)(-1) for the ethanol·dimethylamine and methanol·dimethylamine complexes, respectively. The determined ΔH, ΔG and ΔS values of the two complexes are similar, as expected by the similarity to their donor molecules ethanol and methanol. Values of ΔH, ΔG and ΔS in chemical reactions are often obtained from quantum chemical calculations. However, these calculated values have limited accuracy and large variations are found using different methods. The accuracy of the present ΔH, ΔG and ΔS values is such that the benchmarking of theoretical methods is possible. PMID:27523902

  6. Removal of complex-conjugate ambiguity in SDOCT by using phase shiftings

    NASA Astrophysics Data System (ADS)

    Cai, Wenyuan; Jiang, Zhuqing; Huang, Haochong

    2012-12-01

    The three-step or many steps phase shifting method is usually employed to resolve the complex-conjugate ambiguity in Spectral-domain optical coherence tomography (SD-OCT). However it reduces the image quality and also the imaging speed is slow. In this paper two steps phase-shifting is used in digital image processing to resolve the complex-conjugate ambiguity and improves the quality of reconstructed image in SD-OCT. In the two-step phase shifting method the phase shifting operation is used only once which simplified the experiment and also the effect of relative error in SD-OCT on image quality is eliminated.

  7. Statistical energy analysis of complex structures, phase 2

    NASA Technical Reports Server (NTRS)

    Trudell, R. W.; Yano, L. I.

    1980-01-01

    A method for estimating the structural vibration properties of complex systems in high frequency environments was investigated. The structure analyzed was the Materials Experiment Assembly, (MEA), which is a portion of the OST-2A payload for the space transportation system. Statistical energy analysis (SEA) techniques were used to model the structure and predict the structural element response to acoustic excitation. A comparison of the intial response predictions and measured acoustic test data is presented. The conclusions indicate that: the SEA predicted the response of primary structure to acoustic excitation over a wide range of frequencies; and the contribution of mechanically induced random vibration to the total MEA is not significant.

  8. MOLECULAR SIMULATION OF PHASE EQUILIBRIA FOR COMPLEX FLUIDS

    SciTech Connect

    Athanassios Z. Panagiotopoulos

    2009-09-09

    The general area of this project was the development and application of novel molecular simulation methods for prediction of thermodynamic and structural properties of complex polymeric, surfactant and ionic fluids. Over this project period, we have made considerable progress in developing novel algorithms to meet the computational challenges presented by the strong or long-range interactions in these systems and have generated data for well-defined mod-els that can be used to test theories and compare to experimental data. Overall, 42 archival papers and many invited and contributed presentations and lectures have been based on work supported by this project. 6 PhD, 1 M.S. and 2 postdoctoral students have been associated with this work, as listed in the body of the report.

  9. Acute phase proteins in cattle after exposure to complex stress.

    PubMed

    Lomborg, S R; Nielsen, L R; Heegaard, P M H; Jacobsen, S

    2008-10-01

    Stressors such as weaning, mixing and transportation have been shown to lead to increased blood concentrations of acute phase proteins (APP), including serum amyloid A (SAA) and haptoglobin, in calves. This study was therefore undertaken to assess whether SAA and haptoglobin levels in blood mirror stress in adult cattle. Six clinically healthy Holstein cows and two Holstein heifers were transported for four to six hours to a research facility, where each animal was housed in solitary tie stalls. Blood samples for evaluation of leukocyte counts and serum SAA and haptoglobin concentrations were obtained before (0-sample) and at 8, 24 and 48 hours after the start of transportation. Upon arrival the animals gave the impression of being anxious, and they appeared to have difficulty coping with isolation and with being tied on the slippery floors of the research stable. Serum concentrations of SAA and haptoglobin increased significantly in response to the stressors (P < 0.01 and 0.05 at 48 hours, respectively). Additionally, the animals had transient neutrophilia at 8 and 24 hours (P < 0.05). In conclusion, the results of the study suggest that SAA and haptoglobin may serve as markers of stress in adult cattle. PMID:18461465

  10. Topological feature and phase structure of QCD at complex chemical potential

    NASA Astrophysics Data System (ADS)

    Kashiwa, Kouji; Ohnishi, Akira

    2015-11-01

    The pseudo-critical temperature of the confinement-deconfinement transition and the phase transition surface are investigated by using the complex chemical potential. We can interpret the imaginary chemical potential as the Aharonov-Bohm phase, then the analogy of the topological order suggests that the Roberge-Weiss endpoint would define the pseudo-critical temperature. The behavior of the Roberge-Weiss endpoint at small real quark chemical potential is investigated with the perturbative expansion. The expected QCD phase diagram at complex chemical potential is presented.

  11. Acoustic radiation force expressed using complex phase shifts and momentum-transfer cross sections.

    PubMed

    Zhang, Likun; Marston, Philip L

    2016-08-01

    Acoustic radiation force is expressed using complex phase shifts of partial wave scattering functions and the momentum-transfer cross section, herein incorporated into acoustics from quantum mechanisms. Imaginary parts of the phase shifts represent dissipation in the object and/or in the boundary layer adjacent to the object. The formula simplifies the force as summation of functions of complex phase shifts of adjacent partial waves involving differences of real parts and sums of imaginary parts, providing an efficient way of exploring the force parameter-space. The formula for the force is proportional to a generalized momentum-transfer cross section for plane waves and no dissipation. PMID:27586777

  12. Topological phase transition of a fractal spin system: The relevance of the network complexity

    NASA Astrophysics Data System (ADS)

    Torres, Felipe; Rogan, José; Kiwi, Miguel; Valdivia, Juan Alejandro

    2016-05-01

    A new type of collective excitations, due to the topology of a complex random network that can be characterized by a fractal dimension DF, is investigated. We show analytically that these excitations generate phase transitions due to the non-periodic topology of the DF > 1 complex network. An Ising system, with long range interactions, is studied in detail to support the claim. The analytic treatment is possible because the evaluation of the partition function can be decomposed into closed factor loops, in spite of the architectural complexity. The removal of the infrared divergences leads to an unconventional phase transition, with spin correlations that are robust against thermal fluctuations.

  13. The phase delay and its complex time: From stationary states up to wave packets

    SciTech Connect

    Grossel, Ph.

    2013-03-15

    Complex time is often invoked about tunneling effect where the classical phase delay is completed with a crucial filter effect. Usually the complex times are obtained by considering the flux-flux correlation function, but this can be obtained by a very simple approach using the search of the maximum of the generalized complex phase function, including the amplitude of the wave function. Various aspects of the phase delay are presented in the case of wave packets impinging on simple or resonant quantum barriers. Formal links with the classical mechanics give birth to quasi-trajectories of the quantum particle, totally compatible with the quantum mechanics. - Highlights: Black-Right-Pointing-Pointer The stationary phase method is extended in including the variations of the spectra. Black-Right-Pointing-Pointer The complex phase delay leads to a complex trajectory inside and out-side the barrier. Black-Right-Pointing-Pointer Examples of quasi-trajectories are given in case of different quantum barriers. Black-Right-Pointing-Pointer Phase delays are specified for resonant tunneling or above-barrier wave-packets. Black-Right-Pointing-Pointer The coherence between the quasi-trajectories and quantum mechanics is shown.

  14. Induction of phase 3 of the migrating motor complex in human small intestine by trimebutine.

    PubMed

    Chaussade, S; Grandjouan, S; Couturier, D; Thierman-Duffaud, D; Henry, J F

    1987-01-01

    The effects of trimebutine, a drug used in the treatment of various gastrointestinal motility disorders, have been investigated fed and fasted healthy subjects. Duodenojejunal motility was recorded manometrically with a 4-lumen probe. Trimebutine 50 or 100 mg was injected i.v. 3 or 25 min after observing a spontaneous Phase 3 complex in the fasted state. Other experiments were done in the postprandial state and after intravenous naloxone 0.8 mg. In the fasted state, trimebutine 100 mg, injected 25 min after a spontaneous Phase 3 complex consistently induced a premature Phase 3 complex. The mean duration of the migrating motor complex cycle decreased from 86.4 +/- 10.8 min to 32.5 +/- 1.0 min. Trimebutine 50 mg injected 3 and 25 min after a spontaneous Phase 3 complex did not significantly modify the periodicity of the migrating motor complex. Trimebutine 100 mg initiated Phase 3-like activity in the post-prandial state. Previous intravenous administration of naloxone 0.8 mg (Narcan) suppressed the stimulatory action of TMB. Thus, trimebutine is able to modify the motility pattern in the small intestine of man, possibly by acting at opioid receptors. PMID:2820749

  15. Supramolecular reactivity in the gas phase: investigating the intrinsic properties of non-covalent complexes.

    PubMed

    Cera, Luca; Schalley, Christoph A

    2014-03-21

    The high vacuum inside a mass spectrometer offers unique conditions to broaden our view on the reactivity of supramolecules. Because dynamic exchange processes between complexes are efficiently suppressed, the intrinsic and intramolecular reactivity of the complexes of interest is observed. Besides this, the significantly higher strength of non-covalent interactions in the absence of competing solvent allows processes to occur that are unable to compete in solution. The present review highlights a series of examples illustrating different aspects of supramolecular gas-phase reactivity ranging from the dissociation and formation of covalent bonds in non-covalent complexes through the reactivity in the restricted inner phase of container molecules and step-by-step mechanistic studies of organocatalytic reaction cycles to cage contraction reactions, processes induced by electron capture, and finally dynamic molecular motion within non-covalent complexes as unravelled by hydrogen-deuterium exchange processes performed in the gas phase. PMID:24435245

  16. Dynamic equilibrium dissolution of complex nonaqueous phase liquid mixtures into the aqueous phase.

    PubMed

    Schluep, Mathias; Gälli, René; Imboden, Dieter M; Zeyer, Josef

    2002-07-01

    Human health risks posed by hazardous substances seeping from a pool of nonaqueous phase liquids (NAPLs) into groundwater change over time because the more soluble compounds such as benzene, toluene, ethylbenzene, and xylene (BTEX) dissolve faster into the aqueous phase than less soluble compounds such as polycyclic aromatic hydrocarbons (PAH). Long-term dissolution from diesel fuel into the aqueous phase was determined experimentally in a continuous flow-through system using the slow-stirring method. The data obtained are interpreted using a dynamic equilibrium dissolution model based on Raoult's law. The predicted temporal development of aqueous concentrations are in good agreement with the experimental results. When a compound in the NAPL approaches complete depletion, a tailing behavior is observed, which is assigned to nonequilibrium effects, such as mass transfer limitations in the NAPL phase. The model predicted an increase of the mean molar mass of the diesel fuel of 1.5% over the entire experimental period. It should be noted that, if the dissolution process were to proceed further, the change in the mean molar mass could become significant and render the simple model inaccurate. Yet the simple model supports the assessment of initial action after a contamination event as well as the planning of long-term remedial strategies. PMID:12109733

  17. A REVIEW OF THE EARLY DEVELOPMENT OF THE THERMODYNAMICS OF THE COMPLEX COACERVATION PHASE SEPARATION

    PubMed Central

    Veis, Arthur

    2011-01-01

    Coacervation was defined as the phenomenon in which a colloidal dispersion separated into colloid-rich (the coacervate), and colloid-poor phases, both with the same solvent. Complex coacervation covered the situation in which a mixture of two polymeric polyions with opposite charge separated into liquid dilute and concentrated phases, in the same solvent, with both phases, at equilibrium, containing both polyions. Voorn and Overbeek provided the first theoretical analysis of complex coacervation by applying Flory-Huggins polymer statistics to model the random mixing of the polyions and their counter ions in solution, assuming completely random mixing of the polyions in each phase, with the electrostatic free energy, ΔGelect, providing the driving force. However, experimentally complete randomness does not apply: polyion size, heterogeneity, chain stiffness and charge density (σ) all affect the equilibrium phase separation and phase concentrations. Moreover, in pauci-disperse systems multiple phases are often observed. As an alternative, Veis and Aranyi proposed the formation of charge paired Symmetrical Aggregates (SA) as an initial step, followed by phase separation driven by the interaction parameter, χ23, combining both entropy and enthalpy factors other than the ΔGelect electrostatic term. This two stage path to equilibrium phase separation allows for understanding and quantifying and modeling the diverse aggregates produced by interactions between polyampholyte molecules of different charge density, σ, and intrinsic polyion structure. PMID:21377640

  18. Single Sublattice Endotaxial Phase Separation Driven by Charge Frustration in a Complex Oxide

    PubMed Central

    2013-01-01

    Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation. PMID:23750709

  19. Defect-mediated spatial complexity and chaos in a phase-conjugate resonator

    NASA Technical Reports Server (NTRS)

    Indebetouw, Guy; Liu, Siuying R.

    1992-01-01

    We have studied the spatiotemporal dynamics of a phase-conjugate resonator. The cavity Fresnel number is used to vary the degree of transverse confinement of the system. The generation and subsequent motion of the phase defects in the wave front are seen to mediate the system's dynamics. The number of defects and the complexity of their motion increases as the confinement is relaxed, leading the system through a sequence of bifurcations and eventually to chaos.

  20. Phase transformations of hydrocarbon accumulations in the Upper Cretaceous complex of the Northeast Caucasus

    SciTech Connect

    Reznikov, A.N.; Yaroshenko, A.A.

    1982-10-01

    The geologic structure and development of the Northeast Caucasus has produced a complex distribution of hydrocarbons in different phases throughout Upper Cretaceous deposits. A comprehensive study of the thermobaric conditions in the region are presented so that the patterns of hydrocarbon phase transformations can be identified. In addition the maturation of the geologic formations in the area that led to the oil formation is discussed. (JMT)

  1. Complex phase diagram of Ba1 -xNaxFe2As2 : A multitude of phases striving for the electronic entropy

    NASA Astrophysics Data System (ADS)

    Wang, L.; Hardy, F.; Böhmer, A. E.; Wolf, T.; Schweiss, P.; Meingast, C.

    2016-01-01

    The low-temperature electronic phase diagram of Ba1 -xNaxFe2As2 , obtained using high-resolution thermal-expansion and specific-heat measurements, is shown to be considerably more complex than previously reported, containing nine different phases. Besides the magnetic C2 and reentrant C4 phases, we find evidence for an additional, presumably magnetic, phase below the usual spin-density-wave transition, as well as a possible incommensurate magnetic phase. All these phases coexist and compete with superconductivity, which is particularly strongly suppressed by the C4-magnetic phase due to a strong reduction of the electronic entropy available for pairing in this phase.

  2. Complex phase diagram of Ba1-xNaxFe2As2: a multitude of phases striving for the electronic entropy

    NASA Astrophysics Data System (ADS)

    Meingast, Christoph; Wang, Liran; Hardy, Frederic; Boehmer, Anna; Schweiss, Peter; Wolf, Thomas

    The low-temperature electronic phase diagram of Ba1-NaxFe2As2, obtained using high-resolution thermal-expansion and specific-heat measurements, is shown to be considerably more complex than previously reported, containing nine different phases. Besides the magnetic C2 and reentrant C4 phases, we find evidence for an additional, presumably magnetic, phase below the usual SDW transition, as well as a possible incommensurate magnetic phase. All these phases coexist and compete with superconductivity, which is particularly strongly suppressed by the C4-magnetic phase due to a strong reduction of the electronic entropy available for pairing in this phase.

  3. Temperature evolution of nickel sulphide phases from thiourea complex and their exchange bias effect

    SciTech Connect

    Kumar, Nitesh; Raman, N.; Sundaresan, A.

    2013-12-15

    Considering the very complex phase diagram of nickel sulphide, it is quite challenging to stabilize pure phases from a single precursor. Here, we obtain nanoparticles of various phases of nickel sulphide by decomposing nickel–thiourea complex at different temperatures. The first phase in the evolution is the one with the maximum sulphur content, namely, NiS{sub 2} nanoparticles obtained at 400 °C. As the temperature is increased, nanoparticles of phases with lesser sulphur content, NiS (600 °C) and Ni{sub 3}S{sub 2} (800 °C) are formed. NiS{sub 2} nanoparticles exhibit weak ferromagnetic transition at 30 K and show a large exchange bias at 2 K. NiS nanoparticles are antiferromagnetic and show relatively smaller exchange bias effect. On the other hand, Ni{sub 3}S{sub 2} nanoparticles exhibit very weak temperature dependent magnetization. Electrical measurements show that both NiS{sub 2} and NiS are semiconductors whereas Ni{sub 3}S{sub 2} is a metal. - Graphical abstract: Pure phases of NiS{sub 2}, NiS and Ni{sub 3}S{sub 2} have been obtained by thermal decomposition of nickel–thiourea complex wherein, NiS{sub 2} nanoparticles exhibit remarkable exchange bias effect at 2 K. - Highlights: • NiS{sub 2}, NiS and Ni{sub 3}S{sub 2} nanoparticles are obtained by thermal decomposition of nickel–thiourea complex at different temperatures. • As the temperature is increased, nickel sulphide phase with lesser sulphur content is obtained. • NiS{sub 2} nanoparticles show good exchange bias property which can be explained by antiferromagnetic core and ferromagnetic shell model. • NiS{sub 2} and NiS are semiconducting while Ni{sub 3}S{sub 2} shows metallic behavior.

  4. On the phase diagram of reentrant condensation in polyelectrolyte-liposome complexation

    NASA Astrophysics Data System (ADS)

    Sennato, S.; Bordi, F.; Cametti, C.

    2004-09-01

    Complexation of polyions with oppositely charged spherical liposomes has been investigated by means of dynamic light scattering measurements and a well-defined reentrant condensation has been observed. The phase diagram of charge inversion, recently derived [T. T. Nguyen and B. I. Shklovskii, J. Chem. Phys. 115, 7298 (2001)] for the complexation of DNA with charged spherical macroions, has been employed in order to define the boundaries of the region where polyion-liposome complexes begin to condense, forming larger aggregates, and where aggregates dissolve again, towards isolated polyion-coated-liposome complexes. A reasonable good agreement is observed in the case of complexes formed by negatively charged polyacrylate sodium salt polyions and liposomes built up by cationic lipids (dioleoyltrimethylammoniumpropane), in an extended liposome concentration range.

  5. Negative results in phase III trials of complex interventions: cause for concern or just good science?

    PubMed

    Crawford, Mike J; Barnicot, Kirsten; Patterson, Sue; Gold, Christian

    2016-07-01

    Not all interventions that show promise in exploratory trials will be supported in phase III studies. But the high failure rate in recent trials of complex mental health interventions is a concern. Proper consideration of trial processes and greater use of adaptive trial designs could ensure better use of available resources. PMID:27369475

  6. Complex dark-field contrast in grating-based x-ray phase contrast imaging

    NASA Astrophysics Data System (ADS)

    Yang, Yi; Tang, Xiangyang

    2015-03-01

    Without assuming that the sub-pixel microstructures of an object to be imaged distribute in space randomly, we investigate the influence of the object's microstructures on grating-based x-ray phase contrast imaging. Our theoretical analysis and 3D computer simulation study based on the paraxial Fresnel-Kirchhoff theory show that the existing dark-field contrast can be generalized into a complex dark-field contrast in a way such that its imaginary part quantifies the effect of the object's sub-pixel microstructures on the phase of intensity oscillations. A method based on the phase-attenuation duality that holds for soft tissues to be imaged at high x-ray energies is proposed to retrieve the imaginary part of the complex dark-field contrast for imaging. In comparison to the existing dark-field contrast, the imaginary part of complex dark-field contrast exhibits significantly stronger selectivity on the shape of the object's sub-pixel microstructures. Thus the x-ray imaging corresponding to the imaginary part of complex dark-field contrast can provide additional and complementary information to that corresponding to the attenuation contrast, phase contrast and the existing dark-field contrast.

  7. Phase Transitions in Development of Writing Fluency from a Complex Dynamic Systems Perspective

    ERIC Educational Resources Information Center

    Baba, Kyoko; Nitta, Ryo

    2014-01-01

    This study explored patterns in L2 writing development by focusing on one of the linguistic features of texts (fluency) from a complex dynamic systems perspective. It investigated whether two English-as-a-foreign-language university students would experience discontinuous change (phase transition) in their writing fluency through repetition of a…

  8. Full range complex spectral domain optical coherence tomography without additional phase shifters.

    PubMed

    Baumann, Bernhard; Pircher, Michael; Götzinger, Erich; Hitzenberger, Christoph K

    2007-10-01

    We demonstrate a new full range complex spectral domain optical coherence tomography (FRC SD-OCT) method. Other than FRC SD-OCT systems reported in literature, which employed devices such as electro-/acousto optic modulators or piezo-driven mirrors providing the phase modulations necessary for retrieval of the complex-valued signal, the system presented works without any additional phase shifting device. The required phase shift is introduced by the galvanometer scanner used for transversally scanning the sample beam. By means of a slight displacement of the probe beam with respect to the scanning mirror's pivot axis, the sample arm length and thus the phase is continuously modulated as the beam is scanned in lateral direction. From such modulated spectral data, the complex-valued data yielding a twofold increase of accessible depth range can be calculated using an algorithm based on the Hilbert transform. To demonstrate the performance of our method quantitative measurements of the suppression of mirror images as a function of induced phase shift were performed. In order to validate the FRC SD-OCT technique for high-speed imaging of biological tissue, we present full-range images of the human anterior chamber in vivo. PMID:19550607

  9. Structural infection and anomalous phase sequences in complex oxides prepared from nanodispersed components

    SciTech Connect

    Shmytko, I. M. Strukova, G. K.; Kudrenko, E. A.

    2006-12-15

    The complex oxides prepared by solid-phase synthesis from nanoscopic components are studied using X-ray diffraction. It is demonstrated that the use of nanoscopic components in the solid-phase synthesis of lutetium borate LuBO{sub 3} and europium molybdate Eu{sub 2}(MoO{sub 4}){sub 3} leads to anomalous sequences of phase transformations in these compounds: the vaterite {sup {yields}} calcite {r_reversible} vaterite sequence for LuBO{sub 3} and the {beta} {sup {yields}} {alpha} {r_reversible} {beta} sequence for Eu{sub 2}(MoO{sub 4}){sub 3} are observed instead of the previously known sequences, namely, the calcite {r_reversible} vaterite sequence for LuBO{sub 3} and the {alpha} {r_reversible} {beta} sequence for Eu{sub 2}(MoO{sub 4}){sub 3}. The revealed anomalous sequences do not depend on the procedure used for preparing reactants and are determined by the nanoscopic sizes of the initial components. It is found that microscopic additions of a number of simple oxides can suppress the kinetics of solid-phase synthesis of particular complex oxides and initiate the formation of new phases in the synthesis of other complex oxides (the so-called structural infection effect)

  10. Reverse-phase HPLC of benzylpropionitrile dithiocarbamate complexes for the determination of priority pollutant metals

    SciTech Connect

    Park, Y.J.

    1990-01-01

    A new dithiocarbamate, benzylpropionitrile dithiocarbamate (BPDTC), has been synthesized for use in metal analysis. The HPLC behavior of metal chelates of BPDTC has been investigated for the simultaneous determination of antimony, cadmium, chromium, copper, mercury, nickel, lead, selenium, thallium, and zinc, all of which are on the Environmental Protection Agency's list of priority pollutant metals. Metals are extracted into dichloromethane as BPDTC chelates, and then separated on a C-18 column. Cobalt is added as an internal standard. The effects of pH and of three organic modifiers (methanol, acetonitrile, tetrahydrofuran) of the mobile phase on retention time have been investigated. Addition of dichloromethane to the mobile phase increases solubility and chelate stability, and improves the separation of metal BPDTC complexes. BPDTC is added to the aqueous mobile phase to reduce on-column dissociation of the complexes. Detection limits at 260 nm are in the range of 0.1 to 3 ppb using a 1 liter sample.

  11. Low-noise multiple watermarks technology based on complex double random phase encoding method

    NASA Astrophysics Data System (ADS)

    Zheng, Jihong; Lu, Rongwen; Sun, Liujie; Zhuang, Songlin

    2010-11-01

    Based on double random phase encoding method (DRPE), watermarking technology may provide a stable and robust method to protect the copyright of the printing. However, due to its linear character, DRPE exist the serious safety risk when it is attacked. In this paper, a complex coding method, which means adding the chaotic encryption based on logistic mapping before the DRPE coding, is provided and simulated. The results testify the complex method will provide better security protection for the watermarking. Furthermore, a low-noise multiple watermarking is studied, which means embedding multiple watermarks into one host printing and decrypt them with corresponding phase keys individually. The Digital simulation and mathematic analysis show that with the same total embedding weight factor, multiply watermarking will improve signal noise ratio (SNR) of the output printing image significantly. The complex multiply watermark method may provide a robust, stability, reliability copyright protection with higher quality printing image.

  12. Three-phase hollow fiber liquid-phase microextraction of organophosphorous nerve agent degradation products from complex samples.

    PubMed

    Desoubries, Charlotte; Chapuis-Hugon, Florence; Bossée, Anne; Pichon, Valérie

    2012-07-01

    Degradation products of chemical warfare agents are considered as important environmental and biological markers of chemical attacks. Alkyl methylphosphonic acids (AMPAs), resulting from the fast hydrolysis of nerve agents, such as sarin and soman, and the methylphosphonic acid (MPA), final degradation product of AMPAs, were determined from complex matrices by using an emergent and miniaturized extraction technique, the hollow fiber liquid-phase microextraction (HF-LPME), before their analysis by liquid chromatography coupled to mass spectrometry (LC-MS). After studying different conditions of separation in the reversed phase LC-MS analysis, the sample treatment method was set up. The three-phase HF-LPME was carried out by using a porous polypropylene (PP) hollow fiber impregnated with 1-octanol that separates the donor and acceptor aqueous media. Various extraction parameters were evaluated such as the volume of the sample, the effect of the pH and the salt addition to the sample, the pH of the acceptor phase, the extraction temperature, the stirring speed of the sample, the immersion time in the organic solvent and the time of extraction. The optimum conditions were applied to the determination of MPA and five AMPAs in real samples, such as surface waters and urine. Compounds were extracted from a 3 mL acidified sample into only 6 μL of alkaline water without any other pretreatment of the complex matrices. Enrichment factors (EFs) higher than 170 were obtained for three less polar AMPAs. Limits of quantification (LOQs) in the 0.013-5.3 ng mL(-1) range were obtained after microextraction of AMPAs from river water and in the range of 0.056-4.8 ng mL(-1) from urine samples with RSD values between 1 and 9%. PMID:22705170

  13. Endosomal Sorting Complex Required for Transport (ESCRT) Complexes Induce Phase-separated Microdomains in Supported Lipid Bilayers*

    PubMed Central

    Boura, Evzen; Ivanov, Vassili; Carlson, Lars-Anders; Mizuuchi, Kiyoshi; Hurley, James H.

    2012-01-01

    The endosomal sorting complex required for transport (ESCRT) system traffics ubiquitinated cargo to lysosomes via an unusual membrane budding reaction that is directed away from the cytosol. Here, we show that human ESCRT-II self-assembles into clusters of 10–100 molecules on supported lipid bilayers. The ESCRT-II clusters are functional in that they bind to ubiquitin and the ESCRT-III subunit VPS20 at nanomolar concentrations on membranes with the same stoichiometries observed in solution and in crystals. The clusters only form when cholesterol is included in the lipid mixture at >10 mol %. The clusters induce the formation of ordered membrane domains that exclude the dye 1,1′-dioctadecyl-3,3,3′,3′-tetramethylindodicarbo-cyanine perchlorate. These results show that ESCRT complexes are capable of inducing lateral lipid phase separation under conditions where the lipids themselves do not spontaneously phase-separate. This property could facilitate ESCRT-mediated membrane budding. PMID:22718754

  14. High-speed spectral calibration by complex FIR filter in phase-sensitive optical coherence tomography

    PubMed Central

    Kim, Sangmin; Raphael, Patrick D.; Oghalai, John S.; Applegate, Brian E.

    2016-01-01

    Swept-laser sources offer a number of advantages for Phase-sensitive Optical Coherence Tomography (PhOCT). However, inter- and intra-sweep variability leads to calibration errors that adversely affect phase sensitivity. While there are several approaches to overcoming this problem, our preferred method is to simply calibrate every sweep of the laser. This approach offers high accuracy and phase stability at the expense of a substantial processing burden. In this approach, the Hilbert phase of the interferogram from a reference interferometer provides the instantaneous wavenumber of the laser, but is computationally expensive. Fortunately, the Hilbert transform may be approximated by a Finite Impulse-Response (FIR) filter. Here we explore the use of several FIR filter based Hilbert transforms for calibration, explicitly considering the impact of filter choice on phase sensitivity and OCT image quality. Our results indicate that the complex FIR filter approach is the most robust and accurate among those considered. It provides similar image quality and slightly better phase sensitivity than the traditional FFT-IFFT based Hilbert transform while consuming fewer resources in an FPGA implementation. We also explored utilizing the Hilbert magnitude of the reference interferogram to calculate an ideal window function for spectral amplitude calibration. The ideal window function is designed to carefully control sidelobes on the axial point spread function. We found that after a simple chromatic correction, calculating the window function using the complex FIR filter and the reference interferometer gave similar results to window functions calculated using a mirror sample and the FFT-IFFT Hilbert transform. Hence, the complex FIR filter can enable accurate and high-speed calibration of the magnitude and phase of spectral interferograms. PMID:27446666

  15. High-speed spectral calibration by complex FIR filter in phase-sensitive optical coherence tomography.

    PubMed

    Kim, Sangmin; Raphael, Patrick D; Oghalai, John S; Applegate, Brian E

    2016-04-01

    Swept-laser sources offer a number of advantages for Phase-sensitive Optical Coherence Tomography (PhOCT). However, inter- and intra-sweep variability leads to calibration errors that adversely affect phase sensitivity. While there are several approaches to overcoming this problem, our preferred method is to simply calibrate every sweep of the laser. This approach offers high accuracy and phase stability at the expense of a substantial processing burden. In this approach, the Hilbert phase of the interferogram from a reference interferometer provides the instantaneous wavenumber of the laser, but is computationally expensive. Fortunately, the Hilbert transform may be approximated by a Finite Impulse-Response (FIR) filter. Here we explore the use of several FIR filter based Hilbert transforms for calibration, explicitly considering the impact of filter choice on phase sensitivity and OCT image quality. Our results indicate that the complex FIR filter approach is the most robust and accurate among those considered. It provides similar image quality and slightly better phase sensitivity than the traditional FFT-IFFT based Hilbert transform while consuming fewer resources in an FPGA implementation. We also explored utilizing the Hilbert magnitude of the reference interferogram to calculate an ideal window function for spectral amplitude calibration. The ideal window function is designed to carefully control sidelobes on the axial point spread function. We found that after a simple chromatic correction, calculating the window function using the complex FIR filter and the reference interferometer gave similar results to window functions calculated using a mirror sample and the FFT-IFFT Hilbert transform. Hence, the complex FIR filter can enable accurate and high-speed calibration of the magnitude and phase of spectral interferograms. PMID:27446666

  16. Nonlinear light behaviors near phase transition in non-parity-time-symmetric complex waveguides.

    PubMed

    Nixon, Sean; Yang, Jianke

    2016-06-15

    Many classes of non-parity-time (PT)-symmetric waveguides with arbitrary gain and loss distributions still possess all-real linear spectrum or exhibit phase transition. In this Letter, nonlinear light behaviors in these complex waveguides are probed analytically near a phase transition. Using multi-scale perturbation methods, a nonlinear ordinary differential equation (ODE) is derived for the light's amplitude evolution. This ODE predicts that a single class of these non-PT-symmetric waveguides supports soliton families and amplitude-oscillating solutions both above and below linear phase transition, in close analogy with PT-symmetric systems. For the other classes of waveguides, the light's intensity always amplifies under the effect of nonlinearity, even if the waveguide is below the linear phase transition. These analytical predictions are confirmed by direct computations of the full system. PMID:27304279

  17. Nonlinear light behaviors near phase transition in non-parity-time-symmetric complex waveguides

    NASA Astrophysics Data System (ADS)

    Nixon, Sean; Yang, Jianke

    2016-06-01

    Many classes of non-parity-time (PT) symmetric waveguides with arbitrary gain and loss distributions still possess all-real linear spectrum or exhibit phase transition. In this article, nonlinear light behaviors in these complex waveguides are probed analytically near a phase transition. Using multi-scale perturbation methods, a nonlinear ordinary differential equation (ODE) is derived for the light's amplitude evolution. This ODE predicts that the first class of these non-PT-symmetric waveguides support continuous families of solitons and robust amplitude-oscillating solutions both above and below phase transition, in close analogy with PT-symmetric systems. For the other classes of waveguides, the light's intensity always amplifies under the effect of nonlinearity even if the waveguide is below phase transition. These analytical predictions are confirmed by direct computations of the full system.

  18. Temperature-dependent phase transitions of a complex biological membrane in zeptoliter volumes

    SciTech Connect

    Nikiforov, Maxim; Hohlbauch, Sophia; King, William P; Voitchovsky, K; Contera, S Antoranz; Jesse, Stephen; Kalinin, Sergei V; Proksch, Roger

    2011-01-01

    Phase transitions in purple membrane have been a topic of debate for the past two decades. In this work we present studies of a reversible transition of purple membrane in the 50 60 C range in zeptoliter volumes under different heating regimes (global heating and local heating). The temperature of the reversible phase transition is 52 5 C for both local and global heating, supporting the hypothesis that this transition is mainly due to a structural rearrangement of bR molecules and trimers. To achieve high resolution measurements of temperature-dependent phase transitions, a new scanning probe microscopy-based method was developed. We believe that our new technique can be extended to other biological systems and can contribute to the understanding of inhomogeneous phase transitions in complex systems.

  19. High pressure-low temperature phase diagram of barium: Simplicity versus complexity

    NASA Astrophysics Data System (ADS)

    Desgreniers, Serge; Tse, John S.; Matsuoka, Takahiro; Ohishi, Yasuo; Li, Quan; Ma, Yanming

    2015-11-01

    Barium holds a distinctive position among all elements studied upon densification. Indeed, it was the first example shown to violate the long-standing notion that high compression of simple metals should preserve or yield close-packed structures. From modest pressure conditions at room temperature, barium transforms at higher pressures from its simple structures to the extraordinarily complex atomic arrangements of the incommensurate and self-hosting Ba-IV phases. By a detailed mapping of the pressure/temperature structures of barium, we demonstrate the existence of another crystalline arrangement of barium, Ba-VI, at low temperature and high pressure. The simple structure of Ba-VI is unlike that of complex Ba-IV, the phase encountered in a similar pressure range at room temperature. First-principles calculations predict Ba-VI to be stable at high pressure and superconductive. The results illustrate the complexity of the low temperature-high pressure phase diagram of barium and the significant effect of temperature on structural phase transformations.

  20. High pressure–low temperature phase diagram of barium: Simplicity versus complexity

    SciTech Connect

    Desgreniers, Serge; Tse, John S.; Matsuoka, Takahiro; Ohishi, Yasuo

    2015-11-30

    Barium holds a distinctive position among all elements studied upon densification. Indeed, it was the first example shown to violate the long-standing notion that high compression of simple metals should preserve or yield close-packed structures. From modest pressure conditions at room temperature, barium transforms at higher pressures from its simple structures to the extraordinarily complex atomic arrangements of the incommensurate and self-hosting Ba-IV phases. By a detailed mapping of the pressure/temperature structures of barium, we demonstrate the existence of another crystalline arrangement of barium, Ba-VI, at low temperature and high pressure. The simple structure of Ba-VI is unlike that of complex Ba-IV, the phase encountered in a similar pressure range at room temperature. First-principles calculations predict Ba-VI to be stable at high pressure and superconductive. The results illustrate the complexity of the low temperature-high pressure phase diagram of barium and the significant effect of temperature on structural phase transformations.

  1. Gas-Phase Photoluminescence Characterization of Stoichiometrically Pure Nonanuclear Lanthanoid Hydroxo Complexes Comprising Europium or Gadolinium.

    PubMed

    Greisch, Jean-François; Chmela, Jiří; Harding, Michael E; Klopper, Wim; Kappes, Manfred M; Schooss, Detlef

    2016-04-01

    Gas-phase photoluminescence measurements involving mass-spectrometric techniques enable determination of the properties of selected molecular systems with knowledge of their exact composition and unaffected by matrix effects such as solvent interactions or crystal packing. The resulting reduced complexity facilitates a comparison with theory. Herein, we provide a detailed report of the intrinsic luminescence properties of nonanuclear europium(III) and gadolinium(III) 9-hydroxyphenalen-1-one (HPLN) hydroxo complexes. Luminescence spectra of [Eu9(PLN)16(OH)10](+) ions reveal an europium-centered emission dominated by a 4-fold split Eu(III) hypersensitive transition, while photoluminescence lifetime measurements for both complexes support an efficient europium sensitization via a PLN-centered triplet-state manifold. The combination of gas-phase measurements with density functional theory computations and ligand-field theory is used to discuss the antiprismatic core structure of the complexes and to shed light on the energy-transfer mechanism. This methodology is also employed to fit a new set of parameters, which improves the accuracy of ligand-field computations of Eu(III) electronic transitions for gas-phase species. PMID:26974169

  2. Characterization of fish gelatin-gum arabic complex coacervates as influenced by phase separation temperature.

    PubMed

    Anvari, Mohammad; Pan, Cheol-Ho; Yoon, Won-Byong; Chung, Donghwa

    2015-08-01

    The rheological and structural characteristics of fish gelatin (FG)-gum arabic (GA) complex coacervate phase, separated from an aqueous mixture of 1% FG and 1% GA at pH 3.5, were investigated as influenced by phase separation temperature. Decreasing the phase separation temperature from 40 to 10 °C lead to: (1) the formation of a coacervate phase with a larger volume fraction and higher biopolymer concentrations, which is more viscous, more structural resistant at low shear rates, more shear-thinning at high shear rates, and more condensed in microstructure, (2) a solid-like elastic behavior of the phase separated at 10 °C at a high oscillatory frequency, (3) the increase in gelling and melting temperatures of the coacervate phase (3.7-3.9 °C and 6.2-6.9 °C, respectively), (4) the formation of a more rigid and thermo-stable coacervate gel. The coacervate phase is regarded as a homogeneously networked biopolymer matrix dispersed with water vacuoles and its gel as a weak physical gel reinforced by FG-GA attractive electrostatic interactions. PMID:26054661

  3. Mapping the Complex Phase Behaviors of Aqueous Mixtures of κ-Carrageenan and Type B Gelatin.

    PubMed

    Cao, Yiping; Wang, Lu; Zhang, Ke; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O

    2015-07-30

    We report a detailed and complete phase diagram for an aqueous mixture of oppositely charged gelling biopolymers, type B gelatin and κ-carrageenan (KC) at pH 7.0. The phase diagram is studied in the ionic strength-temperature coordinate by means of turbidity, rheological and differential scanning calorimetric measurements, and macroscopic phase compositional analysis. Seven phase regions are identified, including (I) compatible region, (II) electrostatically induced associative phase separation (EIAPS) region, (III) hydrogen bonding induced associative phase separation (HBIAPS) region, (IV) coexistence of EIAPS and HBIAPS, (V) segregative phase separation (SPS) region, (VI) coexistence of HBIAPS and SPS, and (VII) SPS trapped by gelation. The HBIAPS reported for the first time here is attributed to the extensive hydrogen bonding formation between gelatin and KC above their conformational transition temperatures, as probed by addition of urea and methylene blue as well as by 2D (1)H-(1)H NOESY NMR. NaCl is found to have dual effects on HBIAPS. The electrostatic complexation at lower ionic strength facilitates the formation of hydrogen bonds between gelatin and KC and hence the HBIAPS. It is believed that the local structural arrangement of gelatin molecules or the change in local solvent environment prior to triple helix formation during cooling enables the formation of hydrogen bonds with KC. PMID:26147592

  4. Temperature evolution of nickel sulphide phases from thiourea complex and their exchange bias effect

    NASA Astrophysics Data System (ADS)

    Kumar, Nitesh; Raman, N.; Sundaresan, A.

    2013-12-01

    Considering the very complex phase diagram of nickel sulphide, it is quite challenging to stabilize pure phases from a single precursor. Here, we obtain nanoparticles of various phases of nickel sulphide by decomposing nickel-thiourea complex at different temperatures. The first phase in the evolution is the one with the maximum sulphur content, namely, NiS2 nanoparticles obtained at 400 °C. As the temperature is increased, nanoparticles of phases with lesser sulphur content, NiS (600 °C) and Ni3S2 (800 °C) are formed. NiS2 nanoparticles exhibit weak ferromagnetic transition at 30 K and show a large exchange bias at 2 K. NiS nanoparticles are antiferromagnetic and show relatively smaller exchange bias effect. On the other hand, Ni3S2 nanoparticles exhibit very weak temperature dependent magnetization. Electrical measurements show that both NiS2 and NiS are semiconductors whereas Ni3S2 is a metal.

  5. Influence of Ionic Complexes on Phase Behavior of Polystyrene-b-poly(methyl methacrylate) Copolymers

    SciTech Connect

    Wang,J.; Chen, W.; Roy, C.; Sievert, J.; Russell, T.

    2008-01-01

    The influence of ionic complexes on phase behavior of PS-b-PMMA copolymers over a wide range of molecular weights and PS volume fractions was investigated by small-angle X-ray scattering (SAXS), grazing incidence small-angle X-ray scattering (GISAXS), transmission electron microscopy (TEM), and neutron reflectivity (NR). The disorder-to-order transition (DOT) in both symmetric and asymmetric copolymers indicates that the overall Flory-Huggins segmental interaction parameter, eff, between polystyrene (PS) and poly(methyl methacrylate) (PMMA) blocks with lithium-PMMA complexes is increased compared to that of the neat copolymers. This enhanced eff further results in an order-to-order transition (OOT), from spheres to cylinders, and an increase in the ordering and spacing of microdomains. Moreover, transitional metal ionic complexes, such as copper-PMMA complexes, are found to have the similar influence on phase behavior of PS-b-PMMA copolymers. The formation of ionic complexes in the copolymers not only offers a parameter to tune the degree of microphase separation of PS-b-PMMA copolymers but also provides a way to fabricate multifunctional materials.

  6. Incorporation of radionuclides into mineral phases via a thermally unstable complexant ligand

    SciTech Connect

    Apblett, A.W.; Georgieva, G.D.; Mague, J.T.

    1993-12-31

    The complexation and thermal behavior of pyruvic acid oxime (PAO) with representative cations associated with nuclear reprocessing waste has been investigated. This ligand has the dual advantage that it precipitates most of the cations from solution and these complexes decompose at ca. 150{degrees}C to CO{sub 2}, acetonitrile, and, initially, the metal hydroxide. Introduction of the appropriate elements required for Synroc phases to a simulated waste stream followed by NaPAO and disodium fumarate leads to precipitation of a metalorganic Synroc precursor in which the components have been intimately mixed at the molecular level. This approach circumvents incorporation of alkali metals in the final ceramic.

  7. Description and control of dissociation channels in gas-phase protein complexes

    NASA Astrophysics Data System (ADS)

    Thachuk, Mark; Fegan, Sarah K.; Raheem, Nigare

    2016-08-01

    Using molecular dynamics simulations of a coarse-grained model of the charged apo-hemoglobin protein complex, this work expands upon our initial report [S. K. Fegan and M. Thachuk, J. Am. Soc. Mass Spectrom. 25, 722-728 (2014)] about control of dissociation channels in the gas phase using specially designed charge tags. Employing a charge hopping algorithm and a range of temperatures, a variety of dissociation channels are found for activated gas-phase protein complexes. At low temperatures, a single monomer unfolds and becomes charge enriched. At higher temperatures, two additional channels open: (i) two monomers unfold and charge enrich and (ii) two monomers compete for unfolding with one eventually dominating and the other reattaching to the complex. At even higher temperatures, other more complex dissociation channels open with three or more monomers competing for unfolding. A model charge tag with five sites is specially designed to either attract or exclude charges. By attaching this tag to the N-terminus of specific monomers, the unfolding of those monomers can be decidedly enhanced or suppressed. In other words, using charge tags to direct the motion of charges in a protein complex provides a mechanism for controlling dissociation. This technique could be used in mass spectrometry experiments to direct forces at specific attachment points in a protein complex, and hence increase the diversity of product channels available for quantitative analysis. In turn, this could provide insight into the function of the protein complex in its native biological environment. From a dynamics perspective, this system provides an interesting example of cooperative behaviour involving motions with differing time scales.

  8. Violation of Lee-Yang circle theorem for Ising phase transitions on complex networks

    NASA Astrophysics Data System (ADS)

    Krasnytska, M.; Berche, B.; Holovatch, Yu.; Kenna, R.

    2015-09-01

    The Ising model on annealed complex networks with degree distribution decaying algebraically as p(K)∼ K-λ has a second-order phase transition at finite temperature if λ>3 . In the absence of space dimensionality, λ controls the transition strength; classical mean-field exponents apply for λ >5 but critical exponents are λ-dependent if λ < 5 . Here we show that, as for regular lattices, the celebrated Lee-Yang circle theorem is obeyed for the former case. However, unlike on regular lattices where it is independent of dimensionality, the circle theorem fails on complex networks when λ < 5 . We discuss the importance of this result for both theory and experiments on phase transitions and critical phenomena. We also investigate the finite-size scaling of Lee-Yang zeros in both regimes as well as the multiplicative logarithmic corrections which occur at λ=5 .

  9. Activation of gas-phase uranyl: from an oxo to a nitrido complex.

    PubMed

    Gong, Yu; Vallet, Valérie; Michelini, Maria del Carmen; Rios, Daniel; Gibson, John K

    2014-01-01

    The uranyl moiety, UO2(2+), is ubiquitous in the chemistry of uranium, the most prevalent actinide. Replacing the strong uranium-oxygen bonds in uranyl with other ligands is very challenging, having met with only limited success. We report here uranyl oxo bond activation in the gas phase to form a terminal nitrido complex, a previously elusive transformation. Collision induced dissociation of gas-phase UO2(NCO)Cl2(-) in an ion trap produced the nitrido oxo complex, NUOCl2(-), and CO2. NUOCl2(-) was computed by DFT to have Cs symmetry and a singlet ground state. The computed bond length and order indicate a triple U-N bond. Endothermic activation of UO2(NCO)Cl2(-) to produce NUOCl2(-) and neutral CO2 was computed to be thermodynamically more favorable than NCO ligand loss. Complete reaction pathways for the CO2 elimination process were computed at the DFT level. PMID:24354492

  10. Phase locking route behind complex periodic windows in a forced oscillator

    NASA Astrophysics Data System (ADS)

    Jan, Hengtai; Tsai, Kuo-Ting; Kuo, Li-wei

    2013-09-01

    Chaotic systems have complex reactions against an external driving force; even in cases with low-dimension oscillators, the routes to synchronization are diverse. We proposed a stroboscope-based method for analyzing driven chaotic systems in their phase space. According to two statistic quantities generated from time series, we could realize the system state and the driving behavior simultaneously. We demonstrated our method in a driven bi-stable system, which showed complex period windows under a proper driving force. With increasing periodic driving force, a route from interior periodic oscillation to phase synchronization through the chaos state could be found. Periodic windows could also be identified and the circumstances under which they occurred distinguished. Statistical results were supported by conditional Lyapunov exponent analysis to show the power in analyzing the unknown time series.

  11. Phase transitions via selective elemental vacancy engineering in complex oxide thin films

    PubMed Central

    Lee, Sang A.; Jeong, Hoidong; Woo, Sungmin; Hwang, Jae-Yeol; Choi, Si-Young; Kim, Sung-Dae; Choi, Minseok; Roh, Seulki; Yu, Hosung; Hwang, Jungseek; Kim, Sung Wng; Choi, Woo Seok

    2016-01-01

    Defect engineering has brought about a unique level of control for Si-based semiconductors, leading to the optimization of various opto-electronic properties and devices. With regard to perovskite transition metal oxides, O vacancies have been a key ingredient in defect engineering, as they play a central role in determining the crystal field and consequent electronic structure, leading to important electronic and magnetic phase transitions. Therefore, experimental approaches toward understanding the role of defects in complex oxides have been largely limited to controlling O vacancies. In this study, we report on the selective formation of different types of elemental vacancies and their individual roles in determining the atomic and electronic structures of perovskite SrTiO3 (STO) homoepitaxial thin films fabricated by pulsed laser epitaxy. Structural and electronic transitions have been achieved via selective control of the Sr and O vacancy concentrations, respectively, indicating a decoupling between the two phase transitions. In particular, O vacancies were responsible for metal-insulator transitions, but did not influence the Sr vacancy induced cubic-to-tetragonal structural transition in epitaxial STO thin film. The independent control of multiple phase transitions in complex oxides by exploiting selective vacancy engineering opens up an unprecedented opportunity toward understanding and customizing complex oxide thin films. PMID:27033718

  12. Phase transitions via selective elemental vacancy engineering in complex oxide thin films

    NASA Astrophysics Data System (ADS)

    Lee, Sang A.; Jeong, Hoidong; Woo, Sungmin; Hwang, Jae-Yeol; Choi, Si-Young; Kim, Sung-Dae; Choi, Minseok; Roh, Seulki; Yu, Hosung; Hwang, Jungseek; Kim, Sung Wng; Choi, Woo Seok

    2016-04-01

    Defect engineering has brought about a unique level of control for Si-based semiconductors, leading to the optimization of various opto-electronic properties and devices. With regard to perovskite transition metal oxides, O vacancies have been a key ingredient in defect engineering, as they play a central role in determining the crystal field and consequent electronic structure, leading to important electronic and magnetic phase transitions. Therefore, experimental approaches toward understanding the role of defects in complex oxides have been largely limited to controlling O vacancies. In this study, we report on the selective formation of different types of elemental vacancies and their individual roles in determining the atomic and electronic structures of perovskite SrTiO3 (STO) homoepitaxial thin films fabricated by pulsed laser epitaxy. Structural and electronic transitions have been achieved via selective control of the Sr and O vacancy concentrations, respectively, indicating a decoupling between the two phase transitions. In particular, O vacancies were responsible for metal-insulator transitions, but did not influence the Sr vacancy induced cubic-to-tetragonal structural transition in epitaxial STO thin film. The independent control of multiple phase transitions in complex oxides by exploiting selective vacancy engineering opens up an unprecedented opportunity toward understanding and customizing complex oxide thin films.

  13. Phase transitions via selective elemental vacancy engineering in complex oxide thin films.

    PubMed

    Lee, Sang A; Jeong, Hoidong; Woo, Sungmin; Hwang, Jae-Yeol; Choi, Si-Young; Kim, Sung-Dae; Choi, Minseok; Roh, Seulki; Yu, Hosung; Hwang, Jungseek; Kim, Sung Wng; Choi, Woo Seok

    2016-01-01

    Defect engineering has brought about a unique level of control for Si-based semiconductors, leading to the optimization of various opto-electronic properties and devices. With regard to perovskite transition metal oxides, O vacancies have been a key ingredient in defect engineering, as they play a central role in determining the crystal field and consequent electronic structure, leading to important electronic and magnetic phase transitions. Therefore, experimental approaches toward understanding the role of defects in complex oxides have been largely limited to controlling O vacancies. In this study, we report on the selective formation of different types of elemental vacancies and their individual roles in determining the atomic and electronic structures of perovskite SrTiO3 (STO) homoepitaxial thin films fabricated by pulsed laser epitaxy. Structural and electronic transitions have been achieved via selective control of the Sr and O vacancy concentrations, respectively, indicating a decoupling between the two phase transitions. In particular, O vacancies were responsible for metal-insulator transitions, but did not influence the Sr vacancy induced cubic-to-tetragonal structural transition in epitaxial STO thin film. The independent control of multiple phase transitions in complex oxides by exploiting selective vacancy engineering opens up an unprecedented opportunity toward understanding and customizing complex oxide thin films. PMID:27033718

  14. Organometallic complexes with biological molecules. XVIII. Alkyltin(IV) cephalexinate complexes: synthesis, solid state and solution phase investigations.

    PubMed

    Di Stefano, R; Scopelliti, M; Pellerito, C; Casella, G; Fiore, T; Stocco, G C; Vitturi, R; Colomba, M; Ronconi, L; Sciacca, I D; Pellerito, L

    2004-03-01

    Dialkyltin(IV) and trialkyltin(IV) complexes of the deacetoxycephalo-sporin-antibiotic cephalexin [7-(d-2-amino-2-phenylacetamido)-3-methyl-3-cephem-4-carboxylic acid] (Hceph) have been synthesized and investigated both in solid and solution phase. Analytical and thermogravimetric data supported the general formula Alk(2)SnOHceph(.)H(2)O and Alk(3)Snceph(.)H(2)O (Alk=Me, n-Bu), while structural information has been gained by FT-IR, (119)Sn Mössbauer and (1)H, (13)C, (119)Sn NMR data. In particular, IR results suggested polymeric structures both for Alk(2)SnOHceph(.)H(2)O and Alk(3)Snceph(.)H(2)O. Moreover, cephalexin appears to behave as monoanionic tridentate ligand coordinating the tin(IV) atom through ester-type carboxylate, as well as through beta-lactam carbonyl oxygen atoms and the amino nitrogen donor atoms in Alk(2)SnOHceph(.)H(2)O complexes. On the basis of (119)Sn Mössbauer spectroscopy it could be inferred that tin(IV) was hexacoordinated in such complexes in the solid state, showing skew trapezoidal configuration. As far as Alk(3)Sn(IV)ceph(.)H(2)O derivatives are concerned, cephalexin coordinated the Alk(3)Sn moiety through the carboxylate acting as a bridging bidentate monoanionic group. Again, (119)Sn Mössbauer spectroscopy led us to propose a trigonal configuration around the tin(IV) atom, with R(3)Sn equatorial disposition and bridging carboxylate oxygen atoms in the axial positions. The nature of the complexes in solution state was investigated by using (1)H, (13)C and (119)Sn NMR spectroscopy. Finally, the cytotoxic activity of organotin(IV) cephalexinate derivatives has been tested using two different chromosome-staining techniques Giemsa and CMA(3), towards spermatocyte chromosomes of the mussel Brachidontes pharaonis (Mollusca: Bivalvia). Colchicinized-like mitoses (c-mitoses) on slides obtained from animals exposed to organotin(IV) cephalexinate compounds, demonstrated the high mitotic spindle-inhibiting potentiality of these chemicals

  15. Influence of salt bridge interactions on the gas-phase stability of DNA/peptide complexes

    NASA Astrophysics Data System (ADS)

    Alves, Sandra; Woods, Amina; Delvolvé, Alice; Tabet, Jean Claude

    2008-12-01

    Negative ion mode electrospray ionization mass spectrometry was used to study DNA duplexes-peptide interaction. In the present study, we show that peptides that contain two adjacent basic residues interact noncovalently with DNA single strand or duplex. Fragmentation of the complexes between peptides containing basic residues and DNA were studied under collisions and showed unexpected dissociation pathways, as previously reported for peptide-peptide interactions. The binary complexes are dissociated either along fragmentation of the covalent bonds of the peptide backbone and/or along the single DNA strand backbone cleavage without disruption of noncovalent interaction, which demonstrates the strong binding of peptide to the DNA strand. Sequential MS/MS and MSn were further performed on ternary complexes formed between duplexes and peptides to investigate the nature of interaction. The CID spectra showed as major pathway the disruption of the noncovalent interactions and the formation of binary complexes and single-strand ions, directed by the nucleic acid gas-phase acidity. Indeed, a preferential formation of complexes with thymidine containing single strands is observed. An alternative pathway is also detected, in which complexes are dissociated along the covalent bond of the peptide and/or DNA according to the basicity. Our experimental data suggest the presence of strong salt bridge interactions between DNA and peptides containing basic residues.

  16. Phase effects in masking by harmonic complexes: detection of bands of speech-shaped noise.

    PubMed

    Deroche, Mickael L D; Culling, John F; Chatterjee, Monita

    2014-11-01

    When phase relationships between partials of a complex masker produce highly modulated temporal envelopes on the basilar membrane, listeners may detect speech information from temporal dips in the within-channel masker envelopes. This source of masking release (MR) is however located in regions of unresolved masker partials and it is unclear how much of the speech information in these regions is really needed for intelligibility. Also, other sources of MR such as glimpsing in between resolved masker partials may provide sufficient information from regions that disregard phase relationships. This study simplified the problem of speech recognition to a masked detection task. Target bands of speech-shaped noise were restricted to frequency regions containing either only resolved or only unresolved masker partials, as a function of masker phase relationships (sine or random), masker fundamental frequency (F0) (50, 100, or 200 Hz), and masker spectral profile (flat-spectrum or speech-shaped). Although masker phase effects could be observed in unresolved regions at F0s of 50 and 100 Hz, it was only at 50-Hz F0 that detection thresholds were ever lower in unresolved than in resolved regions, suggesting little role of envelope modulations for harmonic complexes with F0s in the human voice range and at moderate level. PMID:25373972

  17. Laser Spectroscopic Study of Cold Gas-Phase Host-Guest Complexes of Crown Ethers.

    PubMed

    Ebata, Takayuki; Inokuchi, Yoshiya

    2016-06-01

    The structure, molecular recognition, and inclusion effect on the photophysics of guest species are investigated for neutral and ionic cold host-guest complexes of crown ethers (CEs) in the gas phase. Here, the cold neutral host-guest complexes are produced by a supersonic expansion technique and the cold ionic complexes are generated by the combination of electrospray ionization (ESI) and a cryogenically cooled ion trap. The host species are 3n-crown-n (3nCn; n = 4, 5, 6, 8) and (di)benzo-3n-crown-n ((D)B3nCn; n = 4, 5, 6, 8). For neutral guests, we have chosen water and aromatic molecules, such as phenol and benzenediols, and as ionic species we have chosen alkali-metal ions (M(+) ). The electronic spectra and isomer-specific vibrational spectra for the complexes are observed with various laser spectroscopic methods: laser-induced fluorescence (LIF); ultraviolet-ultraviolet hole-burning (UV-UV HB); and IR-UV double resonance (IR-UV DR) spectroscopy. The obtained spectra are analyzed with the aid of quantum chemical calculations. We will discuss how the host and guest species change their flexible structures for forming best-fit stable complexes (induced fitting) and what kinds of interactions are operating for the stabilization of the complexes. For the alkali metal ion•CE complexes, we investigate the solvation effect by attaching water molecules. In addition to the ground-state stabilization problem, we will show that the complexation leads to a drastic effect on the excited-state electronic structure and dynamics of the guest species, which we call a "cage-like effect". PMID:27006080

  18. Cooperativity or phase transition? Unfolding transition of DNA cationic surfactant complex

    NASA Astrophysics Data System (ADS)

    Mel'nikov, Sergey M.; Sergeyev, Vladimir G.; Yoshikawa, Kenichi; Takahashi, Hiroshi; Hatta, Ichiro

    1997-11-01

    We recently reported that single duplex DNA, with the size above the order of several tens kilobase pairs, undergoes a large discrete transition from an elongated coil into a collapsed globule with the addition of a cationic surfactant. In the present article, we describe the manner of the unfolding transition of compact long DNA, or globule DNA, complexed with cationic surfactants, cetyltrimethylammonium bromide (CTAB) and distearyldimethylammonium bromide (D18DAB), as is induced by the addition of sodium bromide. The conformational dynamics of individual single duplex T4DNA molecules was directly observed with the use of fluorescence microscopy. We found that on the level of individual DNAs, the salt-induced unfolding transition of the globules is largely discrete, or first-order phase transition for the both complexes with CTAB and D18DAB. On the other hand, for the ensemble average of the DNAs, the transition is discrete with CTAB but is continuous (sigmoidal) with D18DAB. The discreteness for the coil-globule transition in the ensemble of DNAs complexed with CTAB is attributed to the existence of the phase transition in whole over the bulk solution: the sphere-rod transition in surfactant micelles. On the other hand, for D18DAB such phase transition on the micelle structure in the bulk solution seems to be absent. In correspondence to such a large difference on the manner of the transition, x-ray diffraction analysis indicates marked difference on the structure of DNA complexes with CTAB and with D18DAB.

  19. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  20. Phase behavior of electrostatically complexed polyelectrolyte gels using an embedded fluctuation model.

    PubMed

    Audus, Debra J; Gopez, Jeffrey D; Krogstad, Daniel V; Lynd, Nathaniel A; Kramer, Edward J; Hawker, Craig J; Fredrickson, Glenn H

    2015-02-14

    Nanostructured, responsive hydrogels formed due to electrostatic interactions have promise for applications such as drug delivery and tissue mimics. These physically cross-linked hydrogels are composed of an aqueous solution of oppositely charged triblocks with charged end-blocks and neutral, hydrophilic mid-blocks. Due to their electrostatic interactions, the end-blocks microphase separate and form physical cross-links that are bridged by the mid-blocks. The structure of this system was determined using a new, efficient embedded fluctuation (EF) model in conjunction with self-consistent field theory. The calculations using the EF model were validated against unapproximated field-theoretic simulations with complex Langevin sampling and were found consistent with small angle X-ray scattering (SAXS) measurements on an experimental system. Using both the EF model and SAXS, phase diagrams were generated as a function of end-block fraction and polymer concentration. Several structures were observed including a body-centered cubic sphere phase, a hexagonally packed cylinder phase, and a lamellar phase. Finally, the EF model was used to explore how parameters that directly relate to polymer chemistry can be tuned to modify the resulting phase diagram, which is of practical interest for the development of new hydrogels. PMID:25567551

  1. Design of phase-only, binary phase-only, and complex ternary matched filters with increased signal-to-noise ratios for colored noise

    NASA Technical Reports Server (NTRS)

    Kumar, B. V. K. V.; Juday, Richard D.

    1991-01-01

    An algorithm is provided for treating nonwhite additive noise in determining regions of support for phase-only filters, binary phase-only filters, and complex ternary matched filters. It is analytically shown to be optimal in the signal-to-noise ratio sense. It extends earlier research that assumed white noise.

  2. Phase Transition in Postsynaptic Densities Underlies Formation of Synaptic Complexes and Synaptic Plasticity.

    PubMed

    Zeng, Menglong; Shang, Yuan; Araki, Yoichi; Guo, Tingfeng; Huganir, Richard L; Zhang, Mingjie

    2016-08-25

    Postsynaptic densities (PSDs) are membrane semi-enclosed, submicron protein-enriched cellular compartments beneath postsynaptic membranes, which constantly exchange their components with bulk aqueous cytoplasm in synaptic spines. Formation and activity-dependent modulation of PSDs is considered as one of the most basic molecular events governing synaptic plasticity in the nervous system. In this study, we discover that SynGAP, one of the most abundant PSD proteins and a Ras/Rap GTPase activator, forms a homo-trimer and binds to multiple copies of PSD-95. Binding of SynGAP to PSD-95 induces phase separation of the complex, forming highly concentrated liquid-like droplets reminiscent of the PSD. The multivalent nature of the SynGAP/PSD-95 complex is critical for the phase separation to occur and for proper activity-dependent SynGAP dispersions from the PSD. In addition to revealing a dynamic anchoring mechanism of SynGAP at the PSD, our results also suggest a model for phase-transition-mediated formation of PSD. PMID:27565345

  3. Prestack depth migration for complex 2D structure using phase-screen propagators

    SciTech Connect

    Roberts, P.; Huang, Lian-Jie; Burch, C.; Fehler, M.; Hildebrand, S.

    1997-11-01

    We present results for the phase-screen propagator method applied to prestack depth migration of the Marmousi synthetic data set. The data were migrated as individual common-shot records and the resulting partial images were superposed to obtain the final complete Image. Tests were performed to determine the minimum number of frequency components required to achieve the best quality image and this in turn provided estimates of the minimum computing time. Running on a single processor SUN SPARC Ultra I, high quality images were obtained in as little as 8.7 CPU hours and adequate images were obtained in as little as 4.4 CPU hours. Different methods were tested for choosing the reference velocity used for the background phase-shift operation and for defining the slowness perturbation screens. Although the depths of some of the steeply dipping, high-contrast features were shifted slightly the overall image quality was fairly insensitive to the choice of the reference velocity. Our jests show the phase-screen method to be a reliable and fast algorithm for imaging complex geologic structures, at least for complex 2D synthetic data where the velocity model is known.

  4. Significance of chamber pressure to complex multi-phase physics in jet engine fuel injection processes

    NASA Astrophysics Data System (ADS)

    Dahms, Rainer; Oefelein, Joseph

    2014-11-01

    Injection processes in jet engines at chamber pressures in excess of the thermodynamic critical pressure of the liquid fuel are not well understood. Under some conditions, a distinct two-phase interface may not exist anymore which eliminates the presence of classical spray atomization phenomena. A comprehensive model for jet engine fuel injections is derived to quantify the conditions under which the interfacial dynamics transition to diffusion-dominated mixing processes without surface tension. At certain conditions, the model shows two-phase interfaces with substantially increased thicknesses and distinctively reduced mean free paths in comparison to ambient pressure conditions. Then, the underlying assumptions of a distinct two-phase interface do not apply anymore and the interface along with its surface tension is shown to deteriorate as it broadens substantially. As a consequence of this physical complexity, the conceptual view of spray atomization and evaporation as an appropriate model for jet engine injection processes is, contrary to conventional wisdom, questionable at certain operating conditions. Instead, a Large Eddy Simulation using a dense-fluid approximation is applied which takes the complex thermo-physics of real-fluid behavior into account.

  5. Novel complex MAD phasing and RNase H structural insights using selenium oligonucleotides

    SciTech Connect

    Abdur, Rob; Gerlits, Oksana O.; Gan, Jianhua; Jiang, Jiansheng; Salon, Jozef; Kovalevsky, Andrey Y.; Chumanevich, Alexander A.; Weber, Irene T.; Huang, Zhen

    2014-02-01

    Selenium-derivatized oligonucleotides may facilitate phase determination and high-resolution structure determination for protein–nucleic acid crystallography. The Se atom-specific mutagenesis (SAM) strategy may also enhance the study of nuclease catalysis. The crystal structures of protein–nucleic acid complexes are commonly determined using selenium-derivatized proteins via MAD or SAD phasing. Here, the first protein–nucleic acid complex structure determined using selenium-derivatized nucleic acids is reported. The RNase H–RNA/DNA complex is used as an example to demonstrate the proof of principle. The high-resolution crystal structure indicates that this selenium replacement results in a local subtle unwinding of the RNA/DNA substrate duplex, thereby shifting the RNA scissile phosphate closer to the transition state of the enzyme-catalyzed reaction. It was also observed that the scissile phosphate forms a hydrogen bond to the water nucleophile and helps to position the water molecule in the structure. Consistently, it was discovered that the substitution of a single O atom by a Se atom in a guide DNA sequence can largely accelerate RNase H catalysis. These structural and catalytic studies shed new light on the guide-dependent RNA cleavage.

  6. Exact calculations of phase and membrane equilibria for complex fluids by Monte Carlo simulation

    SciTech Connect

    Panagiotopoulos, A.Z.

    1990-08-28

    The general objective of this project is the investigation of phase equilibria for complex fluids using a novel methodology, Monte Carlo simulation in the Gibbs ensemble. The methodology enables the direct determination of the properties of two coexisting fluid phases (e.g. a liquid at equilibrium with its vapor) from a single computer experiment, and is applicable to multicomponent systems with arbitrary equilibrium constraints imposed. The specific goals of this work are to adapt the Gibbs technique to (a) highly asymmetric mixtures with large differences in size and potential energies of interaction (b) chain molecules and (c) ionic systems. Significant progress has been made in all three areas. In this paper, we will briefly describe the progress made in each area, using the same numbering scheme for the tasks as in the original proposal.

  7. The steady-state phase distribution of the motor switch complex model of Halobacterium salinarum.

    PubMed

    del Rosario, Ricardo C H; Diener, Francine; Diener, Marc; Oesterhelt, Dieter

    2009-12-01

    Steady-state analysis is performed on the kinetic model for the switch complex of the flagellar motor of Halobacterium salinarum (Nutsch et al.). The existence and uniqueness of a positive steady-state of the system is established and it is demonstrated why the steady-state is centered around the competent phase, a state of the motor in which it is able to respond to light stimuli. It is also demonstrated why the steady-state shifts to the refractory phase when the steady-state value of the response regulator CheYP increases. This work is one aspect of modeling in systems biology wherein the mathematical properties of a model are established. PMID:19857501

  8. Deciphering the internal complexity of living cells with quantitative phase microscopy: a multiscale approach

    NASA Astrophysics Data System (ADS)

    Martinez-Torres, Cristina; Laperrousaz, Bastien; Berguiga, Lotfi; Boyer-Provera, Elise; Elezgaray, Juan; Nicolini, Franck E.; Maguer-Satta, Veronique; Arneodo, Alain; Argoul, Françoise

    2015-09-01

    The distribution of refractive indices (RIs) of a living cell contributes in a nonintuitive manner to its optical phase image and quite rarely can be inverted to recover its internal structure. The interpretation of the quantitative phase images of living cells remains a difficult task because (1) we still have very little knowledge on the impact of its internal macromolecular complexes on the local RI and (2) phase changes produced by light propagation through the sample are mixed with diffraction effects by the internal cell bodies. We propose to implement a two-dimensional wavelet-based contour chain detection method to distinguish internal boundaries based on their greatest optical path difference gradients. These contour chains correspond to the highest image phase contrast and follow the local RI inhomogeneities linked to the intracellular structural intricacy. Their statistics and spatial distribution are the morphological indicators suited for comparing cells of different origins and/or to follow their transformation in pathologic situations. We use this method to compare nonadherent blood cells from primary and laboratory culture origins and to assess the internal transformation of hematopoietic stem cells by the transduction of the BCR-ABL oncogene responsible for the chronic myelogenous leukemia.

  9. Colloidal TiO2 nanocrystals prepared from peroxotitanium complex solutions: phase evolution from different precursors.

    PubMed

    Seok, Sang Il; Vithal, Muga; Chang, Jeong Ah

    2010-06-01

    We report the preparation of nanocrystalline anatase and rutile TiO(2) from aqueous peroxotitanium complex (PTC) solutions and their characterization by powder X-ray diffraction (XRD), infrared spectroscopy, and Raman spectroscopy. The phase evolution of TiO(2) prepared using PTC derived from different precursors, i.e., TiCl(4) and titanium tetraisopropoxide (TTIP), is related to the nature of the intermediate steps. Phase-pure nanoanatase was formed in PTC solution derived from TiCl(4), while a mixture of minor anatase and dominant rutile were prepared from PTC when TTIP was used as precursor. On the other hand, in the case of calcining PTC powders in air, a pure anatase phase of TiO(2) was obtained, regardless of the precursor used. Thus, the formation and attachment of hydrated TiO(6) units or TiO(2)·xH(2)O under a different environment, especially pH, plays a critical role in determining the phase during the crystallization of TiO(2). PMID:20227087

  10. Wound-up phase turbulence in the complex Ginzburg-Landau equation

    NASA Astrophysics Data System (ADS)

    Montagne, R.; Hernández-García, E.; Amengual, A.; San Miguel, M.

    1997-07-01

    We consider phase turbulent regimes with nonzero winding number in the one-dimensional complex Ginzburg-Landau equation. We find that phase turbulent states with winding number larger than a critical one are only transients and decay to states within a range of allowed winding numbers. The analogy with the Eckhaus instability for nonturbulent waves is stressed. The transition from phase to defect turbulence is interpreted as an ergodicity breaking transition that occurs when the range of allowed winding numbers vanishes. We explain the states reached at long times in terms of three basic states, namely, quasiperiodic states, frozen turbulence states, and riding turbulence states. Justification and some insight into them are obtained from an analysis of a phase equation for nonzero winding number: Rigidly moving solutions of this equation, which correspond to quasiperiodic and frozen turbulence states, are understood in terms of periodic and chaotic solutions of an associated system of ordinary differential equations. A short report of some of our results has already been published [R. Montagne et al., Phys. Rev. Lett. 77, 267 (1996)].

  11. Detecting critical state before phase transition of complex systems by hidden Markov model

    NASA Astrophysics Data System (ADS)

    Liu, Rui; Chen, Pei; Li, Yongjun; Chen, Luonan

    Identifying the critical state or pre-transition state just before the occurrence of a phase transition is a challenging task, because the state of the system may show little apparent change before this critical transition during the gradual parameter variations. Such dynamics of phase transition is generally composed of three stages, i.e., before-transition state, pre-transition state, and after-transition state, which can be considered as three different Markov processes. Thus, based on this dynamical feature, we present a novel computational method, i.e., hidden Markov model (HMM), to detect the switching point of the two Markov processes from the before-transition state (a stationary Markov process) to the pre-transition state (a time-varying Markov process), thereby identifying the pre-transition state or early-warning signals of the phase transition. To validate the effectiveness, we apply this method to detect the signals of the imminent phase transitions of complex systems based on the simulated datasets, and further identify the pre-transition states as well as their critical modules for three real datasets, i.e., the acute lung injury triggered by phosgene inhalation, MCF-7 human breast cancer caused by heregulin, and HCV-induced dysplasia and hepatocellular carcinoma.

  12. Evolution of pattern complexity in the Cahn-Hilliard theory of phase separation

    SciTech Connect

    Gameiro, Marcio; Mischaikow, Konstantin; Wanner, Thomas . E-mail: wanner@math.gmu.edu

    2005-02-01

    Phase separation processes in compound materials can produce intriguing and complicated patterns. Yet, characterizing the geometry of these patterns quantitatively can be quite challenging. In this paper we propose the use of computational algebraic topology to obtain such a characterization. Our method is illustrated for the complex microstructures observed during spinodal decomposition and early coarsening in both the deterministic Cahn-Hilliard theory, as well as in the stochastic Cahn-Hilliard-Cook model. While both models produce microstructures that are qualitatively similar to the ones observed experimentally, our topological characterization points to significant differences. One particular aspect of our method is its ability to quantify boundary effects in finite size systems.

  13. Chemical Frustration. A Design Principle for the Discovery of New Complex Alloy and Intermetallic Phases, Final Report

    SciTech Connect

    Fredrickson, Daniel C

    2015-06-23

    Final technical report for "Chemical Frustration: A Design Principle for the Discovery of New Complex Alloy and Intermetallic Phases" funded by the Office of Science through the Materials Chemistry Program of the Office of Basic Energy Sciences.

  14. Evolution of phase and morphology of titanium dioxide induced from peroxo titanate complex aqueous solution.

    PubMed

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2010-01-01

    We demonstrate the growth of anatase TiO2 in nanospheres and rutile TiO2 in nanorods, by the hydrolysis of titanium tetraisopropoxide (TTIP) in the presence of hydrogen peroxide at 100 degrees C using sol-gel method. X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), scanning electron microscopy (SEM), and surface area measurement techniques are used to characterize the phase and shape developments of TiO2 obtained from peroxo titanate complex in an aqueous solution at 100 degrees C. Peroxo titanate complexes were prepared by a reaction of titanium hydroxide, formed by hydrolysis of titanium tetraisopropoxide (TTIP), and different amounts of hydrogen peroxide (H2O2). TEM and XRD investigations reveal that the size of spheres (anatase) and rods (rutile) are about 8 nm (diameter) and about 13 x 29 nm approximately 20 x 75 nm (width x length) respectively. The influence of molar ratio of H2O2/TTIP on the phase and morphology of TiO2 is presented. A mixture of anatase spheres and short rutile rods are formed at low H2O2/TTIP ratio while predominantly rutile a quit long rods are formed at higher H2O2/TTIP ratio. PMID:20352827

  15. Crystallization of and selenomethionine phasing strategy for a SETMAR-DNA complex.

    PubMed

    Chen, Qiujia; Georgiadis, Millie

    2016-09-01

    Transposable elements have played a critical role in the creation of new genes in all higher eukaryotes, including humans. Although the chimeric fusion protein SETMAR is no longer active as a transposase, it contains both the DNA-binding domain (DBD) and catalytic domain of the Hsmar1 transposase. The amino-acid sequence of the DBD has been virtually unchanged in 50 million years and, as a consequence, SETMAR retains its sequence-specific binding to the ancestral Hsmar1 terminal inverted repeat (TIR) sequence. Thus, the DNA-binding activity of SETMAR is likely to have an important biological function. To determine the structural basis for the recognition of TIR DNA by SETMAR, the design of TIR-containing oligonucleotides and SETMAR DBD variants, crystallization of DBD-DNA complexes, phasing strategies and initial phasing experiments are reported here. An unexpected finding was that oligonucleotides containing two BrdUs in place of thymidines produced better quality crystals in complex with SETMAR than their natural counterparts. PMID:27599863

  16. Deciphering complex, functional structures with synchrotron-based absorption and phase contrast tomographic microscopy

    NASA Astrophysics Data System (ADS)

    Stampanoni, M.; Reichold, J.; Weber, B.; Haberthür, D.; Schittny, J.; Eller, J.; Büchi, F. N.; Marone, F.

    2010-09-01

    Nowadays, thanks to the high brilliance available at modern, third generation synchrotron facilities and recent developments in detector technology, it is possible to record volumetric information at the micrometer scale within few minutes. High signal-to-noise ratio, quantitative information on very complex structures like the brain micro vessel architecture, lung airways or fuel cells can be obtained thanks to the combination of dedicated sample preparation protocols, in-situ acquisition schemes and cutting-edge imaging analysis instruments. In this work we report on recent experiments carried out at the TOMCAT beamline of the Swiss Light Source [1] where synchrotron-based tomographic microscopy has been successfully used to obtain fundamental information on preliminary models for cerebral fluid flow [2], to provide an accurate mesh for 3D finite-element simulation of the alveolar structure of the pulmonary acinus [3] and to investigate the complex functional mechanism of fuel cells [4]. Further, we introduce preliminary results on the combination of absorption and phase contrast microscopy for the visualization of high-Z nanoparticles in soft tissues, a fundamental information when designing modern drug delivery systems [5]. As an outlook we briefly discuss the new possibilities offered by high sensitivity, high resolution grating interferomtery as well as Zernike Phase contrast nanotomography [6].

  17. Vibrational Spectroscopy of Mass Selected [UO2(ligand)n]2+ Complexes in the Gas Phase

    SciTech Connect

    Gary S. Groenewold; Anita Gianotto; Michael Vanstipdonk; Kevin C. Cossel; David T. Moore,; Nick Polfer; Jos Oomens

    2006-03-01

    The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch, and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm-1 for [UO2(CH3COCH3)2]2+, and was systematically red shifted to 1000 and 988 cm-1 by the addition of a third and fourth acetone ligands, respectively, which was consistent with more donation of electron density to the uranium center in complexes with higher coordination number. The experimental measurements were in good agreement with values generated computationally using LDA, B3LYP, and ZORA-PW91 approaches. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from 2 to 4, and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes although the magnitude of the red shift in the uranyl frequency upon addition more acetonitrile ligands was smaller than for acetone, consistent with the more modest nucleophilic nature of acetonitrile. This conclusion was amplified by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3 to 6 cm-1.

  18. Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid.

    PubMed

    Garrigosa, Anna Maria; Gusmão, Rui; Ariño, Cristina; Díaz-Cruz, José Manuel; Esteban, Miquel

    2007-10-15

    The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. -10 degrees for Cd-PMA and ca. -15 degrees for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents. PMID:19073101

  19. Complexity measure and quantum shape-phase transitions in the two-dimensional limit of the vibron model.

    PubMed

    Romera, Elvira; Calixto, Manuel; Nagy, Ágnes

    2014-07-01

    We obtain a characterization of quantum shape-phase transitions in the terms of complexity measures in the two-dimensional limit of the vibron model based on the spectrum generating algebra U(3). Complexity measures (in terms of the Rényi entropies) have been calculated for different values of the control parameter for the ground state of this model giving sharp signatures of the quantum shape-phase transition from linear to bent molecules. PMID:24948526

  20. Realist complex intervention science: Applying realist principles across all phases of the Medical Research Council framework for developing and evaluating complex interventions

    PubMed Central

    Fletcher, Adam; Jamal, Farah; Moore, Graham; Evans, Rhiannon E.; Murphy, Simon; Bonell, Chris

    2016-01-01

    The integration of realist evaluation principles within randomised controlled trials (‘realist RCTs’) enables evaluations of complex interventions to answer questions about what works, for whom and under what circumstances. This allows evaluators to better develop and refine mid-level programme theories. However, this is only one phase in the process of developing and evaluating complex interventions. We describe and exemplify how social scientists can integrate realist principles across all phases of the Medical Research Council framework. Intervention development, modelling, and feasibility and pilot studies need to theorise the contextual conditions necessary for intervention mechanisms to be activated. Where interventions are scaled up and translated into routine practice, realist principles also have much to offer in facilitating knowledge about longer-term sustainability, benefits and harms. Integrating a realist approach across all phases of complex intervention science is vital for considering the feasibility and likely effects of interventions for different localities and population subgroups. PMID:27478401

  1. DNA-Encoded Solid-Phase Synthesis: Encoding Language Design and Complex Oligomer Library Synthesis

    PubMed Central

    2015-01-01

    The promise of exploiting combinatorial synthesis for small molecule discovery remains unfulfilled due primarily to the “structure elucidation problem”: the back-end mass spectrometric analysis that significantly restricts one-bead-one-compound (OBOC) library complexity. The very molecular features that confer binding potency and specificity, such as stereochemistry, regiochemistry, and scaffold rigidity, are conspicuously absent from most libraries because isomerism introduces mass redundancy and diverse scaffolds yield uninterpretable MS fragmentation. Here we present DNA-encoded solid-phase synthesis (DESPS), comprising parallel compound synthesis in organic solvent and aqueous enzymatic ligation of unprotected encoding dsDNA oligonucleotides. Computational encoding language design yielded 148 thermodynamically optimized sequences with Hamming string distance ≥ 3 and total read length <100 bases for facile sequencing. Ligation is efficient (70% yield), specific, and directional over 6 encoding positions. A series of isomers served as a testbed for DESPS’s utility in split-and-pool diversification. Single-bead quantitative PCR detected 9 × 104 molecules/bead and sequencing allowed for elucidation of each compound’s synthetic history. We applied DESPS to the combinatorial synthesis of a 75 645-member OBOC library containing scaffold, stereochemical and regiochemical diversity using mixed-scale resin (160-μm quality control beads and 10-μm screening beads). Tandem DNA sequencing/MALDI-TOF MS analysis of 19 quality control beads showed excellent agreement (<1 ppt) between DNA sequence-predicted mass and the observed mass. DESPS synergistically unites the advantages of solid-phase synthesis and DNA encoding, enabling single-bead structural elucidation of complex compounds and synthesis using reactions normally considered incompatible with unprotected DNA. The widespread availability of inexpensive oligonucleotide synthesis, enzymes, DNA sequencing, and

  2. Low temperature pathways to Chevrel phases via reduced molybdenum sulfide cluster complexes

    NASA Astrophysics Data System (ADS)

    Shane, H.

    1993-03-01

    The initial cluster compound, Na(2y)Mo(6)S(8+y) py(sub x), was discovered by reacting Mo(6)Cl(12) with higher stoichiometries of sodium hydrosulfide and sodium butoxide in butanol/pyridine. This compound can subsequently undergo ligand exchange reactions to form a variety of cluster complexes. Single-crystal structure determinations are reported for the pyridine (py), piperidine (pip), and pyrrolidine (pyrr) complexes: triclinic Mo(6)S(8)(PY)(6) (center dot) 1.65py, cubic Mo(6)S(8)(py)(6) (center dot) 2py, Mo(6)S(8)(pip)(6) (center dot) 7pip, and Mo(6)S(8) (pyrr)(6) (center dot) 1pyrr. Delegation of the cluster complexes was explored. Direct heating under dynamic vacuum led to incomplete delegation. Reactions with tin and lead resulted in formation of corresponding Chevrel phase compounds along with MoS(2). Thermolysis reactions in the presence of flowing ammonia gas resulted in further delegation than was evidenced for reactions explored in vacuo. Solution reactions with strong acids were studied in an attempt to protonate the ligands and thus make them better leaving groups only limited success was achieved. A new preparative route was developed for ternary molybdenum sulfides. Cation exchange reactions with Na(2y)Mo(6)S(8+y)(MeOH)(x) were used to form the cobalt, tin, lead, and holmium compounds. Preliminary hydrodesulfurization studies on the sodium and cobalt compounds showed that they possess larger surface areas and thiophene conversion percentages than Chevrel phases, but a lower HDS rate.

  3. Structural evolution of polyelectrolyte-complex-core micelles and ordered-phase bulk materials

    NASA Astrophysics Data System (ADS)

    Tirrell, Matthew; Krogstad, Daniel; Kramer, Edward

    2015-03-01

    The kinetics of formation and structural evolution of novel polyelectrolyte complex materials formed by the assembly of water-soluble di- and tri-block copolymers, with one neutral block and one block either cationic or anionic, have been investigated. The mechanism and speed of the assembly process, and the organization of these domains, were probed using dynamic mechanical spectroscopy and small angle X-ray scattering (SAXS). SAXS revealed that the equilibrium morphologies of both the di-block copolymer and the tri-block copolymer materials were generally qualitatively the same with some apparent quantitative differences in phase boundaries, possibly attributable to lack of full equilibration. Slow kinetics and difficulties in reaching equilibrium phase structures, especially in tri-block materials, is a principal message of this article. Detailed analysis of the SAXS data revealed that the tri-block copolymer materials formed ordered phases via a nucleation and growth pathway and that the addition of small amounts (~20%) of corresponding di-block copolymers increased the rate of structure formation and enhanced several key physical properties. This work was supported by the U.S. Department of Energy Office of Science Program in Basic Energy Sciences, Materials Sciences and Engineering Division.

  4. Applications of Wang-Landau sampling to determine phase equilibria in complex fluids

    NASA Astrophysics Data System (ADS)

    Ganzenmüller, Georg; Camp, Philip J.

    2007-10-01

    Applications of the Wang-Landau algorithm for simulating phase coexistence at fixed temperature are presented. The number density is sampled using either volume scaling or particle insertion/deletion. The resulting algorithms, while being conceptually easy, are of comparable efficiency to existing multicanonical methods but with the advantage that neither the chemical potential nor the pressure at phase coexistence has to be estimated in advance of the simulation. First, we benchmark the algorithm against literature results for the vapor-liquid transition in the Lennard-Jones fluid. We then demonstrate the general applicability of the algorithm by studying vapor-liquid coexistence in two examples of complex fluids: charged soft spheres, which exhibit a transition similar to that in the restricted primitive model of ionic fluids, being characterized by strong ion pairing in the vapor phase; and Stockmayer fluids with high dipole strengths, in which the constituent particles aggregate to form chains, and for which the very existence of a transition has been widely debated. Finally, we show that the algorithm can be used to locate a weak isotropic-nematic transition in a fluid of Gay-Berne mesogens.

  5. Applications of Wang-Landau sampling to determine phase equilibria in complex fluids.

    PubMed

    Ganzenmüller, Georg; Camp, Philip J

    2007-10-21

    Applications of the Wang-Landau algorithm for simulating phase coexistence at fixed temperature are presented. The number density is sampled using either volume scaling or particle insertion/deletion. The resulting algorithms, while being conceptually easy, are of comparable efficiency to existing multicanonical methods but with the advantage that neither the chemical potential nor the pressure at phase coexistence has to be estimated in advance of the simulation. First, we benchmark the algorithm against literature results for the vapor-liquid transition in the Lennard-Jones fluid. We then demonstrate the general applicability of the algorithm by studying vapor-liquid coexistence in two examples of complex fluids: charged soft spheres, which exhibit a transition similar to that in the restricted primitive model of ionic fluids, being characterized by strong ion pairing in the vapor phase; and Stockmayer fluids with high dipole strengths, in which the constituent particles aggregate to form chains, and for which the very existence of a transition has been widely debated. Finally, we show that the algorithm can be used to locate a weak isotropic-nematic transition in a fluid of Gay-Berne mesogens. PMID:17949170

  6. Novel complex MAD phasing and RNase H structural insights using selenium oligonucleotides

    PubMed Central

    Abdur, Rob; Gerlits, Oksana O.; Gan, Jianhua; Jiang, Jiansheng; Salon, Jozef; Kovalevsky, Andrey Y.; Chumanevich, Alexander A.; Weber, Irene T.; Huang, Zhen

    2014-01-01

    The crystal structures of protein–nucleic acid complexes are commonly determined using selenium-derivatized proteins via MAD or SAD phasing. Here, the first protein–nucleic acid complex structure determined using selenium-derivatized nucleic acids is reported. The RNase H–RNA/DNA complex is used as an example to demonstrate the proof of principle. The high-resolution crystal structure indicates that this selenium replacement results in a local subtle unwinding of the RNA/DNA substrate duplex, thereby shifting the RNA scissile phosphate closer to the transition state of the enzyme-catalyzed reaction. It was also observed that the scissile phosphate forms a hydrogen bond to the water nucleophile and helps to position the water molecule in the structure. Consistently, it was discovered that the substitution of a single O atom by a Se atom in a guide DNA sequence can largely accelerate RNase H catalysis. These structural and catalytic studies shed new light on the guide-dependent RNA cleavage. PMID:24531469

  7. Gas Phase Uranyl Activation: Formation of a Uranium Nitrosyl Complex from Uranyl Azide

    SciTech Connect

    Gong, Yu; De Jong, Wibe A.; Gibson, John K.

    2015-05-13

    Activation of the oxo bond of uranyl, UO22+, was achieved by collision induced dissociation (CID) of UO2(N3)Cl2– in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2– was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2– resulted in the loss of N2 to form UO(NO)Cl2–, in which the “inert” uranyl oxo bond has been activated. Formation of UO2Cl2– via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2– complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2– complex shows that the side-on bonded NO moiety can be considered as NO3–, suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2– to form UO(NO)Cl2– and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2– and UO2Cl2–. The observation of UO2Cl2– during CID is most likely due to the absence of an energy barrier for neutral ligand loss.

  8. Gas phase uranyl activation: formation of a uranium nitrosyl complex from uranyl azide.

    PubMed

    Gong, Yu; de Jong, Wibe A; Gibson, John K

    2015-05-13

    Activation of the oxo bond of uranyl, UO2(2+), was achieved by collision induced dissociation (CID) of UO2(N3)Cl2(-) in a quadrupole ion trap mass spectrometer. The gas phase complex UO2(N3)Cl2(-) was produced by electrospray ionization of solutions of UO2Cl2 and NaN3. CID of UO2(N3)Cl2(-) resulted in the loss of N2 to form UO(NO)Cl2(-), in which the "inert" uranyl oxo bond has been activated. Formation of UO2Cl2(-) via N3 loss was also observed. Density functional theory computations predict that the UO(NO)Cl2(-) complex has nonplanar Cs symmetry and a singlet ground state. Analysis of the bonding of the UO(NO)Cl2(-) complex shows that the side-on bonded NO moiety can be considered as NO(3-), suggesting a formal oxidation state of U(VI). Activation of the uranyl oxo bond in UO2(N3)Cl2(-) to form UO(NO)Cl2(-) and N2 was computed to be endothermic by 169 kJ/mol, which is energetically more favorable than formation of NUOCl2(-) and UO2Cl2(-). The observation of UO2Cl2(-) during CID is most likely due to the absence of an energy barrier for neutral ligand loss. PMID:25906363

  9. Gas-liquid two-phase flow structure in the multi-scale weighted complexity entropy causality plane

    NASA Astrophysics Data System (ADS)

    Tang, Yi; Zhao, An; Ren, Ying-yu; Dou, Fu-Xiang; Jin, Ning-De

    2016-05-01

    The multi-scale weighted complexity entropy causality plane (MS-WCECP) is proposed for characterizing the physical structure of complex system. Firstly we use the method to investigate typical nonlinear time series. Compared with the multi-scale complexity entropy causality plane (MS-CECP), the MS-WCECP can not only uncover the dynamic information loss of complex system with the increase of scale, but also can characterize the complexity of nonlinear dynamic system. In particular, the algorithm of MS-WCECP performs strong anti-noise ability. Then we calculate the MS-WCECP for the conductance fluctuating signals measured from vertical upward gas-liquid two-phase flow experiments in a small diameter pipe, the results demonstrate that the MS-WCECP is a useful approach for exploring the stability and complexity in gas-liquid two-phase flows.

  10. Photoreactions in the gas-phase complexes of Mg(*+)-dioxanes.

    PubMed

    Liu, Haichuan; Hu, Yihua; Yang, Shihe; Guo, Wenyue; Fu, Qingtao; Wang, Ling

    2006-04-01

    Photoreactions in the gas-phase complexes Mg(*+)(1,4-dioxane) (1) and Mg(*+)(1,3-dioxane) (1M) have been examined in the wavelength region of 230-440 nm. Photoproduct assignments are facilitated with the help of deuterium substitution experiments. The main energy relaxation channel for both photoexcited complexes is the evaporation of Mg(*+). Also observed from 1 are rich photoproducts with m/z 28, 41, 54-58, 67, 69, and 88; the most abundant one at m/z 54 is designated to Mg(*+)(O=CH(2)). In marked contrast, the photolysis of 1M yields only Mg(*+)(O=CH(2)) other than Mg(*+). Density functional calculations are performed to obtain optimized geometries and potential energy surfaces of 1 and 1M. Although Mg(*+)(chair-1,4-C(4)H(8)O(2)) (1a) and Mg(*+)(boat-1,4-C(4)H(8)O(2)) (1b) are comparable in energy, the much better agreement of the experimental action spectrum of Mg(*+)(1,4-C(4)H(8)O(2)) with the calculated absorption spectrum of 1a than with that of 1b indicates the predominance of 1a in the source due to the stability of the chair-1,4-dioxane. For photoreactions, the C-O bond is found to be much more prone to rupture than the C-C bond due to the coordination of O to Mg(+) in the parent complexes. Photoreaction mechanisms are discussed in terms of two key insertion complexes, which rationalize all of the observed photoproducts. PMID:16571042

  11. In vivoimaging of human vasculature in the chorioretinal complex using phase-variance contrast method with phase-stabilized 1 - μ m swept-source optical coherence tomography

    NASA Astrophysics Data System (ADS)

    Poddar, Raju; Kim, Dae Yu; Werner, John S.; Zawadzki, Robert J.

    2014-12-01

    We present a noninvasive phase-variance (pv)-based motion contrast method for depth-resolved imaging of the human chorioretinal complex microcirculation with a newly developed phase-stabilized high speed (100-kHz A-scans/s) 1-μm swept-source optical coherence tomography (SSOCT) system. Compared to our previous spectral-domain (spectrometer based) pv-spectral domain OCT (SDOCT) system, this system has the advantages of higher sensitivity, reduced fringe wash-out for high blood flow speeds and deeper penetration in choroid. High phase stability SSOCT imaging was achieved by using a computationally efficient phase stabilization approach. This process does not require additional calibration hardware and complex numerical procedures. Our phase stabilization method is simple and can be employed in a variety of SSOCT systems. Examples of vasculature in the chorioretinal complex imaged by pv-SSOCT from normal as well as diseased eyes are presented and compared to retinal images of the same subjects acquired with fluorescein angiography and indocyanine green angiography. Observations of morphology of vascular perfusion in chorioretinal complex visualized by our method are listed.

  12. An HPLC chromatographic framework to analyze the β-cyclodextrin/solute complexation mechanism using a carbon nanotube stationary phase.

    PubMed

    Aljhni, Rania; Andre, Claire; Lethier, Lydie; Guillaume, Yves Claude

    2015-11-01

    A carbon nanotube (CNT) stationary phase was used for the first time to study the β-cyclodextrin (β-CD) solute complexation mechanism using high performance liquid chromatography (HPLC). For this, the β-CD was added at various concentrations in the mobile phase and the effect of column temperature was studied on both the retention of a series of aniline and benzoic acid derivatives with the CNT stationary phase and their complexation mechanism with β-CD. A decrease in the solute retention factor was observed for all the studied molecules without change in the retention order. The apparent formation constant KF of the inclusion complex β-CD/solute was determined at various temperatures. Our results showed that the interaction of β-CD with both the mobile phase and the stationary phase interfered in the complex formation. The enthalpy and entropy of the complex formation (ΔHF and ΔSF) between the solute molecule and CD were determined using a thermodynamic approach. Negative enthalpies and entropies indicated that the inclusion process of the studied molecule in the CD cavity was enthalpically driven and that the hydrogen bonds between carboxylic or aniline groups and the functional groups on the β-CD rim play an important role in the complex formation. PMID:26452814

  13. The little elongation complex functions at initiation and elongation phases of snRNA gene transcription.

    PubMed

    Hu, Deqing; Smith, Edwin R; Garruss, Alexander S; Mohaghegh, Nima; Varberg, Joseph M; Lin, Chengqi; Jackson, Jessica; Gao, Xin; Saraf, Anita; Florens, Laurence; Washburn, Michael P; Eissenberg, Joel C; Shilatifard, Ali

    2013-08-22

    The small nuclear RNA (snRNA) genes have been widely used as a model system for understanding transcriptional regulation due to the unique aspects of their promoter structure, selectivity for either RNA polymerase (Pol) II or III, and because of their unique mechanism of termination that is tightly linked with the promoter. Recently, we identified the little elongation complex (LEC) in Drosophila that is required for the expression of Pol II-transcribed snRNA genes. Here, using Drosophila and mammalian systems, we provide genetic and molecular evidence that LEC functions in at least two phases of snRNA transcription: an initiation step requiring the ICE1 subunit, and an elongation step requiring ELL. PMID:23932780

  14. The Little Elongation Complex functions at initiation and elongation phases of snRNA gene transcription

    PubMed Central

    Hu, Deqing; Smith, Edwin R.; Garruss, Alexander S.; Mohaghegh, Nima; Varberg, Joseph M.; Lin, Chengqi; Jackson, Jessica; Gao, Xin; Saraf, Anita; Florens, Laurence; Washburn, Michael P.; Eissenberg, Joel C.; Shilatifard, Ali

    2014-01-01

    SUMMARY The small nuclear RNA (snRNA) genes have been widely used as a model system for understanding transcriptional regulation due to the unique aspects of their promoter structure, selectivity for either RNA Polymerase (Pol) II or III, and because of their unique mechanism of termination that is tightly linked with the promoter. Recently, we identified the Little Elongation Complex (LEC) in Drosophila that is required for the expression of Pol II-transcribed snRNA genes. Here, using Drosophila and mammalian systems, we provide genetic and molecular evidence that LEC functions in at least two phases of snRNA transcription: an initiation step requiring the ICE1 subunit, and an elongation step requiring ELL. PMID:23932780

  15. Complex phase error and motion estimation in synthetic aperture radar imaging

    NASA Astrophysics Data System (ADS)

    Soumekh, M.; Yang, H.

    1991-06-01

    Attention is given to a SAR wave equation-based system model that accurately represents the interaction of the impinging radar signal with the target to be imaged. The model is used to estimate the complex phase error across the synthesized aperture from the measured corrupted SAR data by combining the two wave equation models governing the collected SAR data at two temporal frequencies of the radar signal. The SAR system model shows that the motion of an object in a static scene results in coupled Doppler shifts in both the temporal frequency domain and the spatial frequency domain of the synthetic aperture. The velocity of the moving object is estimated through these two Doppler shifts. It is shown that once the dynamic target's velocity is known, its reconstruction can be formulated via a squint-mode SAR geometry with parameters that depend upon the dynamic target's velocity.

  16. Automated pathologies detection in retina digital images based on complex continuous wavelet transform phase angles.

    PubMed

    Lahmiri, Salim; Gargour, Christian S; Gabrea, Marcel

    2014-10-01

    An automated diagnosis system that uses complex continuous wavelet transform (CWT) to process retina digital images and support vector machines (SVMs) for classification purposes is presented. In particular, each retina image is transformed into two one-dimensional signals by concatenating image rows and columns separately. The mathematical norm of phase angles found in each one-dimensional signal at each level of CWT decomposition are relied on to characterise the texture of normal images against abnormal images affected by exudates, drusen and microaneurysms. The leave-one-out cross-validation method was adopted to conduct experiments and the results from the SVM show that the proposed approach gives better results than those obtained by other methods based on the correct classification rate, sensitivity and specificity. PMID:26609393

  17. Monitoring the formation of carbide crystal phases during the thermal decomposition of 3d transition metal dicarboxylate complexes

    SciTech Connect

    Huba, ZJ; Carpenter, EE

    2014-06-06

    Single molecule precursors can help to simplify the synthesis of complex alloys by minimizing the amount of necessary starting reagents. However, single molecule precursors are time consuming to prepare with very few being commercially available. In this study, a simple precipitation method is used to prepare Fe, Co, and Ni fumarate and succinate complexes. These complexes were then thermally decomposed in an inert atmosphere to test their efficiency as single molecule precursors for the formation of metal carbide phases. Elevated temperature X-ray diffraction was used to identify the crystal phases produced upon decomposition of the metal dicarboxylate complexes. Thermogravimetric analysis coupled with an infrared detector was used to identify the developed gaseous decomposition products. All complexes tested showed a reduction from the starting M2+ oxidation state to the M oxidation state, upon decomposition. Also, each complex tested showed CO2 and H2O as gaseous decomposition products. Nickel succinate, iron succinate, and iron fumarate complexes were found to form carbide phases upon decomposition. This proves that transition metal dicarboxylate salts can be employed as efficient single molecule precursors for the formation of metal carbide crystal phases.

  18. Gas Phase Chemistry and Molecular Complexity: How Far Do They Go?

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia

    2016-07-01

    The accumulation of organic molecules of increasing complexity is believed to be an important step toward the emergence of life. But how massive organic synthesis could occur in primitive Earth, i.e. a water-dominated environment, is a matter of debate. Two alternative theories have been suggested so far: endogenous and exogenous synthesis. In the first theory, the synthesis of simple organic molecules having a strong prebiotic potential (simple prebiotic molecules SPMs, such as H2CO, HCN, HC3N, NH2CHO) occurred directly on our planet starting from simple parent molecules of the atmosphere, liquid water and various energy sources. Miller's experiment was a milestone in this theory, but it was later recognized that the complexity of a planet cannot be reproduced in a single laboratory experiment. Some SPMs have been identified in the N2-dominated atmosphere of Titan (a massive moon of Saturn), which is believed to be reminiscent of the primitive terrestrial atmosphere. As such, the atmosphere of Titan represents a planetary scale laboratory for the comprehension of SPM formation in an environment close enough to primitive Earth and is the current frontier in the endogenous theory exploration. In the exogenous theory, SPMs came from space, the carriers being comets, asteroids and meteorites. The rationale behind this suggestion is that plenty of SPMs have been observed in interstellar clouds (ISCs), including star-forming regions, and in small bodies like comets, asteroids and meteorites. Therefore, the basic idea is that SPMs were formed in the solar nebula, preserved during the early phases of the Solar System formation in the body of comets/asteroids/meteorites and finally delivered to Earth by cometary and meteoritic falls. In this contribution, the status of our knowledge on how SPMs can be formed in the gas phase, either in the primitive terrestrial atmosphere or in the cold nebula from which the Solar System originated, will be presented. Particular attention

  19. Phase behavior of polyion-surfactant ion complex salts: effects of surfactant chain length and polyion length.

    PubMed

    Svensson, Anna; Norrman, Jens; Piculell, Lennart

    2006-06-01

    The aqueous phase behavior of a series of complex salts, containing cationic surfactants with polymeric counterions, has been investigated by visual inspection and small-angle X-ray scattering (SAXS). The salts were alkyltrimethylammonium polyacrylates, CxTAPAy, based on all combinations of five surfactant chain lengths (C6, C8, C10, C12, and C16) and two lengths of the polyacrylate chain (30 and 6 000 repeating units). At low water contents, all complex salts except C6TAPA6000 formed hexagonal and/or cubic Pm3n phases, with the hexagonal phase being favored by lower water contents. The aggregate dimensions in the liquid crystalline phases changed with the surfactant chain length. The determined micellar aggregation numbers of the cubic phases indicated that the micelles were only slightly aspherical. At high water contents, the C6TAPAy salts were miscible with water, whereas the other complex salts featured wide miscibility gaps with a concentrated phase in equilibrium with a (sometimes very) dilute aqueous solution. Thus, the attraction between oppositely charged surfactant aggregates and polyions decreases with decreasing surfactant chain length, and with decreasing polyion length, resulting in an increased miscibility with water. The complex salt with the longest surfactant chains and polyions gave the widest miscibility gap, with a concentrated hexagonal phase in equilibrium with almost pure water. A decrease in the attraction led to cubic-micellar and micellar-micellar coexistence in the miscibility gap and to an increasing concentration of the complex salt in the dilute phase. For each polyion length, the mixtures for the various surfactant chain lengths were found to conform to a global phase diagram, where the surfactant chain length played the role of an interaction parameter. PMID:16722736

  20. Complex magnetic phases in non-centrosymmetric heavy fermion CeCoGe3

    NASA Astrophysics Data System (ADS)

    Wu, Shan; Stock, Chris; Petrovic, Cedomir; Rodriguez-Rivera, J. A.; Broholm, Collin

    The non-centrosymmetric nature of the tetragonal heavy fermion system CeCoGe3 has attracted much interest in the high pressure superconducting state of the material. We have explored the related ambient pressure magnetism using neutron scattering. There are three successive phase transitions at TN 1 ~ 21 K , TN 2 ~ 12 K and TN 3 ~ 8 K. The upper transition greatly enhances the susceptibility and there are meta-magnetic transitions in the lower T phases. We confirmed the previously determined AFM spin structure for TN 2 < T complex commensurate structure that can be described as intertwined antiferromagnetic segments. We also report inelastic magnetic neutron scattering, which is dominated by the periodicity of the chemical cell rather than the magnetic unit cell. The work at IQM was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Material Sciences and Engineering, under Grant No. DEFG02-08ER46544.

  1. Discontinuous phase transition in a core contact process on complex networks

    NASA Astrophysics Data System (ADS)

    Chae, Huiseung; Yook, Soon-Hyung; Kim, Yup

    2015-02-01

    To understand the effect of generalized infection processes, we suggest and study the core contact process (CCP) on complex networks. In CCP an uninfected node is infected when at least k different infected neighbors of the node select the node for the infection. The healing process is the same as that of the normal CP. It is analytically and numerically shown that discontinuous transitions occur in CCP on random networks and scale-free networks depending on infection rate and initial density of infected nodes. The discontinuous transitions include hybrid transitions with β = 1/2 and β = 1. The asymptotic behavior of the phase boundary related to the initial density is found analytically and numerically. The mapping between CCP with k and static (k+1)-core percolation is supposed from the (k+1)-core structure in the active phase and the hybrid transition with β = 1/2. From these properties of CCP one can see that CCP is one of the dynamical processes for the k-core structure on real networks.

  2. Design of off-axis mirrors for the phase-induced amplitude apodization complex mask coronagraph

    NASA Astrophysics Data System (ADS)

    Pluzhnik, Eugene; Guyon, Olivier; Belikov, Ruslan; Bendek, Eduardo

    2016-01-01

    The phase-induced amplitude apodization complex mask coronagraph (PIAACMC) provides an efficient way to control diffraction propagation effects caused by the central obstruction/segmented mirrors of the telescope. PIAACMC can be optimized in a way that takes into account both chromatic diffraction effects caused by the telescope obstructed aperture and the tip-tilt sensitivity of the coronagraph. As a result, unlike classic phase-induced amplitude apodization (PIAA), the PIAACMC mirror shapes are often slightly asymmetric even for an on-axis configuration and require more care in calculating off-axis shapes when an off-axis configuration is preferred. A method to design off-axis PIAA mirror shapes given an on-axis mirror design is presented. The algorithm is based on geometrical ray tracing and is able to calculate off-axis PIAA mirror shapes for an arbitrary geometry of the input and output beams. The method is demonstrated using the third generation PIAACMC design for WFIRST-AFTA telescope. Geometrical optics design issues related to the off-axis diffraction propagation effects are also discussed.

  3. One-Step Liquid-Phase Synthesis of Carbon Nanotubes with Catalyst Precursors of Organometallic Complexes

    NASA Astrophysics Data System (ADS)

    Yamagiwa, Kiyofumi; Kikitsu, Tomoka; Yamashita, Shunsuke; Kuwano, Jun

    2011-01-01

    This paper describes a simple, low cost one-step liquid-phase process for the synthesis of highly aligned carbon nanotube (CNT) arrays (HACNTAs). Highly pure HACNTAs were grown on a stainless steel substrate by resistance-heating in methanol solution containing one of the organometallic complex catalyst precursors, ferrocene Fe(C5H5)2 and iron pentacarbonyl Fe(CO)5. Effects of the catalyst precursors on the formation and morphologies of HACNTAs were examined. A small amount of non-aligned multi-walled CNTs (MWCNTs) were grown from 1 mM Fe(C5H5)2 methanol solution. Highly pure HACNTAs composed of MWCNTs were readily grown from 10 and 40 mM Fe(C5H5)2 methanol solutions by this one-step liquid-phase process. From the Fe(CO)5 methanol solution, HACNTAs were prepared even at a very low Fe(CO)5 concentration of 0.01 mM, which was about 1/1000 lower than that of Fe(C5H5)2. The optimal low concentration is attributed to the low decomposition temperature of Fe(CO)5.

  4. Natural history of chronic hepatitis B: Phases in a complex relationship

    PubMed Central

    Croagh, Catherine MN; Lubel, John S

    2014-01-01

    Chronic hepatitis B (CHB) is a condition of global prevalence and its sequelae include cirrhosis and hepatocellular carcinoma. The natural history of CHB is a complex interplay of virological, environmental and host factors. The dynamic relationship between the virus and host evolves over the duration of the infection and different phases of the disease have been observed and described. These have been conceptualized in terms of the state of balance between the host immune system and the hepatitis B virus and have been given the labels immune tolerant, immune clearance, immune control and immune escape although other nomenclature is also used. Host factors, such as age at infection, determine progression to chronicity. Virological factors including hepatitis B viral load, mutations and genotype also have an impact on the adverse outcomes of the infection, as do hepatotoxic cofactors such as alcohol. Our understanding of the natural history of CHB has evolved significantly over the past few decades and characterizing the phase of disease of CHB remains an integral part of managing this virus in the clinic. PMID:25132755

  5. A Screening Approach for the Discovery of Mechanochromic Gold(I) Isocyanide Complexes with Crystal-to-Crystal Phase Transitions.

    PubMed

    Seki, Tomohiro; Takamatsu, Yuki; Ito, Hajime

    2016-05-18

    Mechanoinduced phase transitions of emissive organic crystalline materials have received much attention. Although a variety of such luminescent mechanochromic compounds have been reported, it is challenging to develop mechanochromic compounds with crystal-to-crystal phase transitions in which precise structural information about molecular arrangements can be obtained. Here, we report a screening approach to explore mechanochromic compounds exhibiting a crystal-to-crystal phase transition. We prepared 48 para-substituted (R(1)) phenyl[para-substituted (R(2)) phenyl isocyanide]gold(I) complexes designated R(1)-R(2) (six R(1) and eight R(2) substituents) and then performed three-step screening experiments. The first screening step was selection of emissive complexes under UV light, which gave 37 emissive R(1)-R(2) complexes. The second screening step involved evaluation of the mechanochromic properties by emission spectroscopy. Twenty-eight complexes were found to be mechanochromic. The third screening step involved preparation of single crystals, reprecipitated powders, and ground powders of the 28 mechanochromic R(1)-R(2) complexes. The changes in the powder diffraction patterns of these complexes induced by mechanical stimulation were investigated. Two compounds exhibited a crystal-to-crystal phase transition upon mechanical stimulation, including the previously reported H-H complex. Single crystals of the as-prepared and ground forms of the newly discovered CF3-CN complex were obtained. Density functional theory calculations indicated that the mechanoinduced red-shifted emission of CF3-CN is caused by formation of aurophilic interactions. Comparison of the crystal structures of CF3-CN with those of the other complexes suggests that the weaker intermolecular interactions in the as-prepared form are an important structural factor for the observed mechanoinduced crystal-to-crystal phase transition. PMID:27070308

  6. Molecular recognition using corona phase complexes made of synthetic polymers adsorbed on carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zhang, Jingqing; Landry, Markita P.; Barone, Paul W.; Kim, Jong-Ho; Lin, Shangchao; Ulissi, Zachary W.; Lin, Dahua; Mu, Bin; Boghossian, Ardemis A.; Hilmer, Andrew J.; Rwei, Alina; Hinckley, Allison C.; Kruss, Sebastian; Shandell, Mia A.; Nair, Nitish; Blake, Steven; Şen, Fatih; Şen, Selda; Croy, Robert G.; Li, Deyu; Yum, Kyungsuk; Ahn, Jin-Ho; Jin, Hong; Heller, Daniel A.; Essigmann, John M.; Blankschtein, Daniel; Strano, Michael S.

    2013-12-01

    Understanding molecular recognition is of fundamental importance in applications such as therapeutics, chemical catalysis and sensor design. The most common recognition motifs involve biological macromolecules such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific molecule. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chemical adsorption, also form a new corona phase that exhibits highly selective recognition for specific molecules. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodynamic model of surface interactions in which the dissociation constants can be tuned by perturbing the chemical structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-infrared, as we show by tracking riboflavin diffusion in murine macrophages.

  7. Variational regularization of complex deautoconvolution and phase retrieval in ultrashort laser pulse characterization

    NASA Astrophysics Data System (ADS)

    Anzengruber, Stephan W.; Bürger, Steven; Hofmann, Bernd; Steinmeyer, Günter

    2016-03-01

    The SD-SPIDER method for the characterization of ultrashort laser pulses requires the solution of a nonlinear integral equation of autoconvolution type with a device-based kernel function. Taking into account the analytical background of a variational regularization approach for solving the corresponding ill-posed operator equation formulated in complex-valued L 2-spaces over finite real intervals, we suggest and evaluate numerical procedures using NURBS and the TIGRA method for calculating the regularized solutions in a stable manner. In this context, besides the complex deautoconvolution problem with noisy but full data, a phase retrieval problem is introduced which adapts to the experimental state of the art in laser optics. For the treatment of this problem facet, which is formulated as a tensor product operator equation, we derive the well-posedness of variational regularization methods. Case studies with synthetic and real optical data show the capability of the implemented approach as well as its limitations due to measurement deficits.

  8. EXAFS Phase Retrieval Solution Tracking for Complex Multi-Component System: Synthesized Topological Inverse Computation

    NASA Astrophysics Data System (ADS)

    Lee, Jay Min; Yang, Dong-Seok; Bunker, Grant B.

    2013-04-01

    Using the FEFF kernel A(k,r), we describe the inverse computation from χ(k)-data to g(r)-solution in terms of a singularity regularization method based on complete Bayesian statistics process. In this work, we topologically decompose the system-matched invariant projection operators into two distinct types, (A+AA+A) and (AA+AA+), and achieved Synthesized Topological Inversion Computation (STIC), by employing a 12-operator-closed-loop emulator of the symplectic transformation. This leads to a numerically self-consistent solution as the optimal near-singular regularization parameters are sought, dramatically suppressing instability problems connected with finite precision arithmetic in ill-posed systems. By statistically correlating a pair of measured data, it was feasible to compute an optimal EXAFS phase retrieval solution expressed in terms of the complex-valued χ(k), and this approach was successfully used to determine the optimal g(r) for a complex multi-component system.

  9. Sampling strategies for accurate computational inferences of gametic phase across highly polymorphic major histocompatibility complex loci

    PubMed Central

    2011-01-01

    Background Genes of the Major Histocompatibility Complex (MHC) are very popular genetic markers among evolutionary biologists because of their potential role in pathogen confrontation and sexual selection. However, MHC genotyping still remains challenging and time-consuming in spite of substantial methodological advances. Although computational haplotype inference has brought into focus interesting alternatives, high heterozygosity, extensive genetic variation and population admixture are known to cause inaccuracies. We have investigated the role of sample size, genetic polymorphism and genetic structuring on the performance of the popular Bayesian PHASE algorithm. To cover this aim, we took advantage of a large database of known genotypes (using traditional laboratory-based techniques) at single MHC class I (N = 56 individuals and 50 alleles) and MHC class II B (N = 103 individuals and 62 alleles) loci in the lesser kestrel Falco naumanni. Findings Analyses carried out over real MHC genotypes showed that the accuracy of gametic phase reconstruction improved with sample size as a result of the reduction in the allele to individual ratio. We then simulated different data sets introducing variations in this parameter to define an optimal ratio. Conclusions Our results demonstrate a critical influence of the allele to individual ratio on PHASE performance. We found that a minimum allele to individual ratio (1:2) yielded 100% accuracy for both MHC loci. Sampling effort is therefore a crucial step to obtain reliable MHC haplotype reconstructions and must be accomplished accordingly to the degree of MHC polymorphism. We expect our findings provide a foothold into the design of straightforward and cost-effective genotyping strategies of those MHC loci from which locus-specific primers are available. PMID:21615903

  10. The gas phase origin of complex organic molecules precursors in prestellar cores

    NASA Astrophysics Data System (ADS)

    Bacmann, A.; Faure, A.

    2016-05-01

    Complex organic molecules (COMs) have long been observed in the warm regions surrounding nascent protostars. The recent discovery of oxygen-bearing COMs like methyl formate or dimethyl ether in prestellar cores (Bacmann et al. [2]), where gas and dust temperatures rarely exceed 10-15 K, has challenged the previously accepted models according to which COM formation relied on the diffusion of heavy radicals on warm (˜30 K) grains. Following these detections, new questions have arisen: do non-thermal processes play a role in increasing radical mobility or should new gas-phase routes be explored? The radicals involved in the formation of the aforementioned COMs, HCO and CH3O represent intermediate species in the grain-surface synthesis of methanol which proceeds via successive hydrogenations of CO molecules in the ice. We present here observations of methanol and its grain-surface precursors HCO, H2CO, CH3O in a sample of prestellar cores and derive their relative abundances. We find that the relative abundances HCO:H2CO:CH3O:CH3OH are constant across the core sample, close to 10:100:1:100. Our results also show that the amounts of HCO and CH3O are consistent with a gas-phase synthesis of these species from H2CO and CH3OH via radical-neutral or ion-molecule reactions followed by dissociative recombinations. Thus, while grain chemistry is necessary to explain the abundances of the parent volatile CH3OH, and possibly H2CO, the reactive species HCO and CH3O might be daughter molecules directly produced in the gas-phase.

  11. Properties of hydrogen and hydrogen-vacancy complexes in the rutile phase of titanium dioxide

    NASA Astrophysics Data System (ADS)

    Filippone, F.; Mattioli, G.; Alippi, P.; Amore Bonapasta, A.

    2009-12-01

    The interaction of atomic H with host atoms and oxygen vacancies (VO) in the rutile phase of the TiO2 metal oxide has been investigated by using density-functional theory-local spin density (DFT-LSD) and DFT-LSD+U theoretical methods. The achieved results show that H in rutile presents quite different and peculiar properties with respect to other semiconductors and metal oxides. It behaves indeed neither as an amphoteric impurity, as it does in Si and GaAs, nor as a shallow donor, as it has been proposed in ZnO. Moreover, H in rutile represents a failure of a theoretical model proposing a universal alignment of the H-induced electronic level in the energy gaps of semiconductors, which predicts a shallow donor behavior of H in ZnO and TiO2 . Present results show indeed that H behaves as a deep donor in rutile and always forms an OH+ complex, independent of the position of the Fermi energy. This very unusual behavior of H can be accounted for by a peculiar property of TiO2 regarding its capability of localizing extra electrons at Ti+3 sites. The electron lost by H can be accommodated indeed by a Ti+4 atom which evolves in a Ti+3 defect. This accounts for the deep behavior of H and implies that the electronic level it induces in the TiO2 energy gap has, actually, a Ti+3 character quite similar to that characterizing an O vacancy (VO) , thus distinguishing H in rutile from H in other semiconductors. Finally, H can form stable H-VO complexes where it takes the place of the missing O atom by forming a bond with a prevailing ionic character, at variance with a multicenter bond model proposed for the same complexes in ZnO.

  12. Physico-Chemical Properties and Phase Behavior of the Ionic Liquid-β-Cyclodextrin Complexes

    PubMed Central

    Rogalski, Marek; Modaressi, Ali; Magri, Pierre; Mutelet, Fabrice; Grydziuszko, Aleksandra; Wlazło, Michał; Domańska, Urszula

    2013-01-01

    The solubility of β-cyclodextrin (β-CD) in ionic liquids (ILs) and the activity coefficients at infinite dilution ( γ13∞) of more than 20 solutes (alkanes, aromatic hydrocarbons, alcohols) were measured in four chosen ionic liquids, their mixtures with β-CD, and in the β-CD at high temperatures from 338 to 398 K using the inverse gas chromatography. The intermolecular interactions, inclusion complexes and the possible increasing of the solubility of β-CD in water using the IL are presented. The solubility of β-CD in ten chosen hydrophobic ILs at the temperature T = 423 K was detected. The solid-liquid phase diagrams (SLE) of {IL (1) + β-CD (2)} binary systems at the high mole fraction of the IL were measured for three systems (1-ethyl-3-methylimidazolium chloride, [EMIM][Cl], 1-ethyl-3-methylimidazolium bromide, [EMIM][Br]; and for 1-butyl-3-methylimidazolium chloride, [BMIM][Cl]). The eutectic points were determined at the high IL concentration for all binary systems. The intermolecular interaction and the possibility of inclusion complexes of the IL and/or solvents with β-CD were discussed. The infrared spectroscopy, IR was used for the description of the intermolecular interactions in the (β-CD + IL) systems. It was shown via the activity coefficients at infinite dilution results that the inclusion complexes are dependent on the temperature. The addition of β-CD to the IL does not improve the selectivity of the separation of the aliphatics from aromatics. PMID:23945559

  13. Spatial cross modulation method using a random diffuser and phase-only spatial light modulator for constructing arbitrary complex fields.

    PubMed

    Shibukawa, Atsushi; Okamoto, Atsushi; Takabayashi, Masanori; Tomita, Akihisa

    2014-02-24

    We propose a spatial cross modulation method using a random diffuser and a phase-only spatial light modulator (SLM), by which arbitrary complex-amplitude fields can be generated with higher spatial resolution and diffraction efficiency than off-axis and double-phase computer-generated holograms. Our method encodes the original complex object as a phase-only diffusion image by scattering the complex object using a random diffuser. In addition, all incoming light to the SLM is consumed for a single diffraction order, making a diffraction efficiency of more than 90% possible. This method can be applied for holographic data storage, three-dimensional displays, and other such applications. PMID:24663718

  14. Bond Activation by Metal-Carbene Complexes in the Gas Phase.

    PubMed

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-03-15

    "Bare" metal-carbene complexes, when generated in the gas phase and exposed to thermal reactions under (near) single-collision conditions, exhibit rather unique reactivities in addition to the well-known metathesis and cyclopropanation processes. For example, at room temperature the unligated [AuCH2](+) complex brings about efficient C-C coupling with methane to produce C2Hx (x = 4, 6), and the couple [TaCH2](+)/CO2 gives rise to the generation of the acetic acid equivalent CH2═C═O. Entirely unprecedented is the thermal extrusion of a carbon atom from halobenzenes (X = F, Cl, Br, I) by [MCH2](+) (M = La, Hf, Ta, W, Re, Os) and its coupling with the methylene ligand to deliver C2H2 and [M(X)(C5H5)](+). Among the many noteworthy C-N bond-forming processes, the formation of CH3NH2 from [RhCH2](+)/NH3, the generation of CH2═NH2(+) from [MCH2](+)/NH3 (M = Pt, Au), and the production of [PtCH═NH2](+) from [PtCH2](+)/NH3 are of particular interest. The latter species are likely to be involved as intermediates in the platinum-mediated large-scale production of HCN from CH4/NH3 (the DEGUSSA process). In this context, a few examples are presented that point to the operation of co-operative effects even at a molecular level. For instance, in the coupling of CH4 with NH3 by the heteronuclear clusters [MPt](+) (M = coinage metal), platinum is crucial for the activation of methane, while the coinage metal M controls the branching ratio between the C-N bond-forming step and unwanted soot formation. For most of the gas-phase reactions described in this Account, detailed mechanistic insight has been derived from extensive computational work in conjunction with time-honored labeling and advanced mass-spectrometry-based experiments, and often a coherent description of the experimental findings has been achieved. As for some transition metals, in particular those from the third row, the metal-carbene complexes can be formed directly from methane, coupling of the so

  15. Phase-equilibrium modelling of blueschists from the Vestgötabreen Complex (SW Svalbard)

    NASA Astrophysics Data System (ADS)

    Kośmińska, Karolina; Majka, Jarosław; Manecki, Maciej; Lorenz, Henning; Kozub, Gabriela

    2014-05-01

    In Svalbard Archipelago, blueschists are known from Motalafjella area (Oscar II Land). They belong to the Vestgötabreen Complex, which is divided into a Lower (LU) and Upper Unit (UU). The former is composed of high pressure-low temperature (HP-LT) metasediments. The latter consists mainly of blueschists and eclogites. Various radiometric dating yielded an age of c. 470 Ma for the HP-LT metamorphism in the Motalafjella area. The pressure-temperature (P-T) conditions for carpholite-bearing schists from LU have been estimated to c. 16 kbar and 330-450°C (Agard et al., 2005), whereas eclogites from UU indicate peak conditions of 18-24 kbar and 580-640°C (Hirajima et al., 1988). During the fieldwork in 2011, blueschists were also discovered at the western coast of Nordenskiöld Land. They form isolated bodies enclosed within metasedimentary units, but their tectonic position is still under debate. Preliminary P-T estimates indicate peak pressure conditions of c. 17 kbar and 480°C (Kośmińska et al., in revision). The age of metamorphism is unknown, however P-T conditions as well as metamorphic assemblage suggest that the blueschists from Nordenskiöld Land may be an equivalent of these in the Vestgötabreen Complex. Samples of blueschists from UU have been collected on Skipperryggen. They consist mainly of glaucophane, garnet, white micas (phengite and paragonite), rutile, lawsonite and chlorite. The garnet typically forms euhedral to subhedral porphyroblasts which contain voluminous inclusions. Its composition varies from Alm63Prp13Grs22Sps2 in the cores to Alm60Prp19Grs20Sps1 in the rims. The change in chemical zoning is rather gradual. The garnet shows bowl-shaped pyrope profiles and opposite almandine trends. The P-T conditions were estimated using phase equilibrium modeling. Preliminary modeling in the NCKFMMnASHTO system yields peak pressure conditions at c. 20 kbar and 520°C. The estimated P-T conditions for the blueschists from Skipperryggen are in

  16. Solid Phase Biosensors for Arsenic or Cadmium Composed of A trans Factor and cis Element Complex

    PubMed Central

    Siddiki, Mohammad Shohel Rana; Kawakami, Yasunari; Ueda, Shunsaku; Maeda, Isamu

    2011-01-01

    The presence of toxic metals in drinking water has hazardous effects on human health. This study was conducted to develop GFP-based-metal-binding biosensors for on-site assay of toxic metal ions. GFP-tagged ArsR and CadC proteins bound to a cis element, and lost the capability of binding to it in their As- and Cd-binding conformational states, respectively. Water samples containing toxic metals were incubated on a complex of GFP-tagged ArsR or CadC and cis element which was immobilized on a solid surface. Metal concentrations were quantified with fluorescence intensity of the metal-binding states released from the cis element. Fluorescence intensity obtained with the assay significantly increased with increasing concentrations of toxic metals. Detection limits of 1 μg/L for Cd(II) and 5 μg/L for As(III) in purified water and 10 µg/L for Cd(II) and As(III) in tap water and bottled mineral water were achieved by measurement with a battery-powered portable fluorometer after 15-min and 30-min incubation, respectively. A complex of freeze dried GFP-tagged ArsR or CadC binding to cis element was stable at 4 °C and responded to 5 μg/L As(III) or Cd(II). The solid phase biosensors are sensitive, less time-consuming, portable, and could offer a protocol for on-site evaluation of the toxic metals in drinking water. PMID:22346629

  17. Solid phase biosensors for arsenic or cadmium composed of A trans factor and cis element complex.

    PubMed

    Siddiki, Mohammad Shohel Rana; Kawakami, Yasunari; Ueda, Shunsaku; Maeda, Isamu

    2011-01-01

    The presence of toxic metals in drinking water has hazardous effects on human health. This study was conducted to develop GFP-based-metal-binding biosensors for on-site assay of toxic metal ions. GFP-tagged ArsR and CadC proteins bound to a cis element, and lost the capability of binding to it in their As- and Cd-binding conformational states, respectively. Water samples containing toxic metals were incubated on a complex of GFP-tagged ArsR or CadC and cis element which was immobilized on a solid surface. Metal concentrations were quantified with fluorescence intensity of the metal-binding states released from the cis element. Fluorescence intensity obtained with the assay significantly increased with increasing concentrations of toxic metals. Detection limits of 1 μg/L for Cd(II) and 5 μg/L for As(III) in purified water and 10 µg/L for Cd(II) and As(III) in tap water and bottled mineral water were achieved by measurement with a battery-powered portable fluorometer after 15-min and 30-min incubation, respectively. A complex of freeze dried GFP-tagged ArsR or CadC binding to cis element was stable at 4 °C and responded to 5 μg/L As(III) or Cd(II). The solid phase biosensors are sensitive, less time-consuming, portable, and could offer a protocol for on-site evaluation of the toxic metals in drinking water. PMID:22346629

  18. Multivariate multiscale complex network analysis of vertical upward oil-water two-phase flow in a small diameter pipe

    NASA Astrophysics Data System (ADS)

    Gao, Zhong-Ke; Yang, Yu-Xuan; Zhai, Lu-Sheng; Dang, Wei-Dong; Yu, Jia-Liang; Jin, Ning-De

    2016-02-01

    High water cut and low velocity vertical upward oil-water two-phase flow is a typical complex system with the features of multiscale, unstable and non-homogenous. We first measure local flow information by using distributed conductance sensor and then develop a multivariate multiscale complex network (MMCN) to reveal the dispersed oil-in-water local flow behavior. Specifically, we infer complex networks at different scales from multi-channel measurements for three typical vertical oil-in-water flow patterns. Then we characterize the generated multiscale complex networks in terms of network clustering measure. The results suggest that the clustering coefficient entropy from the MMCN not only allows indicating the oil-in-water flow pattern transition but also enables to probe the dynamical flow behavior governing the transitions of vertical oil-water two-phase flow.

  19. Metal-ligand redox reactions in gas-phase quaternary peptide-metal complexes by electrospray ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Vaisar, T.; Gatlin, C. L.; Turecek, F.

    1997-03-01

    The dipeptides Phe-Leu, Leu-Phe, Leu-Ala, and Ala-Leu form quaternary complexes of the type [Cu(II)(peptide - 2H+M)bpy]+ in the gas phase when electrosprayed in the presence of Cu(II) salts, 2.2'-bipyridyl (bpy), and an alkali hydroxide (MOH). The gas-phase complexes decarboxylate on collisional activation at low ion kinetic energies. The resulting ions undergo unusual eliminations of neutral Na, K, and Rb, which depend on the peptide structure. The ionization energy of the decarboxylated Phe-Leu-Cu-bpy complex was bracketed at 4.2 eV. Other collision-induced dissociations also depend on the alkali metal ion and the peptide structure. Ab initio calculations on a model system are reported and used to discuss the electronic properties of the peptide complexes.

  20. Multivariate multiscale complex network analysis of vertical upward oil-water two-phase flow in a small diameter pipe.

    PubMed

    Gao, Zhong-Ke; Yang, Yu-Xuan; Zhai, Lu-Sheng; Dang, Wei-Dong; Yu, Jia-Liang; Jin, Ning-De

    2016-01-01

    High water cut and low velocity vertical upward oil-water two-phase flow is a typical complex system with the features of multiscale, unstable and non-homogenous. We first measure local flow information by using distributed conductance sensor and then develop a multivariate multiscale complex network (MMCN) to reveal the dispersed oil-in-water local flow behavior. Specifically, we infer complex networks at different scales from multi-channel measurements for three typical vertical oil-in-water flow patterns. Then we characterize the generated multiscale complex networks in terms of network clustering measure. The results suggest that the clustering coefficient entropy from the MMCN not only allows indicating the oil-in-water flow pattern transition but also enables to probe the dynamical flow behavior governing the transitions of vertical oil-water two-phase flow. PMID:26833427

  1. Multivariate multiscale complex network analysis of vertical upward oil-water two-phase flow in a small diameter pipe

    PubMed Central

    Gao, Zhong-Ke; Yang, Yu-Xuan; Zhai, Lu-Sheng; Dang, Wei-Dong; Yu, Jia-Liang; Jin, Ning-De

    2016-01-01

    High water cut and low velocity vertical upward oil-water two-phase flow is a typical complex system with the features of multiscale, unstable and non-homogenous. We first measure local flow information by using distributed conductance sensor and then develop a multivariate multiscale complex network (MMCN) to reveal the dispersed oil-in-water local flow behavior. Specifically, we infer complex networks at different scales from multi-channel measurements for three typical vertical oil-in-water flow patterns. Then we characterize the generated multiscale complex networks in terms of network clustering measure. The results suggest that the clustering coefficient entropy from the MMCN not only allows indicating the oil-in-water flow pattern transition but also enables to probe the dynamical flow behavior governing the transitions of vertical oil-water two-phase flow. PMID:26833427

  2. Characterization of Horizontal Gas-Liquid Two-Phase Flow Using Markov Model-Based Complex Network

    NASA Astrophysics Data System (ADS)

    Hu, Li-Dan; Jin, Ning-De; Gao, Zhong-Ke

    2013-05-01

    Horizontal gas-liquid two-phase flow widely exists in many physical systems and chemical engineering processes. Compared with vertical upward gas-liquid two-phase flow, investigations on dynamic behavior underlying horizontal gas-liquid flows are quite limited. Complex network provides a powerful framework for time series analysis of complex dynamical systems. We use a network generation method based on Markov transition probability to infer directed weighted complex networks from signals measured from horizontal gas-liquid two-phase flow experiment and find that the networks corresponding to different flow patterns exhibit different network structure. To investigate the dynamic characteristics of horizontal gas-liquid flows, we construct a number of complex networks under different flow conditions, and explore the network indices for each constructed network. In addition, we investigate the sample entropy of different flow patterns. Our results suggest that the network statistic can well represent the complexity in the transition among different flow patterns and further allows characterizing the interface fluctuation behavior in horizontal gas-liquid two-phase flow.

  3. Identification of Guest-Host Inclusion Complexes in the Gas Phase by Electrospray Ionization-Mass Spectrometry

    ERIC Educational Resources Information Center

    Mendes, De´bora C.; Ramamurthy, Vaidhyanathan; Da Silva, Jose´ P.

    2015-01-01

    In this laboratory experiment, students follow a step-by-step procedure to prepare and study guest-host complexes in the gas phase using electrospray ionization-mass spectrometry (ESI-MS). Model systems are the complexes of hosts cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) with the guest 4-styrylpyridine (SP). Aqueous solutions of CB7 or CB8…

  4. Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

    SciTech Connect

    Rutkowski, Philip X; Michelini, Maria C.; Bray, Travis H.; Russo, Nino; Marcalo, Joaquim; Gibson, John K.

    2011-02-11

    Hydration of ytterbium (III) halide/hydroxide ions produced by electrospray ionization was studied in a quadrupole ion trap mass spectrometer and by density functional theory (DFT). Gas-phase YbX{sub 2}{sup +} and YbX(OH){sup +} (X = OH, Cl, Br, or I) were found to coordinate from one to four water molecules, depending on the ion residence time in the trap. From the time dependence of the hydration steps, relative reaction rates were obtained. It was determined that the second hydration was faster than both the first and third hydrations, and the fourth hydration was the slowest; this ordering reflects a combination of insufficient degrees of freedom for cooling the hot monohydrate ion and decreasing binding energies with increasing hydration number. Hydration energetics and hydrate structures were computed using two approaches of DFT. The relativistic scalar ZORA approach was used with the PBE functional and all-electron TZ2P basis sets; the B3LYP functional was used with the Stuttgart relativistic small-core ANO/ECP basis sets. The parallel experimental and computational results illuminate fundamental aspects of hydration of f-element ion complexes. The experimental observations - kinetics and extent of hydration - are discussed in relationship to the computed structures and energetics of the hydrates. The absence of pentahydrates is in accord with the DFT results, which indicate that the lowest energy structures have the fifth water molecule in the second shell.

  5. Supersaturation-limited and Unlimited Phase Transitions Compete to Produce the Pathway Complexity in Amyloid Fibrillation.

    PubMed

    Adachi, Masayuki; So, Masatomo; Sakurai, Kazumasa; Kardos, József; Goto, Yuji

    2015-07-17

    Although amyloid fibrils and amorphous aggregates are two types of aggregates formed by denatured proteins, their relationship currently remains unclear. We used β2-microglobulin (β2m), a protein responsible for dialysis-related amyloidosis, to clarify the mechanism by which proteins form either amyloid fibrils or amorphous aggregates. When ultrasonication was used to accelerate the spontaneous fibrillation of β2m at pH 2.0, the effects observed depended on ultrasonic power; although stronger ultrasonic power effectively accelerated fibrillation, excessively strong ultrasonic power decreased the amount of fibrils formed, as monitored by thioflavin T fluorescence. An analysis of the products formed indicated that excessively strong ultrasonic power generated fibrillar aggregates that retained β-structures but without high efficiency as seeds. On the other hand, when the spontaneous fibrillation of β2m was induced at higher concentrations of NaCl at pH 2.0 with stirring, amorphous aggregates became more dominant than amyloid fibrils. These apparent complexities in fibrillation were explained comprehensively by a competitive mechanism in which supersaturation-limited reactions competed with supersaturation-unlimited reactions. We link the kinetics of protein aggregation and a conformational phase diagram, in which supersaturation played important roles. PMID:26063798

  6. POD evaluation using simulation: A phased array UT case on a complex geometry part

    NASA Astrophysics Data System (ADS)

    Dominguez, Nicolas; Reverdy, Frederic; Jenson, Frederic

    2014-02-01

    The use of Probability of Detection (POD) for NDT performances demonstration is a key link in products lifecycle management. The POD approach is to apply the given NDT procedure on a series of known flaws to estimate the probability to detect with respect to the flaw size. A POD is relevant if and only if NDT operations are carried out within the range of variability authorized by the procedure. Such experimental campaigns require collection of large enough datasets to cover the range of variability with sufficient occurrences to build a reliable POD statistics, leading to expensive costs to get POD curves. In the last decade research activities have been led in the USA with the MAPOD group and later in Europe with the SISTAE and PICASSO projects based on the idea to use models and simulation tools to feed POD estimations. This paper proposes an example of application of POD using simulation on the inspection procedure of a complex -full 3D- geometry part using phased arrays ultrasonic testing. It illustrates the methodology and the associated tools developed in the CIVA software. The paper finally provides elements of further progress in the domain.

  7. Complex defect in pyrite and its structure model derived from geometric phase analysis.

    PubMed

    Németh, Péter; Dódony, István; Pósfai, Mihály; Buseck, Peter R

    2013-10-01

    New methods for defect analysis can lead to improved interpretation of experimental data and thus better understanding of material properties. Although transmission electronmicroscopy (TEM) has been used to study defects for many decades, interpretive ambiguities can arise for cases that seem simple or even trivial.Using geometric phase analysis (GPA), an image processing procedure, we show that an apparent simple line defect in pyrite has an entirely different character. It appears to be a b = ½[100] edge dislocation as viewed in a [001] high-resolution TEM (HRTEM) image, but the measured u(x) and u(y) displacements are asymmetric, which is inconsistent with a simple line dislocation. Instead, the defect is best understood as a terminating {101} marcasite slab in pyrite. The simulated HRTEM image based on this model reproduces the defect contrast and illustrates the power of GPA analysis for (1) avoiding potential pitfalls of misinterpreting apparently simple defects in HRTEM images, (2) detecting differences in elastic properties at the atomic scale, and (3) providing data for the positions of atom columns, thereby facilitating the construction of structure models for complex defects. PMID:23773546

  8. Hydrogen-bonded glycine-HCN complexes in gas phase: structure, energetics, electric properties and cooperativity

    NASA Astrophysics Data System (ADS)

    Machado da Silva, Arnaldo; Chakrabarty, Sumana; Chaudhuri, Puspitapallab

    2015-03-01

    Twelve hydrogen-bonded complexes of glycine and hydrogen cyanide have been studied using high-level quantum-chemical calculations in gas phase. In particular, six 1:1 glycine-HCN dimers and six 1:2 glycine-HCN trimers have been considered. Besides the characteristics of the hydrogen bonds and their effect on molecular structure and energetics, several molecular electric properties have been calculated utilising two different models: MP2/6-31++G(d,p) and DFT-B3LYP/6-31++G(d,p). Although the structural parameters calculated by the two models are similar, equilibrium electronic energies of the clusters show model dependence. The lowest energy dimer is same in both the models which is ca. 3.0 kcal/mol more stable than the highest energy dimer. However, the lowest energy trimer is different in two methods. The energetic difference of stability between the highest and lowest trimer is 4.2 kcal/mol (4.4 kcal/mol) at an MP2 (B3LYP) level of calculation. The bond angles of glycine, in particular, are quite sensitive to the hydrogen-bond formation. Four out of six trimers are found to be strongly cooperative in both the models. Significant changes of dipole moments and polarisabilities of isolated glycine and hydrogen cyanide are observed due to the formation of hydrogen bonding. The Rayleigh scattering intensities of all clusters are much larger than those of their constituent monomers.

  9. Investigation of the kinetic process of solid phase microextraction in complex sample.

    PubMed

    Jiang, Ruifen; Xu, Jianqiao; Lin, Wei; Wen, Sijia; Zhu, Fang; Luan, Tiangang; Ouyang, Gangfeng

    2015-11-01

    The presence of complex matrix in the aquatic system affects the environmental behavior of hydrophobic organic compounds (HOCs). In the current study, an automated solid-phase microextraction (SPME) desorption method was employed to study the effect of 2-hydroxypropyl-β-cyclodextrin (β-HPCD) on the kinetic process of 5 selected polyaromatic hydrocarbons (PAHs) desorbing from the fiber in aqueous sample. The results showed that the added β-HPCD facilitated the desorption rates of PAHs from SPME fiber coating, and the enhancement effect can be predicted by a proposed theoretical model. Based on this model, the kinetic parameters of organic compounds desorbing from the SPME fiber can be determined, and the calculated results showed good agreement with the experimental data. In addition, the effect of temperature on the desorption kinetic was investigated. The results found that the SPME desorption time constant increased as the sampling temperature elevated, and followed the Arrhenius equation. Also, the temperature facilitated the desorption of HOCs from the bound matrix so that increased the lability degrees of the bound compounds. Finally, a calibration method based on the proposed theoretical model was developed and applied for the analysis of unknown sample. PMID:26572846

  10. Implementation of a complex multi-phase equation of state for cerium and its correlation with experiment

    SciTech Connect

    Cherne, Frank J; Jensen, Brian J; Elkin, Vyacheslav M

    2009-01-01

    The complexity of cerium combined with its interesting material properties makes it a desirable material to examine dynamically. Characteristics such as the softening of the material before the phase change, low pressure solid-solid phase change, predicted low pressure melt boundary, and the solid-solid critical point add complexity to the construction of its equation of state. Currently, we are incorporating a feedback loop between a theoretical understanding of the material and an experimental understanding. Using a model equation of state for cerium we compare calculated wave profiles with experimental wave profiles for a number of front surface impact (cerium impacting a plated window) experiments. Using the calculated release isentrope we predict the temperature of the observed rarefaction shock. These experiments showed that the release state occurs at different magnitudes, thus allowing us to infer where dynamic {gamma} - {alpha} phase boundary is.

  11. Symptom Complexes at the Earliest Phases of Rheumatoid Arthritis: A Synthesis of the Qualitative Literature

    PubMed Central

    Stack, Rebecca J; Sahni, Melanie; Mallen, Christian D; Raza, Karim

    2013-01-01

    Objective Understanding the features and patterns of symptoms that characterize the earliest stages of rheumatoid arthritis (RA) is of considerable importance if patients are to be identified and started on treatment early. However, little is known about the characteristics of symptoms at the onset of a disease that eventually progresses to RA. Methods A systematic review of qualitative peer-reviewed publications was conducted to identify the earliest symptoms associated with the onset of RA. A total of 1,736 abstracts were searched to identify relevant publications. Twenty-six publications were identified, assessed for quality, and subjected to analysis informed by thematic and grounded theory frameworks. Results Several interacting themes describing the early symptoms of RA were identified, including swelling, pain and tenderness, stiffness, fatigue and weakness, and the emotional impact of symptoms. For each symptom, different and evolving intensities were described; in some cases, patterns of symptom onset and symptom complexes at the onset of RA were highlighted. Importantly, this review has emphasized major deficiencies in the literature. None of the studies reviewed originally aimed to explore symptoms at RA onset (often discussions about symptom onset were secondary to the study's primary aim). Also, many of the articles identified sampled people diagnosed with RA many years previously, making their recollection of symptoms at onset less reliable. Conclusion In order for clinicians to fully understand the earliest phases of disease, the nature of symptoms at onset needs to be understood. The current work represents a useful starting point, but this area needs further qualitative investigation, followed by quantitative explorations of symptom clusters and their associated features. PMID:23926091

  12. The relationship between microstructure and damage evolution in hot-rolled complex-phase steel sheet

    NASA Astrophysics Data System (ADS)

    Bell, Grant A. S.

    Complex-phase (CP) steels are employed in applications that require high-strength and good edge formability. These steels derive their strength from a fine-grained bainite-ferrite microstructure, and alloying to provide solid-solution and precipitation strengthening. CP steels are produced industrially through a process of controlled rolling and cooling to produce desirable microstructures. Hole-expansion tests are typically used as a measure of edge formability for applications such as stretch-flanges. It has been shown that CP microstructures are susceptible to large fluctuations in hole-expansion performance with little change in processing or resulting tensile properties. The steel's characteristics of damage evolution are critical to the hole-expansion performance. This study investigates the role of microstructure in the development of damage in CP microstructural variants. Two variant pairs of different thicknesses were produced from the leading and trailing edge of industrially produced hot-rolled sheet. Each pair consisted of a variant with poor hole-expansion performance, and a variant with good hole-expansion performance. Each variant was tested via interrupted double-notched uniaxial tension testing to induce damage. Damage evolution in each variant was quantified by X-ray micro-computed tomography (XmicroCT), and supplementary optical micrography. The damage results were correlated with microstructural characteristics. It was shown that poor hole-expansion variants failed by intergranular fracture. In these variants, void damage induced by hard martensite and retained austenite was not critical in producing failure. Purely void-damaged microstructures failed by ductile fracture, whereas cracked microstructures failed in a mixed brittle-ductile failure initiated by planar cracks. Microstructural banding of large elongated ferrite grains correlated with the existence of intergranular planar fractures.

  13. Pseudotachylyte in the Tananao Metamorphic Complex, Taiwan: Occurrence and dynamic phase changes of fossil earthquakes

    NASA Astrophysics Data System (ADS)

    Chu, Hao-Tsu; Hwang, Shyh-Lung; Shen, Pouyan; Yui, Tzen-Fu

    2012-12-01

    Pseudotachylyte veins and cataclasites were studied in the mylonitized granitic gneiss of the Tananao Metamorphic Complex at Hoping, Eastern Taiwan. The aphanitic pseudotachylyte veins vary in thickness, ranging from millimeters to about 1 cm. Field and optical microscopic observations show that such pseudotachylyte veins cut across cataclasites, which, in turn, transect the mylonitized granitic gneiss. Scanning electron microscopic images also show that both the pseudotachylyte veins and the cataclasites have been metasomatized by a K-rich fluid, resulting in the replacement of Na-plagioclase by K-feldspar (veins). Analytical electron microscopic observations reveal further details of physical and chemical changes (mainly fragmentation, dislocations, cleaving-healing with inclusions and relic voids, and retention of high-temperature albite) of quartz and feldspar in crushed grains. Pseudotachylytes occur as dark veins having a higher content of chlorite-biotite, clinozoisite-epidote and titanite fragments than cataclasites. These veins, coupled with hematite/jarosite-Fe-rich amorphous shell/carbonaceous material, indicate that crushing, healing/sintering, and inhomogeneous melt/fluid infiltration involving incipient and intermediate/high temperature melt patches, before and/or contemporaneous with the metasomatic K-rich fluid, prevailed in a coupled or sequential manner in the faulting event to form nonequilibrium phase assemblage. The chlorite-biotite, carbonaceous material and other nanoscale minerals could be vulnerable in future earthquakes under the influence of water. The timing of the formation of these pseudotachylyte veins should be later than the area's age of mylonitization of granitic gneiss of approximately 4.1-3.0 Ma (Wang et al., 1998). The formation of pseudotachylytes registers the fossil earthquakes during early stages in the exhumation history of the uplifting Taiwan Mountain belt since the Plio-Pleistocene Arc-Continent collision.

  14. Duality in Phase Space and Complex Dynamics of an Integrated Pest Management Network Model

    NASA Astrophysics Data System (ADS)

    Yuan, Baoyin; Tang, Sanyi; Cheke, Robert A.

    Fragmented habitat patches between which plants and animals can disperse can be modeled as networks with varying degrees of connectivity. A predator-prey model with network structures is proposed for integrated pest management (IPM) with impulsive control actions. The model was analyzed using numerical methods to investigate how factors such as the impulsive period, the releasing constant of natural enemies and the mode of connections between the patches affect pest outbreak patterns and the success or failure of pest control. The concept of the cluster as defined by Holland and Hastings is used to describe variations in results ranging from global synchrony when all patches have identical fluctuations to n-cluster solutions with all patches having different dynamics. Heterogeneity in the initial densities of either pest or natural enemy generally resulted in a variety of cluster oscillations. Surprisingly, if n > 1, the clusters fall into two groups one with low amplitude fluctuations and the other with high amplitude fluctuations (i.e. duality in phase space), implying that control actions radically alter the system's characteristics by inducing duality and more complex dynamics. When the impulsive period is small enough, i.e. the control strategy is undertaken frequently, the pest can be eradicated. As the period increases, the pest's dynamics shift from a steady state to become chaotic with periodic windows and more multicluster oscillations arise for heterogenous initial density distributions. Period-doubling bifurcation and periodic halving cascades occur as the releasing constant of the natural enemy increases. For the same ecological system with five differently connected networks, as the randomness of the connectedness increases, the transient duration becomes smaller and the probability of multicluster oscillations appearing becomes higher.

  15. Poly-phase Deformation Recorded in the Core of the Coast Plutonic Complex, Western British Columbia

    NASA Astrophysics Data System (ADS)

    Hamblock, J. M.; Andronicos, C. L.; Hurtado, J. M.

    2006-05-01

    of orthogneiss was concurrent with S2 deformation of the amphibolite gneiss. Tectonic strains calculated by the Rf-φ method using mafic enclaves in the orthogneiss vary from 4 to 10 within an area <1 km2, suggesting strong strain gradients during D2. S3 foliations strike WNW-ESE to E-W and dip shallowly to the south, suggesting NNE-SSW to N-S shortening. L3 lineations plunge shallowly to the SW and SE, and are associated low-angle shear bands with greenschist facies mineral assemblages which overprint higher temperature assemblages. Deformation phase D4 is characterized by low temperature, brittle deformation as shown by discrete fault surfaces with abundant chlorite. The following tectonic history can be determined based on structural observations. Amphibolite and immature sedimentary material formed from supracrustal (e.g. basalt flows?) and intrusive protoliths. These units were then intruded by the gabbro- diorite, which was deformed by right and left lateral shear zones sometime after crystallization. Both the amphibolite and gabbro-diorite were intruded by the orthogneiss, which was emplaced as sills during right and left lateral shearing and F2 folding. This geologic history is similar to that preserved in other parts of the Coast Plutonic Complex where dextral transpression and sinistral transtension are documented. The localization of low angle normal shear zones with greenschist facies mineral assemblages suggests extension occurred during cooling of the arc.

  16. Insoluble Fe-humic acid complex as a solid-phase electron mediator for microbial reductive dechlorination.

    PubMed

    Zhang, Chunfang; Zhang, Dongdong; Li, Zhiling; Akatsuka, Tetsuji; Yang, Suyin; Suzuki, Daisuke; Katayama, Arata

    2014-06-01

    We report that the insoluble Fe-HA complex, which was synthesized with both commercial Aldrich humic acid (HA) and natural HA, functions as a solid-phase electron mediator (EM) for the anaerobic microbial dechlorination of pentachlorophenol. Spectroscopic characterizations and sequential Fe extraction demonstrated that the Fe-HA complex was predominated with Na4P2O7-labile Fe (represented as the organically bound Fe fraction) and poorly ordered Fe fraction (the fraction left in the residue after the sequential extraction), which were associated with different possible binding processes with carboxylate and phenolic groups. The change in the electron-mediating activity caused by Fe extraction indicated that the electron-mediating function of the Fe-HA complex is attributable to the Na4P2O7-labile Fe fraction. The Fe-HA complex also accelerated the microbial reduction of Fe(III) oxide, which suggested the presence of multiple electron-mediating functions in the complex. The electron shuttle assay showed that the Fe-HA complex had an electron-accepting capacity of 0.82 mequiv g(-1) dry Fe-HA complex. The presence of redox-active moieties in the Fe-HA complex was verified by cyclic voltammetry analysis of the sample after electrical reduction, with a redox potential estimated at 0.02 V (vs a standard hydrogen electrode). PMID:24758743

  17. Low-complexity optical phase noise suppression in CO-OFDM system using recursive principal components elimination.

    PubMed

    Hong, Xiaojian; Hong, Xuezhi; He, Sailing

    2015-09-01

    A low-complexity optical phase noise suppression approach based on recursive principal components elimination, R-PCE, is proposed and theoretically derived for CO-OFDM systems. Through frequency domain principal components estimation and elimination, signal distortion caused by optical phase noise is mitigated by R-PCE. Since matrix inversion and domain transformation are completely avoided, compared with the case of the orthogonal basis expansion algorithm (L = 3) that offers a similar laser linewidth tolerance, the computational complexities of multiple principal components estimation are drastically reduced in the R-PCE by factors of about 7 and 5 for q = 3 and 4, respectively. The feasibility of optical phase noise suppression with the R-PCE and its decision-aided version (DA-R-PCE) in the QPSK/16QAM CO-OFDM system are demonstrated by Monte-Carlo simulations, which verify that R-PCE with only a few number of principal components q ( = 3) provides a significantly larger laser linewidth tolerance than conventional algorithms, including the common phase error compensation algorithm and linear interpolation algorithm. Numerical results show that the optimal performance of R-PCE and DA-R-PCE can be achieved with a moderate q, which is beneficial for low-complexity hardware implementation. PMID:26368499

  18. High-Resolution Solid-State NMR Investigation of the Phase Transition in Decamethylferrocene-Acenaphthenequinone Charge-Transfer Complex

    NASA Astrophysics Data System (ADS)

    Nakamura, Hideaki; Kuwahara, Daisuke; Mochida, Tomoyuki

    2009-10-01

    A charge-transfer complex composed of decamethylferrocene (D) and acenaphthenequinone (A) was prepared. The material was a 1:1 neutral complex with a mixed-stack structure and exhibited a phase transition at -16 °C. High-resolution 13C and 1H NMR spectroscopy revealed that an inclination of A with respect to D occurs below the phase-transition temperature. The 1H spin-diffusion rates of the complex undergoing high-speed magic-angle spinning (MAS) were measured to determine the shortest 1H-1H distance r between D and A. To analyze the experimental results, we derived the analytical expression of the spin-diffusion rate Wz for a homonuclear multispin system undergoing MAS. It was found that Wz for the complex is proportional only to 1/r6 under high-speed MAS conditions. On the basis of this relationship and the crystal structure at 20 °C, it was determined that the shortest 1H-1H distance r at -27.7 °C (below the phase transition temperature) is 0.4 Å shorter than that at 20 °C. Given this information, a plausible model of the low-temperature structure is discussed.

  19. Controlling the phase structures of polymer/surfactant complexes by changing macromolecular architecture and adding n-alcohols.

    PubMed

    Percebom, Ana Maria; Loh, Watson

    2016-03-15

    Phase behavior of complex salts formed by a cationic surfactant and different ethoxylated polyions was investigated in water and with addition of two n-alcohols of different chain lengths: n-butanol and n-decanol. The polyion possesses a main chain of methacrylic acid randomly grafted with oligo(ethylene oxide) chains. Strong electrostatic interaction between the anionic main chain and the cationic surfactant hexadecyltrimethylammonium (C16TA) leads to the formation of C16TAP(MA-MAEO(n)) x:y complex salts. Modifications in polyion structure, such as changes in the proportion of grafted comonomers and in the side chain length caused differences in the overall balance of interactions with water and n-alcohols, altering the complex salt solubility and, consequently, the formed liquid-crystalline structures. The role of n-decanol as a cosurfactant was verified, but the hydrophilic side chains expanded the capacity of the formed liquid crystalline phases to incorporate water. Additionally, a novel structure, probably cubic bicontinuous (Pn3m), was observed coexisting with lamellar phases at low water concentration. Because n-butanol is known for being a good solvent for poly(ethylene oxide), these side chains intensified the role of this short chain n-alcohol as cosolvent for C16TAP(MA-MAEO(n)) x:y complex salts, favoring the formation of disordered solutions, including a bicontinuous microemulsion. PMID:26752433

  20. A 4-D dataset for validation of crystal growth in a complex three-phase material, ice cream

    NASA Astrophysics Data System (ADS)

    Rockett, P.; Karagadde, S.; Guo, E.; Bent, J.; Hazekamp, J.; Kingsley, M.; Vila-Comamala, J.; Lee, P. D.

    2015-06-01

    Four dimensional (4D, or 3D plus time) X-ray tomographic imaging of phase changes in materials is quickly becoming an accepted tool for quantifying the development of microstructures to both inform and validate models. However, most of the systems studied have been relatively simple binary compositions with only two phases. In this study we present a quantitative dataset of the phase evolution in a complex three-phase material, ice cream. The microstructure of ice cream is an important parameter in terms of sensorial perception, and therefore quantification and modelling of the evolution of the microstructure with time and temperature is key to understanding its fabrication and storage. The microstructure consists of three phases, air cells, ice crystals, and unfrozen matrix. We perform in situ synchrotron X-ray imaging of ice cream samples using in-line phase contrast tomography, housed within a purpose built cold-stage (-40 to +20oC) with finely controlled variation in specimen temperature. The size and distribution of ice crystals and air cells during programmed temperature cycling are determined using 3D quantification. The microstructural evolution of three-phase materials has many other important applications ranging from biological to structural and functional material, hence this dataset can act as a validation case for numerical investigations on faceted and non-faceted crystal growth in a range of materials.

  1. Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii).

    PubMed

    Dau, Phuong D; Shuh, David K; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J; Gibson, John K

    2016-08-01

    The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf(II) is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf(II)(CH3SO2)3(-), prepared in the gas phase by reductive elimination of CH3SO2 from Cf(III)(CH3SO2)4(-). Comparison with synthesis of the corresponding Sm and Cm complexes reveals reduction of Cf(III) and Sm(III), and no evidence for reduction of Cm(III). This reflects the comparative 3+/2+ reduction potentials: Cf(3+) (-1.60 V) ≈ Sm(3+) (-1.55 V) ≫ Cm(3+) (-3.7 V). Association of O2 to the divalent complexes is attributed to formation of superoxides, with recovery of the trivalent oxidation state. The new gas-phase chemistry of californium, now the heaviest element to have been studied in this manner, provides evidence for Cf(II) coordination complexes and similar chemistry of Cf and Sm. PMID:27424652

  2. Gas-phase coordination complexes of dipositive plutonyl, PuO2(2+): chemical diversity across the actinyl series.

    PubMed

    Rios, Daniel; Rutkowski, Philip X; Van Stipdonk, Michael J; Gibson, John K

    2011-06-01

    We report the first transmission of solvent-coordinated dipositive plutonyl ion, Pu(VI)O(2)(2+), from solution to the gas phase by electrospray ionization (ESI) of plutonyl solutions in water/acetone and water/acetonitrile. ESI of plutonyl and uranyl solutions produced the isolable gas-phase complexes, [An(VI)O(2)(CH(3)COCH(3))(4,5,6)](2+), [An(VI)O(2)(CH(3)COCH(3))(3)(H(2)O)](2+), and [An(VI)O(2)(CH(3)CN)(4)](2+); additional complex compositions were observed for uranyl. In accord with relative actinyl stabilities, U(VI)O(2)(2+) > Pu(VI)O(2)(2+) > Np(VI)O(2)(2+), the yields of plutonyl complexes were about an order of magnitude less than those of uranyl, and dipositive neptunyl complexes were not observed. Collision-induced dissociation (CID) of the dipositive coordination complexes in a quadrupole ion trap produced doubly- and singly-charged fragment ions; the fragmentation products reveal differences in underlying chemistries of plutonyl and uranyl, including the lower stability of Pu(VI) as compared with U(VI). Particularly notable was the distinctive CID fragment ion, [Pu(IV)(OH)(3)](+) from [Pu(VI)O(2)(CH(3)COCH(3))(6)](2+), where the plutonyl structure has been disrupted and the tetravalent plutonium hydroxide produced; this process was not observed for uranyl. PMID:21517017

  3. Oxidation of 2-propanol ligands during collision-induced dissociation of a gas-phase uranyl complex

    NASA Astrophysics Data System (ADS)

    van Stipdonk, Michael J.; Chien, Winnie; Anbalagan, Victor; Gresham, Garold L.; Groenewold, Gary S.

    2004-10-01

    We demonstrate, by way of multi-stage tandem mass spectrometry and extensive deuterium labeling, that 2-propanol is converted to acetone, and 2-propoxide to acetaldehyde, when monopositive 2-propanol-coordinated uranyl-ligand cations are subjected to collision-induced dissociation in the gas-phase environment of an ion trap mass spectrometer. A species with formula [(UO2OCH(CH3)2)(HOCH(CH3)2)]+, derived from dissociation of the gas-phase precursor [(UO2NO3)(HOCH(CH3)2)3]+ eliminates two H atoms and CH3 in consecutive stages to generate a monopositive complex composed of the U(V) species UO2+ coordinated by acetone and acetaldehyde, i.e. [UO2+(OC(CH3)2)(OC(H)CH3)]. Dissociation of this latter ion resulted in elimination of the two coordinating carbonyl ligands in two consecutive dissociation stages to leave UO2+. Analogous reactions were not observed for uranyl complexes containing 1-propanol or 2-methyl-2-propanol, or for cationic complexes with divalent metals such as Ni2+, Co2+, Pb2+ and Ca2+. One explanation for these reactions is bond insertion by the metal center in the bis-ligated uranyl complex, which would be expected to have an LUMO consisting of unoccupied 6d-orbitals that would confer transition metal-like behavior on the complex.

  4. Phase behavior and structure of stable complexes between a long polyanion and a branched polycation

    NASA Astrophysics Data System (ADS)

    Mengarelli, Valentina; Zeghal, Mehdi; Auvray, Loïc; Clemens, Daniel

    2011-08-01

    The association between oppositely charged branched polyethylenimine (BPEI) and polymethacrylic acid (PMA) in the dilute regime is investigated using turbidimetric titration and electrophoretic mobility measurements. The complexation is controlled by tuning continuously the pH-sensitive charge of the polyacid in acidic solution. The formation of soluble and stable positively charged complexes is a cooperative process characterized by the existence of two regimes of weak and strong complexation. In the regime of weak complexation, a long PMA chain overcharged by several BPEI molecules forms a binary complex. As the charge of the polyacid increases, these binary complexes condense at a well defined charge ratio of the mixture to form large positively charged aggregates. The overcharging and the existence of two regimes of complexation are analyzed in the light of recent theories. The structure of the polyelectrolytes is investigated at higher polymer concentration by small angle neutron scattering. Binary complexes of finite size present an open structure where the polyacid chains connecting a small number of BPEI molecules have shrunk slightly. In the condensed complexes, BPEI molecules, wrapped by polyacid chains, form networks of stretched necklaces.

  5. Passage of TBP-uranyl complexes from aqueous-organic interface to the organic phase: insights from molecular dynamics simulation.

    PubMed

    Sahu, Pooja; Ali, Sk Musharaf; Shenoy, Kalasanka Trivikram

    2016-08-24

    The present study reports molecular dynamics simulations for biphasic systems comprising tributyl phosphate (TBP) in dodecane and uranyl nitrate in the aqueous phase, which are key chemical species in the well-known Pu-U extraction (PUREX) process. An attempt has been made to understand the nature of interface and mechanism of 'TBP associated uranyl' crossing under neutral and acidic conditions. Results show that the solvent density undergoes large fluctuation near the interface depending on the nature of the aqueous-organic phase. The study provides compelling evidence of experimentally observed reorganization of interfacial complexes at the interface and their structural reformation during extraction. It has been observed that the surface active nature of TBP and their interfacial coverage is modulated by the nature of incorporated solute species and their location with respect to the interface. Also, the TBP structuring near the interface is destroyed when an acidic interface is considered rather than a neutral one which favors the uranyl extraction. With an acidic interface, the water humidity of organic phase was observed to be increased in the experiments. Furthermore, the acid/water solubility in the organic phase was observed to be influenced by selection of acid models and their concentration. Simulations with high acid concentration show water pocket formation in the organic phase. However, in the case of dissociated ions or a mixture of both, no such water pool is observed and the extracted water remains dispersed in the organic phase, having the tendency to be replaced by HNO3 because of preferred TBP·HNO3 complexation over TBP·H2O. Most remarkably, the present study makes evident the TBP-induced charge redistribution of uranyl complexes during migration from the interface to the bulk organic phase, which contributes to drive uranyl complexes such as UO2·NO3·4TBP, UO2·5TBP and UO2·NO3·3TBP·HNO3 in the organic phase, and this was reestablished by

  6. New chelating reagents for preconcentration, separation, determination of metal complexes by high performance liquid chromatography and solid phase extraction

    SciTech Connect

    Qian, Yan wen.

    1991-12-03

    A general scheme is outlined for rapid determination of metal cations by complexation and subsequent HPLC separation. The synthesis and general properties are described for several new thiohydrazone chelating reagents. Solubility considerations suggest that the metal complexes have a positive charge. Excellent chromatographic separations are obtained for mixtures of up to seven metal complexes. Addition of a positively charged additive to the eluent is shown to have a significant effect on both the retention times and sharpness of the chromatographic peaks. Separation of the metal complexes on resins with a permanent charge is also shown to be feasible. Two new hydrazone reagents have been synthesized and characterized. Trace metal ions in aqueous solution are complexed by one of the hydrazones and the resulting metal complexes are solid phase extracted onto a mini cation-exchange or polymeric column. The uptake of metal complexes is complete and the elution step is fast and complete. The quantitative recoveries of metal ions determined by both spectrophotometric method and ICP-MS are very satisfactory and agree with each other.

  7. Spectroscopic Characterization and Reactivity of Triplet and Quintet Iron(IV) Oxo Complexes in the Gas Phase

    PubMed Central

    Andris, Erik; Jašík, Juraj; Gómez, Laura

    2016-01-01

    Abstract Closely structurally related triplet and quintet iron(IV) oxo complexes with a tetradentate aminopyridine ligand were generated in the gas phase, spectroscopically characterized, and their reactivities in hydrogen‐transfer and oxygen‐transfer reactions were compared. The spin states were unambiguously assigned based on helium tagging infrared photodissociation (IRPD) spectra of the mass‐selected iron complexes. It is shown that the stretching vibrations of the nitrate counterion can be used as a spectral marker of the central iron spin state. PMID:26878833

  8. The Nonlinear Phase Response Curve of the Human Circadian Pacemaker and How Complex Behaviors Might Arise in Nature

    NASA Astrophysics Data System (ADS)

    Leder, Ron S.

    2002-08-01

    Our example from nature is two groups of about 10,000 cells in the brain called Suprachiasmatic Nuclei (SCN) and how light can entrain free running endogenous periodic behavior via the retina's connection to the SCN. Our major question is how a complex behavior like this can arise in nature. Finally presented is a mathematical model and simulation showing how simple periodic signals can be coupled to produce spatio-temporal chaotic behavior and how two complex signals can combine to produce simple coherent behavior with a hypothetical analogy to phase resetting in biological circadian pacemakers.

  9. Rotational Analysis of Phase Plane Curves: Complex and Pure Imaginary Eigenvalues

    ERIC Educational Resources Information Center

    Murray, Russell H.

    2005-01-01

    Although the phase plane can be plotted and analyzed using an appropriate software package, the author found it worthwhile to engage the students with the theorem and the two proofs. The theorem is a powerful tool that provides insight into the rotational behavior of the phase plane diagram in a simple way: just check the signs of c and [alpha].…

  10. Time-domain Vander-Lugt filters for in-fiber complex (amplitude and phase) optical pulse shaping.

    PubMed

    Fernández-Ruiz, María R; Huh, Jeonghyun; Azaña, José

    2016-05-01

    The time-domain counterpart of spatial Vander-Lugt filters is proposed for the first time, to the best of our knowledge. The concept enables reshaping an ultrashort optical pulse into a desired complex (amplitude and phase) arbitrary temporal pulse waveform using a setup configuration similar to that of previously demonstrated fiber-optic time-domain pulse-intensity shapers, i.e., using a single temporal amplitude modulator between two opposite-dispersive all-fiber media. The proposal is experimentally validated through reconfigurable generation of two complex-valued pulse shapes, namely, a 60 ps asymmetrical triangular pulse with controlled parabolic phase and a 4-symbol 16-QAM picosecond pulse code sequence. PMID:27128089

  11. Compression of ultra-long microwave pulses using programmable microwave photonic phase filtering with > 100 complex-coefficient taps.

    PubMed

    Song, Minhyup; Torres-Company, Victor; Wu, Rui; Metcalf, Andrew J; Weiner, Andrew M

    2014-03-24

    Microwave photonic filters with arbitrary phase response can be achieved by merging high-repetition-rate electro-optic frequency comb technology with line-by-line pulse shaping. When arranged in an interferometric configuration, the filter features a number of programmable complex-coefficient taps equal to the number of available comb lines. In this work, we use an ultrabroadband comb generator resulting in a microwave photonic phase filter with >100 complex-coefficient taps. We demonstrate the potential of this filter by performing programmable chirp control of ultrawideband waveforms that extend over long (>10 ns) temporal apertures. This work opens new possibilities for compensating realistic linear distortion impairments on ultrabroadband wireless signals spanning over dozens of nanosecond temporal apertures. PMID:24663981

  12. Efficient Covalent Bond Formation in Gas-Phase Peptide-Peptide Ion Complexes with the Photoleucine Stapler.

    PubMed

    Shaffer, Christopher J; Andrikopoulos, Prokopis C; Řezáč, Jan; Rulíšek, Lubomír; Tureček, František

    2016-04-01

    Noncovalent complexes of hydrophobic peptides GLLLG and GLLLK with photoleucine (L*) tagged peptides G(L* n L m )K (n = 1,3, m = 2,0) were generated as singly charged ions in the gas phase and probed by photodissociation at 355 nm. Carbene intermediates produced by photodissociative loss of N2 from the L* diazirine rings underwent insertion into X-H bonds of the target peptide moiety, forming covalent adducts with yields reaching 30%. Gas-phase sequencing of the covalent adducts revealed preferred bond formation at the C-terminal residue of the target peptide. Site-selective carbene insertion was achieved by placing the L* residue in different positions along the photopeptide chain, and the residues in the target peptide undergoing carbene insertion were identified by gas-phase ion sequencing that was aided by specific (13)C labeling. Density functional theory calculations indicated that noncovalent binding to GL*L*L*K resulted in substantial changes of the (GLLLK + H)(+) ground state conformation. The peptide moieties in [GL*L*LK + GLLLK + H](+) ion complexes were held together by hydrogen bonds, whereas dispersion interactions of the nonpolar groups were only secondary in ground-state 0 K structures. Born-Oppenheimer molecular dynamics for 100 ps trajectories of several different conformers at the 310 K laboratory temperature showed that noncovalent complexes developed multiple, residue-specific contacts between the diazirine carbons and GLLLK residues. The calculations pointed to the substantial fluidity of the nonpolar side chains in the complexes. Diazirine photochemistry in combination with Born-Oppenheimer molecular dynamics is a promising tool for investigations of peptide-peptide ion interactions in the gas phase. Graphical Abstract ᅟ. PMID:26817657

  13. Efficient Covalent Bond Formation in Gas-Phase Peptide-Peptide Ion Complexes with the Photoleucine Stapler

    NASA Astrophysics Data System (ADS)

    Shaffer, Christopher J.; Andrikopoulos, Prokopis C.; Řezáč, Jan; Rulíšek, Lubomír; Tureček, František

    2016-04-01

    Noncovalent complexes of hydrophobic peptides GLLLG and GLLLK with photoleucine (L*) tagged peptides G(L* n L m )K (n = 1,3, m = 2,0) were generated as singly charged ions in the gas phase and probed by photodissociation at 355 nm. Carbene intermediates produced by photodissociative loss of N2 from the L* diazirine rings underwent insertion into X-H bonds of the target peptide moiety, forming covalent adducts with yields reaching 30%. Gas-phase sequencing of the covalent adducts revealed preferred bond formation at the C-terminal residue of the target peptide. Site-selective carbene insertion was achieved by placing the L* residue in different positions along the photopeptide chain, and the residues in the target peptide undergoing carbene insertion were identified by gas-phase ion sequencing that was aided by specific 13C labeling. Density functional theory calculations indicated that noncovalent binding to GL*L*L*K resulted in substantial changes of the (GLLLK + H)+ ground state conformation. The peptide moieties in [GL*L*LK + GLLLK + H]+ ion complexes were held together by hydrogen bonds, whereas dispersion interactions of the nonpolar groups were only secondary in ground-state 0 K structures. Born-Oppenheimer molecular dynamics for 100 ps trajectories of several different conformers at the 310 K laboratory temperature showed that noncovalent complexes developed multiple, residue-specific contacts between the diazirine carbons and GLLLK residues. The calculations pointed to the substantial fluidity of the nonpolar side chains in the complexes. Diazirine photochemistry in combination with Born-Oppenheimer molecular dynamics is a promising tool for investigations of peptide-peptide ion interactions in the gas phase.

  14. Phase Studies of Model Biomembranes: Complex Behavior of DSPC/DOPC/Cholesterol

    PubMed Central

    Zhao, Jiang; Wu, Jing; Heberle, Frederick A.; Mills, Thalia T.; Klawitter, Paul; Huang, Grace; Costanza, Greg; Feigenson, Gerald W.

    2009-01-01

    We have undertaken a series of experiments to examine the behavior of individual components of cell membranes. Here we report an initial stage of these experiments, in which the properties of a chemically simple lipid mixture are carefully mapped onto a phase diagram. Four different experimental methods were used to establish the phase behavior of the 3-component mixture DSPC/DOPC/chol: (1) confocal fluorescence microscopy observation of giant unilamellar vesicles, GUVs; (2) FRET from perylene to C20:0-DiI; (3) fluorescence of dilute dyes C18:2-DiO and C20:0-DiI; and (4) wide angle x-ray diffraction. This particular 3-component mixture was chosen, in part, for a high level of immiscibility of the components in order to facilitate solving the phase behavior at all compositions. At 23 °C, a large fraction of the possible compositions for this mixture give rise to a solid phase. A region of 3-phase coexistence of {Lα + Lβ + Lo} was detected and defined based on a combination of fluorescence microscopy of GUVs, FRET, and dilute C20:0-DiI fluorescence. At very low cholesterol concentrations, the solid phase is the tilted-chain phase Lβ′. Most of the phase boundaries have been determined to within a few percent of the composition. Measurements of the perturbations of the boundaries of this accurate phase diagram could serve as a means to understand the behaviors of a range of added lipids and proteins. PMID:17825247

  15. Low-complexity feed-forward carrier phase estimation for M-ary QAM based on phase search acceleration by quadratic approximation.

    PubMed

    Xiang, Meng; Fu, Songnian; Deng, Lei; Tang, Ming; Shum, Perry; Liu, Deming

    2015-07-27

    Blind phase search (BPS) algorithm for M-QAM has excellent tolerance to laser linewidth at the expense of rather high computation complexity (CC). Here, we first theoretically obtain the quadratic relationship between the test angle and corresponding distance matric during the BPS implementation. Afterwards, we propose a carrier phase estimation (CPE) based on a two-stage BPS with quadratic approximation (QA). Instead of searching the phase blindly with fixed step-size for the BPS algorithm, QA can significantly accelerate the speed of phase searching. As a result, a group factor of 2.96/3.05, 4.55/4.67 and 2.27/2.3 (in the form of multipliers/adders) reduction of CC is achieved for 16QAM, 64QAM and 256QAM, respectively, in comparison with the traditional BPS scheme. Meanwhile, a guideline for determining the summing filter block length is put forward during performance optimization. Under the condition of optimum filter block length, our proposed scheme shows similar performance as traditional BPS scheme. At 1 dB required E(S)/N(0) penalty @ BER = 10(-2), our proposed CPE scheme can tolerate a times symbol duration productΔf⋅T(S) of 1.7 × 10(-4), 6 × 10(-5) and 1.5 × 10(-5) for 16/64/256-QAM, respectively. PMID:26367577

  16. Agent-based spin model for financial markets on complex networks: Emergence of two-phase phenomena

    NASA Astrophysics Data System (ADS)

    Kim, Yup; Kim, Hong-Joo; Yook, Soon-Hyung

    2008-09-01

    We study a microscopic model for financial markets on complex networks, motivated by the dynamics of agents and their structure of interaction. The model consists of interacting agents (spins) with local ferromagnetic coupling and global antiferromagnetic coupling. In order to incorporate more realistic situations, we also introduce an external field which changes in time. From numerical simulations, we find that the model shows two-phase phenomena. When the local ferromagnetic interaction is balanced with the global antiferromagnetic interaction, the resulting return distribution satisfies a power law having a single peak at zero values of return, which corresponds to the market equilibrium phase. On the other hand, if local ferromagnetic interaction is dominant, then the return distribution becomes double peaked at nonzero values of return, which characterizes the out-of-equilibrium phase. On random networks, the crossover between two phases comes from the competition between two different interactions. However, on scale-free networks, not only the competition between the different interactions but also the heterogeneity of underlying topology causes the two-phase phenomena. Possible relationships between the critical phenomena of spin system and the two-phase phenomena are discussed.

  17. Information geometric analysis of phase transitions in complex patterns: the case of the Gray-Scott reaction–diffusion model

    NASA Astrophysics Data System (ADS)

    Har-Shemesh, Omri; Quax, Rick; Hoekstra, Alfons G.; Sloot, Peter M. A.

    2016-04-01

    The Fisher–Rao metric from information geometry is related to phase transition phenomena in classical statistical mechanics. Several studies propose to extend the use of information geometry to study more general phase transitions in complex systems. However, it is unclear whether the Fisher–Rao metric does indeed detect these more general transitions, especially in the absence of a statistical model. In this paper we study the transitions between patterns in the Gray-Scott reaction–diffusion model using Fisher information. We describe the system by a probability density function that represents the size distribution of blobs in the patterns and compute its Fisher information with respect to changing the two rate parameters of the underlying model. We estimate the distribution non-parametrically so that we do not assume any statistical model. The resulting Fisher map can be interpreted as a phase-map of the different patterns. Lines with high Fisher information can be considered as boundaries between regions of parameter space where patterns with similar characteristics appear. These lines of high Fisher information can be interpreted as phase transitions between complex patterns.

  18. Phase-field simulations of GaN growth by selective area epitaxy from complex mask geometries

    NASA Astrophysics Data System (ADS)

    Aagesen, Larry K.; Coltrin, Michael E.; Han, Jung; Thornton, Katsuyo

    2015-05-01

    Three-dimensional phase-field simulations of GaN growth by selective area epitaxy were performed. The model includes a crystallographic-orientation-dependent deposition rate and arbitrarily complex mask geometries. The orientation-dependent deposition rate can be determined from experimental measurements of the relative growth rates of low-index crystallographic facets. Growth on various complex mask geometries was simulated on both c-plane and a-plane template layers. Agreement was observed between simulations and experiment, including complex phenomena occurring at the intersections between facets. The sources of the discrepancies between simulated and experimental morphologies were also investigated. The model provides a route to optimize masks and processing conditions during materials synthesis for solar cells, light-emitting diodes, and other electronic and opto-electronic applications.

  19. Phase-field simulations of GaN growth by selective area epitaxy from complex mask geometries

    SciTech Connect

    Aagesen, Larry K.; Thornton, Katsuyo; Coltrin, Michael E.; Han, Jung

    2015-05-21

    Three-dimensional phase-field simulations of GaN growth by selective area epitaxy were performed. The model includes a crystallographic-orientation-dependent deposition rate and arbitrarily complex mask geometries. The orientation-dependent deposition rate can be determined from experimental measurements of the relative growth rates of low-index crystallographic facets. Growth on various complex mask geometries was simulated on both c-plane and a-plane template layers. Agreement was observed between simulations and experiment, including complex phenomena occurring at the intersections between facets. The sources of the discrepancies between simulated and experimental morphologies were also investigated. The model provides a route to optimize masks and processing conditions during materials synthesis for solar cells, light-emitting diodes, and other electronic and opto-electronic applications.

  20. Phase-field simulations of GaN growth by selective area epitaxy on complex mask geometries

    DOE PAGESBeta

    Aagesen, Larry K.; Coltrin, Michael Elliott; Han, Jung; Thornton, Katsuyo

    2015-05-15

    Three-dimensional phase-field simulations of GaN growth by selective area epitaxy were performed. Furthermore, this model includes a crystallographic-orientation-dependent deposition rate and arbitrarily complex mask geometries. The orientation-dependent deposition rate can be determined from experimental measurements of the relative growth rates of low-index crystallographic facets. Growth on various complex mask geometries was simulated on both c-plane and a-plane template layers. Agreement was observed between simulations and experiment, including complex phenomena occurring at the intersections between facets. The sources of the discrepancies between simulated and experimental morphologies were also investigated. We found that the model provides a route to optimize masks andmore » processing conditions during materials synthesis for solar cells, light-emitting diodes, and other electronic and opto-electronic applications.« less

  1. Phase-field simulations of GaN growth by selective area epitaxy on complex mask geometries

    SciTech Connect

    Aagesen, Larry K.; Coltrin, Michael Elliott; Han, Jung; Thornton, Katsuyo

    2015-05-15

    Three-dimensional phase-field simulations of GaN growth by selective area epitaxy were performed. Furthermore, this model includes a crystallographic-orientation-dependent deposition rate and arbitrarily complex mask geometries. The orientation-dependent deposition rate can be determined from experimental measurements of the relative growth rates of low-index crystallographic facets. Growth on various complex mask geometries was simulated on both c-plane and a-plane template layers. Agreement was observed between simulations and experiment, including complex phenomena occurring at the intersections between facets. The sources of the discrepancies between simulated and experimental morphologies were also investigated. We found that the model provides a route to optimize masks and processing conditions during materials synthesis for solar cells, light-emitting diodes, and other electronic and opto-electronic applications.

  2. New Pathways for the Formation of Complex Organics and Prebiotic Synthesis in the Gas Phase

    NASA Astrophysics Data System (ADS)

    El-Shall, M. S.

    2010-04-01

    We study the formation mechanisms of complex organics that are present in interstellar clouds. The reaction of acetylene ion with water produces vinyl alcohol while the reaction of benzene ion with acetylene produces naphthalene-type ion.

  3. Surface complexation reaction for phase transfer of hydrophobic quantum dot from nonpolar to polar medium.

    PubMed

    Bhandari, Satyapriya; Roy, Shilaj; Pramanik, Sabyasachi; Chattopadhyay, Arun

    2014-09-01

    Chemical reaction between oleate-capped Zn(x)Cd(1-x)S quantum dots (Qdots) and 8-hydroxyquinoline (HQ) led to formation of a surface complex, which was accompanied by transfer of hydrophobic Qdots from nonpolar (hexane) to polar (water) medium with high efficiency. The stability of the complex on the surface was achieved via involvement of dangling sulfide bonds. Moreover, the transferred hydrophilic Qdots--herein called as quantum dot complex (QDC)--exhibited new and superior optical properties in comparison to bare inorganic complexes with retention of the dimension and core structure of the Qdots. Finally, the new and superior optical properties of water-soluble QDC make them potentially useful for biological--in addition to light emitting device (LED)--applications. PMID:25133937

  4. Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2004-01-01

    Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

  5. The complexity of consenting to clinical research in phase I pediatric cancer studies.

    PubMed

    Schechter, Tal; Grant, Ronald

    2015-02-01

    The principal aim of phase I studies is to define the recommended dosing of drugs for phase II studies through assessment of drug pharmacokinetics and observation of the drug's toxicity profile. In the setting of pediatric oncology, the use of an experimental drug in phase I study is offered when prognosis is poor. Thus, phase I oncology studies are not given to patients with a primary purpose of an intent to cure. They may offer little to no treatment benefit and carry a potential toxic effect. They may offer other benefits such as improved quality of life and relief of pain, however. Three parties are involved in the informed consent process: the parents, patients, and physicians. Families report hope as the main cause for enrollment. Physicians focus on providing information so families can decide about participation. Physicians also try to maintain hope despite understanding the nature of the disease. This makes the informed consent complicated for all parties involved in the process. The purpose of this review is to discuss the aims of phase I studies in pediatric oncology and to convey the ethical challenges that patients, parents, and physicians are facing when discussing informed consent with potential study participants. PMID:25573671

  6. Ligand field spectroscopy of Cu(II) and Ag(II) complexes in the gas phase: theory and experiment.

    PubMed

    Puskar, Ljiljana; Cox, Hazel; Goren, Alan; Aitken, Georgina D C; Stace, Anthony J

    2003-01-01

    Ligand field spectra have been recorded in the gas phase for the two series of complexes containing either Cu(II) or Ag(II) in association with pyridine. Where comparisons are possible, the gas phase spectra match those recorded in the condensed phase; however, for Ag(II) systems the results differ in interpretation. The Ag(II) data are attributed to a ligand-to-metal charge transfer process, and the Cu(II) data (spectral region and extinction coefficient) match the characteristics of a d-d transition. A detailed theoretical analysis of two complexes. [Cu(py)4]2+ and [Ag(py)4]2+ provides evidence of a minimum energy, D4h structure and two less stable D2h and D2d structures within approximately 60 kJ mol(-1). From these structures it is possible to identify a range of optically and vibronically allowed transitions that could contribute to spectra observed in the gas phase. In the case of calculations on [Ag(py)4]2+ there is strong evidence of an electronic transition that would account for the observation of charge transfer in the experiments. Less detailed calculations on [Cu(py)6]2+ and [Ag(py)6]2+ show structural evidence of extensive Jahn Teller distortion. Taken together with incremental binding energies calculated for complexes containing between two and six pyridine molecules, these results show that the level of theory adopted is capable of providing a semi-quantitative understanding of the experimental data. PMID:14527220

  7. Volta phase plate cryo-EM of the small protein complex Prx3.

    PubMed

    Khoshouei, Maryam; Radjainia, Mazdak; Phillips, Amy J; Gerrard, Juliet A; Mitra, Alok K; Plitzko, Jürgen M; Baumeister, Wolfgang; Danev, Radostin

    2016-01-01

    Cryo-EM of large, macromolecular assemblies has seen a significant increase in the numbers of high-resolution structures since the arrival of direct electron detectors. However, sub-nanometre resolution cryo-EM structures are rare compared with crystal structure depositions, particularly for relatively small particles (<400 kDa). Here we demonstrate the benefits of Volta phase plates for single-particle analysis by time-efficient cryo-EM structure determination of 257 kDa human peroxiredoxin-3 dodecamers at 4.4 Å resolution. The Volta phase plate improves the applicability of cryo-EM for small molecules and accelerates structure determination. PMID:26817416

  8. Volta phase plate cryo-EM of the small protein complex Prx3

    NASA Astrophysics Data System (ADS)

    Khoshouei, Maryam; Radjainia, Mazdak; Phillips, Amy J.; Gerrard, Juliet A.; Mitra, Alok K.; Plitzko, Jürgen M.; Baumeister, Wolfgang; Danev, Radostin

    2016-01-01

    Cryo-EM of large, macromolecular assemblies has seen a significant increase in the numbers of high-resolution structures since the arrival of direct electron detectors. However, sub-nanometre resolution cryo-EM structures are rare compared with crystal structure depositions, particularly for relatively small particles (<400 kDa). Here we demonstrate the benefits of Volta phase plates for single-particle analysis by time-efficient cryo-EM structure determination of 257 kDa human peroxiredoxin-3 dodecamers at 4.4 Å resolution. The Volta phase plate improves the applicability of cryo-EM for small molecules and accelerates structure determination.

  9. Origin of non-linearity in phase solubility: solubilisation by cyclodextrin beyond stoichiometric complexation.

    PubMed

    Nicol, Thomas W J; Matubayasi, Nobuyuki; Shimizu, Seishi

    2016-06-01

    The low solubility of drugs, which poses a serious problem in drug development, can in part be overcome by the use of cyclodextrins (CDs) and their derivatives. Here, the key to solubilisation is identified as the formation of inclusion complexes with the drug molecule. If inclusion complexation were the only contribution to drug solubility, it would increase linearly with CD concentration (as per the Higuchi-Connors model); this is because inclusion complexation is a 1 : 1 stoichiometric process. However, solubility curves often deviate from this linearity, whose mechanism is yet to be understood. Here we aim to clarify the origin of such non-linearity, based on the Kirkwood-Buff and the McMillan-Mayer theories of solutions. The rigorous statistical thermodynamic theory shows that non-linearity of solubilisation can be rationalised by two contributions: CD-drug interaction and the drug-induced change of CD-CD interaction. PMID:27206059

  10. Calibration of the complex matrix effects on the sampling of polycyclic aromatic hydrocarbons in milk samples using solid phase microextraction.

    PubMed

    Lin, Wei; Wei, Songbo; Jiang, Ruifen; Zhu, Fang; Ouyang, Gangfeng

    2016-08-24

    Solid phase microextraction (SPME), a simple, fast and promising sampling technique, has been widely used for complex sample analysis. However, complex matrices could modify the absorption property of coatings as well as the uptake kinetics of analytes, eventually biasing the quantification results. In the current study, we demonstrated the feasibility of a developed calibration method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in complex milk samples. Effects of the complex matrices on the SPME sampling process and the sampling conditions were investigated. Results showed that short exposure time (pre-equilibrium SPME, PE-SPME) could increase the lifetime of coatings, and the complex matrices in milk samples could significantly influence the sampling kinetics of SPME. In addition, the optimized sampling time, temperature and dilution factor for PAHs were 10 min, 85 °C and 20, respectively. The obtained LODs and LOQs of all the PAHs were 0.1-0.8 ng/mL and 1.4-4.7 ng/mL, respectively. Furthermore, the accuracy of the proposed PE-SPME method for milk sampling was validated by the recoveries of the studied compounds in two concentration levels, which ranged from 75% to 110% for all the compounds. Finally, the proposed method was applied to the screening of PAHs in milk samples. PMID:27497004

  11. Separation of dialkyl sulfides by metallo-mesogenic stationary phases for complexation gas chromatography.

    PubMed

    Chen, Jian-Lian; Liu, Chuen-Ying

    2007-08-17

    A copper mesogenic side-chain polymer (P-C(15)CuC(18)) was cross-linked onto the capillary wall as a stationary film for gas chromatography (GC) separation of alkyl sulfides. These organic sulfides are of interest for their large health impact because of their wide range of volatiles and high reactivities toward metals. Different GC parameters for optimal separation efficiency are discussed for use with a mesogenic polymer column along with flame photometric detection (FPD). Both the carrier gas flow-rate and column temperature were studied to determine the relationship of plate height to the chemical structure of the solutes, as well as to determine the morphology of the mesogenic polymer. Van 't Hoff plots show phase transitions of the stationary mesophase as the column temperature was varied. The results reveal that the separation mechanism might be based on ligand exchange and polarity interaction between the analytes and the stationary phase, with the vapor pressure of the analytes also being important. The former interaction dominates in the lamellar crystalline phase and the latter interaction dominates in the hexagonal columnar-discotic phase. With high reproducibility for retention time (RSD< or =0.37%) and for peak area (RSD< or =5.16%), the GC-FPD system produced linear calibration graphs (r> or =0.9918) for the determination of 13 sulfides with a detection limit below 2.5 ng. PMID:17568598

  12. "Sounds of Intent", Phase 2: Gauging the Music Development of Children with Complex Needs

    ERIC Educational Resources Information Center

    Ockelford, A.; Welch, G.; Jewell-Gore, L.; Cheng, E.; Vogiatzoglou, A.; Himonides, E.

    2011-01-01

    This article reports the latest phase of research in the "Sounds of intent" project, which is seeking, as a long-term goal, to map musical development in children and young people with severe, or profound and multiple learning difficulties (SLD or PMLD). Previous exploratory work had resulted in a framework of six putative music-developmental…

  13. A comparative study of penalization and phase field methods for the solution of the diffusion equation in complex geometries

    NASA Astrophysics Data System (ADS)

    Tauriello, Gerardo; Koumoutsakos, Petros

    2015-02-01

    We present a comparative study of penalization and phase field methods for the solution of the diffusion equation in complex geometries embedded using simple Cartesian meshes. The two methods have been widely employed to solve partial differential equations in complex and moving geometries for applications ranging from solid and fluid mechanics to biology and geophysics. Their popularity is largely due to their discretization on Cartesian meshes thus avoiding the need to create body-fitted grids. At the same time, there are questions regarding their accuracy and it appears that the use of each one is confined by disciplinary boundaries. Here, we compare penalization and phase field methods to handle problems with Neumann and Robin boundary conditions. We discuss extensions for Dirichlet boundary conditions and in turn compare with methods that have been explicitly designed to handle Dirichlet boundary conditions. The accuracy of all methods is analyzed using one and two dimensional benchmark problems such as the flow induced by an oscillating wall and by a cylinder performing rotary oscillations. This comparative study provides information to decide which methods to consider for a given application and their incorporation in broader computational frameworks. We demonstrate that phase field methods are more accurate than penalization methods on problems with Neumann boundary conditions and we present an error analysis explaining this result.

  14. Phase-Contrast versus Off-Axis Illumination: Is a More Complex Microscope Always More Powerful?

    ERIC Educational Resources Information Center

    Hostounsky, Zdenek; Pelc, Radek

    2007-01-01

    In this article, a practical demonstration suitable for any biology college classroom is presented. With the examples of a complex biological specimen (slug's radula) and a simple reference specimen (electron microscopical grid imprint in gelatin), both of which can be easily prepared, the capabilities of two imaging modes commonly used in optical…

  15. First Principles Studies of Phase Stability and Reaction Dynamics in Complex Metal Hydrides

    SciTech Connect

    Chou, Mei-Yin

    2014-09-29

    Complex metal hydrides are believed to be one of the most promising materials for developing hydrogen storage systems that can operate under desirable conditions. At the same time, these are also a class of materials that exhibit intriguing properties. We have used state-of-the-art computational techniques to study the fundamental properties of these materials.

  16. Phase 5 storage (Project W-112) Central Waste Complex operational readiness review, final report

    SciTech Connect

    Wight, R.H.

    1997-05-30

    This document is the final report for the RFSH conducted, Contractor Operational Readiness Review (ORR) for the Central Waste Complex (CWC) Project W-112 and Interim Safety Basis implementation. As appendices, all findings, observations, lines of inquiry and the implementation plan are included.

  17. Phase diagrams of the Bose-Hubbard model and the Haldane-Bose-Hubbard model with complex hopping amplitudes

    NASA Astrophysics Data System (ADS)

    Kuno, Yoshihito; Nakafuji, Takashi; Ichinose, Ikuo

    2015-12-01

    In this paper, we study Bose-Hubbard models on square and honeycomb lattices with complex hopping amplitudes, which are feasible by recent experiments of cold atomic gases in optical lattices. To clarify phase diagrams, we use extended quantum Monte Carlo simulations (eQMC). For the system on the square lattice, the complex hopping is realized by an artificial magnetic field. We found that vortex-solid states form for certain set of magnetic field, i.e., the magnetic field with the flux quanta per plaquette f =p /q , where p and q are co-prime natural numbers. For the system on the honeycomb lattice, we add the next-nearest-neighbor complex hopping. The model is a bosonic analog of the Haldane-Hubbard model. By means of eQMC, we study the model with both weak and strong onsite repulsions. Numerical study shows that the model has a rich phase diagram. We also found that in the system defined on the honeycomb lattice of the cylinder geometry, an interesting edge state appears.

  18. Improved in vivo imaging of human blood circulation in the chorioretinal complex using phase variance method with new phase stabilized 1 μm swept-source optical coherence tomography (pv-SSOCT)

    NASA Astrophysics Data System (ADS)

    Poddar, Raju; Kim, Dae Yu; Werner, John S.; Zawadzki, Robert J.

    2014-02-01

    We demonstrate the feasibility of our newly developed phase stabilized high-speed (100 kHz A-scans/s) 1 μm sweptsource optical coherence tomography (SSOCT) system with the phase-variance based motion contrast method for visualization of human chorioretinal complex microcirculation. Compared to our previously reported spectral domain (spectrometer based) phase-variance (pv)-SDOCT system it has advantages of higher sensitivity, reduced fringe washout for high blood flow speeds and deeper penetration in choroid. High phase stability SSOCT imaging was achieved by using a computationally efficient phase stabilization approach. This process does not require additional calibration hardware and complex numerical procedures. Our phase stabilization method is simple and can be employed in a variety of SS-OCT systems. Examples of vasculature in the chorioretinal complex imaged by pv-SSOCT is presented and compared to retinal images of the same volunteers acquired with fluorescein angiography (FA) and indocyanine green angiography (ICGA).

  19. Phase Retrieval from Modulus Using Homeomorphic Signal Processing and the Complex Cepstrum: An Algorithm for Lightning Protection Systems

    SciTech Connect

    Clark, G A

    2004-06-08

    In general, the Phase Retrieval from Modulus problem is very difficult. In this report, we solve the difficult, but somewhat more tractable case in which we constrain the solution to a minimum phase reconstruction. We exploit the real-and imaginary part sufficiency properties of the Fourier and Hilbert Transforms of causal sequences to develop an algorithm for reconstructing spectral phase given only spectral modulus. The algorithm uses homeomorphic signal processing methods with the complex cepstrum. The formal problem of interest is: Given measurements of only the modulus {vert_bar}H(k){vert_bar} (no phase) of the Discrete Fourier Transform (DFT) of a real, finite-length, stable, causal time domain signal h(n), compute a minimum phase reconstruction {cflx h}(n) of the signal. Then compute the phase of {cflx h}(n) using a DFT, and exploit the result as an estimate of the phase of h(n). The development of the algorithm is quite involved, but the final algorithm and its implementation are very simple. This work was motivated by a Phase Retrieval from Modulus Problem that arose in LLNL Defense Sciences Engineering Division (DSED) projects in lightning protection for buildings. The measurements are limited to modulus-only spectra from a spectrum analyzer. However, it is desired to perform system identification on the building to compute impulse responses and transfer functions that describe the amount of lightning energy that will be transferred from the outside of the building to the inside. This calculation requires knowledge of the entire signals (both modulus and phase). The algorithm and software described in this report are proposed as an approach to phase retrieval that can be used for programmatic needs. This report presents a brief tutorial description of the mathematical problem and the derivation of the phase retrieval algorithm. The efficacy of the theory is demonstrated using simulated signals that meet the assumptions of the algorithm. We see that for

  20. Phase behavior and complex crystal structures of self-assembled tethered nanoparticle telechelics.

    PubMed

    Marson, Ryan L; Phillips, Carolyn L; Anderson, Joshua A; Glotzer, Sharon C

    2014-01-01

    Motivated by growing interest in the self-assembly of nanoparticles for applications such as photonics, organic photovoltaics, and DNA-assisted designer crystals, we explore the phase behavior of tethered spherical nanoparticles. Here, a polymer tether is used to geometrically constrain a pair of nanoparticles creating a tethered nanoparticle "telechelic". Using simulation, we examine how varying architectural features, such as the size ratio of the two end-group nanospheres and the length of the flexible tether, affects the self-assembled morphologies. We demonstrate not only that this hybrid building block maintains the same phase diversity as linear triblock copolymers, allowing for a variety of nanoparticle materials to replace polymer blocks, but also that new structures not previously reported are accessible. Our findings imply a robust underlying ordering mechanism is common among these systems, thus allowing flexibility in synthesis approaches to achieve a target morphology. PMID:24641517

  1. Properties of clusters in the gas phase. V - Complexes of neutral molecules onto negative ions

    NASA Technical Reports Server (NTRS)

    Keesee, R. G.; Lee, N.; Castleman, A. W., Jr.

    1980-01-01

    Ion-molecules association reactions of the form A(-)(B)n-1 + B = A(-)(B)n were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl(-), I(-), and NO2(-) with n ranging from one to three or four, and onto SO2(-) and SO3(-) with n equal to one; and (2) carbon dioxide onto Cl(-), I(-), NO2(-), CO3(-), and SO3(-) with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions.

  2. Volta phase plate cryo-EM of the small protein complex Prx3

    PubMed Central

    Khoshouei, Maryam; Radjainia, Mazdak; Phillips, Amy J.; Gerrard, Juliet A.; Mitra, Alok K.; Plitzko, Jürgen M.; Baumeister, Wolfgang; Danev, Radostin

    2016-01-01

    Cryo-EM of large, macromolecular assemblies has seen a significant increase in the numbers of high-resolution structures since the arrival of direct electron detectors. However, sub-nanometre resolution cryo-EM structures are rare compared with crystal structure depositions, particularly for relatively small particles (<400 kDa). Here we demonstrate the benefits of Volta phase plates for single-particle analysis by time-efficient cryo-EM structure determination of 257 kDa human peroxiredoxin-3 dodecamers at 4.4 Å resolution. The Volta phase plate improves the applicability of cryo-EM for small molecules and accelerates structure determination. PMID:26817416

  3. Broadband terahertz wave deflection based on C-shape complex metamaterials with phase discontinuities.

    PubMed

    Zhang, Xueqian; Tian, Zhen; Yue, Weisheng; Gu, Jianqiang; Zhang, Shuang; Han, Jiaguang; Zhang, Weili

    2013-09-01

    A broadband terahertz wave deflector based on metasurface induced phase discontinuities is reported. Various frequency components ranging from 0.43 to 1.0 THz with polarization orthogonal to the incidence are deflected into a broad range of angles from 25° to 84°. A Fresnel zone plate consequently developed from the beam deflector is capable of focusing a broadband terahertz radiation. PMID:23787976

  4. Ultrasound temporal-spatial phase-interference in complex composite media; a comparison of experimental measurement and simulation prediction.

    PubMed

    Al-Qahtani, Saeed M; Langton, Christian M

    2016-09-01

    The propagation of ultrasound through solid:liquid complex composite media such as cancellous bone suffers from a lack of a comprehensive understanding of the dependence upon density and structure. Assuming that a propagating ultrasound wave may be considered as an array of parallel sonic rays, we may determine the transit time of each by the relative proportion of the two constituents. A transit time spectrum (TTS) describes the proportion of sonic rays having a particular transit time between the minimum (tmin) and maximum (tmax) values; representing, for example, entire bone tissue and marrow respectively in the case of cancellous bone. Langton has proposed that the primary ultrasound attenuation mechanism in such media is phase-interference. The phase-interference of two or more ultrasound pulses detected at a phase-sensitive transducer has both temporal and spatial components. The temporal component is primarily dependent upon the transit time difference (dt) between the pulses and the propagating pulse-length (PL). The spatial component is primarily dependent upon the lateral separation (ds) of the detectedpulses of differing transit time and the lateral dimension of the ultrasound receive transducer aperture (dL). The aim of the paper was to explore these temporal and spatial dependencies through a comparison of experimental measurement and computer simulation in solid:liquid models of varying temporal and spatial complexity. Transmission measurements at nominal ultrasound frequencies of 1MHz and 5MHz were performed, thereby investigating the dependency upon period. The results demonstrated an overall agreement between experimental measurement and computer simulation of 87±16% and 85±12% for temporal and spatial components respectively. It is envisaged that a comprehensive understanding of ultrasound propagation through complex structures such as cancellous bone could provide an improved non-invasive tool for osteoporosis assessment. PMID:27318839

  5. Gas-phase unfolding and disassembly reveals stability differences in ligand-bound multiprotein complexes.

    PubMed

    Hyung, Suk-Joon; Robinson, Carol V; Ruotolo, Brandon T

    2009-04-24

    Mass spectrometry (MS) is widely used to assess the binding of small molecules to proteins and their complexes. In many cases, subtle differences in the stability afforded by binding of ligands to protein assemblies cannot be detected by MS. Here we show that monitoring the unfolding of protein subunits, using ion mobility-MS, allows differentiation of the effects of ligand binding not normally observed by MS alone. Using wild-type and disease-associated variants of tetrameric transthyretin, MS data indicate that populations of the variant protein are less stable than wild-type. Ion mobility-MS, however, is able to show that the natural ligand of transthyretin, thyroxine, provides a larger stability increase to the tetramer composed of variant subunits than to the wild-type protein-ligand complex. Overall, therefore, our results have implications for small-molecule drug design directed at multiprotein targets. PMID:19389624

  6. Morphological and phase evolution of TiO 2 nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

    NASA Astrophysics Data System (ADS)

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2009-04-01

    Nanosized anatase and rutile TiO 2 having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H 2O 2) in water/isopropanol media by a facile sol-gel process. The TiO 2 nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO 2 are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given.

  7. Complex surface three-dimensional shape measurement method based on defocused Gray code plus phase-shifting

    NASA Astrophysics Data System (ADS)

    Zeng, Zhuohuan; Fu, Yanjun; Li, Biao; Chai, Minggang

    2016-08-01

    Binary pattern defocused projection method can overcome the nonlinear gamma of the projector, as well as filter high harmonics and high-frequency noise. However, high-accuracy three-dimensional (3-D) shape measurement of complex surface using it still remains a challenge. Therefore, a novel Gray code plus phase-shifting method based on defocusing is proposed to solve the problem. The edges of Gray code patterns become blurred owing to defocus, which makes the recovery of accurate Gray code patterns difficult. To solve this problem, the positive and inverse Gray code patterns are projected to obtain threshold values, which are used to achieve the binarization of Gray code patterns. This method is robust and suitable for different defocus levels. Compared with the traditional Gray code plus phase-shifting method, the experimental results prove the effectiveness and feasibility of the proposed method.

  8. Effects of phase I complex decongestive physiotherapy on physical functions and depression levels in breast cancer related lymph edema

    PubMed Central

    Atalay, Orçin Telli; Özkir, Anıl; Çalik, Bilge Başakçi; Baskan, Emre; Taşkin, Harun

    2015-01-01

    [Purpose] Breast cancer-related upper extremity lymph edema is known to cause physical, functional and psychological impairments in women after modified radical mastectomy. The aim of this study was to investigate the effects of phase I Complex Decongestive Physiotherapy (CDP) on physical functions and depression levels in women with breast cancer-related upper extremity lymph edema. [Subjects and Methods] Fifty-eight subjects with breast cancer-related upper extremity lymph edema were the subjects of this study. The arm circumference, shoulder range of motion (ROM), muscle strength and depression levels of the subjects were assessed before and after phase I CDP treatment. [Results] After phase I CDP, there was a statistically significant reduction in circumference measurements at all levels of the affected arm. There was not any statistically significant difference in muscle strength after CDP. The shoulder ROM improved after treatment. There was a significant reduction in the Beck Depression Inventory score. A significant positive correlation was found between depression levels and circumference measurement. [Conclusion] Based on the results we suggest that by reducing limb volume, beside improving physical functions, phase I CDP can affect psychological status, especially depression which is very common in women with breast cancer-related upper extremity lymph edema. PMID:25931748

  9. Deposition of rare-earth phosphate, fluoride, and oxysulfide films by gas-phase thermolysis of {beta}-diketonate complexes

    SciTech Connect

    Gorshkov, N.I.; Suglobov, D.N.; Sidorenko, G.V.

    1995-07-01

    Rare-earth fluoride, phosphate, and oxysulfide films have been obtained by gas-phase thermolysis of appropriate rare-earth mixed-ligand and tris-chelate {beta}-diketonate complexes. Gas-phase thermolysis of Ln(PTFA){sub 3} {center_dot}HMPA and Ln(HFA){sub 3}{center_dot}2HMPA (PTFA is pivaloyltrifluoroacetonate ligand and HFA is hexafluoracetylacetonate ligand, HMPA is hexamethylphosphoric triamide, Ln = Nd, Eu, Er) in a flow of air or N{sub 2}O yields a finely dispersed phosphate phase. Thermolysis of Ln(HFA){sub 3} {center_dot}DME (Ln = Nd, Eu, Er, DME is 1,2-dimethoxyethane) yields carbon-free fluoride films, whereas in the case of Er(HFA){sub 3}{center_dot}2H{sub 2}O and Er(PTFA){sub 3} erbium oxyfluoride and oxide films are deposited. Thermolysis of Nd(DPM){sub 3} (DPM is dipivaloylmethanate ligand) in hydrogen sulfide flow yields and Nd{sub 2}O{sub 2}S phase.

  10. Complexity of spatiotemporal traffic phenomena in flow of identical drivers: Explanation based on fundamental hypothesis of three-phase theory

    NASA Astrophysics Data System (ADS)

    Kerner, Boris S.

    2012-03-01

    Based on numerical simulations of a stochastic three-phase traffic flow model, we reveal the physics of the fundamental hypothesis of three-phase theory that, in contrast with a fundamental diagram of classical traffic flow theories, postulates the existence of a two-dimensional (2D) region of steady states of synchronized flow where a driver makes an arbitrary choice of a space gap (time headway) to the preceding vehicle. We find that macroscopic and microscopic spatiotemporal effects of the entire complexity of traffic congestion observed up to now in real measured traffic data can be explained by simulations of traffic flow consisting of identical drivers and vehicles, if a microscopic model used in these simulations incorporates the fundamental hypothesis of three-phase theory. It is shown that the driver's choice of space gaps within the 2D region of synchronized flow associated with the fundamental hypothesis of three-phase theory can qualitatively change types of congested patterns that can emerge at a highway bottleneck. In particular, if drivers choose long enough spaces gaps associated with the fundamental hypothesis, then general patterns, which consist of synchronized flow and wide moving jams, do not emerge independent of the flow rates and bottleneck characteristics: Even at a heavy bottleneck leading to a very low speed within congested patterns, only synchronized flow patterns occur in which no wide moving jams emerge spontaneously.

  11. Menstrual cycle phase alters women's sexual preferences for composers of more complex music

    PubMed Central

    Charlton, Benjamin D.

    2014-01-01

    Over 140 years ago Charles Darwin first argued that birdsong and human music, having no clear survival benefit, were obvious candidates for sexual selection. Whereas the first contention is now universally accepted, his theory that music is a product of sexual selection through mate choice has largely been neglected. Here, I provide the first, to my knowledge, empirical support for the sexual selection hypothesis of music evolution by showing that women have sexual preferences during peak conception times for men that are able to create more complex music. Two-alternative forced-choice experiments revealed that woman only preferred composers of more complex music as short-term sexual partners when conception risk was highest. No preferences were displayed when women chose which composer they would prefer as a long-term partner in a committed relationship, and control experiments failed to reveal an effect of conception risk on women's preferences for visual artists. These results suggest that women may acquire genetic benefits for offspring by selecting musicians able to create more complex music as sexual partners, and provide compelling support for Darwin's assertion ‘that musical notes and rhythm were first acquired by the male or female progenitors of mankind for the sake of charming the opposite sex’. PMID:24759864

  12. Menstrual cycle phase alters women's sexual preferences for composers of more complex music.

    PubMed

    Charlton, Benjamin D

    2014-06-01

    Over 140 years ago Charles Darwin first argued that birdsong and human music, having no clear survival benefit, were obvious candidates for sexual selection. Whereas the first contention is now universally accepted, his theory that music is a product of sexual selection through mate choice has largely been neglected. Here, I provide the first, to my knowledge, empirical support for the sexual selection hypothesis of music evolution by showing that women have sexual preferences during peak conception times for men that are able to create more complex music. Two-alternative forced-choice experiments revealed that woman only preferred composers of more complex music as short-term sexual partners when conception risk was highest. No preferences were displayed when women chose which composer they would prefer as a long-term partner in a committed relationship, and control experiments failed to reveal an effect of conception risk on women's preferences for visual artists. These results suggest that women may acquire genetic benefits for offspring by selecting musicians able to create more complex music as sexual partners, and provide compelling support for Darwin's assertion 'that musical notes and rhythm were first acquired by the male or female progenitors of mankind for the sake of charming the opposite sex'. PMID:24759864

  13. Coherence and polarization of electromagnetic beams modulated by random phase screens and their changes through complex ABCD optical systems.

    PubMed

    Hanson, Steen G; Wang, Wei; Jakobsen, Michael L; Takeda, Mitsuo

    2008-09-01

    The change of coherence and polarization of an electromagnetic beam modulated by a random anisotropic phase screen passing through any optical system is found within the framework of complex ABCD-matrix theory This means that the formalism can treat imaging and Fourier transform and free-space optical systems, as well as fractional Fourier transform systems, with finite-size limiting apertures of Gaussian transmission shape. Thus, the current paper shall be considered as a continuation, extension, and generalization of a previous work by Shirai and Wolf [J. Opt. Soc. Am. A21, 1907 (2004)]. It will be shown that the inclusion of apertures in the optical system strongly influences not only the propagation of spatial coherence but also the degree of polarization of a propagating field. Analytical expressions of coherence and polarization propagation will be given in terms of the matrix elements for any complex optical system. PMID:18758562

  14. An Unexpected Gas-Phase Binding Motif for Metal Dication Complexation with Peptides: Irmpd Spectroscopic Structure Determination

    NASA Astrophysics Data System (ADS)

    Dunbar, Robert C.; Steill, Jeffrey; Polfer, Nicolas; Berden, Giel; Oomens, Jos

    2011-06-01

    The favorable orientation of the amide linkage and the aromatic side chain of N-terminal Phe or Trp leads to several favorable motifs for metal ion binding to dipeptides, having distinct characteristics in the IR spectrum. Infrared multiple photon photodissociation spectroscopy using the FELIX free electron laser has enabled clear resolution of these isomeric forms. The spectral patterns of complexes of small dications (Mg2+, Ni2+ and Co2+) reveal an unexpected new isomeric form, in which the metal ion displaces the amide hydrogen, forming a metal-nitrogen bond with covalent character which is unprecedented in such gas-phase complexes. Spectra of the ions were acquired by irradiating the cell of the Fourier-transform ion cyclotron resonance mass spectrometer with infrared light from the FELIX laser at wavelengths in the approximate range 500 to 1900 Cm-1.

  15. Vibrational Spectroscopy of Mass-Selected [UO2(ligand)n]2+ Complexes in the Gas Phase: Comparison with Theory

    SciTech Connect

    Gary S. Groenewold; Anita K. Gianotto

    2006-03-01

    The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the OdUdO stretch and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric OdUdO stretching frequency was measured at 1017 cm-1 for [UO2(CH3COCH3)2]2+ and was systematically red shifted to 1000 and 988 cm-1 by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from two to four and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes, although the uranyl asymmetric stretching frequencies were greater than those measured for acetone complexes having equivalent coordination, which is consistent with the fact that acetonitrile is a weaker nucleophile than is acetone. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3-6 cm-1.

  16. Experimental and Theoretical Studies on the Fragmentation of Gas-Phase Uranyl-, Neptunyl- and Plutonyl-Diglycolamide Complexes

    SciTech Connect

    Gong, Yu; Hu, Han-Shi; Rao, Linfeng; Li, Jun; Gibson, John K.

    2013-10-10

    Fragmentation of actinyl(VI) complexes UVIO2(L)22+, NpVIO2(L)22+ and PuVIO2(L)22+ (L = tetramethyl-3-oxa-glutaramide, TMOGA) produced by electrospray ionization was examined in the gas phase by collision induced dissociation (CID) in a quadrupole ion trap mass spectrometer. Cleavage of the C-Oether bond was observed for all three complexes, with dominant products being UVIO2(L)(L-86)+ with charge reduction, and NpVIO2(L)(L-101)2+ and PuVIO2(L)(L-101)2+ with charge conservation. The neptunyl and plutonyl complexes also exhibited substantial L+ loss to give pentavalent complexes NpVO2(L)+ and PuVO2(L)+, whereas the uranyl complex did not, consistent with the comparative An 5f-orbital energies and the AnVIO22+/AnVO2+ (An = U, Np, Pu) reduction potentials. CID of NpVO2(L)2+ and PuVO2(L)2+ was dominated by neutral ligand loss to form NpVO2(L)+ and PuVO2(L)+, which hydrated by addition of residual water in the ion trap; UVO2(L)2+ was not observed. Theoretical calculations of the structures and bonding of the AnVIO2(L)22+ complexes using density functional theory reveal that the metal centers are coordinated by six oxygen atoms from the two TMOGA ligands. The results are compared with radiolytic decomposition of TMOGA in solution.

  17. Measuring spatiotemporal intensity-and-phase complexity of multimode fiber output pulses

    NASA Astrophysics Data System (ADS)

    Guang, Zhe; Rhodes, Michelle; Trebino, Rick

    2016-03-01

    We demonstrate ultrashort pulse spatiotemporal field measurement for multimode optical fibers, using a singleframe characterization technique, called Spatially and Temporally Resolved Intensity and Phase Evaluation Device: Full Information from a Single Hologram (STRIPED FISH). We measure STRIPED FISH traces and retrieve the pulse field E(x,y,t) or equivalently E(x,y,ω), to generate movies revealing the field structure induced by propagating modes, due to their differences in field spatial distribution, modal propagation velocity and modal dispersion inside the fiber. We launch femtosecond pulses near 800nm from Ti: Sapphire laser to investigate linearly polarized modes LP01, LP11, LP02 and LP21 in multimode fibers.

  18. Ground State of Magnetic Dipoles on a Two-Dimensional Lattice: Structural Phases in Complex Plasmas

    SciTech Connect

    Feldmann, J. D.; Kalman, G. J.; Hartmann, P.; Rosenberg, M.

    2008-02-29

    We study analytically and by molecular dynamics simulations the ground state configuration of a system of magnetic dipoles fixed on a two-dimensional lattice. We find different phases, in close agreement with previous results. Building on this result and on the minimum energy requirement we determine the equilibrium lattice configuration, the magnetic order (ferromagnetic versus antiferromagnetic), and the magnetic polarization direction of a system of charged mesoscopic particles with magnetic dipole moments, in the domain where the strong electrostatic coupling leads to a crystalline ground state. Orders of magnitudes of the parameters of the system relevant to possible future dusty plasma experiments are discussed.

  19. Polarization screening-induced magnetic phase gradients at complex oxide interfaces.

    PubMed

    Spurgeon, Steven R; Balachandran, Prasanna V; Kepaptsoglou, Despoina M; Damodaran, Anoop R; Karthik, J; Nejati, Siamak; Jones, Lewys; Ambaye, Haile; Lauter, Valeria; Ramasse, Quentin M; Lau, Kenneth K S; Martin, Lane W; Rondinelli, James M; Taheri, Mitra L

    2015-01-01

    Thin-film oxide heterostructures show great potential for use in spintronic memories, where electronic charge and spin are coupled to transport information. Here we use a La0.7Sr0.3MnO3 (LSMO)/PbZr0.2Ti0.8O3 (PZT) model system to explore how local variations in electronic and magnetic phases mediate this coupling. We present direct, local measurements of valence, ferroelectric polarization and magnetization, from which we map the phases at the LSMO/PZT interface. We combine these experimental results with electronic structure calculations to elucidate the microscopic interactions governing the interfacial response of this system. We observe a magnetic asymmetry at the LSMO/PZT interface that depends on the local PZT polarization and gives rise to gradients in local magnetic moments; this is associated with a metal-insulator transition at the interface, which results in significantly different charge-transfer screening lengths. This study establishes a framework to understand the fundamental asymmetries of magnetoelectric coupling in oxide heterostructures. PMID:25879160

  20. [Solid phase microextraction (SPME) of sample preparation during of a complex biological matrix in biotransformation studies].

    PubMed

    Kroll, C; Borchert, H H

    1998-03-01

    Within the scope of the investigation of drug metabolism in keratinocytes solid phase microextraction (SPME) was investigated as a suitable method for sample preparation. The application of SPME is based on the fact, that a amount of analyte is absorbed by the polymer fiber at equilibrium, and the fiber is localized on a tip of a GC-syringe. The stable nitroxyl radical TEMPO (2,2,6,6-tetramthylpiperidine-1-oxyl) and its apolar metabolite 2,2,6,6-tetramethylpiperidine were analyzed by SPME and subsequent GC using thymol as internal standard. By means of the headspace-technique and an apolar fiber the recovery rate of TEMPO and the metabolite was nearly 100% and the precision was high. However, the results of the direct SPME were unsatisfactory. In comparison with conventional liquid/liquid extraction and solid phase extraction SPE the SPME proved the best results with regard to recovery rate and precision. Furthermore, the main advantages of SPME are the renunciation of organic solvents, the saving of time, the possibility to reuse the fiber about 100-150 times and the option for a complete automatisation of the extraction procedure. PMID:9547519

  1. Complex Method for Angular-Spectral Analysis of Volume Phase Diffraction Gratings Recorded in Photopolymers

    NASA Astrophysics Data System (ADS)

    Vojtíšek, P.; Květoň, M.; Richter, I.

    2016-02-01

    Photopolymer recording materials are nowadays widely used for recording of diffraction gratings and other diffraction elements. For obtaining the best performance of these diffraction gratings for desired applications, it is important to assess these gratings from many different perspectives. In this contribution, we present an experimental and characterization approach to an analysis of diffraction gratings recorded into photopolymer materials. This approach is able to provide a complex and very illustrative description of these gratings response and, with accordance to the theory, information about some important grating parameters, such as a spatial period, slant angle, etc., as well. This approach is based on the measurement of a grating response for a wide range of angles and wavelengths and then on the construction and subsequent analysis of maps in the angular-spectral plane. It is shown that the measurements are in a good agreement with the theoretical predictions based on either approximate (Kogelniks coupled wave theory) or rigorous (RCWA) techniques and that this approach provides complex and detailed characterization of the grating response which can be used for additional optimization or decision of applicability of measured sample gratings.

  2. Mechanistic studies on the gas-phase dehydrogenation of alkanes at cyclometalated platinum complexes.

    PubMed

    Butschke, Burkhard; Schwarz, Helmut

    2012-10-29

    In the ion/molecule reactions of the cyclometalated platinum complexes [Pt(L-H)](+) (L=2,2'-bipyridine (bipy), 2-phenylpyridine (phpy), and 7,8-benzoquinoline (bq)) with linear and branched alkanes C(n)H(2n+2) (n=2-4), the main reaction channels correspond to the eliminations of dihydrogen and the respective alkenes in varying ratios. For all three couples [Pt(L-H)](+)/C(2)H(6), loss of C(2)H(4) dominates clearly over H(2) elimination; however, the mechanisms significantly differs for the reactions of the "rollover"-cyclometalated bipy complex and the classically cyclometalated phpy and bq complexes. While double hydrogen-atom transfer from C(2)H(6) to [Pt(bipy-H)](+), followed by ring rotation, gives rise to the formation of [Pt(H)(bipy)](+), for the phpy and bq complexes [Pt(L-H)](+), the cyclometalated motif is conserved; rather, according to DFT calculations, formation of [Pt(L-H)(H(2))](+) as the ionic product accounts for C(2)H(4) liberation. In the latter process, [Pt(L-H)(H(2))(C(2)H(4))](+) (that carries H(2) trans to the nitrogen atom of the heterocyclic ligand) serves, according to DFT calculation, as a precursor from which, due to the electronic peculiarities of the cyclometalated ligand, C(2)H(4) rather than H(2) is ejected. For both product-ion types, [Pt(H)(bipy)](+) and [Pt(L-H)(H(2))](+) (L=phpy, bq), H(2) loss to close a catalytic dehydrogenation cycle is feasible. In the reactions of [Pt(bipy-H)](+) with the higher alkanes C(n)H(2n+2) (n=3, 4), H(2) elimination dominates over alkene formation; most probably, this observation is a consequence of the generation of allyl complexes, such as [Pt(C(3)H(5))(bipy)](+). In the reactions of [Pt(L-H)](+) (L=phpy, bq) with propane and n-butane, the losses of the alkenes and dihydrogen are of comparable intensities. While in the reactions of "rollover"-cyclometalated [Pt(bipy-H)](+) with C(n)H(2n+2) (n=2-4) less than 15 % of the generated product ions are formed by C-C bond-cleavage processes, this value is

  3. CAWSES November 7-8, 2004, Superstorm: Complex Solar and Interplanetary Features in the Post-Solar Maximum Phase

    NASA Technical Reports Server (NTRS)

    Tsurutani, Bruce T.; Echer, Ezequiel; Guarnieri, Fernando L.; Kozyra, J. U.

    2008-01-01

    The complex interplanetary structures during 7 to 8 Nov 2004 are analyzed to identify their properties as well as resultant geomagnetic effects and the solar origins. Three fast forward shocks, three directional discontinuities and two reverse waves were detected and analyzed in detail. The three fast forward shocks 'pump' up the interplanetary magnetic field from a value of approx.4 nT to 44 nT. However, the fields after the shocks were northward, and magnetic storms did not result. The three ram pressure increases were associated with major sudden impulses (SI + s) at Earth. A magnetic cloud followed the third forward shock and the southward Bz associated with the latter was responsible for the superstorm. Two reverse waves were detected, one at the edge and one near the center of the magnetic cloud (MC). It is suspected that these 'waves' were once reverse shocks which were becoming evanescent when they propagated into the low plasma beta MC. The second reverse wave caused a decrease in the southward component of the IMF and initiated the storm recovery phase. It is determined that flares located at large longitudinal distances from the subsolar point were the most likely causes of the first two shocks without associated magnetic clouds. It is thus unlikely that the shocks were 'blast waves' or that magnetic reconnection eroded away the two associated MCs. This interplanetary/solar event is an example of the extremely complex magnetic storms which can occur in the post-solar maximum phase.

  4. Phase transition and vapochromism in molecular assemblies of a polymorphic zinc(II) Schiff-base complex.

    PubMed

    Oliveri, Ivan Pietro; Malandrino, Graziella; Di Bella, Santo

    2014-09-15

    This paper reports for the first time the irreversible thermally induced phase transition, accompanied by color change, and the vapochromic behavior of an amphiphilic, Lewis acidic Zn(II) Schiff-base complex, through detailed X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry, and optical absorption studies. The unprecedented irreversible phase transition for such kind of complexes is associated with a thermal, lamellar-to-hexagonal columnar structural transition, which involves a different arrangement of each molecular unit within the assembled structure, H- and J-type aggregates, respectively, responsible for the thermochromic behavior. The vapochromism, investigated either in powder samples or in thermally annealed cast films, is related to the formation of 1:1 adducts upon exposure to vapors of strong Lewis bases and implies dramatic optical absorption variations and naked-eye observation of the change in color from red-brown to red. The chemisorption process is fast, completely reversible, reproducible, and selective for amines. The reversible switching of the chemisorption-desorption process in cast films is demonstrated by successive cycles, amine exposure and subsequent heating, by monitoring the substantial optical absorption changes in the visible region. Vapochromism of this material can potentially be used to detect vapors of volatile amines. PMID:25148651

  5. Direct imaging of complex nano- to microscale interfaces involving solid, liquid, and gas phases.

    PubMed

    Rykaczewski, Konrad; Landin, Trevan; Walker, Marlon L; Scott, John Henry J; Varanasi, Kripa K

    2012-10-23

    Surfaces with special wetting properties not only can efficiently repel or attract liquids such as water and oils but also can prevent formation of biofilms, ice, and clathrate hydrates. Predicting the wetting properties of these special surfaces requires detailed knowledge of the composition and geometry of the interfacial region between the droplet and the underlying substrate. In this work we introduce a 3D quantitative method for direct nanoscale visualization of such interfaces. Specifically, we demonstrate direct nano- to microscale imaging of complex fluidic interfaces using cryostabilization in combination with cryogenic focused ion beam milling and SEM imaging. We show that application of this method yields quantitative information about the interfacial geometry of water condensate on superhydrophilic, superhydrophobic, and lubricant-impregnated surfaces with previously unattainable nanoscale resolution. This type of information is crucial to a fundamental understanding as well as the design of surfaces with special wetting properties. PMID:23020195

  6. Gas-Phase Terahertz Spectroscopy and the Study of Complex Interstellar Chemistry

    NASA Astrophysics Data System (ADS)

    Braakman, Rogier

    2010-11-01

    Terahertz spectroscopy holds great promise in the advancement of the field of astrochemistry. The sensitive observation of interstellar THz radiation is expected to lower detection limits and allow the study of larger and more complex species than is currently possible at millimeter wavelengths, which will place further constraints on chemical models and permit a direct comparison to the organic compounds seen in carbonaceous chondrites. With the successful recent launch of the Herschel Space Telescope, which will give high-fidelity access to interstellar THz radiation for the first time, and the completion of the Atacama Large Millimeter Array (ALMA) by 2013, the THz astronomy era is upon us. Unfortunately, laboratory THz spectroscopy presents significant challenges and will be soon be lagging behind the newly available observational platforms. Technologies to extend the capabilities of high-resolution spectroscopic systems into the THz domain are actively being pursued on many fronts, but affordable systems that are broadly tunable, sensitive and achieve the necessary resolution are not yet available. The work in this thesis should therefore be seen as part of the effort in the transition from centimeter-/millimeter-wave to THz spectroscopy that is currently taking place in the astrochemistry community. As part of this thesis, observational searches for the complex organics hydroxyacetone (CH3COCH2OH), 2-cyanoethanol (OHCH 2CH2CN) and methoxyacetonitrile (CH3OCH2 CN) were attempted at millimeter wavelengths. The unsuccessful nature of these searches highlight the current limits of studying interstellar chemistry using pure rotational spectroscopy. The characterization of the laboratory spectra of these molecules is nonetheless important as it will aid in the assignment and description of the rotational substructure and band shapes of their THz torsional spectra, features that may allow their interstellar detection; and this thesis presents methods by which such

  7. Modeling Three-Phase Compositional Flow on Complex 3D Unstructured Grids with Higher-Order Finite Element Methods

    NASA Astrophysics Data System (ADS)

    Moortgat, J.; Firoozabadi, A.

    2013-12-01

    Most problems of interest in hydrogeology and subsurface energy resources involve complex heterogeneous geological formations. Such domains are most naturally represented in numerical reservoir simulations by unstructured computational grids. Finite element methods are a natural choice to describe fluid flow on unstructured meshes, because the governing equations can be readily discretized for any grid-element geometry. In this work, we consider the challenging problem of fully compositional three-phase flow in 3D unstructured grids, discretized by tetrahedra, prisms, or hexahedra, and compare to simulations on 3D structured grids. We employ a combination of mixed hybrid finite element methods to solve for the pressure and flux fields in a fractional flow formulation, and higher-order discontinuous Galerkin methods for the mass transport equations. These methods are well suited to simulate flow in heterogeneous and fractured reservoirs, because they provide a globally continuous pressure and flux field, while allowing for sharp discontinuities in the phase properties, such as compositions and saturations. The increased accuracy from using higher-order methods improves the modeling of highly non-linear flow, such as gravitational and viscous fingering. We present several numerical examples to study convergence rates and the (lack of) sensitivity to gridding/mesh orientation, and mesh quality. These examples consider gravity depletion, water and gas injection in oil saturated subsurface reservoirs with species exchange between up to three fluid phases. The examples demonstrate the wide applicability of our chosen finite element methods in the study of challenging multiphase flow problems in porous, geometrically complex, subsurface media.

  8. Formation of Complex Organics by Gas Phase and Intracluster Ion-Molecule Reactions Involving Acetylene and Hydrogen Cyanide

    NASA Astrophysics Data System (ADS)

    El-Shall, S.; Hamed, A.; Soliman, A. R.; Momoh, P. O.

    2011-05-01

    Many complex organics including polycyclic aromatic hydrocarbons are present in flames and combustion processes as well as in interstellar clouds and solar nebulae. Here, we present evidence for the formation of complex covalent organics by gas phase and intracluster reactions of the benzene, phenylium, pyridine, pyrimidine, phenylacetylene and benzonitrile cations with acetylene and hydrogen cyanide molecules. These reactions are studied using mass-selected ion mobility, chemical reactivity, collisional dissociation, and ab initio calculations. Measurements of collision cross sections in helium provide structural information on the adducts and allow probing structural changes at different temperatures (isomerization). We observed multiple additions of five acetylene molecules on the pyridine cation at room temperature. This is a remarkable result considering that only two acetylene molecules were added to the phenyl cation and no addition was observed on the benzene cation at room temperature. The experimental results are in full agreement with the ab initio calculations which predict that the first and second acetylenes add to the pyridine ion in barrierless, highly exothermic reactions. Similar reactions have been observed for the pyrimidine radical cation although the extent of the addition reactions is limited to only two acetylene molecules at room temperature. The results provide the first evidence for the incorporation of nitrogen in the formation cyclic hydrocarbons via the gas phase reactions of pyridine and pyrimidine ions with acetylene molecules. In addition, the formation of covalent adducts in the ionized acetylene/HCN system will be reported for the first time. Sequential reactions leading to the formation of pyridine and pyrimidine radical cations and higher adducts are observed over a wide range of temperature and pressure. The formation of these covalent adducts may represent a general class of addition reactions that can form complex

  9. Design Implementation and Testing of a VLSI High Performance ASIC for Extracting the Phase of a Complex Signal

    NASA Astrophysics Data System (ADS)

    Altmeyer, Ronald C.

    2002-09-01

    This thesis documents the research, circuit design, and simulation testing of a VLSI (Very Large Scale Integration) ASIC which extracts phase angle information from a complex sampled signal using the arctangent relationship: (phi=tan/-1 (Q/1). Specifically, the circuit will convert the In-Phase and Quadrature terms into their corresponding phase angle. The design specifications were to implement the design in CMOS (Complementary Metal Oxide Semiconductors) technology with a minimum transistor count and ability to operate at a clock frequency of 700 MHz. Research on the arctangent function was performed to determine mathematical calculation methods and the CORDIC method was chosen to achieve the stated design specifications. MATLAB simulations were used to calculate and verify accuracy and to implement Quine-McClusky logic minimization. T-SPICE netlists were generated and simulations were run to determine transistor and circuit electrical operation and timing. Finally, overall circuit logic functionality of all possible input combinations was completed using a VHDL (VHSIC(Very High Speed Integrated Circuit) Hardware Description Language) simulation program.

  10. Effect of cooling-heating rate on sol-gel transformation of fish gelatin-gum arabic complex coacervate phase.

    PubMed

    Anvari, Mohammad; Chung, Donghwa

    2016-10-01

    The objective of this study was to characterize influence of different cooling and heating rates on gelation of fish gelatin (FG)-gum arabic (GA) complex coacervate phase using rheological measurements. For the coacervate phase prepared at 10°C, the gelling temperature, melting temperature, gel strength, and stress relaxation decreased with increasing cooling or heating rate, however, no gelation was observed at the highest cooling rate of 0.05°C/min. Similar trends were obtained for the coacervates phase prepared at 30°C, but the gelation did not occur at a cooling rate of 0.033 or 0.05°C/min. The results indicated that rheological properties of FG-GA coacervate gels were highly dependent to the cooling process, where more thermos-stable and stronger gels formed at slower cooling. This was probably because of higher degree of molecular rearrangements, more hydrogen bindings, and formation of greater junction zones into the gel network at slower cooling rates. However, all of the FG-GA coacervate gels obtained at different cooling rates were classified as a weak physical gel. PMID:27246375

  11. Development of a full automation solid phase microextraction method for investigating the partition coefficient of organic pollutant in complex sample.

    PubMed

    Jiang, Ruifen; Lin, Wei; Wen, Sijia; Zhu, Fang; Luan, Tiangang; Ouyang, Gangfeng

    2015-08-01

    A fully automated solid phase microextraction (SPME) depletion method was developed to study the partition coefficient of organic compound between complex matrix and water sample. The SPME depletion process was conducted by pre-loading the fiber with a specific amount of organic compounds from a proposed standard gas generation vial, and then desorbing the fiber into the targeted samples. Based on the proposed method, the partition coefficients (Kmatrix) of 4 polyaromatic hydrocarbons (PAHs) between humic acid (HA)/hydroxypropyl-β-cyclodextrin (β-HPCD) and aqueous sample were determined. The results showed that the logKmatrix of 4 PAHs with HA and β-HPCD ranged from 3.19 to 4.08, and 2.45 to 3.15, respectively. In addition, the logKmatrix values decreased about 0.12-0.27 log units for different PAHs for every 10°C increase in temperature. The effect of temperature on the partition coefficient followed van't Hoff plot, and the partition coefficient at any temperature can be predicted based on the plot. Furthermore, the proposed method was applied for the real biological fluid analysis. The partition coefficients of 6 PAHs between the complex matrices in the fetal bovine serum and water were determined, and compared to ones obtained from SPME extraction method. The result demonstrated that the proposed method can be applied to determine the sorption coefficients of hydrophobic compounds between complex matrix and water in a variety of samples. PMID:26118804

  12. Complex Structures in the Reentrant Phase Diagram of HoNi_2B_2C

    NASA Astrophysics Data System (ADS)

    Childers, J.; Zhang, J.; Olinger, A., Jr.; Metlushko, V.; Delong, L.; Canfield, P.

    1996-03-01

    HoNi_2B_2C exhibits a resistive onset to superconductivity near 9.0 K, followed by transitions to incommensurate magnetic order (IMO) at 6.0 K and 5.5 K, and commensurate antiferromagnetic order (AFM) at TN = 5.2 K. Vibrating reed (VR) and resistance data reveal two previously unobserved lines of magnetic anomalies in both the upper superconducting (SC) and lower reentrant SC regions for H || a*b*. The wide region between the upper onset of SC and the first magnetic anomaly reflects weak vortex pinning, possibly due to a subtle buildup of IMO from well above 8K. The interplay between SC and magnetic order is evident in abrupt displacements of transition lines to IMO near their crossing with the reentrant normal transition line for 5.2phase transitions. * Funded by NSF Grant #EHR-9108764 ** Funded by DoE DER/OBS Contract #W-7405-Eng-82

  13. An Efficient Implementation of the GMC Micromechanics Model for Multi-Phased Materials with Complex Microstructures

    NASA Technical Reports Server (NTRS)

    Pindera, Marek-Jerzy; Bednarcyk, Brett A.

    1997-01-01

    An efficient implementation of the generalized method of cells micromechanics model is presented that allows analysis of periodic unidirectional composites characterized by repeating unit cells containing thousands of subcells. The original formulation, given in terms of Hill's strain concentration matrices that relate average subcell strains to the macroscopic strains, is reformulated in terms of the interfacial subcell tractions as the basic unknowns. This is accomplished by expressing the displacement continuity equations in terms of the stresses and then imposing the traction continuity conditions directly. The result is a mixed formulation wherein the unknown interfacial subcell traction components are related to the macroscopic strain components. Because the stress field throughout the repeating unit cell is piece-wise uniform, the imposition of traction continuity conditions directly in the displacement continuity equations, expressed in terms of stresses, substantially reduces the number of unknown subcell traction (and stress) components, and thus the size of the system of equations that must be solved. Further reduction in the size of the system of continuity equations is obtained by separating the normal and shear traction equations in those instances where the individual subcells are, at most, orthotropic. The reformulated version facilitates detailed analysis of the impact of the fiber cross-section geometry and arrangement on the response of multi-phased unidirectional composites with and without evolving damage. Comparison of execution times obtained with the original and reformulated versions of the generalized method of cells demonstrates the new version's efficiency.

  14. Fragmentation pathways analysis for the gas phase dissociation of protonated carnosine-oxaliplatin complexes.

    PubMed

    Ritacco, Ida; Moustafa, Eslam M; Sicilia, Emilia; Russo, Nino; Shoeib, Tamer

    2015-03-14

    Collision-induced dissociation (CID) experiments on the protonated carnosine-oxaliplatin complex, [Carnosine + OxPt + H](+) using several collision energies were shown to yield nine different fragment ions. Energy-resolved CID experiments on [Carnosine + OxPt + H](+) showed that the generation of the product ion [Carnosine - H + Pt(dach)](+) (where dach is 1,2-diaminocyclohexane) is the lowest energy process. At slightly higher collision energies, the loss of neutral carnosine from [Carnosine + OxPt + H](+) to produce [OxPt + H](+) was observed, followed by the loss of oxaliplatin from the same precursor ion to produce [Carnosine + H](+). At significantly higher energies, the ion [OxPt - CO2 + H](+) was shown to be formed, while the last two investigated ions [Carnosine + OxPt - CO2 + H](+) and [Carnosine - NH3 - H + Pt(dach)](+) did not attain any significant relative abundance. Density functional calculations at the B3LYP/LANL2DZ level were employed to probe the fragmentation mechanisms that account for all experimental data. The lowest free energy barriers for the generation of each of the ions [Carnosine - H + Pt(dach)](+), [OxPt + H](+), [Carnosine + H](+), [Carnosine + OxPt - CO2 + H](+) and [Carnosine - NH3 - H + Pt(dach)](+) from [Carnosine + OxPt + H](+) according to the fragmentation mechanisms offered here were calculated to be 31.9, 38.8, 49.3, 75.2, and 85.6 kcal mol(-1), respectively. PMID:25325236

  15. Velocimetry with refractive index matching for complex flow configurations, phase 1

    NASA Technical Reports Server (NTRS)

    Thompson, B. E.; Vafidis, C.; Whitelaw, J. H.

    1987-01-01

    The feasibility of obtaining detailed velocity field measurements in large Reynolds number flow of the Space Shuttle Main Engine (SSME) main injector bowl was demonstrated using laser velocimetry and the developed refractive-index-matching technique. An experimental system to provide appropriate flow rates and temperature control of refractive-index-matching fluid was designed and tested. Test results are presented to establish the feasibility of obtaining accurate velocity measurements that map the entire field including the flow through the LOX post bundles: sample mean velocity, turbulence intensity, and spectral results are presented. The results indicate that a suitable fluid and control system is feasible for the representation of complex rocket-engine configurations and that measurements of velocity characteristics can be obtained without the optical access restrictions normally associated with laser velocimetry. The refractive-index-matching technique considered needs to be further developed and extended to represent other rocket-engine flows where current methods either cannot measure with adequate accuracy or they fail.

  16. Acute social stress before the planning phase improves memory performance in a complex real life-related prospective memory task.

    PubMed

    Glienke, Katharina; Piefke, Martina

    2016-09-01

    Successful execution of intentions, but also the failure to recall are common phenomena in everyday life. The planning, retention, and realization of intentions are often framed as the scientific concept of prospective memory. The current study aimed to examine the influence of acute stress on key dimensions of complex "real life" prospective memory. To this end, we applied a prospective memory task that involved the planning, retention, and performance of intentions during a fictional holiday week. Forty healthy males participated in the study. Half of the subjects were stressed with the Socially Evaluated Cold Pressor Test (SECPT) before the planning of intentions, and the other half of the participants underwent a control procedure at the same time. Salivary cortisol was used to measure the effectiveness of the SECPT stress induction. Stressed participants did not differ from controls in planning accuracy. However, when we compared stressed participants with controls during prospective memory retrieval, we found statistically significant differences in PM across the performance phase. Participants treated with the SECPT procedure before the planning phase showed improved prospective memory retrieval over time, while performance of controls declined. Particularly, there was a significant difference between the stress and control group for the last two days of the holiday week. Interestingly, control participants showed significantly better performance for early than later learned items, which could be an indicator of a primacy effect. This differential effect of stress on performance was also found in time- and event-dependent prospective memory. Our results demonstrate for the first time, that acute stress induced before the planning phase may improve prospective memory over the time course of the performance phase in time- and event-dependent prospective memory. Our data thus indicate that prospective memory can be enhanced by acute stress. PMID:27370532

  17. Statistical description of complex nuclear phases in supernovae and proto-neutron stars

    NASA Astrophysics Data System (ADS)

    Raduta, Ad. R.; Gulminelli, F.

    2010-12-01

    We develop a phenomenological statistical model for dilute star matter at finite temperature, in which free nucleons are treated within a mean-field approximation and nuclei are considered to form a loosely interacting cluster gas. Its domain of applicability, that is, baryonic densities ranging from about ρ>108 g/cm3 to normal nuclear density, temperatures between 1 and 20 MeV, and proton fractions between 0.5 and 0, makes it suitable for the description of baryonic matter produced in supernovae explosions and proto-neutron stars. The first finding is that, contrary to the common belief, the crust-core transition is not first order, and for all subsaturation densities matter can be viewed as a continuous fluid mixture between free nucleons and massive nuclei. As a consequence, the equations of state and the associated observables do not present any discontinuity over the whole thermodynamic range. We further investigate the nuclear matter composition over a wide range of densities and temperatures. At high density and temperature our model accounts for a much larger mass fraction bound in medium nuclei with respect to traditional approaches as Lattimer-Swesty, with sizable consequences on the thermodynamic quantities. The equations of state agree well with the presently used EOS only at low temperatures and in the homogeneous matter phase, while important differences are present in the crust-core transition region. The correlation among the composition of baryonic matter and neutrino opacity is finally discussed, and we show that the two problems can be effectively decoupled.

  18. Single-phase microemulsification of a complex light-nonaqueous-phase-liquid: Laboratory evaluation of several mixtures of surfactant/alcohol solutions

    SciTech Connect

    Rhue, R.D.; Rao, P.S.C.; Annable, M.D.

    1999-08-01

    A recent advance in conventional pump-and-treat technology for aquifer remediation involves the use of surfactant-alcohol mixtures that will form a clear, transparent, thermodynamically stable oil-in-water microemulsion on contact with a residual non-aqueous-phase-liquid (NAPL). An initial screening of 86 commercial-grade surfactants for aqueous solubility resulted in selection of 58 that were further tested in batch experiments to evaluate the capacity to solubilize a complex NAPL waste collected from a Superfund site (Operable Unit OU-1) at Hill AFB, UT. The selected group of 58 surfactants represented six classes of anionic, nine classes of nonionic, and one class of amphoteric surfactants. Batch studies on NAPL solubilization identified a number of surfactants suitable for use in the field demonstration phase of the project; a further criterion in surfactant selection was that the flushing solution had a viscosity <2 cp. The best surfactants among this group had HLB (hydrophilic-lipophilic balance) values between 12 and 13, and solubilized 10 to 20 g L{sup {minus}1} of the OU-1 NAPL when the surfactant concentration was 3%. Column tests using NAPL-coated glass beads showed that the more efficient surfactants could remove >90% of the NAPL after flushing with <10 pore volumes. Brij 97, an ethoxylated alcohol ether surfactant, showed a high capacity for solubilizing the OU-1 NAPL. In a column test using contaminated Hill AFB aquifer material, flushing with a mixture of 3% Brij 97 and 2.5% n-pentanol removed essentially all of the mass of nine target analytes in the NAPL after flushing with <10 pore volumes without mobilizing the NAPL or destabilizing aquifer colloids.

  19. Phase-induced amplitude apodization complex mask coronagraph mask fabrication, characterization, and modeling for WFIRST-AFTA

    NASA Astrophysics Data System (ADS)

    Kern, Brian; Guyon, Olivier; Belikov, Ruslan; Wilson, Daniel; Muller, Richard; Sidick, Erkin; Balasubramanian, Bala; Krist, John; Poberezhskiy, Ilya; Tang, Hong

    2016-01-01

    This work describes the fabrication, characterization, and modeling of a second-generation occulting mask for a phase-induced amplitude apodization complex mask coronagraph, designed for use on the WFIRST-AFTA mission. The mask has many small features (˜micron lateral scales) and was fabricated at the Jet Propulsion Laboratory Microdevices Laboratory, then characterized using a scanning electron microscope, atomic force microscope, and optical interferometric microscope. The measured fabrication errors were then fed to a wavefront control model which predicts the contrast performance of a full coronagraph. The expected coronagraphic performance using this mask is consistent with observing ˜15 planetary targets with WFIRST-AFTA in a reasonable time (<1 day/target).

  20. Characterization of sodium carboxymethylcellulose-gelatin complex coacervation by chemical analysis of the coacervate and equilibrium fluid phases.

    PubMed

    Koh, G L; Tucker, I G

    1988-05-01

    The complex coacervation of sodium carboxymethylcellulose (SCMC) and gelatin has been characterized by chemical analyses of the coacervate and equilibrium fluid phases. The phenol-sulphuric acid (for SCMC) and Lowry (for gelatin) assays were used. Chemically analysed coacervate yield was used to predict optimum coacervation conditions, which occurred at a SCMC-gelatin mixing ratio of 3:7 at pH 3.5. The effects of pH, colloid mixing ratio and total colloid concentration on coacervate yield and composition were studied. The colloid mixing ratio, at which the peak coacervate yields occurred varied with coacervation pH. Increase in the total colloid concentration suppressed coacervation, resulting in a coacervate of higher water content. A similar coacervation mechanism was seen for two viscosity grades SCMC. However, because of the different degree of substitution of these two grades the SCMC-gelatin coacervates had different SCMC contents. PMID:2899623

  1. Numerical simulation of two-phase flows in complex geometries by combining two different immersed-boundary methods

    NASA Astrophysics Data System (ADS)

    Yin, Bo; Luo, Haoxiang

    2010-11-01

    Two-phase flows in various industrial applications often occur in complex geometries. To simulate this type of flows, we have combined two different immersed-boundary methods to handle the fluid-fluid and the fluid-solid interfaces separately. For the fluid-fluid interface, a diffuse-interface method is employed where the discontinuities of the material properties and the traction jump are all regularized using an approximate Dirac's Delta function. For the fluid-solid interface, ghost nodes and a local flow reconstruction are employed to complement the finite-difference discretization and to incorporate the boundary conditions. A single-block Cartesian mesh is used to discretize the entire domain. Both 2D and 3D codes have been implemented. Validation and code applications will be demonstrated at the conference. *Supported by the ACS Petroleum Research Fund.

  2. Fast Quantitation of Target Analytes in Small Volumes of Complex Samples by Matrix-Compatible Solid-Phase Microextraction Devices.

    PubMed

    Piri-Moghadam, Hamed; Ahmadi, Fardin; Gómez-Ríos, German Augusto; Boyacı, Ezel; Reyes-Garcés, Nathaly; Aghakhani, Ali; Bojko, Barbara; Pawliszyn, Janusz

    2016-06-20

    Herein we report the development of solid-phase microextraction (SPME) devices designed to perform fast extraction/enrichment of target analytes present in small volumes of complex matrices (i.e. V≤10 μL). Micro-sampling was performed with the use of etched metal tips coated with a thin layer of biocompatible nano-structured polypyrrole (PPy), or by using coated blade spray (CBS) devices. These devices can be coupled either to liquid chromatography (LC), or directly to mass spectrometry (MS) via dedicated interfaces. The reported results demonstrated that the whole analytical procedure can be carried out within a few minutes with high sensitivity and quantitation precision, and can be used to sample from various biological matrices such as blood, urine, or Allium cepa L single-cells. PMID:27158909

  3. Characterization of Carbon-Rich Phases in a Complex Microstructure of a Commercial X80 Pipeline Steel

    NASA Astrophysics Data System (ADS)

    Morales, E. V.; Bott, I. S.; Silva, R. A.; Morales, A. M.; de Souza, L. F. G.

    2016-05-01

    The wide use of the term M/A constituent conceals many complexities about shape, size, and composition. This work uses metallographic techniques and transmission electron microscopy to characterize the entire microstructure development which is observed during continuous cooling in a commercial X80 pipeline steel. A general model is presented which allows calculating the volume fractions of martensite and retained austenite, as well as their compositions in these carbon-rich phases of the M/A constituent for this commercial pipeline steel. This approach takes into account the allotriomorphic ferrite formation and the massive alloyed carbide precipitation before the acicular ferrite formation. Two morphologies (in the film and blocky forms) of the M/A constituent were registered. The calculated M/A volume fraction resulted in agreement with the fraction of this constituent experimentally obtained through the optical microscopy observations. This allowed the justification of the very small volumetric fraction of the M/A constituent with the film morphology.

  4. Solid-phase extraction strategies to surmount body fluid sample complexity in high-throughput mass spectrometry-based proteomics.

    PubMed

    Bladergroen, Marco R; van der Burgt, Yuri E M

    2015-01-01

    For large-scale and standardized applications in mass spectrometry- (MS-) based proteomics automation of each step is essential. Here we present high-throughput sample preparation solutions for balancing the speed of current MS-acquisitions and the time needed for analytical workup of body fluids. The discussed workflows reduce body fluid sample complexity and apply for both bottom-up proteomics experiments and top-down protein characterization approaches. Various sample preparation methods that involve solid-phase extraction (SPE) including affinity enrichment strategies have been automated. Obtained peptide and protein fractions can be mass analyzed by direct infusion into an electrospray ionization (ESI) source or by means of matrix-assisted laser desorption ionization (MALDI) without further need of time-consuming liquid chromatography (LC) separations. PMID:25692071

  5. Characterization of Carbon-Rich Phases in a Complex Microstructure of a Commercial X80 Pipeline Steel

    NASA Astrophysics Data System (ADS)

    Morales, E. V.; Bott, I. S.; Silva, R. A.; Morales, A. M.; de Souza, L. F. G.

    2016-07-01

    The wide use of the term M/A constituent conceals many complexities about shape, size, and composition. This work uses metallographic techniques and transmission electron microscopy to characterize the entire microstructure development which is observed during continuous cooling in a commercial X80 pipeline steel. A general model is presented which allows calculating the volume fractions of martensite and retained austenite, as well as their compositions in these carbon-rich phases of the M/A constituent for this commercial pipeline steel. This approach takes into account the allotriomorphic ferrite formation and the massive alloyed carbide precipitation before the acicular ferrite formation. Two morphologies (in the film and blocky forms) of the M/A constituent were registered. The calculated M/A volume fraction resulted in agreement with the fraction of this constituent experimentally obtained through the optical microscopy observations. This allowed the justification of the very small volumetric fraction of the M/A constituent with the film morphology.

  6. Diorganotin(IV) N-acetyl-L-cysteinate complexes: synthesis, solid state, solution phase, DFT and biological investigations.

    PubMed

    Pellerito, Lorenzo; Prinzivalli, Cristina; Casella, Girolamo; Fiore, Tiziana; Pellerito, Ornella; Giuliano, Michela; Scopelliti, Michelangelo; Pellerito, Claudia

    2010-07-01

    Diorganotin(IV) complexes of N-acetyl-L-cysteine (H(2)NAC; (R)-2-acetamido-3-sulfanylpropanoic acid) have been synthesized and their solid and solution-phase structural configurations investigated by FTIR, Mössbauer, (1)H, (13)C and (119)Sn NMR spectroscopy. FTIR results suggested that in R(2)Sn(IV)NAC (R = Me, Bu, Ph) complexes NAC(2-) behaves as dianionic tridentate ligand coordinating the tin(IV) atom, through ester-type carboxylate, acetate carbonyl oxygen atom and the deprotonated thiolate group. From (119)Sn Mössbauer spectroscopy it could be inferred that the tin atom is pentacoordinated, with equatorial R(2)Sn(IV) trigonal bipyramidal configuration. In DMSO-d(6) solution, NMR spectroscopic data showed the coordination of one solvent molecule to tin atom, while the coordination mode of the ligand through the ester-type carboxylate and the deprotonated thiolate group was retained in solution. DFT (Density Functional Theory) study confirmed the proposed structures in solution phase as well as the determination of the most probable stable ring conformation. Biological investigations showed that Bu(2)SnCl(2) and NAC2 induce loss of viability in HCC cells and only moderate effects in non-tumor Chang liver cells. NAC2 showed lower cytotoxic activity than Bu(2)SnCl(2), suggesting that the binding with NAC(2-) modulates the marked cytotoxic activity exerted by Bu(2)SnCl(2). Therefore, these novel butyl derivatives could represent a new class of anticancer drugs. PMID:20421134

  7. A comprehensive review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes

    PubMed Central

    Caffrey, Martin

    2015-01-01

    The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for large proteins and complexes is outlined. Experimental phasing by heavy-atom derivatization, soaking or co-crystallization is routine and the approaches that have been implemented to date are described. An overview and a breakdown by family and function of the close to 200 published

  8. A comprehensive review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes.

    PubMed

    Caffrey, Martin

    2015-01-01

    The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for large proteins and complexes is outlined. Experimental phasing by heavy-atom derivatization, soaking or co-crystallization is routine and the approaches that have been implemented to date are described. An overview and a breakdown by family and function of the close to 200 published

  9. A comprehensive review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes

    SciTech Connect

    Caffrey, Martin

    2015-01-01

    A comprehensive and up-to-date review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes is reported. Recent applications of the method for in situ serial crystallography at X-ray free-electron lasers and synchrotrons are described. The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for

  10. Full-matrix capture with phased shift migration for flaw detection in layered objects with complex geometry.

    PubMed

    Lukomski, Tomasz

    2016-08-01

    This paper introduces a method for an ultrasonic imaging with a phased array based on a wave migration algorithm. The method allows for imaging layered objects with lateral velocity variations such as objects with a complex geometry or layers that are not perpendicular to the array's axis. The full-matrix capture ensures that there is enough information to reconstruct an image even when the wave indication angle is large. The method is implemented in a omega-k domain. The proposed algorithm is first tested in a single simulation of a concave object with side drilled holes under the concave surface. For evaluating the algorithm's performance three experiments are presented: one with a tilted object (surface not perpendicular with respect to the array axis) with side drilled holes and two experiments of an object with concave surface and two artificial defects under it. The results presented in the paper verify that the proposed method reconstructs images from the data gathered with the phased array. PMID:27235778

  11. Experimental and numerical investigation of shock wave propagation through complex geometry, gas continuous, two-phase media

    SciTech Connect

    Chien-Chih Liu, J.

    1993-12-31

    The work presented here investigates the phenomenon of shock wave propagation in gas continuous, two-phase media. The motivation for this work stems from the need to understand blast venting consequences in the HYLIFE inertial confinement fusion (ICF) reactor. The HYLIFE concept utilizes lasers or heavy ion beams to rapidly heat and compress D-T targets injected into the center of a reactor chamber. A segmented blanket of falling molten lithium or Li{sub 2}BeF{sub 4} (Flibe) jets encircles the reactor`s central cavity, shielding the reactor structure from radiation damage, absorbing the fusion energy, and breeding more tritium fuel. X-rays from the fusion microexplosion will ablate a thin layer of blanket material from the surfaces which face toward the fusion site. This generates a highly energetic vapor, which mostly coalesces in the central cavity. The blast expansion from the central cavity generates a shock which propagates through the segmented blanket - a complex geometry, gas-continuous two-phase medium. The impulse that the blast gives to the liquid as it vents past, the gas shock on the chamber wall, and ultimately the liquid impact on the wall are all important quantities to the HYLIFE structural designers.

  12. G1 phase arrest induced by Wilms tumor protein WT1 is abrogated by cyclin/CDK complexes.

    PubMed Central

    Kudoh, T; Ishidate, T; Moriyama, M; Toyoshima, K; Akiyama, T

    1995-01-01

    WT1, the Wilms tumor-suppressor gene, maps to the human chromosomal region 11p13 and encodes a transcriptional repressor, WT1, implicated in controlling normal urogenital development. Microinjection of the WT1 cDNA into quiescent cells or cells in early to mid G1 phase blocked serum-induced cell cycle progression into S phase. The activity of WT1 varied significantly depending on the presence or absence of an alternatively spliced region located upstream of the zinc finger domain. The inhibitory activity of WT1 was abrogated by the overexpression of cyclin E/CDK2 as well as cyclin D1/CDK4. Furthermore, both CDK4- and CDK2-associated kinase activities were downregulated in cells overexpressing WT1, whereas the levels of CDK4, CDK2, and cyclin D1 expression were unchanged. These findings suggest that inhibition of the activity of cyclin/CDK complexes may be involved in mediating the WT1-induced cell cycle block. Images Fig. 1 Fig. 2 PMID:7753836

  13. Effect of Metals in Biomimetic Dimetal Complexes on Affinity and Gas-Phase Protection of Phosphate Esters.

    PubMed

    Svane, Simon; Jørgensen, Thomas J D; McKenzie, Christine J; Kjeldsen, Frank

    2015-07-21

    Although the biomimetic dimetal complex [LGa2(OH)2(H2O)2](3+) [L = 2,6-bis((N,N'-bis(2-picolyl)amino)methyl)-4-tertbutylphenolate] provides efficient protection against phosphate loss in phosphopeptides upon collision-induced dissociation tandem mass spectrometry (CID MS/MS), the underlying mechanism remains unknown. Here, we explored the mechanism in detail and investigated the selective binding to phosphate groups in solution. Dimetal complexes containing combinations of Ga(3+), In(3+), Fe(3+), Co(3+), Zn(2+), Cu(2+), and V(2+) were reacted with HPO4(2-), phosphoserine, and a phosphopeptide (FQpSEEQQQTEDELQDK, abbreviated "βcas") and studied with isothermal titration calorimetry (ITC), CID MS/MS, and density functional theory (DFT). Ka for HPO4(2-) binding scaled with the metal charge and was 35-fold larger for [LGa2(OH)2(H2O)2](3+) (3.08 ± 0.31 × 10(6) M(-1)) than for [LZn2(HCOO)2](+). CID MS/MS of [LGa2(βcas)](n+) revealed protection against phosphate detachment (<3% of the total ion intensity). Phosphate detachment from βcas was 22-40% and increased to 42-71% when bound to dimetal complexes of lower charge than {LGa2}(5+). CID data suggests that facile metal-phosphate dissociation is associated with proton transfer from the intermediate oxazoline ring formed in the phosphopeptide to the metal-phosphate complex. The observed phosphate stabilization was attributed to a significant reduction in the gas-phase basicity (GB) of the phosphate group when bound to {LGa2}(5+)/{LIn2}(5+) complex cores. Absence of proton transfer results in formation of an ion-zwitterion intermediate with a greater dissociation threshold. This hypothesis is supported by DFT calculations for [LGa2(PO4)](2+), [LGaZn(PO4)](+), [LZn2(PO4)], and 2,4-dimethyl-3-oxazoline showing that [LGa2(PO4)](2+) is the only compound with a substantial lower GB (321 kJ/mol less) than 2,4-dimethyl-3-oxazoline. PMID:26068532

  14. Condensed Phase Membrane Introduction Mass Spectrometry with Direct Electron Ionization: On-line Measurement of PAHs in Complex Aqueous Samples.

    PubMed

    Termopoli, Veronica; Famiglini, Giorgio; Palma, Pierangela; Cappiello, Achille; Vandergrift, Gregory W; Krogh, Erik T; Gill, Chris G

    2016-02-01

    Polycyclic aromatic hydrocarbons (PAHs) are USEPA regulated priority pollutants. Their low aqueous solubility requires very sensitive analytical methods for their detection, typically involving preconcentration steps. Presented is the first demonstrated ‘proof of concept’ use of condensed phase membrane introduction mass spectrometry (CP-MIMS) coupled with direct liquid electron ionization (DEI) for the direct, on-line measurement of PAHs in aqueous samples. DEI is very well suited for the ionization of PAHs and other nonpolar compounds, and is not significantly influenced by the co-elution of matrix components. Linear calibration data for low ppb levels of aqueous naphthalene, anthracene, and pyrene is demonstrated, with measured detection limits of 4 ppb. Analytical response times (t10%–90% signal rise) ranged from 2.8 min for naphthalene to 4.7 min for pyrene. Both intra- and interday reproducibility has been assessed (<3% and 5% RSD, respectively). Direct measurements of ppb level PAHs spiked in a variety of real, complex environmental sample matrices is examined, including natural waters, sea waters, and a hydrocarbon extraction production waste water sample. For these spiked, complex samples, direct PAH measurement by CP-MIMS-DEI yielded minimal signal suppression from sample matrix effects (81%–104%). We demonstrate the use of this analytical approach to directly monitor real-time changes in aqueous PAH concentrations with potential applications for continuous on-line monitoring strategies and binding/adsorption studies in heterogeneous samples. PMID:26471041

  15. Condensed Phase Membrane Introduction Mass Spectrometry with Direct Electron Ionization: On-line Measurement of PAHs in Complex Aqueous Samples

    NASA Astrophysics Data System (ADS)

    Termopoli, Veronica; Famiglini, Giorgio; Palma, Pierangela; Cappiello, Achille; Vandergrift, Gregory W.; Krogh, Erik T.; Gill, Chris G.

    2016-02-01

    Polycyclic aromatic hydrocarbons (PAHs) are USEPA regulated priority pollutants. Their low aqueous solubility requires very sensitive analytical methods for their detection, typically involving preconcentration steps. Presented is the first demonstrated `proof of concept' use of condensed phase membrane introduction mass spectrometry (CP-MIMS) coupled with direct liquid electron ionization (DEI) for the direct, on-line measurement of PAHs in aqueous samples. DEI is very well suited for the ionization of PAHs and other nonpolar compounds, and is not significantly influenced by the co-elution of matrix components. Linear calibration data for low ppb levels of aqueous naphthalene, anthracene, and pyrene is demonstrated, with measured detection limits of 4 ppb. Analytical response times (t10%-90% signal rise) ranged from 2.8 min for naphthalene to 4.7 min for pyrene. Both intra- and interday reproducibility has been assessed (<3% and 5% RSD, respectively). Direct measurements of ppb level PAHs spiked in a variety of real, complex environmental sample matrices is examined, including natural waters, sea waters, and a hydrocarbon extraction production waste water sample. For these spiked, complex samples, direct PAH measurement by CP-MIMS-DEI yielded minimal signal suppression from sample matrix effects (81%-104%). We demonstrate the use of this analytical approach to directly monitor real-time changes in aqueous PAH concentrations with potential applications for continuous on-line monitoring strategies and binding/adsorption studies in heterogeneous samples.

  16. Development and characterization of a new polyampholyte-surfactant complex applied to the solid phase extraction of bisphenol-A.

    PubMed

    Martínez, J M Lázaro; Denis, M F Leal; Denaday, L R; Dall' Orto, V Campo

    2009-12-15

    This paper presents a material that has both hydrophilic and hydrophobic domains, obtained by combination of a polyampholyte with a surfactant. This material was fully characterized by different spectroscopic techniques and microscopy. Bisphenol-A (BPA) was chosen as a model molecule to study the interaction with compounds of intermediate polarity. We explored the kinetics and equilibrium of BPA on the surface of the polyampholyte-surfactant complex and found a significantly high loading capacity (2.02 mmol g(-1)) and complete binding from solutions at concentration levels below 100 micromol L(-1). The complex was encapsulated in agarose gel to be used as solid phase for extraction of BPA from food simulants in contact with polycarbonate bottles under different treatments. Bisphenol was preconcentrated, extracted and analysed by liquid chromatography with an amperometric detector. The instrumental detection limit of the technique was 10 microg L(-1), which was lowered to 0.14 microg L(-1) by the preconcentration step. The BPA released from baby bottles was 2.1 ng cm(-2) (sigma(n-1): 0.1) in the first use with distilled water. PMID:19836553

  17. Reactions of hot deuterium atoms with OCS in the gas phase and in OCS--DI complexes

    SciTech Connect

    Boehmer, E.; Mikhaylichenko, K.; Wittig, C. )

    1993-11-01

    Reactions of photolytically prepared hot deuterium atoms with OCS have been investigated: (i) under gas phase, single collision, arrested relaxation (i.e., bulk) conditions; and (ii) by photoinitiating reactions within weakly bound OCS--DI complexes. Nascent SD([ital X] [sup 2][Pi], [ital v]=0) rotational, spin--orbit, and [Lambda]-doublet populations were obtained for the photolysis wavelengths 250, 225, and 223 nm by using [ital A] [sup 2][Sigma][l arrow][ital X] [sup 2][Pi] laser induced fluorescence (LIF). The reason for using deuterium is strictly experimental: [ital A] [sup 2][Sigma] predissociation rates are considerably smaller for SD than for SH. The SD ([ital v]=0) rotational distribution was found to be very cold and essentially the same for both bulk and complexed conditions; the most probable rotational energy is [similar to]180 cm[sup [minus]1]. No bias in [Lambda]-doublet populations was detected. Spin--orbit excitation for bulk conditions was estimated to be [[sup 2][Pi][sub 1/2

  18. Tunable complex magnetic states of epitaxial core-shell metal oxide nanocrystals fabricated by the phase decomposition method

    NASA Astrophysics Data System (ADS)

    Chang, S. J.; Lam, T. N.; Yang, C. Y.; Chen, Y. L.; Chu, Y. H.; Chueh, Y. L.; Tseng, Y. C.

    2016-07-01

    We report on the successful fabrication of epitaxial-discrete Co x Fe3‑x O4/CoO magnetic nanostructures on a SrTiO3 substrate as well as the results of a thorough investigation of the magnetic cross-reactions of the two phases in the vicinity of the epitaxial junction. These nanostructures were originally prepared as Fe3O4-CoO core-shell structures through the phase decomposition of bismuth perovskite precursors by pulsed-laser deposition. An antiphase boundary emerged during the structural/electronic transition from the CoO core to the Co1‑x Fe2+X O4 shell; this then developed into a ferrimagnetic/antiferromagnetic interface. Uncompensated spins (UCS) arose from the Co x Fe3‑x O4/CoO interface as a result of strong ferrimagnetic–antiferromagnetic interactions. A notable exchange bias as well as a significant exchange enhancement was observed owing to the UCS, which had a locking effect because of the decoupling of the Co1‑x Fe2+X O4/CoO reversal from the antiphase boundary. Control of the precursor ratio allowed for the fine-tuning of the Co1‑x Fe2+X O4 phase and the associated locking behaviors. This, in turn, allowed the anisotropy and coercivity of the nanostructures to be manipulated. Thus, we were able to create and thoroughly understand a complex epitaxial configuration with tunable structural and magnetic properties. This study should open new opportunities with regard to current magnetic oxide technology, which requires novel methods for pursuing extremity of controllable properties over an atomic landscape.

  19. Broken ergodicity, memory effect, and rejuvenation in Taylor-phase and decagonal Al3(Mn,Pd,Fe) complex intermetallics

    NASA Astrophysics Data System (ADS)

    Dolinšek, J.; Slanovec, J.; Jagličić, Z.; Heggen, M.; Balanetskyy, S.; Feuerbacher, M.; Urban, K.

    2008-02-01

    The Taylor-phase complex intermetallic compound T-Al3Mn , its solid solutions with Pd and Fe, T-Al3(Mn,Pd) and T-Al3(Mn,Fe) , and the related decagonal d-Al-Mn-Fe quasicrystal belong to the class of magnetically frustrated spin systems that exhibit rich out-of-equilibrium spin dynamics in the nonergodic phase below the spin-freezing temperature Tf . Performing large variety of magnetic experiments as a function of temperature, magnetic field, aging time tw , and different thermal histories, we investigated broken-ergodicity phenomena of (i) a difference in the field-cooled and zero-field-cooled susceptibilities, (ii) the frequency-dependent freezing temperature, Tf(ν) , (iii) hysteresis and remanence, (iv) ultraslow decay of the thermoremanent magnetization, (v) the memory effect (a state of the spin system reached upon isothermal aging can be retrieved after a negative temperature cycle), and (vi) “rejuvenation” (small positive temperature cycle within the nonergodic phase erases the effect of previous aging). We show that the phenomena involving isothermal aging periods (the memory effect, rejuvenation, and the ultraslow decay of the thermoremanent magnetization) get simple explanation by considering that during aging under steady external conditions, localized spin regions quasiequilibrate into more stable configurations, so that higher thermal energy is needed to destroy these regions by spin flipping, as compared to the thermal energy required to reverse a frustrated spin in a disordered spin-glass configuration that forms in the case of no aging. Common to all the investigated broken-ergodicity phenomena is the slow approach of a magnetically frustrated spin system toward a global equilibrium, which can never be reached on accessible experimental time scales due to macroscopic equilibration times.

  20. Phosphoprotein Isotope-Coded Solid-Phase Tag Approach for Enrichment and Quantitative Analysis of Phosphopeptides from Complex Mixtures

    SciTech Connect

    Qian, Weijun ); Goshe, Michael B.; Camp, David G. ); Yu, Li-Rong ); Tang, Keqi ); Smith, Richard D. )

    2003-10-15

    Many cellular processes are regulated by reversible protein phosphorylation and the ability to identify and quantify phosphoproteins from proteomes is essential for gaining a better understanding of these dynamic cellular processes. However, a sensitive, efficient and global method capable of addressing the phosphoproteome has yet to be developed. Here we describe an improved stable-isotope labeling method using a Phosphoprotein Isotope-coded Solid-phase Tag (PhIST) for isolating and measuring the relative abundance of phosphorylated peptides from complex peptide mixtures resulting from the enzymatic digestion of extracted proteins. The PhIST approach is an extension of the previously reported Phosphoprotein Isotope-coded Affinity Tag (PhIAT)approach developed by our laboratory1-2, where the O-phosphate moiety on phosphoseryl or phosphothreonyl residues were derivatized by hydroxide ion-medated B-elimination followed by the addition of 1,2-ethanedithiol (EDT). Instead of using the biotin affinity tag, peptides containing the EDT moiety were captured and labeled in one step using isotope-coded solid-phase reagents containing either light (12C6, 14N) or heavy (13C6, 15N) stable isotopes. The captured peptides labeled with the isotope-coded tags were released from the solid-phase support by UV photocleavage and analyzed by capillary LC-MS/MS. The efficiency and sensitivity of the PhIST labeling approach for identification of phosphopeptides from mixtures was demonstrated using casein phosphoproteins. Its utility for proteomic applications is demonstrated by the labeling of soluble proteins from human breast cancer cell line.

  1. Infrared Multiple Photon Dissociation Spectroscopy of a Gas-Phase Oxo-Molybdenum Complex with 1,2-Dithiolene Ligands

    PubMed Central

    2015-01-01

    Electrospray ionization (ESI) in the negative ion mode was used to create anionic, gas-phase oxo-molybdenum complexes with dithiolene ligands. By varying ESI and ion transfer conditions, both doubly and singly charged forms of the complex, with identical formulas, could be observed. Collision-induced dissociation (CID) of the dianion generated exclusively the monoanion, while fragmentation of the monoanion involved decomposition of the dithiolene ligands. The intrinsic structure of the monoanion and the dianion were determined by using wavelength-selective infrared multiple-photon dissociation (IRMPD) spectroscopy and density functional theory calculations. The IRMPD spectrum for the dianion exhibits absorptions that can be assigned to (ligand) C=C, C–S, C—C≡N, and Mo=O stretches. Comparison of the IRMPD spectrum to spectra predicted for various possible conformations allows assignment of a pseudo square pyramidal structure with C2v symmetry, equatorial coordination of MoO2+ by the S atoms of the dithiolene ligands, and a singlet spin state. A single absorption was observed for the oxidized complex. When the same scaling factor employed for the dianion is used for the oxidized version, theoretical spectra suggest that the absorption is the Mo=O stretch for a distorted square pyramidal structure and doublet spin state. A predicted change in conformation upon oxidation of the dianion is consistent with a proposed bonding scheme for the bent-metallocene dithiolene compounds [Lauher, J. W.; Hoffmann, R. J. Am. Chem. Soc.1976, 98, 1729−1742], where a large folding of the dithiolene moiety along the S···S vector is dependent on the occupancy of the in-plane metal d-orbital. PMID:24988369

  2. Phase controlled colour tuning of samarium and europium complexes and excellent photostability of their PVA encapsulated materials. Structural elucidation, photophysical parameters and the energy transfer mechanism in the Eu(3+) complex by Sparkle/PM3 calculations.

    PubMed

    Dar, Wakeel Ahmed; Iftikhar, K

    2016-06-01

    Luminescent [Sm(acac)3(pyz)2] (1) and [Eu(acac)3(pyz)2] (2) complexes (acac is the anion of acetylacetone and pyz is pyrazine) have been synthesized and thoroughly characterized by microanalyses, TGA, DTA, IR, ESI-MS(+) and NMR spectroscopy. The photophysical properties of these complexes have been investigated. The Sparkle/PM3 model was utilized for predicting the ground-state geometry of (2). The Judd-Ofelt intensity parameters, radiative parameters, intramolecular energy transfer rates and quantum efficiency are calculated and discussed. The intramolecular energy transfer rates predict that the major energy transfer (96%) is from the ligand triplet state to the levels (5)D1 (74.53%) and (5)D0 (21.87%) of the Eu(3+) ion, in the complex. Complexes (1) and (2) were analysed for colour tuning properties and these show varying colours upon changing phases. This property would possibly allow the use of these complexes as 'colour indicators'. The photoluminescence and photostability of the thin hybrid films of both complexes (1) and (2) in polyvinyl alcohol (PVA) are investigated and discussed. The hybrid films of (1) and (2) are quite robust due to their higher photostability. An important feature of complex (2) is that the excitation window extends close to the visible range (393 nm). The lasing property of the Eu(3+) complex in various phases is also presented. PMID:27157414

  3. Solid-Phase Synthesis as a Platform for the Discovery of New Ruthenium Complexes for Efficient Release of Photocaged Ligands with Visible Light

    PubMed Central

    Sharma, Rajgopal; Knoll, Jessica D.; Ancona, Nicholas; Martin, Phillip D.; Turro, Claudia; Kodanko, Jeremy J.

    2015-01-01

    Ruthenium-based photocaging groups have important applications as biological tools and show great potential as therapeutics. A method was developed to rapidly synthesize, screen and identify ruthenium-based caging groups that release nitriles upon irradiation with visible light. A diverse library of tetra- and pentadentate ligands was synthesized on polystyrene resin. Ruthenium complexes of the general formula [Ru(L)(MeCN)n]m+ (n = 1–3, m = 1–2) were generated from these ligands on solid phase, then cleaved from resin for photochemical analysis. Data indicate a wide range of spectral tuning and reactivity with visible light. Three complexes that showed strong absorbance in the visible range were synthesized by solution phase for comparison. Photochemical behavior of solution- and solid-phase complexes was in good agreement, confirming that the library approach is useful in identifying candidates with desired photoreactivity in short order, avoiding time consuming chromatography and compound purification. PMID:25611351

  4. High temperature-induced phase transitions in Sr{sub 2}GdRuO{sub 6} complex perovskite

    SciTech Connect

    Triana, C.A.; Corredor, L.T.; Landinez Tellez, D.A.; Roa-Rojas, J.

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Crystal structure, thermal expansion and phase transitions at high-temperature of Sr{sub 2}GdRuO{sub 6} perovskite has been investigated. Black-Right-Pointing-Pointer X-ray diffraction pattern at 298 K of Sr{sub 2}GdRuO{sub 6} corresponds to monoclinic perovskite-type structure with P2{sub 1}/n space group. Black-Right-Pointing-Pointer Evolution of X-ray diffraction patterns at high-temperature shows that the Sr{sub 2}GdRuO{sub 6} perovskite suffers two-phase transitions. Black-Right-Pointing-Pointer At 573 K the X-ray diffraction pattern of Sr{sub 2}GdRuO{sub 6} corresponds to monoclinic perovskite-type structure with I2/m space group. Black-Right-Pointing-Pointer At 1273 K the Sr{sub 2}GdRuO{sub 6} perovskite suffers a complete phase-transition from monoclinic I2/m (no. 12) to tetragonal I4/m (no. 87). -- Abstract: The crystal structure behavior of the Sr{sub 2}GdRuO{sub 6} complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K {<=} T {<=} 1273 K. Measurements of X-ray diffraction at room-temperature and Rietveld analysis of the experimental patterns show that this compound crystallizes in a monoclinic perovskite-like structure, which belongs to the P2{sub 1}/n (no. 14) space group and 1:1 ordered arrangement of Ru{sup 5+} and Gd{sup 3+} cations over the six-coordinate M sites. Experimental lattice parameters were obtained to be a =5.8103(5) Angstrom-Sign , b =5.8234(1) Angstrom-Sign , c =8.2193(9) Angstrom-Sign , V = 278.11(2) Angstrom-Sign {sup 3} and angle {beta} = 90.310(5) Degree-Sign . The high-temperature analysis shows the occurrence of two-phase transitions on this material. First, at 573 K it adopts a monoclinic perovskite-type structure with I2/m (no. 12) space group with lattice parameters a = 5.8275(6) Angstrom-Sign , b = 5.8326(3) Angstrom-Sign , c = 8.2449(2) Angstrom-Sign , V = 280.31(3) Angstrom-Sign {sup 3} and angle {beta} = 90.251(3) Degree-Sign . Close

  5. Exchange coupling transformations in Cu (II) heterospin complexes of “breathing crystals” under structural phase transitions

    SciTech Connect

    Morozov, Vitaly A.; Petrova, Marina V.; Lukzen, Nikita N.

    2015-08-15

    Family of “breathing crystals” is the polymer-chain complexes of Cu(hfac){sub 2} with nitroxides. The polymer chains consist of one-, two- or three-spin clusters. The “breathing crystals” experience simultaneous magnetic and Jahn-Teller type structural phase transitions with change of total cluster spin and drastic change of bond lengths (ca. 10-12%). For the first time the intra-cluster magnetic couplings in ”breathing crystals” have been calculated both by band structure methods GGA + U and hybrid DFT (B3LYP and PBE0) for the isolated exchange clusters. The temperature dependence of the magnetic coupling constant was calculated for two polymer-chain compounds of the “breathing crystal” family - C{sub 21}H{sub 19}CuF{sub 12}N{sub 4}O{sub 6} with the chains containing two-spin clusters and C{sub 22}H{sub 21}CuF{sub 12}N{sub 4}O{sub 6} with the chains of alternating three-spin clusters and one-spin sites. It was found that adding a Hubbard-like parameter not only to the copper 3d electrons but also to the oxygen 2p electrons (GGA + U{sub d} + U{sub p} approach) results in an improved description of exchange coupling in the “breathing crystal” compounds. At the same time treatment of the isolated clusters by a large basis hybrid DFT with high computational cost provides a similar quality fit of the experimental magneto-chemical data as that for the GGA + U{sub d} + U{sub p} band structure calculation scheme. Our calculations also showed that in spite of the abrupt transformation of the magnetic coupling constant under the phase transition, the band gap in the “breathing crystals” remains about the same value with temperature decrease.

  6. Murine cytomegalovirus perturbs endosomal trafficking of major histocompatibility complex class I molecules in the early phase of infection.

    PubMed

    Tomas, Maja Ilić; Kucić, Natalia; Mahmutefendić, Hana; Blagojević, Gordana; Lucin, Pero

    2010-11-01

    Murine cytomegalovirus (MCMV) functions interfere with protein trafficking in the secretory pathway. In this report we used Δm138-MCMV, a recombinant virus with a deleted viral Fc receptor, to demonstrate that MCMV also perturbs endosomal trafficking in the early phase of infection. This perturbation had a striking impact on cell surface-resident major histocompatibility complex class I (MHC-I) molecules due to the complementary effect of MCMV immunoevasins, which block their egress from the secretory pathway. In infected cells, constitutively endocytosed cell surface-resident MHC-I molecules were arrested and retained in early endosomal antigen 1 (EEA1)-positive and lysobisphosphatidic acid (LBPA)-negative perinuclear endosomes together with clathrin-dependent cargo (transferrin receptor, Lamp1, and epidermal growth factor receptor). Their progression from these endosomes into recycling and degradative routes was inhibited. This arrest was associated with a reduction of the intracellular content of Rab7 and Rab11, small GTPases that are essential for the maturation of recycling and endolysosomal domains of early endosomes. The reduced recycling of MHC-I in Δm138-MCMV-infected cells was accompanied by their accelerated loss from the cell surface. The MCMV function that affects cell surface-resident MHC-I was activated in later stages of the early phase of viral replication, after the expression of known immunoevasins. MCMV without the three immunoevasins (the m04, m06, and m152 proteins) encoded a function that affects endosomal trafficking. This function, however, was not sufficient to reduce the cell surface expression of MHC-I in the absence of the transport block in the secretory pathway. PMID:20719942

  7. In vivo imaging of human vasculature in the chorioretinal complex using phase-variance contrast method with phase-stabilized 1-μm swept-source optical coherence tomography

    PubMed Central

    Poddar, Raju; Kim, Dae Yu; Werner, John S.; Zawadzki, Robert J.

    2014-01-01

    Abstract. We present a noninvasive phase-variance (pv)–based motion contrast method for depth-resolved imaging of the human chorioretinal complex microcirculation with a newly developed phase-stabilized high speed (100-kHz A-scans/s) 1-μm swept-source optical coherence tomography (SSOCT) system. Compared to our previous spectral-domain (spectrometer based) pv-spectral domain OCT (SDOCT) system, this system has the advantages of higher sensitivity, reduced fringe wash-out for high blood flow speeds and deeper penetration in choroid. High phase stability SSOCT imaging was achieved by using a computationally efficient phase stabilization approach. This process does not require additional calibration hardware and complex numerical procedures. Our phase stabilization method is simple and can be employed in a variety of SSOCT systems. Examples of vasculature in the chorioretinal complex imaged by pv-SSOCT from normal as well as diseased eyes are presented and compared to retinal images of the same subjects acquired with fluorescein angiography and indocyanine green angiography. Observations of morphology of vascular perfusion in chorioretinal complex visualized by our method are listed. PMID:25517255

  8. In vivo imaging of human vasculature in the chorioretinal complex using phase-variance contrast method with phase-stabilized 1-μm swept-source optical coherence tomography.

    PubMed

    Poddar, Raju; Kim, Dae Yu; Werner, John S; Zawadzki, Robert J

    2014-12-01

    We present a noninvasive phase-variance (pv)–based motion contrast method for depth-resolved imaging of the human chorioretinal complex microcirculation with a newly developed phase-stabilized high speed (100-kHz A-scans/s) 1-μm swept- ource optical coherence tomography (SSOCT) system. Compared to our previous spectral-domain (spectrometer based) pv-spectral domain OCT (SDOCT) system, this system has the advantages of higher sensitivity, reduced fringe wash-out for high blood flow speeds and deeper penetration in choroid. High phase stability SSOCT imaging was achieved by using a computationally efficient phase stabilization approach. This process does not require additional calibration hardware and complex numerical procedures. Our phase stabilization method is simple and can be employed in a variety of SSOCT systems. Examples of vasculature in the chorioretinal complex imaged by pv-SSOCT from normal as well as diseased eyes are presented and compared to retinal images of the same subjects acquired with fluorescein angiography and indocyanine green angiography. Observations of morphology of vascular perfusion in chorioretinal complex visualized by our method are listed. PMID:25517255

  9. A combined Phase I and II open-label study on the immunomodulatory effects of seaweed extract nutrient complex

    PubMed Central

    Myers, Stephen P; O’Connor, Joan; Fitton, J Helen; Brooks, Lyndon; Rolfe, Margaret; Connellan, Paul; Wohlmuth, Hans; Cheras, Phil A; Morris, Carol

    2011-01-01

    Background: Isolated fucoidans from brown marine algae have been shown to have a range of immune-modulating effects. This exploratory study aimed to determine whether a seaweed nutrient complex containing a blend of extracts from three different species of brown algae plus nutrients is safe to administer and has biological potential as an immune modulator. The study was undertaken as an open-label combined Phase I and II study. Methods: Participants (n = 10) were randomized to receive the study medication at either a 100 mg (n = 5) or 1000 mg (n = 5) dose over 4 weeks. The primary outcome measurement was in vivo changes in lymphocyte subsets. The secondary outcome measures were ex vivo changes in T-lymphocyte (CD4 and CD8) activation, phagocytosis of granulocytes and monocytes, T helper 1/T helper 2 cytokines, and serum oxygen radical absorbance capacity. Results: The preparation was found to be safe over the 4 weeks at both doses tested. There were no clinically relevant changes to blood measurements of hemopoietic, hepatic, or renal function. Immunomodulatory measurements showed no dose response between the two doses. The combined results from the two doses demonstrated a significant increase in cytotoxic T cell numbers and phagocytic capacity in monocytes, and a significant decrease in levels of the inflammatory cytokine interleukin 6. A separate analysis of the 100 mg dose (n = 5) alone showed a significant linear component over time (P < 0.05) for phagocytosis by both granulocytes and monocytes. Conclusion: The seaweed nutrient complex was safe to use when taken orally over 4 weeks. The preparation was demonstrated to have potential as an immune modulator, and this bioactivity deserves further exploration. PMID:21383915

  10. Fast numerical autofocus of multispectral complex fields in digital holographic microscopy with a criterion based on the phase in the Fourier domain.

    PubMed

    Dohet-Eraly, Jérôme; Yourassowsky, Catherine; Dubois, Frank

    2016-09-01

    The knowledge of the complex amplitude of optical fields, that is, both quantitative phase and intensity, enables numeric reconstruction along the optical axis. Nonetheless, a criterion is required for autofocusing. This Letter presents a robust and rapid refocusing criterion suitable for color interferometric digital holographic microscopy, and, more generally, for applications where complex amplitude is known for at least two different wavelengths. This criterion uses the phase in the Fourier domain, which is compared among wavelengths. It is applicable whatever the nature of the observed object: opaque, refractive, or both mixed. The method is validated with simulated and experimental holograms. PMID:27607975

  11. Co(II), Mn(II), and Cr(III) iminodiacetate complexes heterogenized on silica gel in the liquid-phase oxidation of cyclohexene

    SciTech Connect

    Berentsveig, V.V.; Barinova, T.V.; Lisichkin, G.V.; Nga, C.B.

    1985-06-01

    A study was carried out on the catalytic properties of Co(II), Mn(II), and Cr(III) iminodiacetate complexes heterogenized on silica gel. The liquid-phase oxidation of cyclohexene in the presence of these catalysts proceeds mainly by a heterogeneous-homogeneous radical chain methanism. Variation in the selectivity of this liquid-phase reaction is possible by changing the nature of the transition metal ion.

  12. The Role of Accessory Phases in the Sm-Nd Isotope Systematics of the Acasta Gneiss Complex

    NASA Astrophysics Data System (ADS)

    Bauer, A.; Fisher, C. M.; Vervoort, J. D.; Bowring, S. A.

    2015-12-01

    The Acasta Gneiss Complex (AGC) of the Slave Craton in the Northwest Territories, Canada, contains some of Earth's oldest continental crust. It is characterized by a range of compositionally diverse gneisses with crystallization ages of 3.3 to > 4.0 Ga1-5. The AGC has undergone a multistage history of metamorphism and deformation. Given these post-crystallization processes, the extent of Nd isotope heterogeneity suggested by published4-7 whole rock Sm-Nd analyses of these rocks has been called into question. Criticisms include the likelihood of mixed lithologies at the hand-sample scale and the potential for open-system behavior of the Sm-Nd isotopic system in these rocks. We obtained whole rock compositional, Sm-Nd and Lu-Hf isotope data paired with Hf in zircon and Nd in titanite and apatite data to further evaluate the isotope record, and use U-Pb and Lu-Hf of zircon as a basis for identifying mixed or complex samples. Preferential preservation of Lu-Hf over Sm-Nd isotope systematics in multiply deformed, complex rocks may be controlled by the minerals that dominate the Hf and Nd budgets, with the majority of the Hf effectively sheltered in zircon and the Nd largely hosted in accessory phases such as apatite and titanite. This composite dataset enables us to evaluate the possibility that Hf and Nd isotopic systematics have been decoupled in these samples that have such critical bearing on our understanding of early crust-forming processes. [1]Bowring and Williams (1999). CoMP, 134(1), 3-16. [2]Iizuka, T. et al. (2006) Geology, 34(4), 245-248. [3]Iizuka et al (2007). Precambrian Res, 153(3), 179-208. [4]Bowring et al. 1989. Nature, 340: 222-225. [5]Mojzsis et al. (2014). GCA, 133, 68-96. [6]Bowring and Housh (1995) Science 269, 1535-1540. [7]Moorbath et al (1997) Chem. Geol. 135, 213-231.

  13. Electric field-assisted solid phase extraction and cleanup of ionic compounds in complex food matrices: Fluoroquinolones in eggs.

    PubMed

    Ribeiro, Cyntia Cabral; Orlando, Ricardo Mathias; Rohwedder, Jarbas José Rodrigues; Reyes, Felix Guillermo Reyes; Rath, Susanne

    2016-05-15

    The use of electric fields as additional driving forces in sample preparation techniques is an innovative approach that is environmentally friendly, straightforward, and able to overcome several limitations of conventional sample preparation procedures. In this work, the advantages of electric field-assisted solid phase extraction (E-SPE) using syringe-type cartridges were demonstrated for the extraction of four fluoroquinolones (FQs) in their anionic forms. The FQs were extracted from eggs and subsequently determined by UHPLC-MS/MS. The use of electric fields during the washing and final elution steps resulted in a significant improvement of the extraction efficiencies for almost all FQs when compared to conventional SPE. Intra- and inter-day assays showed coefficients of variation below 10%. The better cleanup also resulted in the appearance of less precipitated matter in the final eluate, as well as reduced matrix effects. The results showed that the electrophoretic forces derived from electric fields are a promising way of significantly increasing the extraction efficiency of ionic analytes, while minimizing matrix effects associated with complex samples. PMID:26992547

  14. Singular Values for Products of Complex Ginibre Matrices with a Source: Hard Edge Limit and Phase Transition

    NASA Astrophysics Data System (ADS)

    Forrester, Peter J.; Liu, Dang-Zheng

    2016-05-01

    The singular values squared of the random matrix product {Y = {Gr G_{r-1}} ldots G1 (G0 + A)}, where each {Gj} is a rectangular standard complex Gaussian matrix while A is non-random, are shown to be a determinantal point process with the correlation kernel given by a double contour integral. When all but finitely many eigenvalues of A* A are equal to bN, the kernel is shown to admit a well-defined hard edge scaling, in which case a critical value is established and a phase transition phenomenon is observed. More specifically, the limiting kernel in the subcritical regime of {0 < b < 1} is independent of b, and is in fact the same as that known for the case b = 0 due to Kuijlaars and Zhang. The critical regime of b = 1 allows for a double scaling limit by choosing {{b = (1 - τ/√{N})^{-1}}}, and for this the critical kernel and outlier phenomenon are established. In the simplest case r = 0, which is closely related to non-intersecting squared Bessel paths, a distribution corresponding to the finite shifted mean LUE is proven to be the scaling limit in the supercritical regime of {b > 1} with two distinct scaling rates. Similar results also hold true for the random matrix product {Tr T_{r-1} ldots T1 (G0 + A)}, with each {Tj} being a truncated unitary matrix.

  15. Analytical developments for the determination of monomethylmercury complexes with low molecular mass thiols by reverse phase liquid chromatography hyphenated to inductively coupled plasma mass spectrometry.

    PubMed

    Bouchet, Sylvain; Björn, Erik

    2014-04-25

    The behavior of monomethylmercury (MMHg) is markedly influenced by its distribution among complexes with low molecular mass (LMM) thiols but analytical methodologies dedicated to measure such complexes are very scarce up to date. In this work, we selected 15 LMM thiols often encountered in living organisms and/or in the environment and evaluated the separation of the 15 corresponding MMHg-thiol complexes by various high performance liquid chromatography (HPLC) columns. Two C18 (Phenomenex Synergi Hydro-RP and LunaC18(2)), two phenyl (Inertsil Ph 3 and 5μm) and one mixed-mode (Restek Ultra IBD) stationary phases were tested for their retention and resolution capacities of the various complexes. The objective was to find simple separation conditions with low organic contents in the mobile phase to provide optimal conditions for detection by inductively coupled plasma mass spectrometry (ICPMS). The 15 complexes were synthesized in solution and characterized by electrospray ionization-mass spectrometry (ESI-MS). The C18 columns tested were either not resolutive enough or too retentive. The 3μm phenyl stationary phase was able to resolve 10 out of the 15 complexes in less than 25min, under isocratic conditions. The mixed-mode column was especially effective at separating the most hydrophilic complexes (6 complexes out of the 15), corresponding to the main LMM thiols found in living organisms. The detection limits (DLs) for these two columns were in the low nanomolar range and overall slightly better for the phenyl column. The possibilities offered by such methodology were exemplified by monitoring the time-course concentrations of four MMHg-thiol complexes within a phytoplankton incubation containing MMHg in the presence of an excess of four added thiols. PMID:24657146

  16. Spectroscopic and electrochemical studies on the interaction of an inclusion complex of β-cyclodextrin with 2,6-dinitrophenol in aqueous and solid phases

    NASA Astrophysics Data System (ADS)

    Srinivasan, K.; Stalin, T.; Shanmugapriya, A.; Sivakumar, K.

    2013-03-01

    The inclusion complex of 2,6-dinitrophenol (2,6-DNP) with β-cyclodextrin (β-CD) in solution phase was studied by UV-visible spectrophotometer and electrochemical (cyclic voltammetry) methods. The prototropic behaviors of 2,6-DNP were studied. The binding constant of 'β-CD:2,6-DNP' inclusion complex was calculated using Benesi-Hildebrand plot at 303 K. Thermodynamic parameter (ΔG) involved in the complex formation also calculated. It indicates that the reaction is spontaneous and exergonic process. Formation of solid inclusion complex between β-CD and 2,6-DNP was characterized by 1H NMR, FT-IR, XRD techniques and SEM morphological studies. The β-CD:2,6-DNP inclusion complex obtained by molecular docking studies is in good correlation with the results obtained through experimental methods.

  17. Computational Thermodynamic Study to Predict Complex Phase Equilibria in the Nickel-Base Superalloy Rene N6

    NASA Technical Reports Server (NTRS)

    Copland, Evan H.; Jacobson, Nathan S.; Ritzert, Frank J.

    2001-01-01

    A previous study by Ritzert et al. on the formation and prediction of topologically closed packed (TCP) phases in the nickel-base superalloy Rene' N6 is re-examined with computational thermodynamics. The experimental data on phase distribution in forty-four alloys with a composition within the patent limits of the nickel-base superalloy Rene' N6 provide a good basis for comparison to and validation of a commercial nickel superalloy database used with ThermoCalc. Volume fraction of the phases and partitioning of the elements are determined for the forty-four alloys in this dataset. The baseline heat treatment of 400 h at 1366 K was used. This composition set is particularly interesting since small composition differences lead to dramatic changes in phase composition. In general the calculated values follow the experimental trends. However, the calculations indicated no TCP phase formation when the experimental measurements gave a volume percent of TCP phase less than 2 percent. When TCP phases were predicted, the calculations under-predict the volume percent of TCP phases by a factor of 2 to 8. The calculated compositions of the gamma and gamma' phases show fair agreement with the measurements. However, the calculated compositions of the P Phase do not agree with those measured. This may be due to inaccuracies in the model parameters for P phase and/or issues with the microprobe analyses of these phases. In addition, phase fraction diagrams and sigma and P phase solvus temperatures are calculated for each of the alloys. These calculations indicate that P phase is the primary TCP phase formed for the alloys considered here at 1366 K. Finally, a series of isopleths are calculated for each of the seven alloying elements. These show the effect of each alloying element on creating TCP phases.

  18. Enantioseparation of mandelic acid derivatives by high performance liquid chromatography with substituted β-cyclodextrin as chiral mobile phase additive and evaluation of inclusion complex formation

    PubMed Central

    Tong, Shengqiang; Zhang, Hu; Shen, Mangmang

    2014-01-01

    The enantioseparation of ten mandelic acid derivatives was performed by reverse phase high performance liquid chromatography with hydroxypropyl-β-cyclodextrin (HP-β-CD) or sulfobutyl ether-β-cyclodextrin (SBE-β-CD) as chiral mobile phase additives, in which inclusion complex formations between cyclodextrins and enantiomers were evaluated. The effects of various factors such as the composition of mobile phase, concentration of cyclodextrins and column temperature on retention and enantioselectivity were studied. The peak resolutions and retention time of the enantiomers were strongly affected by the pH, the organic modifier and the type of β-cyclodextrin in the mobile phase, while the concentration of buffer solution and temperature had a relatively low effect on resolutions. Enantioseparations were successfully achieved on a Shimpack CLC-ODS column (150×4.6 mm i.d., 5 μm). The mobile phase was a mixture of acetonitrile and 0.10 mol L-1 of phosphate buffer at pH 2.68 containing 20 mmol L-1 of HP-β-CD or SBE-β-CD. Semi-preparative enantioseparation of about 10 mg of α-cyclohexylmandelic acid and α-cyclopentylmandelic acid were established individually. Cyclodextrin-enantiomer complex stoichiometries as well as binding constants were investigated. Results showed that stoichiomertries for all the inclusion complex of cyclodextrin-enantiomers were 1:1. PMID:24893270

  19. Complex anisotropy beneath the Peruvian flat-slab from frequency-dependent, multiple-phase shear wave splitting analysis

    NASA Astrophysics Data System (ADS)

    Eakin, C. M.; Long, M. D.

    2013-05-01

    Flat or shallow subduction is a relatively widespread global occurrence but the dynamics remain poorly understood. In particular, the interaction between flat-slabs and the surrounding mantle flow has yet to be studied in detail. In this study measurements of seismic anisotropy are utilized to investigate mantle flow beneath the Peruvian flat-slab segment, the largest present-day region of flat-subduction. A detailed shear wave splitting analysis is conducted at a long-running seismic station (NNA) located near Lima, Peru. Measurements of apparent splitting parameters (fast direction φ and delay time δt) for SKS, ScS and local S phases from 86 events were obtained. Well defined frequency dependence and back-azimuthal variability is observed, indicating the likely presence of complex anisotropy. Forward modeling the observations with two or three layers of anisotropy reveals a likely layer with a trench-parallel fast axis overlying a layer(s) with a more trench-normal fast geometry. In order to further constrain the anisotropic geometry, source-side splitting from events originating within the slab measured at distant stations have been analyzed. Beneath the flat-slab segment, trench-normal fast splitting directions in the sub-slab mantle were found and likely trench-parallel anisotropy within the slab itself. This sub-slab pattern contradicts observations from elsewhere in South America for 'normal' (i.e. more steeply dipping) slab conditions. It is similar, however, to inferences from other shallowly dipping subduction zones around the world. While there is an apparent link between slab dip and the surrounding mantle flow, at least beneath Peru, the precise nature of the relationship requires further investigation.

  20. Complex anisotropy beneath the Peruvian flat slab from frequency-dependent, multiple-phase shear wave splitting analysis

    NASA Astrophysics Data System (ADS)

    Eakin, Caroline M.; Long, Maureen D.

    2013-09-01

    Flat or shallow subduction is a relatively widespread global occurrence, but the dynamics remain poorly understood. In particular, the interaction between flat slabs and the surrounding mantle flow has yet to be studied in detail. Here we present measurements of seismic anisotropy to investigate mantle flow beneath the Peruvian flat-slab segment, the largest present-day region of flat subduction. We conduct a detailed shear wave splitting analysis at a long-running seismic station (NNA) located near Lima, Peru. We present measurements of apparent splitting parameters (fast direction φ and delay time δt) for SKS, ScS, and local S phases from 80 events. We observe well-defined frequency dependence and backazimuthal variability, indicating the likely presence of complex anisotropy. Forward modeling the observations with two or three layers of anisotropy reveals a likely layer with a trench-normal fast direction underlying a layer with a more trench-oblique (to trench-subparallel) fast direction. In order to further constrain the anisotropic geometry, we analyzed the source-side splitting from events originating within the slab measured at distant stations. Beneath the flat-slab segment, we found trench-normal fast splitting directions in the subslab mantle, while within the dipping portion of the slab further to the east, likely trench-subparallel anisotropy within the slab itself. This subslab pattern contradicts observations from elsewhere in South America for "normal" (i.e., more steeply dipping) slab conditions. It is similar, however, to inferences from other shallowly dipping subduction zones around the world. While there is an apparent link between slab dip and the surrounding mantle flow, at least beneath Peru, the precise nature of the relationship remains to be clarified.

  1. One ring to bind them all: shape-selective complexation of phenylenediamine isomers with cucurbit[6]uril in the gas phase.

    PubMed

    Dearden, David V; Ferrell, Tyler A; Asplund, Matthew C; Zilch, Lloyd W; Julian, Ryan R; Jarrold, Martin F

    2009-02-12

    We examined complexes between cucurbit[6]uril and each of ortho-, meta-, and para-phenylenediamine using computational methods, Fourier transform ion cyclotron resonance mass spectrometry, and ion mobility spectrometry. These fundamental gas phase studies show that the lowest energy binding sites for ortho- and meta-phenylenediamine are on the exterior of cucurbit[6]uril, whereas para-phenylenediamine preferentially binds in the interior, in a pseudorotaxane fashion. This conclusion is based on reactivity of each of the complexes with tert-butylamine, where the ortho- and meta-phenylenediamine complexes exchange with tert-butylamine, whereas the para-phenylenediamine complex undergoes two slow additions without displacement. Further, under sustained off-resonance irradiation conditions, the ortho- and meta-phenylenediamine complexes fragment easily via losses of neutral phenylenediamine, whereas the para-phenylenediamine complex fragments at higher energies primarily via cleavage of covalent bonds in the cucurbituril. Finally, ion mobility studies show ion populations for the ortho- and meta-phenylenediamine complexes that primarily have collision cross sections consistent with external complexation, whereas the para-phenylenediamine complex has a collision cross section that is smaller, the same as that of protonated cucurbit[6]uril within experimental error. In agreement with experiment, computational studies indicate that at the HF/6-31G* and B3LYP/6-31G*//HF/6-31G* levels of theory external complexation is favored for ortho- and meta-phenylenediamine, whereas internal complexation is lower in energy for para-phenylenediamine. In contrast, MP2/6-31G*//HF-6-31G* calculations predict internal complexation for all three isomers. PMID:19146442

  2. Orc1 Binding to Mitotic Chromosomes Precedes Spatial Patterning during G1 Phase and Assembly of the Origin Recognition Complex in Human Cells.

    PubMed

    Kara, Nihan; Hossain, Manzar; Prasanth, Supriya G; Stillman, Bruce

    2015-05-01

    Replication of eukaryotic chromosomes occurs once every cell division cycle in normal cells and is a tightly controlled process that ensures complete genome duplication. The origin recognition complex (ORC) plays a key role during the initiation of DNA replication. In human cells, the level of Orc1, the largest subunit of ORC, is regulated during the cell division cycle, and thus ORC is a dynamic complex. Upon S phase entry, Orc1 is ubiquitinated and targeted for destruction, with subsequent dissociation of ORC from chromosomes. Time lapse and live cell images of human cells expressing fluorescently tagged Orc1 show that Orc1 re-localizes to condensing chromatin during early mitosis and then displays different nuclear localization patterns at different times during G1 phase, remaining associated with late replicating regions of the genome in late G1 phase. The initial binding of Orc1 to mitotic chromosomes requires C-terminal amino acid sequences that are similar to mitotic chromosome-binding sequences in the transcriptional pioneer protein FOXA1. Depletion of Orc1 causes concomitant loss of the mini-chromosome maintenance (Mcm2-7) helicase proteins on chromatin. The data suggest that Orc1 acts as a nucleating center for ORC assembly and then pre-replication complex assembly by binding to mitotic chromosomes, followed by gradual removal from chromatin during the G1 phase. PMID:25784553

  3. Infrared spectroscopy and ab initio study of hydrogen bonded Cl3CD·N(CH3)3 complex in the gas phase

    NASA Astrophysics Data System (ADS)

    Rutkowski, K. S.; Melikova, S. M.; Linok, O. V.; Czarnik-Matusewicz, B.; Rospenk, M.

    2015-02-01

    FTIR spectra of the gas phase Cl3CD + TMA mixture have been studied at room temperature in ∼800-4000 cm-1 frequency domain. The formation of the H-bonded Cl3CD…TMA complex has been detected. Spectroscopic parameters of the band ascribed to the complex were evaluated. MP2 frozen core ab initio calculations have been carried out with the Pople-type 6-311++G(d,p) basis set. The equilibrium geometries and harmonic vibrational frequencies of the complex were obtained using CP-corrected gradient techniques. The ''freq = anharm'' option has been tested for Cl3CD monomer and Cl3CD…TMA complex to examine possible anharmonic effects on the vibrations localized on the proton donor. The effects of Darling-Dennison and Fermi resonances on the frequency of the stretching vibration of the CH proton donor were analyzed.

  4. Disentangling the history of complex multi-phased shell beds based on the analysis of 3D point cloud data

    NASA Astrophysics Data System (ADS)

    Harzhauser, Mathias; Djuricic, Ana; Mandic, Oleg; Dorninger, Peter; Nothegger, Clemens; Székely, Balázs; Molnár, Gábor; Pfeifer, Norbert

    2015-04-01

    Shell beds are key features in sedimentary records throughout the Phanerozoic. The interplay between burial rates and population productivity is reflected in distinct degrees of shelliness. Consequently, shell beds may provide informations on various physical processes, which led to the accumulation and preservation of hard parts. Many shell beds pass through a complex history of formation being shaped by more than one factor. In shallow marine settings, the composition of shell beds is often strongly influenced by winnowing, reworking and transport. These processes may cause considerable time averaging and the accumulation of specimens, which have lived thousands of years apart. In the best case, the environment remained stable during that time span and the mixing does not mask the overall composition. A major obstacle for the interpretation of shell beds, however, is the amalgamation of shell beds of several depositional units in a single concentration, as typically for tempestites and tsunamites. Disentangling such mixed assemblages requires deep understanding of the ecological requirements of the taxa involved - which is achievable for geologically young shell beds with living relatives - and a statistic approach to quantify the contribution by the various death assemblages. Furthermore it requires understanding of sedimentary processes potentially involved into their formation. Here we present the first attempt to describe and decipher such a multi-phase shell-bed based on a high resolution digital surface model (1 mm) combined with ortho-photos with a resolution of 0.5 mm per pixel. Documenting the oyster reef requires precisely georeferenced data; owing to high redundancy of the point cloud an accuracy of a few mm was achieved. The shell accumulation covers an area of 400 m2 with thousands of specimens, which were excavated by a three months campaign at Stetten in Lower Austria. Formed in an Early Miocene estuary of the Paratethys Sea it is mainly composed

  5. Atomic-level imaging of Mo-V-O complex oxide phase intergrowth, grain boundaries, and defects using HAADF-STEM

    PubMed Central

    Pyrz, William D.; Blom, Douglas A.; Sadakane, Masahiro; Kodato, Katsunori; Ueda, Wataru; Vogt, Thomas; Buttrey, Douglas J.

    2010-01-01

    In this work, we structurally characterize defects, grain boundaries, and intergrowth phases observed in various Mo-V-O materials using aberration-corrected high-angle annular dark-field (HAADF) imaging within a scanning transmission electron microscope (STEM). Atomic-level imaging of these preparations clearly shows domains of the orthorhombic M1-type phase intergrown with the trigonal phase. Idealized models based on HAADF imaging indicate that atomic-scale registry at the domain boundaries can be seamless with several possible trigonal and M1-type unit cell orientation relationships. The alignment of two trigonal domains separated by an M1-type domain or vice versa can be predicted by identifying the number of rows/columns of parallel symmetry operators. Intergrowths of the M1 catalyst with the M2 phase or with the Mo5O14-type phase have not been observed. The resolution enhancements provided by aberration-correction have provided new insights to the understanding of phase equilibria of complex Mo-V-O materials. This study exemplifies the utility of STEM for the characterization of local structure at crystalline phase boundaries. PMID:20308579

  6. Gas-Phase Coordination Complexes of UVIO{2/2+}, NpVIO{2/2+}, and PuVIO{2/2+} with Dimethylformamide

    NASA Astrophysics Data System (ADS)

    Rutkowski, Philip X.; Rios, Daniel; Gibson, John K.; van Stipdonk, Michael J.

    2011-11-01

    Electrospray ionization of actinyl perchlorate solutions in H2O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [AnVIO2(DMF)3(H2O)]2+ and [AnVIO2(DMF)4]2+, where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI).

  7. Surface-Induced Dissociation Mass Spectra as a Tool for Distinguishing Different Structural Forms of Gas-Phase Multimeric Protein Complexes.

    PubMed

    Quintyn, Royston S; Zhou, Mowei; Yan, Jing; Wysocki, Vicki H

    2015-12-01

    One attractive feature of ion mobility mass spectrometry (IM-MS) lies in its ability to provide experimental collision cross section (CCS) measurements, which can be used to distinguish different conformations that a protein complex may adopt during its gas-phase unfolding. However, CCS values alone give no detailed information on subunit structure within the complex. Consequently, structural characterization typically requires molecular modeling, which can have uncertainties without experimental support. One method of obtaining direct experimental evidence on the structures of these intermediates is utilizing gas-phase activation techniques that can effectively dissociate the complexes into substructures while preserving the native topological information. The most commonly used activation method, collision-induced dissociation (CID) with low-mass target gases, typically leads to unfolding of monomers of a protein complex. Here, we describe a method that couples IM-MS and surface-induced dissociation (SID) to dissociate the source-activated precursors of three model protein complexes: C-reactive protein (CRP), transthyretin (TTR), and concanavalin A (Con A). The results of this study confirm that CID involves the unfolding of the protein complex via several intermediates. More importantly, our experiments also indicate that retention of similar CCS between different intermediates does not guarantee retention of structure. Although CID spectra (at a given collision energy) of source-activated, mass-selected precursors do not distinguish between native-like, collapsed, and expanded forms of a protein complex, dissociation patterns and/or average charge states of monomer products in SID of each of these forms are unique. PMID:26499904

  8. Peptide-lanthanide cation equilibria in aqueous phase. I. Bound shifts for L-carnosine-praseodymium complexes

    NASA Astrophysics Data System (ADS)

    Mossoyan, J.; Asso, M.; Benlian, D.

    L-Carnosine complexes of Pr 3+ were characterized in aqueous solution by 1H NMR and potentiometric titration. A rigorous treatment of chemical shifts and pH variation data with lanthanide concentration is presented. Two different forms of the peptide ligand, forming simultaneously two complexes, were taken into account. At low pH values the cation is only coordinated at the carboxylate site of the ligand in a weak complex ( β2 = 6) whereas in neutral solution a stronger complex ( β1 = 37) is present as a consequence of the deprotonation of the imidazole ring. The computation of induced bound shifts † 2 and Δ1 for resonating nuclei of the peptide in both forms yields consistent figures. These provide the experimental basis for a conformational model which is usually not obtainable for labile complexes with low stability constants.

  9. New two dimensional liquid-phase colorimetric assay based on old iodine-starch complexation for the naked-eye quantitative detection of analytes.

    PubMed

    Nie, Jinfang; Brown, Tom; Zhang, Yun

    2016-06-14

    A new type of quantitative point-of-care liquid-phase colorimetric assay (LPCA) termed as two dimensional (2D) LPCA is designed using old iodine-starch complexation reaction firstly discovered in 1814. The naked-eye 2D LPCA's utility is well demonstrated with the simple, low-cost, portable detection and quantification of model analytes in buffer and/or human serum samples without the use of external electronic readers. PMID:27074248

  10. Ion Mobility-Mass Spectrometry Analysis of Cross-Linked Intact Multiprotein Complexes: Enhanced Gas-Phase Stabilities and Altered Dissociation Pathways.

    PubMed

    Samulak, Billy M; Niu, Shuai; Andrews, Philip C; Ruotolo, Brandon T

    2016-05-17

    Analysis of protein complexes by ion mobility-mass spectrometry is a valuable method for the rapid assessment of complex composition, binding stoichiometries, and structures. However, capturing labile, unknown protein assemblies directly from cells remains a challenge for the technology. Furthermore, ion mobility-mass spectrometry measurements of complexes, subcomplexes, and subunits are necessary to build complete models of intact assemblies, and such data can be difficult to acquire in a comprehensive fashion. Here, we present the use of novel mass spectrometry cleavable cross-linkers and tags to stabilize intact protein complexes for ion mobility-mass spectrometry. Our data reveal that tags and linkers bearing permanent charges are superior stabilizers relative to neutral cross-linkers, especially in the context of retaining compact forms of the assembly under a wide array of activating conditions. In addition, when cross-linked protein complexes are collisionally activated in the gas phase, a larger proportion of the product ions produced are often more compact and reflect native protein subcomplexes when compared with unmodified complexes activated in the same fashion, greatly enabling applications in structural biology. PMID:27078797

  11. Structural characterization of gas-phase cysteine and cysteine methyl ester complexes with zinc and cadmium dications by infrared multiple photon dissociation spectroscopy.

    PubMed

    Coates, Rebecca A; McNary, Christopher P; Boles, Georgia C; Berden, Giel; Oomens, Jos; Armentrout, P B

    2015-10-21

    Structural characterization of gas-phase ions of cysteine (Cys) and cysteine methyl ester (CysOMe) complexed to zinc and cadmium is investigated by infrared multiple photon dissociation (IRMPD) action spectroscopy using a free electron laser in combination with density functional theory calculations. IRMPD spectra are measured for [Zn(Cys-H)](+), [Cd(Cys-H)](+), [Zn(CysOMe-H)](+), [Cd(CysOMe-H)](+) and CdCl(+)(CysOMe) and are accompanied by quantum mechanical calculations of the predicted linear absorption spectra at the B3LYP/6-311+G(d,p) (Zn(2+) complexes) and B3LYP/def2TZVP levels (Cd(2+) complexes). On the basis of these experiments and calculations, the conformation that best reproduces the IRMPD spectra for the complexes of the deprotonated amino acids, [M(Cys-H)](+) and [M(CysOMe-H)](+), is a charge-solvated (CS) tridentate structure where the metal dication binds to the amine and carbonyl groups of the amino acid backbone and the deprotonated sulfur atom of the side chain, [N,CO,S(-)]. The intact amino acid complex, CdCl(+)(CysOMe) binds in the equivalent motif [N,CO,S]. These binding motifs are in agreement with the predicted ground structures of these complexes at the B3LYP, B3LYP-GD3BJ (with empirical dispersion corrections), B3P86, and MP2(full) levels. PMID:25880327

  12. Exploring dynamic property of traffic flow time series in multi-states based on complex networks: Phase space reconstruction versus visibility graph

    NASA Astrophysics Data System (ADS)

    Tang, Jinjun; Liu, Fang; Zhang, Weibin; Zhang, Shen; Wang, Yinhai

    2016-05-01

    A new method based on complex network theory is proposed to analyze traffic flow time series in different states. We use the data collected from loop detectors on freeway to establish traffic flow model and classify the flow into three states based on K-means method. We then introduced two widely used methods to convert time series into networks: phase space reconstruction and visibility graph. Furthermore, in phase space reconstruction, we discuss how to determine delay time constant and embedding dimension and how to select optimal critical threshold in terms of cumulative degree distribution. In the visibility graph, we design a method to construct network from multi-variables time series based on logical OR. Finally, we study and compare the statistic features of the networks converted from original traffic time series in three states based on phase space and visibility by using the degree distribution, network structure, correlation of the cluster coefficient to betweenness and degree-degree correlation.

  13. X-Ray Diffraction and Mössbauer Spectroscopy Studies of Pressure-Induced Phase Transitions in a Mixed-Valence Trinuclear Iron Complex.

    PubMed

    Madsen, Solveig R; Gunnlaugsson, Haraldur P; Moggach, Stephen A; Eikeland, Espen; Wu, Lai-Chin; Leupold, Olaf; Overgaard, Jacob; Iversen, Bo B

    2016-07-01

    The mixed-valence complex Fe3 O(cyanoacetate)6 (H2 O)3 (1) has been studied by single-crystal X-ray diffraction analysis at pressures up to 5.3(1) GPa and by (synchrotron) Mössbauer spectroscopy at pressures up to 8(1) GPa. Crystal structure refinements were possible up to 4.0(1) GPa. In this pressure range, 1 undergoes two pressure-induced phase transitions. The first phase transition at around 3 GPa is isosymmetric and involves a 60° rotation of 50 % of the cyanoacetate ligands. The second phase transition at around 4 GPa reduces the symmetry from rhombohedral to triclinic. Mössbauer spectra show that the complex becomes partially valence-trapped after the second phase transition. This sluggish pressure-induced valence-trapping is in contrast to the very abrupt valence-trapping observed when compound 1 is cooled from 130 to 120 K at ambient pressure. PMID:27245642

  14. Ligand field photofragmentation spectroscopy of [Ag(L){sub N}]{sup 2+} complexes in the gas phase: Experiment and theory

    SciTech Connect

    Guan, Jingang; Puskar, Ljiljana; Esplugas, Ricardo O.; Cox, Hazel; Stace, Anthony J.

    2007-08-14

    Experiments have been undertaken to record photofragmentation spectra from a series of [Ag(L){sub N}]{sup 2+} complexes in the gas phase. Spectra have been obtained for silver(II) complexed with the ligands (L): acetone, 2-pentanone, methyl-vinyl ketone, pyridine, and 4-methyl pyridine (4-picoline) with N in the range of 4-7. A second series of experiments using 1,1,1,3-fluoroacetone, acetonitrile, and CO{sub 2} as ligands failed to show any evidence of photofragmentation. Interpretation of the experimental data has come from time-dependent density functional theory (TDDFT), which very successfully accounts for trends in the spectra in terms of subtle differences in the properties of the ligands. Taking a sample of three ligands, acetone, pyridine, and acetonitrile, the calculations show all the spectral transitions to involve ligand-to-metal charge transfer, and that wavelength differences (or lack of spectra) arise from small changes in the energies of the molecular orbitals concerned. The calculations account for an absence in the spectra of any effects due to Jahn-Teller distortion, and they also reveal structural differences between complexes where the coordinating atom is either oxygen or nitrogen that have implications for the stability of silver(II) compounds. Where possible, comparisons have also been made with the physical properties of condensed phase silver(II) complexes.

  15. Immobilization of metal-humic acid complexes in anaerobic granular sludge for their application as solid-phase redox mediators in the biotransformation of iopromide in UASB reactors.

    PubMed

    Cruz-Zavala, Aracely S; Pat-Espadas, Aurora M; Rangel-Mendez, J Rene; Chazaro-Ruiz, Luis F; Ascacio-Valdes, Juan A; Aguilar, Cristobal N; Cervantes, Francisco J

    2016-05-01

    Metal-humic acid complexes were synthesized and immobilized by a granulation process in anaerobic sludge for their application as solid-phase redox mediators (RM) in the biotransformation of iopromide. Characterization of Ca- and Fe-humic acid complexes revealed electron accepting capacities of 0.472 and 0.556milli-equivalentsg(-1), respectively. Once immobilized, metal-humic acid complexes significantly increased the biotransformation of iopromide in upflow anaerobic sludge blanket (UASB) reactors. Control UASB reactor (without humic material) achieved 31.6% of iopromide removal, while 80% was removed in UASB reactors supplied with each metal-humic acid complex. Further analyses indicated multiple transformation reactions taking place in iopromide including deiodination, N-dealkylation, decarboxylation and deacetylation. This is the first successful application of immobilized RM, which does not require a supporting material to maintain the solid-phase RM in long term operation of bioreactors. The proposed redox catalyst could be suitable for enhancing the redox conversion of different recalcitrant pollutants present in industrial effluents. PMID:26868154

  16. Tuning the photoluminescence of condensed-phase cyclic trinuclear Au(I) complexes through control of their aggregated structures by external stimuli

    NASA Astrophysics Data System (ADS)

    Fujisawa, Kaori; Yamada, Shigeyuki; Yanagi, Yukihiro; Yoshioka, Yasunori; Kiyohara, Ayumi; Tsutsumi, Osamu

    2015-03-01

    A series of new cyclic trinuclear Au(I) complexes with alkoxy side chains of various lengths were synthesized as photoluminescence materials. None of the complexes emitted luminescence in solution; however, some showed photoluminescence in the crystalline phase. Single crystal X-ray structural analyses revealed that an intermolecular interaction between two Au atoms (aurophilic interaction) existed only in the emissive complexes, which formed molecular aggregates in the crystal. Because isolated molecules show no luminescence in the present system, we conclude that only molecules aggregated via aurophilic interactions can luminesce. We demonstrated that luminescence properties, such as colour and intensity, were very sensitive to the aggregated structure of the molecules. We also found that such luminescence properties can be controlled by a change in the aggregated structure induced by external stimuli, such as heat, solvent, and mechanical stress.

  17. New method for computer analysis of complex intermetallic compounds and nanocluster model of the samson phase Cd{sub 3}Cu{sub 4}

    SciTech Connect

    Blatov, V. A.; Ilyushin, G. D.

    2010-12-15

    A new method is proposed for the computer analysis of crystal structures of complex intermetallic compounds (with more than 1000 atoms per unit cell) using a developed algorithm of the complete decomposition of the 3D graph of the structure into nanocluster substructures. This method has been implemented in the TOPOS software package and approved successfully in an analysis of the complex Cu{sub 3}Cd{sub 4} structure (Samson phase). Cu{sub 3}Cd{sub 4} structure models were used to establish a structural relationship between nanoclusters in this intermetallic compound and nanoclusters in other complex crystal structures: ZrZn{sub 22}, Ru{sub 7}Mg{sub 44}, NaCd{sub 2}, and Mg{sub 2}Al{sub 3}.

  18. Phase diagram of 3β-[N-(N ,N-dimethylaminoethane)-carbamoyl]- cholesterol-dioleoylphosphatidylethanolamine/DNA complexes suggests strategies for efficient lipoplex transfection

    NASA Astrophysics Data System (ADS)

    Pozzi, Daniela; Amenitsch, Heinz; Marchini, Cristina; Caracciolo, Giulio

    2010-05-01

    Synchrotron small angle x-ray scattering and electrophoresis on agarose gels have been applied to construct the phase diagram of the ternary complex made up of the cationic lipid 3β-[N-(N ,N-dimethylaminoethane)-carbamoyl]-cholesterol, the neutral lipid dioleoylphosphatidylethanolamine and DNA. We show that nominally charge-neutral complexes coexist with free DNA, while excess cationic charge is necessary to protect all the genetic cargo. Such an extra-charge requirement diminishes as the molar fraction of neutral lipid in the bilayer increases. Furthermore, complexes with very different membrane composition and charge ratio exhibit the very same DNA protection ability. The relevance of results for transfection studies is discussed.

  19. Complete structural characterization of metallacyclic complexes in solution-phase using simultaneously X-ray diffraction and molecular dynamics simulation.

    PubMed

    Megyes, Tünde; Bálint, Szabolcs; Bakó, Imre; Grósz, Tamás; Pálinkás, Gábor

    2008-07-23

    Wide-angle X-ray diffraction and molecular dynamics simulation has been used to perform complete structural characterization of nitromethane solution of a 16-membered gold(I) ring. The joint application of these two methods was an adequate tool to describe not only the structure of the complex but also the solvation properties of the complex in nitromethane and the effect of the solvation on the bulk structure. It has been found that a relatively diffuse slightly distorted solvation shell is formed around the complex, following the shape of the molecule. Nitromethane molecules in the solvation sphere are distributed randomly; no special orientation can be detected. The interaction energy of the complex with nitromethane molecules is attractive. In bulk, besides the antiparallel orientation of the nitromethane molecules, T-shape orientation and long-range order in antidipole orientation can also be detected. PMID:18576617

  20. Two-phase and three-dimensional simulations of complex fluid-sediment transport down a slope and impacting water bodies

    NASA Astrophysics Data System (ADS)

    Pudasaini, Shiva P.; Kattel, Parameshwari; Kafle, Jeevan; Pokhrel, Puskar R.; Khattri, Khim B.

    2014-05-01

    We present a technique that simulates transport and flow of a real two-phase fluid (a mixture of fluid and sediment particles) down three-dimensional slopes and channels. This technique combines novel mechanics formulations and modeling into a unified high-resolution framework, providing a unique opportunity to simulate two-phase subearial landslides and debris flows with dynamically changing concentrations of solid particles. This mixture then impacts downslope with particle-laden fluid reservoirs, rivers, fjords, lakes, or oceans. This results in a super tsunami wave in the fluid body, while the submarine debris flow moves along the bathymetry. The same modelling technique can be applied to simulate rock-ice avalanches and turbidity currents with changing physical properties and mechanical responses of the phases that enhances the flow mobility. These results fundamentally advance our present knowledge associated with the complex mechanics and dynamics of multi-phase geophysical mass flows, including the subearial and submarine sediment transport and deposition processes. Our findings contribute significantly to our understanding of mixing and separation between phases, generation and propagation of special solid and fluid structures, and phase-transitions during the flow process. Finally, these results provide new insights into the evolution of morphodynamics of steep mountain slopes and channels. References Pudasaini, S. P. A general two-phase debris flow model. Journal of Geophysical Research, 117, F03010, 2012. doi: 10.1029/2011JF002186. Pudasaini, S. P. and Miller, S. A. A real two-phase submarine debris flow and tsunami. American Institute of Physics Proceedings, 1479, 197-200, 2012. doi: 10.1063/1.4756096.

  1. The gas-phase bis-uranyl nitrate complex [(UO2)(2)(NO3)(5)](-): infrared spectrum and structure

    SciTech Connect

    Gary S. Groenewold; Michael J. van Stipdonk; Jos Oomens; Wibe de Jong; Michael E. McIlwain

    2011-12-01

    The infrared spectrum of the bis-uranyl nitrate complex [(UO{sub 2}){sub 2}(NO{sub 3}){sub 5}]{sup -} was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate nu3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex [(UO{sub 2}){sub 2}(NO{sub 3}){sub 5}]{sup -} compared to the mono-complex [UO{sub 2}(NO{sub 3}){sub 3}]{sup -}, as indicated by a higher O-U-O asymmetric stretching (nu3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the {nu}{sub 3} frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The structure was calculated using density functional theory (B3LYP functional), which produced a structure in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  2. The gas-phase bis-uranyl nitrate complex [(UO2)2(NO3)5]-: infrared spectrum and structure

    SciTech Connect

    Groenewold, G. S.; van Stipdonk, Michael J.; Oomens, Jos; De Jong, Wibe A.; McIIwain, Michael E.

    2011-12-01

    The infrared spectrum of the bis-uranyl nitrate complex [(UO2)2(NO3)5]- was measured in the gas phase using multiple photon dissociation (IRMPD). Intense absorptions corresponding to the nitrate symmetric and asymmetric vibrations, and the uranyl asymmetric vibration were observed. The nitrate v3 vibrations indicate the presence of nitrate in a bridging configuration bound to both uranyl cations, and probably two distinct pendant nitrates in the complex. The coordination environment of the nitrate ligands and the uranyl cations were compared to those in the mono-uranyl complex. Overall, the uranyl cation is more loosely coordinated in the bis-uranyl complex [(UO2)2(NO3)5]- compared to the mono-complex [UO2(NO3)3]-, as indicated by a higher O-U-O asymmetric stretching (v3) frequency. However, the pendant nitrate ligands are more strongly bound in the bis-complex than they are in the mono-uranyl complex, as indicated by the v3 frequencies of the pendant nitrate, which are split into nitrosyl and O-N-O vibrations as a result of bidentate coordination. These phenomena are consistent with lower electron density donation per uranyl by the nitrate bridging two uranyl centers compared to that of a pendant nitrate in the mono-uranyl complex. The lowest energy structure predicted by density functional theory (B3LYP functional) calculations was one in which the two uranyl molecules bridged by a single nitrate coordinated in a bis-bidentate fashion. Each uranyl molecule was coordinated by two pendant nitrate ligands. The corresponding vibrational spectrum was in excellent agreement with the IRMPD measurement, confirming the structural assignment.

  3. The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/

    NASA Technical Reports Server (NTRS)

    Lee, N.; Castleman, A. W., Jr.; Keesee, R. G.

    1980-01-01

    Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.

  4. Proteomic analysis reveals that COP9 signalosome complex subunit 7A (CSN7A) is essential for the phase transition of migratory locust.

    PubMed

    Tong, Xi-Wen; Chen, Bing; Huang, Li-Hua; Feng, Qi-Li; Kang, Le

    2015-01-01

    The migratory locust displays a reversible, density-dependent transition between the two phases of gregaria and solitaria. This phenomenon is a typical kind of behavior plasticity. Here, we report that COP9 signalosome complex subunit 7A (CSN7A) is involved in the regulation of locust phase transition. Firstly, 90 proteins were identified to express differentially between the two phases by quantitative proteomic analysis. Gregaria revealed higher levels in proteins related to structure formation, melanism and energy metabolism, whereas solitaria had more abundant proteins related to digestion, absorption and chemical sensing. Subsequently, ten proteins including CSN7A were found to reveal differential mRNA expression profiles between the two phases. The CSN7A had higher mRNA level in the gregaria as compared with the solitaria, and the mRNA amount in the gregaria decreased remarkably during the 32 h-isolation. However, the mRNA level in the solitaria kept constant during the crowding rearing. Finally and importantly, RNA interference of CSN7A in gregaria resulted in obvious phase transition towards solitaria within 24 h. It suggests that CSN7A plays an essential role in the transition of gregaria towards solitaria in the migratory locust. To our knowledge, it's the first time to report the role of CSN in behavior plasticity of animals. PMID:26212173

  5. Magnetic properties and complex magnetic phase diagram in non-centrosymmetric EuRhGe3 and EuIrGe3 single crystals

    NASA Astrophysics Data System (ADS)

    Maurya, Arvind; Bonville, P.; Kulkarni, R.; Thamizhavel, A.; Dhar, S. K.

    2016-03-01

    We report the magnetic properties of two Eu based compounds, single crystalline EuIrGe3 and EuRhGe3, inferred from magnetisation, electrical transport, heat capacity and 151Eu Mössbauer spectroscopy. These previously known compounds crystallise in the non-centrosymmetric, tetragonal, I4 mm, BaNiSn3-type structure. Single crystals of EuIrGe3 and EuRhGe3 were grown using a high temperature solution growth method using In as flux. EuIrGe3 exhibits two magnetic transition temperatures TN1 = 12.4 K, and TN 2 = 7.3 K, whereas EuRhGe3 presents a single one at TN = 12 K. 151Eu Mössbauer spectra show evidence for a cascade of transitions from paramagnetic to incommensurate amplitude modulated followed by an equal moment phase at lower temperature in EuIrGe3. This latter phase alone occurs in EuRhGe3. In both compounds, the magnetisation measured up to 14 T suggests that the equal moment magnetic phase has a spiral spin arrangement. The field induced reorientations are also well documented in the magnetotransport data. A superzone gap is observed for the current density J ∥ [001], which is enhanced by a transverse magnetic field. The magnetic phase diagram constructed from all the data is complex, revealing the presence of many phases in the H - T space.

  6. A phase-field approach to no-slip boundary conditions in dissipative particle dynamics and other particle models for fluid flow in geometrically complex confined systems.

    PubMed

    Xu, Zhijie; Meakin, Paul

    2009-06-21

    Dissipative particle dynamics (DPD) is an effective mesoscopic particle model with a lower computational cost than molecular dynamics because of the soft potentials that it employs. However, the soft potential is not strong enough to prevent the DPD particles that are used to represent the fluid from penetrating solid boundaries represented by stationary DPD particles. A phase-field variable, phi(x,t), is used to indicate the phase at point x and time t, with a smooth transition from -1 (phase 1) to +1 (phase 2) across the interface. We describe an efficient implementation of no-slip boundary conditions in DPD models that combines solid-liquid particle-particle interactions with reflection at a sharp boundary located with subgrid scale accuracy using the phase field. This approach can be used for arbitrarily complex flow geometries and other similar particle models (such as smoothed particle hydrodynamics), and the validity of the model is demonstrated by DPD simulations of flow in confined systems with various geometries. PMID:19548707

  7. Proteomic analysis reveals that COP9 signalosome complex subunit 7A (CSN7A) is essential for the phase transition of migratory locust

    PubMed Central

    Tong, Xi-Wen; Chen, Bing; Huang, Li-Hua; Feng, Qi-Li; Kang, Le

    2015-01-01

    The migratory locust displays a reversible, density-dependent transition between the two phases of gregaria and solitaria. This phenomenon is a typical kind of behavior plasticity. Here, we report that COP9 signalosome complex subunit 7A (CSN7A) is involved in the regulation of locust phase transition. Firstly, 90 proteins were identified to express differentially between the two phases by quantitative proteomic analysis. Gregaria revealed higher levels in proteins related to structure formation, melanism and energy metabolism, whereas solitaria had more abundant proteins related to digestion, absorption and chemical sensing. Subsequently, ten proteins including CSN7A were found to reveal differential mRNA expression profiles between the two phases. The CSN7A had higher mRNA level in the gregaria as compared with the solitaria, and the mRNA amount in the gregaria decreased remarkably during the 32 h-isolation. However, the mRNA level in the solitaria kept constant during the crowding rearing. Finally and importantly, RNA interference of CSN7A in gregaria resulted in obvious phase transition towards solitaria within 24 h. It suggests that CSN7A plays an essential role in the transition of gregaria towards solitaria in the migratory locust. To our knowledge, it’s the first time to report the role of CSN in behavior plasticity of animals. PMID:26212173

  8. Complex phase compositions in nanostructured coatings as evidenced by photoelectron spectroscopy: The case of Al-Si-N hard coatings

    NASA Astrophysics Data System (ADS)

    Pélisson-Schecker, Aude; Hug, Hans Josef; Patscheider, Jörg

    2010-07-01

    The chemical state evolution of the Al-Si-N thin films at various Si contents is investigated by x-ray photoelectron spectroscopy (XPS). The detailed evolution of the Al 2p, Si 2p, and N 1s photoelectrons line positions and widths are used to identify different chemical environments as the Si content is changed. The results are compared to x-ray diffraction (XRD) data that indicate the formation of a two-phase Al1-xSixN/SiNy composite when the solubility limit of 6 at. % of Si in AlN is exceeded. In contrast to XRD data, no particular effect is observed in the XPS data at the solubility limit of Si. Instead, two compositional regions can be identified that are separated by a distinct change in the evolution of core level binding energy differences and chemical shifts at about 10-15 at. % of Si. This silicon concentration is identified as the onset of the formation of a SiNy intergranular phase that is a few monolayers thick, having a chemical bonding similar to that in bulk silicon nitride. The observed changes in the XPS data coincide well with the structural changes in the material at different silicon contents. The unambiguous identification of phases, especially of minority phases from XPS data, is, however, not possible.

  9. Phase- and shape-controlled synthesis of cadmium hydroxyl chloride microstructures via an ammonia-assisted conversion of 1D CdQCl (Q=quinoline) complex microwires

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Ni, Yonghong; Hong, Jianming

    2013-11-01

    In this paper we reported a NH3·H2O-assisted solvothermal route for successful synthesis of cadmium hydroxyl chlorides (Cdx(OH)yClz) microstructures with different phases and shapes, employing 1D CdQCl (Q=quinoline) complex microwires as the precursor. Experiments contained two processes: firstly, CdQCl complex microwires with 500-600 nm in diameter and several hundreds of micrometers in length were prepared by the complexation between CdCl2·2.5H2O and quinoline at room temperature; then, CdQCl microwires were solvothermally treated at 150 °C for 10 h in the presences of different amounts of NH3·H2O to produce Cdx(OH)yClz microstructures with various phases and shapes. The as-obtained precursor and Cdx(OH)yClz microstructures were characterized by scanning electron microscopy, transmission electron microscopy, Infrared spectrometry and X-ray powder diffraction. Experiments showed that hexagonal Cd(OH)Cl was obtained from water-methanol system, while rhombohedral Cd4(OH)5Cl3 from methanol system. Also, it was found that the shapes of Cdx(OH)yClz could be tuned by the amounts of NH3·H2O. Furthermore, the UV diffuse reflection and photoluminescence spectra of the precursor and Cdx(OH)yClz were also investigated.

  10. Working memory activation of neural networks in the elderly as a function of information processing phase and task complexity.

    PubMed

    Charroud, Céline; Steffener, Jason; Le Bars, Emmanuelle; Deverdun, Jérémy; Bonafe, Alain; Abdennour, Meriem; Portet, Florence; Molino, François; Stern, Yaakov; Ritchie, Karen; Menjot de Champfleur, Nicolas; Akbaraly, Tasnime N

    2015-11-01

    Changes in working memory are sensitive indicators of both normal and pathological brain aging and associated disability. The present study aims to further understanding of working memory in normal aging using a large cohort of healthy elderly in order to examine three separate phases of information processing in relation to changes in task load activation. Using covariance analysis, increasing and decreasing neural activation was observed on fMRI in response to a delayed item recognition task in 337 cognitively healthy elderly persons as part of the CRESCENDO (Cognitive REServe and Clinical ENDOphenotypes) study. During three phases of the task (stimulation, retention, probe), increased activation was observed with increasing task load in bilateral regions of the prefrontal cortex, parietal lobule, cingulate gyrus, insula and in deep gray matter nuclei, suggesting an involvement of central executive and salience networks. Decreased activation associated with increasing task load was observed during the stimulation phase, in bilateral temporal cortex, parietal lobule, cingulate gyrus and prefrontal cortex. This spatial distribution of decreased activation is suggestive of the default mode network. These findings support the hypothesis of an increased activation in salience and central executive networks and a decreased activation in default mode network concomitant to increasing task load. PMID:26456114

  11. [EFFICACY AND SECURITY OF A CONVENTIONAL PROCEDURE OF PLASMAPHERESIS IN COMPLEX OF TREATMENT OF NONBILIARY ACUTE PANCREATITIS IN EARLY PHASE OF THE DISEASE].

    PubMed

    Mishalov, V G; Markulan, L Yu; Matveyev, R M

    2016-02-01

    Abstract Efficacy and security of a plasmapheresis procedure in complex of treatment of nonbiliary acute pancreatitis in early phase of the disease were established, basing on the treatment results analysis in 48 patients. The plasmapheresis results were estimated in accordance to changes revealed in the intoxication leukocytic index (ILI), a general protein (GP) content, general calcium (GC) in the blood plasm and of the activated partial thrombin time (APTHT). Application of plasmapheresis in patients, suffering purulent pancreatitis in the enzymal phase, have guaranteed a staged reduction of ILI by (34.86 ± 1.27)%, the APTHT enhancement from (35.15 ± 0.37) to (52.01 ± 0.62) sec, a trustworthy lowering of the GP by (4.35 ± 0.02) g/L at average and of GC in a blood plasmby (10.45 ± 0.38)%. PMID:27244915

  12. ALS Mutations Disrupt Phase Separation Mediated by α-Helical Structure in the TDP-43 Low-Complexity C-Terminal Domain.

    PubMed

    Conicella, Alexander E; Zerze, Gül H; Mittal, Jeetain; Fawzi, Nicolas L

    2016-09-01

    RNA-binding protein TDP-43 mediates essential RNA processing but forms cytoplasmic neuronal inclusions via its C-terminal domain (CTD) in amyotrophic lateral sclerosis (ALS). It remains unclear if aggregated TDP-43 is neurotoxic and if ∼50 ALS-associated missense mutations in TDP-43 CTD promote aggregation, or if loss of normal function plays a role in disease. Recent work points to the ability of related proteins to assemble into functional phase-separated ribonucleoprotein granules via their structurally disordered prion-like domains. Here, we provide atomic details on the structure and assembly of the low-complexity CTD of TDP-43 into liquid-liquid phase-separated in vitro granules and demonstrate that ALS-associated variants disrupt interactions within granules. Using nuclear magnetic resonance spectroscopy, simulation, and microscopy, we find that a subregion cooperatively but transiently folds into a helix that mediates TDP-43 phase separation. ALS-associated mutations disrupt phase separation by inhibiting interaction and helical stabilization. Therefore, ALS-associated mutations can disrupt TDP-43 interactions, affecting function beyond encouraging aggregation. PMID:27545621

  13. Time- and Space-Resolved SAXS Experiments Inform on Phase Transition Kinetics in Hydrated, Liquid-Crystalline Films of Polyion-Surfactant Ion "Complex Salts".

    PubMed

    Li, Joaquim; Gustavsson, Charlotte; Piculell, Lennart

    2016-05-24

    Detailed time- and space-resolved SAXS experiments show the variation with hydration of liquid crystalline structures in ethanol-cast 5-80 μm thick films of polyion-surfactant ion "complex salts" (CS). The CS were dodecyl- (C12) or hexadecyl- (C16) trimethylammonium surfactants with polyacrylate (DP 25 or 6000) counter-polyions. The experiments were carried out on vertical films in humid air above a movable water bath, so that gradients of hydration were generated, which could rapidly be altered. Scans over different positions along a film, kept fixed relative to the bath, showed that the surfactant aggregates of the various liquid-crystalline CS structures grow in cross-sectional area with decreasing hydration. This behavior is attributed to the low water content. Studies of films undergoing rapid dehydration, made possible by the original experimental setup, gave strong evidence that some of the investigated systems remain kinetically trapped for minutes in a nonequilibrium Pm3n micellar cubic phase before switching to the equilibrium P6mm 2D hexagonal phase. Both the length of the polyion and the length of the surfactant hydrocarbon "tail" affect the kinetics of the phase transition. The slowness of the cubic-to-hexagonal structural transition is attributed to the fact that it requires major rearrangements of the polyions and surfactant ions relative to each other. By contrast, other structure changes, such as between the hexagonal and rectangular phases, were observed to occur much more rapidly. PMID:27153140

  14. Optical heterodyning of the phase-tuned femtosecond optical Kerr gate signal for the determination of complex third-order susceptibilities

    NASA Astrophysics Data System (ADS)

    Orczyk, M. E.; Samoc, M.; Swiatkiewicz, J.; Manickam, N.; Tomoaia-Cotisel, M.; Prasad, P. N.

    1992-06-01

    It is shown that ultrafast optically stimulated birefringence and dichroism may be conveniently investigated by combining polarization sensitive optically heterodyned detection with phase tune-up between the optical Kerr gate signal and the local oscillator. The real and the imaginary parts of complex third-order optical nonlinearity can be effectively separated and their values and signs determined. 60 fs pulses at 620 nm were used in experiments carried on tetrahydrofuran solutions of canthaxanthin, a carotenoid important for photobiology. The values of both parts of the complex second hyperpolarizability gamma as well as the sign of its real part determined by this method compare well with that obtained from the concentration dependence method employing the homodyne-detection optical Kerr gate technique.

  15. Complexation-flocculation combined with microwave-assisted headspace solid-phase microextraction in determining the binding constants of hydrophobic organic pollutants to dissolved humic substances.

    PubMed

    Hsieh, Ping-Chieh; Lee, Chon-Lin; Jen, Jen-Fon; Chang, Kuei-Chen

    2015-02-21

    The binding constants, KDOC, of selected polycyclic aromatic hydrocarbons (PAHs)-phenanthrene, anthracene, fluoranthene, and pyrene-to dissolved humic substances (DHS) were determined by complexation-flocculation combined with microwave-assisted headspace solid-phase microextraction (CF-MA-HS-SPME). The results obtained are comparable with KDOC data reported in the literature. No disruption of the PAH to DHS binding equilibrium was observed during the complexation-flocculation process. The present study, which is the first to determine KDOC by CF-MA-HS-SPME, provides an alternative approach to determine the KDOC of PAHs. CF-MA-HS-SPME provides some advantages over other methods, such as no limitation of fluorescent compounds, greater determination speed, and the capability of measuring various compounds simultaneously. PMID:25568896

  16. Epitope mapping of 7S cashew antigen in complex with antibody by solution-phase H/D exchange monitored by FT-ICR mass spectrometry.

    PubMed

    Guan, Xiaoyan; Noble, Kyle A; Tao, Yeqing; Roux, Kenneth H; Sathe, Shridhar K; Young, Nicolas L; Marshall, Alan G

    2015-06-01

    The potential epitope of a recombinant food allergen protein, cashew Ana o 1, reactive to monoclonal antibody, mAb 2G4, has been mapped by solution-phase amide backbone H/D exchange (HDX) monitored by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Purified mAb 2G4 was incubated with recombinant Ana o 1 (rAna o 1) to form antigen:monoclonal antibody (Ag:mAb) complexes. Complexed and uncomplexed (free) rAna o 1 were then subjected to HDX-MS analysis. Five regions protected from H/D exchange upon mAb binding are identified as potential conformational epitope-contributing segments. PMID:26169135

  17. Gas-phase reactions of molecular oxygen with uranyl(V) anionic complexes-synthesis and characterization of new superoxides of uranyl(VI).

    PubMed

    Lucena, Ana F; Carretas, José M; Marçalo, Joaquim; Michelini, Maria C; Gong, Yu; Gibson, John K

    2015-04-16

    Gas-phase complexes of uranyl(V) ligated to anions X(-) (X = F, Cl, Br, I, OH, NO3, ClO4, HCO2, CH3CO2, CF3CO2, CH3COS, NCS, N3), [UO2X2](-), were produced by electrospray ionization and reacted with O2 in a quadrupole ion trap mass spectrometer to form uranyl(VI) anionic complexes, [UO2X2(O2)](-), comprising a superoxo ligand. The comparative rates for the oxidation reactions were measured, ranging from relatively fast [UO2(OH)2](-) to slow [UO2I2](-). The reaction rates of [UO2X2](-) ions containing polyatomic ligands were significantly faster than those containing the monatomic halogens, which can be attributed to the greater number of vibrational degrees of freedom in the polyatomic ligands to dissipate the energy of the initial O2-association complexes. The effect of the basicity of the X(-) ligands was also apparent in the relative rates for O2 addition, with a general correlation between increasing ligand basicity and O2-addition efficiency for polyatomic ligands. Collision-induced dissociation of the superoxo complexes showed in all cases loss of O2 to form the [UO2X2](-) anions, indicating weaker binding of the O2(-) ligand compared to the X(-) ligands. Density functional theory computations of the structures and energetics of selected species are in accord with the experimental observations. PMID:25807358

  18. Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric datasets

    NASA Astrophysics Data System (ADS)

    Wyche, K. P.; Monks, P. S.; Smallbone, K. L.; Hamilton, J. F.; Alfarra, M. R.; Rickard, A. R.; McFiggans, G. B.; Jenkin, M. E.; Bloss, W. J.; Ryan, A. C.; Hewitt, C. N.; MacKenzie, A. R.

    2015-01-01

    Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modeling in order, ultimately, to identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least squares-discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Furthermore, a holistic view of results across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidized gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be

  19. Mapping gas-phase organic reactivity and concomitant secondary organic aerosol formation: chemometric dimension reduction techniques for the deconvolution of complex atmospheric data sets

    NASA Astrophysics Data System (ADS)

    Wyche, K. P.; Monks, P. S.; Smallbone, K. L.; Hamilton, J. F.; Alfarra, M. R.; Rickard, A. R.; McFiggans, G. B.; Jenkin, M. E.; Bloss, W. J.; Ryan, A. C.; Hewitt, C. N.; MacKenzie, A. R.

    2015-07-01

    Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i

  20. Determination of vanadium as 4-(2-pyridylazo)resorcinol-hydrogen peroxide ternary complexes by ion-interaction reversed-phase liquid chromatography.

    PubMed

    Vachirapatama, Narumol; Dicinoski, Greg W; Townsend, Ashley T; Haddad, Paul R

    2002-05-17

    The separation and determination of the vanadium(V) ternary complex formed with 4-(2-pyridylazo)resorcinol (PAR) and hydrogen peroxide using ion-interaction reversed-phase high-performance liquid chromatography on a C18 column has been investigated. The optimal mobile phase was a methanol-water solution (32:68, v/v) containing 3 mM tetrabutylammonium bromide, 5 mM acetic acid and 5 mM citrate buffer at pH 7, with absorbance detection at 540 nm. The stoichiometry of the ternary complex of vanadium at pH 6 in 10 mM acetate buffer using the mole ratio and Job's method by HPLC indicated that the mole ratio of V(V):PAR:H2O2 was 1:1:1. The optimal conditions for precolumn formation of the ternary complex were 10 mM acetate, 7 mM H2O2, 0.3 mM PAR, and pH 6. The method gave relative standard deviations of retention time, peak area and peak height for the ternary complex of 0.187, 0.45 and 0.57%, respectively. The detection limit (at a signal-to-noise ratio of 3) for V(V) was 0.09 ng/ml in the digested sample using a 100-microl injection loop (or 0.09 microg/g in the solid fertiliser sample). The method was applied to the analysis of fertilisers (phosphate rocks and nitrogen, phosphorus and potassium fertiliser). The results for vanadium obtained by the HPLC method agreed well with those from magnetic sector inductively coupled plasma MS analysis. PMID:12108654

  1. Experimental and numerical investigation of shock wave propagation through complex geometry, gas continuous, two-phase media

    SciTech Connect

    Liu, J. Chien-Chih

    1993-10-01

    The work presented here investigates the phenomenon of shock wave propagation in gas continuous, two-phase media. The motivation for this work stems from the need to understand blast venting consequences in the HYLIFE inertial confinement fusion (ICF) reactor. The HYLIFE concept utilizes lasers or heavy ion beams to rapidly heat and compress D-T targets injected into the center of a reactor chamber. A segmented blanket of failing molten lithium or Li{sub 2}BeF{sub 4} (Flibe) jets encircles the reactors central cavity, shielding the reactor structure from radiation damage, absorbing the fusion energy, and breeding more tritium fuel.

  2. Tailoring the physical properties of Ni-based single-phase equiatomic alloys by modifying the chemical complexity

    NASA Astrophysics Data System (ADS)

    Jin, K.; Sales, B. C.; Stocks, G. M.; Samolyuk, G. D.; Daene, M.; Weber, W. J.; Zhang, Y.; Bei, H.

    2016-02-01

    Equiatomic alloys (e.g. high entropy alloys) have recently attracted considerable interest due to their exceptional properties, which might be closely related to their extreme disorder induced by the chemical complexity. In order to understand the effects of chemical complexity on their fundamental physical properties, a family of (eight) Ni-based, face-center-cubic (FCC), equiatomic alloys, extending from elemental Ni to quinary high entropy alloys, has been synthesized, and their electrical, thermal, and magnetic properties are systematically investigated in the range of 4-300 K by combining experiments with ab initio Korring-Kohn-Rostoker coherent-potential-approximation (KKR-CPA) calculations. The scattering of electrons is significantly increased due to the chemical (especially magnetic) disorder. It has weak correlation with the number of elements but strongly depends on the type of elements. Thermal conductivities of the alloys are largely lower than pure metals, primarily because the high electrical resistivity suppresses the electronic thermal conductivity. The temperature dependence of the electrical and thermal transport properties is further discussed, and the magnetization of five alloys containing three or more elements is measured in magnetic fields up to 4 T.

  3. Tailoring the physical properties of Ni-based single-phase equiatomic alloys by modifying the chemical complexity

    DOE PAGESBeta

    Jin, Ke; Sales, Brian C.; Stocks, George Malcolm; Samolyuk, German D.; Daene, Markus; Weber, William J.; Zhang, Yanwen; Bei, Hongbin

    2016-02-01

    We discovered that equiatomic alloys (e.g. high entropy alloys) have recently attracted considerable interest due to their exceptional properties, which might be closely related to their extreme disorder induced by the chemical complexity. To understand the effects of chemical complexity on their fundamental physical properties, a family of (eight) Ni-based, face-center-cubic (FCC), equiatomic alloys, extending from elemental Ni to quinary high entropy alloys, has been synthesized, and their electrical, thermal, and magnetic properties are systematically investigated in the range of 4–300 K by combining experiments with ab initio Korring-Kohn-Rostoker coherent-potential-approximation (KKR-CPA) calculations. The scattering of electrons is significantly increased duemore » to the chemical (especially magnetic) disorder. It has weak correlation with the number of elements but strongly depends on the type of elements. Thermal conductivities of the alloys are largely lower than pure metals, primarily because the high electrical resistivity suppresses the electronic thermal conductivity. Moreover, the temperature dependence of the electrical and thermal transport properties is further discussed, and the magnetization of five alloys containing three or more elements is measured in magnetic fields up to 4 T.« less

  4. Tailoring the physical properties of Ni-based single-phase equiatomic alloys by modifying the chemical complexity

    PubMed Central

    Jin, K.; Sales, B. C.; Stocks, G. M.; Samolyuk, G. D.; Daene, M.; Weber, W. J.; Zhang, Y.; Bei, H.

    2016-01-01

    Equiatomic alloys (e.g. high entropy alloys) have recently attracted considerable interest due to their exceptional properties, which might be closely related to their extreme disorder induced by the chemical complexity. In order to understand the effects of chemical complexity on their fundamental physical properties, a family of (eight) Ni-based, face-center-cubic (FCC), equiatomic alloys, extending from elemental Ni to quinary high entropy alloys, has been synthesized, and their electrical, thermal, and magnetic properties are systematically investigated in the range of 4–300 K by combining experiments with ab initio Korring-Kohn-Rostoker coherent-potential-approximation (KKR-CPA) calculations. The scattering of electrons is significantly increased due to the chemical (especially magnetic) disorder. It has weak correlation with the number of elements but strongly depends on the type of elements. Thermal conductivities of the alloys are largely lower than pure metals, primarily because the high electrical resistivity suppresses the electronic thermal conductivity. The temperature dependence of the electrical and thermal transport properties is further discussed, and the magnetization of five alloys containing three or more elements is measured in magnetic fields up to 4 T. PMID:26832223

  5. Influence of a recent Transition Model on Complex Nonsteady Boundary Layer Flows with Dynamic Stall and Multiple Phases

    NASA Astrophysics Data System (ADS)

    Lavely, Adam; Kinzel, Michael; Vijayakumar, Ganesh; Brasseur, James; Paterson, Eric; Lindau, Jules

    2010-11-01

    Computational fluid dynamics (CFD) simulations are prone to inaccuracies associated with incorrectly formulated physical models. Common in CFD is the spurious treatment as locally laminar flow regions as turbulent, resulting in incorrect turbulent-boundary-layer profiles, separated-flow behavior, and local skin-friction coefficients. The combined effects impacts global measures like drag, lift coefficient, and wake intensity. Recently, Menter & Langtry (AIAA 47 2009) developed a transition model applicable to unsteady three-dimensional CFD codes that shows promise to improve the prediction of local laminar regions. Our aim is to evaluate the accuracy of this model with the additional complexities of unsteady flow around rotating wind turbine blades and multiphase flows using codes designed within OpenFOAM. We investigate how transition and locally laminar flow regions impact various complex problems of interest including: (1) stationary S809 airfoil through stall, (2) an oscillating S809 airfoil in dynamic stall, and (3) a ventilated gaseous cavity in a liquid flow. We will evaluate the efficacy of the model by comparing with experimental results, and shall evaluate the impact on integral measures and flow details. Supported by NSF & DOE.

  6. High-energy collision-activated and electron-transfer dissociation of gas-phase complexes of tryptophan with Na+, K+, and Ca2+

    NASA Astrophysics Data System (ADS)

    Fujihara, Akimasa; Sha, Yuki; Matsuo, Sou; Toyoda, Michisato; Hayakawa, Shigeo

    2014-10-01

    The structure and reactivity of gas-phase complexes of tryptophan (Trp) with Na+, K+, and Ca2+ were examined by high-energy collision-activated dissociation (CAD) and electron transfer dissociation (ETD) using alkali metal targets. In the CAD spectra of M+Trp (M = Na and K), neutral Trp loss was the primary dissociation pathway, and the product ion of collision-induced intracomplex electron transfer from the indole π ring of Trp to the alkali metal ion was observed, indicating a charge-solvated structure in which Trp is non-zwitterionic. The NH3 loss observed in the CAD spectrum of Ca2+Trp2 is ascribed to a CZ (mixed charge-solvated/zwitterionic)-type structure, in which one Trp is non-zwitterionic and the other Trp adopts a zwitterionic structure with an NH3+ moiety. The H atom and NH3 losses observed in the ETD spectrum of Ca2+Trp2 indicate the formation of a hypervalent radical in the complex, R-NH3, via electron transfer from the alkali metal target to the NH3+ group of the CZ-type structure. Ca2+ attachment to Trp cluster induces the zwitterionic structure of Trp in the gas phase, and an electron transfer to the zwitterionic Trp forms the hypervalent radical as a reaction intermediate.

  7. Coupling solid-phase microextraction with ambient mass spectrometry using surface coated wooden-tip probe for rapid analysis of ultra trace perfluorinated compounds in complex samples.

    PubMed

    Deng, Jiewei; Yang, Yunyun; Fang, Ling; Lin, Li; Zhou, Haiyun; Luan, Tiangang

    2014-11-18

    Coupling solid-phase microextraction (SPME) with ambient mass spectrometry using surface coated wooden-tip probe was achieved for the first time and applied in the analysis of ultra trace perfluorinated compounds (PFCs) in complex environmental and biological samples. We modified n-octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride on the surface of sharp wooden tip via silanization to form a novel SPME probe, which was then used for highly selective enrichment of PFCs from complex matrices and applied as a solid substrate to induce electrospray ionization for mass spectrometric analysis. The porous structural surface together with the dual extraction mechanisms (reversed phase adsorption and ion exchange adsorption) demonstrated that the SPME probe has an outstanding enrichment capacity, enhancing sensitivity by approximately 4000-8000 folds for the detection in aqueous samples, and 100-500-fold in whole blood and milk samples. The method showed good linearity, with correlation coefficient values (r(2)) of no less than 0.9931 for eight target PFCs. The limits of detection and qualification of the eight PFCs were 0.06-0.59 and 0.21-1.98 ng/L, respectively. Quantification of real samples was achieved by isotope internal standard calibration curve method or isotope dilution method, and ultratrace levels of PFCs present in lake water, river water, whole blood, and milk samples had been successfully detected and qualified. PMID:25354323

  8. Flow-injection in-line complexation for ion-pair reversed phase high performance liquid chromatography of some metal-4-(2-pyridylazo) resorcinol chelates.

    PubMed

    Srijaranai, Supalax; Chanpaka, Saiphon; Kukusamude, Chutima; Grudpan, Kate

    2006-02-28

    Flow injection (FI) was coupled to ion-pair reversed phase high performance liquid chromatography (IP-RPHPLC) for the simultaneous analysis of some metal-4-(2-pyridylazo) resorcinol (PAR) chelates. A simple reverse flow injection (rFI) set-up was used for in-line complexation of metal-PAR chelates prior to their separation by IP-RPHPLC. The rFI conditions were: injection volume of PAR 85muL, flow rate of metal stream 4.5mLmin(-1), concentration of PAR 1.8x10(-4)molL(-1) and the mixing coil length of 150cm. IP-RPHPLC was carried out using a C(18)muBondapak column with the mobile phase containing 37% acetonitrile, 3.0mmolL(-1) acetate buffer pH 6.0 and 6.2mmolL(-1) tetrabutylammonium bromide (TBABr) at a flow rate of 1.0mLmin(-1) and visible detection at 530 and 440nm. The analysis cycle including in-line complexation and separation by IP-RPHPLC was 16min, which able to separate Cr(VI) and the PAR chelates of Co(II), Ni(II) and Cu(II). PMID:18970520

  9. Vibrational Spectroscopy of Mass-Selected [UO₂(ligand)n]²⁺ Complexes in the Gas Phase: Comparison with Theory

    SciTech Connect

    Groenewold, G. S.; Gianotto, Anita K.; Cossel, Kevin C.; Van Stipdonk, Michael J.; Moore, David T.; Polfer, Nick; Oomens, Jos; De Jong, Wibe A.; Visscher, Lucas

    2006-03-18

    The gas-phase infrared spectra of discrete uranyl ([UO₂]²⁺) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch, and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm⁻¹ for [UO₂(CH₃COCH₃)₂]²⁺ and was systematically red shifted to 1000 and 988 cm⁻¹ by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from 2 to 4, and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO₂(CH₃CN)n]²⁺ complexes, although the magnitude of the red shift in the uranyl frequency upon addition of more acetonitrile ligands was smaller than for acetone, consistent with the more modest nucleophilic nature of acetonitrile. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3 to 6 cm⁻¹.

  10. Pancharatnam-Berry phase optical elements for generation and control of complex light: generalized superelliptical q-plates

    NASA Astrophysics Data System (ADS)

    Piccirillo, Bruno; Kumar, Vijay; Marrucci, Lorenzo; Santamato, E.

    2015-03-01

    We present newly conceived liquid-crystal-based retardation waveplates in which the optic axis distribution has a "superelliptically" symmetric azimuthal structure with a topological charge q superimposed. Such devices, named superelliptical q-plates, act as polarization-to-spatial modes converters that can be used to produce optical beams having peculiar spiral spectra. These spectra reflect the topological charge of the optic axis distribution as well as the symmetry properties of the underlying superellipse. The peculiar capability of q-plates of producing optical modes entangled with respect to spin and orbital angular momentum is here extended to superelliptical q-plates in order to create more complex optical modes structurally inseparable with respect to polarization and spatial degrees of freedom. Such superelliptical modes can play a crucial role in studying polarization singularities or to develop polarization metrology.

  11. Micro-scale Complexity in Iron-Sulfide Phases in Precambrian Sedimentary Rocks Determined by Synchrotron Microprobe Spectroscopy

    NASA Astrophysics Data System (ADS)

    Webb, S.; Johnson, J. E.; Slotznick, S. P.; Roach, C.; Fischer, W. W.

    2014-12-01

    The record of sedimentary pyrite forms the foundation for most isotope records working to define the coupled evolution and behavior of the ancient iron and sulfur cycles. In order to assess the strengths and limitations of records derived from pyrite-rich rocks (e.g. iron speciation, sulfur isotope ratios), we need to understand more about the processes that form and alter sedimentary pyrite. From samples of the Archean/early Proterozoic Transvaal and middle Proterozoic Belt Supergroups, petrography reveals that what might operationally be called sedimentary pyrite has complex textures that hint at a rich process history of sulfur mineralization. A common limitation of virtually all proxy measurements employed to date is that they operate on 'bulk' samples, typically gram-sized or larger pieces. As such, they lose the ability to relate geochemistry to petrography at the scale of mineral grains. Many of the sedimentary pyrites in the Transvaal Supergroup exhibit complex redox and electronic structures of S and Fe, with crystals of pyrite, pyrrhotite, and sulfate-bearing minerals throughout. Parallel application of multiple techniques on the same samples across micron bases spatial scales, provide an opportunity to diagnose issues resulting from post-depositional alteration of sedimentary rocks. We have integrated light and electron microscopy for petrography, electron microprobe and synchrotron XRF for elemental composition, synchrotron X-ray spectroscopy for redox and chemical state, and secondary ion mass spectrometry (SIMS) for isotopic composition. The coupling of these tools allows in essence "images" of the proxy data at the micrometer scale, giving a wide array of textural and mineralogical information designed to inform and untangle the complicated histories of these early Precambrian rocks.

  12. A systematic procedure to build a relaxed dense-phase atomistic representation of a complex amorphous polymer using a coarse-grained modeling approach

    PubMed Central

    Li, Xianfeng; Latour, Robert A.

    2009-01-01

    A systematic procedure has been developed to construct a relaxed dense-phase atomistic structure of a complex amorphous polymer. The numerical procedure consists of (1) coarse graining the atomistic model of the polymer into a mesoscopic model based on an iterative algorithm for potential inversion from distribution functions of the atomistic model, (2) relaxation of the coarse grained chain using a molecular dynamics scheme, and (3) recovery of the atomistic structure by reverse mapping based on the superposition of atomistic counterparts on the corresponding coarse grained coordinates. These methods are demonstrated by their application to construct a relaxed, dense-phase model of poly(DTB succinate), which is an amorphous tyrosine-derived biodegradable polymer that is being developed for biomedical applications. Both static and dynamic properties from the coarse-grained and atomistic simulations are analyzed and compared. The coarse-grained model, which contains the essential features of the DTB succinate structure, successfully described both local and global structural properties of the atomistic chain. The effective speedup compared to the corresponding atomistic simulation is substantially above 102, thus enabling simulation times to reach well into the characteristic experimental regime. The computational approach for reversibly bridging between coarse-grained and atomistic models provides an efficient method to produce relaxed dense-phase all-atom molecular models of complex amorphous polymers that can subsequently be used to study and predict the atomistic-level behavior of the polymer under different environmental conditions in order to optimally design polymers for targeted applications. PMID:20161121

  13. Direct observation of the phase space footprint of a painting injection in the Rapid Cycling Synchrotron at the Japan Proton Accelerator Research Complex

    NASA Astrophysics Data System (ADS)

    Saha, P. K.; Shobuda, Y.; Hotchi, H.; Hayashi, N.; Takayanagi, T.; Harada, H.; Irie, Y.

    2009-04-01

    The 3 GeV Rapid Cycling Synchrotron (RCS) at Japan Proton Accelerator Research Complex is nearly at the operational stage with regard to the beam commissioning aspects. Recently, the design painting injection study has been commenced with the aim of high output beam power at the extraction. In order to observe the phase space footprint of the painting injection, a method was developed utilizing a beam position monitor (BPM) in the so-called single pass mode. The turn-by-turn phase space coordinates of the circulating beam directly measured using a pair of BPMs entirely positioned in drift space, and the calculated transfer matrices from the injection point to the pair of BPMs with several successive turns were used together in order to obtain the phase space footprint of the painting injection. There are two such pairs of BPMs placed in two different locations in the RCS, the results from which both agreed and were quite consistent with what was expected.

  14. Nano-scale imaging and spectroscopy of plasmonic systems, thermal near-fields, and phase separation in complex oxides

    NASA Astrophysics Data System (ADS)

    Jones, Andrew C.

    -rods. Strong spatial field variation on lengths scales as short as 20 nm is observed associated with the dipolar and quadrupolar modes of both systems with details sensitively depending on the nanoparticle structure and environment. In light of recent publications predicting distinct spectral characteristics of thermal electromagnetic near-fields, I demonstrate the extension of s-SNOM techniques through the implementation of a heated atomic force microscope (AFM) tip acting as its own intrinsic light source for the characterization of thermal near-fields. Here, I detail the spectrally distinct and orders of magnitude enhanced resonant spectral near-field energy density associated with vibrational, phonon, and phonon-polariton modes. Modeling the thermal light scattering by the AFM, the scattering cross-section for thermal light may be related to the electromagnetic local density of states (EM-LDOS) above a surface. Lastly, the unique capability of s-SNOM techniques to characterize phase separation phenomena in correlated electron systems is discussed. This measurement capability provides new microscopic insight into the underlying mechanisms of the rich phase transition behavior exhibited by these materials. As a specific example, the infrared s-SNOM mapping of the metal-insulator transition and the associated nano-domain formation in individual VO2 micro-crystals subject to substrate stress is presented. Our results have important implications for the interpretation of the investigations of conventional polycrystalline thin films where the mutual interaction of constituent crystallites may affect the nature of phase separation processes.

  15. Self-Assembly of Nanostructured, Complex, Multi-cation Films via Spontaneous Phase Separation and Strain-driven Ordering

    SciTech Connect

    Goyal, Amit; Wee, Sung Hun; Stocks, George Malcolm; Zuev, Yuri L; More, Karren Leslie; Meng, Jianyong; Zhong, Jianxin

    2013-01-01

    Spontaneous self-assembly of a multi-cation nanophase in another multi-cation matrix phase is a promising bottom-up approach to fabricate novel, nanocomposite structures for a range of applications. In an effort to understand the mechanisms for such self-assembly, we report on complimentary experimental and theoretical studies to first understand and then control or guide the self-assembly of insulating BaZrO3 (BZO) nanodots within REBa2Cu3O7- (RE=rare earth elements including Y, REBCO) superconducting films. It was determined that the strain field developed around BZO nanodots embedded in REBCO matrix is a key driving force dictating the self-assembly of BZO nanodots along REBCO c-axis. The size selection and spatial ordering of BZO self-assembly were simulated using thermodynamic and kinetic models. The BZO self-assembly was controllable by tuning the interphase strain field. REBCO superconducting films with BZO defects arrays self-assembled to align in both vertical (REBCO c-axis) and horizontal (REBCO ab-planes) directions, resulted in the maximized pinning and Jc performance for all field angles with smaller angular Jc anisotropy. The work has broad implications for fabrication of controlled self-assembled nanostructures for a range of applications via strain-tuning.

  16. Seeing Below the Drop: Direct Nano-to-microscale Imaging of Complex Interfaces involving Solid, Liquid, and Gas Phases

    NASA Astrophysics Data System (ADS)

    Rykaczewski, Konrad; Landin, Trevan; Walker, Marlon L.; Scott, John Henry J.; Varanasi, Kripa K.

    2012-11-01

    Nanostructured surfaces with special wetting properties have the potential to transform number of industries, including power generation, water desalination, gas and oil production, and microelectronics thermal management. Predicting the wetting properties of these surfaces requires detailed knowledge of the geometry and the composition of the contact volume linking the droplet to the underlying substrate. Surprisingly, a general nano-to-microscale method for direct imaging of such interfaces has previously not been developed. Here we introduce a three dimensional imaging method which resolves this one-hundred-year-old metrology gap in wetting research. Specifically, we demonstrate direct nano-to-microscale imaging of complex fluidic interfaces using cryofixation in combination with cryo-FIB/SEM. We show that application of this method yields previously unattainable quantitative information about the interfacial geometry of water condensed on silicon nanowire forests with hydrophilic and hydrophobic surface termination in the presence or absence of an intermediate water repelling oil. We also discuss imaging artifacts and the advantages of secondary and backscatter electron imaging, Energy Dispersive Spectrometry (EDS), and three dimensional FIB/SEM tomography.

  17. Characterization of solid-phase extraction of Fe(III) by unloaded polyurethane foam as thiocyanate complex.

    PubMed

    de Almeida, Gil Nunes; de Sousa, Leandro M; Pereira Netto, Annibal D; Cassella, Ricardo J

    2007-11-01

    This work presents a detailed study about the adsorption of iron(III)-thiocyanate complexes onto unloaded polyether-type polyurethane foam (PUF). A novel strategy was employed for this purpose, utilizing the adjustment of the plug cylinder of PUF to the arm of an overhead stirrer. The system was characterized in relation to equilibrium and kinetic aspects and it was modeled by applying Langmuir and Freundlich isotherms. The results obtained showed that adsorption occurs on a monolayer and that external transport of the solute from solution to adsorbent was the rate-determining mechanism. A maximum adsorption capacity of 2.06 x 10(-4) mol Fe g(-1) was obtained under established experimental conditions (0.5 mol L(-1) SCN(-) and 0.005 mol L(-1) HCl). Sequential extraction experiments were carried out by changing PUF in time intervals previously defined (5, 20, and 40 min), and the obtained results showed that it is possible to remove around 95% of the Fe(III) in solution through five consecutive extractions of 5 min with five 200 mg PUF cylinders. PMID:17662992

  18. The mucoid switch in Pseudomonas aeruginosa represses quorum sensing systems and leads to complex changes to stationary phase virulence factor regulation.

    PubMed

    Ryall, Ben; Carrara, Marta; Zlosnik, James E A; Behrends, Volker; Lee, Xiaoyun; Wong, Zhen; Lougheed, Kathryn E; Williams, Huw D

    2014-01-01

    The opportunistic pathogen Pseudomonas aeruginosa chronically infects the airways of Cystic Fibrosis (CF) patients during which it adapts and undergoes clonal expansion within the lung. It commonly acquires inactivating mutations of the anti-sigma factor MucA leading to a mucoid phenotype, caused by excessive production of the extracellular polysaccharide alginate that is associated with a decline in lung function. Alginate production is believed to be the key benefit of mucA mutations to the bacterium in the CF lung. A phenotypic and gene expression characterisation of the stationary phase physiology of mucA22 mutants demonstrated complex and subtle changes in virulence factor production, including cyanide and pyocyanin, that results in their down-regulation upon entry into stationary phase but, (and in contrast to wildtype strains) continued production in prolonged stationary phase. These findings may have consequences for chronic infection if mucoid P. aeruginosa were to continue to make virulence factors under non-growing conditions during infection. These changes resulted in part from a severe down-regulation of both AHL-and AQ (PQS)-dependent quorum sensing systems. In trans expression of the cAMP-dependent transcription factor Vfr restored both quorum sensing defects and virulence factor production in early stationary phase. Our findings have implications for understanding the evolution of P. aeruginosa during CF lung infection and it demonstrates that mucA22 mutation provides a second mechanism, in addition to the commonly occurring lasR mutations, of down-regulating quorum sensing during chronic infection this may provide a selection pressure for the mucoid switch in the CF lung. PMID:24852379

  19. The Mucoid Switch in Pseudomonas aeruginosa Represses Quorum Sensing Systems and Leads to Complex Changes to Stationary Phase Virulence Factor Regulation

    PubMed Central

    Ryall, Ben; Carrara, Marta; Zlosnik, James E. A.; Behrends, Volker; Lee, Xiaoyun; Wong, Zhen; Lougheed, Kathryn E.; Williams, Huw D.

    2014-01-01

    The opportunistic pathogen Pseudomonas aeruginosa chronically infects the airways of Cystic Fibrosis (CF) patients during which it adapts and undergoes clonal expansion within the lung. It commonly acquires inactivating mutations of the anti-sigma factor MucA leading to a mucoid phenotype, caused by excessive production of the extracellular polysaccharide alginate that is associated with a decline in lung function. Alginate production is believed to be the key benefit of mucA mutations to the bacterium in the CF lung. A phenotypic and gene expression characterisation of the stationary phase physiology of mucA22 mutants demonstrated complex and subtle changes in virulence factor production, including cyanide and pyocyanin, that results in their down-regulation upon entry into stationary phase but, (and in contrast to wildtype strains) continued production in prolonged stationary phase. These findings may have consequences for chronic infection if mucoid P. aeruginosa were to continue to make virulence factors under non-growing conditions during infection. These changes resulted in part from a severe down-regulation of both AHL-and AQ (PQS)-dependent quorum sensing systems. In trans expression of the cAMP-dependent transcription factor Vfr restored both quorum sensing defects and virulence factor production in early stationary phase. Our findings have implications for understanding the evolution of P. aeruginosa during CF lung infection and it demonstrates that mucA22 mutation provides a second mechanism, in addition to the commonly occurring lasR mutations, of down-regulating quorum sensing during chronic infection this may provide a selection pressure for the mucoid switch in the CF lung. PMID:24852379

  20. Advances in Chemical Physics, Volume 130, 2-Volume Set, Geometric Structures of Phase Space in Multi-Dimensional Chaos: Applications to Chemical Reaction Dynamics in Complex Systems

    NASA Astrophysics Data System (ADS)

    Rice, Stuart A.; Toda, Mikito; Komatsuzaki, Tamiki; Konishi, Tetsuro; Berry, R. Stephen

    2005-01-01

    Edited by Nobel Prize winner Ilya Prigogine and renowned authority Stuart A. Rice, the Advances in Chemical Physics series provides a forum for critical, authoritative evaluations in every area of the discipline. In a format that encourages the expression of individual points of view, experts in the field present comprehensive analyses of subjects of interest. Advances in Chemical Physics remains the premier venue for presentations of new findings in its field. Volume 130 consists of three parts including: Part I: Phase Space Geometry of Multi-dimensional Dynamical Systems and Reaction Processes Part II Complex Dynamical Behavior in Clusters and Proteins, and Data Mining to Extract Information on Dynamics Part III New directions in Multi-Dimensional Chaos and Evolutionary Reactions

  1. The petrology of the layered gabbro intrusion, eastern gabbro, Coldwell alkaline complex, Northwestern Ontario, Canada: evidence for multiple phases of intrusion in a ring dyke

    NASA Astrophysics Data System (ADS)

    Shaw, Cliff S. J.

    1997-07-01

    The Coldwell alkaline complex is a large (> 350 km 2) gabbro and syenite intrusion on the north shore of Lake Superior. It was emplaced at 1108 Ma during early magmatic activity associated with the formation of the Mid-Continent Rift of North America. The eastern gabbro forms a partial ring dyke on the outer margin of the complex and consists of at least three discrete intrusions. The largest of these is the layered gabbro that comprises a 300 m thick fine- to medium-grained basal unit overlain by up to 1100 m of variably massive to layered gabbroic cumulates which vary from olivine gabbro to anorthosite. Several xenoliths of Archaean metamorphic rocks that range in size from 10's to 100's of meters are present in the central part of the intrusion. Within discrete horizons in the layered gabbro are many centimeter- to meter-scale, gabbroic xenoliths. The main cumulus minerals, in order of crystallization, are plagioclase, olivine and clinopyroxene ± Fe-Ti oxides. Biotite and Fe-Ti-oxide are the dominant intercumulus phases. Orthopyroxene occurs not as a cumulus phase but as peritectic overgrowths on cumulus olivine. A detailed petrographic and mineral chemical study of samples from two stratigraphically controlled traverses through the layered gabbro indicates that the stratigraphy cannot be correlated along the 33 km strike of the ring dyke. Mineral compositions show both normal and reversed fractionation trends. These patterns are interpreted to record at least three separate intrusions of magma into restricted dilatant zones within the ring dyke possibly associated with ongoing caldera collapse. Calculations of parental melt composition using mineral — melt equilibria show that even the most primitive gabbros crystallized from an evolved magma with mg# of 0.42-0.49. The presence of orthopyroxene overgrowths on cumulus olivine suggests rising silica activity in the melt during crystallization and implies a subalkaline parentage for the layered gabbro.

  2. What do fault patterns reveal about the latest phase of extension within the Northern Snake Range metamorphic core complex, Nevada, USA?

    NASA Astrophysics Data System (ADS)

    Ismat, Zeshan; Riley, Paul; Lerback, Jory

    2016-08-01

    The Northern Snake Range is a classic example of a metamorphic core complex, Basin-and-Range province, United States. It is composed of a plastically deformed footwall and a brittlely deformed hanging wall, separated by the Northern Snake Range low-angle detachment (NSRD). Brittle deformation, however, is not confined to the hanging wall. This paper focuses on exposures in Cove Canyon, located on the SE flank of the Northern Snake Range, where penetrative, homogeneous faults are well exposed throughout the hanging wall, footwall and NSRD, and overprint early plastic deformation. These late-stage fault sets assisted Eocene-Miocene extension. Detailed analysis of the faults reveals the following: (1) The shortening direction defined by faults is similar to the shortening direction defined by the stretching lineation in the footwall mylonites, indicating that the extensional kinematic history remained unchanged as the rocks were uplifted into the elastico-frictional regime. (2) After ∼17 Ma, extension may have continued entirely within elastic-frictional regime via cataclastic flow. (3) This latest deformation phase may have been accommodated by a single, continuous event. (3) Faults within NSRD boudins indicate that deformation within the detachment zone was non-coaxial during the latest phase of extension.

  3. Analysis of 3d complex structure and heterogeneity effects on formation and propagation of regional phases in Eurasia. Final report, 15 August 1992-30 September 1994

    SciTech Connect

    Lay, T.; Wu, R.S.

    1994-12-13

    This document is the final report for this grant to develop new three-dimensional wave propagation techniques for high frequency waves in heterogeneous media. The report is divided into four sections, each being a published paper sponsored by this grant. In the first section we formulate a one-way wide-angle elastic wave propagation method for arbitrarily heterogeneous media in both the space and wavenumber domains using elastic Rayleigh integrals and local elastic Born scattering theory. In the second section this complex phase screen method is compared with fourth-order finite differences and exact eigenfunction expansion calculations for two-dimensional inhomogeneous media to assess the accuracy of the one-way propagation algorithm. In the third section, an observational study of continental margin structure influence on Lg propagation is presented, using data from the former Soviet stations for nuclear explosions at Novaya Zemlya. We find that bathymetric features can be correlated with energy levels of Lg, suggesting that waveguide structure influences regional phase energy partitioning. This idea is pursued in the fourth section, using Eurasian earthquake and nuclear explosion data along with information about the crustal structure in Eurasia. We develop empirical relations that reduce the scatter in the P/Lg discriminant at low frequency.

  4. Morphological and phase evolution of TiO{sub 2} nanocrystals prepared from peroxotitanate complex aqueous solution: Influence of acetic acid

    SciTech Connect

    Chang, Jeong Ah; Vithal, Muga; Baek, In Chan; Seok, Sang Il

    2009-04-15

    Nanosized anatase and rutile TiO{sub 2} having different shape, phase and size have been prepared from aqueous solutions of peroxo titanium complex starting from titanium(IV) isopropoxide (TTIP), acetic acid and hydrogen peroxide (H{sub 2}O{sub 2}) in water/isopropanol media by a facile sol-gel process. The TiO{sub 2} nanocrystals are characterized by powder X-ray diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, TEM, high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) techniques. The influence of pH and the sequence of addition of reaction contents on the phase and morphology of TiO{sub 2} are studied. The reasons for the observation of only anatase and/or mixture of anatase and rutile are given. - Graphical abstract: The morphology of TiO{sub 2} depends on the sequence of addition of AcOH and H{sub 2}O{sub 2} from the system of titanium isopropoxide and acetic acid (AcOH) in the presence of H{sub 2}O{sub 2}.

  5. Solid phase extraction of chromium(VI) from aqueous solutions by adsorption of its diphenylcarbazide complex on a mixed bed adsorbent (acid activated montmorillonite-silica gel) column.

    PubMed

    Rajesh, N; Mishra, Braja Gopal; Pareek, Pawan Kumar

    2008-02-01

    A novel approach has been developed for the solid phase extraction of chromium(VI) based on the adsorption of its diphenylcarbazide complex on a mixture of acid activated montmorillonite (AAM)-silica gel column. The effect of various parameters such as acidity, stability of the column, sample volume, interfering ions, etc., were studied in detail. The adsorbed complex could be easily eluted using polyethylene glycol-sulfuric acid mixture and the concentration of chromium has been determined using visible spectrophotometry. The calibration graph was linear in the range 0-1microgmL(-1) chromium(VI) with a detection limit of 6microgL(-1). A highest preconcentration factor of 25 could be obtained for 250mL sample volume using glass wool as support for the mixed bed adsorbent. Chromium(VI) could be effectively separated from other ions such as nickel, copper, zinc, chloride, sulfate, nitrate, etc., and the method has been successfully applied to study the recovery of chromium in electroplating waste water and spiked water samples. PMID:17604681

  6. Joint NMR and Solid-Phase Microextraction-Gas Chromatography Chemometric Approach for Very Complex Mixtures: Grape and Zone Identification in Wines.

    PubMed

    Martin-Pastor, Manuel; Guitian, Esteban; Riguera, Ricardo

    2016-06-21

    In very complex mixtures, classification by chemometric methods may be limited by the difficulties to extract from the NMR or gas chromatography/mass spectrometry (GC/MS) experimental data information useful for a reliable classification. The joint analysis of both data has showed its superiority in the biomedical field but is scarcely used in foodstuffs and never in wine in spite of the complexity of their spectra and classification. In this article we show that univariate and multivariate principal component analysis-discriminant analysis (PCA-DA) statistics applied to the combined (1)H NMR and solid-phase microextraction-gas chromatography (SPME-GC) data of a collection of 270 wines from Galicia (northwest Spain) allows a discrimination and classification not attainable from the separate data, distinguishing wines from autochthonous and nonautochthonous grapes, mono- from the plurivarietals, and identifying, in part, the geographical subzone of origin of the albariño wines. A general and automatable protocol, based on the signal integration of selected ROIs (regions of interest), is proposed that allows the fast and reliable identification of the grape in Galician wines. PMID:27247992

  7. Solid phase extraction of chromium(VI) from aqueous solutions by adsorption of its diphenylcarbazide complex on a mixed bed adsorbent (acid activated montmorillonite-silica gel) column

    NASA Astrophysics Data System (ADS)

    Rajesh, N.; Mishra, Braja Gopal; Pareek, Pawan Kumar

    2008-02-01

    A novel approach has been developed for the solid phase extraction of chromium(VI) based on the adsorption of its diphenylcarbazide complex on a mixture of acid activated montmorillonite (AAM)-silica gel column. The effect of various parameters such as acidity, stability of the column, sample volume, interfering ions, etc., were studied in detail. The adsorbed complex could be easily eluted using polyethylene glycol-sulfuric acid mixture and the concentration of chromium has been determined using visible spectrophotometry. The calibration graph was linear in the range 0-1 μg mL -1 chromium(VI) with a detection limit of 6 μg L -1. A highest preconcentration factor of 25 could be obtained for 250 mL sample volume using glass wool as support for the mixed bed adsorbent. Chromium(VI) could be effectively separated from other ions such as nickel, copper, zinc, chloride, sulfate, nitrate, etc., and the method has been successfully applied to study the recovery of chromium in electroplating waste water and spiked water samples.

  8. In Bacillus subtilis LutR is part of the global complex regulatory network governing the adaptation to the transition from exponential growth to stationary phase.

    PubMed

    Irigül-Sönmez, Öykü; Köroğlu, Türkan E; Öztürk, Büşra; Kovács, Ákos T; Kuipers, Oscar P; Yazgan-Karataş, Ayten

    2014-02-01

    The lutR gene, encoding a product resembling a GntR-family transcriptional regulator, has previously been identified as a gene required for the production of the dipeptide antibiotic bacilysin in Bacillus subtilis. To understand the broader regulatory roles of LutR in B. subtilis, we studied the genome-wide effects of a lutR null mutation by combining transcriptional profiling studies using DNA microarrays, reverse transcription quantitative PCR, lacZ fusion analyses and gel mobility shift assays. We report that 65 transcriptional units corresponding to 23 mono-cistronic units and 42 operons show altered expression levels in lutR mutant cells, as compared with lutR(+) wild-type cells in early stationary phase. Among these, 11 single genes and 25 operons are likely to be under direct control of LutR. The products of these genes are involved in a variety of physiological processes associated with the onset of stationary phase in B. subtilis, including degradative enzyme production, antibiotic production and resistance, carbohydrate utilization and transport, nitrogen metabolism, phosphate uptake, fatty acid and phospholipid biosynthesis, protein synthesis and translocation, cell-wall metabolism, energy production, transfer of mobile genetic elements, induction of phage-related genes, sporulation, delay of sporulation and cannibalism, and biofilm formation. Furthermore, an electrophoretic mobility shift assay performed in the presence of both SinR and LutR revealed a close overlap between the LutR and SinR targets. Our data also revealed a significant overlap with the AbrB regulon. Together, these findings reveal that LutR is part of the global complex, interconnected regulatory systems governing adaptation of bacteria to the transition from exponential growth to stationary phase. PMID:24196425

  9. A CENP-S/X complex assembles at the centromere in S and G2 phases of the human cell cycle

    PubMed Central

    Dornblut, Carsten; Quinn, Nadine; Monajambashi, Shamci; Prendergast, Lisa; van Vuuren, Chelly; Münch, Sandra; Deng, Wen; Leonhardt, Heinrich; Cardoso, M. Cristina; Hoischen, Christian; Diekmann, Stephan; Sullivan, Kevin F.

    2014-01-01

    The functional identity of centromeres arises from a set of specific nucleoprotein particle subunits of the centromeric chromatin fibre. These include CENP-A and histone H3 nucleosomes and a novel nucleosome-like complex of CENPs -T, -W, -S and -X. Fluorescence cross-correlation spectroscopy and Förster resonance energy transfer (FRET) revealed that human CENP-S and -X exist principally in complex in soluble form and retain proximity when assembled at centromeres. Conditional labelling experiments show that they both assemble de novo during S phase and G2, increasing approximately three- to fourfold in abundance at centromeres. Fluorescence recovery after photobleaching (FRAP) measurements documented steady-state exchange between soluble and assembled pools, with CENP-X exchanging approximately 10 times faster than CENP-S (t1/2 ∼ 10 min versus 120 min). CENP-S binding to sites of DNA damage was quite distinct, with a FRAP half-time of approximately 160 s. Fluorescent two-hybrid analysis identified CENP-T as a uniquely strong CENP-S binding protein and this association was confirmed by FRET, revealing a centromere-bound complex containing CENP-S, CENP-X and CENP-T in proximity to histone H3 but not CENP-A. We propose that deposition of the CENP-T/W/S/X particle reveals a kinetochore-specific chromatin assembly pathway that functions to switch centromeric chromatin to a mitosis-competent state after DNA replication. Centromeres shuttle between CENP-A-rich, replication-competent and H3-CENP-T/W/S/X-rich mitosis-competent compositions in the cell cycle. PMID:24522885

  10. Preliminary construction of integral analysis for characteristic components in complex matrices by in-house fabricated solid-phase microextraction fibers combined with gas chromatography-mass spectrometry.

    PubMed

    Tang, Zhentao; Hou, Wenqian; Liu, Xiuming; Wang, Mingfeng; Duan, Yixiang

    2016-08-26

    Integral analysis plays an important role in study and quality control of substances with complex matrices in our daily life. As the preliminary construction of integral analysis of substances with complex matrices, developing a relatively comprehensive and sensitive methodology might offer more informative and reliable characteristic components. Flavoring mixtures belonging to the representatives of substances with complex matrices have now been widely used in various fields. To better study and control the quality of flavoring mixtures as additives in food industry, an in-house fabricated solid-phase microextraction (SPME) fiber was prepared based on sol-gel technology in this work. The active organic component of the fiber coating was multi-walled carbon nanotubes (MWCNTs) functionalized with hydroxyl-terminated polydimethyldiphenylsiloxane, which integrate the non-polar and polar chains of both materials. In this way, more sensitive extraction capability for a wider range of compounds can be obtained in comparison with commercial SPME fibers. Preliminarily integral analysis of three similar types of samples were realized by the optimized SPME-GC-MS method. With the obtained GC-MS data, a valid and well-fit model was established by partial least square discriminant analysis (PLS-DA) for classification of these samples (R2X=0.661, R2Y=0.996, Q2=0.986). The validity of the model (R2=0.266, Q2=-0.465) has also approved the potential to predict the "belongingness" of new samples. With the PLS-DA and SPSS method, further screening out the markers among three similar batches of samples may be helpful for monitoring and controlling the quality of the flavoring mixtures as additives in food industry. Conversely, the reliability and effectiveness of the GC-MS data has verified the comprehensive and efficient extraction performance of the in-house fabricated fiber. PMID:27457562

  11. Phase transitions and photoinduced transformations at high pressure in the molecular donor-acceptor fullerene complex {Cd(dedtc)2}2 · C60

    NASA Astrophysics Data System (ADS)

    Meletov, K. P.; Konarev, D. V.; Tolstikova, A. O.

    2015-06-01

    The Raman spectra of crystals of C60 fullerene-cadmium diethyldithiocarbamate molecular donor-acceptor complexes {Cd(dedtc)2}2 · C60 were measured at pressures of up to 17 GPa, and the crystal lattice parameters of these complexes were determined at pressures of up to 6 GPa. An increase in pressure up to ˜2 GPa leads to changes in the Raman spectra, which are manifested by splitting of the intramolecular H g (1)- H g (8) phonon modes and by softening of the A g (2) mode of the C60 molecule. A further increase in pressure up to 17 GPa does not induce significant new changes to the Raman spectra, while a decrease is accompanied by the reverse transformation at a pressure of about 2 GPa. The pressure dependence of the lattice parameters also exhibits a reversible feature at 2 GPa related to a jumplike decrease in compressibility. All these data are indicative of a phase transition in the vicinity of 2 GPa related to the formation of covalent bonds between C60 molecules and, probably, the appearance of C120 dimers in fullerene layers. It was also found that, in the pressure interval from 2 to 6.3 GPa, the Raman spectra of complexes exhibit photoinduced transformations under prolonged exposure to laser radiation with a wavelength of λ = 532 nm and power density up to 5000 W/cm2. These changes are manifested by splitting and softening of the A g (2) mode and resemble analogous changes accompanying the photopolymerization of C60 fullerene. The intensity of new bands exhibits exponential growth with increasing exposure time. The photopolymer yield depends on both the laser radiation power and external pressure. The A g (2) mode splitting under irradiation can be related to the formation of photo-oligomers with various numbers of intermolecular covalent bonds per C60 molecule.

  12. Unexpected Spin-Crossover and a Low-Pressure Phase Change in an Iron(II)/Dipyrazolylpyridine Complex Exhibiting a High-Spin Jahn- Teller Distortion.

    PubMed

    Kershaw Cook, Laurence J; Thorp-Greenwood, Flora L; Comyn, Tim P; Cespedes, Oscar; Chastanet, Guillaume; Halcrow, Malcolm A

    2015-07-01

    The synthesis of 4-methyl-2,6-di(pyrazol-1-yl)pyridine (L) and four salts of [FeL2]X2 (X– = BF(4)(–), 1; X– = ClO(4)(–), 2; X– = PF(6)(–), 3; X– = CF3SO(3)(–), 4) are reported. Powder samples of 1 and 2 both exhibit abrupt, hysteretic spin-state transitions on cooling, with T(1/2)↓ = 204 and T(1/2)↑ = 209 K (1), and T(1/2)↓ = 175 and T(1/2)↑ = 193 K (2). The 18 K thermal hysteresis loop for 2 is unusually wide for a complex of this type. Single crystal structures of 2 show it to exhibit a Jahn–Teller-distorted six-coordinate geometry in its high-spin state, which would normally inhibit spin-crossover. Bulk samples of 1 and 2 are isostructural by X-ray powder diffraction, and undergo a crystallographic phase change during their spin-transitions. At temperatures below T(1/2), exposing both compounds to 10(–5) Torr pressure inside the powder diffractometer causes a reversible transformation back to the high-temperature crystal phase. Consideration of thermodynamic data implies this cannot be accompanied by a low → high spin-state change, however. Both compounds also exhibit the LIESST effect, with 2 exhibiting an unusually high T(LIESST) of 112 K. The salts 3 and 4 are respectively high-spin and low-spin between 3 and 300 K, with crystalline 3 exhibiting a more pronounced version of the same Jahn–Teller distortion. PMID:26351707

  13. Unexpected Spin-Crossover and a Low-Pressure Phase Change in an Iron(II)/Dipyrazolylpyridine Complex Exhibiting a High-Spin Jahn-Teller Distortion.

    PubMed

    Kershaw Cook, Laurence J; Thorp-Greenwood, Flora L; Comyn, Tim P; Cespedes, Oscar; Chastanet, Guillaume; Halcrow, Malcolm A

    2015-07-01

    The synthesis of 4-methyl-2,6-di(pyrazol-1-yl)pyridine (L) and four salts of [FeL2]X2 (X(-) = BF4(-), 1; X(-) = ClO4(-), 2; X(-) = PF6(-), 3; X(-) = CF3SO3(-), 4) are reported. Powder samples of 1 and 2 both exhibit abrupt, hysteretic spin-state transitions on cooling, with T1/2↓ = 204 and T1/2↑ = 209 K (1), and T1/2↓ = 175 and T1/2↑ = 193 K (2). The 18 K thermal hysteresis loop for 2 is unusually wide for a complex of this type. Single crystal structures of 2 show it to exhibit a Jahn-Teller-distorted six-coordinate geometry in its high-spin state, which would normally inhibit spin-crossover. Bulk samples of 1 and 2 are isostructural by X-ray powder diffraction, and undergo a crystallographic phase change during their spin-transitions. At temperatures below T1/2, exposing both compounds to 10(-5) Torr pressure inside the powder diffractometer causes a reversible transformation back to the high-temperature crystal phase. Consideration of thermodynamic data implies this cannot be accompanied by a low → high spin-state change, however. Both compounds also exhibit the LIESST effect, with 2 exhibiting an unusually high T(LIESST) of 112 K. The salts 3 and 4 are respectively high-spin and low-spin between 3 and 300 K, with crystalline 3 exhibiting a more pronounced version of the same Jahn-Teller distortion. PMID:26052980

  14. Development of new portable miniaturize solid phase microextraction of silver-APDC complex using micropipette tip in-syringe system couple with electrothermal atomic absorption spectrometry.

    PubMed

    Naeemullah; Kazi, Tasneem Gul; Afridi, Hassan Imran; Shah, Faheem; Arain, Sadaf Sadia; Arain, Salma Aslam; Panhwar, Abdul Haleem; Arain, Mariam Shahzadi; Samoon, Muhammad Kashif

    2016-02-01

    An innovative and simple miniaturized solid phase microextraction (M-SPME) method, was developed for preconcentration and determination of silver(I) in the fresh and waste water samples. For M-SPME, a micropipette tip packed with activated carbon cloth (ACC) as sorbent, in a syringe system. The size, morphology and elemental composition of ACC before and after adsorption of analyte have been characterized by scanning electron microscopy and energy dispersive spectroscopy. The sample solution treated with a complexing reagent, ammonium pyrrolidine dithiocarbamate (APDC), was drawn into the syringe filled with ACC and dispensed manually for 2 to 10 aspirating/dispensing cycle. Then the Ag- complex sorbed on the ACC in micropipette was quantitatively eluted by drawing and dispensing of different concentrations of acids for 2 to 5 aspirating/dispensing cycles. The extracted Ag ions with modifier were injected directly into the electrothermal atomic absorption spectrometry for analysis. The influence of different variables on the extraction efficiency, including the concentration of ligand, pH, sample volume, eluent type, concentration and volume was investigated. Validity and accuracy of the developed method was checked by the standard addition method. Reliability of the proposed methodology was checked by the relative standard deviation (%RSD), which was found to be <5%. Under the optimized experimental variables, the limits of detection (LOD) and enhancement factors (EF), were obtained to be 0.86 ng L(-1) and 120, respectively. The proposed method was successfully applied for the determination of trace levels of silver ions in fresh and waste water samples. PMID:26520476

  15. Development of new portable miniaturize solid phase microextraction of silver-APDC complex using micropipette tip in-syringe system couple with electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Naeemullah; Kazi, Tasneem Gul; Afridi, Hassan Imran; Shah, Faheem; Arain, Sadaf Sadia; Arain, Salma Aslam; Panhwar, Abdul Haleem; Arain, Mariam Shahzadi; Samoon, Muhammad Kashif

    2016-02-01

    An innovative and simple miniaturized solid phase microextraction (M-SPME) method, was developed for preconcentration and determination of silver(I) in the fresh and waste water samples. For M-SPME, a micropipette tip packed with activated carbon cloth (ACC) as sorbent, in a syringe system. The size, morphology and elemental composition of ACC before and after adsorption of analyte have been characterized by scanning electron microscopy and energy dispersive spectroscopy. The sample solution treated with a complexing reagent, ammonium pyrrolidine dithiocarbamate (APDC), was drawn into the syringe filled with ACC and dispensed manually for 2 to 10 aspirating/dispensing cycle. Then the Ag- complex sorbed on the ACC in micropipette was quantitatively eluted by drawing and dispensing of different concentrations of acids for 2 to 5 aspirating/dispensing cycles. The extracted Ag ions with modifier were injected directly into the electrothermal atomic absorption spectrometry for analysis. The influence of different variables on the extraction efficiency, including the concentration of ligand, pH, sample volume, eluent type, concentration and volume was investigated. Validity and accuracy of the developed method was checked by the standard addition method. Reliability of the proposed methodology was checked by the relative standard deviation (%RSD), which was found to be < 5%. Under the optimized experimental variables, the limits of detection (LOD) and enhancement factors (EF), were obtained to be 0.86 ng L- 1 and 120, respectively. The proposed method was successfully applied for the determination of trace levels of silver ions in fresh and waste water samples.

  16. A rapid screening procedure for the analysis of proliferation compounds in complex matrices using solid phase microextraction (SPME) and SPME with in-situ derivatization

    SciTech Connect

    Alcaraz, A.; Hulsey, S.S.; Andresen, B.D.

    1995-12-31

    A variety of methods have been established using advanced chromatographic techniques and new detection systems for the analysis of chemical signatures associated with nuclear and chemical weapon (CW) proliferation. Most of these analytical methods are used in the laboratory and seldom applied in the field. The Chemical Weapons Convention (an international treaty to ban chemical weapons) may require the rapid on-site analysis of environmental samples which contain CW agents, their precursors, and/or their degradation products. In addition to the fact that certain countries are involved in CW non-compliance, there is a current uncertainty regarding nuclear proliferation. This also creates new demands on sample work-up and analytical instrumentation use in the field. The isolation and identification of unique chemical signatures in complex samples such as soils, waste tanks, and decontamination solutions would determine non-compliance. However, a primary area of detection research continues to be sample preparation. Most of the established sample cleanup technologies involve liquid/liquid, Soxhlet, or most recently, solid phase extraction (SPE). Despite the success of these traditional sample preparation techniques, they are time consuming and require multi-step procedures (especially when preparing samples for gas chromatographic mass-spectrometric analysis). The goal of this work is to demonstrate the advantages of utilizing SPME and SPME in-situ derivatization techniques to eliminate time consuming steps necessary to prepare a sample for on-site GC-MS. The authors` approach was to compare two SPME fibers and to develop methods to facilitate the isolation of polar and moderately polar proliferation compounds from complex environmental samples. This work will help to evaluate current SPME technologies for use during on-site environmental monitoring analysis.

  17. A new ion imprinted polymer based on Ru(III)-thiobarbituric acid complex for solid phase extraction of ruthenium(III) prior to its determination by ETAAS.

    PubMed

    Zambrzycka, Elżbieta; Godlewska-Żyłkiewicz, Beata

    2014-01-01

    A new ruthenium ion imprinted polymer was prepared from the Ru(III) 2-thiobarbituric acid complex (the template), methacrylic acid or acrylamide (the functional monomers), and ethylene glycol dimethacrylate (the cross-linking agent) using 2,2'-azobisisobutyronitrile as the radical initiator. The ion imprinted polymer was characterized and used as a selective sorbent for the solid phase extraction of Ru(III) ions. The effects of type of functional monomer, sample volume, solution pH and flow rate on the extraction efficiency were studied in the dynamic mode. Ru(III) ion was quantitatively retained on the sorbents in the pH range from 3.5 to 10, and can be eluted with 4 mol L(-1) aqueous ammonia. The affinity of Ru(III) for the ion imprinted polymer based on the acrylamide monomer is weaker than that for the polymer based on the methacrylic acid monomer, which therefore was used in interference studies and in analytical applications. Following extraction of Ru(III) ions with the imprint and their subsequent elution from the polymer with aqueous ammonia, Ru(III) was detected by electrothermal atomic absorption spectrometry with a detection limit of 0.21 ng mL(-1). The method was successfully applied to the determination of trace amounts of Ru(III) in water, waste, road dust and platinum ore (CRM SARM 76) with a reproducibility (expressed as RSD) below 6.4 %. FigureThe new ion imprinted polymer was prepared and used for the separation of ruthenium from water and most complex environmental samples, such as road dust and platinum ore (CRM SARM 76) prior ETAAS determination. PMID:24966442

  18. Phase transitions and photoinduced transformations at high pressure in the molecular donor-acceptor fullerene complex (Cd(dedtc){sub 2}){sub 2} · C{sub 60}

    SciTech Connect

    Meletov, K. P.; Konarev, D. V.; Tolstikova, A. O.

    2015-06-15

    The Raman spectra of crystals of C{sub 60} fullerene-cadmium diethyldithiocarbamate molecular donor-acceptor complexes (Cd(dedtc){sub 2}){sub 2} · C{sub 60} were measured at pressures of up to 17 GPa, and the crystal lattice parameters of these complexes were determined at pressures of up to 6 GPa. An increase in pressure up to ∼2 GPa leads to changes in the Raman spectra, which are manifested by splitting of the intramolecular H{sub g}(1)-H{sub g}(8) phonon modes and by softening of the A{sub g}(2) mode of the C{sub 60} molecule. A further increase in pressure up to 17 GPa does not induce significant new changes to the Raman spectra, while a decrease is accompanied by the reverse transformation at a pressure of about 2 GPa. The pressure dependence of the lattice parameters also exhibits a reversible feature at 2 GPa related to a jumplike decrease in compressibility. All these data are indicative of a phase transition in the vicinity of 2 GPa related to the formation of covalent bonds between C{sub 60} molecules and, probably, the appearance of C{sub 120} dimers in fullerene layers. It was also found that, in the pressure interval from 2 to 6.3 GPa, the Raman spectra of complexes exhibit photoinduced transformations under prolonged exposure to laser radiation with a wavelength of λ = 532 nm and power density up to 5000 W/cm{sup 2}. These changes are manifested by splitting and softening of the A{sub g}(2) mode and resemble analogous changes accompanying the photopolymerization of C{sub 60} fullerene. The intensity of new bands exhibits exponential growth with increasing exposure time. The photopolymer yield depends on both the laser radiation power and external pressure. The A{sub g}(2) mode splitting under irradiation can be related to the formation of photo-oligomers with various numbers of intermolecular covalent bonds per C{sub 60} molecule.

  19. Impact of WFIRST-AFTA line-of-sight jitter distributions on phase-induced amplitude apodization complex mask coronagraph science yield

    NASA Astrophysics Data System (ADS)

    Kern, Brian

    2016-01-01

    A framework for evaluating the science yield of a coronagraph in the presence of a variety of line-of-sight jitter environments is described and the use of a tip-tilt threshold for improving science yield is proposed. The current expectations of the WFIRST-AFTA mission are used for specific distributions of line-of-sight jitter, including the current expectations for tip-tilt correction using a low-order wavefront sensor/control. The effect of the residual tip-tilt on the phase-induced amplitude apodization complex mask coronagraph (PIAACMC) architecture is considered, because the performance of the PIAACMC architecture is expected to be dominated by tip-tilt sensitivity, implying that this treatment has a large impact on the final science yield. The most important outcomes of this study are that the rms residual tip-tilt expected after correction is 0.6 mas rms/axis and that by eliminating some science frames during analysis through a tip-tilt threshold, the number of planets observable increases by ˜25% for the 550-nm imaging channel. The number of known radial velocity planets expected to be observed ranges from 29 to 78 at 550 nm and from 9 to 12 at 890 nm.

  20. Negative Regulation of p21Waf1/Cip1 by Human INO80 Chromatin Remodeling Complex Is Implicated in Cell Cycle Phase G2/M Arrest and Abnormal Chromosome Stability

    PubMed Central

    Cao, Lingling; Ding, Jian; Dong, Liguo; Zhao, Jiayao; Su, Jiaming; Wang, Lingyao; Sui, Yi; Zhao, Tong; Wang, Fei; Jin, Jingji; Cai, Yong

    2015-01-01

    We previously identified an ATP-dependent human Ino80 (INO80) chromatin remodeling complex which shares a set of core subunits with yeast Ino80 complex. Although research evidence has suggested that INO80 complex functions in gene transcription and genome stability, the precise mechanism remains unclear. Herein, based on gene expression profiles from the INO80 complex-knockdown in HeLa cells, we first demonstrate that INO80 complex negatively regulates the p21Waf1/Cip1 (p21) expression in a p53-mediated mechanism. In chromatin immunoprecipitation (ChIP) and a sequential ChIP (Re-ChIP) assays, we determined that the INO80 complex and p53 can bind to the same promoter region of p21 gene (-2.2kb and -1.0kb upstream of the p21 promoter region), and p53 is required for the recruitment of the INO80 complex to the p21 promoter. RNAi knockdown strategies of INO80 not only led to prolonged progression of cell cycle phase G2/M to G1, but it also resulted in abnormal chromosome stability. Interestingly, high expression of p21 was observed in most morphologically-changed cells, suggesting that negative regulation of p21 by INO80 complex might be implicated in maintaining the cell cycle process and chromosome stability. Together, our findings will provide a theoretical basis to further elucidate the cellular mechanisms of the INO80 complex. PMID:26340092

  1. Solid-phase microextraction low temperature plasma mass spectrometry for the direct and rapid analysis of chemical warfare simulants in complex mixtures.

    PubMed

    Dumlao, Morphy C; Jeffress, Laura E; Gooding, J Justin; Donald, William A

    2016-06-21

    Solid-phase microextraction (SPME) is directly integrated with low temperature plasma ionisation mass spectrometry to rapidly detect organophosphate chemical warfare agent simulants and their hydrolysis products in chemical mixtures, including urine. In this sampling and ionization method, the fibre serves: (i) to extract molecules from their native environment, and (ii) as the ionization electrode that is used to desorb and ionize molecules directly from the SPME surface. By use of a custom fabricated SPME fibre consisting of a stainless steel needle coated with a Linde Type A (LTA) zeolitic microporous material and low temperature plasma mass spectrometry, protonated dimethyl methylphosphonate (DMMP), diethyl ethylphosphonate (DEEP) and pinacolyl methylphosphonic acid (PinMPA) can be detected at less than 100 ppb directly in water and urine. Organophosphates were not readily detected by this approach using an uncoated needle in negative control experiments. The use of the LTA coating significantly outperformed the use of a high alumina Zeolite Socony Mobil-5 (ZSM-5) coating of comparable thickness that is significantly less polar than LTA. By conditioning the LTA probe by immersion in an aqueous CuSO4 solution, the ion abundance for protonated DMMP increased by more than 300% compared to that obtained without any conditioning. Sample recovery values were between 96 and 100% for each analyte. The detection of chemical warfare agent analogues and hydrolysis products required less than 2 min per sample. A key advantage of this sampling and ionization method is that analyte ions can be directly and rapidly sampled from chemical mixtures, such as urine and seawater, without sample preparation or chromatography for sensitive detection by mass spectrometry. This ion source should prove beneficial for portable mass spectrometry applications because relatively low detection limits can be obtained without the use of compressed gases, fluid pumps, and lasers. Moreover, the

  2. Influence of the larval phase on connectivity: strong differences in the genetic structure of brooders and broadcasters in the Ophioderma longicauda species complex.

    PubMed

    Weber, A A-T; Mérigot, B; Valière, S; Chenuil, A

    2015-12-01

    Closely related species with divergent life history traits are excellent models to infer the role of such traits in genetic diversity and connectivity. Ophioderma longicauda is a brittle star species complex composed of different genetic clusters, including brooders and broadcasters. These species diverged very recently and some of them are sympatric and ecologically syntopic, making them particularly suitable to study the consequences of their trait differences. At the scale of the geographic distribution of the broadcasters (Mediterranean Sea and northeastern Atlantic), we sequenced the mitochondrial marker COI and genotyped an intron (i51) for 788 individuals. In addition, we sequenced 10 nuclear loci newly developed from transcriptome sequences, for six sympatric populations of brooders and broadcasters from Greece. At the large scale, we found a high genetic structure within the brooders (COI: 0.07 < F(ST) < 0.65) and no polymorphism at the nuclear locus i51. In contrast, the broadcasters displayed lower genetic structure (0 < F(ST) < 0.14) and were polymorphic at locus i51. At the regional scale, the multilocus analysis confirmed the contrasting genetic structure between species, with no structure in the broadcasters (global F(ST) < 0.001) and strong structure in the brooders (global F(ST) = 0.49), and revealed a higher genetic diversity in broadcasters. Our study showed that the lecithotrophic larval stage allows on average a 50-fold increase in migration rates, a 280-fold increase in effective size and a threefold to fourfold increase in genetic diversity. Our work, investigating complementary genetic markers on sympatric and syntopic taxa, highlights the strong impact of the larval phase on connectivity and genetic diversity. PMID:26547515

  3. Combining gas phase electron capture and IRMPD action spectroscopy to probe the electronic structure of a metastable reduced organometallic complex containing a non-innocent ligand.

    PubMed

    Katari, Madanakrishna; Payen de la Garanderie, Eleonore; Nicol, Edith; Steinmetz, Vincent; van der Rest, Guillaume; Carmichael, Duncan; Frison, Gilles

    2015-10-21

    Combining electron capture dissociation mass spectrometry and infrared multiple photon dissociation action spectroscopy allows the formation, selection and characterisation of reduced metal complexes containing non-innocent ligands. Zinc complexes containing diazafluorenone ligands have been studied and the localisation of the single electron on the metal atom in the mono-ligated complex has been demonstrated. PMID:26051020

  4. Phase equilibrium in poly(rA).poly(rU) complexes with Cd2+ and Mg2+ ions, studied by ultraviolet, infrared, and vibrational circular dichroism spectroscopy.

    PubMed

    Blagoi, Yurii; Gladchenko, Galina; Nafie, Laurence A; Freedman, Teresa B; Sorokin, Victor; Valeev, Vladimir; He, Yanan

    2005-08-01

    Ultraviolet (UV) and infrared (IR) absorption and vibrational circular dichroism (VCD) spectroscopy were used to study conformational transitions in the double-stranded poly(rA). poly(rU) and its components-single-stranded poly(rA) and poly(rU) in buffer solution (pH 6.5) with 0.1M Na+ and different Mg2+ and Cd2+ (10(-6) to 10(-2) M) concentrations. Transitions were induced by elevated temperature that changed from 10 up to 96 degrees C. IR absorption and VCD spectra in the base-stretching region were obtained for duplex, triplex, and single-stranded forms of poly(rA) . poly(rU) at [Mg2+],[Cd2+]/[P] = 0.3. For single-stranded polynucleotides, the kind of conformational transition (ordering --> disordering --> compaction, aggregation) is conditioned by the dominating type of Me2+-polymer complex that in turn depends on the ion concentration range. The phase diagram obtained for poly(rA) . poly(rU) has a triple point ([Cd2+] approximately 10(-4)M) at which the helix-coil (2 --> 1) transition is replaced with a disproportion transition 2AU --> A2U + poly(rA) (2 --> 3) and the subsequent destruction of the triple helix (3 --> 1). The 2 --> 1 transitions occur in the narrow temperature interval of 2 degrees -5 degrees . Unlike 2 --> 1 and 3 --> 1 melting, the disproportion 2 --> 3 transition is a slightly cooperative one and observed over a wide temperature range. At [Me2+] approximately 10(-3) M, the temperature interval of A2U stability is not less than 20 degrees C. In the case of Cd2+, it increases with the rise of ion concentration due to the decrease of T(m) (2-->3). The T(m) (3-->1) value is practically unchanged up to [Cd2+] approximately 10(-3)M. Differences between diagrams for Mg(2+) and Cd2+ result from the various kinds of ion binding to poly(rA).poly-(rU) and poly(rA). PMID:15892121

  5. Water-soluble oxoglaucine-Y(III), Dy(III) complexes: in vitro and in vivo anticancer activities by triggering DNA damage, leading to S phase arrest and apoptosis.

    PubMed

    Wei, Jian-Hua; Chen, Zhen-Feng; Qin, Jiao-Lan; Liu, Yan-Cheng; Li, Zhu-Quan; Khan, Taj-Malook; Wang, Meng; Jiang, Yan-Hua; Shen, Wen-Ying; Liang, Hong

    2015-07-01

    Complexes of yttrium(III) and dysprosium(III) with the traditional Chinese medicine active ingredient oxoglaucine (OG), namely [Y(OG)2(NO3)3]·CH3OH (1) and [Dy(OG)2(NO3)3]·H2O (2), were synthesized and characterized by elemental analysis, IR, ESI-MS, (1)H and (13)C NMR as well as single-crystal X-ray diffraction analysis. In vitro the complexes exhibited higher anticancer activity than the free ligand OG against the tested cancer cell lines. Among the tested cell lines, HepG2 is the most sensitive to the complexes. Complex 2 can trigger DNA damage in HepG2 cells, resulting in cell cycle arrest in the S phase and leading to cell apoptosis. The S phase cell-cycle arrest is caused via the ATM (ataxia-telangiectasia mutated)-Chk2-Cdc25A pathway. Chk2 is phosphorylated and activated in an ATM-dependent manner. It, in turn, phosphorylates Cdc25A phosphatise on serine124, causing the inactivation of Cdc25A in ubiquitin-mediated proteolytic degradation. The cyclin-Cdk complexes of the S phase could also be inhibited by limited supply of cyclins A and E. This irreversible cell cycle arrest process ultimately induces mitochondria-involved apoptotic cell death via the activation of Bcl-2 protein. Complex e2 ffectively inhibited tumour growth in the BEL-7402 xenograft mouse model and exhibited higher safety in vivo than cisplatin. PMID:26017376

  6. Gas-phase coordination complexes of U(VI)O2(2+), Np(VI)O2(2+), and Pu(VI)O2(2+) with dimethylformamide.

    PubMed

    Rutkowski, Philip X; Rios, Daniel; Gibson, John K; Van Stipdonk, Michael J

    2011-11-01

    Electrospray ionization of actinyl perchlorate solutions in H(2)O with 5% by volume of dimethylformamide (DMF) produced the isolatable gas-phase complexes, [An(VI)O(2)(DMF)(3)(H(2)O)](2+) and [An(VI)O(2)(DMF)(4)](2+), where An = U, Np, and Pu. Collision-induced dissociation confirmed the composition of the dipositive coordination complexes, and produced doubly- and singly-charged fragment ions. The fragmentation products reveal differences in underlying chemistries of uranyl, neptunyl, and plutonyl, including the lower stability of Np(VI) and Pu(VI) compared with U(VI). PMID:21952769

  7. FIELD IMPLEMENTATION OF A WINSOR TYPE I SURFACTANT/ALCOHOL MIXTURE FOR IN SITU SOLUBILIZATION OF A COMPLEX LNAPL AS A SINGLE-PHASE MICROEMULSION

    EPA Science Inventory

    A Winsor Type I surfactant/alcohol mixture was used as an in situ flushing agent to solubilize a muticomponent nonaqueous phase liquid (NAPL) as a single-phase microemulsion (SPME) in a hydraulically isolated test cell at Hill Air Force Base (AFB), Utah. The surfactant (polyoxye...

  8. Synthesis of the Pb-based superconductor of the Pb3201 phase (Pb 2Cu)Sr 0.9La 1.1CuO 6+δ by the modified polymerized complex method

    NASA Astrophysics Data System (ADS)

    Kato, Masatsune; Sakuma, Atsushi; Noji, Takashi; Koike, Yoji

    1996-02-01

    We have succeeded in obtaining single-phase samples of the Pb3201 phase (Pb 2Cu)Sr 0.9La 1.1CuO 6+δ by the modified polymerized complex method. At the first step of the synthesis, a transparent gel is found to be obtained by increasing the molar ratio of citric acid to total metal ions up to 5 without controlling the pH of the solution and without ethylene glycol. Secondly, the precursor is prepared by calcining the transparent gel. Finally, highly homogeneous samples with the onset temperature of the superconducting transition, ∼ 37 K, are obtained by sintering the precursor and subsequently annealing it. Moreover, the Pb3201 phase is found to be stable only for x = 1.1 in (Pb 2Cu)Sr 2- xLa xCuO 6+δ.

  9. Evolution of composition of major mineral phases in layered complex of ophiolite assemblage: Evidence for the Voykar ophiolites (Polar urals, Russia)

    USGS Publications Warehouse

    Sharkov, E.V.; Chistyakov, A.V.; Laz'ko, E. E.; Quick, J.E.

    1999-01-01

    We present a detailed study of compositional variation of major minerals through a cross section of the layered complex of the Late Devonian Voykar ophiolite assemblage (Polar Urals). The principal characteristics of this layered complex suggest crystallization from a periodically replenished open magma system in a tectonically dynamic, oceanic environment. The complex may be described in terms of two sequences of cumulus rocks, or megarhythms, that each display an upward progression from ultramafic to gabbroic composition. A transitional zone between the megarhythms is characterized by an upwardly reverse lithologic progression from gabbroic to ultramafic composition. Broad cryptic variation in mineral composition over intervals >100 m parallel changes in the lithologic abundances and suggest changes in the rate of magma supply relative to crystallization and(or) tapping of different mantle sources that had been previously depleted to different degrees. The mineralogy, mineral compositions and isotopic composition of the layered complex coupled with the association of the Voykar ophiolite with island-arc complexes suggest that it most likely formed in a back-arc basin.

  10. A dynamic phase-field model for structural transformations and twinning: Regularized interfaces with transparent prescription of complex kinetics and nucleation. Part I: Formulation and one-dimensional characterization

    NASA Astrophysics Data System (ADS)

    Agrawal, Vaibhav; Dayal, Kaushik

    2015-12-01

    The motion of microstructural interfaces is important in modeling twinning and structural phase transformations. Continuum models fall into two classes: sharp-interface models, where interfaces are singular surfaces; and regularized-interface models, such as phase-field models, where interfaces are smeared out. The former are challenging for numerical solutions because the interfaces need to be explicitly tracked, but have the advantage that the kinetics of existing interfaces and the nucleation of new interfaces can be transparently and precisely prescribed. In contrast, phase-field models do not require explicit tracking of interfaces, thereby enabling relatively simple numerical calculations, but the specification of kinetics and nucleation is both restrictive and extremely opaque. This prevents straightforward calibration of phase-field models to experiment and/or molecular simulations, and breaks the multiscale hierarchy of passing information from atomic to continuum. Consequently, phase-field models cannot be confidently used in dynamic settings. This shortcoming of existing phase-field models motivates our work. We present the formulation of a phase-field model - i.e., a model with regularized interfaces that do not require explicit numerical tracking - that allows for easy and transparent prescription of complex interface kinetics and nucleation. The key ingredients are a re-parametrization of the energy density to clearly separate nucleation from kinetics; and an evolution law that comes from a conservation statement for interfaces. This enables clear prescription of nucleation - through the source term of the conservation law - and kinetics - through a distinct interfacial velocity field. A formal limit of the kinetic driving force recovers the classical continuum sharp-interface driving force, providing confidence in both the re-parametrized energy and the evolution statement. We present some 1D calculations characterizing the formulation; in a

  11. Modified Graded Motor Imagery for Complex Regional Pain Syndrome Type 1 of the Upper Extremity in the Acute Phase: A Patient Series

    ERIC Educational Resources Information Center

    Lagueux, Emilie; Charest, Joelle; Lefrancois-Caron, Eve; Mauger, Marie-Eve; Mercier, Emilie; Savard, Kim; Tousignant-Laflamme, Yannick

    2012-01-01

    Complex regional pain syndrome (CRPS) is a pathologic condition in which the painful experience is disproportionate in time and intensity in comparison with the inciting event. At present, the pathophysiology of CRPS is not well understood. Several studies have indicated that cortical reorganization plays a role in the persistence of the symptoms.…

  12. A computational study on some viable targets for gas-phase synthesis of metal complexes of the cyclic (B6C)-2 and their bonding pattern.

    PubMed

    Shahbazian, Shant; Alizadeh, Shadi

    2008-10-16

    In this account, a detailed computational study is conducted to verify the geometric, energetic, and electronic properties of the planar cyclic (B 6C) (-2) (as the simplest carrier of hexacoordinate carbon) within some metal complexes. The [M(B 6C)] ((-)) (M = Li, Na, K) and [M(B 6C)] (M = Be, Mg, Ca) series are employed for this purpose. Relevant ab initio calculations at both DFT and post-HF levels vividly demonstrate that this dianion is stabilized considerably in the electric field generated by cations, whereas the geometrical and electronic properties of this ring remain almost intact in these complexes. The complementary topological analysis of charge densities confirms that cyclic (B 6C) (-2) within these complexes exhibits the same topological patterns as the naked dianion, thus confirming the presence of an unusual charge density distribution in this dianion. An electrostatic model is proposed that not only qualitatively but also quantitatively explains the observed computational trends in these complexes. This model successfully traces the polarization of the central carbon atom of the ring in the presence of a hard, multiply charged cation. To facilitate experimental detection, the photoelectron spectra of the [M(B 6C)] ((-)) (M = Li, Na, K) series are computed and the dominant features are extracted. Although considered species are not global minima on their potential energy hypersurfaces, their kinetic stabilities are verified and demonstrated unequivocally. PMID:18816031

  13. Gas Phase Conformations and Methyl Internal Rotation for 2-PHENYLETHYL Methyl Ether and its Argon Van Der Waals Complex from Fourier Transform Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gurusinghe, Ranil M.; Tubergen, Michael

    2015-06-01

    A mini-cavity microwave spectrometer was used to record the rotational spectra arising from 2-phenylethyl methyl ether and its weakly bonded argon complex in the frequency range of 10.5 - 22 GHz. Rotational spectra were found for two stable conformations of the monomer: anti-anti and gauche-anti, which are 1.4 kJ mol-1 apart in energy at wB97XD/6-311++G(d,p) level. Doubled rotational transitions, arising from internal motion of the methyl group, were observed for both conformers. The program XIAM was used to fit the rotational constants, centrifugal distortion constants, and barrier to internal rotation to the measured transition frequencies of the A and E internal rotation states. The best global fit values of the rotational constants for the anti-anti conformer are A= 3799.066(3) MHz, B= 577.95180(17) MHz, C= 544.7325(3) MHz and the A state rotational constants of the gauche-anti conformer are A= 2676.1202(7) MHz, B= 760.77250(2) MHz, C= 684.78901(2) MHz. The rotational spectrum of 2-phenylethyl methyl ether - argon complex is consistent with the geometry where argon atom lies above the plane of the benzene moiety of gauche-anti conformer. Tunneling splittings were too small to resolve within experimental accuracy, likely due to an increase in three fold potential barrier when the argon complex is formed. Fitted rotational constants are A= 1061.23373(16) MHz, B= 699.81754(7) MHz, C= 518.33553(7) MHz. The lowest energy solvated ether - water complex with strong intermolecular hydrogen bonding has been identified theoretically. Progress on the assignment of the water complex will also be presented.

  14. Formation of Iron Complexes from Trifluoroacetic Acid Based Liquid Chromatography Mobile Phases as Interference Ions in LC-ESI-MS Analysis

    PubMed Central

    Shukla, Anil; Zhang, Rui; Orton, Daniel; Zhao, Rui; Clauss, Therese; Moore, Ronald; Smith, Richard

    2011-01-01

    Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid that severely interfered with sample analysis. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are composed of three components; clusters of trifluoroacetic acid, clusters of mass 159 and iron. Formation of these ions is inhibited by removing trifluoroacetic acid from the mobile phases and using formic acid in its place, replacing the stainless steel union with a titanium union or by adding a small blank fused silica capillary column between the chromatography column and the electrospray tip via a stainless steel union without any adverse effects to chromatographic separation, peak broadening or peptide identifications. PMID:21504012

  15. Formation of iron complexs from trifluoroacetic acid based liquid chromatography mobile phases as interference ions in liquid chromatography/electrospray ionization mass spectrometric analysis

    SciTech Connect

    Shukla, Anil K.; Zhang, Rui; Orton, Daniel J.; Zhao, Rui; Clauss, Therese RW; Moore, Ronald J.; Smith, Richard D.

    2011-05-30

    Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are not due to any contamination from solvents and chemicals used for mobile and stationary phases or from the laboratory atmospheric environment. Instead these ions are clusters of trifluoroacetic acid formed in association with acetonitrile, water and iron from the stainless steel union used to connect the column with the electrospray tip and to apply high voltage; the molecular formulae are Fe+((OH)(H2O)2)9(CF3COOH)5 and Fe+((OH)(H2O)2)6 (CF3COOH)5.

  16. Changes in Phase Composition of NaAlH{sub 4}+FeCl{sub 2} Complex Hydride Exposed to Air

    SciTech Connect

    Roupcova, P.; Schneeweiss, O.

    2010-07-13

    Phase composition in AlNaH{sub 4} doped with FeCl{sub 2} was studied by Moessbauer spectroscopy and X-ray diffraction and stabilities in Ar and air were compared. The results show that the hydride disappeared during the exposition to air. The major sodium alanate hydride traps gaseous impurities and transforms to Na{sub 2}CO{sub 3} and Al(OH){sub 3}.

  17. Fast phase processing in off-axis holography using multiplexing with complex encoding and live-cell fluctuation map calculation in real-time.

    PubMed

    Girshovitz, Pinhas; Shaked, Natan T

    2015-04-01

    We present efficient algorithms for rapid reconstruction of quantitative phase maps from off-axis digital holograms. The new algorithms are aimed at speeding up the conventional Fourier-based algorithm. By implementing the new algorithms on a standard personal computer, while using only a single-core processing unit, we were able to reconstruct the unwrapped phase maps from one megapixel off-axis holograms at frame rates of up to 45 frames per second (fps). When phase unwrapping is not required, the same algorithms allow frame rates of up to 150 fps for one megapixel off-axis holograms. In addition to obtaining real-time quantitative visualization of the sample, the increased frame rate allows integrating additional calculations as a part of the reconstruction process, providing sample-related information that was not available in real time until now. We use these new capabilities to extract, for the first time to our knowledge, the dynamic fluctuation maps of red blood cells at frame rate of 31 fps for one megapixel holograms. PMID:25968715

  18. Studies on 2H NMR and single crystal X-ray diffraction of thermochromic bis ( N, N-diethyl-1,2-ethanediamine) nickel(II) complexes with and without structural phase transitions

    NASA Astrophysics Data System (ADS)

    Ikeda, Ryuichi; Kotani, Kyoko; Ohki, Hiroshi; Ishimaru, Shin'ichi; Okamoto, Ken-Ichi; Ghosh, Ashutosh

    1995-02-01

    The thermochromic complex bis( N, N-diethyl-1,2-ethanediamine) ((C 2H 5) 2NC 2H 4NH 2) nickel(II) perchlorate([Ni(dieten) 2](ClO 4) 2) was studied by single crystal X-ray diffraction and found to form a triclinic lattice with space group P 1¯, a = 8.108(1) Å, b = 8.835(1) Å, c = 9.736(1) Å, α = 94.24(1)°, β = 114.28(1)°, γ = 116.49(1)°, and Z = 1 being isomorphous with that of [Cu(dieten) 2](ClO 4) 2 which has been reported to have a thermochromic phase transition. The temperature dependences of 2H NMR spectra in [Ni(dieten- d2) 2]X 2 (dieten- d2: (C 2H 5) 2NC 2H 4ND 2; X: ClO 4, BF 4, Br, NO 3, I) were observed and quadrupole coupling constants e2Qq and asymmetry parameters η were evaluated. Below room temperature, an almost rigid structure of the ND 2 group was derived by analyzing the spectra. For perchlorate and tetrafluoroborate with colour changes at respective phase transition temperatures ( Tc), quadrupole parameters were also changed discontinuously at Tc. The analysis of spectra observed above Tc afforded two-site jumps of the N-D bond by angles of 52-55° supporting the ring-puckering model of the five-membered chelate ring. However, iodide having no phase transition showed continuous changes of both e2Qq and η values with increasing temperature up to 450 K. These results which cannot be attributed to the puckering motion were explained by whole complex reorientation. These molecular motions are discussed in connection with the colour change observed in these complexes.

  19. Complexation of carboxylate anions with the arginine gas-phase amino acid: Effects of chain length on the geometry of extended ion binding

    NASA Astrophysics Data System (ADS)

    Luxford, Thomas F. M.; Milner, Edward M.; Yoshikawa, Naruo; Bullivant, Chad; Dessent, Caroline E. H.

    2013-07-01

    Complexation of deprotonated carboxylic acids with arginine was investigated using collision-induced dissociation to probe the nature of isolated carboxylate-amino acid interactions as a function of anion size. Monocarboxylic CH3(CH2)nCOO-·Arg (n = 3-7, 9, 10) and dicarboxylic acid COOH(CH2)nCOO-·Arg (n = 3-5, 7-10) complexes were investigated. For the dicarboxylic acid clusters, chain length has a significant effect on the %fragmentation energies with the n = 9, 10 systems fragmenting at significantly lower energies than the corresponding shorter chain systems. Molecular mechanics calculations suggest that this fragmentation energy shift is associated with the longer-chain dicarboxylic acid-Arg clusters switching to ring structures.

  20. Multivalency in the gas phase: H/D exchange reactions unravel the dynamic "rock 'n' roll" motion in dendrimer-dendrimer complexes.

    PubMed

    Qi, Zhenhui; Schlaich, Christoph; Schalley, Christoph A

    2013-10-25

    Noncovalent dendrimer-dendrimer complexes were successfully ionized by electrospray ionization of partly protonated amino-terminated polypropylene amine (POPAM) and POPAM dendrimers fully functionalized with benzo[21]crown-7 on all branches. Hydrogen/deuterium exchange (HDX) experiments conducted on dendrimer-dendrimer complexes in the high vacuum of a mass spectrometer give rise to a complete exchange of all labile NH hydrogen atoms. As crown ethers represent noncovalent protective groups against HDX reactions on the ammonium group to which they are coordinated, this result provides evidence for a very dynamic binding situation: each crown is mobile enough to move from one ammonium binding site to another. Schematically, one might compare this motion with two rock 'n' roll dancers that swirl around each other without completely losing all contact at any time. Although the multivalent attachment certainly increases the overall affinity, the "microdynamics" of individual site binding and dissociation remains fast. PMID:24105808

  1. Broadband Microwave Spectroscopy as a Tool to Study the Structures of Odorant Molecules and Weakly Bound Complexes in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Zinn, Sabrina; Betz, Thomas; Medcraft, Chris; Schnell, Melanie

    2015-06-01

    The rotational spectrum of trans-cinnamaldehyde ((2E)-3-phenylprop-2-enal) has been obtained with chirped-pulse microwave spectroscopy in the frequency range of 2 - 8.5 GHz. The odorant molecule is the essential component in cinnamon oil and causes the characteristic smell. In the measured high-resolution spectrum, we were able to assign the rotational spectra of two conformers of trans-cinnamaldehyde as well as all singly 13C-substituted species of the lowest-energy conformer in natural abundance. Two different methods were used to determine the structure from the rotational constants, which will be compared within this contribution. In addition, the current progress of studying ether-alcohol complexes, aiming at an improved understanding of the interplay between hydrogen bonding and dispersion interaction, will be reported. Here, a special focus is placed on the complexes of diphenylether with small aliphatic alcohols.

  2. Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: A dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Yingjie; Karatchevtseva, Inna; Bhadbhade, Mohan; Tran, Toan Trong; Aharonovich, Igor; Fanna, Daniel J.; Shepherd, Nicholas D.; Lu, Kim; Li, Feng; Lumpkin, Gregory R.

    2016-02-01

    With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H2phb) or terephthalic acid (H2tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO2)2(Hphb)2(phb)(DMF)(H2O)3]·4H2O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a μ2-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO2)(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with μ4-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C-O-U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated.

  3. Covalent functionalization of multi-wall carbon nanotubes (MWNTs) by nickel(II) Schiff-base complex: Synthesis, characterization and liquid phase oxidation of phenol with hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Salavati-Niasari, Masoud; Bazarganipour, Mehdi

    2008-12-01

    The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, hydroxyl functionalized nickel(II) Schiff-base has been covalently anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis, UV-vis, diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The results suggest that the symmetrical Schiff-base; N, N'-bis(4-hydroxysalicylidene)-ethylene-1,2-diamine; H 2[(OH) 2-salen]; is a bivalent anion with tetradentate N 2O 2 donors derived from the phenolic oxygen and azomethine nitrogen. The formula was found to be [Ni((OH) 2-salen)] for the 1:1 non-electrolytic complex. Multi-wall carbon nanotubes covalently anchored nickel(II) complex ([Ni((OH) 2-salen)]@MWNTs) catalyze the oxidation of phenol with H 2O 2. Oxidation of phenol catalyzed by this complex gave catechol and hydroquinone as major products. A suitable reaction condition has been optimized for [Ni((OH) 2-salen)]@MWNTs by considering the effect of various parameters such as reaction time and amount of oxidant, different solvents, concentration of substrate, etc. for the maximum transformation of phenol.

  4. 4,4'-, 5,5'-, and 6,6'-dimethyl-2,2'-bipyridyls: The structures, phase transitions, vibrations, and methyl group tunneling of their complexes with chloranilic acid

    NASA Astrophysics Data System (ADS)

    Bator, G.; Sawka-Dobrowolska, W.; Sobczyk, L.; Grech, E.; Nowicka-Scheibe, J.; Pawlukojć, A.; Wuttke, J.; Baran, J.; Owczarek, M.

    2011-07-01

    The crystal and molecular structures of 4,4'- and 6,6'-dimethyl-2,2'-bipyridyl complexes with 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (chloranilic acid, CLA) have been determined and compared with those of the complex with the 5,5'-derivative, which is known to possess interesting antiferroelectric properties. In the crystalline state, all three compounds form hydrogen bonded chains with N+-H...O- and O-H...N bridges on both sides of the bipyridyl constituent. The comparison of three derivatives indicates that the N+-H...O- hydrogen bonds are shortest for the 5,5'-dimethyl complex. The 4,4'- and 6,6'-derivatives do not show any ferroelectric feature. The 6,6'-one is, however, characterized by a continuous phase transition, revealed in the differential scanning calorimetry, dilatometric, and dielectric characteristics. The tunneling splitting measured by neutron backscattering in the energy range ±30 μeV for the neat dimethyl bipyridyls and their complexes with CLA indicates that the different splittings are primarily due to the crystal packing effect and that charge transfer between interacting compounds plays only a minor role.

  5. Phase equilibria and crystal structure of the complex oxides in the Ln-Ba-Co-O (Ln=Nd, Sm) systems

    SciTech Connect

    Gavrilova, L.Ya.; Aksenova, T.V.; Volkova, N.E.; Podzorova, A.S.; Cherepanov, V.A.

    2011-08-15

    The phase equilibria in the Ln-Ba-Co-O (Ln=Nd, Sm) systems were systematically studied at 1100 deg. C in air. The homogeneity ranges and crystal structure of the solid solutions: Ln{sub 2-x}Ba{sub x}O{sub 3-{delta}} (0phase diagrams for the Ln-Ba-Co-O (Ln=Nd, Sm) systems to the compositional triangle of metallic components were presented. - Graphical Abstract: Projections of isobaric isothermal phase diagrams of the Nd-Ba-Co-O system and Sm-Ba-Co-O system. Highlights: > Phase equilibria in the Ln-Ba-Co-O systems (Ln=Nd, Sm). > The homogeneity range for Nd{sub 2-x}Ba{sub x}O{sub 3-{delta}} solid solutions at studied conditions 0 The homogeneity range for Sm{sub 2-x}Ba{sub x}O{sub 3-{delta}} solid solutions at studied conditions 0 Nd{sub 3-y}Ba{sub y}Co{sub 2}O{sub 7} solid solutions within the range 0.7{<=}y{<=}0.8. > BaCo{sub 1-z}Sm{sub z}O{sub 3-{delta}} solid solutions within the range 0.1{<=}z{<=}0.2.

  6. Intrinsic affinities of alkali cations for 15-crown-5 and 18-crown-6: Bond dissociation energies of gas-phase M{sup +}-crown ether complexes

    SciTech Connect

    More, M.B.; Ray, D.; Armentrout, P.B.

    1999-01-20

    Bond dissociation energies (BDEs) of M{sup +}[c-(C{sub 2}H{sub 4}O){sub 5}] and M{sup +}[c-(C{sub 2}H{sub 4}O){sub 6}] for M = Na, K, Rb, and Cs are reported. The BDEs are determined experimentally by analysis of the thresholds for collision-induced dissociation of the cation-crown ether complexes by xenon measured by using guided ion beam mass spectrometry. In all cases, the primary and lowest energy dissociation channel observed experimentally in endothermic loss of the ligand molecule. The cross section thresholds are interpreted to yield 0 and 298 K BDEs after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. For both 18-crown-6 and 15-crown-5, the BDEs decrease monotonically with increasing cation size. These results indicate that the intrinsic affinity of c-(C{sub 2}H{sub 4}O){sub 5} and c-(C{sub 2}H{sub 4}O){sub 6} for M{sup +} is determined principally by the charge density of the cation not by the ratio of the ionic radius to the cavity size. The BDEs reported here are in fair agreement with recent ab initio calculations at the MP2 level with 6-31+G* basis sets. The experimental values are systematically smaller than the computed values by 8 {+-} 2 kJ/mol per metal-oxygen interaction. The existence of less strongly bound isomers in the experimental apparatus for Rb{sup +}(15-crown-5) and Cs{sup +}(15-crown-5) appears likely, but their absence for Na{sup +} and K{sup +} complexes indicates interesting metal-dependent dynamics to the formation of such isomers.

  7. Double proton transfer and one-electron oxidation behavior in double H-bonded glycinamide-glycine complex in the gas phase.

    PubMed

    Li, Ping; Bu, Yuxiang

    2005-04-30

    The behaviors of double proton transfer (DPT) occurring in a representative glycinamide-glycine complex have been investigated employing the B3LYP/6-311++G** level of theory. Thermodynamic and especially kinetic parameters, such as tautomerization energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the DPT process including geometrical changes, interaction energies, and deformation energies have also been studied. Analogous to that of tautomeric process assisted with a formic acid molecule, the participation of a glycine molecule favors the proceeding of the proton transfer (PT) for glycinamide compared with that without mediator-assisted case. The DPT process proceeds with a concerted mechanism rather than a stepwise one because no zwitterionic complexes have been located during the DPT process. The barrier heights are 12.14 and 0.83 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 3.10 and 2.66 kcal/mol to 9.04 and -1.83 kcal/mol with further inclusion of zero-point vibrational energy (ZPVE) corrections, where the disappearance of the reverse barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to those of DPTs occurring between glycinamide and formic acid (or formamide). Additionally, the oxidation process for the double H-bonded glycinamide-glycine complex has also been investigated. The oxidated product is characterized by a distonic radical cation due to the fact that one-electron oxidation takes place on glycine fragment and a proton has been transferred from glycine to glycinamide fragment spontaneously. As a result, the vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 8.71 and 7.85 eV, respectively, where both of them have been reduced by about 0.54 (1.11) and 0.75 (1.13) eV relative to those of isolated glycinamide (glycine

  8. Theoretical predictions of properties and gas-phase chromatography behaviour of carbonyl complexes of group-6 elements Cr, Mo, W, and element 106, Sg.

    PubMed

    Pershina, V; Anton, J

    2013-05-01

    Fully relativistic, four-component density functional theory electronic structure calculations were performed for M(CO)6 of group-6 elements Cr, Mo, W, and element 106, Sg, with an aim to predict their adsorption behaviour in the gas-phase chromatography experiments. It was shown that seaborgium hexacarbonyl has a longer M-CO bond, smaller ionization potential, and larger polarizability than the other group-6 molecules. This is explained by the increasing relativistic expansion and destabilization of the (n - 1)d AOs with increasing Z in the group. Using results of the calculations, adsorption enthalpies of the group-6 hexacarbonyls on a quartz surface were predicted via a model of physisorption. According to the results, -ΔHads should decrease from Mo to W, while it should be almost equal--within the experimental error bars--for W and Sg. Thus, we expect that in the future gas-phase chromatography experiments it will be almost impossible--what concerns ΔHads--to distinguish between the W and Sg hexacarbonyls by their deposition on quartz. PMID:23656128

  9. Theoretical predictions of properties and gas-phase chromatography behaviour of carbonyl complexes of group-6 elements Cr, Mo, W, and element 106, Sg

    NASA Astrophysics Data System (ADS)

    Pershina, V.; Anton, J.

    2013-05-01

    Fully relativistic, four-component density functional theory electronic structure calculations were performed for M(CO)6 of group-6 elements Cr, Mo, W, and element 106, Sg, with an aim to predict their adsorption behaviour in the gas-phase chromatography experiments. It was shown that seaborgium hexacarbonyl has a longer M-CO bond, smaller ionization potential, and larger polarizability than the other group-6 molecules. This is explained by the increasing relativistic expansion and destabilization of the (n - 1)d AOs with increasing Z in the group. Using results of the calculations, adsorption enthalpies of the group-6 hexacarbonyls on a quartz surface were predicted via a model of physisorption. According to the results, -ΔHads should decrease from Mo to W, while it should be almost equal - within the experimental error bars - for W and Sg. Thus, we expect that in the future gas-phase chromatography experiments it will be almost impossible - what concerns ΔHads - to distinguish between the W and Sg hexacarbonyls by their deposition on quartz.

  10. Chemometric investigation of complex equilibria in solution phase II: Sensitivity of chemical models for the interaction of AADH and FAH with Ni(II) in aqueous medium.

    PubMed

    Babu, A R; Krishna, D M; Rao, R S

    1993-12-01

    A detailed study of the species formed in the complex equilibria involving adipic acid dihydrazide (AADH)/2-furoic acid hydrazide (FAH) with Ni(II) using pH titration with glass electrode is performed. The results of modeling studies and effect of errors on the equilibrium constants of AADH/FAH with Ni(II) refined by the non-linear least squares program MINIQUAD75 are reported. Based on the expert system approach developed in our laboratory for the species formed from secondary formation data (n and n (H)), several preliminary chemical models were tested. For the four species identified (MLH, ML, ML(2)H, ML(2)), an exhaustive search of a different combination of models (15) was performed. Then other suspected minor species (ML(2)H(2), ML(3) and ML(3)H) were tested. The final best fit chemical model was found to contain ML(3)H to an extent of 3% along with the other four major species. In order to ascertain the accuracy of the stability constants and consequently distribution of the species, a detailed error analysis is attempted. As the existing least squares procedures cannot suppress the systematic errors, three-dimensional plots of the simultaneous effects of pH and TLO:TMO (1.5:1 to 5:1) on the percentage of species are drawn which are of immense use in arriving at optimum conditions for the preparation of a complex of definite stoichiometry. PMID:18965865

  11. Self-Assembly, Supramolecular Organization, and Phase Behavior of L-Alanine Alkyl Esters (n = 9-18) and Characterization of Equimolar L-Alanine Lauryl Ester/Lauryl Sulfate Catanionic Complex.

    PubMed

    Sivaramakrishna, D; Swamy, Musti J

    2015-09-01

    A homologous series of l-alanine alkyl ester hydrochlorides (AEs) bearing 9-18 C atoms in the alkyl chain have been synthesized and characterized with respect to self-assembly, supramolecular structure, and phase transitions. The CMCs of AEs bearing 11-18 C atoms were found to range between 0.1 and 10 mM. Differential scanning calorimetric (DSC) studies showed that the transition temperatures (Tt), enthalpies (ΔHt) and entropies (ΔSt) of AEs in the dry state exhibit odd-even alternation, with the odd-chain-length compounds having higher Tt values, but the even-chain-length homologues showing higher values of ΔHt and ΔSt. In DSC measurements on hydrated samples, carried out at pH 5.0 and pH 10.0 (where they exist in cationic and neutral forms, respectively), compounds with 13-18 C atoms in the alkyl chain showed sharp gel-to-liquid crystalline phase transitions, and odd-even alternation was not seen in the thermodynamic parameters. The molecular structure, packing properties, and intermolecular interactions of AEs with 9 and 10 C atoms in the alkyl chain were determined by single crystal X-ray diffraction, which showed that the alkyl chains are packed in a tilted interdigitated bilayer format. d-Spacings obtained from powder X-ray diffraction studies exhibited a linear dependence on the alkyl chain length, suggesting that the other AEs also adopt an interdigitated bilayer structure. Turbidimetric, fluorescence spectroscopic, and isothermal titration calorimetric (ITC) studies established that in aqueous dispersions l-alanine lauryl ester hydrochloride (ALE·HCl) and sodium dodecyl sulfate (SDS) form an equimolar complex. Transmission electron microscopic and DSC studies indicate that the complex exists as unilamellar liposomes, which exhibit a sharp phase transition at ∼39 °C. The aggregates were disrupted at high pH, suggesting that the catanionic complex would be useful to develop a base-labile drug delivery system. ITC studies indicated that ALE·HCl forms

  12. Complex polarization-phase and spatial-frequency selections of laser images of blood-plasma films in diagnostics of changes in their polycrystalline structure

    NASA Astrophysics Data System (ADS)

    Ushenko, Yu. A.; Angelskii, P. O.; Dubolazov, A. V.; Karachevtsev, A. O.; Sidor, M. I.; Mintser, O. P.; Oleinichenko, B. P.; Bizer, L. I.

    2013-10-01

    We present a theoretical formalism of correlation phase analysis of laser images of human blood plasma with spatial-frequency selection of manifestations of mechanisms of linear and circular birefringence of albumin and globulin polycrystalline networks. Comparative results of the measurement of coordinate distributions of the correlation parameter—the modulus of the degree of local correlation of amplitudes—of laser images of blood plasma taken from patients of three groups—healthy patients (donors), rheumatoid-arthritis patients, and breast-cancer patients—are presented. We investigate values and ranges of change of statistical (the first to fourth statistical moments), correlation (excess of autocorrelation functions), and fractal (slopes of approximating curves and dispersion of extrema of logarithmic dependences of power spectra) parameters of coordinate distributions of the degree of local correlation of amplitudes. Objective criteria for diagnostics of occurrence and differentiation of inflammatory and oncological states are determined.

  13. High Field Optomagnetic (OM) Polarization-Phase Selective (PPS) Monitoring of Structures and Controlling Reaction Agents Mechanisms in Complex Molecular Systems

    NASA Astrophysics Data System (ADS)

    Rupnik, Kresimir

    2014-03-01

    Using OM techniques, including new high filed 25T Split-Florida magnet at NHMF Laboratory, we have recently observed unusual metal cluster structures and electron transfer patterns in complex molecular systems of biomedical and material science interest. We report here some of the new technological solutions and (many) challenges that face OM and (quantum) control research. Of particular interest is identification of fast (10-100s fs) highly correlated electrons spin and vibrational coupling interpreted using adaptive molecular-photonic interaction models. Our observations question interpretations of previously proposed electron spin structure models and mechanisms and\\ indicate possible new controlling mechanisms through highly selective coupled channels that combine different specific redox and photonic agents. A portion of this work from 2008 to 2013 was performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement No. DMR-1157490, and 0654118 and the U.S. Department of Energy.

  14. Electrosonic spray ionization. A gentle technique for generating folded proteins and protein complexes in the gas phase and for studying ion-molecule reactions at atmospheric pressure.

    PubMed

    Takáts, Zoltán; Wiseman, Justin M; Gologan, Bogdan; Cooks, R Graham

    2004-07-15

    Electrosonic spray ionization (ESSI), a variant on electrospray ionization (ESI), employs a traditional micro ESI source with supersonic nebulizing gas. The high linear velocity of the nebulizing gas provides efficient pneumatic spraying of the charged liquid sample. The variable electrostatic potential can be tuned to allow efficient and gentle ionization. This ionization method is successfully applied to aqueous solutions of various proteins at neutral pH, and its performance is compared to that of the nanospray and micro ESI techniques. Evidence for efficient desolvation during ESSI is provided by the fact that the peak widths for various multiply charged protein ions are an order of magnitude narrower than those for nanospray. Narrow charge-state distributions compared to other ESI techniques are observed also; for most of the proteins studied, more than 90% of the protein ions can be accumulated in one charge state using ESSI when optimizing conditions. The fact that the abundant charge state is normally as low or lower than that recorded by ESI or nanospray indicates that folded protein ions are generated. The sensitivity of the ionization technique to high salt concentrations is comparable to that of nanospray, but ESSI is considerably less sensitive to high concentrations of organic additives such as glycerol or 2-amino-2-(hydroxymethyl)-1,3-propanediol (Tris base). Noncovalent complexes are observed in the case of myoglobin, protein kinase A/ATP complex, and other proteins. The extent of dissociation of protein ions in ESSI is comparable to or even smaller than that in the case of nanospray, emphasizing the gentle nature of the method. The unique features of ESSI are ascribed to very efficient spraying and the low internal energy supplied to the ions. Evidence is provided that the method is capable of generating fully desolvated protein ions at atmospheric pressure. This allows the technique to be used for the study of ion-molecule reactions at atmospheric

  15. New reversed phase-high performance liquid chromatographic method for selective separation of yttrium from all rare earth elements employing nitrilotriacetate complexes in anion exchange mode.

    PubMed

    Dybczyński, Rajmund S; Kulisa, Krzysztof; Pyszynska, Marta; Bojanowska-Czajka, Anna

    2015-03-20

    Separation of Y from other rare earth elements (REE) is difficult because of similarity of its ionic radius to ionic radii of Tb, Dy and Ho. In the new RP-HPLC system with C18 column, tetra-n-butyl ammonium hydroxide (TBAOH) as an ion interaction reagent (IIR), nitrilotriacetic acid (NTA) as a complexing agent at pH=2.8-3.5, and post column derivatization with Arsenazo III, yttrium is eluted in the region of light REE, between Nd and Sm and is base line separated from Nd and Sm and even from promethium. Simple model employing literature data on complex formation of REE with NTA and based on anion exchange mechanism was developed to foresee the order of elution of individual REE. The model correctly predicted that lanthanides up to Tb will be eluted in the order of increasing Atomic Number (At.No.) but all heavier REE will show smaller retention factors than Tb. Concurrent UV/VIS detection at 658nm and the use of radioactive tracers together with γ-ray spectrometric measurements made possible to establish an unique elution order of elution of REE: La, Ce, Pr, Nd, Pm, Y, Sm, Er, Ho, Tm, Yb, Eu, Lu, Dy+Gd, Tb, Sc. The real place of Y however, in this elution series differs from that predicted by the model (Y between Sm and Eu). The method described in this work enables selective separation of Y from La, Ce, Pr, Nd, Pm, Sm and all heavier REE treated as a group. PMID:25700726

  16. Kinetics and mechanism of electron transfer reaction of single and double chain surfactant cobalt(III) complex by Fe2+ ions in liposome (dipalmitoylphosphotidylcholine) vesicles: effects of phase transition

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

    In this study, we report the kinetics of reduction reactions of single and double chain surfactant cobalt(III) complexes of octahedral geometry, cis-[Co(en)2(4AMP)(DA)](ClO4)3 and cis-[Co(dmp)2(C12H25NH2)2](ClO4)3 (en = ethylenediamine, dmp = 1,3-diaminopropane, 4AMP = 4-aminopropane, C12H25NH2 = dodecylamine) by Fe2+ ion in dipalmitoylphosphotidylcholine (DPPC) vesicles at different temperatures under pseudo first-order conditions. The kinetics of these reactions is followed by spectrophotometry method. The reactions are found to be second order and the electron transfer is postulated as outer sphere. The remarkable findings in the present investigation are that, below the phase transition temperature of DPPC, the rate decreases with an increase in the concentration of DPPC, while above the phase transition temperature the rate increases with an increase in the concentration of DPPC. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes. Besides, comparing the values of rate constants of these outer-sphere electron transfer reactions in the absence and in the presence of DPPC, the rate constant values in the presence of DPPC are always found to be greater than in the absence of DPPC. This is ascribed to the double hydrophobic fatty acid chain in the DPPC that gives the molecule an overall tubular shape due to the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes more suitable for vesicle aggregation which facilitates lower activation energy, and consequently higher rate is observed in the presence of DPPC. The activation parameters (ΔS# and ΔH#) of the reactions at different temperatures have been calculated which corroborate the kinetics of the reaction.

  17. Phases and Phase Transitions

    NASA Astrophysics Data System (ADS)

    Gitterman, Moshe

    2014-09-01

    In discussing phase transitions, the first thing that we have to do is to define a phase. This is a concept from thermodynamics and statistical mechanics, where a phase is defined as a homogeneous system. As a simple example, let us consider instant coffee. This consists of coffee powder dissolved in water, and after stirring it we have a homogeneous mixture, i.e., a single phase. If we add to a cup of coffee a spoonful of sugar and stir it well, we still have a single phase -- sweet coffee. However, if we add ten spoonfuls of sugar, then the contents of the cup will no longer be homogeneous, but rather a mixture of two homogeneous systems or phases, sweet liquid coffee on top and coffee-flavored wet sugar at the bottom...

  18. A Phase I Trial of Samarium-153-Lexidronam Complex for Treatment of Clinically Nonmetastatic High-Risk Prostate Cancer: First Report of a Completed Study

    SciTech Connect

    Valicenti, Richard K.; Trabulsi, Edouard; Intenzo, Charles; Lavarino, Jorosali; Xu Yihuan; Chervoneva, Inna

    2011-03-01

    Purpose: We completed a Phase I trial to determine the maximum tolerated dose of samarium-153 EDTMP ({sup 153}Sm) with hormonal therapy (HT) and radiation therapy (RT) in high-risk clinically nonmetastatic prostate cancer. Methods and Materials: High-risk M0 prostate cancer patients (prostate-specific antigen >20 ng/mL, Gleason score >7, or >T3) were eligible for this prospective trial of dose-escalated radioactive {sup 153}Sm-EDTMP (.25-2.0 mCi/kg) as primary or postoperative therapy. After 1 month of HT, we administered {sup 153}Sm-EDTMP followed by 4 more months of HT, 46.8 Gy to the pelvic region and 23.4 Gy to the prostate target (TD = 70.2 Gy). The primary endpoint was Grade III toxicity or higher by the National Cancer Institute Common Toxicity Criteria. Results: Twenty-nine patients enrolled (median prostate-specific antigen = 8.2 ng/mL, 27/29 (93%) T stage {>=}T2b, 24/29 (83%) had Gleason >7) and received {sup 153}Sm-EDTMP (.25 mCi/kg, 4 patients; 0.5 mCi/kg, 4 patients; 0.75 mCi/kg, 6 patients; 1.0 mCi/kg, 6 patients; 1.5 mCi/kg, 5 patients; 2.0mCi/kg, 4 patients). Twenty-eight patients underwent all planned therapy without delays (1 patient required surgery before the start of RT). With a median follow-up time of 23 months, there were 2 patients (7 %) experiencing Grade III hematologic toxicity. There were no other Grade III or IV side effects. Conclusions: Our trial demonstrates that 2 mCi/kg {sup 153}Sm -EDTMP with HT and RT was safe and feasible in men with high-risk M0 prostate cancer. A Phase II study to test this treatment is currently underway by the Radiation Therapy Oncology Group.

  19. Frequency discriminator/phase detector

    NASA Technical Reports Server (NTRS)

    Crow, R. B.

    1974-01-01

    Circuit provides dual function of frequency discriminator/phase detector which reduces frequency acquisition time without adding to circuit complexity. Both frequency discriminators, in evaluated frequency discriminator/phase detector circuits, are effective two decades above and below center frequency.

  20. Exploring the complex magnetic phase diagram of Ce2PdGe3 : A neutron powder diffraction and μ SR study

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, A.; Ritter, C.; Adroja, D. T.; Coomer, F. C.; Strydom, A. M.

    2016-07-01

    The magnetic state of the tetragonal compound Ce2PdGe3 , which crystallizes in the space group P 42/m m c , a derivative of the α -ThSi2 structure, has been investigated by magnetic susceptibility, heat capacity, muon spin relaxation (μ SR ), and neutron diffraction measurements. Heat capacity data indicate two separate magnetic phase transitions at TN1=10.7 K and TN 2=2.3 K. The presence of bulk long-range magnetic order is confirmed by our μ SR study below 11 K, where a drop of nearly 2/3 in the muon initial asymmetry and a sharp increase in the muon depolarization rate were observed. Neutron powder diffraction reveals that only one out of two Ce sites becomes magnetically ordered with magnetic propagation vector κ =(0 ) at TN1,adopting an antiferromagnetic arrangement of magnetic moments μCe3+=1.78 (1 ) μB along the c axis. At TN 2 the second Ce site orders similarly, following the same magnetic propagation vector κ =(0 ) , showing, however, at the same time a significant ferromagnetic component within the tetragonal basal plane. A second propagation vector, κ =(1/2 ,0 ,1/2 ) , appears concomitantly at TN 2.

  1. Effect of separation dimensions on resolution and throughput using very narrow-range IEF for 2-DE after solution phase isoelectric fractionation of a complex proteome.

    PubMed

    Lee, KiBeom; Pi, KyungBae

    2009-04-01

    This paper describes how the lengths of the first and second dimensions in narrow pH-range 2-DE affect the number of detected protein spots, by analysis of human breast carcinoma cell line lysates prefractionated by solution phase IEF. The aim is to maximize throughput while minimizing experimental costs. In this study, systematic evaluation of narrow-range IPG strip lengths showed that separation distances were very important, with dramatic increases in resolution when longer gels were used. Compared with 7 cm minigels, maximal resolution was obtained using 18 and 24 cm IPG strips. Systematic evaluation of SDS-PAGE gel length showed a far weaker influence of separation length on resolution in the second dimension compared with that observed for the IEF dimension. There was little benefit in using separation distances greater than 12-15 cm, at least with currently available electrophoresis units. The work shows that regions of the IPG strip not containing any proteins can be excised to fit a smaller gel if prefractionation using IEF in solution has been performed. As expected, larger 2-DE gel volumes resulting from the use of longer IPG strips and second dimension gels decreased detection sensitivity when equal protein loads were used. However, this effect could be readily eliminated by increasing the loads applied to IPG strips. PMID:19301322

  2. Solid Waste Operations Complex W-113, Detail Design Report (Title II). Volume 2: Solid waste retrieval facilities -- Phase 1, detail design drawings

    SciTech Connect

    1995-09-01

    The Solid Waste Retrieval Facility--Phase 1 (Project W113) will provide the infrastructure and the facility required to retrieve from Trench 04, Burial ground 4C, contact handled (CH) drums and boxes at a rate that supports all retrieved TRU waste batching, treatment, storage, and disposal plans. This includes (1) operations related equipment and facilities, viz., a weather enclosure for the trench, retrieval equipment, weighing, venting, obtaining gas samples, overpacking, NDE, NDA, shipment of waste and (2) operations support related facilities, viz., a general office building, a retrieval staff change facility, and infrastructure upgrades such as supply and routing of water, sewer, electrical power, fire protection, roads, and telecommunication. Title I design for the operations related equipment and facilities was performed by Raytheon/BNFL, and that for the operations support related facilities including infrastructure upgrade was performed by KEH. These two scopes were combined into an integrated W113 Title II scope that was performed by Raytheon/BNFL. Volume 2 provides the complete set of the Detail Design drawings along with a listing of the drawings. Once approved by WHC, these drawings will be issued and baselined for the Title 3 construction effort.

  3. CrowdPhase: crowdsourcing the phase problem

    SciTech Connect

    Jorda, Julien; Sawaya, Michael R.; Yeates, Todd O.

    2014-06-01

    The idea of attacking the phase problem by crowdsourcing is introduced. Using an interactive, multi-player, web-based system, participants work simultaneously to select phase sets that correspond to better electron-density maps in order to solve low-resolution phasing problems. The human mind innately excels at some complex tasks that are difficult to solve using computers alone. For complex problems amenable to parallelization, strategies can be developed to exploit human intelligence in a collective form: such approaches are sometimes referred to as ‘crowdsourcing’. Here, a first attempt at a crowdsourced approach for low-resolution ab initio phasing in macromolecular crystallography is proposed. A collaborative online game named CrowdPhase was designed, which relies on a human-powered genetic algorithm, where players control the selection mechanism during the evolutionary process. The algorithm starts from a population of ‘individuals’, each with a random genetic makeup, in this case a map prepared from a random set of phases, and tries to cause the population to evolve towards individuals with better phases based on Darwinian survival of the fittest. Players apply their pattern-recognition capabilities to evaluate the electron-density maps generated from these sets of phases and to select the fittest individuals. A user-friendly interface, a training stage and a competitive scoring system foster a network of well trained players who can guide the genetic algorithm towards better solutions from generation to generation via gameplay. CrowdPhase was applied to two synthetic low-resolution phasing puzzles and it was shown that players could successfully obtain phase sets in the 30° phase error range and corresponding molecular envelopes showing agreement with the low-resolution models. The successful preliminary studies suggest that with further development the crowdsourcing approach could fill a gap in current crystallographic methods by making it

  4. Selective solid-phase microextraction of explosives using fibers coated with the La (III) complex of p-di (4,4,5,5,6,6,6-hepafluoro-1,3-hexanediony) benzene

    SciTech Connect

    Harvey, Scott D.

    2008-12-12

    This research demonstrates enhanced capture of explosives on polydimethylsiloxane (PDMS) solid-phase microextraction (SPME) fibers coated with a metal beta-diketonate polymer, [La(III) complex of p-di(4,4,5,5,6,6,6-heptafluoro-1,3-hexanedionyl)benzene, La(dihed)], compared to PDMS control fibers. SPME sampling was performed in an explosives bunker where the concentration of 2,4,6-trinitrotoluene (TNT) was estimated at less than 3 parts-per-trillion (v/v). Analysis by gas chromatography/mass spectrometry showed an approximate ten-fold enhancement in the quantity of 2,4-dinitrotoluene captured on La(dihed) over the control fiber. La(dihed) sampling also resulted in a strong signal for TNT, whereas this explosive was well below the detection limit (1 pg on fiber) on the control fiber.

  5. Penetrating the Elusive Mechanism of Copper-Mediated Fluoromethylation in the Presence of Oxygen through the Gas-Phase Reactivity of Well-Defined [LCuO](+) Complexes with Fluoromethanes (CH(4-n)Fn, n = 1-3).

    PubMed

    Rijs, Nicole J; González-Navarrete, Patricio; Schlangen, Maria; Schwarz, Helmut

    2016-03-01

    Traveling wave ion mobility spectrometry (TWIMS) isomer separation was exploited to react the particularly well-defined ionic species [LCuO](+) (L = 1,10-phenanthroline) with the neutral fluoromethane substrates CH(4-n)Fn (n = 1-3) in the gas phase. Experimentally, the monofluoromethane substrate (n = 1) undergoes both hydrogen-atom transfer, forming the copper hydroxide complex [LCuOH](•+) and concomitantly a CH2F(•) radical, and oxygen-atom transfer, yielding the observable ionic product [LCu](+) plus the neutral oxidized substrate [C,H3,O,F]. DFT calculations reveal that the mechanism for both product channels relies on the initial C-H bond activation of the substrate. Compared to nonfluorinated methane, the addition of fluorine to the substrate assists the reactivity through a lowering of the C-H bond energy and reaction preorganization (through noncovalent interaction in the encounter complex). A two-state reactivity scenario is mandatory for the oxidation, which competitively results in the unusual fluoromethanol product, CH2FOH, or the decomposed products, CH2O and HF, with the latter channel being kinetically disfavored. Difluoromethane (n = 2) is predicted to undergo the analogous reactions at room temperature, although the reactions are less favored than those of monofluoromethane. The reaction of trifluoromethane (n = 3, fluoroform) through C-H activation is kinetically hindered under ambient conditions but might be expected to occur in the condensed phase upon heating or with further lowering of reaction barriers through templation with counterions, such as potassium. Overall, formation of CH(3-n)Fn(•) and CH(3-n)FnOH occurs under relatively gentle energetic conditions, which sheds light on their potential as reactive intermediates in fluoromethylation reactions mediated by copper in the presence of oxygen. PMID:26859159

  6. A dynamic phase-field model for structural transformations and twinning: Regularized interfaces with transparent prescription of complex kinetics and nucleation. Part II: Two-dimensional characterization and boundary kinetics

    NASA Astrophysics Data System (ADS)

    Agrawal, Vaibhav; Dayal, Kaushik

    2015-12-01

    A companion paper presented the formulation of a phase-field model - i.e., a model with regularized interfaces that do not require explicit numerical tracking - that allows for easy and transparent prescription of complex interface kinetics and nucleation. The key ingredients were a re-parametrization of the energy density to clearly separate nucleation from kinetics; and an evolution law that comes from a conservation statement for interfaces. This enables clear prescription of nucleation through the source term of the conservation law and of kinetics through an interfacial velocity field. This model overcomes an important shortcoming of existing phase-field models, namely that the specification of kinetics and nucleation is both restrictive and extremely opaque. In this paper, we present a number of numerical calculations - in one and two dimensions - that characterize our formulation. These calculations illustrate (i) highly-sensitive rate-dependent nucleation; (ii) independent prescription of the forward and backward nucleation stresses without changing the energy landscape; (iii) stick-slip interface kinetics; (iii) the competition between nucleation and kinetics in determining the final microstructural state; (iv) the effect of anisotropic kinetics; and (v) the effect of non-monotone kinetics. These calculations demonstrate the ability of this formulation to precisely prescribe complex nucleation and kinetics in a simple and transparent manner. We also extend our conservation statement to describe the kinetics of the junction lines between microstructural interfaces and boundaries. This enables us to prescribe an additional kinetic relation for the boundary, and we examine the interplay between the bulk kinetics and the junction kinetics.

  7. Phase Holograms In PMMA

    NASA Technical Reports Server (NTRS)

    Maker, Paul D.; Muller, Richard E.

    1994-01-01

    Complex, computer-generated phase holograms written in thin films of poly(methyl methacrylate) (PMMA) by process of electron-beam exposure followed by chemical development. Spatial variations of phase delay in holograms quasi-continuous, as distinquished from stepwise as in binary phase holograms made by integrated-circuit fabrication. Holograms more precise than binary holograms. Greater continuity and precision results in decreased scattering loss and increased imaging efficiency.

  8. Infrared Multiphoton Dissociation Spectroscopy of a Gas-Phase Complex of Uranyl and 3-Oxa-Glutaramide: An Extreme Red-Shift of the [O=U=O]²⁺ Asymmetric Stretch

    SciTech Connect

    Gibson, John K.; Hu, Hanshi; Van Stipdonk, Michael J.; Berden, Giel; Oomens, Jos; Li, Jun

    2015-04-09

    The gas-phase complex UO₂(TMOGA)₂²⁺ (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700–1800 cm⁻¹ was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm⁻¹ (<1%) and a maximum deviation of 21 cm⁻¹ (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν₃ mode, which appeared at 965 cm⁻¹ and was predicted by DFT as 953 cm⁻¹. This ν₃ frequency is red-shifted relative to bare uranyl, UO₂²⁺, by ca. 150 cm⁻¹ due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO₂(acetone)₄²⁺. The uranyl ν₃ frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH₂. The computed ν₃ for UO₂(TMGA)₂²⁺, 950 cm⁻¹, is essentially the same as that for UO₂(TMOGA)₂²⁺, suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν₃ asymmetric stretching frequencies for the three actinyl complexes, UO₂(TMOGA)₂²⁺, NpO₂(TMOGA)₂²⁺ and PuO₂(TMOGA)₂²⁺, are comparable. This similarity is discussed in the context of the relationship between ν₃ and intrinsic actinide-oxygen bond energies in actinyl complexes.

  9. Infrared multiphoton dissociation spectroscopy of a gas-phase complex of uranyl and 3-oxa-glutaramide: an extreme red-shift of the [O═U═O](2+) asymmetric stretch.

    PubMed

    Gibson, John K; Hu, Han-Shi; Van Stipdonk, Michael J; Berden, Giel; Oomens, Jos; Li, Jun

    2015-04-01

    The gas-phase complex UO2(TMOGA)2(2+) (TMOGA = tetramethyl-3-oxa-glutaramide) prepared by electrospray ionization was characterized by infrared multiphoton dissociation (IRMPD) spectroscopy. The IRMPD spectrum from 700-1800 cm(-1) was interpreted using a computational study based on density functional theory. The predicted vibrational frequencies are in good agreement with the measured values, with an average deviation of only 8 cm(-1) (<1%) and a maximum deviation of 21 cm(-1) (<2%). The only IR peak assigned to the linear uranyl moiety was the asymmetric ν3 mode, which appeared at 965 cm(-1) and was predicted by DFT as 953 cm(-1). This ν3 frequency is red-shifted relative to bare uranyl, UO2(2+), by ca. 150 cm(-1) due to electron donation from the TMOGA ligands. Based on the degree of red-shifting, it is inferred that two TMOGA oxygen-donor ligands have a greater effective gas basicity than the four monodentate acetone ligands in UO2(acetone)4(2+). The uranyl ν3 frequency was also computed for uranyl coordinated by two TMGA ligands, in which the central Oether of TMOGA has been replaced by CH2. The computed ν3 for UO2(TMGA)2(2+), 950 cm(-1), is essentially the same as that for UO2(TMOGA)2(2+), suggesting that electron donation to uranyl from the Oether of TMOGA is minor. The computed ν3 asymmetric stretching frequencies for the three actinyl complexes, UO2(TMOGA)2(2+), NpO2(TMOGA)2(2+) and PuO2(TMOGA)2(2+), are comparable. This similarity is discussed in the context of the relationship between ν3 and intrinsic actinide-oxygen bond energies in actinyl complexes. PMID:25785482

  10. CrowdPhase: crowdsourcing the phase problem.

    PubMed

    Jorda, Julien; Sawaya, Michael R; Yeates, Todd O

    2014-06-01

    The human mind innately excels at some complex tasks that are difficult to solve using computers alone. For complex problems amenable to parallelization, strategies can be developed to exploit human intelligence in a collective form: such approaches are sometimes referred to as `crowdsourcing'. Here, a first attempt at a crowdsourced approach for low-resolution ab initio phasing in macromolecular crystallography is proposed. A collaborative online game named CrowdPhase was designed, which relies on a human-powered genetic algorithm, where players control the selection mechanism during the evolutionary process. The algorithm starts from a population of `individuals', each with a random genetic makeup, in this case a map prepared from a random set of phases, and tries to cause the population to evolve towards individuals with better phases based on Darwinian survival of the fittest. Players apply their pattern-recognition capabilities to evaluate the electron-density maps generated from these sets of phases and to select the fittest individuals. A user-friendly interface, a training stage and a competitive scoring system foster a network of well trained players who can guide the genetic algorithm towards better solutions from generation to generation via gameplay. CrowdPhase was applied to two synthetic low-resolution phasing puzzles and it was shown that players could successfully obtain phase sets in the 30° phase error range and corresponding molecular envelopes showing agreement with the low-resolution models. The successful preliminary studies suggest that with further development the crowdsourcing approach could fill a gap in current crystallographic methods by making it possible to extract meaningful information in cases where limited resolution might otherwise prevent initial phasing. PMID:24914965

  11. CrowdPhase: crowdsourcing the phase problem

    PubMed Central

    Jorda, Julien; Sawaya, Michael R.; Yeates, Todd O.

    2014-01-01

    The human mind innately excels at some complex tasks that are difficult to solve using computers alone. For complex problems amenable to parallelization, strategies can be developed to exploit human intelligence in a collective form: such approaches are sometimes referred to as ‘crowdsourcing’. Here, a first attempt at a crowdsourced approach for low-resolution ab initio phasing in macromolecular crystallography is proposed. A collaborative online game named CrowdPhase was designed, which relies on a human-powered genetic algorithm, where players control the selection mechanism during the evolutionary process. The algorithm starts from a population of ‘individuals’, each with a random genetic makeup, in this case a map prepared from a random set of phases, and tries to cause the population to evolve towards individuals with better phases based on Darwinian survival of the fittest. Players apply their pattern-recognition capabilities to evaluate the electron-density maps generated from these sets of phases and to select the fittest individuals. A user-friendly interface, a training stage and a competitive scoring system foster a network of well trained players who can guide the genetic algorithm towards better solutions from generation to generation via gameplay. CrowdPhase was applied to two synthetic low-resolution phasing puzzles and it was shown that players could successfully obtain phase sets in the 30° phase error range and corresponding molecular envelopes showing agreement with the low-resolution models. The successful preliminary studies suggest that with further development the crowdsourcing approach could fill a gap in current crystallographic methods by making it possible to extract meaningful information in cases where limited resolution might otherwise prevent initial phasing. PMID:24914965

  12. Cosmic Complexity

    NASA Technical Reports Server (NTRS)

    Mather, John C.

    2012-01-01

    What explains the extraordinary complexity of the observed universe, on all scales from quarks to the accelerating universe? My favorite explanation (which I certainty did not invent) ls that the fundamental laws of physics produce natural instability, energy flows, and chaos. Some call the result the Life Force, some note that the Earth is a living system itself (Gaia, a "tough bitch" according to Margulis), and some conclude that the observed complexity requires a supernatural explanation (of which we have many). But my dad was a statistician (of dairy cows) and he told me about cells and genes and evolution and chance when I was very small. So a scientist must look for me explanation of how nature's laws and statistics brought us into conscious existence. And how is that seemll"!gly Improbable events are actually happening a!1 the time? Well, the physicists have countless examples of natural instability, in which energy is released to power change from simplicity to complexity. One of the most common to see is that cooling water vapor below the freezing point produces snowflakes, no two alike, and all complex and beautiful. We see it often so we are not amazed. But physlc!sts have observed so many kinds of these changes from one structure to another (we call them phase transitions) that the Nobel Prize in 1992 could be awarded for understanding the mathematics of their common features. Now for a few examples of how the laws of nature produce the instabilities that lead to our own existence. First, the Big Bang (what an insufficient name!) apparently came from an instability, in which the "false vacuum" eventually decayed into the ordinary vacuum we have today, plus the most fundamental particles we know, the quarks and leptons. So the universe as a whole started with an instability. Then, a great expansion and cooling happened, and the loose quarks, finding themselves unstable too, bound themselves together into today's less elementary particles like protons and

  13. Cosmic Complexity

    NASA Technical Reports Server (NTRS)

    Mather, John C.

    2012-01-01

    What explains the extraordinary complexity of the observed universe, on all scales from quarks to the accelerating universe? My favorite explanation (which I certainty did not invent) ls that the fundamental laws of physics produce natural instability, energy flows, and chaos. Some call the result the Life Force, some note that the Earth is a living system itself (Gaia, a "tough bitch" according to Margulis), and some conclude that the observed complexity requires a supernatural explanation (of which we have many). But my dad was a statistician (of dairy cows) and he told me about cells and genes and evolution and chance when I was very small. So a scientist must look for me explanation of how nature's laws and statistics brought us into conscious existence. And how is that seemll"!gly Improbable events are actually happening a!1 the time? Well, the physicists have countless examples of natural instability, in which energy is released to power change from simplicity to complexity. One of the most common to see is that cooling water vapor below the freezing point produces snowflakes, no two alike, and all complex and beautiful. We see it often so we are not amazed. But physlc!sts have observed so many kinds of these changes from one structure to another (we call them phase transitions) that the Nobel Prize in 1992 could be awarded for understanding the mathematics of their common features. Now for a few examples of how the laws of nature produce the instabilities that lead to our own existence. First, the Big Bang (what an insufficient name!) apparently came from an instability, in which the "false vacuum" eventually decayed into the ordinary vacuum we have today, plus the most fundamental particles we know, the quarks and leptons. So the universe as a whole started with an instability. Then, a great expansion and cooling happened, and the loose quarks, finding themselves unstable too, bound themselves together into today's less elementary particles like protons and

  14. Launching Complex Tasks

    ERIC Educational Resources Information Center

    Jackson, Kara J.; Shahan, Emily C.; Gibbons, Lynsey K.; Cobb, Paul A.

    2012-01-01

    Mathematics lessons can take a variety of formats. In this article, the authors discuss lessons organized around complex mathematical tasks. These lessons usually unfold in three phases. First, the task is introduced to students. Second, students work on solving the task. Third, the teacher "orchestrates" a concluding whole-class discussion in…

  15. Bisthienylethene Th2im and its complex (Th2imH)2[ReCl6]: crystalline-phase photochromism, and photochemical regulation of luminescence and magnetic properties.

    PubMed

    Gong, Dan-Ping; Chen, Jun-Feng; Zhao, Yue; Cao, Deng-Ke

    2016-02-16

    Molecular assembly of bisthienylethene Th2im () and [ReCl6](2-) anions leads to the complex (Th2imH)2[ReCl6] (), in which a [ReCl6](2-) anion connects two equivalent Th2imH(+) cations through ClN/C hydrogen bonds. Crystal structures of and indicate that two thiophene groups of each Th2im/Th2imH(+) molecule adopt a photoactive antiparallel conformation. Thus, two compounds show crystalline-phase photochromism (CPP), i.e. reversible structural transformation between the open form and the closed form upon alternately irradiating the sample with UV light (365 nm) and visible light (574 nm for , 624 nm for ). It was found that the CPP behaviors of and could regulate their luminescence and/or magnetic properties. Their solid-state emissions (433, 448, 482, 531 and 570 nm for , and 460, 489, 535 and 593 nm for ) exhibited weaker intensities after UV irradiation with 365 nm light. Besides CPP and luminescence, compound shows field-induced slow magnetic relaxation. Before and after UV irradiation, this compound revealed different magnetic behaviors, including the differences in the shape of the χMT vs. T plot, D parameter, and the values of the relaxation barrier Ueff and the preexponential factor τ0. PMID:26790478

  16. High performance solid-phase extraction cleanup method coupled with gas chromatography-triple quadrupole mass spectrometry for analysis of polychlorinated naphthalenes and dioxin-like polychlorinated biphenyls in complex samples.

    PubMed

    Li, Fang; Jin, Jing; Tan, Dongqin; Xu, Jiazhi; Dhanjai; Ni, Yuwen; Zhang, Haijun; Chen, Jiping

    2016-05-27

    A solid-phase extraction (SPE) cleanup method was developed to purify the sample extracts for the analysis of polychlorinated naphthalenes (PCNs) and dioxin-like polychlorinated biphenyls (dl-PCBs). Monodisperse magnesium oxide (MgO) microspheres and basic alumina were used as SPE adsorbents. Important parameters of the SPE procedure were optimized, including the amount of basic alumina and the type and volume of the washing and elution solvents. The optimized SPE cleanup method exhibited excellent purification performance for the removal of organochlorinated compounds, lipid compounds, sulfur, and pigments. Additionally, it was found that the retention activities of congeners differed with the number and position of the chlorine substituents in PCNs. In this study, an analytical method based on a combination of accelerated solvent extraction (ASE) coupled with SPE cleanup and gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) is proposed for the analysis of PCNs and dl-PCBs in complex samples (sediment, pine needle, and scallop samples). The analytical method demonstrates good linearity, acceptable recovery (63-148%) and precision (relative standard deviations less than 26%). The limits of detection (LODs) of PCN and dl-PCB congeners were in the range of 0.6-19.1pgg(-1) and 0.4-8.6pgg(-1), respectively. The PCNs and dl-PCBs levels in these samples ranged from 0.16 to 3.07ngg(-1) dry weight (dw) and from undetectable to 0.07ngg(-1) dw, respectively. PMID:27130583

  17. Templated blue phases.

    PubMed

    Ravnik, Miha; Fukuda, Jun-ichi

    2015-11-21

    Cholesteric blue phases of a chiral liquid crystal are interesting examples of self-organised three-dimensional nanostructures formed by soft matter. Recently it was demonstrated that a polymer matrix introduced by photopolymerization inside a bulk blue phase not only stabilises the host blue phase significantly, but also serves as a template for blue phase ordering. We show with numerical modelling that the transfer of the orientational order of the blue phase to the surfaces of the polymer matrix, together with the resulting surface anchoring, can account for the templating behaviour of the polymer matrix inducing the blue phase ordering of an achiral nematic liquid crystal. Furthermore, tailoring the anchoring conditions of the polymer matrix surfaces can bring about orientational ordering different from those of bulk blue phases, including an intertwined complex of the polymer matrix and topological line defects of orientational order. Optical Kerr response of templated blue phases is explored, finding large Kerr constants in the range of K = 2-10 × 10(-9) m V(-2) and notable dependence on the surface anchoring strength. More generally, the presented numerical approach is aimed to clarify the role and actions of templating polymer matrices in complex chiral nematic fluids, and further to help design novel template-based materials from chiral liquid crystals. PMID:26412643

  18. Complexity Survey.

    ERIC Educational Resources Information Center

    Gordon, Sandra L.; Anderson, Beth C.

    To determine whether consensus existed among teachers about the complexity of common classroom materials, a survey was administered to 66 pre-service and in-service kindergarten and prekindergarten teachers. Participants were asked to rate 14 common classroom materials as simple, complex, or super-complex. Simple materials have one obvious part,…

  19. Communication complexity and information complexity

    NASA Astrophysics Data System (ADS)

    Pankratov, Denis

    Information complexity enables the use of information-theoretic tools in communication complexity theory. Prior to the results presented in this thesis, information complexity was mainly used for proving lower bounds and direct-sum theorems in the setting of communication complexity. We present three results that demonstrate new connections between information complexity and communication complexity. In the first contribution we thoroughly study the information complexity of the smallest nontrivial two-party function: the AND function. While computing the communication complexity of AND is trivial, computing its exact information complexity presents a major technical challenge. In overcoming this challenge, we reveal that information complexity gives rise to rich geometrical structures. Our analysis of information complexity relies on new analytic techniques and new characterizations of communication protocols. We also uncover a connection of information complexity to the theory of elliptic partial differential equations. Once we compute the exact information complexity of AND, we can compute exact communication complexity of several related functions on n-bit inputs with some additional technical work. Previous combinatorial and algebraic techniques could only prove bounds of the form theta( n). Interestingly, this level of precision is typical in the area of information theory, so our result demonstrates that this meta-property of precise bounds carries over to information complexity and in certain cases even to communication complexity. Our result does not only strengthen the lower bound on communication complexity of disjointness by making it more exact, but it also shows that information complexity provides the exact upper bound on communication complexity. In fact, this result is more general and applies to a whole class of communication problems. In the second contribution, we use self-reduction methods to prove strong lower bounds on the information

  20. Moon Phases

    ERIC Educational Resources Information Center

    Riddle, Bob

    2010-01-01

    When teaching Moon phases, the focus seems to be on the sequence of Moon phases and, in some grade levels, how Moon phases occur. Either focus can sometimes be a challenge, especially without the use of models and observations of the Moon. In this month's column, the author describes some of the lessons that he uses to teach the phases of the Moon…

  1. The effect of everolimus on renal angiomyolipoma in patients with tuberous sclerosis complex being treated for subependymal giant cell astrocytoma: subgroup results from the randomized, placebo-controlled, Phase 3 trial EXIST-1

    PubMed Central

    Kingswood, J. Chris; Jozwiak, Sergiusz; Belousova, Elena D.; Frost, Michael D.; Kuperman, Rachel A.; Bebin, E. Martina; Korf, Bruce R.; Flamini, J. Robert; Kohrman, Michael H.; Sparagana, Steven P.; Wu, Joyce Y.; Brechenmacher, Thomas; Stein, Karen; Berkowitz, Noah; Bissler, John J.; Franz, David N.

    2014-01-01

    Background Tuberous sclerosis complex (TSC) is characterized by benign tumours in multiple organs, including the brain, kidneys, skin, lungs and heart. Our objective was to evaluate everolimus, an mTOR inhibitor, in the treatment of angiomyolipoma in patients with subependymal giant cell astrocytoma (SEGA) associated with TSC. Methods EXamining everolimus In a Study of Tuberous Sclerosis Complex-1 (NCT00789828), a prospective, double-blind, randomized, placebo-controlled, Phase 3 study, examined everolimus in treating SEGA associated with TSC. Patients with serial SEGA growth from pre-baseline to baseline scans were randomly assigned (2:1) to receive 4.5 mg/m2/day everolimus (target blood trough: 5–15 ng/mL; n = 78) or placebo (n = 39). Angiomyolipoma response rates were analysed in patients (n = 44) with target baseline angiomyolipoma lesions (≥1 angiomyolipoma; longest diameter ≥1.0 cm). An angiomyolipoma response rate, defined as the proportion of patients with confirmed angiomyolipoma response, was assessed by kidney CT or MRI screening at baseline, at 12, 24 and 48 weeks and annually. Results Angiomyolipoma response rates were 53.3% (16/30) and 0% (0/14) for everolimus- and placebo-treated patients, respectively. Angiomyolipoma reductions ≥50% in the sum of volumes of all target lesions were seen only in everolimus-treated patients (56.5, 78.3 and 80.0%) compared with placebo-treated patients (0% at each time point) at Weeks 12, 24 and 48, respectively. Greater percentages of everolimus-treated patients had angiomyolipoma reductions ≥30% at these same time points (82.6, 100 and 100% versus 8.3, 18.2 and 16.7% for everolimus versus placebo, respectively). Conclusions Everolimus showed efficacy in reducing angiomyolipoma lesion volume in patients with SEGA associated with TSC. The trial is registered with ClinicalTrials.gov, number NCT00789828; http://clinicaltrials.gov/ct2/show/NCT00789828?term=EXIST-1&rank=1. PMID:24729041

  2. Complex Variability of the Hα Emission Line Profile of the T Tauri Binary System KH 15D: The Influence of Orbital Phase, Occultation by the Circumbinary Disk, and Accretion Phenomena

    NASA Astrophysics Data System (ADS)

    Hamilton, Catrina M.; Johns-Krull, Christopher M.; Mundt, Reinhard; Herbst, William; Winn, Joshua N.

    2012-06-01

    We have obtained 48 high-resolution echelle spectra of the pre-main-sequence eclipsing binary system KH 15D (V582 Mon, P = 48.37 days, e ~ 0.6, MA = 0.6 M ⊙, MB = 0.7 M ⊙). The eclipses are caused by a circumbinary disk (CBD) seen nearly edge on, which at the epoch of these observations completely obscured the orbit of star B and a large portion of the orbit of star A. The spectra were obtained over five contiguous observing seasons from 2001/2002 to 2005/2006 while star A was fully visible, fully occulted, and during several ingress and egress events. The Hα line profile shows dramatic changes in these time series data over timescales ranging from days to years. A fraction of the variations are due to "edge effects" and depend only on the height of star A above or below the razor sharp edge of the occulting disk. Other observed variations depend on the orbital phase: the Hα emission line profile changes from an inverse P-Cygni-type profile during ingress to an enhanced double-peaked profile, with both a blue and a red emission component, during egress. Each of these interpreted variations are complicated by the fact that there is also a chaotic, irregular component present in these profiles. We find that the complex data set can be largely understood in the context of accretion onto the stars from a CBD with gas flows as predicted by the models of eccentric T Tauri binaries put forward by Artymowicz & Lubow, Günther & Kley, and de Val-Borro et al. In particular, our data provide strong support for the pulsed accretion phenomenon, in which enhanced accretion occurs during and after perihelion passage.

  3. Room temperature ionic liquid-based dispersive liquid phase microextraction for the separation/preconcentration of trace Cd(2+) as 1-(2-pyridylazo)-2-naphthol (PAN) complex from environmental and biological samples and determined by FAAS.

    PubMed

    Khan, Sumaira; Soylak, Mustafa; Kazi, Tasneem Gul

    2013-12-01

    The current work develops a new green methodology for the separation/preconcentration of cadmium ions (Cd(2+)) using room temperature ionic liquid-dispersive liquid phase microextraction (RTIL-DLME) prior to analysis by flame atomic absorption spectrometry with microsample introduction system. Room temperature ionic liquids (RTIL) are considered "Green Solvents" for their thermally stable and non-volatile properties, here 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] was used as an extractant. The preconcentration of Cd(2+) in different waters and acid digested scalp hair samples were complexed with 1-(2-pyridylazo)-2-naphthol and extracted into the fine drops of RTILs. Some significant factors influencing the extraction efficiency of Cd(2+) and its subsequent determination, including pH, amount of ligand, volume of RTIL, dispersant solvent, sample volume, temperature, and incubation time were investigated in detail. The limit of detection and the enhancement factor under the optimal conditions were 0.05 μg/L and 50, respectively. The relative standard deviation of 100 μg/L Cd(2+) was 4.3 %. The validity of the proposed method was checked by determining Cd(2+) in certified reference material (TM-25.3 fortified water). The sufficient recovery (>98 %) of Cd(2+) with the certified value. The mean concentrations of Cd in lake water 13.2, waste water 15.7 and hair sample 16.8 μg/L, respectively and the developed method was applied satisfactorily to the preconcentration and determination of Cd(2+) in real samples. PMID:24197606

  4. COMPLEX VARIABILITY OF THE H{alpha} EMISSION LINE PROFILE OF THE T TAURI BINARY SYSTEM KH 15D: THE INFLUENCE OF ORBITAL PHASE, OCCULTATION BY THE CIRCUMBINARY DISK, AND ACCRETION PHENOMENA

    SciTech Connect

    Hamilton, Catrina M.; Johns-Krull, Christopher M.; Mundt, Reinhard; Herbst, William; Winn, Joshua N. E-mail: cmj@rice.edu E-mail: wherbst@wesleyan.edu

    2012-06-01

    We have obtained 48 high-resolution echelle spectra of the pre-main-sequence eclipsing binary system KH 15D (V582 Mon, P = 48.37 days, e {approx} 0.6, M{sub A} = 0.6 M{sub Sun }, M{sub B} = 0.7 M{sub Sun }). The eclipses are caused by a circumbinary disk (CBD) seen nearly edge on, which at the epoch of these observations completely obscured the orbit of star B and a large portion of the orbit of star A. The spectra were obtained over five contiguous observing seasons from 2001/2002 to 2005/2006 while star A was fully visible, fully occulted, and during several ingress and egress events. The H{alpha} line profile shows dramatic changes in these time series data over timescales ranging from days to years. A fraction of the variations are due to 'edge effects' and depend only on the height of star A above or below the razor sharp edge of the occulting disk. Other observed variations depend on the orbital phase: the H{alpha} emission line profile changes from an inverse P-Cygni-type profile during ingress to an enhanced double-peaked profile, with both a blue and a red emission component, during egress. Each of these interpreted variations are complicated by the fact that there is also a chaotic, irregular component present in these profiles. We find that the complex data set can be largely understood in the context of accretion onto the stars from a CBD with gas flows as predicted by the models of eccentric T Tauri binaries put forward by Artymowicz and Lubow, Guenther and Kley, and de Val-Borro et al. In particular, our data provide strong support for the pulsed accretion phenomenon, in which enhanced accretion occurs during and after perihelion passage.

  5. Phase-field modeling of multi-phase solidification

    NASA Astrophysics Data System (ADS)

    Nestler, Britta; Wheeler, Adam A.

    2002-08-01

    A phase-field model for a general class of multi-phase metallic alloys is now proposed which describes both multi-phase solidification phenomena as well as polycrystalline grain structures. The model serves as a computational method to simulate the motion and kinetics of multiple phase boundaries and enables the visualization of the diffusion processes and of the phase transitions in multi-phase systems. Numerical simulations are presented which illustrate the capability of the phase-field model to recover a variety of complex experimental growth structures. In particular, the phase-field model can be used to simulate microstructure evolutions in eutectic, peritectic and monotectic alloys. In addition, polycrystalline grain structures with effects such as wetting, grain growth, symmetry properties of adjacent triple junctions in thin film samples and stability criteria at multiple junctions are described by phase-field simulations.

  6. Complex derivatives

    NASA Astrophysics Data System (ADS)

    Battiston, Stefano; Caldarelli, Guido; Georg, Co-Pierre; May, Robert; Stiglitz, Joseph

    2013-03-01

    The intrinsic complexity of the financial derivatives market has emerged as both an incentive to engage in it, and a key source of its inherent instability. Regulators now faced with the challenge of taming this beast may find inspiration in the budding science of complex systems.

  7. Designing Complexity

    ERIC Educational Resources Information Center

    Glanville, Ranulph

    2007-01-01

    This article considers the nature of complexity and design, as well as relationships between the two, and suggests that design may have much potential as an approach to improving human performance in situations seen as complex. It is developed against two backgrounds. The first is a world view that derives from second order cybernetics and radical…

  8. Lipid Bilayers: Clusters, Domains and Phases

    PubMed Central

    Ackerman, David G.; Feigenson, Gerald W.

    2015-01-01

    In this chapter we discuss the complex mixing behavior of plasma membrane lipids. To do so, we first introduce the plasma membrane and membrane mixtures often used to model its complexity. We then discuss the nature of lipid phase behavior in bilayers and the distinction between these phases and other manifestations of nonrandom mixing found in one-phase mixtures, such as clusters, micelles, and microemulsions. Finally, we demonstrate the applicability of Gibbs phase diagrams to the study of increasingly complex model membrane systems, with a focus on phase coexistence, morphology and their implications for the cell plasma membrane. PMID:25658342

  9. Phase chaos in coupled oscillators.

    PubMed

    Popovych, Oleksandr V; Maistrenko, Yuri L; Tass, Peter A

    2005-06-01

    A complex high-dimensional chaotic behavior, phase chaos, is found in the finite-dimensional Kuramoto model of coupled phase oscillators. This type of chaos is characterized by half of the spectrum of Lyapunov exponents being positive and the Lyapunov dimension equaling almost the total system dimension. Intriguingly, the strongest phase chaos occurs for intermediate-size ensembles. Phase chaos is a common property of networks of oscillators of very different natures, such as phase oscillators, limit-cycle oscillators, and chaotic oscillators, e.g., Rössler systems. PMID:16089804

  10. Phase chaos in coupled oscillators

    NASA Astrophysics Data System (ADS)

    Popovych, Oleksandr V.; Maistrenko, Yuri L.; Tass, Peter A.

    2005-06-01

    A complex high-dimensional chaotic behavior, phase chaos, is found in the finite-dimensional Kuramoto model of coupled phase oscillators. This type of chaos is characterized by half of the spectrum of Lyapunov exponents being positive and the Lyapunov dimension equaling almost the total system dimension. Intriguingly, the strongest phase chaos occurs for intermediate-size ensembles. Phase chaos is a common property of networks of oscillators of very different natures, such as phase oscillators, limit-cycle oscillators, and chaotic oscillators, e.g., Rössler systems.

  11. Predicting complex mineral structures using genetic algorithms.

    PubMed

    Mohn, Chris E; Kob, Walter

    2015-10-28

    We show that symmetry-adapted genetic algorithms are capable of finding the ground state of a range of complex crystalline phases including layered- and incommensurate super-structures. This opens the way for the atomistic prediction of complex crystal structures of functional materials and mineral phases. PMID:26441052

  12. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  13. Carney Complex

    MedlinePlus

    ... Screening guidelines may change over time as new technologies are developed and more is learned about Carney complex. It is important to talk with your doctor about appropriate screening tests. Learn more about what to expect when having ...

  14. Complex master slave interferometry.

    PubMed

    Rivet, Sylvain; Maria, Michael; Bradu, Adrian; Feuchter, Thomas; Leick, Lasse; Podoleanu, Adrian

    2016-02-01

    A general theoretical model is developed to improve the novel Spectral Domain Interferometry method denoted as Master/Slave (MS) Interferometry. In this model, two functions, g and h are introduced to describe the modulation chirp of the channeled spectrum signal due to nonlinearities in the decoding process from wavenumber to time and due to dispersion in the interferometer. The utilization of these two functions brings two major improvements to previous implementations of the MS method. A first improvement consists in reducing the number of channeled spectra necessary to be collected at Master stage. In previous MSI implementation, the number of channeled spectra at the Master stage equated the number of depths where information was selected from at the Slave stage. The paper demonstrates that two experimental channeled spectra only acquired at Master stage suffice to produce A-scans from any number of resolved depths at the Slave stage. A second improvement is the utilization of complex signal processing. Previous MSI implementations discarded the phase. Complex processing of the electrical signal determined by the channeled spectrum allows phase processing that opens several novel avenues. A first consequence of such signal processing is reduction in the random component of the phase without affecting the axial resolution. In previous MSI implementations, phase instabilities were reduced by an average over the wavenumber that led to reduction in the axial resolution. PMID:26906857

  15. A theoretical investigation of the energetics and spectroscopic properties of the gas-phase linear proton-bound cation-molecule complexes, XCH(+)-N2 (X = O, S).

    PubMed

    Begum, Samiyara; Subramanian, Ranga

    2016-01-01

    The structural features, spectroscopic properties, and interaction energies of the linear proton-bound complexes of OCH(+) and its sulfur analog SCH(+) with N2 were investigated using the high-level ab initio methods MP2 and CCSD(T) as well as density functional theory with the aug-cc-pVXZ (X = D, T) basis sets. The rotational constants along with the vibrational frequencies of the cation-molecule complexes are reported here. A comparison of the interaction energies of the OCH(+)-N2 and SCH(+)-N2 complexes with those of the OCH(+)-CO and OCH(+)-OC complexes was also performed. The energies of all the complexes were determined at the complete basis set (CBS) limit. CS shows higher proton affinity at the C site than CO does, so the complex OCH(+)-N2 is relatively strongly bound and has a higher interaction energy than the SCH(+)-N2 complex. Symmetry-adapted perturbation theory (SAPT) was used to decompose the total interaction energies of the complexes into the attractive electrostatic interaction energy (E elst), induction energy (E ind), dispersion energy (E disp), and repulsive exchange energy (E exch). We found that the ratio of E ind to E disp is large for these linear proton-bound complexes, meaning that inductive effects are favored in these complexes. The bonding characteristics of the linear complexes were elucidated using natural bond orbital (NBO) theory. NBO analysis showed that the attractive interaction is caused by NBO charge transfer from the lone pair on N to the σ*(C-H) antibonding orbital in XCH(+)-N2 (X = O, S). The quantum theory of atoms in molecules (QTAIM) was used to analyze the strengths of the various bonds within and between the cation and molecule in each of these proton-bound complexes in terms of the electron density at bond critical points (BCP). Graphical Abstract Linear proton-bound complexes of OCH(+)-N2 and SCH(+)-N2. In these complexes, inductive effect is favored over dispersive effect. The attractive interaction is the NBO

  16. Structure of complexes between aluminum chloride and other chlorides, 2: Alkali-(chloroaluminates). Gaseous complexes

    NASA Technical Reports Server (NTRS)

    Hargittai, M.

    1980-01-01

    The structural chemistry of complexes between aluminum chloride and other metal chlorides is important both for practice and theory. Condensed-phase as well as vapor-phase complexes are of interest. Structural information on such complexes is reviewed. The first emphasis is given to the molten state because of its practical importance. Aluminum chloride forms volatile complexes with other metal chlorides and these vapor-phase complexes are dealt with in the second part. Finally, the variations in molecular shape and geometrical parameters are summarized.

  17. PHASE DETECTOR

    DOEpatents

    Kippenhan, D.O.

    1959-09-01

    A phase detector circuit is described for use at very high frequencies of the order of 50 megacycles. The detector circuit includes a pair of rectifiers inverted relative to each other. One voltage to be compared is applied to the two rectifiers in phase opposition and the other voltage to be compared is commonly applied to the two rectifiers. The two result:ng d-c voltages derived from the rectifiers are combined in phase opposition to produce a single d-c voltage having amplitude and polarity characteristics dependent upon the phase relation between the signals to be compared. Principal novelty resides in the employment of a half-wave transmission line to derive the phase opposing signals from the first voltage to be compared for application to the two rectifiers in place of the transformer commonly utilized for such purpose in phase detector circuits for operation at lower frequency.

  18. Complex networks: Patterns of complexity

    NASA Astrophysics Data System (ADS)

    Pastor-Satorras, Romualdo; Vespignani, Alessandro

    2010-07-01

    The Turing mechanism provides a paradigm for the spontaneous generation of patterns in reaction-diffusion systems. A framework that describes Turing-pattern formation in the context of complex networks should provide a new basis for studying the phenomenon.

  19. Holographic complexity in gauge/string superconductors

    NASA Astrophysics Data System (ADS)

    Momeni, Davood; Mansoori, Seyed Ali Hosseini; Myrzakulov, Ratbay

    2016-05-01

    Following a methodology similar to [1], we derive a holographic complexity for two dimensional holographic superconductors (gauge/string superconductors) with backreactions. Applying a perturbation method proposed by Kanno in Ref. [2], we study behaviors of the complexity for a dual quantum system near critical points. We show that when a system moves from the normal phase (T >Tc) to the superconductor phase (T complexity will be divergent.

  20. Combustion 2000: Phase II

    SciTech Connect

    Unknown

    1999-11-01

    The goals of the program are to develop a coal-fired high performance power generation system (HIPPS) that is capable of: thermal efficiency (HHV) {ge} 47%; NOx, SOx, and particulates {le} 10% NSPS (New Source Performance Standard); coal providing {ge} 65% of heat input; all solid wastes benign; and cost of electricity {le} 90% of present plants. Phase 1, which began in 1992, focused on the analysis of various configurations of indirectly fired cycles and on technical assessments of alternative plant subsystems and components, including performance requirements, developmental status, design options, complexity and reliability, and capital and operating costs. Phase 1 also included preliminary R and D and the preparation of designs for HIPPS commercial plants approximately 300 MWe in size. This Phase, Phase 2, had as its initial objective the development of a complete design base for the construction and operation of a HIPPS prototype plant to be constructed in Phase 3. As part of a descoping initiative, the Phase 3 program has been eliminated and work related to the commercial plant design has been ended. The rescoped program retained a program of engineering research and development focusing on high temperature heat exchangers, e.g. HITAF development (Task 2); a rescoped Task 6 that is pertinent to Vision 21 objectives and focuses on advanced cycle analysis and optimization, integration of gas turbines into complex cycles, and repowering designs; and preparation of the Phase 2 Technical Report (Task 8). This rescoped program deleted all subsystem testing (Tasks 3, 4,and 5) and the development of a site-specific engineering design and test plan for the HIPPS prototype plant (Task 7). Work reported herein is from: Task 2.1 HITAF Combustors; Task 2.2 HITAF Air Heaters; and Task 6 HIPPS Commercial Plant Design Update.

  1. Researching Complexity.

    ERIC Educational Resources Information Center

    Sumara, Dennis J.

    2000-01-01

    Discusses what Complexity Theory (presented as a rubric that collects theoretical understandings from a number of domains such as ecology, biology, neurology, and education) suggests about mind, selfhood, intelligence, and practices of reading, and the import of these reconceptualizations to reader-response researchers. Concludes that developing…

  2. Complex Clouds

    Atmospheric Science Data Center

    2013-04-16

    ...     View Larger Image The complex structure and beauty of polar clouds are highlighted by these images acquired ... Multi-angle Imaging SpectroRadiometer observes the daylit Earth continuously from pole to pole, and every 9 days views the entire globe ...

  3. Amorphic complexity

    NASA Astrophysics Data System (ADS)

    Fuhrmann, G.; Gröger, M.; Jäger, T.

    2016-02-01

    We introduce amorphic complexity as a new topological invariant that measures the complexity of dynamical systems in the regime of zero entropy. Its main purpose is to detect the very onset of disorder in the asymptotic behaviour. For instance, it gives positive value to Denjoy examples on the circle and Sturmian subshifts, while being zero for all isometries and Morse-Smale systems. After discussing basic properties and examples, we show that amorphic complexity and the underlying asymptotic separation numbers can be used to distinguish almost automorphic minimal systems from equicontinuous ones. For symbolic systems, amorphic complexity equals the box dimension of the associated Besicovitch space. In this context, we concentrate on regular Toeplitz flows and give a detailed description of the relation to the scaling behaviour of the densities of the p-skeletons. Finally, we take a look at strange non-chaotic attractors appearing in so-called pinched skew product systems. Continuous-time systems, more general group actions and the application to cut and project quasicrystals will be treated in subsequent work.

  4. Complex interactions

    NASA Astrophysics Data System (ADS)

    de Régules, Sergio

    2016-04-01

    Complexity science – which describes phenomena such as collective and emergent behaviour – is the focus of a new centre where researchers are examining everything from the spread of influenza to what a healthy heartbeat looks like. Sergio de Régules reports.

  5. SAR Image Complex Pixel Representations

    SciTech Connect

    Doerry, Armin W.

    2015-03-01

    Complex pixel values for Synthetic Aperture Radar (SAR) images of uniform distributed clutter can be represented as either real/imaginary (also known as I/Q) values, or as Magnitude/Phase values. Generally, these component values are integers with limited number of bits. For clutter energy well below full-scale, Magnitude/Phase offers lower quantization noise than I/Q representation. Further improvement can be had with companding of the Magnitude value.

  6. Representing SAR complex image pixels

    NASA Astrophysics Data System (ADS)

    Doerry, A. W.

    2016-05-01

    Synthetic Aperture Radar (SAR) images are often complex-valued to facilitate specific exploitation modes. Furthermore, these pixel values are typically represented with either real/imaginary (also known as I/Q) values, or as Magnitude/Phase values, with constituent components comprised of integers with limited number of bits. For clutter energy well below full-scale, Magnitude/Phase offers lower quantization noise than I/Q representation. Further improvement can be had with companding of the Magnitude value.

  7. Managing complexity of aerospace systems

    NASA Astrophysics Data System (ADS)

    Tamaskar, Shashank

    Growing complexity of modern aerospace systems has exposed the limits of conventional systems engineering tools and challenged our ability to design them in a timely and cost effective manner. According to the US Government Accountability Office (GAO), in 2009 nearly half of the defense acquisition programs are expecting 25% or more increase in unit acquisition cost. Increase in technical complexity has been identified as one of the primary drivers behind cost-schedule overruns. Thus to assure the affordability of future aerospace systems, it is increasingly important to develop tools and capabilities for managing their complexity. We propose an approach for managing the complexity of aerospace systems to address this pertinent problem. To this end, we develop a measure that improves upon the state-of-the-art metrics and incorporates key aspects of system complexity. We address the problem of system decomposition by presenting an algorithm for module identification that generates modules to minimize integration complexity. We demonstrate the framework on diverse spacecraft and show the impact of design decisions on integration cost. The measure and the algorithm together help the designer track and manage complexity in different phases of system design. We next investigate how complexity can be used as a decision metric in the model-based design (MBD) paradigm. We propose a framework for complexity enabled design space exploration that introduces the idea of using complexity as a non-traditional design objective. We also incorporate complexity with the component based design paradigm (a sub-field of MBD) and demonstrate it on several case studies. The approach for managing complexity is a small but significant contribution to the vast field of complexity management. We envision our approach being used in concert with a suite of complexity metrics to provide an ability to measure and track complexity through different stages of design and development. This will not

  8. Complex Hybrid Inflation and Baryogenesis

    SciTech Connect

    Delepine, David; Martinez, Carlos; Urena-Lopez, L. Arturo

    2007-04-20

    We propose a hybrid inflation model with a complex waterfall field which contains an interaction term that breaks the U(1) global symmetry associated with the waterfall field charge. We show that the asymmetric evolution of the real and imaginary parts of the complex field during the phase transition at the end of inflation translates into a charge asymmetry. The latter strongly depends on the vacuum expectation value of the waterfall field, which is well constrained by diverse cosmological observations.

  9. Dissolution de phases minérales MSiO3 ( M Cu, Co, Ni, Zn, Mg) imparfaitement cristallisées au contact de solutions d'agents complexants organiques (porphyrines, amino-acides, asphaltènes)

    NASA Astrophysics Data System (ADS)

    Bergaya, F.; Perruchot, A.; Van Damme, H.

    1983-05-01

    The kinetic and thermodynamic aspects of the dissolution of ill-organized ("gels") high surface area silicates of general formula MO- SiO2- nH2O( M = Cu, Co, Ni, Zn, Mg) in the presence of the following organic compounds have been investigated: meso-tetraphenylporphyrin (H 2TPP, water insoluble), mesotetra(N-methylpyridyl)porphyrin (H 3TMPyP, water soluble), glycine, and asphaltenes. Kinetic aspects were emphasised in the case of H 2TMPyP. The initial rate of the gross dissolution complexation process followed almost quantitatively (passing from one metal to another) the complexation rate of M2+ ions by H 2TMPyP in a purely homogeneous medium, suggesting that the rate limiting step of the overall process is not related to the chemical or physical processes occurring in the solid particles or at the solid-solution interface, but is simply the complexation, in the solution, of the M2+ ions released by the gel particles. Thermodynamic aspects were emphasised in the case of glycine. The total amount of metal which is extracted at equilibrium can be reasonably well predicted from a simple model which takes into account (i) the stability constant of the metal-glycine complex. (ii) the "solubility product" of the gel particles in water. The results obtained with asphaltones are closer to those obtained with glycine than to those obtained with porphyrins, suggesting that porphyrins represent only a minor population in the complexing functional groups of asphaltenes.

  10. Complex high-temperature phase transitions in Li{sub 2}B{sub 12}H{sub 12} and Na{sub 2}B{sub 12}H{sub 12}

    SciTech Connect

    Verdal, Nina; Her, Jae-Hyuk; Stavila, Vitalie; Soloninin, Alexei V.; Babanova, Olga A.; Skripov, Alexander V.; Udovic, Terrence J.; Rush, John J.

    2014-04-01

    Differential scanning calorimetry measurements of Li{sub 2}B{sub 12}H{sub 12} and Na{sub 2}B{sub 12}H{sub 12} indicate hysteretic transformations to high-temperature phases at ≈615 K and 529 K, respectively, upon heating (1 K/min) from room temperature. X-ray and neutron powder diffraction measurements corroborate the phase-change behavior. For Li{sub 2}B{sub 12}H{sub 12}, the diffraction data are consistent with a previous study suggesting that the overall face-centered-cubic arrangement of icosahedral B{sub 12}H{sub 12}{sup 2−} anions is maintained upon transformation to the high-temperature polymorph, although the anions are now orientationally disordered and the Li{sup +} cations crystallographically disordered within an enlarged lattice. For Na{sub 2}B{sub 12}H{sub 12}, the diffraction data indicate the existence of three different high-temperature phases in addition to the known low-temperature monoclinic phase. The highest-temperature structure possesses Im3{sup -}m symmetry and exhibits a body-centered-cubic arrangement of orientationally disordered anions. The interstitial, disordered Na{sup +} cations appear to favor off-center positions within the distorted tetrahedral sites formed by the anions in this structure. An intermediate Pm3{sup -}n-symmetric phase at lower temperature is the result of a partial ordering of this higher-temperature structure. A third, minor, face-centered-cubic phase coexists with these high-temperature polymorphs. {sup 1}H NMR measurements of Li{sub 2}B{sub 12}H{sub 12} and Na{sub 2}B{sub 12}H{sub 12} reveal an approximately two-orders-of-magnitude increase in the reorientational jump rate of the anions in both cases upon transformation to their high-temperature structures. The enhanced anion mobilities were corroborated by neutron scattering fixed-window scans across the respective phase boundaries. The inherent cation disorder associated with these high-temperature polymorphs suggests their potential use as superionic

  11. Managing Complexity

    SciTech Connect

    Chassin, David P.; Posse, Christian; Malard, Joel M.

    2004-08-01

    Physical analogs have shown considerable promise for understanding the behavior of complex adaptive systems, including macroeconomics, biological systems, social networks, and electric power markets. Many of today’s most challenging technical and policy questions can be reduced to a distributed economic control problem. Indeed, economically-based control of large-scale systems is founded on the conjecture that the price-based regulation (e.g., auctions, markets) results in an optimal allocation of resources and emergent optimal system control. This paper explores the state of the art in the use physical analogs for understanding the behavior of some econophysical systems and to deriving stable and robust control strategies for them. In particular we review and discussion applications of some analytic methods based on the thermodynamic metaphor according to which the interplay between system entropy and conservation laws gives rise to intuitive and governing global properties of complex systems that cannot be otherwise understood.

  12. Singlet oxygen O2(a1Δg) formation via UV-excitation of isoprene-oxygen C5H8-O2 encounter complexes in gas phase

    NASA Astrophysics Data System (ADS)

    Pyryaeva, Alexandra P.; Goldort, Veniamin G.; Kochubei, Sergei A.; Baklanov, Alexey V.

    2014-08-01

    Photogeneration of singlet oxygen O2(a1Δg) resulted from photoexcitation at 248 and 266 nm of isoprene-oxygen mixtures at elevated oxygen pressure has been investigated. Pulse energy and oxygen pressure dependence of the singlet oxygen yield indicate one-quantum photoexcitation of the encounter complex isoprene-oxygen C5H8-O2 as a source of O2(a1Δg). Suggested mechanism of O2(a1Δg) photogeneration involves direct excitation of complex with simultaneous change of both partner spins like that observed in van der Waals complex C5H8-O2 [Vidma et al., J. Chem. Phys. 137 (2012) 054305]. Other supposed pathways involve collision-induced photogeneration of Herzberg III state O2(A'3Δg) or triplet isoprene as the intermediates.

  13. Solid State Collapse of a High-Spin Square-Planar Fe(II) Complex, Solution Phase Dynamics, and Electronic Structure Characterization of an Fe(II)2 Dimer.

    PubMed

    Pascualini, Matias E; Stoian, Sebastian A; Ozarowski, Andrew; Abboud, Khalil A; Veige, Adam S

    2016-06-01

    Square-planar high-spin Fe(II) molecular compounds are rare, and until recently, the only four examples of non-macrocyclic or sterically driven molecular compounds of this kind shared a common FeO4 core. The trianionic pincer-type ligand [CF3-ONO]H3 (1) supports the high-spin square-planar Fe(II) complex {[CF3-ONO]FeCl}{Li(Sv)2}2 (2). In the solid state, 2 forms the dimer complex {[CF3-ONO]Fe}2{(μ-Cl)2(μ-LiTHF)4} (3) in 96% yield by simply applying a vacuum or stirring it with pentane for 2 h. A detailed high-frequency electron paramagnetic resonance and field-dependent (57)Fe Mössbauer investigation of 3 revealed a weak antiferromagnetic exchange interaction between the local iron spins which exhibit a zero-field splitting tensor characterized by negative D parameter. In solution, 2 is in equilibrium with the solvento complex {[CF3-ONO]FeCl(THF)}{Li2(Sv)4} (2·Sv) and the dimer 3. A combination of frozen solution (57)Fe Mössbauer spectroscopy and single crystal X-ray crystallography helped elucidate the solvent dependent equilibrium between these three species. The oxidation chemistry of 2·Sv was investigated. Complex 2 reacts readily with the one-electron oxidizing agent CuCl2 to give the Fe(III) complex {[CF3-ONO]FeCl2}{Li(THF)2}2 (4). Also, 2·Sv reacts with 2 equiv of TlPF6 to form the Fe(III) complex [CF3-ONO]Fe(THF)3 (5). PMID:27182796

  14. New quenched-in fluorite-type materials in the Bi{sub 2}O{sub 3}-La{sub 2}O{sub 3}-PbO system: Synthesis and complex phase behaviour up to 750 {sup o}C

    SciTech Connect

    Webster, Nathan A.S.; Hartlieb, Karel J.; Saines, Paul J.; Ling, Chris D.; Lincoln, Frank J.

    2011-04-15

    Research highlights: {yields} New quenched-in fluorite-type materials synthesised by solid state reaction. {yields} Compositions (BiO{sub 1.5}){sub 0.94-x}(LaO{sub 1.5}){sub 0.06}(PbO){sub x}, x = 0.02, 0.03, 0.04 and 0.05. {yields} Variable-temperature X-ray diffraction data collected in the range of 400-750 {sup o}C. {yields} Fluorite-type structure transforms during heating, complex phase behaviour characterised. {yields} Tetragonal, monoclinic, rhombohedral and bcc phases identified. -- Abstract: New quenched-in fluorite-type materials with composition (BiO{sub 1.5}){sub 0.94-x}(LaO{sub 1.5}){sub 0.06}(PbO){sub x}, x = 0.02, 0.03, 0.04 and 0.05, were synthesised by solid state reaction. The new materials undergo a number of phase transformations during heating between room temperature and 750 {sup o}C, as indicated by differential thermal analysis. Variable temperature X-ray diffraction performed on the material (BiO{sub 1.5}){sub 0.92}(LaO{sub 1.5}){sub 0.06}(PbO){sub 0.02} revealed that the quenched-in fcc fluorite-type material first undergoes a transformation to a {beta}-Bi{sub 2}O{sub 3}-type tetragonal phase around 400 {sup o}C. In the range 450-700 {sup o}C, {alpha}-Bi{sub 2}O{sub 3}-type monoclinic, Bi{sub 12}PbO{sub 19}-type bcc and {beta}{sub 1}/{beta}{sub 2}-type rhombohedral phases, and what appeared to be a {epsilon}-type monoclinic phase, were observed, before a single-phase fluorite-type material was regained at 750 {sup o}C.

  15. Venus Phasing.

    ERIC Educational Resources Information Center

    Riddle, Bob

    1997-01-01

    Presents a science activity designed to introduce students to the geocentric and heliocentric models of the universe. Helps students discover why phase changes on Venus knocked Earth out of the center of the universe. (DKM)

  16. Solid-phase enzyme immunoassay or radioimmunoassay for the detection of immune complexes based on their recognition by conglutinin: conglutinin-binding test. A comparative study with 125I-labelled C1q binding and Raji-cell RIA tests

    PubMed Central

    Casali, P.; Bossus, A.; Carpentier, Nicole A.; Lambert, P.-H.

    1977-01-01

    Bovine conglutinin was used in a solid-phase assay for the detection of immune complexes. In a first step, the tested serum sample is incubated in polypropylene tubes coated with conglutinin to allow C3-coated immune complexes to bind to solid-phase conglutinin. In a second step, the conglutinin-bound complexes are detected using an enzyme-conjugated or radiolabelled anti-immunoglobulin antibody. The conglutinin-binding (KgB) test does not suffer from the interference of DNA, heparin or endotoxins. Its limit of sensitivity for aggregated IgG is 3 μg/ml undiluted human serum. Immune complexes prepared in vitro using tetanus toxoid, or DNA, and corresponding antibodies in human sera could be detected at various antigen/antibody ratios and at antibody concentrations lower than 8 μg/ml. The KgB test allowed for the detection of immune complexes in sera from patients with systemic lupus erythematosus, rheumatoid arthritis, idiopathic vasculitis, leprosy and leukemia. These sera were also tested using the 125I-labelled Clq-binding activity (BA) test and the KgB test simultaneously, and a significant rank order correlation was observed. In patients with leukemia, a significant correlation was observed using three tests, KgB, 125I-labelled Clq BA and Raji-cell radioimmunoassay (RIA). Therefore, the KgB test appears as a simple and reproducible method, utilizing a very stable reagent, with a sensitivity and specificity comparable to the other tests studied and allowing for clinical application. PMID:332422

  17. Emergent complex neural dynamics

    NASA Astrophysics Data System (ADS)

    Chialvo, Dante R.

    2010-10-01

    A large repertoire of spatiotemporal activity patterns in the brain is the basis for adaptive behaviour. Understanding the mechanism by which the brain's hundred billion neurons and hundred trillion synapses manage to produce such a range of cortical configurations in a flexible manner remains a fundamental problem in neuroscience. One plausible solution is the involvement of universal mechanisms of emergent complex phenomena evident in dynamical systems poised near a critical point of a second-order phase transition. We review recent theoretical and empirical results supporting the notion that the brain is naturally poised near criticality, as well as its implications for better understanding of the brain.

  18. Laparoscopic Chromopertubation, Myomectomy with Opening of the Uterine Cavity and Hysteroscopy during the Early Implantation Phase of an Undetected Pregnancy: Delivery of a Child with a Complex Brain Malformation

    PubMed Central

    Mann, C.; Karl, K.; Ertl-Wagner, B.; Weigand, H.; Thaler, C. J.

    2016-01-01

    A previously infertile woman underwent laparoscopic myomectomy involving opening of the uterine cavity and chromopertubation that showed closed Fallopian tubes during the early implantation stage of an undetected pregnancy. The pregnancy was not terminated, and a child with a complex brain malformation was delivered at 37 weeks of gestation by Cesarean section. PMID:27570253

  19. Probing the microsolvation of a quaternary ion complex: gas phase vibrational spectroscopy of (NaSO4(-))2(H2O)(n=0-6, 8).

    PubMed

    Wende, Torsten; Heine, Nadja; Yacovitch, Tara I; Asmis, Knut R; Neumark, Daniel M; Jiang, Ling

    2016-01-01

    We report infrared multiple photon dissociation spectra of cryogenically-cooled (NaSO4(-))2(H2O)n dianions (n = 0-6, 8) in the spectral range of the sulfate stretching and bending modes (580-1750 cm(-1)). Characteristic absorption bands and structural trends are identified based on a comparison to harmonic spectra of minimum-energy structures. The bare quarternary complex (NaSO4(-))2 exhibits a C2h structure containing two fourfold-coordinated sodium cations in-between the two chelating sulfate dianions. Its stepwise solvation is driven by an interplay of SO4(2-)-H2O and Na(+)-H2O interactions. The first water binds in a tridentate intersulfate-bridging fashion. The second and third water molecules bind to the sulfate groups at either end of the complex, which is followed by the onset of water hydrogen-bond network formation. In contrast to the binary ion pair, NaSO4(-), no clear evidence for the disruption of the quaternary ion complex upon microhydration is found up to n = 8, underlining its remarkable stability and suggesting that the formation of quaternary ion complexes plays a central role in the initial stages of prenucleation in aqueous Na2SO4 solutions. PMID:26608709

  20. Complex Systems

    PubMed Central

    Goldberger, Ary L.

    2006-01-01

    Physiologic systems in health and disease display an extraordinary range of temporal behaviors and structural patterns that defy understanding based on linear constructs, reductionist strategies, and classical homeostasis. Application of concepts and computational tools derived from the contemporary study of complex systems, including nonlinear dynamics, fractals and “chaos theory,” is having an increasing impact on biology and medicine. This presentation provides a brief overview of an emerging area of biomedical research, including recent applications to cardiopulmonary medicine and chronic obstructive lung disease. PMID:16921107

  1. [Carney complex].

    PubMed

    Kacerovská, D; Michal, M; Síma, R; Grossmann, P; Kazakov, D V

    2011-10-01

    Carney complex is a clinically and genetically heterogeneous disease, with at least two genetic loci including the PRKAR1A gene located on chromosome 17 and the CNC2 locus mapped to chromosome 2. Clinically this syndrome is characterized by multiple myxomas occurring in different anatomic sites, mucocutaneous pigmentary lesions, and a variety of non-endocrine and endocrine tumors, often causing endocrine abnormalities, involving various organs. Knowledge of morphological findings in CNC patients with their typical locations is necessary to raise suspicion of this syndrome by pathologists. Confirmation of the diagnosis allows regular clinical check-ups and early treatment of these patients. PMID:22145222

  2. Carney complex.

    PubMed

    Espiard, Stéphanie; Bertherat, Jérôme

    2013-01-01

    Carney complex is a rare, dominantly inherited multiple endocrine neoplasia syndrome, affecting endocrine glands as the adrenal cortex (causing Cushing's syndrome), the pituitary and the thyroid. It is associated with many other nonendocrine tumors, including cardiac myxomas, testicular tumors, melanotic schwannoma, breast myxomatosis, and abnormal pigmentation (lentiginosis) or myxomas of the skin. The gene located on the CNC1 locus was identified 12 years ago as the regulatory subunit 1A (R1A) of the protein kinase A (PRKAR1A) located at 17q22-24. Inactivating heterozygous germline mutations of PRKAR1A are observed in about two thirds of Carney complex patients with some genotype-phenotype correlation useful for follow-up and prognosis. More rarely, mutations of phosphodiesterase genes have been reported in patients presenting mainly with Cushing's syndrome. In vitro and in vivo studies help to understand how R1A inactivation leads to tumorigenesis. PRKAR1A appears to be a relatively weak tumorigenic signal which can cooperate with other signaling pathways and tumor suppressors. PMID:23652670

  3. Phase unwrapping via graph cuts.

    PubMed

    Bioucas-Dias, José M; Valadão, Gonçalo

    2007-03-01

    Phase unwrapping is the inference of absolute phase from modulo-2pi phase. This paper introduces a new energy minimization framework for phase unwrapping. The considered objective functions are first-order Markov random fields. We provide an exact energy minimization algorithm, whenever the corresponding clique potentials are convex, namely for the phase unwrapping classical Lp norm, with p > or = 1. Its complexity is KT (n, 3n), where K is the length of the absolute phase domain measured in 2pi units and T (n, m) is the complexity of a max-flow computation in a graph with n nodes and m edges. For nonconvex clique potentials, often used owing to their discontinuity preserving ability, we face an NP-hard problem for which we devise an approximate solution. Both algorithms solve integer optimization problems by computing a sequence of binary optimizations, each one solved by graph cut techniques. Accordingly, we name the two algorithms PUMA, for phase unwrappping max-flow/min-cut. A set of experimental results illustrates the effectiveness of the proposed approach and its competitiveness in comparison with state-of-the-art phase unwrapping algorithms. PMID:17357730

  4. Self-Assembled Multimetallic/Peptide Complexes: Structures and Unimolecular Reactions of [Mn (GlyGly-H)2n-1 ](+) and Mn+1 (GlyGly-H2n ](2+) Clusters in the Gas Phase.

    PubMed

    Moghaddam, Maryam B; Jami-Alahmadi, Yasaman; Fridgen, Travis D

    2015-10-26

    The unimolecular chemistry and structures of self-assembled complexes containing multiple alkaline-earth-metal dications and deprotonated GlyGly ligands are investigated. Singly and doubly charged ions [Mn (GlyGly-H)n-1 ](+) (n=2-4), [Mn+1 (GlyGly-H)2n ](2+) (n=2,4,6), and [M(GlyGly-H)GlyGly](+) were observed. The losses of 132 Da (GlyGly) and 57 Da (determined to be aminoketene) were the major dissociation pathways for singly charged ions. Doubly charged Mg(2+) clusters mainly lost GlyGly, whereas those containing Ca(2+) or Sr(2+) also underwent charge separation. Except for charge separation, no loss of metal cations was observed. Infrared multiple photon dissociation spectra were the most consistent with the computed IR spectra for the lowest energy structures, in which deprotonation occurs at the carboxyl acid groups and all amide and carboxylate oxygen atoms are complexed to the metal cations. The N-H stretch band, observed at 3350 cm(-1) , is indicative of hydrogen bonding between the amine nitrogen atoms and the amide hydrogen atom. This study represents the first into large self-assembled multimetallic complexes bound by peptide ligands. PMID:26279054

  5. Phased array ghost elimination.

    PubMed

    Kellman, Peter; McVeigh, Elliot R

    2006-05-01

    Parallel imaging may be applied to cancel ghosts caused by a variety of distortion mechanisms, including distortions such as off-resonance or local flow, which are space variant. Phased array combining coefficients may be calculated that null ghost artifacts at known locations based on a constrained optimization, which optimizes SNR subject to the nulling constraint. The resultant phased array ghost elimination (PAGE) technique is similar to the method known as sensitivity encoding (SENSE) used for accelerated imaging; however, in this formulation is applied to full field-of-view (FOV) images. The phased array method for ghost elimination may result in greater flexibility in designing acquisition strategies. For example, in multi-shot EPI applications ghosts are typically mitigated by the use of an interleaved phase encode acquisition order. An alternative strategy is to use a sequential, non-interleaved phase encode order and cancel the resultant ghosts using PAGE parallel imaging. Cancellation of ghosts by means of phased array processing makes sequential, non-interleaved phase encode acquisition order practical, and permits a reduction in repetition time, TR, by eliminating the need for echo-shifting. Sequential, non-interleaved phase encode order has benefits of reduced distortion due to off-resonance, in-plane flow and EPI delay misalignment. Furthermore, the use of EPI with PAGE has inherent fat-water separation and has been used to provide off-resonance correction using a technique referred to as lipid elimination with an echo-shifting N/2-ghost acquisition (LEENA), and may further generalized using the multi-point Dixon method. Other applications of PAGE include cancelling ghosts which arise due to amplitude or phase variation during the approach to steady state. Parallel imaging requires estimates of the complex coil sensitivities. In vivo estimates may be derived by temporally varying the phase encode ordering to obtain a full k-space dataset in a scheme

  6. Phase Won.

    ERIC Educational Resources Information Center

    Kocher, Erik

    2003-01-01

    Describes ten steps involved in successful renovation of a college recreation center. They are as follows: hire the right architect, be realistic about costs, devise a plan, do a mental walk through, approach the renovation in phases, communicate to users, expect lost revenue and displacement issues, continue to communicate with architects and…

  7. Analysis of cardiac fibrillation using phase mapping.

    PubMed

    Clayton, Richard H; Nash, Martyn P

    2015-03-01

    The sequence of myocardial electrical activation during fibrillation is complex and changes with each cycle. Phase analysis represents the electrical activation-recovery process as an angle. Lines of equal phase converge at a phase singularity at the center of rotation of a reentrant wave, and the identification of reentry and tracking of reentrant wavefronts can be automated. We examine the basic ideas behind phase analysis. With the exciting prospect of using phase analysis of atrial electrograms to guide ablation in the human heart, we highlight several recent developments in preprocessing electrograms so that phase can be estimated reliably. PMID:25784022

  8. A computer model for one-dimensional mass and energy transport in and around chemically reacting particles, including complex gas-phase chemistry, multicomponent molecular diffusion, surface evaporation, and heterogeneous reaction

    NASA Technical Reports Server (NTRS)

    Cho, S. Y.; Yetter, R. A.; Dryer, F. L.

    1992-01-01

    Various chemically reacting flow problems highlighting chemical and physical fundamentals rather than flow geometry are presently investigated by means of a comprehensive mathematical model that incorporates multicomponent molecular diffusion, complex chemistry, and heterogeneous processes, in the interest of obtaining sensitivity-related information. The sensitivity equations were decoupled from those of the model, and then integrated one time-step behind the integration of the model equations, and analytical Jacobian matrices were applied to improve the accuracy of sensitivity coefficients that are calculated together with model solutions.

  9. Berry phase in nonlinear systems

    SciTech Connect

    Liu, J.; Fu, L. B.

    2010-05-15

    The Berry phase acquired by an eigenstate that experienced a nonlinear adiabatic evolution is investigated thoroughly. The circuit integral of the Berry connection of the instantaneous eigenstate cannot account for the adiabatic geometric phase, while the Bogoliubov excitations around the eigenstates are found to be accumulated during the nonlinear adiabatic evolution and contribute a finite phase of geometric nature. A two-mode model is used to illustrate our theory. Our theory is applicable to Bose-Einstein condensate, nonlinear light propagation, and Ginzburg-Landau equations for complex order parameters in condensed-matter physics.

  10. Facile removal of high mannose structures prior to extracting complex type N-glycans from de-N-glycosylated peptides retained by C18 solid phase to allow more efficient glycomic mapping

    PubMed Central

    Lin, Chi-Hung; Kuo, Chu-Wei; Jarvis, Donald L; Khoo, Kay-Hooi

    2014-01-01

    The relative amount of high mannose structures within an N-glycomic pool differs from one source to another but quite often it predominates over the larger size complex type structures carrying biologically important glyco-epitopes. An efficient method to separate these two classes of N-glycans would significantly aid in detecting the lower abundant components by mass spectrometry. Capitalizing on an initial observation that only high mannose type structures were recovered in the flow through fraction when PNGase F digested peptides were passed through a C18 cartridge in 0.1% formic acid, we demonstrated here that native complex type N-glycans can be retained by C18 cartridge and to be efficiently separated from both the smaller high mannose type structures, as well as de-N-glycosylated peptides by stepwise elution with increasing acetonitrile concentration. The weak retention of the largely hydrophilic N-glycans on C18 resin is dependent not only on size but also increased by the presence of α6-fucosylation. This was shown by comparing the resulting N-glycomic profiles of the washed and low acetonitrile eluted fractions derived from both a human cancer cell line and an insect cell line. PMID:24174266

  11. Quantum phase magnification

    NASA Astrophysics Data System (ADS)

    Hosten, O.; Krishnakumar, R.; Engelsen, N. J.; Kasevich, M. A.

    2016-06-01

    Quantum metrology exploits entangled states of particles to improve sensing precision beyond the limit achievable with uncorrelated particles. All previous methods required detection noise levels below this standard quantum limit to realize the benefits of the intrinsic sensitivity provided by these states. We experimentally demonstrate a widely applicable method for entanglement-enhanced measurements without low-noise detection. The method involves an intermediate quantum phase magnification step that eases implementation complexity. We used it to perform squeezed-state metrology 8 decibels below the standard quantum limit with a detection system that has a noise floor 10 decibels above the standard quantum limit.

  12. Quantum phase magnification.

    PubMed

    Hosten, O; Krishnakumar, R; Engelsen, N J; Kasevich, M A

    2016-06-24

    Quantum metrology exploits entangled states of particles to improve sensing precision beyond the limit achievable with uncorrelated particles. All previous methods required detection noise levels below this standard quantum limit to realize the benefits of the intrinsic sensitivity provided by these states. We experimentally demonstrate a widely applicable method for entanglement-enhanced measurements without low-noise detection. The method involves an intermediate quantum phase magnification step that eases implementation complexity. We used it to perform squeezed-state metrology 8 decibels below the standard quantum limit with a detection system that has a noise floor 10 decibels above the standard quantum limit. PMID:27339982

  13. Twisted complex superfluids in optical lattices

    NASA Astrophysics Data System (ADS)

    Jürgensen, Ole; Sengstock, Klaus; Lühmann, Dirk-Sören

    2015-09-01

    We show that correlated pair tunneling drives a phase transition to a twisted superfluid with a complex order parameter. This unconventional superfluid phase spontaneously breaks the time-reversal symmetry and is characterized by a twisting of the complex phase angle between adjacent lattice sites. We discuss the entire phase diagram of the extended Bose—Hubbard model for a honeycomb optical lattice showing a multitude of quantum phases including twisted superfluids, pair superfluids, supersolids and twisted supersolids. Furthermore, we show that the nearest-neighbor interactions lead to a spontaneous breaking of the inversion symmetry of the lattice and give rise to dimerized density-wave insulators, where particles are delocalized on dimers. For two components, we find twisted superfluid phases with strong correlations between the species already for surprisingly small pair-tunneling amplitudes. Interestingly, this ground state shows an infinite degeneracy ranging continuously from a supersolid to a twisted superfluid.

  14. Twisted complex superfluids in optical lattices.

    PubMed

    Jürgensen, Ole; Sengstock, Klaus; Lühmann, Dirk-Sören

    2015-01-01

    We show that correlated pair tunneling drives a phase transition to a twisted superfluid with a complex order parameter. This unconventional superfluid phase spontaneously breaks the time-reversal symmetry and is characterized by a twisting of the complex phase angle between adjacent lattice sites. We discuss the entire phase diagram of the extended Bose-Hubbard model for a honeycomb optical lattice showing a multitude of quantum phases including twisted superfluids, pair superfluids, supersolids and twisted supersolids. Furthermore, we show that the nearest-neighbor interactions lead to a spontaneous breaking of the inversion symmetry of the lattice and give rise to dimerized density-wave insulators, where particles are delocalized on dimers. For two components, we find twisted superfluid phases with strong correlations between the species already for surprisingly small pair-tunneling amplitudes. Interestingly, this ground state shows an infinite degeneracy ranging continuously from a supersolid to a twisted superfluid. PMID:26345721

  15. Twisted complex superfluids in optical lattices

    PubMed Central

    Jürgensen, Ole; Sengstock, Klaus; Lühmann, Dirk-Sören

    2015-01-01

    We show that correlated pair tunneling drives a phase transition to a twisted superfluid with a complex order parameter. This unconventional superfluid phase spontaneously breaks the time-reversal symmetry and is characterized by a twisting of the complex phase angle between adjacent lattice sites. We discuss the entire phase diagram of the extended Bose—Hubbard model for a honeycomb optical lattice showing a multitude of quantum phases including twisted superfluids, pair superfluids, supersolids and twisted supersolids. Furthermore, we show that the nearest-neighbor interactions lead to a spontaneous breaking of the inversion symmetry of the lattice and give rise to dimerized density-wave insulators, where particles are delocalized on dimers. For two components, we find twisted superfluid phases with strong correlations between the species already for surprisingly small pair-tunneling amplitudes. Interestingly, this ground state shows an infinite degeneracy ranging continuously from a supersolid to a twisted superfluid. PMID:26345721

  16. [Carney complex].

    PubMed

    Losada Grande, Eladio José; Al Kassam Martínez, Daniel; González Boillos, Margarita

    2011-01-01

    Carney complex (CNC) is an autosomal dominantly inherited syndrome characterized by spotty skin pigmentation, cardiac and cutaneous myxoma, and endocrine overactivity. Skin pigmentation includes lentigines and blue nevi. Myxomas may occur in breast, skin and heart. Cardiac myxomas may be multiple and occur in any cardiac chamber, and are more prone to recurrence. The most common endocrine gland manifestation is an ACTH-independent Cushing's syndrome due to primary pigmented nodular adrenocortical disease (PPNAD). PPNAD may occur isolated, with no other signs of CNC. Pituitary and thyroid glands and gonads are also involved. The PRKAR1A gene, located in 17 q22-24, encodes type 1A regulatory subunit of protein kinase A. Inactivating germline mutations of this gene are found in 70% of patients with CNC. PRKAR1A is a key component of the c-AMP signaling pathway that has been implicated in endocrine tumorigenesis. Many different mutations have been reported in the PRKAR1A gene. In almost all cases the sequence change was predicted to lead to a premature stop codon and the resultant mutant mRNA was subject to nonsense-mediated mRNA decay. There is no clear genotype-phenotype correlation in patients with CNC. Genetic analysis should be performed in all CNC index cases. All affected patients should be monitored for clinical signs of CNC at least once a year. Genetic diagnosis allows for more effective preparation of more appropriate and effective therapeutic strategies and genetic counseling for patients and gene carriers, and to avoid unnecessary tests to relatives not carrying the gene. PMID:21536508

  17. Molecular complexes in close and far away

    PubMed Central

    Klemperer, William; Vaida, Veronica

    2006-01-01

    In this review, gas-phase chemistry of interstellar media and some planetary atmospheres is extended to include molecular complexes. Although the composition, density, and temperature of the environments discussed are very different, molecular complexes have recently been considered as potential contributors to chemistry. The complexes reviewed include strongly bound aggregates of molecules with ions, intermediate-strength hydrogen bonded complexes (primarily hydrates), and weakly bonded van der Waals molecules. In low-density, low-temperature environments characteristic of giant molecular clouds, molecular synthesis, known to involve gas-phase ion-molecule reactions and chemistry at the surface of dust and ice grains is extended here to involve molecular ionic clusters. At the high density and high temperatures found on planetary atmospheres, molecular complexes contribute to both atmospheric chemistry and climate. Using the observational, laboratory, and theoretical database, the role of molecular complexes in close and far away is discussed. PMID:16740667

  18. Compressed sensing phase retrieval with phase diversity

    NASA Astrophysics Data System (ADS)

    Qin, Shun; Hu, Xinqi; Qin, Qiong

    2014-01-01

    The compressed sensing (CS) theory shows that sparse signal can be reconstructed accurately with some randomly observed measurements that are much fewer than what traditional method requires. Since it takes structure of signals into consideration, it has many advantages in the structured signals process. With CS, measuring can be speeded up and the cost of hardware can be decreased significantly. However, it faces great challenge in the amplitude-only measurement. In this article, we study the magnitude-only compressed sensing phase retrieval (CSPR) problem, and propose a practical recovery algorithm. In our algorithm, we introduce the powerful Hybrid-Input-Output algorithm with phase diversity to make our algorithm robust and efficient. A relaxed ℓ0 norm constrain is also introduced to help PR find a sparse solution with fewer measurements, which is demonstrated to be essential and effective to CSPR. We finally successfully apply it into complex-valued object recovery in THz imaging. The numerical results show that the proposed algorithm can recover the object pretty well with fewer measurements than what PR traditionally requires.

  19. Membraneless organelles: Phasing in and out

    NASA Astrophysics Data System (ADS)

    Shorter, James

    2016-06-01

    The low-complexity-protein, liquid phases of membraneless organelles have now been established to selectively partition biomolecules. The specialized microenvironment that they provide differs chemically from the surrounding medium and enables specific nucleic-acid remodelling reactions.

  20. Accessing complexity from genome information

    NASA Astrophysics Data System (ADS)

    Tenreiro Machado, J. A.

    2012-06-01

    This paper studies the information content of the chromosomes of 24 species. In a first phase, a scheme inspired in dynamical system state space representation is developed. For each chromosome the state space dynamical evolution is shed into a two dimensional chart. The plots are then analyzed and characterized in the perspective of fractal dimension. This information is integrated in two measures of the species' complexity addressing its average and variability. The results are in close accordance with phylogenetics pointing quantitative aspects of the species' genomic complexity.