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Sample records for reveal in-situ time-resolved

  1. In situ time-resolved FRET reveals effects of sarcomere length on cardiac thin-filament activation.

    PubMed

    Li, King-Lun; Rieck, Daniel; Solaro, R John; Dong, Wenji

    2014-08-05

    During cardiac thin-filament activation, the N-domain of cardiac troponin C (N-cTnC) binds to Ca(2+) and interacts with the actomyosin inhibitory troponin I (cTnI). The interaction between N-cTnC and cTnI stabilizes the Ca(2+)-induced opening of N-cTnC and is presumed to also destabilize cTnI-actin interactions that work together with steric effects of tropomyosin to inhibit force generation. Recently, our in situ steady-state FRET measurements based on N-cTnC opening suggested that at long sarcomere length, strongly bound cross-bridges indirectly stabilize this Ca(2+)-sensitizing N-cTnC-cTnI interaction through structural effects on tropomyosin and cTnI. However, the method previously used was unable to determine whether N-cTnC opening depends on sarcomere length. In this study, we used time-resolved FRET to monitor the effects of cross-bridge state and sarcomere length on the Ca(2+)-dependent conformational behavior of N-cTnC in skinned cardiac muscle fibers. FRET donor (AEDANS) and acceptor (DDPM)-labeled double-cysteine mutant cTnC(T13C/N51C)AEDANS-DDPM was incorporated into skinned muscle fibers to monitor N-cTnC opening. To study the structural effects of sarcomere length on N-cTnC, we monitored N-cTnC opening at relaxing and saturating levels of Ca(2+) and 1.80 and 2.2-μm sarcomere length. Mg(2+)-ADP and orthovanadate were used to examine the structural effects of noncycling strong-binding and weak-binding cross-bridges, respectively. We found that the stabilizing effect of strongly bound cross-bridges on N-cTnC opening (which we interpret as transmitted through related changes in cTnI and tropomyosin) become diminished by decreases in sarcomere length. Additionally, orthovanadate blunted the effect of sarcomere length on N-cTnC conformational behavior such that weak-binding cross-bridges had no effect on N-cTnC opening at any tested [Ca(2+)] or sarcomere length. Based on our findings, we conclude that the observed sarcomere length-dependent positive

  2. Time-resolved in situ powder X-ray diffraction reveals the mechanisms of molten salt synthesis.

    PubMed

    Moorhouse, Saul J; Wu, Yue; Buckley, Hannah C; O'Hare, Dermot

    2016-11-24

    We report the first use of high-energy monochromatic in situ X-ray powder diffraction to gain unprecedented insights into the chemical processes occurring during high temperature, lab-scale metal oxide syntheses. During the flux synthesis of the n = 4 Aurivillius phase, Bi5Ti3Fe0.5Cr0.5O15 at 950 °C in molten Na2SO4 we observe the progression of numerous metastable phases. Using sequential multiphase Rietveld refinement of the time-dependent in situ XRD data, we are able to obtain mechanistic understanding of this reaction under a range of conditions.

  3. Time-resolved Raman spectroscopy for in situ planetary mineralogy.

    PubMed

    Blacksberg, Jordana; Rossman, George R; Gleckler, Anthony

    2010-09-10

    Planetary mineralogy can be revealed through a variety of remote sensing and in situ investigations that precede any plans for eventual sample return. We briefly review those techniques and focus on the capabilities for on-surface in situ examination of Mars, Venus, the Moon, asteroids, and other bodies. Over the past decade, Raman spectroscopy has continued to develop as a prime candidate for the next generation of in situ planetary instruments, as it provides definitive structural and compositional information of minerals in their natural geological context. Traditional continuous-wave Raman spectroscopy using a green laser suffers from fluorescence interference, which can be large (sometimes saturating the detector), particularly in altered minerals, which are of the greatest geophysical interest. Taking advantage of the fact that fluorescence occurs at a later time than the instantaneous Raman signal, we have developed a time-resolved Raman spectrometer that uses a streak camera and pulsed miniature microchip laser to provide picosecond time resolution. Our ability to observe the complete time evolution of Raman and fluorescence spectra in minerals makes this technique ideal for exploration of diverse planetary environments, some of which are expected to contain strong, if not overwhelming, fluorescence signatures. We discuss performance capability and present time-resolved pulsed Raman spectra collected from several highly fluorescent and Mars-relevant minerals. In particular, we have found that conventional Raman spectra from fine grained clays, sulfates, and phosphates exhibited large fluorescent signatures, but high quality spectra could be obtained using our time-resolved approach.

  4. In Situ Time-Resolved FRET Reveals Effects of Sarcomere Length on Cardiac Thin-Filament Activation

    PubMed Central

    Li, King-Lun; Rieck, Daniel; Solaro, R. John; Dong, Wenji

    2014-01-01

    During cardiac thin-filament activation, the N-domain of cardiac troponin C (N-cTnC) binds to Ca2+ and interacts with the actomyosin inhibitory troponin I (cTnI). The interaction between N-cTnC and cTnI stabilizes the Ca2+-induced opening of N-cTnC and is presumed to also destabilize cTnI–actin interactions that work together with steric effects of tropomyosin to inhibit force generation. Recently, our in situ steady-state FRET measurements based on N-cTnC opening suggested that at long sarcomere length, strongly bound cross-bridges indirectly stabilize this Ca2+-sensitizing N-cTnC–cTnI interaction through structural effects on tropomyosin and cTnI. However, the method previously used was unable to determine whether N-cTnC opening depends on sarcomere length. In this study, we used time-resolved FRET to monitor the effects of cross-bridge state and sarcomere length on the Ca2+-dependent conformational behavior of N-cTnC in skinned cardiac muscle fibers. FRET donor (AEDANS) and acceptor (DDPM)-labeled double-cysteine mutant cTnC(T13C/N51C)AEDANS-DDPM was incorporated into skinned muscle fibers to monitor N-cTnC opening. To study the structural effects of sarcomere length on N-cTnC, we monitored N-cTnC opening at relaxing and saturating levels of Ca2+ and 1.80 and 2.2-μm sarcomere length. Mg2+-ADP and orthovanadate were used to examine the structural effects of noncycling strong-binding and weak-binding cross-bridges, respectively. We found that the stabilizing effect of strongly bound cross-bridges on N-cTnC opening (which we interpret as transmitted through related changes in cTnI and tropomyosin) become diminished by decreases in sarcomere length. Additionally, orthovanadate blunted the effect of sarcomere length on N-cTnC conformational behavior such that weak-binding cross-bridges had no effect on N-cTnC opening at any tested [Ca2+] or sarcomere length. Based on our findings, we conclude that the observed sarcomere length-dependent positive feedback

  5. Evolution of polytypism in GaAs nanowires during growth revealed by time-resolved in situ x-ray diffraction.

    PubMed

    Schroth, Philipp; Köhl, Martin; Hornung, Jean-Wolfgang; Dimakis, Emmanouil; Somaschini, Claudio; Geelhaar, Lutz; Biermanns, Andreas; Bauer, Sondes; Lazarev, Sergey; Pietsch, Ullrich; Baumbach, Tilo

    2015-02-06

    In III-V nanowires the energetic barriers for nucleation in the zinc blende or wurtzite arrangement are typically of a similar order of magnitude. As a result, both arrangements can occur in a single wire. Here, we investigate the evolution of this polytypism in self-catalyzed GaAs nanowires on Si(111) grown by molecular beam epitaxy with time-resolved in situ x-ray diffraction. We interpret our data in the framework of a height dependent Markov model for the stacking in the nanowires. In this way, we extract the mean sizes of faultless wurtzite and zinc blende segments-a key parameter of polytypic nanowires-and their temporal evolution during growth. Thereby, we infer quantitative information on the differences of the nucleation barriers including their evolution without requiring a model of the nucleus.

  6. ED-XAS Data Reveal In-situ Time-Resolved Adsorbate Coverage on Supported Molybdenum Oxide Catalysts during Propane Dehydrogenation

    NASA Astrophysics Data System (ADS)

    Ramaker, David; Gatewood, Daniel; Beale, Andrew M.; Weckhuysen, Bert M.

    2007-02-01

    Energy-Dispersive X-ray Absorption Spectroscopy (ED-XAS) data combined with UV/Vis, Raman, and mass spectrometry data on alumina- and silica-supported molybdenum oxide catalysts under propane dehydrogenation conditions have been previously reported. A novel Δμ adsorbate isolation technique was applied here to the time-resolved (0.1 min) Mo K-edge ED-XAS data by taking the difference of absorption, μ, at t>1 against the initial time, t=0. Further, full multiple scattering calculations using the FEFF 8.0 code are performed to interpret the Δμ signatures. The resulting difference spectra and interpretation provide real time propane coverage and O depletion at the MoOn surface. The propane coverage is seen to correlate with the propene and/or coke production, with the maximum coke formation occurring when the propane coverage is the largest. Combined, these data give unprecedented insight into the complicated dynamics for propane dehydrogenation.

  7. ED-XAS Data Reveal In-situ Time-Resolved Adsorbate Coverage on Supported Molybdenum Oxide Catalysts during Propane Dehydrogenation

    SciTech Connect

    Ramaker, David; Gatewood, Daniel; Beale, Andrew M.; Weckhuysen, Bert M.

    2007-02-02

    Energy-Dispersive X-ray Absorption Spectroscopy (ED-XAS) data combined with UV/Vis, Raman, and mass spectrometry data on alumina- and silica-supported molybdenum oxide catalysts under propane dehydrogenation conditions have been previously reported. A novel {delta}{mu} adsorbate isolation technique was applied here to the time-resolved (0.1 min) Mo K-edge ED-XAS data by taking the difference of absorption, {mu}, at t>1 against the initial time, t=0. Further, full multiple scattering calculations using the FEFF 8.0 code are performed to interpret the {delta}{mu} signatures. The resulting difference spectra and interpretation provide real time propane coverage and O depletion at the MoOn surface. The propane coverage is seen to correlate with the propene and/or coke production, with the maximum coke formation occurring when the propane coverage is the largest. Combined, these data give unprecedented insight into the complicated dynamics for propane dehydrogenation.

  8. Time resolved electron microscopy for in situ experiments

    SciTech Connect

    Campbell, Geoffrey H. McKeown, Joseph T.; Santala, Melissa K.

    2014-12-15

    Transmission electron microscopy has functioned for decades as a platform for in situ observation of materials and processes with high spatial resolution. Yet, the dynamics often remain elusive, as they unfold too fast to discern at these small spatial scales under traditional imaging conditions. Simply shortening the exposure time in hopes of capturing the action has limitations, as the number of electrons will eventually be reduced to the point where noise overtakes the signal in the image. Pulsed electron sources with high instantaneous current have successfully shortened exposure times (thus increasing the temporal resolution) by about six orders of magnitude over conventional sources while providing the necessary signal-to-noise ratio for dynamic imaging. We describe here the development of this new class of microscope and the principles of its operation, with examples of its application to problems in materials science.

  9. Time-Resolved In Situ Measurements During Rapid Alloy Solidification: Experimental Insight for Additive Manufacturing

    DOE PAGES

    McKeown, Joseph T.; Zweiacker, Kai; Liu, Can; ...

    2016-01-27

    In research and industrial environments, additive manufacturing (AM) of metals and alloys is becoming a pervasive technology, though significant challenges remain before widespread implementation of AM can be realized. In situ investigations of rapid alloy solidification with high spatial and temporal resolutions can provide unique experimental insight into microstructure evolution and kinetics that are relevant for AM processing. Hypoeutectic thin-film Al–Cu and Al–Si alloys were investigated using dynamic transmission electron microscopy to monitor pulsed-laser-induced rapid solidification across microsecond timescales. Solid–liquid interface velocities measured from time-resolved images revealed accelerating solidification fronts in both alloys. We observed microstructure evolution, solidification product, andmore » presence of a morphological instability at the solid–liquid interface in the Al–4 at.%Cu alloy are related to the measured interface velocities and small differences in composition that affect the thermophysical properties of the alloys. These time-resolved in situ measurements can inform and validate predictive modeling efforts for AM.« less

  10. Time-Resolved In Situ Measurements During Rapid Alloy Solidification: Experimental Insight for Additive Manufacturing

    SciTech Connect

    McKeown, Joseph T.; Zweiacker, Kai; Liu, Can; Coughlin, Daniel R.; Clarke, Amy J.; Baldwin, J. Kevin; Gibbs, John W.; Roehling, John D.; Imhoff, Seth D.; Gibbs, Paul J.; Tourret, Damien; Wiezorek, Jörg M. K.; Campbell, Geoffrey H.

    2016-01-27

    In research and industrial environments, additive manufacturing (AM) of metals and alloys is becoming a pervasive technology, though significant challenges remain before widespread implementation of AM can be realized. In situ investigations of rapid alloy solidification with high spatial and temporal resolutions can provide unique experimental insight into microstructure evolution and kinetics that are relevant for AM processing. Hypoeutectic thin-film Al–Cu and Al–Si alloys were investigated using dynamic transmission electron microscopy to monitor pulsed-laser-induced rapid solidification across microsecond timescales. Solid–liquid interface velocities measured from time-resolved images revealed accelerating solidification fronts in both alloys. We observed microstructure evolution, solidification product, and presence of a morphological instability at the solid–liquid interface in the Al–4 at.%Cu alloy are related to the measured interface velocities and small differences in composition that affect the thermophysical properties of the alloys. These time-resolved in situ measurements can inform and validate predictive modeling efforts for AM.

  11. Time-Resolved In Situ Measurements During Rapid Alloy Solidification: Experimental Insight for Additive Manufacturing

    NASA Astrophysics Data System (ADS)

    McKeown, Joseph T.; Zweiacker, Kai; Liu, Can; Coughlin, Daniel R.; Clarke, Amy J.; Baldwin, J. Kevin; Gibbs, John W.; Roehling, John D.; Imhoff, Seth D.; Gibbs, Paul J.; Tourret, Damien; Wiezorek, Jörg M. K.; Campbell, Geoffrey H.

    2016-03-01

    Additive manufacturing (AM) of metals and alloys is becoming a pervasive technology in both research and industrial environments, though significant challenges remain before widespread implementation of AM can be realized. In situ investigations of rapid alloy solidification with high spatial and temporal resolutions can provide unique experimental insight into microstructure evolution and kinetics that are relevant for AM processing. Hypoeutectic thin-film Al-Cu and Al-Si alloys were investigated using dynamic transmission electron microscopy to monitor pulsed-laser-induced rapid solidification across microsecond timescales. Solid-liquid interface velocities measured from time-resolved images revealed accelerating solidification fronts in both alloys. The observed microstructure evolution, solidification product, and presence of a morphological instability at the solid-liquid interface in the Al-4 at.%Cu alloy are related to the measured interface velocities and small differences in composition that affect the thermophysical properties of the alloys. These time-resolved in situ measurements can inform and validate predictive modeling efforts for AM.

  12. The molecular pathway to ZIF-7 microrods revealed by in situ time-resolved small- and wide-angle X-ray scattering, quick-scanning extended X-ray absorption spectroscopy, and DFT calculations.

    PubMed

    Goesten, Maarten; Stavitski, Eli; Pidko, Evgeny A; Gücüyener, Canan; Boshuizen, Bart; Ehrlich, Steven N; Hensen, Emiel J M; Kapteijn, Freek; Gascon, Jorge

    2013-06-10

    We present an in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and quick-scanning extended X-ray absorption fine-structure (QEXAFS) spectroscopy study on the crystallization of the metal-organic framework ZIF-7. In combination with DFT calculations, the self-assembly and growth of ZIF-7 microrods together with the chemical function of the crystal growth modulator (diethylamine) are revealed at all relevant length scales, from the atomic to the full crystal size.

  13. Fixed target matrix for femtosecond time-resolved and in situ serial micro-crystallography

    PubMed Central

    Mueller, C.; Marx, A.; Epp, S. W.; Zhong, Y.; Kuo, A.; Balo, A. R.; Soman, J.; Schotte, F.; Lemke, H. T.; Owen, R. L.; Pai, E. F.; Pearson, A. R.; Olson, J. S.; Anfinrud, P. A.; Ernst, O. P.; Dwayne Miller, R. J.

    2015-01-01

    We present a crystallography chip enabling in situ room temperature crystallography at microfocus synchrotron beamlines and X-ray free-electron laser (X-FEL) sources. Compared to other in situ approaches, we observe extremely low background and high diffraction data quality. The chip design is robust and allows fast and efficient loading of thousands of small crystals. The ability to load a large number of protein crystals, at room temperature and with high efficiency, into prescribed positions enables high throughput automated serial crystallography with microfocus synchrotron beamlines. In addition, we demonstrate the application of this chip for femtosecond time-resolved serial crystallography at the Linac Coherent Light Source (LCLS, Menlo Park, California, USA). The chip concept enables multiple images to be acquired from each crystal, allowing differential detection of changes in diffraction intensities in order to obtain high signal-to-noise and fully exploit the time resolution capabilities of XFELs. PMID:26798825

  14. In Situ, Time-Resolved Accelerator Grid Erosion Measurements in the NSTAR 8000 Hour Ion Engine Wear Test

    NASA Technical Reports Server (NTRS)

    Sovey, J.

    1997-01-01

    Time-resolved, in situ measurements of the charge exchange ion erosion pattern on the downstream face of the accelerator grid have been made during an ongoin wear test of the NSTAR 30 cm ion thruster.

  15. In situ, time-resolved tomography for validating models of deformation in semi-solid alloys

    NASA Astrophysics Data System (ADS)

    Kareh, K. M.; Lee, P. D.; Gourlay, C. M.

    2012-07-01

    The development and validation of physically-based models of semi-solid alloy deformation requires experimental data on the microstructural response to load. In this work we present three-dimensional in situ synchrotron results of the indirect extrusion of semi-solid aluminium-copper alloys. Globular Al-15wt.% Cu specimens were deformed at solid fractions of approximately 0.7 during time-resolved x-ray tomography. Key phenomena of the response to load were observed and quantified, with a focus on particle translations and rotations, and the resulting displacement field. This example shows that crystal displacements can be quantified during semi-solid deformation of bulk specimens, allowing for datasets to be produced suitable for validating models of complex phenomena during semi-solid flow.

  16. Fixed target matrix for femtosecond time-resolved and in situ serial micro-crystallography

    DOE PAGES

    Mueller, C.; Marx, A.; Epp, S. W.; ...

    2015-08-18

    We present a crystallography chip enabling in situ room temperature crystallography at microfocus synchrotron beamlines and X-ray free-electron laser (X-FEL) sources. Compared to other in situ approaches, we observe extremely low background and high diffraction data quality. The chip design is robust and allows fast and efficient loading of thousands of small crystals. The ability to load a large number of protein crystals, at room temperature and with high efficiency, into prescribed positions enables high throughput automated serial crystallography with microfocus synchrotron beamlines. In addition, we demonstrate the application of this chip for femtosecond time-resolved serial crystallography at the Linacmore » Coherent Light Source (LCLS, Menlo Park, California, USA). As a result, the chip concept enables multiple images to be acquired from each crystal, allowing differential detection of changes in diffraction intensities in order to obtain high signal-to-noise and fully exploit the time resolution capabilities of XFELs.« less

  17. Assessment of In Situ Time Resolved Shock Experiments at Synchrotron Light Sources*

    NASA Astrophysics Data System (ADS)

    Belak, J.; Ilavsky, J.; Hessler, J. P.

    2005-07-01

    Prior to fielding in situ time resolved experiments of shock wave loading at the Advanced Photon Source, we have performed feasibility experiments assessing a single photon bunch. Using single and poly-crystal Al, Ti, V and Cu shock to incipient spallation on the gas gun, samples were prepared from slices normal to the spall plane of thickness 100-500 microns. In addition, single crystal Al of thickness 500 microns was shocked to incipient spallation and soft recovered using the LLNL e-gun mini-flyer system. The e-gun mini-flyer impacts the sample target producing a 10's ns flat-top shock transient. Here, we present results for imaging, small-angle scattering (SAS), and diffraction. In particular, there is little SAS away from the spall plane and significant SAS at the spall plane, demonstrating the presence of sub-micron voids. * Use of the Advanced Photon Source was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. W-31-109-Eng-38 and work performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

  18. Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra

    NASA Astrophysics Data System (ADS)

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-10-01

    Time-resolved photoelectron spectroscopy is commonly employed with the intention to monitor electronic excited-state dynamics occurring in a neutral molecule. With the help of theory, we show that when excited-state processes occur on similar time scales the different relaxation pathways are completely obscured in the total photoionization signal recorded in the experiment. Using non-adiabatic molecular dynamics and Dyson norms, we calculate the photoionization signal of cytosine and disentangle the transient contributions originating from the different deactivation pathways of its tautomers. In the simulations, the total signal from the relevant keto and enol tautomers can be decomposed into contributions either from the neutral electronic state populations or from the distinct mechanistic pathways across the multiple potential surfaces. The lifetimes corresponding to these contributions cannot be extracted from the experiment, thereby illustrating that new experimental setups are necessary to unravel the intricate non-adiabatic pathways occurring in polyatomic molecules after irradiation by light.

  19. Revealing Deactivation Pathways Hidden in Time-Resolved Photoelectron Spectra

    PubMed Central

    Ruckenbauer, Matthias; Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2016-01-01

    Time-resolved photoelectron spectroscopy is commonly employed with the intention to monitor electronic excited-state dynamics occurring in a neutral molecule. With the help of theory, we show that when excited-state processes occur on similar time scales the different relaxation pathways are completely obscured in the total photoionization signal recorded in the experiment. Using non-adiabatic molecular dynamics and Dyson norms, we calculate the photoionization signal of cytosine and disentangle the transient contributions originating from the different deactivation pathways of its tautomers. In the simulations, the total signal from the relevant keto and enol tautomers can be decomposed into contributions either from the neutral electronic state populations or from the distinct mechanistic pathways across the multiple potential surfaces. The lifetimes corresponding to these contributions cannot be extracted from the experiment, thereby illustrating that new experimental setups are necessary to unravel the intricate non-adiabatic pathways occurring in polyatomic molecules after irradiation by light. PMID:27762396

  20. In-situ time resolved studies of apatite formation pathways - implications for biological and environmental systems

    NASA Astrophysics Data System (ADS)

    Borkiewicz, O.; Rakovan, J.; Cahill, C. L.

    2006-05-01

    The mineral apatite, Ca5(PO4)3(F,OH,Cl), is of great significance in a variety of fields including life and environmental sciences. Apatite is the main constituent of almost all hard tissues of human body and plays major role in the metabolic processes. Recently, it has gained a considerable amount of attention as a promising candidate for the use in the in-situ metal sequestration of metal ions for environmental remediation, sometimes called phosphate induced metal stabilization (PIMS). We report preliminary results of in-situ time resolved X-ray diffraction studies of apatite formation pathways from aqueous solutions, performed at the X7B beamline of the National Synchrotron Light Source at Brookhaven National Laboratory, Upton, NY. A series of experiments with different Ca/P and liquid/solid ratios in the starting material, and range of temperatures were performed. In the first stage of the experiment, calcium acetate and ammonium phosphate solutions are mixed at room temperature, resulting in the formation of an initial precipitate. The solution is then press-filtered and the remaining slurry, of the desired liquid/solid ratio, is placed inside a heating cell and analyzed within 10 min. of the initial precipitation. The initial precipitate was identified as brushite (CaHPO4 - 2H2O) in all experiments, independent of the initial Ca/P ratio in solution). In the experiment conducted at ambient temperature brushite was the only phase present in the solution/slurry throughout the duration of the analysis. Under the conditions of elevated temperature, however, a sequence of phase transitions, from brushite to apatite with intermediate monetite (CaHPO4) was observed. The pathway of the transitions and the final product was independent of both the Ca/P ratio and the temperature of the reaction. The rate of the transformation, however, increased with increasing temperature. Numerous studies of apatite formation from solution using standard X-ray diffraction experiments

  1. The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction.

    PubMed

    Moorhouse, Saul J; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

    2012-08-01

    A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

  2. The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Moorhouse, Saul J.; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

    2012-08-01

    A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

  3. Detection of rhodopsin dimerization in situ by PIE-FCCS, a time-resolved fluorescence spectroscopy.

    PubMed

    Smith, Adam W

    2015-01-01

    Rhodopsin self-associates in the plasma membrane. At low concentrations, the interactions are consistent with a monomer-dimer equilibrium (Comar et al., J Am Chem Soc 136(23):8342-8349, 2014). At high concentrations in native tissue, higher-order clusters have been observed (Fotiadis et al., Nature 421:127-128, 2003). The physiological role of rhodopsin dimerization is still being investigated, but it is clear that a quantitative assessment is essential to determining the function of rhodopsin clusters in vision. To quantify rhodopsin interactions, I will outline the theory and methodology of a specialized time-resolved fluorescence spectroscopy for measuring membrane protein-protein interactions called pulsed-interleaved excitation fluorescence cross-correlation spectroscopy (PIE-FCCS). The strength of this technique is its ability to quantify rhodopsin interactions in situ (i.e., a live cell plasma membrane). There are two reasons for restricting the scope to live cell membranes. First, the compositional heterogeneity of the plasma membrane creates a complex milieu with thousands of lipid, protein, and carbohydrate species. This makes it difficult to infer quaternary interactions from detergent solubilized samples or construct a model phospholipid bilayer that recapitulates all of the interactions present in native membranes. Second, organizational structure and dynamics is a key feature of the plasma membrane, and fixation techniques like formaldehyde cross-linking and vitrification will modulate the interactions. PIE-FCCS is based on two-color fluorescence imaging with time-correlated single-photon counting (TCSPC) (Becker et al., Rev Sci Instrum 70:1835-1841, 1999). By time-tagging every detected photon, the data can be analyzed as a fluorescence intensity distribution, fluorescence lifetime histogram, or fluorescence (cross-)correlation spectra (FCS/FCCS) (Becker, Advanced time-correlated single-photon counting techniques, Springer, Berlin, 2005). These

  4. Time-resolved metabolomics reveals metabolic modulation in rice foliage

    PubMed Central

    Sato, Shigeru; Arita, Masanori; Soga, Tomoyoshi; Nishioka, Takaaki; Tomita, Masaru

    2008-01-01

    Background To elucidate the interaction of dynamics among modules that constitute biological systems, comprehensive datasets obtained from "omics" technologies have been used. In recent plant metabolomics approaches, the reconstruction of metabolic correlation networks has been attempted using statistical techniques. However, the results were unsatisfactory and effective data-mining techniques that apply appropriate comprehensive datasets are needed. Results Using capillary electrophoresis mass spectrometry (CE-MS) and capillary electrophoresis diode-array detection (CE-DAD), we analyzed the dynamic changes in the level of 56 basic metabolites in plant foliage (Oryza sativa L. ssp. japonica) at hourly intervals over a 24-hr period. Unsupervised clustering of comprehensive metabolic profiles using Kohonen's self-organizing map (SOM) allowed classification of the biochemical pathways activated by the light and dark cycle. The carbon and nitrogen (C/N) metabolism in both periods was also visualized as a phenotypic linkage map that connects network modules on the basis of traditional metabolic pathways rather than pairwise correlations among metabolites. The regulatory networks of C/N assimilation/dissimilation at each time point were consistent with previous works on plant metabolism. In response to environmental stress, glutathione and spermidine fluctuated synchronously with their regulatory targets. Adenine nucleosides and nicotinamide coenzymes were regulated by phosphorylation and dephosphorylation. We also demonstrated that SOM analysis was applicable to the estimation of unidentifiable metabolites in metabolome analysis. Hierarchical clustering of a correlation coefficient matrix could help identify the bottleneck enzymes that regulate metabolic networks. Conclusion Our results showed that our SOM analysis with appropriate metabolic time-courses effectively revealed the synchronous dynamics among metabolic modules and elucidated the underlying biochemical

  5. Time-resolved metabolomics reveals metabolic modulation in rice foliage.

    PubMed

    Sato, Shigeru; Arita, Masanori; Soga, Tomoyoshi; Nishioka, Takaaki; Tomita, Masaru

    2008-06-18

    To elucidate the interaction of dynamics among modules that constitute biological systems, comprehensive datasets obtained from "omics" technologies have been used. In recent plant metabolomics approaches, the reconstruction of metabolic correlation networks has been attempted using statistical techniques. However, the results were unsatisfactory and effective data-mining techniques that apply appropriate comprehensive datasets are needed. Using capillary electrophoresis mass spectrometry (CE-MS) and capillary electrophoresis diode-array detection (CE-DAD), we analyzed the dynamic changes in the level of 56 basic metabolites in plant foliage (Oryza sativa L. ssp. japonica) at hourly intervals over a 24-hr period. Unsupervised clustering of comprehensive metabolic profiles using Kohonen's self-organizing map (SOM) allowed classification of the biochemical pathways activated by the light and dark cycle. The carbon and nitrogen (C/N) metabolism in both periods was also visualized as a phenotypic linkage map that connects network modules on the basis of traditional metabolic pathways rather than pairwise correlations among metabolites. The regulatory networks of C/N assimilation/dissimilation at each time point were consistent with previous works on plant metabolism. In response to environmental stress, glutathione and spermidine fluctuated synchronously with their regulatory targets. Adenine nucleosides and nicotinamide coenzymes were regulated by phosphorylation and dephosphorylation. We also demonstrated that SOM analysis was applicable to the estimation of unidentifiable metabolites in metabolome analysis. Hierarchical clustering of a correlation coefficient matrix could help identify the bottleneck enzymes that regulate metabolic networks. Our results showed that our SOM analysis with appropriate metabolic time-courses effectively revealed the synchronous dynamics among metabolic modules and elucidated the underlying biochemical functions. The application of

  6. In situ multipurpose time-resolved spectrometer for monitoring nanoparticle generation in a high-pressure fluid

    SciTech Connect

    Wei, Shaoyu; Saitow, Ken-ichi

    2012-07-15

    We developed a multipurpose time-resolved spectrometer for studying the dynamics of nanoparticles generated by pulsed-laser ablation (PLA) in a high-pressure fluid. The apparatus consists of a high-pressure optical cell and three spectrometers for in situ measurements. The optical cell was designed for experiments at temperatures up to 400 K and pressures up to 30 MPa with fluctuations within {+-}0.1% h{sup -1}. The three spectrometers were used for the following in situ measurements at high pressures: (i) transient absorption spectrum measurements from 350 to 850 nm to investigate the dynamics of nanoparticle generation from nanoseconds to milliseconds after laser irradiation, (ii) absorption spectrum measurements from 220 to 900 nm to observe the time evolution of nanoparticles from seconds to hours after laser ablation, and (iii) dynamic light scattering measurements to track nanoparticles with sizes from 10 nm to 10 {mu}m in the time range from seconds to hours after laser ablation. By combining these three spectrometers, we demonstrate in situ measurements of gold nanoparticles generated by PLA in supercritical fluids. This is the first report of in situ time-resolved measurements of the dynamics of nanoparticles generated in a supercritical fluid.

  7. Mechanism of silver particle formation during photoreduction using in situ time-resolved SAXS analysis.

    PubMed

    Harada, Masafumi; Katagiri, Etsuko

    2010-12-07

    Formation mechanisms of silver (Ag) particles in an aqueous ethanol solution of poly(N-vinyl-2-pyrrolidone) (PVP) by the photoreduction of AgClO(4) were investigated by means of in situ small-angle X-ray scattering (SAXS) measurements. The kinetics of association process (nucleation, growth, and coalescence) of Ag(0) atoms to produce Ag particles was successfully revealed by the quantitative SAXS analysis for the number-average of radius (R(0)), number of particles (n(Ag)), reduced standard deviation (σ(R)/R(0)), and volume fraction (ϕ(Ag)) of Ag particles produced by the photoreduction. The rate of nucleation and growth process during Ag particle formation strongly depend on the initial metal concentration. The time evolution of radius and number of Ag particles indicates that a mechanism of Ag particle formation is composed of different three processes, that is, reduction-nucleation, Ostwald ripening, and particle coalescence. In a rapid reduction-nucleation process, small nuclei or particles (average radius ∼2.5 nm) are produced by an autocatalytic reduction. After the formation of small nuclei or particles proceeds, Ostwald ripening and particle coalescence, predicted by the Lifshitz-Slyozov-Wagner theory (LSW theory), subsequently occur, resulting in the particle growth (average radius ∼11.5 nm).

  8. Structural kinetics of a Pt/C cathode catalyst with practical catalyst loading in an MEA for PEFC operating conditions studied by in situ time-resolved XAFS.

    PubMed

    Ishiguro, Nozomu; Saida, Takahiro; Uruga, Tomoya; Sekizawa, Oki; Nagasawa, Kensaku; Nitta, Kiyofumi; Yamamoto, Takashi; Ohkoshi, Shin-ichi; Yokoyama, Toshihiko; Tada, Mizuki

    2013-11-21

    The structural kinetics of surface events on a Pt/C cathode catalyst in a membrane electrode assembly (MEA) with a practical catalyst loading (0.5 mgPt cm(-2)) for a polymer electrolyte fuel cell were investigated by in situ time-resolved X-ray absorption fine structure analysis (XAFS; time resolution: 100 ms) for the first time. The rate constants of structural changes in the Pt/C cathode catalyst in the MEA during voltage cycling were successfully estimated. For voltage-cycling processes, all reactions (electrochemical reactions and structural changes in the Pt catalyst) in the MEA were found to be much faster than those in an MEA with a thick cathode catalyst layer, but the in situ time-resolved XAFS analysis revealed that significant time lags similarly existed between the electrochemical reactions and the structural changes in the Pt cathode catalyst. The time-resolved XAFS also revealed differences in the structural kinetics of the Pt/C cathode catalyst for the voltage-cycling processes under N2 and air flows at the cathode.

  9. Ion Dynamics in Solid-State Polymer Electrolyte Electrochemical Cells using in situ Time-Resolved Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Richey, Francis; Elabd, Yossef

    2012-02-01

    Understanding ion transport in solid-state polymer electrochemical cells is of great interest for the advancement of cell efficacy. However, currently there is limited experimental knowledge of ion transport on a molecular level. In this study, we report a new spectroelectrochemical experimental technique that provides in situ molecular level detail about cation and anion transport of an ionic liquid in solid-state polymer electrolyte electrochemical cells. In situ time-resolved Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy was utilized to measure the time dependent accumulation of ions at the cathode and anode interface under an applied potential. The results show that the cation and anion of the ionic liquid both transport and accumulate at the cathode under dry conditions, but only the cation accumulates at the cathode under humid conditions. This experiment was coupled with electrochemical impedance spectroscopy to simultaneously measure overall charge transport and cyclic voltammograms.

  10. In-situ straining and time-resolved electron tomography data acquisition in a transmission electron microscope.

    PubMed

    Hata, S; Miyazaki, S; Gondo, T; Kawamoto, K; Horii, N; Sato, K; Furukawa, H; Kudo, H; Miyazaki, H; Murayama, M

    2017-04-01

    This paper reports the preliminary results of a new in-situ three-dimensional (3D) imaging system for observing plastic deformation behavior in a transmission electron microscope (TEM) as a directly relevant development of the recently reported straining-and-tomography holder [Sato K et al. (2015) Development of a novel straining holder for transmission electron microscopy compatible with single tilt-axis electron tomography. Microsc. 64: 369-375]. We designed an integrated system using the holder and newly developed straining and image-acquisition software and then developed an experimental procedure for in-situ straining and time-resolved electron tomography (ET) data acquisition. The software for image acquisition and 3D visualization was developed based on the commercially available ET software TEMographyTM. We achieved time-resolved 3D visualization of nanometer-scale plastic deformation behavior in a Pb-Sn alloy sample, thus demonstrating the capability of this system for potential applications in materials science. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  11. In-situ Characterization of Water-Gas Shift Catalysts using Time-Resolved X-ray Diffraction

    SciTech Connect

    Rodriguez, J.; Hanson, J; Wen, W; Wang, X; Brito, J; Martnez-Arias, A; Fernandez-Garca, M

    2009-01-01

    Time-resolved X-ray diffraction (XRD) has emerged as a powerful technique for studying the behavior of heterogeneous catalysts (metal oxides, sulfides, carbides, phosphides, zeolites, etc.) in-situ during reaction conditions. The technique can identify the active phase of a heterogeneous catalyst and how its structure changes after interacting with the reactants and products (80 K < T < 1200 K; P < 50 atm). In this article, we review a series of recent works that use in-situ time-resolved XRD for studying the water-gas shift reaction (WGS, CO + H2O ? H2 + CO2) over several mixed-metal oxides: CuMoO4, NiMoO4, Ce1-xCuxO2-d and CuFe2O4. Under reaction conditions the oxides undergo partial reduction. Neutral Cu0 (i.e. no Cu1+ or Cu2+ cations) and Ni0 are the active species in the catalysts, but interactions with the oxide support are necessary in order to obtain high catalytic activity. These studies illustrate the important role played by O vacancies in the mechanism for the WGS. In the case of Ce1-xCuxO2-d, Rietveld refinement shows expansions/contractions in the oxide lattice which track steps within the WGS process: CO(gas) + O(oxi) ? CO2(gas) + O(vac); H2O(gas) + O(vac) ? O(oxi) + H2(gas).

  12. In Situ Planetary Mineralogy Using Simultaneous Time Resolved Fluorescence and Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Blacksberg, J.; Rossman , G.R.

    2011-01-01

    Micro-Raman spectroscopy is one of the primary methods of mineralogical analysis in the laboratory, and more recently in the field. Because of its versatility and ability to interrogate rocks in their natural form it is one of the front runners for the next generation of in situ instruments designed to explore adverse set of solar system bodies (e.g. Mars, Venus, the Moon, and other primitive bodies such as asteroids and the Martian moons Phobos and Deimos), as well as for pre-selection of rock and soil samples for potential cache and return missions.

  13. In Situ Planetary Mineralogy Using Simultaneous Time Resolved Fluorescence and Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Blacksberg, J.; Rossman , G.R.

    2011-01-01

    Micro-Raman spectroscopy is one of the primary methods of mineralogical analysis in the laboratory, and more recently in the field. Because of its versatility and ability to interrogate rocks in their natural form it is one of the front runners for the next generation of in situ instruments designed to explore adverse set of solar system bodies (e.g. Mars, Venus, the Moon, and other primitive bodies such as asteroids and the Martian moons Phobos and Deimos), as well as for pre-selection of rock and soil samples for potential cache and return missions.

  14. Time-resolved in-situ measurement of mitochondrial malfunction by energy transfer spectroscopy

    NASA Astrophysics Data System (ADS)

    Schneckenburger, Herbert; Gschwend, Michael H.; Strauss, Wolfgang S. L.; Sailer, Reinhard; Schoch, Lars; Schuh, Alexander; Stock, Karl; Steiner, Rudolf W.; Zipfl, Peter

    1999-07-01

    To establish optical in situ detection of mitochondrial malfunction, non-radiative energy transfer from the coenzyme NADH to the mitochondrial marker rhodamine 123 (R123) was examined. Dual excitation of R123 via energy transfer from excited NADH molecules as well as by direct absorption of light results in two fluorescence signals whose ratio is a measure of mitochondrial NADH. An experimental setup was developed, where these signals are detected simultaneously using a time-gated technique for energy transfer measurements and a frequency selective technique for direct excitation and fluorescence monitoring of R123. Optical and electronic components of the apparatus are described, and preliminary result of cultivated endothelial cells are reported. Results are compared with those obtained from a previously established microscopic system and discussed in view of potential applications.

  15. Development of customised environmental chambers for time-resolved in situ diffraction studies

    NASA Astrophysics Data System (ADS)

    Styles, M. J.; Riley, D. P.

    2010-11-01

    In an effort to mitigate the expense and broaden the applicability of customised environment chambers, researchers at the University of Melbourne and the Australian Nuclear Science and Technology Organisation (ANSTO) have designed and are currently commissioning a modular reaction chamber, capable of separating the necessities of diffraction methodologies from those of the desired sample environment. The In Situ Reaction Chamber (ISRC) abstracts many of the details intrinsic to the diffractometer, allowing users to design inexpensive environmental inserts that may be readily customised to their individual needs. The first insert to be developed for use with the ISRC is a high temperature furnace capable of providing an oxidising sample environment up to 1600°C.

  16. Time-resolved in situ measurement of mitochondrial malfunction by energy transfer spectroscopy

    NASA Astrophysics Data System (ADS)

    Schneckenburger, Herbert; Sailer, Reinhard; Strauss, Wolfgang S.; Lyttek, Marco; Stock, Karl; Zipfl, Peter

    2000-10-01

    To establish optical in situ detection of mitochondrial malfunction, nonradiative energy transfer from the coenzyme NADH to the mitochondrial marker rhodamine 123 (R123) was examined. Dual excitation of R123 via energy transfer from excited NADH molecules as well as by direct absorption of light results in two fluorescence signals whose ratio is a measure of mitochondrial NADH. A screening system was developed in which these signals are detected simultaneously using a time-gated (nanosecond) technique for energy transfer measurements and a frequency selective technique for direct excitation and fluorescence monitoring of R123. Optical and electronic components of the apparatus are described, and results obtained from cultivated endothelial cells are reported. The ratio of fluorescence intensities excited in the near ultraviolet and blue-green spectral ranges increased by a factor 1.5 or 1.35 after inhibition of the mitochondrial respiratory chain by rotenone at cytotoxic or noncytotoxic concentrations, respectively. Concomitantly the amount of mitochondrial NADH increased. Excellent linearity between the number of cells incubated with R123 and fluorescence intensity was found in suspension.

  17. Time-resolved in situ measurement of mitochondrial malfunction by energy transfer spectroscopy.

    PubMed

    Schneckenburger, H; Gschwend, M H; Sailer, R; Strauss, W S; Lyttek, M; Stock, K; Zipfl, P

    2000-10-01

    To establish optical in situ detection of mitochondrial malfunction, nonradiative energy transfer from the coenzyme NADH to the mitochondrial marker rhodamine 123 (R123) was examined. Dual excitation of R123 via energy transfer from excited NADH molecules as well as by direct absorption of light results in two fluorescence signals whose ratio is a measure of mitochondrial NADH. A screening system was developed in which these signals are detected simultaneously using a time-gated (nanosecond) technique for energy transfer measurements and a frequency selective technique for direct excitation and fluorescence monitoring of R123. Optical and electronic components of the apparatus are described, and results obtained from cultivated endothelial cells are reported. The ratio of fluorescence intensities excited in the near ultraviolet and blue-green spectral ranges increased by a factor 1.5 or 1.35 after inhibition of the mitochondrial respiratory chain by rotenone at cytotoxic or noncytotoxic concentrations, respectively. Concomitantly the amount of mitochondrial NADH increased. Excellent linearity between the number of cells incubated with R123 and fluorescence intensity was found in suspension.

  18. Time-Resolved Data Acquisition for In Situ Subsurface Planetary Geochemistry

    NASA Technical Reports Server (NTRS)

    Bodnarik, Julia Gates; Burger, Dan M.; Burger, Arnold; Evans, Larry G.; Parsons, Ann M.; Starr, Richard D.; Stassun, Keivan G.

    2012-01-01

    The current gamma-ray/neutron instrumentation development effort at NASA Goddard Space Flight Center aims to extend the use of active pulsed neutron interrogation techniques to probe the subsurface geochemistry of planetary bodies in situ. All previous NASA planetary science missions, that used neutron and/or gamma-ray spectroscopy instruments, have relied on a constant neutron source produced from galactic cosmic rays. One of the distinguishing features of this effort is the inclusion of a high intensity 14.1 MeV pulsed neutron generator synchronized with a custom data acquisition system to time each event relative to the pulse. With usually only one opportunity to collect data, it is difficult to set a priori time-gating windows to obtain the best possible results. Acquiring time-tagged, event-by-event data from nuclear induced reactions provides raw data sets containing channel/energy, and event time for each gamma ray or neutron detected. The resulting data set can be plotted as a function of time or energy using optimized analysis windows after the data are acquired. Time windows can now be chosen to produce energy spectra that yield the most statistically significant and accurate elemental composition results that can be derived from the complete data set. The advantages of post-processing gamma-ray time-tagged event-by-event data in experimental tests using our prototype instrument will be demonstrated.

  19. Time-resolved Neutron-gamma-ray Data Acquisition for in Situ Subsurface Planetary Geochemistry

    NASA Technical Reports Server (NTRS)

    Bodnarik, Julie G.; Burger, Dan Michael; Burger, A.; Evans, L. G.; Parsons, A. M.; Schweitzer, J. S.; Starr R. D.; Stassun, K. G.

    2013-01-01

    The current gamma-ray/neutron instrumentation development effort at NASA Goddard Space Flight Center aims to extend the use of active pulsed neutron interrogation techniques to probe the subsurface elemental composition of planetary bodies in situ. Previous NASA planetary science missions, that used neutron and/or gamma-ray spectroscopy instruments, have relied on neutrons produced from galactic cosmic rays. One of the distinguishing features of this effort is the inclusion of a high intensity 14.1 MeV pulsed neutron generator synchronized with a custom data acquisition system to time each event relative to the pulse. With usually only one opportunity to collect data, it is difficult to set a priori time-gating windows to obtain the best possible results. Acquiring time-tagged, event-by-event data from nuclear induced reactions provides raw data sets containing channel/energy, and event time for each gamma ray or neutron detected. The resulting data set can be plotted as a function of time or energy using optimized analysis windows after the data are acquired. Time windows can now be chosen to produce energy spectra that yield the most statistically significant and accurate elemental composition results that can be derived from the complete data set. The advantages of post-processing gamma-ray time-tagged event-by-event data in experimental tests using our prototype instrument will be demonstrated.

  20. In situ and time resolved nucleation and growth of silica nanoparticles forming under simulated geothermal conditions

    NASA Astrophysics Data System (ADS)

    Tobler, Dominique J.; Benning, Liane G.

    2013-08-01

    Detailed knowledge of the reaction kinetics of silica nanoparticle formation in cooling supersaturated waters is fundamental to the understanding of many natural processes including biosilicifcation, sinter formation, and silica diagenesis. Here, we quantified the formation of silica nanoparticles from solution as it would occur in geothermal waters. We used an in situ and real-time approach with silica polymerisation being induced by fast cooling of a 230 °C hot and supersaturated silica solution. Experiments were carried out using a novel flow-through geothermal simulator system that was designed to work on-line with either a synchrotron-based small angle X-ray scattering (SAXS) or a conventional dynamic light scattering (DLS) detector system. Our results show that the rate of silica nanoparticle formation is proportional to the silica concentration (640 vs. 960 ppm SiO2), and the first detected particles form spheres of approximately 3 nm in diameter. These initial nanoparticles grow and reach a final particle diameter of approximately 7 nm. Interestingly, neither variations in ionic strength (0.02 vs. 0.06) nor temperature (reactions at 30 to 60 °C, mimicking Earth surface values) seem to affect the formation kinetics or the final size of the silica nanoparticles formed. Comparing these results with our previous data from experiments where silica polymerisation and nanoparticle formation was induced by a drop in pH from 12 to near neutral (pH-induced, Tobler et al., 2009) showed that (a) the mechanisms and kinetics of silica nanoparticle nucleation and growth were unaffected by the means to induce silica polymerisation (T drop or pH drop), both following first order reactions kinetics coupled with a surface controlled reaction mechanism. However, the rates of the formation of silica nanoparticles were substantially (around 50%) slower when polymerisation was induced by fast cooling as opposed to pH change. This was evidenced by the occurrence of an induction

  1. In-SITU, Time-resolved Raman Spectro-micro-topography of an Operating Lithium Ion Battery

    NASA Technical Reports Server (NTRS)

    Luo, Yu; Cai, Wen-Bin; Xing, Xue-Kun; Scherson, Daniel A.

    2003-01-01

    A Raman microscope has been coupled to a computer-controlled, two-dimensional linear translator attached to a custom-designed, sealed optical chamber to allow in situ acquisition of space-, and time-resolved spectra of an operating thin graphite/LiCoO2 Li-ion battery. This unique arrangement made it possible to collect continuously series of Raman spectra from a sharply defined edge of the battery exposing the anode (A), separator (S), and cathode (C), during charge and discharge, while the device was moved back and forth under the fixed focused laser beam along an axis normal to the layered A/S/C plane. Clear spectral evidence was obtained for changes in the amount of Li(+) within particles of graphite in the anode, and, to a lesser extent, of LiCoO2 in the cathode, during battery discharge both as a function of position and time. Analysis of time-resolved Raman spectro-micro-topography (SMT) measurements of the type described in this work are expected to open new prospects for assessing the validity of theoretical models aimed at simulating the flow of Li(+) within Li-ion batteries under operating conditions.

  2. Fixed target matrix for femtosecond time-resolved and in situ serial micro-crystallography

    SciTech Connect

    Mueller, C.; Marx, A.; Epp, S. W.; Zhong, Y.; Kuo, A.; Balo, A. R.; Soman, J.; Schotte, F.; Lemke, H. T.; Owen, R. L.; Pai, E. F.; Pearson, A. R.; Olson, J. S.; Anfinrud, P. A.; Ernst, O. P.; Miller, R. J. Dwayne

    2015-08-18

    We present a crystallography chip enabling in situ room temperature crystallography at microfocus synchrotron beamlines and X-ray free-electron laser (X-FEL) sources. Compared to other in situ approaches, we observe extremely low background and high diffraction data quality. The chip design is robust and allows fast and efficient loading of thousands of small crystals. The ability to load a large number of protein crystals, at room temperature and with high efficiency, into prescribed positions enables high throughput automated serial crystallography with microfocus synchrotron beamlines. In addition, we demonstrate the application of this chip for femtosecond time-resolved serial crystallography at the Linac Coherent Light Source (LCLS, Menlo Park, California, USA). As a result, the chip concept enables multiple images to be acquired from each crystal, allowing differential detection of changes in diffraction intensities in order to obtain high signal-to-noise and fully exploit the time resolution capabilities of XFELs.

  3. Sol-to-Gel Transition in Fast Evaporating Systems Observed by in Situ Time-Resolved Infrared Spectroscopy.

    PubMed

    Innocenzi, Plinio; Malfatti, Luca; Carboni, Davide; Takahashi, Masahide

    2015-06-22

    The in situ observation of a sol-to-gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl4 as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time-resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol-to-gel transition. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. In situ and time-resolved infrared detection of the reactivity induced by electrons in polymer films

    NASA Astrophysics Data System (ADS)

    Bouhier, M.; Vigneron, G.; Ngono-Ravache, Y.; Shirdhonkar, M.; Renault, J. P.; Le Caër, S.

    2017-03-01

    The real time and in situ analysis of chemical reactions such as polymerization reactions, polymer degradation, and oxidation of polymers is of utmost importance. Surprisingly, only few experimental tools allowing this are available. To bridge this gap, we have developed a new experimental setup coupling a 60 keV electron gun with an infrared spectrometer operating in the mid-IR region (800-4000 cm-1) and associated with the rapid scan mode. The measurements are performed using the infrared reflection absorption spectroscopy approach. We worked here with 0.5-25 ms pulses for which the dose per pulse ranges from 4 to 200 kGy. Combining pulse electrons with rapid scan analysis enables performing experiments with a time resolution of 80 ms (and above). Therefore, this new platform can, for instance, give direct insights into reaction mechanisms at stake during the degradation of polymers. First results on a bisphenol A polycarbonate irradiated under vacuum enabling the validation of this new setup and also the recording of time-resolved spectra are presented. Reaction mechanisms are then proposed.

  5. Torsion estimation of particle paths through porous media observed by in-situ time-resolved microtomography.

    PubMed

    Blankenburg, C; Rack, A; Daul, C; Ohser, J

    2017-05-01

    The torsion distribution of cell paths in two-phase flow of a cell suspension through a porous medium is an important quantity for chromatographic processes. It can be estimated from cell tracking in sequences of three-dimensional images of a suspension pumped through the medium, where the images are acquired by in-situ time-resolved microtomography using synchrotron radiation and inline phase contrast modus. This contribution presents a new method for estimating path torsion from discrete positions, where the estimation is based on an appropriate discretization of the differential-geometric formula of the torsion of a space curve. Investigations performed for an alcoholic suspension of silica gel particles pumped through a partially open polyurethane foam show that the shape of the inner surface of the foam has a considerable impact on the particle paths. It turns out that the variance of the torsion for slow particle moving close to the surface is a half order of magnitude smaller than that of fast particles, which underlines the importance of torsion for filter efficiency. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

  6. In situ and time resolved quantification of the kinetics and mechanisms of CaCO3 nucleation and growth

    NASA Astrophysics Data System (ADS)

    Rodriguez-Blanco, J. D.; Shaw, S.; Benning, L. G.

    2009-04-01

    The crystal chemistry, occurrence and relevance of amorphous CaCO3 and its crystalline polymorphs in inorganic and organic environments have been studied for decades and are nowadays relatively well known [1]. However, due to the fast kinetics of the reactions that take place in solution [2], there is virtually no quantitative data available about the kinetics and mechanisms of the nucleation, growth and transformation of these phases in aqueous solutions. In this study we demonstrate that in situ and time resolved synchrotron-based Energy Dispersive X-Ray Diffraction combined with the corresponding solution chemistry and imaging can be successfully applied to evaluate quantitatively kinetic rates and mechanisms of the crystallization and transformation of CaCO3 phases in solution. The precipitation of amorphous calcium carbonate (ACC) and its crystallization to vaterite and calcite was followed in closed thermostated reactors at temperatures between 7.5 and 40˚ C with the time-resolved data collected every 15 secs. The growth/decay of vaterite and calcite diffraction peaks was fitted using a Johnson-Mehl-Avrami-Kolmogorov model [3] to evaluate the kinetics and mechanisms of crystallization [4]. The results show that vaterite grows fast via a 3D growth process following a first order reaction and the subsequent transformation to calcite takes place slower, being controlled by the dissolution of the vaterite precursor. From the temperature dependent data apparent activation energies of nucleation and crystallization for both crystalline CaCO3 polymorphs have been calculated. In addition, wet chemical data and imaging also confirm these findings. Finally, this approach was applied also to other carbonate systems (i.e., dolomite , Ca/Mg carbonates). [1] Reeder R. (1983) Rev. Mineral, 11. [2] Ogino et al. (1987) Geochim. Cosmochim. Acta 51, 2757-2767. [3] Johnson, P.F. and Mehl, R.F. (1939) Reaction kinetics in processes of nucleation and growth. American Institute

  7. In situ and time resolved study of the {gamma}/{alpha}-Fe{sub 2}O{sub 3} transition in nanometric particles

    SciTech Connect

    Belin, T. Millot, N. Bovet, N.; Gailhanou, M.

    2007-08-15

    In situ and real-time study of the {gamma} to {alpha}-Fe{sub 2}O{sub 3} transition is carried out on the H10 beamline at LURE (France). {gamma}-Fe{sub 2}O{sub 3} particles are synthesized by soft chemistry. These particles have an average diameter evaluated by X-ray diffraction of 9{+-}1nm and a specific surface area of 116m{sup 2}g{sup -1}. The size of produced {alpha}-Fe{sub 2}O{sub 3} particles is determined by in situ and time resolved X-ray diffraction measurements at different temperatures. An amazing evolution of size with time is revealed: an abrupt doubling of the {alpha}-Fe{sub 2}O{sub 3} particle size is observed whatever the heating temperature. Some assumptions are given in order to explain this phenomenon which implies at the same time surface energy, granulometric distribution and coalescence of particles. -- A brutal increase of the X-rays coherent domain sizes of the {alpha}-Fe{sub 2}O{sub 3} particles during the {gamma}/{alpha} transition at nanometric scale. Maghemite {gamma}-Fe{sub 2}O{sub 3} particles ({phi}=9{+-}1nm) were heated at 723 K. First germs (or grains) of {alpha}-Fe{sub 2}O{sub 3} were detected with a size of 2 nm.

  8. Fragmentation process during Ho:YAG laser lithotripsy revealed by time-resolved imaging

    NASA Astrophysics Data System (ADS)

    Beghuin, Didier; Delacretaz, Guy P.; Schmidlin, Franz R.; Rink, Klaus

    1998-01-01

    The stone fragmentation process induced during Ho:YAG laser lithotripsy was observed by time-resolved flash video imaging. Possible acoustic transient occurrence was simultaneously monitored with a PVDF needle hydrophone. We used artificial and cystine kidney stones. We observed that, although the fragmentation process is accompanied with the formation of a cavitation bubble, cavitation has a minimal incidence on stone fragmentation. Fragment ejection is mainly due to a direct laser stone heating and vaporization of stone organic constituents and interstitial water. The minimal effect of the cavitation bubble for fragmentation is confirmed by acoustic transients measurements, which reveal weak pressure transients. This is in contrast with the fragmentation mechanisms induced by laser of shorter pulse duration.

  9. Effects of Preferential Solvation Revealed by Time-Resolved Magnetic Field Effects

    PubMed Central

    2017-01-01

    External magnetic fields can impact recombination yields of photoinduced electron transfer reactions by affecting the spin dynamics in transient, spin-correlated radical pair intermediates. For exciplex-forming donor–acceptor systems, this magnetic field effect (MFE) can be investigated sensitively by studying the delayed recombination fluorescence. Here, we investigate the effect of preferential solvation in microheterogeneous solvent mixtures on the radical pair dynamics of the system 9,10-dimethylanthracene (fluorophore)/N,N-dimethylaniline (quencher) by means of time-resolved magnetic field effect (TR-MFE) measurements, wherein the exciplex emission is recorded in the absence and the presence of an external magnetic field using time-correlated single photon counting (TCSPC). In microheterogeneous environments, the MFE of the exciplex emission occurs on a faster time scale than in iso-dielectric homogeneous solvents. In addition, the local polarity reported by the exciplex is enhanced compared to homogeneous solvent mixtures of the same macroscopic permittivity. Detailed analyses of the TR-MFE reveal that the quenching reaction directly yielding the radical ion pair is favored in microheterogeneous environments. This is in stark contrast to homogeneous media, for which the MFE predominantly involves direct formation of the exciplex, its subsequent dissociation to the magneto-sensitive radical pair, and re-encounters. These observations provide evidence for polar microdomains and enhanced caging, which are shown to have a significant impact on the reaction dynamics in microheterogeneous binary solvents. PMID:28263599

  10. Effects of Preferential Solvation Revealed by Time-Resolved Magnetic Field Effects.

    PubMed

    Pham, Van Thi Bich; Hoang, Hao Minh; Grampp, Günter; Kattnig, Daniel Rudolf

    2017-03-06

    External magnetic fields can impact recombination yields of photo-induced electron transfer reactions by affecting the spin dynamics in transient, spin-correlated radical pair intermediates. For exciplex-forming donor-acceptor systems, this magnetic field effect (MFE) can be investigated sensitively by studying the delayed recombination fluorescence. Here, we investigate the effect of preferential solvation in micro-heterogeneous solvent mixtures on the radical pair dynamics of the system 9,10-dimethylanthracene (fluorophore) / N,N-dimethylaniline (quencher) by means of time-resolved magnetic field effect (TR-MFE) measurements, wherein the exciplex emission is recorded in the absence and the presence of an external magnetic field using Time-Correlated Single Photon Counting (TCSPC). In micro-heterogeneous environments, the MFE of the exciplex emission occurs on a faster timescale than in iso-dielectric homogeneous solvents. In addition, the local polarity reported by the exciplex is enhanced compared to homogeneous solvent mixtures of the same macroscopic permittivity. Detailed analyses of the TR-MFE reveal that the quenching reaction directly yielding the radical ion pair is favored in micro-heterogeneous environments. This is in stark contrast to homogeneous media, for which the MFE predominantly involves direct formation of the exciplex, its subsequent dissociation to the magneto-sensitive radical pair, and re-encounters. These observations provide evidence for polar micro-domains and enhanced caging, which are shown to have a significant impact on the reaction dynamics in micro-heterogeneous binary solvents.

  11. Time-Resolved Soft X-ray Diffraction Reveals Transient Structural Distortions of Ternary Liquid Crystals

    PubMed Central

    Quevedo, Wilson; Peth, Christian; Busse, Gerhard; Scholz, Mirko; Mann, Klaus; Techert, Simone

    2009-01-01

    Home-based soft X-ray time-resolved scattering experiments with nanosecond time resolution (10 ns) and nanometer spatial resolution were carried out at a table top soft X-ray plasma source (2.2–5.2 nm). The investigated system was the lyotropic liquid crystal C16E7/paraffin/glycerol/formamide/IR 5. Usually, major changes in physical, chemical, and/or optical properties of the sample occur as a result of structural changes and shrinking morphology. Here, these effects occur as a consequence of the energy absorption in the sample upon optical laser excitation in the IR regime. The liquid crystal shows changes in the structural response within few hundred nanoseconds showing a time decay of 182 ns. A decrease of the Bragg peak diffracted intensity of 30% and a coherent macroscopic movement of the Bragg reflection are found as a response to the optical pump. The Bragg reflection movement is established to be isotropic and diffusion controlled (1 μs). Structural processes are analyzed in the Patterson analysis framework of the time-varying diffraction peaks revealing that the inter-lamellar distance increases by 2.7 Å resulting in an elongation of the coherently expanding lamella crystallite. The present studies emphasize the possibility of applying TR-SXRD techniques for studying the mechanical dynamics of nanosystems. PMID:20087463

  12. Wall current probe: A non-invasive in situ plasma diagnostic for space and time resolved current density distribution measurement

    SciTech Connect

    Baude, R.; Gaboriau, F.; Hagelaar, G. J. M.

    2013-08-15

    In the context of low temperature plasma research, we propose a wall current probe to determine the local charged particle fluxes flowing to the chamber walls. This non-intrusive planar probe consists of an array of electrode elements which can be individually biased and for which the current can be measured separately. We detail the probe properties and present the ability of the diagnostic to be used as a space and time resolved measurement of the ion and electron current density at the chamber walls. This diagnostic will be relevant to study the electron transport in magnetized low-pressure plasmas.

  13. Wall current probe: a non-invasive in situ plasma diagnostic for space and time resolved current density distribution measurement.

    PubMed

    Baude, R; Gaboriau, F; Hagelaar, G J M

    2013-08-01

    In the context of low temperature plasma research, we propose a wall current probe to determine the local charged particle fluxes flowing to the chamber walls. This non-intrusive planar probe consists of an array of electrode elements which can be individually biased and for which the current can be measured separately. We detail the probe properties and present the ability of the diagnostic to be used as a space and time resolved measurement of the ion and electron current density at the chamber walls. This diagnostic will be relevant to study the electron transport in magnetized low-pressure plasmas.

  14. In Vivo Time-Resolved Microtomography Reveals the Mechanics of the Blowfly Flight Motor

    PubMed Central

    Mokso, Rajmund; Wicklein, Martina; Müller, Tonya; Doube, Michael; Stampanoni, Marco; Krapp, Holger G.; Taylor, Graham K.

    2014-01-01

    Dipteran flies are amongst the smallest and most agile of flying animals. Their wings are driven indirectly by large power muscles, which cause cyclical deformations of the thorax that are amplified through the intricate wing hinge. Asymmetric flight manoeuvres are controlled by 13 pairs of steering muscles acting directly on the wing articulations. Collectively the steering muscles account for <3% of total flight muscle mass, raising the question of how they can modulate the vastly greater output of the power muscles during manoeuvres. Here we present the results of a synchrotron-based study performing micrometre-resolution, time-resolved microtomography on the 145 Hz wingbeat of blowflies. These data represent the first four-dimensional visualizations of an organism's internal movements on sub-millisecond and micrometre scales. This technique allows us to visualize and measure the three-dimensional movements of five of the largest steering muscles, and to place these in the context of the deforming thoracic mechanism that the muscles actuate. Our visualizations show that the steering muscles operate through a diverse range of nonlinear mechanisms, revealing several unexpected features that could not have been identified using any other technique. The tendons of some steering muscles buckle on every wingbeat to accommodate high amplitude movements of the wing hinge. Other steering muscles absorb kinetic energy from an oscillating control linkage, which rotates at low wingbeat amplitude but translates at high wingbeat amplitude. Kinetic energy is distributed differently in these two modes of oscillation, which may play a role in asymmetric power management during flight control. Structural flexibility is known to be important to the aerodynamic efficiency of insect wings, and to the function of their indirect power muscles. We show that it is integral also to the operation of the steering muscles, and so to the functional flexibility of the insect flight motor

  15. Laser lithotripsy with the Ho:YAG laser: fragmentation process revealed by time-resolved imaging

    NASA Astrophysics Data System (ADS)

    Schmidlin, Franz R.; Beghuin, Didier; Delacretaz, Guy P.; Venzi, Giordano; Jichlinski, Patrice; Rink, Klaus; Leisinger, Hans-Juerg; Graber, Peter

    1998-07-01

    Improvements of endoscopic techniques have renewed the interest of urologists in laser lithotripsy in recent years. Laser energy can be easily transmitted through flexible fibers thereby enabling different surgical procedures such as cutting, coagulating and lithotripsy. The Ho:YAG laser offers multiple medical applications in Urology, among them stone fragmentation. However, the present knowledge of its fragmentation mechanism is incomplete. The objective was therefore to analyze the fragmentation process and to discuss the clinical implications related to the underlying fragmentation mechanism. The stone fragmentation process during Ho:YAG laser lithotripsy was observed by time resolved flash video imaging. Possible acoustic transient occurrence was simultaneously monitored with a PVDF-needle hydrophone. Fragmentation was performed on artificial and cystine kidney stones in water. We observed that though the fragmentation process is accompanied with the formation of a cavitation bubble, cavitation has only a minimal effect on stone fragmentation. Fragment ejection is mainly due to direct laser stone heating leading to vaporization of organic stone constituents and interstitial water. The minimal effect of the cavitation bubble is confirmed by acoustic transients measurements, which reveal weak pressure transients. Stone fragmentation with the Holmium laser is the result of vaporization of interstitial (stone) water and organic stone constituents. It is not due to the acoustic effects of a cavitation bubble or plasma formation. The fragmentation process is strongly related with heat production thereby harboring the risk of undesired thermal damage. Therefore, a solid comprehension of the fragmentation process is needed when using the different clinically available laser types of lithotripsy.

  16. Ordering of PCDTBT revealed by time-resolved electron paramagnetic resonance spectroscopy of its triplet excitons.

    PubMed

    Biskup, Till; Sommer, Michael; Rein, Stephan; Meyer, Deborah L; Kohlstädt, Markus; Würfel, Uli; Weber, Stefan

    2015-06-22

    Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is shown to be a powerful tool to characterize triplet excitons of conjugated polymers. The resulting spectra are highly sensitive to the orientation of the molecule. In thin films cast on PET film, the molecules' orientation with respect to the surface plane can be determined, providing access to sample morphology on a microscopic scale. Surprisingly, the conjugated polymer investigated here, a promising material for organic photovoltaics, exhibits ordering even in bulk samples. Orientation effects may significantly influence the efficiency of solar cells, thus rendering proper control of sample morphology highly important.

  17. Fluorescence decay characteristics of indole compounds revealed by time-resolved area-normalized emission spectroscopy.

    PubMed

    Otosu, Takuhiro; Nishimoto, Etsuko; Yamashita, Shoji

    2009-03-26

    Time-resolved fluorescence spectroscopy of tryptophan residue has been extensively applied to the studies on structure-function relationships of protein. Regardless of this, the fluorescence decay mechanism and kinetics of tryptophan residue in many proteins still remains unclear. Previous studies have demonstrated that conformational heterogeneity and relaxation dynamics are both involved in the peculiar multiexponential decay kinetics in subnanosecond resolution. In the present study, we characterized the fluorescence decay property of six indole compounds in glycerol by resolving the contribution of conformational heterogeneity and relaxation dynamics. We applied the time-resolved area-normalized fluorescence emission spectrum (TRANES) method for the fluorescence decay analysis. The results of TRANES, time-dependent shift of fluorescence spectral center of gravity, and fluorescence decay simulation demonstrated that the dielectric relaxation process independent of intrinsic rotamer/conformer and the individual fluorescence lifetime gives the peculiarity to the fluorescence decay of indole compounds. These results confirmed that TRANES and time-dependent spectral shift analysis are potent methods to resolve the origin of multiexponential decay kinetics of tryptophyl fluorescence in protein.

  18. Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in-situ time-resolved high-temperature x-ray diffraction (HTXRD) analysis

    SciTech Connect

    Ayturk, Mahmut Engin; Payzant, E Andrew; Speakman, Scott A; Ma, Yi Hua

    2008-01-01

    Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex-situ studies carried by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in-situ time-resolved high temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 C, 550 C and 600 C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500oC, 550oC and 600oC, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. The cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol).

  19. Intercalation chemistry in a LDH system: anion exchange process and staging phenomenon investigated by means of time-resolved, in situ X-ray diffraction.

    PubMed

    Taviot-Guého, Christine; Feng, Yongjun; Faour, Azzam; Leroux, Fabrice

    2010-07-14

    Using time-resolved, in situ energy-dispersive X-ray diffraction (EDXRD), the formation of interstratified LDH structures, with alternate interlayer spaces occupied by different anions, have been demonstrated during anion exchange reactions. Novel hybrid LDH nanostructures can thus be prepared, combining the physicochemical properties of two intercalated anions plus those of the LDH host. A general trend is that inorganic-inorganic anion exchange reactions occur in a one-step process while inorganic-organic exchanges may proceed via a second-stage intermediate, suggesting that staging occurs partly as a result of organic-inorganic separation. Yet, other influencing parameters must be considered such as LDH host composition, LDH affinity for different anions and LDH particle size as well as extrinsic parameters like the reaction temperature. Hence, a correlation between the occurrence of staging phenomenon and the difficulty of the exchange of the initial anion is observed, suggesting that staging is needed to overcome the energy barrier in the case of the exchange by organic anions. Notwithstanding the LiAl(2) system, staging has mainly been observed with Zn(2)Cr LDH host so far, a peculiar LDH composition with a unique Zn/Cr ratio of two and a local order of the cations within the hydroxide layers. The formation of a higher order-staged intermediate than stage two, observed during the exchange reaction of CO(3)(2-) or SO(4)(2-) anions with Zn(2)Cr-tartrate, is in favour of a Daumas-Herold model although this model implies a bending of LDH layers. The analysis of the X-ray powder diffraction pattern of Zn(2)Cr-Cl/tartrate second-stage intermediate, isolated almost as a pure phase during the exchange of Cl(-) with tartrate anions in Zn(2)Cr LDH, indicates a disorder in the stacking sequence and a relative proportion of the two kinds of interlayers slightly different from 50/50. Besides, the microstructural analysis of the XRD pattern reveals a great reduction of the

  20. Structural changes and thermal stability of charged LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy

    DOE PAGES

    Bak, Seong -Min; Hu, Enyuan; Zhou, Yongning; ...

    2014-11-24

    Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time- resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygenmore » release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3¯m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3¯m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. As a result, this systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.« less

  1. Lattice-level observation of the elastic-to-plastic relaxation process with subnanosecond resolution in shock-compressed Ta using time-resolved in situ Laue diffraction

    DOE PAGES

    Wehrenberg, C. E.; Comley, A. J.; Barton, N. R.; ...

    2015-09-29

    We report direct lattice level measurements of plastic relaxation kinetics through time-resolved, in-situ Laue diffraction of shock-compressed single-crystal [001] Ta at pressures of 27-210 GPa. For a 50 GPa shock, a range of shear strains is observed extending up to the uniaxial limit for early data points (<0.6 ns) and the average shear strain relaxes to a near steady state over ~1 ns. For 80 and 125 GPa shocks, the measured shear strains are fully relaxed already at 200 ps, consistent with rapid relaxation associated with the predicted threshold for homogeneous nucleation of dislocations occurring at shock pressure ~65 GPa.more » The relaxation rate and shear stresses are used to estimate the dislocation density and these quantities are compared to the Livermore Multiscale Strength model as well as various molecular dynamics simulations.« less

  2. Revisited: Decomposition or melting? Formation mechanism investigation of LiCoO2 via in-situ time-resolved X-ray diffraction.

    PubMed

    Wicker, Scott A; Walker, Edwin H

    2013-02-18

    We report the first in-situ time-resolved X-ray diffraction investigation in conjunction with a non-isothermal kinetic study using the model-free isoconversional kinetic method to determine the formation mechanism for the solid-state synthesis of electrochemically active LiCoO(2) from Li(2)CO(3) and Co(3)O(4). Detailed information on the phase evolution as well as thermal events during the heating process was clearly observed, explained, and supported. This investigation provides structural as well as kinetic evidence for a multistep reaction and proposes the first plausible formation mechanism for the solid-state synthesis of LiCoO(2).

  3. New large volume hydrothermal reaction cell for studying chemical processes under supercritical hydrothermal conditions using time-resolved in situ neutron diffraction.

    PubMed

    Ok, Kang Min; O'Hare, Dermot; Smith, Ronald I; Chowdhury, Mohammed; Fikremariam, Hanna

    2010-12-01

    The design and testing of a new large volume Inconel pressure cell for the in situ study of supercritical hydrothermal syntheses using time-resolved neutron diffraction is introduced for the first time. The commissioning of this new cell is demonstrated by the measurement of the time-of-flight neutron diffraction pattern for TiO(2) (Anatase) in supercritical D(2)O on the POLARIS diffractometer at the United Kingdom's pulsed spallation neutron source, ISIS, Rutherford Appleton Laboratory. The sample can be studied over a wide range of temperatures (25-450 °C) and pressures (1-355 bar). This novel apparatus will now enable us to study the kinetics and mechanisms of chemical syntheses under extreme environments such as supercritical water, and in particular to study the crystallization of a variety of technologically important inorganic materials.

  4. New large volume hydrothermal reaction cell for studying chemical processes under supercritical hydrothermal conditions using time-resolved in situ neutron diffraction

    NASA Astrophysics Data System (ADS)

    Ok, Kang Min; O'Hare, Dermot; Smith, Ronald I.; Chowdhury, Mohammed; Fikremariam, Hanna

    2010-12-01

    The design and testing of a new large volume Inconel pressure cell for the in situ study of supercritical hydrothermal syntheses using time-resolved neutron diffraction is introduced for the first time. The commissioning of this new cell is demonstrated by the measurement of the time-of-flight neutron diffraction pattern for TiO2 (Anatase) in supercritical D2O on the POLARIS diffractometer at the United Kingdom's pulsed spallation neutron source, ISIS, Rutherford Appleton Laboratory. The sample can be studied over a wide range of temperatures (25-450 °C) and pressures (1-355 bar). This novel apparatus will now enable us to study the kinetics and mechanisms of chemical syntheses under extreme environments such as supercritical water, and in particular to study the crystallization of a variety of technologically important inorganic materials.

  5. Cooperative macromolecular device revealed by meta-analysis of static and time-resolved structures

    SciTech Connect

    Ren, Zhong; Šrajer, Vukica; Knapp, James E.; Royer, Jr., William E.

    2013-04-08

    Here we present a meta-analysis of a large collection of static structures of a protein in the Protein Data Bank in order to extract the progression of structural events during protein function. We apply this strategy to the homodimeric hemoglobin HbI from Scapharca inaequivalvis. We derive a simple dynamic model describing how binding of the first ligand in one of the two chemically identical subunits facilitates a second binding event in the other partner subunit. The results of our ultrafast time-resolved crystallographic studies support this model. We demonstrate that HbI functions like a homodimeric mechanical device, such as pliers or scissors. Ligand-induced motion originating in one subunit is transmitted to the other via conserved pivot points, where the E and F' helices from two partner subunits are 'bolted' together to form a stable dimer interface permitting slight relative rotation but preventing sliding.

  6. In-situ characterization of femtosecond laser-induced crystallization in borosilicate glass using time-resolved surface third-harmonic generation

    SciTech Connect

    Liu, Weimin; Wang, Liang; Han, Fangyuan; Fang, Chong

    2013-11-11

    Coherent phonon dynamics in condensed-phase medium are responsible for important material properties including thermal and electrical conductivities. We report a structural dynamics technique, time-resolved surface third-harmonic generation (TRSTHG) spectroscopy, to capture transient phonon propagation near the surface of polycrystalline CaF{sub 2} and amorphous borosilicate (BK7) glass. Our approach time-resolves the background-free, high-sensitivity third harmonic generation (THG) signal in between the two crossing near-IR pulses. Pronounced intensity quantum beats reveal the impulsively excited low-frequency Raman mode evolution on the femtosecond to picosecond timescale. After amplified laser irradiation, danburite-crystal-like structure units form at the glass surface. This versatile TRSTHG setup paves the way to mechanistically study and design advanced thermoelectrics and photovoltaics.

  7. Time-resolved in situ assembly of the leukotriene-synthetic 5-lipoxygenase/5-lipoxygenase-activating protein complex in blood leukocytes.

    PubMed

    Gerstmeier, Jana; Weinigel, Christina; Rummler, Silke; Rådmark, Olof; Werz, Oliver; Garscha, Ulrike

    2016-01-01

    5-Lipoxygenase (5-LO) catalyzes the initial steps in the biosynthesis of proinflammatory leukotrienes. Upon cell activation, 5-LO translocates to the nuclear membrane where arachidonic acid is transferred by 5-LO-activating protein (FLAP) to 5-LO for metabolism. Although previous data indicate association of 5-LO with FLAP, the in situ assembly of native 5-LO/FLAP complexes remains elusive. Here, we show time-resolved 5-LO/FLAP colocalization by immunofluorescence microscopy and in situ 5-LO/FLAP interaction by proximity ligation assay at the nuclear membrane of Ca(2+)-ionophore A23187-activated human monocytes and neutrophils in relation to 5-LO activity. Although 5-LO translocation and product formation is completed within 1.5-3 min, 5-LO/FLAP interaction is delayed and proceeds up to 30 min. Though monocytes and neutrophils contain comparable amounts of 5-LO protein, neutrophils produce 3-5 times higher levels of 5-LO products due to prolonged activity, accompanied by delayed 5-LO nuclear membrane translocation. Arachidonic acid seemingly acts as adaptor for 5-LO/FLAP assembly, whereas FLAP inhibitors (MK886, 100 nM; BAY X 1005, 3 µM) disrupt the complex. We conclude that FLAP may regulate 5-LO activity in 2 ways: first by inducing an initial flexible association for efficient 5-LO product synthesis, followed by the formation of a tight 5-LO/FLAP complex that terminates 5-LO activity. © FASEB.

  8. The CO oxidation kinetics on supported Pd model catalysts: A molecular beam/in situ time-resolved infrared reflection absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Libuda, J.; Meusel, I.; Hoffmann, J.; Hartmann, J.; Piccolo, L.; Henry, C. R.; Freund, H.-J.

    2001-03-01

    Combining molecular beam techniques and time-resolved infrared reflection absorption spectroscopy (TR-IRAS) we have studied the kinetics of the CO oxidation reaction on an alumina-supported Pd model catalyst. The Pd particles are deposited by metal evaporation under ultrahigh vacuum (UHV) conditions onto a well-ordered alumina film, prepared on a NiAl(110) single crystal. Particle size, density and structure of the Pd deposits have been characterized in previous studies. In the low temperature region, transient and steady-state experiments have been performed over a wide range of CO and oxygen fluxes by crossing two effusive molecular beams on the sample surface. We determine the steady-state CO2 production rate as a function of the CO fraction in the impinging gas flux. Simultaneously, the occupation of CO adsorption sites under steady-state conditions is monitored by in situ IR spectroscopy. The origin of different types of CO2 transients is discussed. In particular we focus on the transient CO2 production after switching off the CO beam. For the model catalyst investigated, detailed reaction rate measurements in combination with time-resolved IRAS show that the origin of the particular transient behavior of the supported model system is not due to the presence of specific adsorption sites on small particles, as has been proposed previously. Instead, we show that the transient behavior can be semiquantitatively simulated on the basis of a simple kinetic model considering a homogeneous surface, and accounting for the inhibition of the dissociative adsorption of O2 at high CO coverage. Moreover, it is discussed how the inherent heterogeneity of the supported particle system can additionally enhance the observed effect.

  9. Time-Resolved, In Situ DRIFTS/EDE/MS Studies on Alumina-Supported Rhodium Catalysts: Effects of Ceriation and Zirconiation on Rhodium–CO Interactions**

    PubMed Central

    Kroner, Anna B; Newton, Mark A; Tromp, Moniek; Roscioni, Otello M; Russell, Andrea E; Dent, Andrew J; Prestipino, Carmelo; Evans, John

    2014-01-01

    The effects of ceria and zirconia on the structure–function properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ-Al2O3) during CO exposure are described. Ceria and zirconia are introduced through two preparation methods: 1) ceria is deposited on γ-Al2O3 from [Ce(acac)3] and rhodium metal is subsequently added, and 2) through the controlled surface modification (CSM) technique, which involves the decomposition of [M(acac)x] (M=Ce, x=3; M=Zr, x=4) on Rh/γ-Al2O3. The structure–function correlations of ceria and/or zirconia-doped rhodium catalysts are investigated by diffuse reflectance infrared Fourier-transform spectroscopy/energy-dispersive extended X-ray absorption spectroscopy/mass spectrometry (DRIFTS/EDE/MS) under time-resolved, in situ conditions. CeOx and ZrO2 facilitate the protection of Rh particles against extensive oxidation in air and CO. Larger Rh core particles of ceriated and zirconiated Rh catalysts prepared by CSM are observed and compared with Rh/γ-Al2O3 samples, whereas supported Rh particles are easily disrupted by CO forming mononuclear Rh geminal dicarbonyl species. DRIFTS results indicate that, through the interaction of CO with ceriated Rh particles, a significantly larger amount of linear CO species form; this suggests the predominance of a metallic Rh phase. PMID:25044889

  10. In-situ Time-Resolved Neutron Diffraction Measurements of Microstructure Variations during Friction Stir Welding in a 6061-T6 Aluminum Alloy

    SciTech Connect

    Woo, Wan Chuck; Wang, Xun-Li; Ungar, Prof Tomas; Feng, Zhili; David, Stan A; Clausen, B; Hubbard, Camden R

    2008-01-01

    The microstructure change is one of the most important research areas in the friction stir welding (FSW). However, direct observation of microstructure changes during FSW has been extremely challenging because many measurement techniques are inapplicable. Recently developed in-situ time-resolved neutron diffraction methodology, which drastically improves the temporal resolution of neutron diffraction, enables to observe the transient microstructure changes during FSW. We installed a portable FSW system in the Spectrometer for MAterials Research at Temperature and Stress (SMARTS) at Los Alamos Neutron Science Center and the FSW was made on 6.35mm-thickness 6061-T6 Al alloy plate. At the same time, the neutron beam was centered on the mid-plane of the Al plate at 8 mm from the tool center (underneath the tool shoulder) and the diffraction peak was continuously measured during welding. The peak broadening analysis has been performed using the Williamson-Hall Method. The result shows that the dislocation density of about 3.2 x 10^15 m-2 duing FSW, which is the significant increse compared to the before (4.5 x 10^14 m-2) and after (4.0 x 10^14 m-2) the FSW. The quantitatively analysis of the grain structure can provide an insight to understand the transient variation of the microstructure during FSW.

  11. In-Situ Observations of Phase Transformations During Welding of 1045 Steel using Spatially Resolved and Time Resolved X-Ray Diffraction

    SciTech Connect

    Elmer, J; Palmer, T; DebRoy, T

    2005-10-28

    Synchrotron-based methods have been developed at Lawrence Livermore National Laboratory (LLNL) for the direct observation of microstructure evolution during welding. These techniques, known as spatially resolved (SRXRD) and time resolved (TRXRD) x-ray diffraction, allow in-situ experiments to be performed during welding and provide direct observations of high temperature phases that form under the intense thermal cycles that occur. This paper presents observations of microstructural evolution that occur during the welding of a medium carbon AISI 1045 steel, using SRXRD to map the phases that are present during welding, and TRXRD to dynamically observe transformations during rapid heating and cooling. SRXRD was further used to determine the influence of welding heat input on the size of the high temperature austenite region, and the time required to completely homogenize this region during welding. These data can be used to determine the kinetics of phase transformations under the steep thermal gradients of welds, as well as benchmark and verify phase transformation models.

  12. H2 Production Through the Water-gas Shift Reaction: An In situ Time-resolved X-ray Diffraction Investigation of Manganese OMS-2 Catalyst

    SciTech Connect

    Hanson, J.C.; Sithambaram, S.; Wen, W.; Njagi, E.; Shen, X.-F.; Suib, S.L.

    2010-10-01

    Manganese oxide octahedral molecular sieve (OMS-2) catalyst prepared by the reflux method was investigated for hydrogen generation via the water-gas shift reaction. Catalysts were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), The Brunauer-Emmett-Teller (BET) surface area and determination of average oxidation state (AOS). The OMS-2 catalyst showed very good catalytic activity for the water-gas shift reaction to generate hydrogen under laboratory conditions. An in situ study was conducted to monitor the structural changes in the catalyst during the water-gas shift reaction using synchrotron radiation-based time-resolved X-ray diffraction (TR-XRD). During the water-gas shift reaction, the mixed valent OMS-2 catalyst undergoes a structural transformation to form Mn{sub 2}O{sub 3} and finally to form MnO. The study showed that OMS-2 catalysts can be used as inexpensive catalysts for hydrogen generation.

  13. H2 production Through the Water-gas Shift Reaction: An in Situ Time-resolved X-ray Diffraction Investigation of Manganese OMS-2 Catalyst

    SciTech Connect

    Sithambaram, S.; Wen, W; Njagi, E; Shen, X; Hanson, J; Suib, S

    2010-01-01

    Manganese oxide octahedral molecular sieve (OMS-2) catalyst prepared by the reflux method was investigated for hydrogen generation via the water-gas shift reaction. Catalysts were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), The Brunauer-Emmett-Teller (BET) surface area and determination of average oxidation state (AOS). The OMS-2 catalyst showed very good catalytic activity for the water-gas shift reaction to generate hydrogen under laboratory conditions. An in situ study was conducted to monitor the structural changes in the catalyst during the water-gas shift reaction using synchrotron radiation-based time-resolved X-ray diffraction (TR-XRD). During the water-gas shift reaction, the mixed valent OMS-2 catalyst undergoes a structural transformation to form Mn{sub 2}O{sub 3} and finally to form MnO. The study showed that OMS-2 catalysts can be used as inexpensive catalysts for hydrogen generation.

  14. Skyrmion Hall effect revealed by direct time-resolved X-ray microscopy

    NASA Astrophysics Data System (ADS)

    Litzius, Kai; Lemesh, Ivan; Krüger, Benjamin; Bassirian, Pedram; Caretta, Lucas; Richter, Kornel; Büttner, Felix; Sato, Koji; Tretiakov, Oleg A.; Förster, Johannes; Reeve, Robert M.; Weigand, Markus; Bykova, Iuliia; Stoll, Hermann; Schütz, Gisela; Beach, Geoffrey S. D.; Kläui, Mathias

    2016-12-01

    Magnetic skyrmions are promising candidates for future spintronic applications such as skyrmion racetrack memories and logic devices. They exhibit exotic and complex dynamics governed by topology and are less influenced by defects, such as edge roughness, than conventionally used domain walls. In particular, their non-zero topological charge leads to a predicted `skyrmion Hall effect', in which current-driven skyrmions acquire a transverse velocity component analogous to charged particles in the conventional Hall effect. Here, we use nanoscale pump-probe imaging to reveal the real-time dynamics of skyrmions driven by current-induced spin-orbit torques. We find that skyrmions move at a well-defined angle ΘSkH that can exceed 30° with respect to the current flow, but in contrast to conventional theoretical expectations, ΘSkH increases linearly with velocity up to at least 100 ms-1. We qualitatively explain our observation based on internal mode excitations in combination with a field-like spin-orbit torque, showing that one must go beyond the usual rigid skyrmion description to understand the dynamics.

  15. Cation Movements during Dehydration and NO2 Desorption in a Ba-Y,FAU zeolite: an in situ Time-resolved X-ray Diffraction Study

    SciTech Connect

    Wang, Xianqin; Hanson, Jonathan C.; Kwak, Ja Hun; Szanyi, Janos; Peden, Charles HF

    2013-02-28

    Synchrotron-based in situ time-resolved X-ray diffraction and Rietveld analysis were used to probe the interactions between BaY, FAU zeolite frameworks and H2O or NO2 molecules. These results provided information about the migration of the Ba2+ cations in the zeolite framework during dehydration and during NO2 adsorption/desorption processes in a water free zeolite. In the hydrated structure water molecules form four double rings of hexagonal ice-like clusters [(H2O)6] in the 12-ring openings of the super-cage. These water rings interacted with the cations and the zeolite framework through four cation/water clusters centered over the four 6-membered rings of the super-cage (site II). Interpenetrating tetrahedral water clusters [(H2O)4] and tetrahedral Ba+2 cation clusters were observed in the sodalite cage. Consistent with the reported FT-IR results, three different ionic NOx species (NO+, NO+-NO2, and NO3-) were observed following NO2 adsorption by the dehydrated Ba-Y,FAU zeolite. The structure of the water and the NOx species were correlated with the interactions between the adsorbates, the cations, and the framework. The population of Ba2+ ions at different cationic positions strongly depended on the amount of bound water or NOx species. Both dehydration and NO2 adsorption/desorption resulted in facile migration of Ba2+ ions among the different cationic positions. Data obtained in this work have provided direct evidence for the Ba2+ cation migration to accommodate the binding of gas molecules. This important feature may play a pivotal role in the strong binding of NO2 to Ba-Y,FAU zeolite, a prerequisite for high catalytic activity in lean NOx reduction catalysis.

  16. Bright and dark triplet states of the negatively charged magnetoexcitons revealed in photoluminescence and time-resolved measurements

    NASA Astrophysics Data System (ADS)

    Munteanu, F. M.; Rickel, D. G.; Perry, C. H.; Kim, Yongmin; Simmons, J. A.; Reno, J. L.

    2000-12-01

    Continuous and time-resolved magnetophotoluminescence measurements of three GaAs/AlxGa1-xAs heterostructures have been made in high magnetic fields. The spectra revealed the presence of a singlet and two triplet states (the so-called ``bright'' and ``dark'' states) of the negatively charged magnetoexciton, in addition to the neutral exciton. For an asymmetrically doped single quantum well sample, the singlet and the dark triplet states converge (and possibly cross) at a field of about 40 T. The two single heterojunction samples on the other hand show no such convergence, and the singlet remains the fundamental state at least in fields to 60 T. The lifetimes of the charged magnetoexcitons increased linearly with field, whereas the neutral exciton was essentially field independent. The results clarify earlier experimental studies, and provide a confirmation of a recent theory of the behavior of charged magnetoexcitons in magnetic fields by Wojs et al. [Phys Rev. B 62, 4630 (2000)].

  17. Charge separation in subcells of triple-junction solar cells revealed by time-resolved photoluminescence spectroscopy.

    PubMed

    Tex, David M; Imaizumi, Mitsuru; Kanemitsu, Yoshihiko

    2015-11-30

    We measure the excitation-wavelength and power dependence of time-resolved photoluminescence (PL) from the top InGaP subcell in a InGaP/GaAs/Ge triple-junction solar cell. The wavelength-dependent data reveals that the PL decays are governed by charge separation. A fast single-exponential PL decay is observed at low excitation power densities, which is the charge separation under short-circuit condition. Under strong excitation a bi-exponential PL decay is observed. Its slow component appears at early times, followed by a faster component at late times. The slow decay is the carrier recombination of the subcell. The following fast component is the charge separation process under reduced built-in potential near the operating point. The subcells electrical conversion efficiency close to the operating point is evaluated using this decay time constant.

  18. In situ time-resolved SAXS study of the formation of mesostructured organically modified silica through modeling of micelles evolution during surfactant-templated self-assembly.

    PubMed

    Michaux, Florentin; Baccile, Niki; Impéror-Clerc, Marianne; Malfatti, Luca; Folliet, Nicolas; Gervais, Christel; Manet, Sabine; Meneau, Florian; Pedersen, Jan Skov; Babonneau, Florence

    2012-12-18

    The mechanisms of formation of organically modified (phenyl, vinyl, and methyl) silica materials with cubic Pm3n and hexagonal p6m periodic mesostructures obtained in one step in the presence of the cetyltrimethylammonium bromide (CTA(+)B) surfactant are reported in this study. Understanding the way these complex materials form is difficult but undoubtedly necessary for controlling the material structure and its properties because of the combined presence of surface organic groups and large surface areas. Here, the mechanism of formation is clarified on the basis of the modeling of time-resolved in situ small angle X-ray scattering (SAXS) experiments, with a specific focus on the micelle evolution during material formation. Their fast self-assembly is followed for the first time with a quick temporal resolution of a few seconds using a third-generation synchrotron radiation source. To better understand the behavior of the complex organic-containing mesostructure, we perform a comparative study with the corresponding organo-free, isostructural materials obtained from three different surfactants (CTA(+), CTEA(+), and CTPA(+)) having a constant chain length (C(16)) and an increasing polar head volume (met-, et-, and prop-). Numerical modeling of SAXS data was crucial to highlighting a systematic sphere-to-rod micellar transition, otherwise undetected, before the formation of the 2D hexagonal phase in both organo-free and organo-containing systems. Then, two different pathways were found in the formation of the cubic Pm3n mesostructure: either an ordering transition from concentrated flocs of spherical micelles (from CTEA(+) or CTPA(+)) for pure TEOS systems or a structural transformation from an intermediate 2D hexagonal mesophase in organosilane systems (from CTA(+)). Combining the comparison between organo-free and organo-containing systems with numerical modeling, we find that the hexagonal-to-cubic phase transition in the organically modified materials seems to be

  19. Time resolved X-ray Dark-Field Tomography Revealing Water Transport in a Fresh Cement Sample.

    PubMed

    Prade, Friedrich; Fischer, Kai; Heinz, Detlef; Meyer, Pascal; Mohr, Jürgen; Pfeiffer, Franz

    2016-06-30

    Grating-based X-ray dark-field tomography is a promising technique for biomedical and materials research. Even if the resolution of conventional X-ray tomography does not suffice to resolve relevant structures, the dark-field signal provides valuable information about the sub-pixel microstructural properties of the sample. Here, we report on the potential of X-ray dark-field imaging to be used for time-resolved three-dimensional studies. By repeating consecutive tomography scans on a fresh cement sample, we were able to study the hardening dynamics of the cement paste in three dimensions over time. The hardening of the cement was accompanied by a strong decrease in the dark-field signal pointing to microstructural changes within the cement paste. Furthermore our results hint at the transport of water from certain limestone grains, which were embedded in the sample, to the cement paste during the process of hardening. This is indicated by an increasing scattering signal which was observed for two of the six tested limestone grains. Electron microscopy images revealed a distinct porous structure only for those two grains which supports the following interpretation of our results. When the water filled pores of the limestone grains empty during the experiment the scattering signal of the grains increases.

  20. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    DOE PAGES

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; ...

    2016-02-26

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase seperated regions. The ability to simultanousely track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of- the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiatedmore » at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, which is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. Lastly, the direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.« less

  1. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    PubMed Central

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, Il Woong; Walko, Donald A.; Dufresne, Eric M.; Jeong, Jaewoo; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-01-01

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems. PMID:26915398

  2. Time resolved X-ray Dark-Field Tomography Revealing Water Transport in a Fresh Cement Sample

    NASA Astrophysics Data System (ADS)

    Prade, Friedrich; Fischer, Kai; Heinz, Detlef; Meyer, Pascal; Mohr, Jürgen; Pfeiffer, Franz

    2016-06-01

    Grating-based X-ray dark-field tomography is a promising technique for biomedical and materials research. Even if the resolution of conventional X-ray tomography does not suffice to resolve relevant structures, the dark-field signal provides valuable information about the sub-pixel microstructural properties of the sample. Here, we report on the potential of X-ray dark-field imaging to be used for time-resolved three-dimensional studies. By repeating consecutive tomography scans on a fresh cement sample, we were able to study the hardening dynamics of the cement paste in three dimensions over time. The hardening of the cement was accompanied by a strong decrease in the dark-field signal pointing to microstructural changes within the cement paste. Furthermore our results hint at the transport of water from certain limestone grains, which were embedded in the sample, to the cement paste during the process of hardening. This is indicated by an increasing scattering signal which was observed for two of the six tested limestone grains. Electron microscopy images revealed a distinct porous structure only for those two grains which supports the following interpretation of our results. When the water filled pores of the limestone grains empty during the experiment the scattering signal of the grains increases.

  3. Time resolved X-ray Dark-Field Tomography Revealing Water Transport in a Fresh Cement Sample

    PubMed Central

    Prade, Friedrich; Fischer, Kai; Heinz, Detlef; Meyer, Pascal; Mohr, Jürgen; Pfeiffer, Franz

    2016-01-01

    Grating-based X-ray dark-field tomography is a promising technique for biomedical and materials research. Even if the resolution of conventional X-ray tomography does not suffice to resolve relevant structures, the dark-field signal provides valuable information about the sub-pixel microstructural properties of the sample. Here, we report on the potential of X-ray dark-field imaging to be used for time-resolved three-dimensional studies. By repeating consecutive tomography scans on a fresh cement sample, we were able to study the hardening dynamics of the cement paste in three dimensions over time. The hardening of the cement was accompanied by a strong decrease in the dark-field signal pointing to microstructural changes within the cement paste. Furthermore our results hint at the transport of water from certain limestone grains, which were embedded in the sample, to the cement paste during the process of hardening. This is indicated by an increasing scattering signal which was observed for two of the six tested limestone grains. Electron microscopy images revealed a distinct porous structure only for those two grains which supports the following interpretation of our results. When the water filled pores of the limestone grains empty during the experiment the scattering signal of the grains increases. PMID:27357449

  4. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy.

    PubMed

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J; Jung, Il Woong; Walko, Donald A; Dufresne, Eric M; Jeong, Jaewoo; Samant, Mahesh G; Parkin, Stuart S P; Freeland, John W; Evans, Paul G; Wen, Haidan

    2016-02-26

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  5. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, Il Woong; Walko, Donald A.; Dufresne, Eric M.; Jeong, Jaewoo; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-02-01

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  6. Time-resolved diffraction and interference: Young's interference with photons of different energy as revealed by time resolution.

    PubMed

    Garcia, N; Saveliev, I G; Sharonov, M

    2002-05-15

    We present time-resolved diffraction and two-slit interference experiments using a streak camera as a detector for femtosecond pulses of photons. These experiments show how the diffraction pattern is built by adding frames of a few photons to each frame. It is estimated that after 300 photons the diffraction pattern emerges. With time resolution we can check the speed of light and put an upper limit of 2 ps at our resolution to the time for wave function collapse in the quantum measurement process. We then produce interference experiments with photons of different energies impinging on the slits, i.e. we know which photon impinges on each slit. We show that for poor time resolution, no interference is observed, but for high time resolution, we have interference that is revealed as beats of 100 GHz frequency. The condition for interference is that the two pulses should overlap spatially at the detector, even if the pulses have different energies but are generated from the same pulse of the laser. The interference seems to be in agreement with classical theory at first sight. However, closer study and analysis of the data show deviations in the visibility of the interference fringes and of their phase. These experiments are discussed in connection with quantum mechanics and it may be concluded that the time resolution provides new data for understanding the longstanding and continuing arguments on wave-particle duality initiated by Newton, Young, Fresnel, Planck and others. A thought experiment is presented in the appendix to try to distinguish the photons at the detector by making it sensitive to colour.

  7. In Situ Observation of High-Pressure Phase Transitions in SiO2 Under Shock Loading Using Time Resolved X-Ray Diffraction

    NASA Astrophysics Data System (ADS)

    Tracy, S. J.; Turneaure, S.; Duffy, T. S.

    2016-12-01

    Quartz is one of the most abundant minerals in Earth's crust and serves as an archetype for silicate minerals generally. The shock metamorphism of silica is important for understanding and interpreting meteorite impact events. Shock compression of quartz is characterized by a phase transition occurring over a broad mixed-phase region ( 10-40 GPa). Despite decades of study, the nature of this transformation and the structure of the high-pressure phase remain poorly understood. In situ x-ray diffraction data on shock-compressed SiO2 was collected at the Dynamic Compression Sector at the Advanced Photon Source. The behavior both single crystal alpha-quartz and fused silica was investigated under dynamic loading through a series real-time synchrotron x-ray diffraction measurements during peak stresses up to 65 GPa. A two-stage light gas gun was used to accelerate LiF flyer plates that impacted the SiO2 samples resulting in a propagating step-like increase in pressure and temperature behind the shock front. Four consecutive x-ray frames, separated by 153 ns, were collected during the transient loading and unloading. These measurements allow for the determination of time-dependent atomic arrangements, demonstrating that both amorphous silica as well as crystalline alpha-quartz transform to stishovite above 36 GPa. These measurements reveal important information about the role of kinetics as well texture development and potential defect structures in the transformed material.

  8. Fluctuation of long-range order in Co-Pt alloy nanoparticles revealed by time-resolved electron microscopy

    NASA Astrophysics Data System (ADS)

    Sato, Kazuhisa; Yasuda, Hidehiro

    2017-04-01

    The development of long-range order in disordered Co-Pt alloy nanoparticles has been atomically resolved in situ with an ultra-high voltage electron microscope equipped with a direct electron detection camera. Electron-irradiation-enhanced ordering occurred at 573 K with 1 MeV electrons at a dose rate of 8.9 × 1024 e/m2s. High-speed (400 frames/s) imaging revealed fluctuations of the c-axis orientation of the L10-type ordered structure. Specifically, the c-axis orientation changes occurred at 2.5-ms intervals. Thus, the atomic ordering rate at 573 K is deduced to be 3 × 10-17 m2/s, which is 1013 times higher than that estimated for interdiffusion in a bulk Co-Pt alloy. The observed kinetic ordering temperature of 573 K is significantly lower than that reported previously (>800 K). The low-temperature ordering may be the result of enhanced atom migration via excess vacancies, 106 times higher than that at thermal equilibrium, introduced by the high-energy electron irradiation.

  9. Direct Observation of Phase Transformations in Austenitic Stainless Steel Welds Using In-situ Spatially Resolved and Time-resolved X-ray Diffraction

    SciTech Connect

    Elmer, J.; Wong, J.; Ressler, T.

    1999-09-23

    Spatially resolved x-ray diffraction (SRXRD) and time resolved x-ray diffraction (TRXRD) were used to investigate real time solid state phase transformations and solidification in AISI type 304 stainless steel gas tungsten arc (GTA) welds. These experiments were conducted at Stanford Synchrotron Radiation Laboratory (SSRL) using a high flux beam line. Spatially resolved observations of {gamma} {leftrightarrow} {delta} solid state phase transformations were performed in the heat affected zone (HAZ) of moving welds and time-resolved observations of the solidification sequence were performed in the fusion zone (FZ) of stationary welds after the arc had been terminated. Results of the moving weld experiments showed that the kinetics of the {gamma}{yields}{delta} phase transformation on heating in the HAZ were sufficiently rapid to transform a narrow region surrounding the liquid weld pool to the {delta} ferrite phase. Results of the stationary weld experiments showed, for the first time, that solidification can occur directly to the {delta} ferrite phase, which persisted as a single phase for 0.5s. Upon solidification to {delta}, the {delta} {yields} {gamma} phase transformation followed and completed in 0.2s as the weld cooled further to room temperature.

  10. Site-specific structural dynamics of α-Synuclein revealed by time-resolved fluorescence spectroscopy: a review

    NASA Astrophysics Data System (ADS)

    Sahay, Shruti; Krishnamoorthy, G.; Maji, Samir K.

    2016-12-01

    Aggregation of α-Synuclein (α-Syn) into amyloid fibrils is known to be associated with the pathogenesis of Parkinson’s disease (PD). Several missense mutations of the α-Syn gene have been associated with rare, early onset familial forms of PD. Despite several studies done so far, the local/residue-level structure and dynamics of α-Syn in its soluble and aggregated fibril form and how these are affected by the familial PD associated mutations are still not clearly understood. Here, we review studies performed by our group as well as other research groups, where time-resolved fluorescence spectroscopy has been used to understand the site-specific structure and dynamics of α-Syn under physiological conditions as well as under conditions that alter the aggregation properties of the protein such as low pH, high temperature, presence of membrane mimics and familial PD associated mutations. These studies have provided important insights into the critical structural properties of α-Syn that may govern its aggregation. The review also highlights time-resolved fluorescence as a promising tool to study the critical conformational transitions associated with early oligomerization of α-Syn, which are otherwise not accessible using other commonly used techniques such as thioflavin T (ThT) binding assay.

  11. Site-specific structural dynamics of α-Synuclein revealed by time-resolved fluorescence spectroscopy: a review.

    PubMed

    Sahay, Shruti; Krishnamoorthy, G; Maji, Samir K

    2016-10-11

    Aggregation of α-Synuclein (α-Syn) into amyloid fibrils is known to be associated with the pathogenesis of Parkinson's disease (PD). Several missense mutations of the α-Syn gene have been associated with rare, early onset familial forms of PD. Despite several studies done so far, the local/residue-level structure and dynamics of α-Syn in its soluble and aggregated fibril form and how these are affected by the familial PD associated mutations are still not clearly understood. Here, we review studies performed by our group as well as other research groups, where time-resolved fluorescence spectroscopy has been used to understand the site-specific structure and dynamics of α-Syn under physiological conditions as well as under conditions that alter the aggregation properties of the protein such as low pH, high temperature, presence of membrane mimics and familial PD associated mutations. These studies have provided important insights into the critical structural properties of α-Syn that may govern its aggregation. The review also highlights time-resolved fluorescence as a promising tool to study the critical conformational transitions associated with early oligomerization of α-Syn, which are otherwise not accessible using other commonly used techniques such as thioflavin T (ThT) binding assay.

  12. Functional Stability of the Human Kappa Opioid Receptor Reconstituted in Nanodiscs Revealed by a Time-Resolved Scintillation Proximity Assay

    PubMed Central

    Hansen, Randi Westh; Wang, Xiaole; Golab, Agnieszka; Bornert, Olivier; Oswald, Christine; Wagner, Renaud; Martinez, Karen Laurence

    2016-01-01

    Long-term functional stability of isolated membrane proteins is crucial for many in vitro applications used to elucidate molecular mechanisms, and used for drug screening platforms in modern pharmaceutical industry. Compared to soluble proteins, the understanding at the molecular level of membrane proteins remains a challenge. This is partly due to the difficulty to isolate and simultaneously maintain their structural and functional stability, because of their hydrophobic nature. Here we show, how scintillation proximity assay can be used to analyze time-resolved high-affinity ligand binding to membrane proteins solubilized in various environments. The assay was used to establish conditions that preserved the biological function of isolated human kappa opioid receptor. In detergent solution the receptor lost high-affinity ligand binding to a radiolabelled ligand within minutes at room temperature. After reconstitution in Nanodiscs made of phospholipid bilayer the half-life of high-affinity ligand binding to the majority of receptors increased 70-fold compared to detergent solubilized receptors—a level of stability that is appropriate for further downstream applications. Time-resolved scintillation proximity assay has the potential to screen numerous conditions in parallel to obtain high levels of stable and active membrane proteins, which are intrinsically unstable in detergent solution, and with minimum material consumption. PMID:27035823

  13. Dislocation-mediated relaxation in nanograined columnar palladium films revealed by on-chip time-resolved HRTEM testing

    PubMed Central

    Colla, M. -S.; Amin-Ahmadi, B.; Idrissi, H.; Malet, L.; Godet, S.; Raskin, J. -P.; Schryvers, D.; Pardoen, T.

    2015-01-01

    The high-rate sensitivity of nanostructured metallic materials demonstrated in the recent literature is related to the predominance of thermally activated deformation mechanisms favoured by a large density of internal interfaces. Here we report time-resolved high-resolution electron transmission microscopy creep tests on thin nanograined films using on-chip nanomechanical testing. Tests are performed on palladium, which exhibited unexpectedly large creep rates at room temperature. Despite the small 30-nm grain size, relaxation is found to be mediated by dislocation mechanisms. The dislocations interact with the growth nanotwins present in the grains, leading to a loss of coherency of twin boundaries. The density of stored dislocations first increases with applied deformation, and then decreases with time to drive additional deformation while no grain boundary mechanism is observed. This fast relaxation constitutes a key issue in the development of various micro- and nanotechnologies such as palladium membranes for hydrogen applications. PMID:25557273

  14. Ultrafast potential energy surface softening of one-dimensional organic conductors revealed by picosecond time-resolved Laue crystallography.

    PubMed

    Messerschmidt, Marc; Tschentscher, Thomas; Cammarata, Marco; Meents, Alke; Sager, Christian; Davaasambuu, Jav; Busse, Gerhard; Techert, Simone

    2010-07-29

    Time-resolved Laue crystallography has been employed to study the structural dynamics of a one-dimensional organic conductor (tetrathiafulvalene-p-chloranil) during photoexcitation in the regime of the neutral to ionic phase transition. Exciting this crystalline system with 800 nm 100 fs long optical pulses leads to ultrafast population of a structural intermediate as early as 50 ps after excitation with a lifetime of at least 10 ns. Starting from the neutral phase, this intermediate has been assigned as a precursor state toward the photoinduced population of the ionic phase. The observed intensity changes are significantly different from comparable equilibrium structures. The interpretation of this structural data is that the potential of this intermediate is being softened during its population in a dynamical process. The depopulation proceeds through thermal processes.

  15. Ultrafast terahertz modulation characteristic of tungsten doped vanadium dioxide nanogranular film revealed by time-resolved terahertz spectroscopy

    SciTech Connect

    Xiao, Yang; Zhai, Zhao-Hui; Zhu, Li-Guo E-mail: huangwanxia@scu.edu.cn; Li, Jun; Peng, Qi-Xian; Li, Ze-Ren; Shi, Qi-Wu; Huang, Wan-Xia E-mail: huangwanxia@scu.edu.cn; Yue, Fang; Hu, Yan-Yan

    2015-07-20

    The ultrafast terahertz (THz) modulation characteristic during photo-induced insulator-to-metal transition (IMT) of undoped and tungsten (W)-doped VO{sub 2} film was investigated at picoseconds time scale using time-resolved THz spectroscopy. W-doping slows down the photo-induced IMT dynamic processes (both the fast non-thermal process and the slow metallic phase propagation process) in VO{sub 2} film and also reduces the pump fluence threshold of photo-induced IMT in VO{sub 2} film. Along with the observed broadening of phase transition temperature window of IMT in W-doped VO{sub 2}, we conclude that W-doping prevents metallic phase domains from percolation. By further extracting carrier properties from photo-induced THz conductivity at several phase transition times, we found that the electron-electron correlation during IMT is enhanced in W-doped VO{sub 2}.

  16. Network theory inspired analysis of time-resolved expression data reveals key players guiding P. patens stem cell development.

    PubMed

    Busch, Hauke; Boerries, Melanie; Bao, Jie; Hanke, Sebastian T; Hiss, Manuel; Tiko, Theodhor; Rensing, Stefan A

    2013-01-01

    Transcription factors (TFs) often trigger developmental decisions, yet, their transcripts are often only moderately regulated and thus not easily detected by conventional statistics on expression data. Here we present a method that allows to determine such genes based on trajectory analysis of time-resolved transcriptome data. As a proof of principle, we have analysed apical stem cells of filamentous moss (P. patens) protonemata that develop from leaflets upon their detachment from the plant. By our novel correlation analysis of the post detachment transcriptome kinetics we predict five out of 1,058 TFs to be involved in the signaling leading to the establishment of pluripotency. Among the predicted regulators is the basic helix loop helix TF PpRSL1, which we show to be involved in the establishment of apical stem cells in P. patens. Our methodology is expected to aid analysis of key players of developmental decisions in complex plant and animal systems.

  17. Time-Resolved X-Ray Solution Scattering Reveals the Structural Photoactivation of a Light-Oxygen-Voltage Photoreceptor.

    PubMed

    Berntsson, Oskar; Diensthuber, Ralph P; Panman, Matthijs R; Björling, Alexander; Hughes, Ashley J; Henry, Léocadie; Niebling, Stephan; Newby, Gemma; Liebi, Marianne; Menzel, Andreas; Henning, Robert; Kosheleva, Irina; Möglich, Andreas; Westenhoff, Sebastian

    2017-06-06

    Light-oxygen-voltage (LOV) receptors are sensory proteins controlling a wide range of organismal adaptations in multiple kingdoms of life. Because of their modular nature, LOV domains are also attractive for use as optogenetic actuators. A flavin chromophore absorbs blue light, forms a bond with a proximal cysteine residue, and induces changes in the surroundings. There is a gap of knowledge on how this initial signal is relayed further through the sensor to the effector module. To characterize these conformational changes, we apply time-resolved X-ray scattering to the homodimeric LOV domain from Bacillus subtilis YtvA. We observe a global structural change in the LOV dimer synchronous with the formation of the chromophore photoproduct state. Using molecular modeling, this change is identified as splaying apart and relative rotation of the two monomers, which leads to an increased separation at the anchoring site of the effector modules. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Electric-field-induced lattice distortion in epitaxial BiFeO3 thin films as determined by in situ time-resolved x-ray diffraction

    NASA Astrophysics Data System (ADS)

    Nakashima, Seiji; Sakata, Osami; Funakubo, Hiroshi; Shimizu, Takao; Ichinose, Daichi; Takayama, Kota; Imai, Yasuhiko; Fujisawa, Hironori; Shimizu, Masaru

    2017-08-01

    Time-resolved X-ray diffraction (XRD) with synchrotron radiation while applying continuous voltage pulses was employed to investigate the electric-field-induced lattice distortion of an epitaxial BiFeO3 (BFO) thin film in a Pt/BFO (1 μm)/SrRuO3 (50 nm)/vicinal SrTiO3 (001) structure. XRD-reciprocal space maps based on the BFO 003, 114, and 1 1 ¯ 4 diffraction spots with and without the application of +15 V (150 kV/cm) to the capacitor demonstrated simultaneous electric-field-induced lattice distortion and crystallographic rotation in the BFO thin film. In response to the application of +15 V, the BFO lattice elongated by 0.08% along the [001]BFO direction and compressed by 0.05% along the [110]BFO direction. In addition, the BFO crystals were rotated by 0.01° along the [ 1 ¯1 ¯ 0]STO direction as a result of electric-field-induced lattice distortion under epitaxial strain along the vertical direction at the step edges of the vicinal substrate.

  19. In situ radiolysis time-resolved ESR studies of spin trapping by DMPO: Re-evalution of hydroxyl radical and hydrated electron trapping rates and spin adduct yields

    SciTech Connect

    Madden, K.P.; Taniguchi, Hitoshi

    1996-05-02

    The second-order rate constants for the reaction of 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) with radiolytically produced hydroxyl radicals and hydrated electrons have been measured in aqueous solution by direct observation of spin adduct initial yield using time-resolved electron spin resonance. The rate constants are 2.8 x 10{sup 9} mol{sup -1} dm{sup 3} S{sup -1} for the DMPO-hydroxyl radical reaction and 3.2 x 10{sup 9} mol{sup -1} dm{sup 3} s{sup -1} for the reaction of DMPO and hydrated electron, using sodium formate and chloroacetic acid as competitive scavengers of the hydroxyl radical and hydrated electron, respectively. The hydrated electron-DMPO competition study determined the fraction of DMPO-H produced directly from radiolytically produced hydrogen atoms as 0.082 of the total DMPO-H yield, indicating that approximately half of the hydrogen atoms react with DMPO to produce non-aminoxyl products. The fraction of the total hydroxyl radical yield leading to DMPO-OH spin adduct was determined to be 0.94, using the bleach of 2,2,6,6-tetramethylpiperidone-N-oxyl by carbon dioxide radical anion as a reference standard. 36 refs., 8 figs., 1 tab.

  20. Kinetics of copper growth on graphene revealed by time-resolved small-angle x-ray scattering

    NASA Astrophysics Data System (ADS)

    Hodas, M.; Siffalovic, P.; Jergel, M.; Pelletta, M.; Halahovets, Y.; Vegso, K.; Kotlar, M.; Majkova, E.

    2017-01-01

    Metal growth on graphene has many applications. Transition metals are known to favor three-dimensional (3D) cluster growth on graphene. Copper is of particular interest for cost-effective surface-supported catalysis applications and as a contact material in electronics. This paper presents an in situ real-time study of Cu growth kinetics on graphene covering all stages preceding formation of a continuous film performed by laboratory-based grazing-incidence small-angle x-ray scattering (GISAXS) technique. In particular, nucleation and 3D cluster growth, coalescence, and percolation stages were identified. The cluster nucleation saturates after reaching a density of 1012c m-2 at ≈1 monolayer thickness. A Kratky plot and a paracrystal model with cumulative structural disorder were necessary to evaluate properly cluster growth and coalescence, respectively. The power law scaling constants 0.27 ±0.05 and 0.81 ±0.02 of the temporal evolution of Cu cluster size suggest the growth of isolated clusters and dynamic cluster coalescence keeping the cluster shape, respectively. Coalescence and percolation thresholds occur at Cu thicknesses of 2 ±0.4 and 8.8 ±0.7 nm , respectively. This paper demonstrates the potential of laboratory-based in situ GISAXS as a vital diagnostic tool for tailoring a large variety of Cu nanostructures on graphene based on an in situ Cu growth monitoring which is applicable in a broad range of deposition times.

  1. In situ time-resolved X-ray diffraction of tobermorite formation in autoclaved aerated concrete: Influence of silica source reactivity and Al addition

    SciTech Connect

    Matsui, Kunio; Kikuma, Jun; Tsunashima, Masamichi; Ishikawa, Tetsuji; Matsuno, Shin-ya; Ogawa, Akihiro; Sato, Masugu

    2011-05-15

    The hydrothermal formation of tobermorite during the processing of autoclaved aerated concrete was investigated by in situ X-ray diffraction (XRD) analysis. High-energy X-rays from a synchrotron radiation source in combination with a newly developed autoclave cell and a photon-counting pixel array detector were used. To investigate the effects of the silica source, reactive quartz from chert and less-reactive quartz from quartz sand were used as starting materials. The effect of Al addition on tobermorite formation was also studied. In all cases, C-S-H, hydroxylellestadite and katoite were clearly observed as intermediates. Acceleration of tobermorite formation by Al addition was clearly observed. However, Al addition did not affect the dissolution rate of quartz. Two pathways, via C-S-H and katoite, were also observed in the Al-containing system. These results suggest that the structure of initially formed C-S-H is important for the subsequent tobermorite formation reactions.

  2. Time-resolved step-scan Fourier transform infrared spectroscopy reveals differences between early and late M intermediates of bacteriorhodopsin.

    PubMed Central

    Rödig, C; Chizhov, I; Weidlich, O; Siebert, F

    1999-01-01

    In this report, from time-resolved step-scan Fourier transform infrared investigations from 15 ns to 160 ms, we provide evidence for the subsequent rise of three different M states that differ in their structures. The first state rises with approximately 3 microseconds to only a small percentage. Its structure as judged from amide I/II bands differs in small but well-defined aspects from the L state. The next M state, which appears in approximately 40 microseconds, has almost all of the characteristics of the "late" M state, i.e., it differs considerably from the first one. Here, the L left arrow over right arrow M equilibrium is shifted toward M, although some percentage of L still persists. In the last M state (rise time approximately 130 microseconds), the equilibrium is shifted toward full deprotonation of the Schiff base, and only small additional structural changes take place. In addition to these results obtained for unbuffered conditions or at pH 7, experiments performed at lower and higher pH are presented. These results are discussed in terms of the molecular changes postulated to occur in the M intermediate to allow the shift of the L/M equilibrium toward M and possibly to regulate the change of the accessibility of the Schiff base necessary for effective proton pumping. PMID:10233083

  3. Spin-orbit torque-driven skyrmion dynamics revealed by time-resolved X-ray microscopy

    DOE PAGES

    Woo, Seonghoon; Song, Kyung Mee; Han, Hee-Sung; ...

    2017-05-24

    Magnetic skyrmions are topologically protected spin textures with attractive properties suitable for high-density and low-power spintronic device applications. Much effort has been dedicated to understanding the dynamical behaviours of the magnetic skyrmions. However, experimental observation of the ultrafast dynamics of this chiral magnetic texture in real space, which is the hallmark of its quasiparticle nature, has so far remained elusive. Here, we report nanosecond-dynamics of a 100nm-diameter magnetic skyrmion during a current pulse application, using a time-resolved pump-probe soft X-ray imaging technique. We demonstrate that distinct dynamic excitation states of magnetic skyrmions, triggered by current-induced spin-orbit torques, can be reliablymore » tuned by changing the magnitude of spin-orbit torques. Our findings show that the dynamics of magnetic skyrmions can be controlled by the spin-orbit torque on the nanosecond time scale, which points to exciting opportunities for ultrafast and novel skyrmionic appl ications in the future.« less

  4. Spin-orbit torque-driven skyrmion dynamics revealed by time-resolved X-ray microscopy

    NASA Astrophysics Data System (ADS)

    Woo, Seonghoon; Song, Kyung Mee; Han, Hee-Sung; Jung, Min-Seung; Im, Mi-Young; Lee, Ki-Suk; Song, Kun Soo; Fischer, Peter; Hong, Jung-Il; Choi, Jun Woo; Min, Byoung-Chul; Koo, Hyun Cheol; Chang, Joonyeon

    2017-05-01

    Magnetic skyrmions are topologically protected spin textures with attractive properties suitable for high-density and low-power spintronic device applications. Much effort has been dedicated to understanding the dynamical behaviours of the magnetic skyrmions. However, experimental observation of the ultrafast dynamics of this chiral magnetic texture in real space, which is the hallmark of its quasiparticle nature, has so far remained elusive. Here, we report nanosecond-dynamics of a 100nm-diameter magnetic skyrmion during a current pulse application, using a time-resolved pump-probe soft X-ray imaging technique. We demonstrate that distinct dynamic excitation states of magnetic skyrmions, triggered by current-induced spin-orbit torques, can be reliably tuned by changing the magnitude of spin-orbit torques. Our findings show that the dynamics of magnetic skyrmions can be controlled by the spin-orbit torque on the nanosecond time scale, which points to exciting opportunities for ultrafast and novel skyrmionic applications in the future.

  5. Mechanism for formation of the lightstruck flavor in beer revealed by time-resolved electron paramagnetic resonance.

    PubMed

    Burns, C S; Heyerick, A; De Keukeleire, D; Forbes, M D

    2001-11-05

    Time-resolved electron paramagnetic resonance (TREPR) data collected during the photodegradation of iso-a-acids (isohumulones), the principal bittering agents from hops in beer, are presented and discussed, and, from the data, the photophysics leading to free-radical production as the primary step in the photodecomposition of iso-alpha-acids towards the development of "skunky" beer are explained. During laser flash photolysis of iso-alpha-acids at 308 nm in toluene/methylcyclohexane (1:1), TREPR spectra exhibit net emissive signals that are strongly spin polarized by the triplet mechanism of chemically induced electron spin polarization. From two potential photochemically active sites, the TREPR data show that although the first site, an enolized beta-triketone, is the primary light-absorbing chromophore, an uphill intramolecular triplet energy transfer process leads to Norrish type I alpha-cleavage at a second site, an alpha-hydroxycarbonyl. The energy transfer mechanism is supported by additional TREPR experiments with chemically modified hop compounds. Structural parameters (hyperfine coupling constants, g factors, line widths) for the observed free radicals, obtained from computer simulations, are presented and discussed.

  6. Time-Resolved Transcriptomics and Bioinformatic Analyses Reveal Intrinsic Stress Responses during Batch Culture of Bacillus subtilis

    PubMed Central

    Blom, Evert-Jan; Ridder, Anja N. J. A.; Lulko, Andrzej T.; Roerdink, Jos B. T. M.; Kuipers, Oscar P.

    2011-01-01

    We have determined the time-resolved transcriptome of the model gram-positive organism B. subtilis during growth in a batch fermentor on rich medium. DNA microarrays were used to monitor gene transcription using 10-minute intervals at 40 consecutive time points. From the growth curve and analysis of all gene expression levels, we identified 4 distinct growth phases and one clear transition point: a lag phase, an exponential growth phase, the transition point and the very clearly separated early and late stationary growth phases. The gene expression profiles suggest the occurrence of stress responses at specific times although no external stresses were applied. The first one is a small induction of the SigB regulon that occurs at the transition point. Remarkably, a very strong response is observed for the SigW regulon, which is highly upregulated at the onset of the late stationary phase. Bioinformatic analyses that were performed on our data set suggest several novel putative motifs for regulator binding. In addition, the expression profiles of several genes appeared to correlate with the oxygen concentration. This data set of the expression profiles of all B. subtilis genes during the entire growth curve on rich medium constitutes a rich repository that can be further mined by the scientific community. PMID:22087258

  7. In situ time-resolved XAFS study on the structural transformation and phase separation of Pt3Sn and PtSn alloy nanoparticles on carbon in the oxidation process.

    PubMed

    Uemura, Y; Inada, Y; Bando, K K; Sasaki, T; Kamiuchi, N; Eguchi, K; Yagishita, A; Nomura, M; Tada, M; Iwasawa, Y

    2011-09-21

    The dynamic behavior and kinetics of the structural transformation of supported bimetallic nanoparticle catalysts with synergistic functions in the oxidation process are fundamental issues to understand their unique catalytic properties as well as to regulate the catalytic capability of alloy nanoparticles. The phase separation and structural transformation of Pt(3)Sn/C and PtSn/C catalysts during the oxidation process were characterized by in situ time-resolved energy-dispersive XAFS (DXAFS) and quick XAFS (QXAFS) techniques, which are element-selective spectroscopies, at the Pt L(III)-edge and the Sn K-edge. The time-resolved XAFS techniques provided the kinetics of the change in structures and oxidation states of the bimetallic nanoparticles on carbon surfaces. The kinetic parameters and mechanisms for the oxidation of the Pt(3)Sn/C and PtSn/C catalysts were determined by time-resolved XAFS techniques. The oxidation of Pt to PtO in Pt(3)Sn/C proceeded via two successive processes, while the oxidation of Sn to SnO(2) in Pt(3)Sn/C proceeded as a one step process. The rate constant for the fast Pt oxidation, which was completed in 3 s at 573 K, was the same as that for the Sn oxidation, and the following slow Pt oxidation rate was one fifth of that for the first Pt oxidation process. The rate constant and activation energy for the Sn oxidation in PtSn/C were similar to those for the Sn oxidation in Pt(3)Sn/C. In the PtSn/C, however, it was hard for Pt oxidation to PtO to proceed at 573 K, where Pt oxidation was strongly affected by the quantity of Sn in the alloy nanoparticles due to swift segregation of SnO(2) nanoparticles/layers on the Pt nanoparticles. The mechanisms for the phase separation and structure transformation in the Pt(3)Sn/C and PtSn/C catalysts are also discussed on the basis of the structural kinetics of the catalysts themselves determined by the in situ time-resolved DXAFS and QXAFS.

  8. Understanding the vibrational distribution in CO2 microwave plasma for production of carbon neutral fuels, using time resolved in-situ spectroscopy

    NASA Astrophysics Data System (ADS)

    van den Bekerom, Dirk; Minea, Teofil; Gatti, Nicola; Peeters, Floran; Zoethout, Erwin; Verreycken, Tiny; Bongers, Waldo; van de Sanden, Richard; van Rooij, Gerard

    2016-09-01

    A microwave plasma could prove to be a cost effective way of converting CO2 to CO. The efficiencies of such a reactor have been shown to be very high, up to 90%. It is currently understood that the preferable vibrational excitation by plasma electrons plays a key role in the efficient CO2 conversion. In the case that Vibrational-Vibrational (VV) relaxation times are much shorter than Vibrational-Translational (VT) relaxation times, molecules are vibrationally excited via intermolecular collisions until the dissociation energy is reached. As the VT-relaxation rate increases with temperature, a low temperature is needed to promote an overpopulation of high vibrational levels. To reduce the temperature, The microwave power was pulsed. Raman-scattering was employed to measure the temperature in the radial center and sides of the plasma, over an axial distance of a few centimeter. The infrared absorption spectrum of the CO2-plasma is recorded using an in-situ step-scan FTIR spectrometer. The absorption bands of higher vibrational levels are visible lower wavenumbers, down to 2000 cm-1. This enables us to look at the evolution of the densities of the vibrational levels. It was found that the vibrational temperature increased during plasma ON-time.

  9. In situ determination of transient pKa changes of internal amino acids of bacteriorhodopsin by using time-resolved attenuated total reflection Fourier-transform infrared spectroscopy.

    PubMed

    Zscherp, C; Schlesinger, R; Tittor, J; Oesterhelt, D; Heberle, J

    1999-05-11

    Active proton transfer through membrane proteins is accomplished by shifts in the acidity of internal amino acids, prosthetic groups, and water molecules. The recently introduced step-scan attenuated total reflection Fourier-transform infrared (ATR/FT-IR) spectroscopy was employed to determine transient pKa changes of single amino acid side chains of the proton pump bacteriorhodopsin. The high pKa of D96 (>12 in the ground state) drops to 7.1 +/- 0.2 (in 1 M KCl) during the lifetime of the N intermediate, quantitating the role of D96 as the internal proton donor of the retinal Schiff base. We conclude from experiments on the pH dependence of the proton release reaction and on point mutants where each of the glutamates on the extracellular surface has been exchanged that besides D85 no other carboxylic group changes its protonation state during proton release. However, E194 and E204 interact with D85, the primary proton acceptor of the Schiff base proton. The C==O stretching vibration of D85 undergoes a characteristic pH-dependent shift in frequency during the M state of wild-type bacteriorhodopsin with a pKa of 5.2 (+/-0.3) which is abolished in the single-site mutants E194Q and E204Q and the quadruple mutant E9Q/E74Q/E194Q/E204Q. The double mutation E9Q/E74Q does not affect the lifetime of the intermediates, ruling out any participation of these residues in the proton transfer chain of bacteriorhodopsin. This study demonstrates that transient changes in acidity of single amino acid residues can be quantified in situ with infrared spectroscopy.

  10. Lattice-level observation of the elastic-to-plastic relaxation process with subnanosecond resolution in shock-compressed Ta using time-resolved in situ Laue diffraction

    SciTech Connect

    Wehrenberg, C. E.; Comley, A. J.; Barton, N. R.; Coppari, F.; Fratanduono, D.; Huntington, C. M.; Maddox, B. R.; Park, H. -S.; Plechaty, C.; Prisbrey, S. T.; Remington, B. A.; Rudd, R. E.

    2015-09-29

    We report direct lattice level measurements of plastic relaxation kinetics through time-resolved, in-situ Laue diffraction of shock-compressed single-crystal [001] Ta at pressures of 27-210 GPa. For a 50 GPa shock, a range of shear strains is observed extending up to the uniaxial limit for early data points (<0.6 ns) and the average shear strain relaxes to a near steady state over ~1 ns. For 80 and 125 GPa shocks, the measured shear strains are fully relaxed already at 200 ps, consistent with rapid relaxation associated with the predicted threshold for homogeneous nucleation of dislocations occurring at shock pressure ~65 GPa. The relaxation rate and shear stresses are used to estimate the dislocation density and these quantities are compared to the Livermore Multiscale Strength model as well as various molecular dynamics simulations.

  11. Time-resolved in situ detection of CO in a shock tube using cavity-enhanced absorption spectroscopy with a quantum-cascade laser near 4.6 µm.

    PubMed

    Sun, Kai; Wang, Shengkai; Sur, Ritobrata; Chao, Xing; Jeffries, Jay B; Hanson, Ronald K

    2014-10-06

    Cavity-enhanced absorption spectroscopy (CEAS) using a mid-infrared DFB quantum-cascade laser is reported for sensitive time-resolved (10 μs) in situ CO measurements in a shock tube. Off-axis alignment and fast scanning of the laser wavelength were used to minimize coupling noise in a low-finesse cavity. An absorption gain factor of 91 was demonstrated, which enabled sub-ppm detection sensitivity for gas temperatures of 1000-2100K in a 15 cm diameter shock tube. This substantial improvement in detection sensitivity compared to conventional single-pass absorption measurements, shows great potential for the study of reaction pathways of high-temperature combustion kinetics mechanisms in shock tubes.

  12. Time-resolved and in-situ X-ray scattering methods beyond photoactivation: Utilizing high-flux X-ray sources for the study of ubiquitous non-photoactive proteins.

    PubMed

    Jain, Rohit; Techert, Simone

    2016-01-01

    X-ray scattering technique, comprising of small-angle/wide-angle X-ray scattering (SAXS/WAXS) techniques is increasingly used to characterize the structure and interactions of biological macromolecules and their complexes in solution. It is a method of choice to characterize the flexible, partially folded and unfolded protein systems. X-ray scattering is the last resort for proteins that cannot be investigated by crystallography or NMR and acts as a complementary technique with different biophysical techniques to answer challenging scientific questions. The marriage of the X-ray scattering technique with the fourth dimension "time" yields structural dynamics and kinetics information for protein motions in hierarchical timescales from picoseconds to days. The arrival of the high-flux X-ray beam at third generation synchrotron sources, exceptional X-ray optics, state-of-the-art detectors, upgradation of X-ray scattering beamlines with microfluidics devices and advanced X-ray scattering data analysis procedures are the important reasons behind the shining years of X-ray scattering technique. The best days of the X-ray scattering technique are on the horizon with the advent of the nanofocus X-ray scattering beamlines and fourth generation X-ray lightsources, i.e., free electron lasers (XFELs). Complementary to the photon-triggered time-resolved X-ray scattering techniques, we will present an overview of the time-resolved and in-situ X-ray scattering techniques for structural dynamics of ubiquitous non-photoactive proteins.

  13. Thermal stability in the blended lithium manganese oxide – Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

    SciTech Connect

    Hu, Enyuan; Bak, Seong Min; Senanayake, Sanjaya D.; Yang, Xiao-Qing; Nam, Kyung-Wan; Zhang, Lulu; Shao, Minhua

    2015-03-01

    Thermal stabilities of a series of blended LiMn2O4(LMO)-LiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25°C-580°C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250°C. Formation of MnO with rocksalt structure started at 520°C. This observation is in contrast to the previous report for chemically delithiate LMO in air, in which a process of λ-MnO2 transforming to β-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumption by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.

  14. Thermal stability in the blended lithium manganese oxide – Lithium nickel cobalt manganese oxide cathode materials: An in situ time-resolved X-Ray diffraction and mass spectroscopy study

    DOE PAGES

    Hu, Enyuan; Bak, Seong Min; Senanayake, Sanjaya D.; ...

    2015-03-01

    Thermal stabilities of a series of blended LiMn2O4(LMO)-LiNi1/3Co1/3Mn1/3O2 (NCM) cathode materials with different weight ratios were studied by in situ time-resolved X-ray diffraction (XRD) combined with mass spectroscopy in the temperature range of 25°C-580°C under helium atmosphere. Upon heating, the electrochemically delithiated LMO changed into Mn3O4 phase at around 250°C. Formation of MnO with rocksalt structure started at 520°C. This observation is in contrast to the previous report for chemically delithiate LMO in air, in which a process of λ-MnO2 transforming to β-MnO2 was observed. Oxygen peak was not observed in all cases, presumably as a result of either consumptionmore » by the carbon or detection limit. CO2 profile correlates well with the phase transition and indirectly suggests the oxygen release of the cathode. Introducing NCM into LMO has two effects: first, it makes the high temperature rock-salt phase formation more complicated with more peaks in CO2 profile due to different MO (M = Ni, Mn, Co) phases; secondly, the onset temperature of CO2 release is lowered, implying lowered oxygen release temperature. Upon heating, XRD patterns indicate the NCM part reacts first, followed by the LMO part. This confirms the better thermal stability of LMO over NCM.« less

  15. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    SciTech Connect

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, II Woong; Walko, Donald A.; Dufresne, Eric M.; Jaewoo, Jeong; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-02-26

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase seperated regions. The ability to simultanousely track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of- the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, which is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. Lastly, the direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  16. Anomalous lattice expansion in yttria stabilized zirconia under simultaneous applied electric and thermal fields: A time-resolved in situ energy dispersive x-ray diffractometry study with an ultrahigh energy synchrotron probe

    NASA Astrophysics Data System (ADS)

    Akdoğan, E. K.; Şavklıyıldız, İ.; Biçer, H.; Paxton, W.; Toksoy, F.; Zhong, Z.; Tsakalakos, T.

    2013-06-01

    Nonisothermal densification in 8% yttria doped zirconia (8YSZ) particulate matter of 250 nm median particle size was studied under 215 V/cm dc electric field and 9 °C/min heating rate, using time-resolved in-situ high temperature energy dispersive x-ray diffractometry with a polychromatic 200 keV synchrotron probe. Densification occurred in the 876-905 °C range, which resulted in 97% of the theoretical density. No local melting at particle-particle contacts was observed in scanning electron micrographs, implying densification was due to solid state mass transport processes. The maximum current draw at 905 °C was 3 A, corresponding to instantaneous absorbed power density of 570 W/cm3. Densification of 8YSZ was accompanied by anomalous elastic volume expansions of the unit cell by 0.45% and 2.80% at 847 °C and 905 °C, respectively. The anomalous expansion at 905 °C at which maximum densification was observed is characterized by three stages: (I) linear stage, (II) anomalous stage, and (III) anelastic recovery stage. The densification in stage I (184 s) and II (15 s) was completed in 199 s, while anelastic relaxation in stage III lasted 130 s. The residual strains (ɛ) at room temperature, as computed from tetragonal (112) and (211) reflections, are ɛ(112) = 0.05% and ɛ(211) = 0.13%, respectively. Time dependence of (211) and (112) peak widths (β) show a decrease with both exhibiting a singularity at 905 °C. An anisotropy in (112) and (211) peak widths of {β(112)/β(211)} = (3:1) magnitude was observed. No phase transformation occurred at 905 °C as verified from diffraction spectra on both sides of the singularity, i.e., the unit cell symmetry remains tetragonal. We attribute the reduction in densification temperature and time to ultrafast ambipolar diffusion of species arising from the superposition of mass fluxes due to Fickian diffusion, thermodiffusion (Soret effect), and electromigration, which in turn are a consequence of a superposition of chemical

  17. Anomalous lattice expansion in yttria stabilized zirconia under simultaneous applied electric and thermal fields: A time-resolved in situ energy dispersive x-ray diffractometry study with an ultrahigh energy synchrotron probe

    SciTech Connect

    Akdogan, E. K.; Savkl Latin-Small-Letter-Dotless-I y Latin-Small-Letter-Dotless-I ld Latin-Small-Letter-Dotless-I z, I.; Bicer, H.; Paxton, W.; Toksoy, F.; Tsakalakos, T.; Zhong, Z.

    2013-06-21

    Nonisothermal densification in 8% yttria doped zirconia (8YSZ) particulate matter of 250 nm median particle size was studied under 215 V/cm dc electric field and 9 Degree-Sign C/min heating rate, using time-resolved in-situ high temperature energy dispersive x-ray diffractometry with a polychromatic 200 keV synchrotron probe. Densification occurred in the 876-905 Degree-Sign C range, which resulted in 97% of the theoretical density. No local melting at particle-particle contacts was observed in scanning electron micrographs, implying densification was due to solid state mass transport processes. The maximum current draw at 905 Degree-Sign C was 3 A, corresponding to instantaneous absorbed power density of 570 W/cm{sup 3}. Densification of 8YSZ was accompanied by anomalous elastic volume expansions of the unit cell by 0.45% and 2.80% at 847 Degree-Sign C and 905 Degree-Sign C, respectively. The anomalous expansion at 905 Degree-Sign C at which maximum densification was observed is characterized by three stages: (I) linear stage, (II) anomalous stage, and (III) anelastic recovery stage. The densification in stage I (184 s) and II (15 s) was completed in 199 s, while anelastic relaxation in stage III lasted 130 s. The residual strains ({epsilon}) at room temperature, as computed from tetragonal (112) and (211) reflections, are {epsilon}{sub (112)} = 0.05% and {epsilon}{sub (211)} = 0.13%, respectively. Time dependence of (211) and (112) peak widths ({beta}) show a decrease with both exhibiting a singularity at 905 Degree-Sign C. An anisotropy in (112) and (211) peak widths of {l_brace} {beta}{sub (112)}/{beta}{sub (211)}{r_brace} = (3:1) magnitude was observed. No phase transformation occurred at 905 Degree-Sign C as verified from diffraction spectra on both sides of the singularity, i.e., the unit cell symmetry remains tetragonal. We attribute the reduction in densification temperature and time to ultrafast ambipolar diffusion of species arising from the

  18. Cooperative protein structural dynamics of homodimeric hemoglobin linked to water cluster at subunit interface revealed by time-resolved X-ray solution scattering

    PubMed Central

    Kim, Jong Goo; Muniyappan, Srinivasan; Oang, Key Young; Kim, Tae Wu; Yang, Cheolhee; Kim, Kyung Hwan; Kim, Jeongho; Ihee, Hyotcherl

    2016-01-01

    Homodimeric hemoglobin (HbI) consisting of two subunits is a good model system for investigating the allosteric structural transition as it exhibits cooperativity in ligand binding. In this work, as an effort to extend our previous study on wild-type and F97Y mutant HbI, we investigate structural dynamics of a mutant HbI in solution to examine the role of well-organized interfacial water cluster, which has been known to mediate intersubunit communication in HbI. In the T72V mutant of HbI, the interfacial water cluster in the T state is perturbed due to the lack of Thr72, resulting in two less interfacial water molecules than in wild-type HbI. By performing picosecond time-resolved X-ray solution scattering experiment and kinetic analysis on the T72V mutant, we identify three structurally distinct intermediates (I1, I2, and I3) and show that the kinetics of the T72V mutant are well described by the same kinetic model used for wild-type and F97Y HbI, which involves biphasic kinetics, geminate recombination, and bimolecular CO recombination. The optimized kinetic model shows that the R-T transition and bimolecular CO recombination are faster in the T72V mutant than in the wild type. From structural analysis using species-associated difference scattering curves for the intermediates, we find that the T-like deoxy I3 intermediate in solution has a different structure from deoxy HbI in crystal. In addition, we extract detailed structural parameters of the intermediates such as E-F distance, intersubunit rotation angle, and heme-heme distance. By comparing the structures of protein intermediates in wild-type HbI and the T72V mutant, we reveal how the perturbation in the interfacial water cluster affects the kinetics and structures of reaction intermediates of HbI. PMID:27158635

  19. Photon Emission and Reabsorption Processes in CH3NH3PbBr3 Single Crystals Revealed by Time-Resolved Two-Photon-Excitation Photoluminescence Microscopy

    NASA Astrophysics Data System (ADS)

    Yamada, Takumi; Yamada, Yasuhiro; Nakaike, Yumi; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2017-01-01

    The dynamical processes of radiative recombination of photocarriers and reabsorption of emitted photons in CH3NH3PbBr3 single crystals are studied using time-resolved two-photon-excitation photoluminescence (PL) microscopy. We find that the PL spectrum and its decay dynamics depend on the excitation-depth profile. As the excitation depth increases, the PL spectrum becomes asymmetric, the peak energy redshifts, and the PL decay time becomes longer. These observations can be well explained by a simple model including photon recycling (photon emission and reabsorption) in thick samples with strong band-to-band transitions and high radiative recombination efficiencies.

  20. Time-resolved microscopy reveals the driving mechanism of particle formation during ultrashort pulse laser ablation of dentin-like ivory.

    PubMed

    Domke, Matthias; Gavrilova, Anna; Rapp, Stephan; Frentzen, Matthias; Meister, Joerg; Huber, Heinz P

    2015-07-01

    In dental health care, the application of ultrashort laser pulses enables dental tissue ablation free from thermal side effects, such as melting and cracking. However, these laser types create undesired micro- and nanoparticles, which might cause a health risk for the patient or surgeon. The aim of this study was to investigate the driving mechanisms of micro- and nanoparticle formation during ultrashort pulse laser ablation of dental tissue. Time-resolved microscopy was chosen to observe the ablation dynamics of mammoth ivory after irradiation with 660 fs laser pulses. The results suggest that nanoparticles might arise in the excited region. The thermal expansion of the excited material induces high pressure in the surrounding bulk tissue, generating a pressure wave. The rarefaction wave behind this pressure wave causes spallation, leading to ejection of microparticles.

  1. Time-resolved microscopy reveals the driving mechanism of particle formation during ultrashort pulse laser ablation of dentin-like ivory

    NASA Astrophysics Data System (ADS)

    Domke, Matthias; Gavrilova, Anna; Rapp, Stephan; Frentzen, Matthias; Meister, Joerg; Huber, Heinz P.

    2015-07-01

    In dental health care, the application of ultrashort laser pulses enables dental tissue ablation free from thermal side effects, such as melting and cracking. However, these laser types create undesired micro- and nanoparticles, which might cause a health risk for the patient or surgeon. The aim of this study was to investigate the driving mechanisms of micro- and nanoparticle formation during ultrashort pulse laser ablation of dental tissue. Time-resolved microscopy was chosen to observe the ablation dynamics of mammoth ivory after irradiation with 660 fs laser pulses. The results suggest that nanoparticles might arise in the excited region. The thermal expansion of the excited material induces high pressure in the surrounding bulk tissue, generating a pressure wave. The rarefaction wave behind this pressure wave causes spallation, leading to ejection of microparticles.

  2. Millifluidics for Chemical Synthesis and Time-resolved Mechanistic Studies

    PubMed Central

    Krishna, Katla Sai; Biswas, Sanchita; Navin, Chelliah V.; Yamane, Dawit G.; Miller, Jeffrey T.; Kumar, Challa S.S.R.

    2013-01-01

    Procedures utilizing millifluidic devices for chemical synthesis and time-resolved mechanistic studies are described by taking three examples. In the first, synthesis of ultra-small copper nanoclusters is described. The second example provides their utility for investigating time resolved kinetics of chemical reactions by analyzing gold nanoparticle formation using in situ X-ray absorption spectroscopy. The final example demonstrates continuous flow catalysis of reactions inside millifluidic channel coated with nanostructured catalyst. PMID:24327099

  3. Ultrafast time-resolved electron diffraction revealing the nonthermal dynamics of near-UV photoexcitation-induced amorphization in Ge2Sb2Te5

    PubMed Central

    Hada, Masaki; Oba, Wataru; Kuwahara, Masashi; Katayama, Ikufumi; Saiki, Toshiharu; Takeda, Jun; Nakamura, Kazutaka G.

    2015-01-01

    Because of their robust switching capability, chalcogenide glass materials have been used for a wide range of applications, including optical storages devices. These phase transitions are achieved by laser irradiation via thermal processes. Recent studies have suggested the potential of nonthermal phase transitions in the chalcogenide glass material Ge2Sb2Te5 triggered by ultrashort optical pulses; however, a detailed understanding of the amorphization and damage mechanisms governed by nonthermal processes is still lacking. Here we performed ultrafast time-resolved electron diffraction and single-shot optical pump-probe measurements followed by femtosecond near-ultraviolet pulse irradiation to study the structural dynamics of polycrystalline Ge2Sb2Te5. The experimental results present a nonthermal crystal-to-amorphous phase transition of Ge2Sb2Te5 initiated by the displacements of Ge atoms. Above the fluence threshold, we found that the permanent amorphization caused by multi-displacement effects is accompanied by a partial hexagonal crystallization. PMID:26314613

  4. Spatial density profile of electrons near the LaAlO{sub 3}/SrTiO{sub 3} heterointerface revealed by time-resolved photoluminescence spectroscopy

    SciTech Connect

    Yamada, Yasuhiro Kanemitsu, Yoshihiko; Sato, Hiroki K.; Hikita, Yasuyuki; Hwang, Harold Y.

    2014-04-14

    The depth profile of the electron density near the LaAlO{sub 3}/SrTiO{sub 3} heterointerface has been studied by means of time-resolved photoluminescence (PL) spectroscopy. A broad blue PL band is observed at 2.9 eV, originating from the two-carrier radiative recombination of interface-induced electrons and photoexcited holes. The PL lifetime of LaAlO{sub 3}/SrTiO{sub 3} heterointerface is dominated by the three-carrier Auger recombination of electrons and holes and is sensitive to electron density. We tuned the probing depth by changing the excitation photon energy and evaluated the carrier-density profile using the relation between the carrier density and the PL lifetime. Our non-contact probe method based on PL spectroscopy indicates that the carriers are confined within several nanometers in depth near the LaAlO{sub 3}/SrTiO{sub 3} heterostructures.

  5. Charge Injection Mechanism at Heterointerfaces in CH3NH3PbI3 Perovskite Solar Cells Revealed by Simultaneous Time-Resolved Photoluminescence and Photocurrent Measurements.

    PubMed

    Handa, Taketo; Tex, David M; Shimazaki, Ai; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2017-03-02

    Organic-inorganic hybrid perovskite solar cells are attracting much attention due to their excellent photovoltaic properties. In these multilayered structures, the device performance is determined by complicated carrier dynamics. Here, we studied photocarrier recombination and injection dynamics in CH3NH3PbI3 perovskite solar cells using time-resolved photoluminescence (PL) and photocurrent (PC) measurements. It is found that a peculiar slowdown in the PL decay time constants of the perovskite layer occurs for higher excitation powers, followed by a decrease of the external quantum efficiency for PC. This indicates that a carrier-injection bottleneck exists at the heterojunction interfaces, which limits the photovoltaic performance of the device in concentrator applications. We conclude that the carrier-injection rate is sensitive to the photogenerated carrier density, and the carrier-injection bottleneck strongly enhances recombination losses of photocarriers in the perovskite layer at high excitation conditions. The physical origin of the bottleneck is discussed based on the result of numerical simulations.

  6. Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection.

    PubMed

    Grills, David C; Farrington, Jaime A; Layne, Bobby H; Lymar, Sergei V; Mello, Barbara A; Preses, Jack M; Wishart, James F

    2014-04-16

    Using a new technique, which combines pulse radiolysis with nanosecond time-resolved infrared (TRIR) spectroscopy in the condensed phase, we have conducted a detailed kinetic and mechanistic investigation of the formation of a Mn-based CO2 reduction electrocatalyst, [Mn((t)Bu2-bpy)(CO)3]2 ((t)Bu2-bpy = 4,4'-(t)Bu2-2,2'-bipyridine), in acetonitrile. The use of TRIR allowed, for the first time, direct observation of all the intermediates involved in this process. Addition of excess [(n)Bu4N][HCO2] to an acetonitrile solution of fac-MnBr((t)Bu2-bpy)(CO)3 results in its quantitative conversion to the Mn-formate complex, fac-Mn(OCHO)((t)Bu2-bpy)(CO)3, which is a precatalyst for the electrocatalytic reduction of CO2. Formation of the catalyst is initiated by one-electron reduction of the Mn-formate precatalyst, which produces the bpy ligand-based radical. This radical undergoes extremely rapid (τ = 77 ns) formate dissociation accompanied by a free valence shift to yield the five-coordinate Mn-based radical, Mn(•)((t)Bu2-bpy)(CO)3. TRIR data also provide evidence that the Mn-centered radical does not bind acetonitrile prior to its dimerization. This reaction occurs with a characteristically high radical-radical recombination rate (2kdim = (1.3 ± 0.1) × 10(9) M(-1) s(-1)), generating the catalytically active Mn-Mn bound dimer.

  7. Time-resolved vibrational spectroscopy

    SciTech Connect

    Tokmakoff, Andrei; Champion, Paul; Heilweil, Edwin J.; Nelson, Keith A.; Ziegler, Larry

    2009-05-14

    This document contains the Proceedings from the 14th International Conference on Time-Resolved Vibrational Spectroscopy, which was held in Meredith, NH from May 9-14, 2009. The study of molecular dynamics in chemical reaction and biological processes using time-resolved spectroscopy plays an important role in our understanding of energy conversion, storage, and utilization problems. Fundamental studies of chemical reactivity, molecular rearrangements, and charge transport are broadly supported by the DOE's Office of Science because of their role in the development of alternative energy sources, the understanding of biological energy conversion processes, the efficient utilization of existing energy resources, and the mitigation of reactive intermediates in radiation chemistry. In addition, time-resolved spectroscopy is central to all fiveof DOE's grand challenges for fundamental energy science. The Time-Resolved Vibrational Spectroscopy conference is organized biennially to bring the leaders in this field from around the globe together with young scientists to discuss the most recent scientific and technological advances. The latest technology in ultrafast infrared, Raman, and terahertz spectroscopy and the scientific advances that these methods enable were covered. Particular emphasis was placed on new experimental methods used to probe molecular dynamics in liquids, solids, interfaces, nanostructured materials, and biomolecules.

  8. Time-resolved optical spectroscopy of wood.

    PubMed

    D'Andrea, C; Farina, A; Comelli, D; Pifferi, A; Taroni, P; Valentini, G; Cubeddu, R; Zoia, L; Orlandi, M; Kienle, A

    2008-05-01

    We have proposed and experimentally demonstrated that picosecond time-resolved optical spectroscopy in the visible/near-infrared (NIR) region (700-1040 nm) is a useful technique for noninvasive characterization of wood. This technique has been demonstrated on both softwood and hardwood samples treated in different ways simulating the aging process suffered by waterlogged woods. In all the cases, alterations of absorption and scattering spectra were observed, revealing changes of chemical and structural composition.

  9. Redefining the Speed Limit of Phase Change Memory Revealed by Time-resolved Steep Threshold-Switching Dynamics of AgInSbTe Devices

    PubMed Central

    Shukla, Krishna Dayal; Saxena, Nishant; Durai, Suresh; Manivannan, Anbarasu

    2016-01-01

    Although phase-change memory (PCM) offers promising features for a ‘universal memory’ owing to high-speed and non-volatility, achieving fast electrical switching remains a key challenge. In this work, a correlation between the rate of applied voltage and the dynamics of threshold-switching is investigated at picosecond-timescale. A distinct characteristic feature of enabling a rapid threshold-switching at a critical voltage known as the threshold voltage as validated by an instantaneous response of steep current rise from an amorphous off to on state is achieved within 250 picoseconds and this is followed by a slower current rise leading to crystallization. Also, we demonstrate that the extraordinary nature of threshold-switching dynamics in AgInSbTe cells is independent to the rate of applied voltage unlike other chalcogenide-based phase change materials exhibiting the voltage dependent transient switching characteristics. Furthermore, numerical solutions of time-dependent conduction process validate the experimental results, which reveal the electronic nature of threshold-switching. These findings of steep threshold-switching of ‘sub-50 ps delay time’, opens up a new way for achieving high-speed non-volatile memory for mainstream computing. PMID:27886266

  10. Complexity of Lipid Domains and Rafts in Giant Unilamellar Vesicles Revealed by Combining Imaging and Microscopic and Macroscopic Time-Resolved Fluorescence

    PubMed Central

    de Almeida, Rodrigo F. M.; Borst, JanWillem; Fedorov, Alexander; Prieto, Manuel; Visser, Antonie J. W. G.

    2007-01-01

    The application of fluorescence lifetime imaging microscopy to study gel/fluid and raftlike lipid domains in giant unilamellar vesicles (GUVs) is demonstrated here. Different regions of the ternary dipalmitoylphosphatidylcholine/dioleoylphosphatidylcholine/cholesterol phase diagram were studied. The head-labeled phospholipid Rhodamine-dioleoylphosphatidylethanolamine (Rhod-DOPE) was used as a fluorescent probe. Gel/fluid and liquid-ordered (lo)/liquid-disordered (ld) phase separation were clearly visualized upon two-photon excitation. Fluorescence intensity decays in different regions of a GUV were also obtained with the microscope in fixed laser-beam configuration. The ensemble behavior of the system was studied by obtaining fluorescence intensity decays of Rhod-DOPE in nongiant vesicle suspensions. The fingerprints for gel/fluid coexistence and for the presence of lo raftlike phase, based on fluorescence lifetime imaging microscopy histograms and images, and on the fluorescence intensity decay parameters of Rhod-DOPE, are presented. The presence of three lipid phases in one single GUV is detected unequivocally. From the comparison of lifetime parameters, it can be concluded that the lo phase is formed in the binary dipalmitoylphosphatidylcholine/cholesterol but not in the dioleoylphosphatidylcholine/cholesterol mixture. The domains apparent in fluorescence intensity images have a more complex substructure revealed by analysis of the lifetime data. The potential applications of this combined imaging/microscopic/macroscopic methodology are discussed. PMID:17449668

  11. Redefining the Speed Limit of Phase Change Memory Revealed by Time-resolved Steep Threshold-Switching Dynamics of AgInSbTe Devices

    NASA Astrophysics Data System (ADS)

    Shukla, Krishna Dayal; Saxena, Nishant; Durai, Suresh; Manivannan, Anbarasu

    2016-11-01

    Although phase-change memory (PCM) offers promising features for a ‘universal memory’ owing to high-speed and non-volatility, achieving fast electrical switching remains a key challenge. In this work, a correlation between the rate of applied voltage and the dynamics of threshold-switching is investigated at picosecond-timescale. A distinct characteristic feature of enabling a rapid threshold-switching at a critical voltage known as the threshold voltage as validated by an instantaneous response of steep current rise from an amorphous off to on state is achieved within 250 picoseconds and this is followed by a slower current rise leading to crystallization. Also, we demonstrate that the extraordinary nature of threshold-switching dynamics in AgInSbTe cells is independent to the rate of applied voltage unlike other chalcogenide-based phase change materials exhibiting the voltage dependent transient switching characteristics. Furthermore, numerical solutions of time-dependent conduction process validate the experimental results, which reveal the electronic nature of threshold-switching. These findings of steep threshold-switching of ‘sub-50 ps delay time’, opens up a new way for achieving high-speed non-volatile memory for mainstream computing.

  12. Structural changes and thermal stability of charged LiNixMnyCozO2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy

    SciTech Connect

    Bak, Seong -Min; Hu, Enyuan; Zhou, Yongning; Yu, Xiqian; Senanayake, Sanjaya D.; Cho, Sung -Jin; Kim, Kwang -Bum; Chung, Kyung Yoon; Yang, Xiao -Qing; Nam, Kyung -Wan

    2014-11-24

    Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time- resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3¯m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3¯m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. As a result, this systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

  13. Time-resolved transcriptome analysis and lipid pathway reconstruction of the oleaginous green microalga Monoraphidium neglectum reveal a model for triacylglycerol and lipid hyperaccumulation.

    PubMed

    Jaeger, Daniel; Winkler, Anika; Mussgnug, Jan H; Kalinowski, Jörn; Goesmann, Alexander; Kruse, Olaf

    2017-01-01

    Oleaginous microalgae are promising production hosts for the sustainable generation of lipid-based bioproducts and as bioenergy carriers such as biodiesel. Transcriptomics of the lipid accumulation phase, triggered efficiently by nitrogen starvation, is a valuable approach for the identification of gene targets for metabolic engineering. An explorative analysis of the detailed transcriptional response to different stages of nitrogen availability was performed in the oleaginous green alga Monoraphidium neglectum. Transcript data were correlated with metabolic data for cellular contents of starch and of different lipid fractions. A pronounced transcriptional down-regulation of photosynthesis became apparent in response to nitrogen starvation, whereas glucose catabolism was found to be up-regulated. An in-depth reconstruction and analysis of the pathways for glycerolipid, central carbon, and starch metabolism revealed that distinct transcriptional changes were generally found only for specific steps within a metabolic pathway. In addition to pathway analyses, the transcript data were also used to refine the current genome annotation. The transcriptome data were integrated into a database and complemented with data for other microalgae which were also subjected to nitrogen starvation. It is available at https://tdbmn.cebitec.uni-bielefeld.de. Based on the transcriptional responses to different stages of nitrogen availability, a model for triacylglycerol and lipid hyperaccumulation is proposed, which involves transcriptional induction of thioesterases, differential regulation of lipases, and a re-routing of the central carbon metabolism. Over-expression of distinct thioesterases was identified to be a potential strategy to increase the oleaginous phenotype of M. neglectum, and furthermore specific lipases were identified as potential targets for future metabolic engineering approaches.

  14. Structural Changes Due to the Deprotonation of the Proton Release Group in the M Photointermediate of Bacteriorhodopsin as Revealed by Time-Resolved FTIR Spectroscopy

    PubMed Central

    Morgan, Joel E.; Vakkasoglu, Ahmet S.; Lugtenburg, Johan; Gennis, Robert B.; Maeda, Akio

    2014-01-01

    One of the steps in the proton pumping cycle of bacteriorhodopsin (BR) is the release of a proton from the proton-release group (PRG) on the extracellular side of the Schiff base. This proton release takes place shortly after deprotonation of the Schiff base (L-to-M transition), and results in an increase in the pKa of Asp85, which is a crucial mechanistic step for one-way proton transfer for the entire photocycle. Deprotonation of the PRG can also be brought about without photoactivation, by raising the pH of the enzyme (pKa of PRG; ~9). Thus comparison of the FTIR difference spectrum for formation of the M intermediate (M minus initial unphotolyzed BR state) at pH 7 to the corresponding spectrum generated at pH 10 may reveal structural changes specifically associated with deprotonation of the PRG. Vibrational bands of BR that change upon M formation are distributed across a broad region between 2120 and 1685 cm−1. This broad band is made up of two parts. The band above 1780 cm−1, which is insensitive to C15-deuteration of the retinal, may be due to a proton delocalized in the PRG. The band between 1725 and 1685 cm−1, on the lower frequency side of the broad band, is sensitive to C15-deuteration. This band may arise from transition dipole coupling of the vibrations of backbone carbonyl groups in helix G with the side chain of Tyr57 and with the C15—H of the Schiff base. In M these broad bands are abolished, and the 3657 cm−1 band, which is due to the disruption of the hydrogen bonding of a water molecule, probably with Arg82, appears. Loss of the interaction of the backbone carbonyl groups in helix G with Tyr57 and the Schiff base, and separation of Tyr57 from Arg82, may be causes of these spectral changes, leading to the stabilization of the protonated Asp85 in M. PMID:18837559

  15. Structural changes due to the deprotonation of the proton release group in the M-photointermediate of bacteriorhodopsin as revealed by time-resolved FTIR spectroscopy.

    PubMed

    Morgan, Joel E; Vakkasoglu, Ahmet S; Lugtenburg, Johan; Gennis, Robert B; Maeda, Akio

    2008-11-04

    One of the steps in the proton pumping cycle of bacteriorhodopsin (BR) is the release of a proton from the proton-release group (PRG) on the extracellular side of the Schiff base. This proton release takes place shortly after deprotonation of the Schiff base (L-to-M transition) and results in an increase in the pKa of Asp85, which is a crucial mechanistic step for one-way proton transfer for the entire photocycle. Deprotonation of the PRG can also be brought about without photoactivation, by raising the pH of the enzyme (pKa of PRG; approximately 9). Thus, comparison of the FTIR difference spectrum for formation of the M intermediate (M minus initial unphotolyzed BR state) at pH 7 to the corresponding spectrum generated at pH 10 may reveal structural changes specifically associated with deprotonation of the PRG. Vibrational bands of BR that change upon M formation are distributed across a broad region between 2120 and 1685 cm(-1). This broad band is made up of two parts. The band above 1780 cm(-1), which is insensitive to C15-deuteration of the retinal, may be due to a proton delocalized in the PRG. The band between 1725 and 1685 cm(-1), on the lower frequency side of the broad band, is sensitive to C15-deuteration. This band may arise from transition dipole coupling of the vibrations of backbone carbonyl groups in helix G with the side chain of Tyr57 and with the C15H of the Schiff base. In M, these broad bands are abolished, and the 3657 cm(-1) band, which is due to the disruption of the hydrogen bonding of a water molecule, probably with Arg82, appears. Loss of the interaction of the backbone carbonyl groups in helix G with Tyr57 and the Schiff base, and separation of Tyr57 from Arg82, may be causes of these spectral changes, leading to the stabilization of the protonated Asp85 in M.

  16. Revealing the radiative and non-radiative relaxation rates of the fluorescent dye Atto488 in a λ/2 Fabry-Pérot-resonator by spectral and time resolved measurements

    NASA Astrophysics Data System (ADS)

    Konrad, Alexander; Metzger, Michael; Kern, Andreas M.; Brecht, Marc; Meixner, Alfred J.

    2016-07-01

    Using a Fabry-Pérot-microresonator with controllable cavity lengths in the λ/2-regime, we show the controlled modification of the vibronic relaxation dynamics of a fluorescent dye molecule in the spectral and time domain. By altering the photonic mode density around the fluorophores we are able to shape the fluorescence spectrum and enhance specifically the probability of the radiative transitions from the electronic excited state to distinct vibronic excited states of the electronic ground state. Analysis and correlation of the spectral and time resolved measurements by a theoretical model and a global fitting procedure allows us to reveal quantitatively the spectrally distributed radiative and non-radiative relaxation dynamics of the respective dye molecule under ambient conditions at the ensemble level.Using a Fabry-Pérot-microresonator with controllable cavity lengths in the λ/2-regime, we show the controlled modification of the vibronic relaxation dynamics of a fluorescent dye molecule in the spectral and time domain. By altering the photonic mode density around the fluorophores we are able to shape the fluorescence spectrum and enhance specifically the probability of the radiative transitions from the electronic excited state to distinct vibronic excited states of the electronic ground state. Analysis and correlation of the spectral and time resolved measurements by a theoretical model and a global fitting procedure allows us to reveal quantitatively the spectrally distributed radiative and non-radiative relaxation dynamics of the respective dye molecule under ambient conditions at the ensemble level. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR02380K

  17. Structural and Electronic Transformations of Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C Cathode Catalysts in Polymer Electrolyte Fuel Cells during Potential-step Operating Processes Characterized by In-situ Time-resolved XAFS

    NASA Astrophysics Data System (ADS)

    Nagamatsu, Shin-ichi; Takao, Shinobu; Samjeské, Gabor; Nagasawa, Kensaku; Sekizawa, Oki; Kaneko, Takuma; Higashi, Kotaro; Uruga, Tomoya; Gayen, Sirshendu; Velaga, Srihari; Saniyal, Milan K.; Iwasawa, Yasuhiro

    2016-06-01

    The dynamic structural and electronic transformations of Pt/C, Pd@Pt(1 ML)/C, Pd@Pt(2 ML)/C cathode catalysts in polymer electrolyte fuel cells (PEFCs) during the potential-step operating processes between 0.4 and 1.4 VRHE (potential vs RHE) were characterized by in-situ (operando) time-resolved Pt LIII-edge quick-XAFS at 100 ms time-resolution. Potential-dependent surface structures and oxidation states of Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticles on carbon at 0.4 and 1.4 VRHE were also analyzed by in-situ Pt LIII-edge and Pd K-edge quick-XAFS. The Pt, Pd@Pt(1 ML) and Pd@Pt(2 ML) nanoparticle surfaces were restructured and disordered at 1.4 VRHE, which were induced by strong Pt-O bonds as well as alloying effects. The rate constants for the changes of Pt valence, CN(Pt-Pt), CN(Pt-Pd) and CN(Pt-O) (CN: coordination number) in the potential-step operating processes were also determined and discussed in relation to the origin of oxygen reduction reaction (ORR) activities of the Pt/C, Pd@Pt(1 ML)/C and Pd@Pt(2 ML)/C cathode catalysts.

  18. Thymine Dimer Formation probed by Time-Resolved Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Schreier, Wolfgang J.; Schrader, Tobias E.; Roller, Florian O.; Gilch, Peter; Zinth, Wolfgang; Kohler, Bern

    Cyclobutane pyrimidine dimers are the major photoproducts formed when DNA is exposed to UV light. Femtosecond time-resolved vibrational spectroscopy reveals that thymine dimers are formed in thymidine oligonucleotides in an ultrafast photoreaction.

  19. Revealing anelasticity and structural rearrangements in nanoscale metallic glass films using in situ TEM diffraction

    PubMed Central

    Sarkar, Rohit; Ebner, Christian; Izadi, Ehsan; Rentenberger, Christian; Rajagopalan, Jagannathan

    2017-01-01

    ABSTRACT We used a novel diffraction-based method to extract the local, atomic-level elastic strain in nanoscale amorphous TiAl films during in situ transmission electron microscopy deformation, while simultaneously measuring the macroscopic strain. The complementary strain measurements revealed significant anelastic deformation, which was independently confirmed by strain rate experiments. Furthermore, the distribution of first nearest-neighbor distances became narrower during loading and permanent changes were observed in the atomic structure upon unloading, even in the absence of macroscopic plasticity. The results demonstrate the capability of in situ electron diffraction to probe structural rearrangements and decouple elastic and anelastic deformation in metallic glasses. PMID:28382229

  20. Growth of Au on Pt icosahedral nanoparticles revealed by low-dose in situ TEM.

    PubMed

    Wu, Jianbo; Gao, Wenpei; Wen, Jianguo; Miller, Dean J; Lu, Ping; Zuo, Jian-Min; Yang, Hong

    2015-04-08

    A growth mode was revealed by an in situ TEM study of nucleation and growth of Au on Pt icosahedral nanoparticles. Quantitative analysis of growth kinetics was carried out based on real-time TEM data, which shows the process involves: (1) deposition of Au on corner sites of Pt icosahedral nanoparticles, (2) diffusion of Au from corners to terraces and edges, and (3) subsequent layer-by-layer growth of Au on Au surfaces to form Pt@Au core-shell nanoparticles. The in situ TEM results indicate diffusion of Au from corner islands to terraces and edges is a kinetically controlled growth, as evidenced by a measurement of diffusion coefficients for these growth processes. We demonstrated that in situ electron microscopy is a valuable tool for quantitative study of nucleation and growth kinetics and can provide new insight into the design and precise control of heterogeneous nanostructures.

  1. Growth of Au on Pt Icosahedral Nanoparticles Revealed by Low-Dose in situ TEM

    SciTech Connect

    Wu, Jianbo; Gao, Wenpei; Wen, Jianguo; Miller, Dean J.; Lu, Ping; Zuo, Jian-Min; Yang, Hong

    2015-04-01

    A growth mode was revealed by an in situ TEM study of nucleation and growth of Au on Pt icosahedral nanoparticles. Quantitative analysis of growth kinetics was carried out based on real- time TEM data, which show the process involves: 1) deposition of Au on corner sites of Pt icosahedral nanoparticles, 2) diffusion of Au from corners to terraces and edges, and 3) subsequent layer-by-layer growth of Au on Au surfaces to form Pt@Au core-shell nanoparticles. The in situ TEM results indicate diffusion of Au from corner islands to terraces and edges is a kinetically controlled growth, as evidenced by a measurement of diffusion coefficients for these growth processes. We demonstrated that in situ electron microscopy is a valuable tool for quantitative study of nucleation and growth kinetics and can provide new insight into the design and precise control of heterogeneous nanostructures.

  2. Surface phenomena revealed by in situ imaging: studies from adhesion, wear and cutting

    NASA Astrophysics Data System (ADS)

    Viswanathan, Koushik; Mahato, Anirban; Yeung, Ho; Chandrasekar, Srinivasan

    2017-03-01

    Surface deformation and flow phenomena are ubiquitous in mechanical processes. In this work we present an in situ imaging framework for studying a range of surface mechanical phenomena at high spatial resolution and across a range of time scales. The in situ framework is capable of resolving deformation and flow fields quantitatively in terms of surface displacements, velocities, strains and strain rates. Three case studies are presented demonstrating the power of this framework for studying surface deformation. In the first, the origin of stick-slip motion in adhesive polymer interfaces is investigated, revealing a intimate link between stick-slip and surface wave propagation. Second, the role of flow in mediating formation of surface defects and wear particles in metals is analyzed using a prototypical sliding process. It is shown that conventional post-mortem observation and inference can lead to erroneous conclusions with regard to formation of surface cracks and wear particles. The in situ framework is shown to unambiguously capture delamination wear in sliding. Third, material flow and surface deformation in a typical cutting process is analyzed. It is shown that a long-standing problem in the cutting of annealed metals is resolved by the imaging, with other benefits such as estimation of energy dissipation and power from the flow fields. In closure, guidelines are provided for profitably exploiting in situ observations to study large-strain deformation, flow and friction phenomena at surfaces that display a variety of time-scales.

  3. Time-Resolved Photoluminescence and Photovoltaics

    SciTech Connect

    Metzger, W. K.; Ahrenkiel, R. K.; Dippo, P.; Geisz, J.; Wanlass, M. W.; Kurtz, S.

    2005-01-01

    The time-resolved photoluminescence (TRPL) technique and its ability to characterize recombination in bulk photovoltaic semiconductor materials are reviewed. Results from a variety of materials and a few recent studies are summarized and compared.

  4. Revealing cyclic hardening mechanism of a TRIP steel by real-time in situ neutron diffraction

    SciTech Connect

    Yu, Dunji; An, Ke; Chen, Yan; Chen, Xu

    2014-01-01

    Real-time in situ neutron diffraction was performed on a transformation-induced plasticity (TRIP) steel under cyclic loading at room temperature. By Rietveld refinement and single peak analysis, the volume fraction and average stress estimates as well as dislocation density of individual phases (austenite and martensite phase) were derived. The results reveal that the volume fraction of martensite phase, instead of individual phase strengthening, should be accounted for the remarkable secondary cyclic hardening.

  5. Time-resolved transillumination and optical tomography

    NASA Astrophysics Data System (ADS)

    de Haller, Emmanuel B.

    1996-01-01

    In response to an invitation by the editor-in-chief, I would like to present the current status of time-domain imaging. With exciting new photon diffusion techniques being developed in the frequency domain and promising optical coherence tomography, time-resolved transillumination is in constant evolution and the subject of passionate discussions during the numerous conferences dedicated to this subject. The purpose of time-resolved optical tomography is to provide noninvasive, high-resolution imaging of the interior of living bodies by the use of nonionizing radiation. Moreover, the use of visible to near-infrared wavelength yields metabolic information. Breast cancer screening is the primary potential application for time-resolved imaging. Neurology and tissue characterization are also possible fields of applications. Time- resolved transillumination and optical tomography should not only improve diagnoses, but the welfare of the patient. As no overview of this technique has yet been presented to my knowledge, this paper briefly describes the various methods enabling time-resolved transillumination and optical tomography. The advantages and disadvantages of these methods, as well as the clinical challenges they face are discussed. Although an analytic and computable model of light transport through tissues is essential for a meaningful interpretation of the transillumination process, this paper will not dwell on the mathematics of photon propagation.

  6. Time resolved thermal lens in edible oils

    NASA Astrophysics Data System (ADS)

    Albuquerque, T. A. S.; Pedreira, P. R. B.; Medina, A. N.; Pereira, J. R. D.; Bento, A. C.; Baesso, M. L.

    2003-01-01

    In this work time resolved thermal lens spectrometry is applied to investigate the optical properties of the following edible oils: soya, sunflower, canola, and corn oils. The experiments were performed at room temperature using the mode mismatched thermal lens configuration. The results showed that when the time resolved procedure is adopted the technique can be applied to investigate the photosensitivity of edible oils. Soya oil presented a stronger photochemical reaction as compared to the other investigated samples. This observation may be relevant for future studies evaluating edible oils storage conditions and also may contribute to a better understanding of the physical and chemical properties of this important foodstuff.

  7. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    SciTech Connect

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Willinger, Marc-Georg; Schloegl, R.

    2016-10-19

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

  8. Revealing the anomalous tensile properties of WS2 nanotubes by in situ transmission electron microscopy.

    PubMed

    Tang, Dai-Ming; Wei, Xianlong; Wang, Ming-Sheng; Kawamoto, Naoyuki; Bando, Yoshio; Zhi, Chunyi; Mitome, Masanori; Zak, Alla; Tenne, Reshef; Golberg, Dmitri

    2013-03-13

    Mechanical properties and fracture behaviors of multiwalled WS2 nanotubes produced by large scale fluidized bed method were investigated under uniaxial tension using in situ transmission electron microscopy probing; these were directly correlated to the nanotube atomic structures. The tubes with the average outer diameter ∼40 nm sustained tensile force of ∼2949 nN and revealed fracture strength of ∼11.8 GPa. Surprisingly, these rather thick WS2 nanotubes could bear much higher loadings than the thin WS2 nanotubes with almost "defect-free" structures studied previously. In addition, the fracture strength of the "thick" nanotubes did not show common size dependent degradation when the tube diameters increased from ∼20 to ∼60 nm. HRTEM characterizations and real time observations revealed that the anomalous tensile properties are related to the intershell cross-linking and geometric constraints from the inverted cone-shaped tube cap structures, which resulted in the multishell loading and fracturing.

  9. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    NASA Astrophysics Data System (ADS)

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-10-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene-graphene and graphene-substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.

  10. Time resolved astronomy with the SALT

    NASA Astrophysics Data System (ADS)

    Buckley, D. A. H.; Crawford, S.; Gulbis, A. A. S.; McPhate, J.; Nordsieck, K. H.; Potter, S. B.; O'Donoghue, D.; Siegmund, O. H. W.; Schellart, P.; Spark, M.; Welsh, B. Y.; Zietsman, E.

    2010-07-01

    While time resolved astronomical observations are not new, the extension of such studies to sub-second time resolution is and has resulted in the opening of a new observational frontier, High Time Resolution Astronomy (HTRA). HTRA studies are well suited to objects like compact binary stars (CVs and X-ray binaries) and pulsars, while asteroseismology of pulsating stars, occultations, transits and the study of transients, will all benefit from such HTRA studies. HTRA has been a SALT science driver from the outset and the first-light instruments, namely the UV-VIS imager, SALTICAM, and the multi-purpose Robert Stobie Spectrograph (RSS), both have high time resolution modes. These are described, together with some observational examples. We also discuss the commissioning observations with the photon counting Berkeley Visible Image Tube camera (BVIT) on SALT. Finally we describe the software tools, developed in Python, to reduce SALT time resolved observations.

  11. Time-resolved photoemission using attosecond streaking

    NASA Astrophysics Data System (ADS)

    Nagele, S.; Pazourek, R.; Wais, M.; Wachter, G.; Burgdörfer, J.

    2014-04-01

    We theoretically study time-resolved photoemission in atoms as probed by attosecond streaking. We review recent advances in the study of the photoelectric efect in the time domain and show that the experimentally accessible time shifts can be decomposed into distinct contributions that stem from the feld-free photoionization process itself and from probe-field induced corrections. We perform accurate quantum-mechanical as well as classical simulations of attosecond streaking for efective one-electron systems and determine all relevant contributions to the time delay with attosecond precision. In particular, we investigate the properties and limitations of attosecond streaking for the transition from short-ranged potentials (photodetachment) to long-ranged Coulomb potentials (photoionization). As an example for a more complex system, we study time-resolved photoionization for endohedral fullerenes A@C60 and discuss how streaking time shifts are modifed due to the interaction of the C60 cage with the probing infrared streaking field.

  12. Time-resolved inverse Raman spectroscopy.

    PubMed

    Rahn, L A

    1982-02-01

    A technique for obtaining sensitive, highly reproducible, time-resolved inverse Raman measurements is reported. Experimental results are presented for the nitrogen vibrational Q branch at a pressure of 10 atm. For these measurements the signal, normalized to the pump-laser energy, exhibits fluctuations of 1.4% (rms) about the average of 500 measurements; these deviations are within a factor of 2 of the quantum noise limit.

  13. Synchrotron x-ray microdiffraction reveals intrinsic structural features of amyloid deposits in situ.

    PubMed

    Briki, Fatma; Vérine, Jérôme; Doucet, Jean; Bénas, Philippe; Fayard, Barbara; Delpech, Marc; Grateau, Gilles; Riès-Kautt, Madeleine

    2011-07-20

    Amyloidoses are increasingly recognized as a major public health concern in Western countries. All amyloidoses share common morphological, structural, and tinctorial properties. These consist of staining by specific dyes, a fibrillar aspect in electron microscopy and a typical cross-β folding in x-ray diffraction patterns. Most studies that aim at deciphering the amyloid structure rely on fibers generated in vitro or extracted from tissues using protocols that may modify their intrinsic structure. Therefore, the fine details of the in situ architecture of the deposits remain unknown. Here, we present to our knowledge the first data obtained on ex vivo human renal tissue sections using x-ray microdiffraction. The typical cross-β features from fixed paraffin-embedded samples are similar to those formed in vitro or extracted from tissues. Moreover, the fiber orientation maps obtained across glomerular sections reveal an intrinsic texture that is correlated with the glomerulus morphology. These results are of the highest importance to understanding the formation of amyloid deposits and are thus expected to trigger new incentives for tissue investigation. Moreover, the access to intrinsic structural parameters such as fiber size and orientation using synchrotron x-ray microdiffraction, could provide valuable information concerning in situ mechanisms and deposit formation with potential benefits for diagnostic and therapeutic purposes. Copyright © 2011 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  14. Metatranscriptomics reveal differences in in situ energy and nitrogen metabolism among hydrothermal vent snail symbionts

    PubMed Central

    Sanders, J G; Beinart, R A; Stewart, F J; Delong, E F; Girguis, P R

    2013-01-01

    Despite the ubiquity of chemoautotrophic symbioses at hydrothermal vents, our understanding of the influence of environmental chemistry on symbiont metabolism is limited. Transcriptomic analyses are useful for linking physiological poise to environmental conditions, but recovering samples from the deep sea is challenging, as the long recovery times can change expression profiles before preservation. Here, we present a novel, in situ RNA sampling and preservation device, which we used to compare the symbiont metatranscriptomes associated with Alviniconcha, a genus of vent snail, in which specific host–symbiont combinations are predictably distributed across a regional geochemical gradient. Metatranscriptomes of these symbionts reveal key differences in energy and nitrogen metabolism relating to both environmental chemistry (that is, the relative expression of genes) and symbiont phylogeny (that is, the specific pathways employed). Unexpectedly, dramatic differences in expression of transposases and flagellar genes suggest that different symbiont types may also have distinct life histories. These data further our understanding of these symbionts' metabolic capabilities and their expression in situ, and suggest an important role for symbionts in mediating their hosts' interaction with regional-scale differences in geochemistry. PMID:23619306

  15. Time resolved optical spectra from MIG welding arc ignitions

    SciTech Connect

    Eriksen, P.

    1985-03-01

    Optical radiation from MIG (GMAW) welding arc ignitions has been measured with a rapid scan spectrometer. The time resolved spectral measurements reveal a substantial overshoot of ultraviolet radiation during the ignition phase of a 200 A aluminum arc. Calculations which follow the ACGIH guidelines show that, at a welding current of 300 A, the unprotected eye at a distance of 0.5 m may suffer a flash after the reception of radiation from only one ignition.

  16. Time-Resolved Measurements in Optoelectronic Microbioanalysis

    NASA Technical Reports Server (NTRS)

    Bearman, Gregory; Kossakovski, Dmitri

    2003-01-01

    A report presents discussion of time-resolved measurements in optoelectronic microbioanalysis. Proposed microbioanalytical laboratory-on-a-chip devices for detection of microbes and toxic chemicals would include optoelectronic sensors and associated electronic circuits that would look for fluorescence or phosphorescence signatures of multiple hazardous biomolecules in order to detect which ones were present in a given situation. The emphasis in the instant report is on gating an active-pixel sensor in the time domain, instead of filtering light in the wavelength domain, to prevent the sensor from responding to a laser pulse used to excite fluorescence or phosphorescence while enabling the sensor to respond to the decaying fluorescence or phosphorescence signal that follows the laser pulse. The active-pixel sensor would be turned on after the laser pulse and would be used to either integrate the fluorescence or phosphorescence signal over several lifetimes and many excitation pulses or else take time-resolved measurements of the fluorescence or phosphorescence. The report also discusses issues of multiplexing and of using time-resolved measurements of fluorophores with known different fluorescence lifetimes to distinguish among them.

  17. Growth mechanism of microporous zincophosphate sodalite revealed by in situ atomic force microscopy.

    PubMed

    Holden, Mark A; Cubillas, Pablo; Attfield, Martin P; Gebbie, James T; Anderson, Michael W

    2012-08-08

    Microporous zincophosphate sodalite crystal growth has been studied in situ by atomic force microscopy. This simple model system permits an in depth investigation of some of the axioms governing crystal growth of nanoporous framework solids in general. In particular, this work reveals the importance of considering the growth of a framework material as the growth of a dense phase material where the framework structure, nonframework cations, and hydrogen-bonded water must all be considered. The roles of the different components of the structure, including the role of strict framework ordering, are disentangled, and all of the growth features, both crystal habit and nanoscopic surface structure, are explained according to a simple set of rules. The work describes, for the first time, both ideal growth and growth leading to defect structures on all of the principal facets of the sodalite structure. Also, the discovery of the presence of anisotropic friction on a framework material is described.

  18. Time-resolved, dual heterodyne phase collection transient grating spectroscopy

    NASA Astrophysics Data System (ADS)

    Dennett, Cody A.; Short, Michael P.

    2017-05-01

    The application of optical heterodyne detection for transient grating spectroscopy (TGS) using a fixed, binary phase mask often relies on taking the difference between signals captured at multiple heterodyne phases. To date, this has been accomplished by manually controlling the heterodyne phase between measurements with an optical flat. In this letter, an optical configuration is presented which allows for collection of TGS measurements at two heterodyne phases concurrently through the use of two independently phase controlled interrogation paths. This arrangement allows for complete, heterodyne amplified TGS measurements to be made in a manner not constrained by a mechanical actuation time. Measurements are instead constrained only by the desired signal-to-noise ratio. A temporal resolution of between 1 and 10 s, demonstrated here on single crystal metallic samples, will allow TGS experiments to be used as an in-situ, time-resolved monitoring technique for many material processing applications.

  19. Time resolved optical tomography of the human forearm

    NASA Astrophysics Data System (ADS)

    Hillman, Elizabeth M. C.; Hebden, Jeremy C.; Schweiger, Martin; Dehghani, Hamid; Schmidt, Florian E. W.; Delpy, David T.; Arridge, Simon R.

    2001-04-01

    A 32-channel time-resolved optical imaging instrument has been developed principally to study functional parameters of the new-born infant brain. As a prelude to studies on infants, the device and image reconstruction methodology have been evaluated on the adult human forearm. Cross-sectional images were generated using time-resolved measurements of transmitted light at two wavelengths. All data were acquired using a fully automated computer-controlled protocol. Images representing the internal scattering and absorbing properties of the arm are presented, as well as images that reveal physiological changes during a simple finger flexion exercise. The results presented in this paper represent the first simultaneous tomographic reconstruction of the internal scattering and absorbing properties of a clinical subject using purely temporal data, with additional co-registered difference images showing repeatable absorption changes at two wavelengths in response to exercise.

  20. Time resolved optical tomography of the human forearm.

    PubMed

    Hillman, E M; Hebden, J C; Schweiger, M; Dehghani, H; Schmidt, F E; Delpy, D T; Arridge, S R

    2001-04-01

    A 32-channel time-resolved optical imaging instrument has been developed principally to study functional parameters of the new-born infant brain. As a prelude to studies on infants, the device and image reconstruction methodology have been evaluated on the adult human forearm. Cross-sectional images were generated using time-resolved measurements of transmitted light at two wavelengths. All data were acquired using a fully automated computer-controlled protocol. Images representing the internal scattering and absorbing properties of the arm are presented, as well as images that reveal physiological changes during a simple finger flexion exercise. The results presented in this paper represent the first simultaneous tomographic reconstruction of the internal scattering and absorbing properties of a clinical subject using purely temporal data, with additional co-registered difference images showing repeatable absorption changes at two wavelengths in response to exercise.

  1. Time-resolved studies of individual molecular rotors.

    PubMed

    Jewell, April D; Tierney, Heather L; Baber, Ashleigh E; Iski, Erin V; Laha, Michael M; Sykes, E Charles H

    2010-07-07

    Thioether molecular rotors show great promise as nanoscale models for exploring the fundamental limits of thermally and electrically driven molecular rotation. By using time-resolved measurements which increase the time resolution of the scanning tunneling microscope we were able to record the dynamics of individual thioether molecular rotors as a function of surface structure, rotor chemistry, thermal energy and electrical excitation. Our results demonstrate that the local surface structure can have a dramatic influence on the energy landscape that the molecular rotors experience. In terms of rotor structure, altering the length of the rotor's alkyl tails allowed the origin of the barrier to rotation to be more fully understood. Finally, time-resolved measurement of electrically excited rotation revealed that vibrational excitation of a C-H bond in the rotor's alkyl tail is an efficient channel with which to excite rotation, and that the excitation is a one-electron process. © 2010 IOP Publishing Ltd

  2. Time resolved Schlieren imaging of DBD actuator flow fields

    NASA Astrophysics Data System (ADS)

    Nourgostar, Cyrus; Oksuz, Lutfi; Hershkowitz, Noah

    2009-10-01

    Schlieren imaging methods measure the first derivative of density in the direction of a knife-edge spatial filter. It has been used extensively in aerodynamic research to visualize the structure of flow fields. With a single barrier planer dielectric barrier discharge (DBD) actuator, Schlieren images clearly show the absence of significant vertical air flow normal to the surface, and no more than few millimeters thick induced boundary layer flow. A gated intensified CCD camera along with a Schlieren system can not only visualize the flow field induced by the actuator, but also temporarily resolve the images of the flow and plasma field. Our time resolved images with triangular applied voltage waveforms indicate that several separate discharge regimes occur during positive and negative going half cycles of single and double barrier DBD actuators. Time resolved Schlieren imaging of both single and double barrier DBDs with different applied waveforms, discharge parameters and electrode geometries reveal important information on the induced flow structure.

  3. Time Resolved Studies Of Adsorbed Species

    NASA Astrophysics Data System (ADS)

    Howard, J.; Nicol, J. M.

    1985-12-01

    A time-resolved Fourier transform IR study of ethyne adsorbed on ZnNaA zeolite yields results very different from those reported for related systems. Initially two species (A and B) are formed by the interaction of C2H2 with the cations. Whereas species A (π-bonded C2H2) was found to be removed immediately on evacuation, species B (probably Zn-acetylide) was not fully removed after 60 mins evacuation. In the presence of the gas phase, bands due to Species A decreased slowly in intensity as new bands due to adsorbed ethanal were observed.

  4. A Direct Interaction between the Sigma-1 Receptor and the hERG Voltage-gated K+ Channel Revealed by Atomic Force Microscopy and Homogeneous Time-resolved Fluorescence (HTRF®)*

    PubMed Central

    Balasuriya, Dilshan; D'Sa, Lauren; Talker, Ronel; Dupuis, Elodie; Maurin, Fabrice; Martin, Patrick; Borgese, Franck; Soriani, Olivier; Edwardson, J. Michael

    2014-01-01

    The sigma-1 receptor is an endoplasmic reticulum chaperone protein, widely expressed in central and peripheral tissues, which can translocate to the plasma membrane and modulate the function of various ion channels. The human ether-à-go-go-related gene encodes hERG, a cardiac voltage-gated K+ channel that is abnormally expressed in many human cancers and is known to interact functionally with the sigma-1 receptor. Our aim was to investigate the nature of the interaction between the sigma-1 receptor and hERG. We show that the two proteins can be co-isolated from a detergent extract of stably transfected HEK-293 cells, consistent with a direct interaction between them. Atomic force microscopy imaging of the isolated protein confirmed the direct binding of the sigma-1 receptor to hERG monomers, dimers, and tetramers. hERG dimers and tetramers became both singly and doubly decorated by sigma-1 receptors; however, hERG monomers were only singly decorated. The distribution of angles between pairs of sigma-1 receptors bound to hERG tetramers had two peaks, at ∼90 and ∼180° in a ratio of ∼2:1, indicating that the sigma-1 receptor interacts with hERG with 4-fold symmetry. Homogeneous time-resolved fluorescence (HTRF®) allowed the detection of the interaction between the sigma-1 receptor and hERG within the plane of the plasma membrane. This interaction was resistant to sigma ligands, but was decreased in response to cholesterol depletion of the membrane. We suggest that the sigma-1 receptor may bind to hERG in the endoplasmic reticulum, aiding its assembly and trafficking to the plasma membrane. PMID:25266722

  5. Time Resolved Raman and Fluorescence Spectrometer for Planetary Mineralogy

    NASA Astrophysics Data System (ADS)

    Blacksberg, Jordana; Rossman, George

    2010-05-01

    Raman spectroscopy is a prime candidate for the next generation of planetary instruments, as it addresses the primary goal of mineralogical analysis which is structure and composition. It does not require sample preparation and provides unique mineral fingerprints, even for mixed phase samples. However, large fluorescence return from many mineral samples under visible light excitation can seriously compromise the quality of the spectra or even render Raman spectra unattainable. Fluorescence interference is likely to be a problem on Mars and is evident in Raman spectra of Martian Meteorites[1]. Our approach uses time resolution for elimination of fluorescence from Raman spectra, allowing for traditional visible laser excitation (532 nm). Since Raman occurs instantaneously with the laser pulse and fluorescence lifetimes vary from nsec to msec depending on the mineral, it is possible to separate them out in time. Complementary information can also be obtained simultaneously using the time resolved fluorescence data. The Simultaneous Spectral Temporal Adaptive Raman Spectrometer (SSTARS) is a planetary instrument under development at the Jet Propulsion Laboratory, capable of time-resolved in situ Raman and fluorescence spectroscopy. A streak camera and pulsed miniature microchip laser provide psec scale time resolution. Our ability to observe the complete time evolution of Raman and fluorescence in minerals provides a foundation for design of pulsed Raman and fluorescence spectrometers in diverse planetary environments. We will discuss the SSTARS instrument design and performance capability. We will also present time-resolved pulsed Raman spectra collected from a relevant set of minerals selected using available data on Mars mineralogy[2]. Of particular interest are minerals resulting from aqueous alteration on Mars. For comparison, we will present Raman spectra obtained using a commercial continuous wave (CW) green (514 nm) Raman system. In many cases using a CW laser

  6. Time Resolved Deposition Measurements in NSTX

    SciTech Connect

    C.H. Skinner; H. Kugel; A.L. Roquemore; J. Hogan; W.R. Wampler; the NSTX team

    2004-08-03

    Time-resolved measurements of deposition in current tokamaks are crucial to gain a predictive understanding of deposition with a view to mitigating tritium retention and deposition on diagnostic mirrors expected in next-step devices. Two quartz crystal microbalances have been installed on NSTX at a location 0.77m outside the last closed flux surface. This configuration mimics a typical diagnostic window or mirror. The deposits were analyzed ex-situ and found to be dominantly carbon, oxygen, and deuterium. A rear facing quartz crystal recorded deposition of lower sticking probability molecules at 10% of the rate of the front facing one. Time resolved measurements over a 4-week period with 497 discharges, recorded 29.2 {micro}g/cm{sup 2} of deposition, however surprisingly, 15.9 {micro}g/cm{sup 2} of material loss occurred at 7 discharges. The net deposited mass of 13.3 {micro}g/cm{sup 2} matched the mass of 13.5 {micro}g/cm{sup 2} measured independently by ion beam analysis. Monte Carlo modeling suggests that transient processes are likely to dominate the deposition.

  7. Time-resolved RNA SHAPE chemistry.

    PubMed

    Mortimer, Stefanie A; Weeks, Kevin M

    2008-12-03

    Selective 2'-hydroxyl acylation analyzed by primer extension (SHAPE) chemistry yields quantitative RNA secondary and tertiary structure information at single nucleotide resolution. SHAPE takes advantage of the discovery that the nucleophilic reactivity of the ribose 2'-hydroxyl group is modulated by local nucleotide flexibility in the RNA backbone. Flexible nucleotides are reactive toward hydroxyl-selective electrophiles, whereas constrained nucleotides are unreactive. Initial versions of SHAPE chemistry, which employ isatoic anhydride derivatives that react on the minute time scale, are emerging as the ideal technology for monitoring equilibrium structures of RNA in a wide variety of biological environments. Here, we extend SHAPE chemistry to a benzoyl cyanide scaffold to make possible facile time-resolved kinetic studies of RNA in approximately 1 s snapshots. We then use SHAPE chemistry to follow the time-dependent folding of an RNase P specificity domain RNA. Tertiary interactions form in two distinct steps with local tertiary contacts forming an order of magnitude faster than long-range interactions. Rate-determining tertiary folding requires minutes despite that no non-native interactions must be disrupted to form the native structure. Instead, overall folding is limited by simultaneous formation of interactions approximately 55 A distant in the RNA. Time-resolved SHAPE holds broad potential for understanding structural biogenesis and the conformational interconversions essential to the functions of complex RNA molecules at single nucleotide resolution.

  8. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    PubMed Central

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; Eres, Gyula; Timpe, Olaf; Fu, Qiang; Ding, Feng; Schloegl, R.; Willinger, Marc-Georg

    2016-01-01

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene–graphene and graphene–substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy and density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite. PMID:27759024

  9. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging

    DOE PAGES

    Wang, Zhu-Jun; Dong, Jichen; Cui, Yi; ...

    2016-10-19

    In the transition from graphene to graphite, the addition of each individual graphene layer modifies the electronic structure and produces a different material with unique properties. Controlled growth of few-layer graphene is therefore of fundamental interest and will provide access to materials with engineered electronic structure. Here we combine isothermal growth and etching experiments with in situ scanning electron microscopy to reveal the stacking sequence and interlayer coupling strength in few-layer graphene. The observed layer-dependent etching rates reveal the relative strength of the graphene graphene and graphene substrate interaction and the resulting mode of adlayer growth. Scanning tunnelling microscopy andmore » density functional theory calculations confirm a strong coupling between graphene edge atoms and platinum. Simulated etching confirms that etching can be viewed as reversed growth. This work demonstrates that real-time imaging under controlled atmosphere is a powerful method for designing synthesis protocols for sp2 carbon nanostructures in between graphene and graphite.« less

  10. Sequential and Coupled Proton and Electron Transfer Events in the S2 → S3 Transition of Photosynthetic Water Oxidation Revealed by Time-Resolved X-ray Absorption Spectroscopy.

    PubMed

    Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2016-12-20

    The choreography of electron transfer (ET) and proton transfer (PT) in the S-state cycle at the manganese-calcium (Mn4Ca) complex of photosystem II (PSII) is pivotal for the mechanism of photosynthetic water oxidation. Time-resolved room-temperature X-ray absorption spectroscopy (XAS) at the Mn K-edge was employed to determine the kinetic isotope effect (KIE = τD2O/τH2O) of the four S transitions in a PSII membrane particle preparation in H2O and D2O buffers. We found a small KIE (1.2-1.4) for manganese oxidation by ET from Mn4Ca to the tyrosine radical (YZ(•+)) in the S0(n) → S1(+) and S1(n) → S2(+) transitions and for manganese reduction by ET from substrate water to manganese ions in the O2-evolving S3(n) → S0(n) step, but a larger KIE (∼1.8) for manganese oxidation in the S2(n) → S3(+) step (subscript, number of accumulated oxidizing equivalents; superscript, charge of Mn4Ca). Kinetic lag phases detected in the XAS transients prior to the respective ET steps were assigned to S3(+) → S3(n) (∼150 μs, H2O; ∼380 μs, D2O) and S2(+) → S2(n) (∼25 μs, H2O; ∼120 μs, D2O) steps and attributed to PT events according to their comparatively large KIE (∼2.4, ∼4.5). Our results suggest that proton movements and molecular rearrangements within the hydrogen-bonded network involving Mn4Ca and its bound (substrate) water ligands and the surrounding amino acid/water matrix govern to different extents the rates of all ET steps but affect particularly strongly the S2(n) → S3(+) transition, assigned as proton-coupled electron transfer. Observation of a lag phase in the classical S2 → S3 transition verifies that the associated PT is a prerequisite for subsequent ET, which completes Mn4Ca oxidation to the all-Mn(IV) level.

  11. In situ structure of trypanosomal ATP synthase dimer reveals a unique arrangement of catalytic subunits

    PubMed Central

    Mühleip, Alexander W.; Dewar, Caroline E.; Schnaufer, Achim; Kühlbrandt, Werner; Davies, Karen M.

    2017-01-01

    We used electron cryotomography and subtomogram averaging to determine the in situ structures of mitochondrial ATP synthase dimers from two organisms belonging to the phylum euglenozoa: Trypanosoma brucei, a lethal human parasite, and Euglena gracilis, a photosynthetic protist. At a resolution of 32.5 Å and 27.5 Å, respectively, the two structures clearly exhibit a noncanonical F1 head, in which the catalytic (αβ)3 assembly forms a triangular pyramid rather than the pseudo-sixfold ring arrangement typical of all other ATP synthases investigated so far. Fitting of known X-ray structures reveals that this unusual geometry results from a phylum-specific cleavage of the α subunit, in which the C-terminal αC fragments are displaced by ∼20 Å and rotated by ∼30° from their expected positions. In this location, the αC fragment is unable to form the conserved catalytic interface that was thought to be essential for ATP synthesis, and cannot convert γ-subunit rotation into the conformational changes implicit in rotary catalysis. The new arrangement of catalytic subunits suggests that the mechanism of ATP generation by rotary ATPases is less strictly conserved than has been generally assumed. The ATP synthases of these organisms present a unique model system for discerning the individual contributions of the α and β subunits to the fundamental process of ATP synthesis. PMID:28096380

  12. Ultrahigh-resolution imaging reveals formation of neuronal SNARE/Munc18 complexes in situ

    PubMed Central

    Pertsinidis, Alexandros; Mukherjee, Konark; Sharma, Manu; Pang, Zhiping P.; Park, Sang Ryul; Zhang, Yunxiang; Brunger, Axel T.; Südhof, Thomas C.; Chu, Steven

    2013-01-01

    Membrane fusion is mediated by complexes formed by SNAP-receptor (SNARE) and Secretory 1 (Sec1)/mammalian uncoordinated-18 (Munc18)-like (SM) proteins, but it is unclear when and how these complexes assemble. Here we describe an improved two-color fluorescence nanoscopy technique that can achieve effective resolutions of up to 7.5-nm full width at half maximum (3.2-nm localization precision), limited only by stochastic photon emission from single molecules. We use this technique to dissect the spatial relationships between the neuronal SM protein Munc18-1 and SNARE proteins syntaxin-1 and SNAP-25 (25 kDa synaptosome-associated protein). Strikingly, we observed nanoscale clusters consisting of syntaxin-1 and SNAP-25 that contained associated Munc18-1. Rescue experiments with syntaxin-1 mutants revealed that Munc18-1 recruitment to the plasma membrane depends on the Munc18-1 binding to the N-terminal peptide of syntaxin-1. Our results suggest that in a primary neuron, SNARE/SM protein complexes containing syntaxin-1, SNAP-25, and Munc18-1 are preassembled in microdomains on the presynaptic plasma membrane. Our superresolution imaging method provides a framework for investigating interactions between the synaptic vesicle fusion machinery and other subcellular systems in situ. PMID:23821748

  13. Chromatin of Trypanosoma cruzi: in situ analysis revealed its unusual structure and nuclear organization.

    PubMed

    Spadiliero, Barbara; Nicolini, Claudio; Mascetti, Giancarlo; Henríquez, Diana; Vergani, Laura

    2002-01-01

    Chromatin of Trypanosoma cruzi is known to be organized in classical nucleosomal filaments, but surprisingly, these filaments do not fold in visible chromosomes and the nuclear envelope is preserved during cell division. Our hypothesis about the role of chromatin structure in regulating gene expression and, more generally, cell functioning, pressed us to verify if chromatin organization is modulated during the parasite life-cycle. To this end, we analyzed in situ the fine structural organization of T. cruzi chromatin by means of an integrated biophysical approach, using differential scanning calorimetry and fluorescence microscopy. We observed that logarithmic forms exhibit a less condensed chromatin with respect to the stationary ones. Thermal analysis revealed that parasite chromatin is organized in three main levels of condensation, barring from the polynucleosomal filament till to superstructured fibers. Besides, the fluorescence images of nuclei showed a characteristic chromatin distribution, with defined domains localized near to the nuclear envelope. While in stationary parasites, these regions are highly condensed, in logarithmic forms they unfold by extending themselves toward the center of nucleus. These observations suggest that, in comparison with higher eukaryotes, in T. cruzi the nuclear envelope plays an unusual and pivotal role in interphase and in mitosis. Copyright 2002 Wiley-Liss, Inc.

  14. In situ structure of trypanosomal ATP synthase dimer reveals a unique arrangement of catalytic subunits.

    PubMed

    Mühleip, Alexander W; Dewar, Caroline E; Schnaufer, Achim; Kühlbrandt, Werner; Davies, Karen M

    2017-01-31

    We used electron cryotomography and subtomogram averaging to determine the in situ structures of mitochondrial ATP synthase dimers from two organisms belonging to the phylum euglenozoa: Trypanosoma brucei, a lethal human parasite, and Euglena gracilis, a photosynthetic protist. At a resolution of 32.5 Å and 27.5 Å, respectively, the two structures clearly exhibit a noncanonical F1 head, in which the catalytic (αβ)3 assembly forms a triangular pyramid rather than the pseudo-sixfold ring arrangement typical of all other ATP synthases investigated so far. Fitting of known X-ray structures reveals that this unusual geometry results from a phylum-specific cleavage of the α subunit, in which the C-terminal αC fragments are displaced by ∼20 Å and rotated by ∼30° from their expected positions. In this location, the αC fragment is unable to form the conserved catalytic interface that was thought to be essential for ATP synthesis, and cannot convert γ-subunit rotation into the conformational changes implicit in rotary catalysis. The new arrangement of catalytic subunits suggests that the mechanism of ATP generation by rotary ATPases is less strictly conserved than has been generally assumed. The ATP synthases of these organisms present a unique model system for discerning the individual contributions of the α and β subunits to the fundamental process of ATP synthesis.

  15. Submicroscopic deletions at the WAGR locus, revealed by nonradioactive in situ hybridization

    SciTech Connect

    Fantes, J.A.; Bickmore, W.A.; Fletcher, J.M.; Hanson, I.M.; Heyningen, V. van ); Ballesta, F. )

    1992-12-01

    Fluorescence in situ hybridization (FISH) with biotin-labeled probes mapping to 11p13 has been used for the molecular analysis of deletions of the WAGR (Wilms tumor, aniridia, genitourinary abnormalities, and mental retardation) locus. They have detected a submicroscopic 11p13 deletion in a child with inherited aniridia who subsequently presented with Wilms tumor in a horseshoe kidney, only revealed at surgery. The mother, who has aniridia, was also found to carry a deletion including both the aniridia candidate gene (AN2) and the Wilms tumor predisposition gene (WT1). This is therefore a rare case of an inherited WAGR deletion. Wilms tumor has so far only been associated with sporadic de novo aniridia cases. The authors have shown that a cosmid probe for a candidate aniridia gene, homologous to the mouse Pax-6 gene, is deleted in cell lines from aniridia patients with previously characterized deletions at 11p13, while another cosmid marker mapping between two aniridia-associated translocation breakpoints (and hence a second candidate marker) is present on both chromosomes. These results support the Pax-6 homologue as a strong candidate for the AN2 gene. FISH with cosmid probes has proved to be a fast and reliable technique for the molecular analysis of deletions. It can be used with limited amounts of material and has strong potential for clinical applications. 41 refs., 1 figs., 3 tabs.

  16. Time-Resolved Conformational Dynamics in Hydrocarbon Chains

    SciTech Connect

    Minitti, Michael P.; Weber, Peter M.

    2007-06-22

    Internal rotation about carbon-carbon bonds allows N,N-dimethyl-2-butanamine (DM2BA) and N,N-dimethyl-3-hexanamine (DM3HA) to assume multiple conformeric structures. We explore the equilibrium composition and dynamics between such conformeric structures using Rydberg fingerprint spectroscopy. Time constants for conformeric interconversion of DM2BA (at 1.79 eV of internal energy) are 19 and 66 ps, and for DM3HA (1.78 eV) 23 and 41 ps. For the first time, a time-resolved and quantitative view of conformational dynamics of flexible hydrocarbon molecules at high temperatures is revealed.

  17. Exploration of CdTe quantum dots as mesoscale pressure sensors via time-resolved shock-compression photoluminescent emission spectroscopy

    SciTech Connect

    Kang, Zhitao; Banishev, Alexandr A.; Christensen, James; Dlott, Dana D.; Lee, Gyuhyon; Scripka, David A.; Breidenich, Jennifer; Summers, Christopher J.; Thadhani, Naresh N.; Xiao, Pan; Zhou, Min

    2016-07-28

    The nanometer size of CdTe quantum dots (QDs) and their unique optical properties, including size-tunable narrow photoluminescent emission, broad absorption, fast photoluminescence decay, and negligible light scattering, are ideal features for spectrally tagging the shock response of localized regions in highly heterogeneous materials such as particulate media. In this work, the time-resolved laser-excited photoluminescence response of QDs to shock-compression was investigated to explore their utilization as mesoscale sensors for pressure measurements and in situ diagnostics during shock loading experiments. Laser-driven shock-compression experiments with steady-state shock pressures ranging from 2.0 to 13 GPa were performed on nanocomposite films of CdTe QDs dispersed in a soft polyvinyl alcohol polymer matrix and in a hard inorganic sodium silicate glass matrix. Time-resolved photoluminescent emission spectroscopy was used to correlate photoluminescence changes with the history of shock pressure and the dynamics of the matrix material surrounding the QDs. The results revealed pressure-induced blueshifts in emitted wavelength, decreases in photoluminescent emission intensity, reductions in peak width, and matrix-dependent response times. Data obtained for these QD response characteristics serve as indicators for their use as possible time-resolved diagnostics of the dynamic shock-compression response of matrix materials in which such QDs are embedded as in situ sensors.

  18. Exploration of CdTe quantum dots as mesoscale pressure sensors via time-resolved shock-compression photoluminescent emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Kang, Zhitao; Banishev, Alexandr A.; Lee, Gyuhyon; Scripka, David A.; Breidenich, Jennifer; Xiao, Pan; Christensen, James; Zhou, Min; Summers, Christopher J.; Dlott, Dana D.; Thadhani, Naresh N.

    2016-07-01

    The nanometer size of CdTe quantum dots (QDs) and their unique optical properties, including size-tunable narrow photoluminescent emission, broad absorption, fast photoluminescence decay, and negligible light scattering, are ideal features for spectrally tagging the shock response of localized regions in highly heterogeneous materials such as particulate media. In this work, the time-resolved laser-excited photoluminescence response of QDs to shock-compression was investigated to explore their utilization as mesoscale sensors for pressure measurements and in situ diagnostics during shock loading experiments. Laser-driven shock-compression experiments with steady-state shock pressures ranging from 2.0 to 13 GPa were performed on nanocomposite films of CdTe QDs dispersed in a soft polyvinyl alcohol polymer matrix and in a hard inorganic sodium silicate glass matrix. Time-resolved photoluminescent emission spectroscopy was used to correlate photoluminescence changes with the history of shock pressure and the dynamics of the matrix material surrounding the QDs. The results revealed pressure-induced blueshifts in emitted wavelength, decreases in photoluminescent emission intensity, reductions in peak width, and matrix-dependent response times. Data obtained for these QD response characteristics serve as indicators for their use as possible time-resolved diagnostics of the dynamic shock-compression response of matrix materials in which such QDs are embedded as in situ sensors.

  19. Time-Resolved Measurements of Carbon Nanotube and Nanohorn Growth

    NASA Astrophysics Data System (ADS)

    Geohegan, David

    2005-11-01

    Mechanisms for carbon nanotube growth have been investigated for both laser vaporization (LV) and chemical vapor deposition (CVD) synthesis techniques through the use of time-resolved, in situ laser-based diagnostics for the measurement of absolute growth rates. Optimization of both the production of loose single-wall carbon nanotubes (SWNTs) by LV and the sustained growth of mm-long, vertically-aligned carbon nanotube arrays (VANTAs) by CVD are described. For SWNT growth by laser co-vaporization of carbon and trace metal catalysts at high (1200 C) temperatures, nanotubes are found to grow at ˜ 1--5 microns/second to lengths of only several microns, as determined by gated-ICCD imaging and laser spectroscopy of the plume of ejected material. Efforts to scale the LV production of SWNTs utilizing an industrial Nd:YAG laser (600 W average power, 1-500 Hz repetition rate, 0.5-10ms pulse width) are described. In addition to vaporizing material at much higher rates, the high-power laser irradiation provides sufficient plasma plume density and temperature to enable the growth of novel single-wall carbon nanohorn (SWNH) structures without the need for metal catalysts in the target. Applications of these SWNH structures as metal catalyst supports will be discussed. Through the application of time-resolved reflectivity and direct imaging, CVD growth of VANTAs from hydrocarbon gases at sustained rates of 0.2 -- 0.5 microns/second have been directly measured over millimeters of length at lower (˜ 700 C) temperatures. Now, through a new laser-CVD setup at the ALPS (Advanced Laser Processing and Synthesis) facility at ORNL, high-power laser heating is being employed for the fast and position-controlled growth of carbon nanotubes on substrates. In situ fast optical pyrometry is employed to record the rapid thermal processing of metal-catalyst-prepared substrates to investigate the nucleation and early growth behavior of CVD-grown nanotubes. New nanotube growth and tunable Raman

  20. Oxygen transport pathways in Ruddlesden–Popper structured oxides revealed via in situ neutron diffraction

    DOE PAGES

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

    2015-09-21

    Ruddlesden-Popper structured oxides, general form An+1BnO3n+1, consist of n-layers of the perovskite structure stacked in between rock-salt layers, and have potential application in solid oxide electrochemical cells and ion transport membrane reactors. Three materials with constant Co/Fe ratio, LaSrCo0.5Fe0.5O4-δ (n = 1), La0.3Sr2.7CoFeO7-δ (n = 2), and LaSr3Co1.5Fe1.5O10-δ (n = 3) were synthesized and studied via in situ neutron powder diffraction between 765 K and 1070 K at a pO2 of 10-1 atm. Then, the structures were fit to a tetragonal I4/mmm space group, and were found to have increased total oxygen vacancy concentration in the order La0.3Sr2.7CoFeO7-δ > LaSr3Co1.5Fe1.5O10-δmore » > LaSrCo0.5Fe0.5O4-δ, following the trend predicted for charge compensation upon increasing Sr2+/La3+ ratio. The oxygen vacancies within the material were almost exclusively located within the perovskite layers for all of the crystal structures with only minimal vacancy formation in the rock-salt layer. Finally, analysis of the concentration of these vacancies at each distinct crystallographic site and the anisotropic atomic displacement parameters for the oxygen sites reveals potential preferred oxygen transport pathways through the perovskite layers.« less

  1. Time-resolved Temperature Measurements in SSPX

    SciTech Connect

    Ludington, A R; Hill, D N; McLean, H S; Moller, J; Wood, R D

    2006-08-14

    We seek to measure time-resolved electron temperatures in the SSPX plasma using soft X-rays from free-free Bremsstrahlung radiation. To increase sensitivity to changes in temperature over the range 100-300 eV, we use two photodiode detectors sensitive to different soft X-ray energies. The detectors, one with a Zr/C coating and the other with a Ti/Pd coating, view the plasma along a common line of sight tangential to the magnetic axis of the spheromak, where the electron temperature is a maximum. The comparison of the signals, over a similar volume of plasma, should be a stronger function of temperature than a single detector in the range of Te< 300 eV. The success of using photodiodes to detect changing temperatures along a chord will make the case for designing an array of the detectors, which could provide a time changing temperature profile over a larger portion of the plasma.

  2. Time resolved ion beam induced charge collection

    SciTech Connect

    SEXTON,FREDERICK W.; WALSH,DAVID S.; DOYLE,BARNEY L.; DODD,PAUL E.

    2000-04-01

    Under this effort, a new method for studying the single event upset (SEU) in microelectronics has been developed and demonstrated. Called TRIBICC, for Time Resolved Ion Beam Induced Charge Collection, this technique measures the transient charge-collection waveform from a single heavy-ion strike with a {minus}.03db bandwidth of 5 GHz. Bandwidth can be expanded up to 15 GHz (with 5 ps sampling windows) by using an FFT-based off-line waveform renormalization technique developed at Sandia. The theoretical time resolution of the digitized waveform is 24 ps with data re-normalization and 70 ps without re-normalization. To preserve the high bandwidth from IC to the digitizing oscilloscope, individual test structures are assembled in custom high-frequency fixtures. A leading-edge digitized waveform is stored with the corresponding ion beam position at each point in a two-dimensional raster scan. The resulting data cube contains a spatial charge distribution map of up to 4,096 traces of charge (Q) collected as a function of time. These two dimensional traces of Q(t) can cover a period as short as 5 ns with up to 1,024 points per trace. This tool overcomes limitations observed in previous multi-shot techniques due to the displacement damage effects of multiple ion strikes that changed the signal of interest during its measurement. This system is the first demonstration of a single-ion transient measurement capability coupled with spatial mapping of fast transients.

  3. Time resolved strain dependent morphological study of electrically conducting nanocomposites

    NASA Astrophysics Data System (ADS)

    Khan, Imran; Mitchell, Geoffrey; Mateus, Artur; Kamma-Lorger, Christina S.

    2015-10-01

    An efficient and reliable method is introduced to understand the network behaviour of nano-fillers in a polymeric matrix under uniaxial strain coupled with small angle x-ray scattering measurements. The nanoparticles (carbon nanotubes) are conductive and the particles form a percolating network that becomes apparent source of electrical conduction and consequently the samples behave as a bulk conductor. Polyurethane based nanocomposites containing 2% w/w multiwall carbon nanotubes are studied. The electrical conductivity of the nanocomposite was (3.28×10-5s/m).The sample was able to be extended to an extension ratio of 1.7 before fracture. A slight variation in the electrical conductivity is observed under uniaxial strain which we attribute to the disturbance of conductive pathways. Further, this work is coupled with in- situ time resolved small angle x-ray scattering measurements using a synchrotron beam line to enable its measurements to be made during the deformation cycle. We use a multiscale structure to model the small angle x-ray data. The results of the analysis are interpreted as the presence of aggregates which would also go some way towards understanding why there is no alignment of the carbon nanotubes.

  4. A Flow-Through Reaction Cell that Couples Time - Resolved Analysis

    SciTech Connect

    A Wall; P Heaney; R Mathur; J Post; J Hanson; P Eng

    2011-12-31

    A non-metallic flow-through reaction cell is described, designed for in situ time-resolved X-ray diffraction coupled with stable isotope analysis. The experimental setup allows the correlation of Cu isotope fractionation with changes in crystal structure during copper sulfide dissolution. This flow-through cell can be applied to many classes of fluid-mineral reactions that involve dissolution or ion exchange.

  5. Evolution of Chromosome 6 of Solanum Species Revealed by Comparative Fluorescence in Situ Hybridization Mapping

    USDA-ARS?s Scientific Manuscript database

    Comparative genome mapping is an important tool in evolutionary research. Here we demonstrate a comparative fluorescent in situ hybridization (FISH) mapping strategy. A set of 13 bacterial artificial chromosome (BAC) clones derived from potato chromosome 6 was used for FISH mapping in seven differen...

  6. Time Resolved FTIR Analysis of Combustion of Ethanol and Gasoline Combustion in AN Internal Combustion Engine

    NASA Astrophysics Data System (ADS)

    White, Allen R.; Sakai, Stephen; Devasher, Rebecca B.

    2011-06-01

    In order to pursue In Situ measurements in an internal combustion engine, a MegaTech Mark III transparent spark ignition engine was modified with a sapphire combustion chamber. This modification will allow the transmission of infrared radiation for time-resolved spectroscopic measurements by an infrared spectrometer. By using a Step-scan equipped Fourier transform spectrometer, temporally resolved infrared spectral data were acquired and compared for combustion in the modified Mark III engine. Measurements performed with the FTIR system provide insight into the energy transfer vectors that precede combustion and also provides an in situ measurement of the progress of combustion. Measurements were performed using ethanol and gasoline.

  7. Oxygen transport pathways in Ruddlesden–Popper structured oxides revealed via in situ neutron diffraction

    SciTech Connect

    Tomkiewicz, Alex C.; Tamimi, Mazin; Huq, Ashfia; McIntosh, Steven

    2015-09-21

    Ruddlesden-Popper structured oxides, general form An+1BnO3n+1, consist of n-layers of the perovskite structure stacked in between rock-salt layers, and have potential application in solid oxide electrochemical cells and ion transport membrane reactors. Three materials with constant Co/Fe ratio, LaSrCo0.5Fe0.5O4-δ (n = 1), La0.3Sr2.7CoFeO7-δ (n = 2), and LaSr3Co1.5Fe1.5O10-δ (n = 3) were synthesized and studied via in situ neutron powder diffraction between 765 K and 1070 K at a pO2 of 10-1 atm. Then, the structures were fit to a tetragonal I4/mmm space group, and were found to have increased total oxygen vacancy concentration in the order La0.3Sr2.7CoFeO7-δ > LaSr3Co1.5Fe1.5O10-δ > LaSrCo0.5Fe0.5O4-δ, following the trend predicted for charge compensation upon increasing Sr2+/La3+ ratio. The oxygen vacancies within the material were almost exclusively located within the perovskite layers for all of the crystal structures with only minimal vacancy formation in the rock-salt layer. Finally, analysis of the concentration of these vacancies at each distinct crystallographic site and the anisotropic atomic displacement parameters for the oxygen sites reveals potential preferred oxygen transport pathways through the perovskite layers.

  8. Portable optical oxygen sensor based on time-resolved fluorescence.

    PubMed

    Chu, Cheng-Shane; Chu, Ssu-Wei

    2014-11-10

    A new, simple signal processing, low-cost technique for the fabrication of a portable oxygen sensor based on time-resolved fluorescence is described. The sensing film uses the oxygen sensing dye platinum meso-tetra (pentfluorophenyl) porphyrin (PtTFPP) embedded in a polymer matrix. The ratio τ0100 measures sensitivity of the sensing film, where τ0 and τ100 represent the detected fluorescence lifetimes from the sensing film exposed to 100% nitrogen and 100% oxygen, respectively. The experimental results reveal that the PtTFPP-doped oxygen sensor has a sensitivity of 2.2 in the 0%-100% range. A preparation procedure for coating the photodiodes with the oxygen sensor film that produces repetitive and reliable sensing devices is proposed. The developed time-resolved optical oxygen sensor is portable, low-cost, has simple signal processing, and lacks optical filter elements. It is a cost-effective alternative to traditional electrochemical-based oxygen sensors and provides a platform for other optical based sensors.

  9. Formulation for Time-resolved Aerodynamic Damping in Dynamic Stall

    NASA Astrophysics Data System (ADS)

    Corke, Thomas; Bowles, Patrick; Coleman, Dusty; Thomas, Flint

    2012-11-01

    A new Hilbert transform formulation of the equation of motion for a pitching airfoil in a uniform stream yields a time resolved aerodynamic damping factor, Ξ (t) = (√{ (Cm2 (t) +C m2 } /αmax) sinψ (t) , where Cm (t) is the instantaneous pitch moment coefficient, and C m (t) is the Hilbert transform of Cm (t) , αmax is the pitching amplitude, and ψ (t) is the time-resolved phase difference between the aerodynamic pitch moment and the instantaneous angle of attack. A Ξ (t) < 0 indicates unstable pressure loading that can be considered a necessary condition to excite stall flutter in an elastic airfoil. This will be illustrated in experiments with conditions producing ``light'' dynamic stall for a range of Mach numbers from 0.3-0.6. These reveal large negative excursions of Ξ (t) during the pitch-up portion of the cycle that correlates with the formation and convection of the dynamic stall vortex. The fact that the cycle-integrated damping coefficient is positive in all these cases underscores how the traditional diagnostic masks much of the physics that underlies the destabilizing effect of the dynamic stall process. This new insight can explain instances of transient limit-cycle growth of helicopter rotor vibrations. Supported by Bell Helicopter.

  10. CCD time-resolved photometry of faint cataclysmic variables. II

    SciTech Connect

    Szkody, P.; Howell, S.B.; Mateo, M.; Kreidl, T.J. Planetary Science Institute, Tucson, AZ Mount Wilson and Las Campanas Observatories, Pasadena, CA Lowell Observatory, Flagstaff, AZ )

    1989-10-01

    Time-resolved optical broad-band light curves obtained from differential photometry on sequential CCD frames of the known or suspected cataclysmic variable FO And, EH Aqr, WX Cet, XX Cet, AL Com, V503 Cyg, AH Eri, CP Eri, IR Gem, RW UMi, PG0134+070, and US 3215 are presented. The analysis of the light curves with coverage of greater than 2 hrs shows repeatable periodicity in five objects. PG0134+070 exhibits eclipses of 1.3-1.8 mag depth with a period of 313 min. V503 Cyg has a 0.7-1.0 mag peak-to-peak modulation with a period of 109 min. IR Gem shows a large modulation at the orbital period of 99 min, and comparison with previous data indicates that this modulation may have an amplitude dependent on outburst phase. AH Eri reveals a 0.1-0.3 mag modulation, at a period of 42 min. Better time-resolved data on AL Com confirm the 0.4-mag variation reported by Howell and Szkody (1988) at a period of 42 min. These latter two short periods likely indicate magnetic systems. There is also some evidence of periodicity in RW UMi and WX Cet which must be confirmed with further data. 25 refs.

  11. [Oncogenic human papillomaviruses in extra-genital Bowen disease revealed by in situ hybridization].

    PubMed

    Derancourt, C; Mougin, C; Chopard Lallier, M; Coumes-Marquet, S; Drobacheff, C; Laurent, R

    2001-01-01

    The association between mucosal oncogenic human papillomaviruses (HPV) and bowenoid papulosis or genital Bowen's disease is well documented. In contrast this association with extra-genital Bowen's disease is poorly studied. The aim of this study was to detect oncogenic (16/18, 31/33/51) and non oncogenic (8/11) mucosal HPV using a in situ hybridization method in 28 skin biopsy specimens of extra-genital Bowen's disease. Twenty-eight cases of extra-genital Bowen's disease seen in the period 1990-96 in the Dermatology department were included: 19 women and 9 men (mean age: 72 years). Bowen's disease locations were: hands and feet (8 cases), limbs (11 cases), face (8 cases), trunk (1 case). Blinded histopathologic examination confirmed the diagnosis of Bowen's disease and signs of HPV infection (koilocytosis). In situ hybridization was performed using three biotinylated probes detecting HPV types 6/11, 16/18, 31/33/51. Oncogenic HPV genoma was detected in 8 skin samples (28.6 p. 100). In all these cases, 16/18 probe was positive and in two cases, both 16/18 and 31/33/51 probes were positive; 4/8 Bowen's diseases of the extremities were positive for HPV. Koilocytes were found in 6/8 of skin samples with positive HPV detection. Mucosal oncogenic HPV are detected by in situ hybridization in 28.6 p. 100 of extra-genital Bowen's disease. In situ hybridization is an easier technique than Southern-Blot hybridization which is the gold standard. Five studies reported similar results and three studies reported different results that we discuss. A precise understanding of oncogenic HPV implication in the development of extra-genital Bowen's disease could lead to the development of new therapeutic strategies (topical cidofovir or imiquimod).

  12. Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy.

    PubMed

    Blasco, Teresa

    2010-12-01

    This tutorial review intends to show the possibilities of in situ solid state NMR spectroscopy in the elucidation of reaction mechanisms and the nature of the active sites in heterogeneous catalysis. After a brief overview of the more usual experimental devices used for in situ solid state NMR spectroscopy measurements, some examples of applications taken from the recent literature will be presented. It will be shown that in situ NMR spectroscopy allows: (i) the identification of stable intermediates and transient species using indirect methods, (ii) to prove shape selectivity in zeolites, (iii) the study of reaction kinetics, and (iv) the determination of the nature and the role played by the active sites in a catalytic reaction. The approaches and methodology used to get this information will be illustrated here summarizing the most relevant contributions on the investigation of the mechanisms of a series of reactions of industrial interest: aromatization of alkanes on bifunctional catalysts, carbonylation reaction of methanol with carbon monoxide, ethylbenzene disproportionation, and the Beckmann rearrangement reaction. Special attention is paid to the research carried out on the role played by carbenium ions and alkoxy as intermediate species in the transformation of hydrocarbon molecules on solid acid catalysts.

  13. Freshening in the South China Sea during 2012 revealed by Aquarius and in situ data

    NASA Astrophysics Data System (ADS)

    Zeng, Lili; Timothy Liu, W.; Xue, Huijie; Xiu, Peng; Wang, Dongxiao

    2014-12-01

    Newly available sea surface salinity (SSS) data from the Aquarius together with in situ hydrographic data are used to explore the spatial and temporal characteristics of SSS in the South China Sea (SCS). Using in situ observations as the reference, an evaluation of daily Aquarius data indicates that there exists a negative bias of 0.45 psu for the version 3.0 data set. The root-mean-square difference for daily Aquarius SSS is about 0.53 psu after correcting the systematic bias, and those for weekly and monthly Aquarius SSSs are 0.45 and 0.29 psu, respectively. Nevertheless, the Aquarius SSS shows a reliable freshening in the SCS in 2012, which is larger than the Aquarius uncertainty. The freshening of up to 0.4 psu in the upper-ocean of the northern SCS was confirmed by in situ observations. This freshening in 2012 was caused by a combined effect of abundant local freshwater flux and limited Kuroshio intrusion. By comparing the Kuroshio intrusion in 2012 with that in 2011, we found the reduction as a relatively important cause for the freshening over the northern SCS. In contrast to the northern SCS, reduced river discharge in 2012 played the leading role to the saltier surface in the region near the Mekong River mouth with respect to 2011.

  14. Time-resolved investigations of the non-thermal ablation process of graphite induced by femtosecond laser pulses

    SciTech Connect

    Kalupka, C. Finger, J.; Reininghaus, M.

    2016-04-21

    We report on the in-situ analysis of the ablation dynamics of the, so-called, laser induced non-thermal ablation process of graphite. A highly oriented pyrolytic graphite is excited by femtosecond laser pulses with fluences below the classic thermal ablation threshold. The ablation dynamics are investigated by axial pump-probe reflection measurements, transversal pump-probe shadowgraphy, and time-resolved transversal emission photography. The combination of the applied analysis methods allows for a continuous and detailed time-resolved observation of the non-thermal ablation dynamics from several picoseconds up to 180 ns. Formation of large, μm-sized particles takes place within the first 3.5 ns after irradiation. The following propagation of ablation products and the shock wave front are tracked by transversal shadowgraphy up to 16 ns. The comparison of ablation dynamics of different fluences by emission photography reveals thermal ablation products even for non-thermal fluences.

  15. Time-resolved spin-dependent processes in magnetic field effects in organic semiconductors

    NASA Astrophysics Data System (ADS)

    Peng, Qiming; Li, Xianjie; Li, Feng

    2012-12-01

    We investigated the time-resolved magnetic field effects (MFEs) in tri-(8-hydroxyquinoline)-aluminum (Alq3) based organic light-emitting diodes (OLEDs) through the transient electroluminescence (EL) method. The values of magneto-electroluminescence (MEL) decrease with the time, and the decreasing slope is proportional to the driving voltage. Specifically, negative MELs are seen when the driving voltage is high enough (V > 11 V). We propose a model to elucidate the spin-dependent processes and theoretically simulate the time-resolved MELs. In particular, this dynamic analysis of time-resolved MELs reveals that the intersystem crossing between singlet and triplet electron-hole pairs and the triplet-triplet annihilation are responsible for the time-resolved MELs at the beginning and enduring periods of the pulse, respectively.

  16. An inexpensive technique for the time resolved laser induced plasma spectroscopy

    SciTech Connect

    Ahmed, Rizwan Ahmed, Nasar; Iqbal, J.; Aslam Baig, M.

    2016-08-15

    We present an efficient and inexpensive method for calculating the time resolved emission spectrum from the time integrated spectrum by monitoring the time evolution of neutral and singly ionized species in the laser produced plasma. To validate our assertion of extracting time resolved information from the time integrated spectrum, the time evolution data of the Cu II line at 481.29 nm and the molecular bands of AlO in the wavelength region (450–550 nm) have been studied. The plasma parameters were also estimated from the time resolved and time integrated spectra. A comparison of the results clearly reveals that the time resolved information about the plasma parameters can be extracted from the spectra registered with a time integrated spectrograph. Our proposed method will make the laser induced plasma spectroscopy robust and a low cost technique which is attractive for industry and environmental monitoring.

  17. Time-resolved polarization study of anisotropy in bacteriorhodopsin

    SciTech Connect

    Wan, Chaozhi; Qian, Jun; Johnson, C.K. )

    1990-11-01

    Time-resolved polarization spectroscopy is sensitive to the orientational dynamics of chromophores, and as a result it can be applied to study internal motion in restrictive environments. This paper describes the application of polarization spectroscopy to the photoactive protein bacteriorhodopsin on time scales from picoseconds to hundreds of microseconds. Anisotropy persists in both the ground-state bacteriorhodopsin population and in the photocycle intermediates due to a population bottleneck in the bacteriorhodopsin photocycle. The time dependence of the polarization signal expected for a sequence of intermediates is described and is shown to be sensitive both to population kinetics and to internal motion. The observed time dependence of the polarization signal reveals internal motion in the purple membrane fragments on the time scale of the K {yields} L transition ({approximately} 1 {mu}s). The results are consistent with the known kinetics of the bacteriorhodopsin photocycle. Evidence is also presented and discussed for a decay component on a time scale of < 50 ps.

  18. Epithelial cells captured from ductal carcinoma in situ reveal a gene expression signature associated with progression to invasive breast cancer

    PubMed Central

    Abuázar, Carolina Sens; de Toledo Osorio, Cynthia Aparecida Bueno; Pinilla, Mabel Gigliola; da Silva, Sabrina Daniela; Camargo, Anamaria Aranha; Silva, Wilson Araujo; e Ferreira, Elisa Napolitano; Brentani, Helena Paula; Carraro, Dirce Maria

    2016-01-01

    Breast cancer biomarkers that can precisely predict the risk of progression of non-invasive ductal carcinoma in situ (DCIS) lesions to invasive disease are lacking. The identification of molecular alterations that occur during the invasion process is crucial for the discovery of drivers of transition to invasive disease and, consequently, biomarkers with clinical utility. In this study, we explored differences in gene expression in mammary epithelial cells before and after the morphological manifestation of invasion, i.e., early and late stages, respectively. In the early stage, epithelial cells were captured from both pre-invasive lesions with distinct malignant potential [pure DCIS as well as the in situ component that co-exists with invasive breast carcinoma lesions (DCIS-IBC)]; in the late stage, epithelial cells were captured from the two distinct morphological components of the same sample (in situ and invasive components). Candidate genes were identified using cDNA microarray and rapid subtractive hybridization (RaSH) cDNA libraries and validated by RT-qPCR assay using new samples from each group. These analyses revealed 26 genes, including 20 from the early and 6 from the late stage. The expression profile based on the 20 genes, marked by a preferential decrease in expression level towards invasive phenotype, discriminated the majority of DCIS samples. Thus, this study revealed a gene expression signature with the potential to predict DCIS progression and, consequently, provides opportunities to tailor treatments for DCIS patients. PMID:27708222

  19. In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework

    NASA Astrophysics Data System (ADS)

    Katsenis, Athanassios D.; Puškarić, Andreas; Štrukil, Vjekoslav; Mottillo, Cristina; Julien, Patrick A.; Užarević, Krunoslav; Pham, Minh-Hao; Do, Trong-On; Kimber, Simon A. J.; Lazić, Predrag; Magdysyuk, Oxana; Dinnebier, Robert E.; Halasz, Ivan; Friščić, Tomislav

    2015-03-01

    Chemical and physical transformations by milling are attracting enormous interest for their ability to access new materials and clean reactivity, and are central to a number of core industries, from mineral processing to pharmaceutical manufacturing. While continuous mechanical stress during milling is thought to create an environment supporting nonconventional reactivity and exotic intermediates, such speculations have remained without proof. Here we use in situ, real-time powder X-ray diffraction monitoring to discover and capture a metastable, novel-topology intermediate of a mechanochemical transformation. Monitoring the mechanochemical synthesis of an archetypal metal-organic framework ZIF-8 by in situ powder X-ray diffraction reveals unexpected amorphization, and on further milling recrystallization into a non-porous material via a metastable intermediate based on a previously unreported topology, herein named katsenite (kat). The discovery of this phase and topology provides direct evidence that milling transformations can involve short-lived, structurally unusual phases not yet accessed by conventional chemistry.

  20. Photosensing performance of branched CdS/ZnO heterostructures as revealed by in situ TEM and photodetector tests.

    PubMed

    Zhang, Chao; Tian, Wei; Xu, Zhi; Wang, Xi; Liu, Jiangwei; Li, Song-Lin; Tang, Dai-Ming; Liu, Dequan; Liao, Meiyong; Bando, Yoshio; Golberg, Dmitri

    2014-07-21

    CdS/ZnO branched heterostructures have been successfully synthesized by combining thermal vapour deposition and a hydrothermal method. Drastic optoelectronic performance enhancement of such heterostructures was revealed, compared to plain CdS nanobelts, as documented by comparative in situ optoelectronic studies on corresponding individual nanostructures using an originally designed laser-compatible transmission electron microscopy (TEM) technique. Furthermore, flexible thin-film based photodetectors based on standard CdS nanobelts and newly prepared CdS/ZnO heterostructures were fabricated on PET substrates, and comparative photocurrent and photo-responsivity measurements thoroughly verified the in situ TEM results. The CdS/ZnO branched heterostructures were found to have better performance than standard CdS nanobelts for optoelectronic applications with respect to the photocurrent to dark current ratio and responsivity.

  1. The origin of molecular mobility during biomass pyrolysis as revealed by in situ (1)H NMR spectroscopy.

    PubMed

    Dufour, Anthony; Castro-Diaz, Miguel; Brosse, Nicolas; Bouroukba, Mohamed; Snape, Colin

    2012-07-01

    The thermochemical conversion of lignocellulosic biomass feedstocks offers an important potential route for the production of biofuels and value-added green chemicals. Pyrolysis is the first phenomenon involved in all biomass thermochemical processes and it controls to a major extent the product composition. The composition of pyrolysis products can be affected markedly by the extent of softening that occurs. In spite of extensive work on biomass pyrolysis, the development of fluidity during the pyrolysis of biomass has not been quantified. This paper provides the first experimental investigation of proton mobility during biomass pyrolysis by in situ (1)H NMR spectroscopy. The origin of mobility is discussed for cellulose, lignin and xylan. The effect of minerals on cellulose mobility is also investigated. Interactions between polymers in the native biomass network are revealed by in situ (1)H NMR analysis. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Photosensing performance of branched CdS/ZnO heterostructures as revealed by in situ TEM and photodetector tests

    NASA Astrophysics Data System (ADS)

    Zhang, Chao; Tian, Wei; Xu, Zhi; Wang, Xi; Liu, Jiangwei; Li, Song-Lin; Tang, Dai-Ming; Liu, Dequan; Liao, Meiyong; Bando, Yoshio; Golberg, Dmitri

    2014-06-01

    CdS/ZnO branched heterostructures have been successfully synthesized by combining thermal vapour deposition and a hydrothermal method. Drastic optoelectronic performance enhancement of such heterostructures was revealed, compared to plain CdS nanobelts, as documented by comparative in situ optoelectronic studies on corresponding individual nanostructures using an originally designed laser-compatible transmission electron microscopy (TEM) technique. Furthermore, flexible thin-film based photodetectors based on standard CdS nanobelts and newly prepared CdS/ZnO heterostructures were fabricated on PET substrates, and comparative photocurrent and photo-responsivity measurements thoroughly verified the in situ TEM results. The CdS/ZnO branched heterostructures were found to have better performance than standard CdS nanobelts for optoelectronic applications with respect to the photocurrent to dark current ratio and responsivity.CdS/ZnO branched heterostructures have been successfully synthesized by combining thermal vapour deposition and a hydrothermal method. Drastic optoelectronic performance enhancement of such heterostructures was revealed, compared to plain CdS nanobelts, as documented by comparative in situ optoelectronic studies on corresponding individual nanostructures using an originally designed laser-compatible transmission electron microscopy (TEM) technique. Furthermore, flexible thin-film based photodetectors based on standard CdS nanobelts and newly prepared CdS/ZnO heterostructures were fabricated on PET substrates, and comparative photocurrent and photo-responsivity measurements thoroughly verified the in situ TEM results. The CdS/ZnO branched heterostructures were found to have better performance than standard CdS nanobelts for optoelectronic applications with respect to the photocurrent to dark current ratio and responsivity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00963k

  3. Millifluidics for time-resolved mapping of the growth of gold nanostructures

    SciTech Connect

    Sai Krishna, Katla; Navin, Chelliah; Biswas, Sanchita; Singh, Varshni; Ham, Kyungmin; Bovencamp, L. S.; Theegala, Chandra; Miller, Jeffrey T; Spivey, James J.; Kumar, Challa S.S.R.

    2013-04-10

    Innovative in situ characterization tools are essential for understanding the reaction mechanisms leading to the growth of nanoscale materials. Though techniques, such as in situ transmission X-ray microscopy, fast single-particle spectroscopy, small-angle X-ray scattering, etc., are currently being developed, these tools are complex, not easily accessible, and do not necessarily provide the temporal resolution required to follow the formation of nanomaterials in real time. Here, we demonstrate for the first time the utility of a simple millifluidic chip for an in situ real time analysis of morphology and dimension-controlled growth of gold nano- and microstructures with a time resolution of 5 ms. The structures formed were characterized using synchrotron radiation-based in situ X-ray absorption spectroscopy, 3-D X-ray tomography, and high-resolution electron microscopy. These gold nanostructures were found to be catalytically active for conversion of 4-nitrophenol into 4-aminophenol, providing an example of the potential opportunities for time-resolved analysis of catalytic reactions. While the investigations reported here are focused on gold nanostructures, the technique can be applied to analyze the time-resolved growth of other types of nanostructured metals and metal oxides. With the ability to probe at least a 10-fold higher concentrations, in comparison with traditional microfluidics, the tool has potential to revolutionize a broad range of fields from catalysis, molecular analysis, biodefense, and molecular biology.

  4. High-resolution telomere fluorescence in situ hybridization reveals intriguing anomalies in germ cell tumors.

    PubMed

    Shekhani, Mohammed Talha; Barber, John R; Bezerra, Stephania M; Heaphy, Christopher M; Gonzalez Roibon, Nilda Diana; Taheri, Diana; Reis, Leonardo O; Guner, Gunes; Joshu, Corinne E; Netto, George J; Meeker, Alan K

    2016-08-01

    Testicular germ cell tumor (TGCT) is the most common malignancy of young men. Most patients are completely cured, which distinguishes these from most other malignancies. Orchiectomy specimens (n=76) were evaluated using high-resolution (single-cell discriminative) telomere-specific fluorescence in situ hybridization (FISH) with simultaneous Oct4 immunofluorescence to describe telomere length phenotype in TGCT neoplastic cells. For the first time, the TGCT precursor lesion, germ cell neoplasia in situ (GCNIS) is also evaluated in depth. The intensity of the signals from cancerous cells was compared to the same patient's reference cells-namely, healthy germ cells (defined as "medium" length) and interstitial/somatic cells (defined as "short" telomere length). We observed short telomeres in most GCNIS and pure seminomas (P=.006 and P=.0005, respectively). In contrast, nonseminomas displayed longer telomeres. Lesion-specific telomere lengths were documented in mixed tumor cases. Embryonal carcinoma (EC) demonstrated the longest telomeres. A fraction of EC displays the telomerase-independent alternative lengthening of telomeres (ALT) phenotype (24% of cases). Loss of ATRX or DAXX nuclear expression was strongly associated with ALT; however, nuclear expression of both proteins was retained in half of ALT-positive ECs. The particular distribution of telomere lengths among TGCT and GCNIS precursors implicate telomeres anomalies in pathogenesis. These results may advise management decisions as well. Copyright © 2016. Published by Elsevier Inc.

  5. Martensitic transformation in a B2-containing CuZr-based BMG composite revealed by in situ neutron diffraction

    DOE PAGES

    Song, Gian; Lee, Chanho; Hong, Sung Hwan; ...

    2017-06-27

    Here, CuZr-based bulk-metallic-glass (BMG) composites reinforced by a B2-type CuZr crystalline-phase (CP) have been widely studied, and exhibit that the plastic deformation of the CP induces martensitic transformation from the B2 to B19', which plays a dominant role in the deformation behavior and mechanical properties. In the present study, 2.0% Co containing CuZr-based BMG composites were investigated using in-situ neutron-diffraction technique. The in-situ neutron-diffraction results reveal the continuous load transfer from the glass matrix to B2 CP and martensitic transformation from the B2 CP to B19' during the deformation of the composite. Moreover, it was found that the martensitic transformationmore » is initiated at the applied stress higher than 1500 MPa, and is significantly suppressed during the deformation, as compared to other 0.5% Co-containing CuZr-based BMG composites. Based on these in-situ neutron-diffraction results, the martensitic transformation is strongly affected by the amount of the addition of Co, which determines the mechanical properties of CP-reinforced BMG composites, such as ductility and hardening capability.« less

  6. Patterns of gene expression in the murine brain revealed by in situ hybridization of brain-specific mRNAs.

    PubMed

    Branks, P L; Wilson, M C

    1986-07-01

    Biochemical differences between neuronal cell populations of the mammalian brain, including selection of neurotransmitters and distinct neural antigens, suggest that the regulation of gene expression plays an important role in defining brain function. Here we describe the use of in situ hybridization to identify cDNA clones of highly regulated mRNA species and to define directly their pattern of gene expression in brain at both gross morphological and cellular levels. One of the selected cDNA clones, pMuBr2, detected a single 3.0 kb mRNA species, which from in situ hybridization appears specific to oligodendroglia cells. Three other cDNA clones, pMuBr3, 8 and 85, identified polyadenylated mRNA transcripts expressed by neuronal cells of the murine brain. Viewed at the gross morphological level, the mRNAs hybridizing to these cDNA sequences exhibit different patterns of abundance distinguishing such brain structures as pons, anterior thalamus, hippocampus, basal ganglia and anterior lobe of the neuroendocrine pituitary gland. At the cellular level, in situ hybridization revealed that these mRNAs are differentially expressed by morphologically and functionally distinct neurons of the cerebellum and hippocampal formation. When examined in the context of known brain function, however, the regulated expression of the neuron-specific mRNAs does not correlate simply with known cellular morphology or previously demonstrated neuronal relationships suggesting novel patterns of gene expression which may contribute to brain function.

  7. Time-resolved pulsed EPR: microwave and optical detection

    SciTech Connect

    Trifunac, A.D.; Smith, J.P.

    1981-01-01

    Time-resolved pulsed EPR spectrometers are described. EPR spectra, kinetic profiles, and relaxation studies are used to illustrate some capabilities of the pulsed EPR experiment. Optical detection of time-resolved EPR spectra of radical ion pairs is used to study radical-ion recombination kinetics, recombination pathways, and the structure of radical anions and cations. 17 figures.

  8. Ultrafast time-resolved vibrational spectroscopies of carotenoids in photosynthesis.

    PubMed

    Hashimoto, Hideki; Sugisaki, Mitsuru; Yoshizawa, Masayuki

    2015-01-01

    This review discusses the application of time-resolved vibrational spectroscopies to the studies of carotenoids in photosynthesis. The focus is on the ultrafast time regime and the study of photophysics and photochemistry of carotenoids by femtosecond time-resolved stimulated Raman and four-wave mixing spectroscopies. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems.

  9. Excitation emission and time-resolved fluorescence spectroscopy of selected varnishes used in historical musical instruments.

    PubMed

    Nevin, Austin; Echard, Jean-Philippe; Thoury, Mathieu; Comelli, Daniela; Valentini, Gianluca; Cubeddu, Rinaldo

    2009-11-15

    The analysis of various varnishes from different origins, which are commonly found on historical musical instruments was carried out for the first time with both fluorescence excitation emission spectroscopy and laser-induced time-resolved fluorescence spectroscopy. Samples studied include varnishes prepared using shellac, and selected diterpenoid and triterpenoid resins from plants, and mixtures of these materials. Fluorescence excitation emission spectra have been collected from films of naturally aged varnishes. In parallel, time-resolved fluorescence spectroscopy of varnishes provides means for discriminating between short- (less than 2.0 ns) and long-lived (greater than 7.5 ns) fluorescence emissions in each of these complex materials. Results suggest that complementary use of the two non destructive techniques allows a better understanding of the main fluorophores responsible for the emission in shellac, and further provides means for distinguishing the main classes of other varnishes based on differences in fluorescence lifetime behaviour. Spectrofluorimetric data and time resolved spectra presented here may form the basis for the interpretation of results from future in situ fluorescence examination and time resolved fluorescence imaging of varnished musical instruments.

  10. In situ X-ray probing reveals fingerprints of surface platinum oxide.

    PubMed

    Friebel, Daniel; Miller, Daniel J; O'Grady, Christopher P; Anniyev, Toyli; Bargar, John; Bergmann, Uwe; Ogasawara, Hirohito; Wikfeldt, Kjartan Thor; Pettersson, Lars G M; Nilsson, Anders

    2011-01-07

    In situ X-ray absorption spectroscopy (XAS) at the Pt L(3) edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard X-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF code and complementary extended X-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

  11. In Situ X-Ray Probing Reveals Fingerprints of Surface Platinum Oxide

    SciTech Connect

    Friebel, Daniel

    2011-08-24

    In situ x-ray absorption spectroscopy (XAS) at the Pt L{sub 3} edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard x-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF8 code and complementary extended x-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

  12. Tribology. Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts.

    PubMed

    Gosvami, N N; Bares, J A; Mangolini, F; Konicek, A R; Yablon, D G; Carpick, R W

    2015-04-03

    Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation.

  13. Laser capture microdissection reveals dose-response of gene expression in situ consequent to asbestos exposure.

    PubMed

    Yin, Qi; Brody, Arnold R; Sullivan, Deborah E

    2007-12-01

    The genes that mediate fibroproliferative lung disease remain to be defined. Prior studies from our laboratory showed by in situ hybridization and immunohistochemistry that the genes coding for tumour necrosis factor alpha, transforming growth factor beta, the platelet-derived growth factor A and B isoforms, and alpha-1 pro-collagen are expressed in fibroproliferative lesions that develop quickly after asbestos inhalation. These five genes, along with matrix metalloproteinase 9, a collagenase found to be increased in several lung diseases, are known to control matrix production and cell proliferation in humans and animals. Here we show by laser capture microdissection that (i) The six genes are expressed at significantly higher levels in the asbestos-exposed mice when comparing the same anatomic regions 'captured' in unexposed mice. (ii) The bronchiolar-alveolar duct (BAD) junctions, where the greatest number of fibres initially deposit, were always significantly higher than the other anatomic regions for each gene. The first alveolar duct bifurcation (ADB) generally was higher than the second ADB, the ADBs were always significantly higher than the airway walls and pleura, and the airway walls and pleura were generally higher than the unexposed tissues. (iii) Animals exposed for 3 days always exhibited significantly higher levels of gene expression at the BAD junctions and ADBs than animals exposed for 2 days. To our knowledge, this is the first demonstration of a dose-response to a toxic particle in situ, and this response appears to be dependent on the number of fibres that deposits at the individual anatomic site.

  14. Laser capture microdissection reveals dose–response of gene expression in situ consequent to asbestos exposure

    PubMed Central

    Yin, Qi; Brody, Arnold R; Sullivan, Deborah E

    2007-01-01

    The genes that mediate fibroproliferative lung disease remain to be defined. Prior studies from our laboratory showed by in situ hybridization and immunohistochemistry that the genes coding for tumour necrosis factor alpha, transforming growth factor beta, the platelet-derived growth factor A and B isoforms, and alpha-1 pro-collagen are expressed in fibroproliferative lesions that develop quickly after asbestos inhalation. These five genes, along with matrix metalloproteinase 9, a collagenase found to be increased in several lung diseases, are known to control matrix production and cell proliferation in humans and animals. Here we show by laser capture microdissection that (i) The six genes are expressed at significantly higher levels in the asbestos-exposed mice when comparing the same anatomic regions ‘captured’ in unexposed mice. (ii) The bronchiolar-alveolar duct (BAD) junctions, where the greatest number of fibres initially deposit, were always significantly higher than the other anatomic regions for each gene. The first alveolar duct bifurcation (ADB) generally was higher than the second ADB, the ADBs were always significantly higher than the airway walls and pleura, and the airway walls and pleura were generally higher than the unexposed tissues. (iii) Animals exposed for 3 days always exhibited significantly higher levels of gene expression at the BAD junctions and ADBs than animals exposed for 2 days. To our knowledge, this is the first demonstration of a dose–response to a toxic particle in situ, and this response appears to be dependent on the number of fibres that deposits at the individual anatomic site. PMID:18039278

  15. In Situ Tagged nsp15 Reveals Interactions with Coronavirus Replication/Transcription Complex-Associated Proteins

    PubMed Central

    Athmer, Jeremiah; Fehr, Anthony R.; Grunewald, Matthew; Smith, Everett Clinton; Denison, Mark R.

    2017-01-01

    ABSTRACT Coronavirus (CoV) replication and transcription are carried out in close proximity to restructured endoplasmic reticulum (ER) membranes in replication/transcription complexes (RTC). Many of the CoV nonstructural proteins (nsps) are required for RTC function; however, not all of their functions are known. nsp15 contains an endoribonuclease domain that is conserved in the CoV family. While the enzymatic activity and crystal structure of nsp15 are well defined, its role in replication remains elusive. nsp15 localizes to sites of RNA replication, but whether it acts independently or requires additional interactions for its function remains unknown. To begin to address these questions, we created an in situ tagged form of nsp15 using the prototypic CoV, mouse hepatitis virus (MHV). In MHV, nsp15 contains the genomic RNA packaging signal (P/S), a 95-bp RNA stem-loop structure that is not required for viral replication or nsp15 function. Utilizing this knowledge, we constructed an internal hemagglutinin (HA) tag that replaced the P/S. We found that nsp15-HA was localized to discrete perinuclear puncta and strongly colocalized with nsp8 and nsp12, both well-defined members of the RTC, but not the membrane (M) protein, involved in virus assembly. Finally, we found that nsp15 interacted with RTC-associated proteins nsp8 and nsp12 during infection, and this interaction was RNA independent. From this, we conclude that nsp15 localizes and interacts with CoV proteins in the RTC, suggesting it plays a direct or indirect role in virus replication. Furthermore, the use of in situ epitope tags could be used to determine novel nsp-nsp interactions in coronaviruses. PMID:28143984

  16. European Flint Landraces Grown In Situ Reveal Adaptive Introgression from Modern Maize

    PubMed Central

    Bitocchi, Elena; Bellucci, Elisa; Rau, Domenico; Albertini, Emidio; Rodriguez, Monica; Veronesi, Fabio; Attene, Giovanna; Nanni, Laura

    2015-01-01

    We have investigated the role of selection in the determination of the detected levels of introgression from modern maize hybrid varieties into maize landraces still cultivated in situ in Italy. We exploited the availability of a historical collection of landraces undertaken before the introduction and widespread use of modern maize, to analyse genomic changes that have occurred in these maize landraces over 50 years of co-existence with hybrid varieties. We have combined a previously published SSR dataset (n=21) with an AFLP loci dataset (n=168) to provide higher resolution power and to obtain a more detailed picture. We show that selection pressures for adaptation have favoured new alleles introduced by migration from hybrids. This shows the potential for analysis of historical introgression even over this short period of 50 years, for an understanding of the evolution of the genome and for the identification of its functionally important regions. Moreover, this demonstrates that landraces grown in situ represent almost unique populations for use for such studies when the focus is on the domesticated plant. This is due to their adaptation, which has arisen from their dynamic evolution under a continuously changing agro-ecological environment, and their capture of new alleles from hybridisation. We have also identified loci for which selection has inhibited introgression from modern germplasm and has enhanced the distinction between landraces and modern maize. These loci indicate that selection acted in the past, during the formation of the flint and dent gene pools. In particular, the locus showing the strongest signals of selection is a Misfit transposable element. Finally, molecular characterisation of the same samples with two different molecular markers has allowed us to compare their performances. Although the genetic-diversity and population-structure analyses provide the same global qualitative pattern, which thus provides the same inferences, there are

  17. Electron-beam irradiation induced conductivity in ZnS nanowires as revealed by in situ transmission electron microscope

    NASA Astrophysics Data System (ADS)

    Liu, Baodan; Bando, Yoshio; Wang, Mingsheng; Zhi, Chunyi; Fang, Xiaosheng; Tang, Chengchun; Mitome, Masanori; Golberg, Dmitri

    2009-08-01

    Electron transport variations in individual ZnS nanowires synthesized through a chemical vapor deposition process were in situ studied in transmission electron microscope under convergent electron-beam irradiation (EBI). It was found that the transport can dramatically be enhanced using proper irradiation conditions. The conductivity mechanism was revealed based on a detailed study of microstructure and composition evolutions under irradiation. EBI-induced Zn-rich domains' appearance and related O doping were mainly responsible for the conductivity improvements. First-principles theoretical calculations additionally indicated that the generation of midbands within a ZnS band gap might also contribute to the improved conductivity.

  18. Attosecond Time-Resolved Autoionization of Argon

    SciTech Connect

    Wang He; Chini, Michael; Chen Shouyuan; Zhang Changhua; Cheng Yan; Wu Yi; Thumm, Uwe; He Feng; Chang Zenghu

    2010-10-01

    Autoionization of argon atoms was studied experimentally by transient absorption spectroscopy with isolated attosecond pulses. The peak position, intensity, linewidth, and shape of the 3s3p{sup 6}np {sup 1}P Fano resonance series (26.6-29.2 eV) were modified by intense few-cycle near infrared laser pulses, while the delay between the attosecond pulse and the laser pulse was changed by a few femtoseconds. Numerical simulations revealed that the experimentally observed splitting of the 3s3p{sup 6}4p {sup 1}P line is caused by the coupling between two short-lived highly excited states in the strong laser field.

  19. Gaia Reveals a Metal-rich, in situ Component of the Local Stellar Halo

    NASA Astrophysics Data System (ADS)

    Bonaca, Ana; Conroy, Charlie; Wetzel, Andrew; Hopkins, Philip F.; Kereš, Dušan

    2017-08-01

    We use the first Gaia data release, combined with the RAVE and APOGEE spectroscopic surveys, to investigate the origin of halo stars within ≲ 3 kpc from the Sun. We identify halo stars kinematically as moving at a relative speed of at least 220 km s-1 with respect to the local standard of rest. These stars are generally less metal-rich than the disk, but surprisingly, half of our halo sample is comprised of stars with [{Fe}/{{H}}]> -1. The orbital directions of these metal-rich halo stars are preferentially aligned with the disk rotation, in sharp contrast with the intrinsically isotropic orbital distribution of the metal-poor halo stars. We find similar properties in the Latte cosmological zoom-in simulation of a Milky Way-like galaxy from the FIRE project. In Latte, metal-rich halo stars formed primarily inside of the solar circle, whereas lower-metallicity halo stars preferentially formed at larger distances (extending beyond the virial radius). This suggests that metal-rich halo stars in the solar neighborhood actually formed in situ within the Galactic disk, rather than having been accreted from satellite systems. These stars, currently on halo-like orbits, therefore have likely undergone substantial radial migration/heating.

  20. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

    PubMed Central

    Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

    2016-01-01

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts. PMID:27514695

  1. Environmental controls of frost cracking revealed through in situ acoustic emission measurements in steep bedrock

    NASA Astrophysics Data System (ADS)

    Girard, Lucas; Gruber, Stephan; Weber, Samuel; Beutel, Jan

    2013-05-01

    Frost cracking, the breakdown of rock by freezing, is one of the most important mechanical weathering processes acting on Earth's surface. Insights on the mechanisms driving frost cracking stem mainly from laboratory and theoretical studies. Transferring insights from such studies to natural conditions, involving jointed bedrock and heterogeneous thermal and hydrological properties, is a major challenge. We address this problem with simultaneous in situ measurements of acoustic emissions, used as proxy of rock damage, and rock temperature/moisture content. The 1 year data set acquired in an Alpine rock wall shows that (1) liquid water content has an important impact on freezing-induced rock damage, (2) sustained freezing can yield much stronger damage than repeated freeze-thaw cycling, and (3) that frost cracking occurs over the full range of temperatures measured extending from 0 down to -15°C. These new measurements yield a slightly different picture than previous field studies where ice segregation appears to play an important role.

  2. In situ imaging reveals the biomass of giant protists in the global ocean.

    PubMed

    Biard, Tristan; Stemmann, Lars; Picheral, Marc; Mayot, Nicolas; Vandromme, Pieter; Hauss, Helena; Gorsky, Gabriel; Guidi, Lionel; Kiko, Rainer; Not, Fabrice

    2016-04-28

    Planktonic organisms play crucial roles in oceanic food webs and global biogeochemical cycles. Most of our knowledge about the ecological impact of large zooplankton stems from research on abundant and robust crustaceans, and in particular copepods. A number of the other organisms that comprise planktonic communities are fragile, and therefore hard to sample and quantify, meaning that their abundances and effects on oceanic ecosystems are poorly understood. Here, using data from a worldwide in situ imaging survey of plankton larger than 600 μm, we show that a substantial part of the biomass of this size fraction consists of giant protists belonging to the Rhizaria, a super-group of mostly fragile unicellular marine organisms that includes the taxa Phaeodaria and Radiolaria (for example, orders Collodaria and Acantharia). Globally, we estimate that rhizarians in the top 200 m of world oceans represent a standing stock of 0.089 Pg carbon, equivalent to 5.2% of the total oceanic biota carbon reservoir. In the vast oligotrophic intertropical open oceans, rhizarian biomass is estimated to be equivalent to that of all other mesozooplankton (plankton in the size range 0.2-20 mm). The photosymbiotic association of many rhizarians with microalgae may be an important factor in explaining their distribution. The previously overlooked importance of these giant protists across the widest ecosystem on the planet changes our understanding of marine planktonic ecosystems.

  3. Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Yi-Fan; Kooyman, Patricia J.; Koper, Marc T. M.

    2016-08-01

    Understanding the atomistic details of how platinum surfaces are oxidized under electrochemical conditions is of importance for many electrochemical devices such as fuel cells and electrolysers. Here we use in situ shell-isolated nanoparticle-enhanced Raman spectroscopy to identify the intermediate stages of the electrochemical oxidation of Pt(111) and Pt(100) single crystals in perchloric acid. Density functional theory calculations were carried out to assist in assigning the experimental Raman bands by simulating the vibrational frequencies of possible intermediates and products. The perchlorate anion is suggested to interact with hydroxyl phase formed on the surface. Peroxo-like and superoxo-like two-dimensional (2D) surface oxides and amorphous 3D α-PtO2 are sequentially formed during the anodic polarization. Our measurements elucidate the process of the electrochemical oxidation of platinum single crystals by providing evidence for the structure-sensitive formation of a 2D platinum-(su)peroxide phase. These results may contribute towards a fundamental understanding of the mechanism of degradation of platinum electrocatalysts.

  4. Proteome-wide analysis reveals an age-associated cellular phenotype of in situ aged human fibroblasts

    PubMed Central

    Waldera-Lupa, Daniel M.; Kalfalah, Faiza; Florea, Ana-Maria; Sass, Steffen; Kruse, Fabian; Rieder, Vera; Tigges, Julia; Fritsche, Ellen; Krutmann, Jean; Busch, Hauke; Boerries, Melanie; Meyer, Helmut E.; Boege, Fritz; Theis, Fabian

    2014-01-01

    We analyzed an ex vivo model of in situ aged human dermal fibroblasts, obtained from 15 adult healthy donors from three different age groups using an unbiased quantitative proteome-wide approach applying label-free mass spectrometry. Thereby, we identified 2409 proteins, including 43 proteins with an age-associated abundance change. Most of the differentially abundant proteins have not been described in the context of fibroblasts’ aging before, but the deduced biological processes confirmed known hallmarks of aging and led to a consistent picture of eight biological categories involved in fibroblast aging, namely proteostasis, cell cycle and proliferation, development and differentiation, cell death, cell organization and cytoskeleton, response to stress, cell communication and signal transduction, as well as RNA metabolism and translation. The exhaustive analysis of protein and mRNA data revealed that 77% of the age-associated proteins were not linked to expression changes of the corresponding transcripts. This is in line with an associated miRNA study and led us to the conclusion that most of the age-associated alterations detected at the proteome level are likely caused post-transcriptionally rather than by differential gene expression. In summary, our findings led to the characterization of novel proteins potentially associated with fibroblast aging and revealed that primary cultures of in situ aged fibroblasts are characterized by moderate age-related proteomic changes comprising the multifactorial process of aging. PMID:25411231

  5. Time Resolved Imaging of Longitudinal Modulations in Intense Beams

    NASA Astrophysics Data System (ADS)

    Tian, Kai

    2007-11-01

    The longitudinal evolution of high intensity beams is not well understood despite its importance to the success of such applications as free electron lasers and light sources, heavy ion inertial fusion, and high energy colliders. For example any amplification of current modulations in an FEL photoinjector can lead to unwanted coherent synchrotron radiation further downstream in compression chicanes or bends. A significant factor usually neglected is the coupling to the transverse dynamics which can strongly affect the longitudinal evolution. Previous experiments at the University of Maryland have revealed much about the longitudinal physics of space-charge dominated beams by monitoring the evolution of longitudinal perturbations. For the first time, experimental results are presented here which reveal the effect of longitudinal perturbations on the transverse beam distribution, with the aid of several new diagnostics that capture detailed time-resolved density images. A longitudinal modulation of the particle density is deliberately generated at the source, and its evolution is tracked downstream using a number of diagnostics such as current monitors, high-resolution energy analyzers, as well as the transverse imaging devices. The latter consist of a high-resolution 16-bit gated camera coupled with very fast emitters such as prompt optical transition radiation (OTR) from an alumina screen, or fast Phosphor screens with 3-ns time resolution. Simulations using the particle-in-cell code WARP are applied to cross-check the experimental results. These experiments and especially the comparisons to simulation represent significant progress towards understanding the longitudinal physics of intense beams.

  6. Interactions of arsenic with calcite surfaces revealed by in situ nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Renard, François; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jörn; Sarret, Géraldine

    2015-06-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in situ study of the evolution of the (10-14) calcite cleavage surface morphology during dissolution and growth in the presence of solutions with various amounts of As(III) or As(V) at room temperature and pH range 6-11 using a flow-through cell connected to an atomic force microscope (AFM). Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  7. Interactions of arsenic with calcite surfaces revealed by in-situ nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Renard, Francois; Putnis, Christine; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hövelmann, Jörn; Sarret, Géraldine

    2015-04-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in-situ study of calcite dissolution and growth in the presence of solutions with various amounts of As(III) or As(V). This was performed at room temperature and pH range 6-9 using a flow through cell connected to an atomic force microscope (AFM), to study the evolution of the (10-14) calcite cleavage surface morphology. Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  8. Hydration effects on gypsum dissolution revealed by in situ nanoscale atomic force microscopy observations

    NASA Astrophysics Data System (ADS)

    Burgos-Cara, A.; Putnis, C. V.; Rodriguez-Navarro, C.; Ruiz-Agudo, E.

    2016-04-01

    Recent work has suggested that the rates of mineral dissolution in aqueous solutions are dependent on the kinetics of dehydration of the ions building the crystal. Dehydration kinetics will be ultimately determined by the competition between ion-water and water-water interactions, which can be significantly modified by the presence of background ions in solution. At low ionic strength, the effect of electrolytes on ion-water (electrostatic) interactions will dominate (Kowacz et al., 2007). By performing macroscopic and in situ, microscopic (atomic force microscopy) dissolution experiments, the effect of background electrolytes on the dissolution kinetics of gypsum (CaSO4·2H2O) {0 1 0} cleavage surfaces is tested at constant, low ionic strength (IS = 0.05) and undersaturation (saturation index, SI = -0.045). Dissolution rates are systematically lower in the presence of 1:1 background electrolytes than in an electrolyte-free solution, regardless of the nature of the electrolyte tested. We hypothesize that stabilization of the hydration shell of calcium by the presence of background ions can explain this result, based on the observed correlations in dissolution rates with the ionic surface tension increment of the background ion in solution. Stabilization of the cation hydration shell should favor dissolution. However, in the case of strongly hydrated ions such as Ca2+, this has a direct entropic effect that reduces the overall ΔG of the system, so that dissolution is energetically less favorable. Overall, these results provide new evidence that supports cation dehydration being the rate-controlling step for gypsum dissolution, as proposed for other minerals such as barite, dolomite and calcite.

  9. In situ cardiac perfusion reveals interspecific variation of intraventricular flow separation in reptiles.

    PubMed

    Joyce, William; Axelsson, Michael; Altimiras, Jordi; Wang, Tobias

    2016-07-15

    The ventricles of non-crocodilian reptiles are incompletely divided and provide an opportunity for mixing of oxygen-poor blood and oxygen-rich blood (intracardiac shunting). However, both cardiac morphology and in vivo shunting patterns exhibit considerable interspecific variation within reptiles. In the present study, we develop an in situ double-perfused heart approach to characterise the propensity and capacity for shunting in five reptile species: the turtle Trachemys scripta, the rock python Python sebae, the yellow anaconda Eunectes notaeus, the varanid lizard Varanus exanthematicus and the bearded dragon Pogona vitticeps To simulate changes in vascular bed resistance, pulmonary and systemic afterloads were independently manipulated and changes in blood flow distribution amongst the central outflow tracts were monitored. As previously demonstrated in Burmese pythons, rock pythons and varanid lizards exhibited pronounced intraventricular flow separation. As pulmonary or systemic afterload was raised, flow in the respective circulation decreased. However, flow in the other circulation, where afterload was constant, remained stable. This correlates with the convergent evolution of intraventricular pressure separation and the large intraventricular muscular ridge, which compartmentalises the ventricle, in these species. Conversely, in the three other species, the pulmonary and systemic flows were strongly mutually dependent, such that the decrease in pulmonary flow in response to elevated pulmonary afterload resulted in redistribution of perfusate to the systemic circuit (and vice versa). Thus, in these species, the muscular ridge appeared labile and blood could readily transverse the intraventricular cava. We conclude that relatively minor structural differences between non-crocodilian reptiles result in the fundamental changes in cardiac function. Further, our study emphasises that functionally similar intracardiac flow separation evolved independently in

  10. Gene expression profiling of lobular carcinoma in situ reveals candidate precursor genes for invasion.

    PubMed

    Andrade, Victor P; Morrogh, Mary; Qin, Li-Xuan; Olvera, Narciso; Giri, Dilip; Muhsen, Shirin; Sakr, Rita A; Schizas, Michail; Ng, Charlotte K Y; Arroyo, Crispinita D; Brogi, Edi; Viale, Agnes; Morrow, Monica; Reis-Filho, Jorge S; King, Tari A

    2015-04-01

    Lobular carcinoma in situ (LCIS) is both a risk indicator and non-obligate precursor of invasive lobular carcinoma (ILC). We sought to characterize the transcriptomic features of LCIS and ILC, with a focus on the identification of intrinsic molecular subtypes of LCIS and the changes involved in the progression from normal breast epithelium to LCIS and ILC. Fresh-frozen classic LCIS, classic ILC, and normal breast epithelium (N) from women undergoing prophylactic or therapeutic mastectomy were prospectively collected, laser-capture microdissected, and subjected to gene expression profiling using Affymetrix HG-U133A 2.0 microarrays. Unsupervised hierarchical clustering of 40 LCIS samples identified 2 clusters of LCIS distinguished by 6431 probe sets (p < 0.001). Genes identifying the clusters included proliferation genes and other genes related to cancer canonical pathways such as TGF beta signaling, p53 signaling, actin cytoskeleton, apoptosis and Wnt-Signaling pathway. A supervised analysis to identify differentially expressed genes (p < 0.001) between normal epithelium, LCIS, and ILC, using 23 patient-matched triplets of N, LCIS, and ILC, identified 169 candidate precursor genes, which likely play a role in LCIS progression, including PIK3R1, GOLM1, and GPR137B. These potential precursor genes map significantly more frequently to 1q and 16q, regions frequently targeted by gene copy number alterations in LCIS and ILC. Here we demonstrate that classic LCIS is a heterogeneous disease at the transcriptomic level and identify potential precursor genes in lobular carcinogenesis. Understanding the molecular heterogeneity of LCIS and the potential role of these potential precursor genes may help personalize the therapy of patients with LCIS. Copyright © 2014 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  11. PREFACE: Time-resolved scanning tunnelling microscopy Time-resolved scanning tunnelling microscopy

    NASA Astrophysics Data System (ADS)

    Zandvliet, Harold J. W.; Lin, Nian

    2010-07-01

    out the potential landscape of the system (often a molecule or an atom) under study [4, 5]. However, the dynamical processes might also be induced by the tunnelling process itself [6, 7]. In the field of molecular science, excited single molecule experiments have been especially performed [8]. As a nice example, we refer to the work of Sykes' group [9] on thioether molecular rotors. In addition, several groups explore the possibility of combining time-resolved scanning tunnelling microscopy with optical techniques [10, 11]. Although the majority of studies that have been performed so far focus on rather simple systems under nearly ideal and well-defined conditions, we anticipate that time-resolved scanning tunnelling microscopy can also be applied in other research areas, such as biology and soft condensed matter, where the experimental conditions are often less ideal. We hope that readers will enjoy this collection of papers and that it will trigger them to further explore the possibilities of this simple, but powerful technique. References [1] Besenbacher F, Laegsgaard E and Stengaard I 2005 Mater. Today 8 26 [2] van Houselt A and Zandvliet H J W 2010 Rev. Mod. Phys. 82 1593 [3] Tringides M C and Hupalo M 2010 J. Phys.: Condens. Matter 22 264002 [4] Ronci F, Colonna S, Cricenti A and Le Lay G 2010 J. Phys.: Condens. Matter 22 264003 [5] van Houselt A, Poelsema B and Zandvliet H J W 2010 J. Phys.: Condens. Matter 22 264004 [6] Sprodowski C, Mehlhorn M and Morgenstern K 2010 J. Phys.: Condens. Matter 22 264005 [7] Saedi A, Poelsema B and Zandvliet H J W 2010 J. Phys.: Condens. Matter 22 264007 [8] Sloan P A 2010 J. Phys.: Condens. Matter 22 264001 [9] Jewell A D, Tierney H L, Baber A E, Iski E V, Laha M M and Sykes E C H 2010 J. Phys.: Condens. Matter 22 264006 [10] Riedel D 2010 J. Phys.: Condens. Matter 22 264009 [11] Terada Y, Yoshida S, Takeuchi O and Shigekawa H 2010 J. Phys.: Condens. Matter 22 264008

  12. Time resolved fluorescence of naproxen in organogel medium

    NASA Astrophysics Data System (ADS)

    Burguete, M. Isabel; Izquierdo, M. Angeles; Galindo, Francisco; Luis, Santiago V.

    2008-07-01

    The interaction between non-steroidal anti-inflammatory drug naproxen and the self assembled fibrillar network created by a low molecular weight organogelator has been probed by means of time resolved fluorescence spectroscopy.

  13. High-speed detector for time-resolved diffraction studies

    PubMed Central

    Singh, Bipin; Miller, Stuart R.; Bhandari, Harish B.; Graceffa, Rita; Irving, Thomas C.; Nagarkar, Vivek V.

    2013-01-01

    There are a growing number of high brightness synchrotron sources that require high-frame-rate detectors to provide the time-scales required for performing time-resolved diffraction experiments. We report on the development of a very high frame rate CMOS X-ray detector for time-resolved muscle diffraction and time-resolved solution scattering experiments. The detector is based on a low-afterglow scintillator, provides a megapixel resolution with frame rates of up to 120,000 frames per second, an effective pixel size of 64 µm, and can be adapted for various X-ray energies. The paper describes the detector design and initial results of time-resolved diffraction experiments on a synchrotron beamline. PMID:24489595

  14. The ULTRA Laser System—For Time-Resolved Spectroscopy

    NASA Astrophysics Data System (ADS)

    Parker, Anthony

    2010-08-01

    Time-resolved vibrational spectroscopy (TRVS) has many unique features and capabilities for elucidating the structural changes of transient species across the fs to ms time frame. The recently developed 10 KHz, 10W ULTRA laser system represents the very latest technology. ULTRA's performance and capabilities will be described for the time resolved infrared, 2D infrared and femtosecond stimulated Raman spectroscopy techniques with examples taken from organometallic intermediates, organic excited states and DNA tertiary structure.

  15. A versatile apparatus for time-resolved photoemission spectroscopy via femtosecond pump-probe experiments.

    PubMed

    Carpene, E; Mancini, E; Dallera, C; Ghiringhelli, G; Manzoni, C; Cerullo, G; De Silvestri, S

    2009-05-01

    A laser-based system for time-resolved photoemission spectroscopy using up to 6.2 eV photons is presented. The versatility of the laser source permits several combinations of pump and probe photon energies with pulse durations of 50-100 fs. The ultrahigh vacuum system, equipped with evaporators, a low energy electron diffraction system and an Auger spectrometer, grants the possibility to grow and characterize thin films in situ. The electron energy analyzer is a time-of-flight spectrometer with a multianode detector allowing high count rates. The performance of the whole experimental setup is investigated on Cu(100), Cu(111), and Ag(111) single crystals.

  16. Seventh international conference on time-resolved vibrational spectroscopy

    SciTech Connect

    Dyer, R.B.; Martinez, M.A.D.; Shreve, A.; Woodruff, W.H.

    1997-04-01

    The International Conference on Time-Resolved Vibrational Spectroscopy (TRVS) is widely recognized as the major international forum for the discussion of advances in this rapidly growing field. The 1995 conference was the seventh in a series that began at Lake Placid, New York, 1982. Santa Fe, New Mexico, was the site of the Seventh International Conference on Time-Resolved Vibrational Spectroscopy, held from June 11 to 16, 1995. TRVS-7 was attended by 157 participants from 16 countries and 85 institutions, and research ranging across the full breadth of the field of time-resolved vibrational spectroscopy was presented. Advances in both experimental capabilities for time-resolved vibrational measurements and in theoretical descriptions of time-resolved vibrational methods continue to occur, and several sessions of the conference were devoted to discussion of these advances and the associated new directions in TRVS. Continuing the interdisciplinary tradition of the TRVS meetings, applications of time-resolved vibrational methods to problems in physics, biology, materials science, and chemistry comprised a large portion of the papers presented at the conference.

  17. Time-resolved neutron imaging at ANTARES cold neutron beamline

    NASA Astrophysics Data System (ADS)

    Tremsin, A. S.; Dangendorf, V.; Tittelmeier, K.; Schillinger, B.; Schulz, M.; Lerche, M.; Feller, W. B.

    2015-07-01

    In non-destructive evaluation with X-rays light elements embedded in dense, heavy (or high-Z) matrices show little contrast and their structural details can hardly be revealed. Neutron radiography, on the other hand, provides a solution for those cases, in particular for hydrogenous materials, owing to the large neutron scattering cross section of hydrogen and uncorrelated dependency of neutron cross section on the atomic number. The majority of neutron imaging experiments at the present time is conducted with static objects mainly due to the limited flux intensity of neutron beamline facilities and sometimes due to the limitations of the detectors. However, some applications require the studies of dynamic phenomena and can now be conducted at several high intensity beamlines such as the recently rebuilt ANTARES beam line at the FRM-II reactor. In this paper we demonstrate the capabilities of time resolved imaging for repetitive processes, where different phases of the process can be imaged simultaneously and integrated over multiple cycles. A fast MCP/Timepix neutron counting detector was used to image the water distribution within a model steam engine operating at 10 Hz frequency. Within <10 minutes integration the amount of water was measured as a function of cycle time with a sub-mm spatial resolution, thereby demonstrating the capabilities of time-resolved neutron radiography for the future applications. The neutron spectrum of the ANTARES beamline as well as transmission spectra of a Fe sample were also measured with the Time Of Flight (TOF) technique in combination with a high resolution beam chopper. The energy resolution of our setup was found to be ~ 0.8% at 5 meV and ~ 1.7% at 25 meV. The background level (most likely gammas and epithermal/fast neutrons) of the ANTARES beamline was also measured in our experiments and found to be on the scale of 3% when no filters are installed in the beam. Online supplementary data available from stacks.iop.org/jinst/10

  18. In situ proteo-metabolomics reveals metabolite secretion by the acid mine drainage bio-indicator, Euglena mutabilis.

    PubMed

    Halter, David; Goulhen-Chollet, Florence; Gallien, Sébastien; Casiot, Corinne; Hamelin, Jérôme; Gilard, Françoise; Heintz, Dimitri; Schaeffer, Christine; Carapito, Christine; Van Dorsselaer, Alain; Tcherkez, Guillaume; Arsène-Ploetze, Florence; Bertin, Philippe N

    2012-07-01

    Euglena mutabilis is a photosynthetic protist found in acidic aquatic environments such as peat bogs, volcanic lakes and acid mine drainages (AMDs). Through its photosynthetic metabolism, this protist is supposed to have an important role in primary production in such oligotrophic ecosystems. Nevertheless, the exact contribution of E. mutabilis in organic matter synthesis remains unclear and no evidence of metabolite secretion by this protist has been established so far. Here we combined in situ proteo-metabolomic approaches to determine the nature of the metabolites accumulated by this protist or potentially secreted into an AMD. Our results revealed that the secreted metabolites are represented by a large number of amino acids, polyamine compounds, urea and some sugars but no fatty acids, suggesting a selective organic matter contribution in this ecosystem. Such a production may have a crucial impact on the bacterial community present on the study site, as it has been suggested previously that prokaryotes transport and recycle in situ most of the metabolites secreted by E. mutabilis. Consequently, this protist may have an indirect but important role in AMD ecosystems but also in other ecological niches often described as nitrogen-limited.

  19. In situ proteo-metabolomics reveals metabolite secretion by the acid mine drainage bio-indicator, Euglena mutabilis

    PubMed Central

    Halter, David; Goulhen-Chollet, Florence; Gallien, Sébastien; Casiot, Corinne; Hamelin, Jérôme; Gilard, Françoise; Heintz, Dimitri; Schaeffer, Christine; Carapito, Christine; Van Dorsselaer, Alain; Tcherkez, Guillaume; Arsène-Ploetze, Florence; Bertin, Philippe N

    2012-01-01

    Euglena mutabilis is a photosynthetic protist found in acidic aquatic environments such as peat bogs, volcanic lakes and acid mine drainages (AMDs). Through its photosynthetic metabolism, this protist is supposed to have an important role in primary production in such oligotrophic ecosystems. Nevertheless, the exact contribution of E. mutabilis in organic matter synthesis remains unclear and no evidence of metabolite secretion by this protist has been established so far. Here we combined in situ proteo-metabolomic approaches to determine the nature of the metabolites accumulated by this protist or potentially secreted into an AMD. Our results revealed that the secreted metabolites are represented by a large number of amino acids, polyamine compounds, urea and some sugars but no fatty acids, suggesting a selective organic matter contribution in this ecosystem. Such a production may have a crucial impact on the bacterial community present on the study site, as it has been suggested previously that prokaryotes transport and recycle in situ most of the metabolites secreted by E. mutabilis. Consequently, this protist may have an indirect but important role in AMD ecosystems but also in other ecological niches often described as nitrogen-limited. PMID:22237547

  20. Tumor invasion unit in gastric cancer revealed by QDs-based in situ molecular imaging and multispectral analysis.

    PubMed

    Hu, Wen-Qing; Fang, Min; Zhao, Hao-Liang; Yan, Shu-Guang; Yuan, Jing-Ping; Peng, Chun-Wei; Yang, Gui-Fang; Li, Yan; Li, Jian-Ding

    2014-04-01

    In tumor tissues, cancer cells, tumor infiltrating macrophages and tumor neo-vessels in close spatial vicinity with one another form tumor invasion unit, which is a biologically important tumor microenvironment of metastasis to facilitate cancer invasion and metastasis. Establishing an in situ molecular imaging technology to simultaneously reveal these three components is essential for the in-depth investigation of tumor invasion unit. In this report, we have developed a computer-aided algorithm by quantum dots (QDs)-based multiplexed molecular imaging technique for such purpose. A series of studies on gastric cancer tumor tissues demonstrated that the tumor invasion unit was correlated with major unfavorable pathological features and worse clinical outcomes, which illustrated the significantly negative impacts and predictive power of tumor invasion unit on patient overall survival. This study confirmed the technical advantages of QDs-based in situ and simultaneous molecular imaging of key cancer molecules to gain deeper insights into the biology of cancer invasion. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Electron-transfer acceleration investigated by time resolved infrared spectroscopy.

    PubMed

    Vlček, Antonín; Kvapilová, Hana; Towrie, Michael; Záliš, Stanislav

    2015-03-17

    Ultrafast electron transfer (ET) processes are important primary steps in natural and artificial photosynthesis, as well as in molecular electronic/photonic devices. In biological systems, ET often occurs surprisingly fast over long distances of several tens of angströms. Laser-pulse irradiation is conveniently used to generate strongly oxidizing (or reducing) excited states whose reactions are then studied by time-resolved spectroscopic techniques. While photoluminescence decay and UV-vis absorption supply precise kinetics data, time-resolved infrared absorption (TRIR) and Raman-based spectroscopies have the advantage of providing additional structural information and monitoring vibrational energy flows and dissipation, as well as medium relaxation, that accompany ultrafast ET. We will discuss three cases of photoinduced ET involving the Re(I)(CO)3(N,N) moiety (N,N = polypyridine) that occur much faster than would be expected from ET theories. [Re(4-N-methylpyridinium-pyridine)(CO)3(N,N)](2+) represents a case of excited-state picosecond ET between two different ligands that remains ultrafast even in slow-relaxing solvents, beating the adiabatic limit. This is caused by vibrational/solvational excitation of the precursor state and participation of high-frequency quantum modes in barrier crossing. The case of Re-tryptophan assemblies demonstrates that excited-state Trp → *Re(II) ET is accelerated from nanoseconds to picoseconds when the Re(I)(CO)3(N,N) chromophore is appended to a protein, close to a tryptophan residue. TRIR in combination with DFT calculations and structural studies reveals an interaction between the N,N ligand and the tryptophan indole. It results in partial electronic delocalization in the precursor excited state and likely contributes to the ultrafast ET rate. Long-lived vibrational/solvational excitation of the protein Re(I)(CO)3(N,N)···Trp moiety, documented by dynamic IR band shifts, could be another accelerating factor. The last

  2. Time-resolved neurite mechanics by thermal fluctuation assessments.

    PubMed

    Gárate, Fernanda; Betz, Timo; Pertusa, María; Bernal, Roberto

    2015-12-30

    In the absence of simple noninvasive measurements, the knowledge of temporal and spatial variations of axons mechanics remains scarce. By extending thermal fluctuation spectroscopy (TFS) to long protrusions, we determine the transverse amplitude thermal fluctuation spectra that allow direct and simultaneous access to three key mechanics parameters: axial tension, bending flexural rigidity and plasma membrane tension. To test our model, we use PC12 cell protrusions-a well-know biophysical model of axons-in order to simplify the biological system under scope. For instance, axial and plasma membrane tension are found in the range of nano Newton and tens of pico Newtons per micron respectively. Furthermore, our results shows that the TFS technique is capable to distinguish quasi-identical protrusions. Another advantage of our approach is the time resolved nature of the measurements. Indeed, in the case of long term experiments on PC12 protrusions, TFS has revealed large temporal, correlated variations of the protrusion mechanics, displaying extraordinary feedback control over the axial tension in order to maintain a constant tension value.

  3. Contrasting behavior of oxygen and iron isotopes in banded iron formation revealed by in situ analysis

    NASA Astrophysics Data System (ADS)

    Beard, B.; Li, W.; Kita, N.; Valley, J. W.; Johnson, C.

    2012-12-01

    Banded iron formations (BIFs) record a period of dramatic secular change in Earth's geologic history, when abundant aqueous Fe(II) was removed from Archean and Proterozoic oceans by oxidation. BIFs are characterized by co-existing of quartz and iron minerals, including oxides and carbonates, and alternating iron-rich and iron-poor layers range from m to in situ measurement of O and Fe isotope ratios in minerals in BIFs provide valuable information about the origin of BIFs, as well as diagenetic and metamorphic effects that were superimposed on primary layering. We analyzed O and Fe isotope compositions of magnetite and hematite in BIFs from the 2.5 Ga Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia. Oxygen isotope ratios were measured by Secondary Ion Mass Spectrometry (SIMS), and Fe isotope ratios were measured by femtosecond Laser ablation Multi-Collector ICP-MS (fs-LA-MC-ICP-MS), with spatial resolutions of 15 mm (O) and 30-50 mm (Fe), and external precisions (2s) of +0.7 ‰ for δ18O and +0.2 ‰ for δ56Fe, respectively. Analysis of δ18O in iron oxides by SIMS employed special tuning with a 3kV primary beam to minimize orientation effects (Huberty et al. 2010 ). For hematite, δ18O values range from -7.1 ‰ to -0.6 ‰, with the majority of data clustering around -4.5 ‰, and δ56Fe values range from -0.50 ‰ to +1.53‰. Magnetite has a δ18O range of -5.6 ‰ to +5.6 ‰ and a δ56Fe range of -0.76 ‰ to +1.33 ‰. Notably, magnetite shows significant O isotope heterogeneity at a mineral grain scale, and the highest δ18O values were commonly measured from Si-rich (1-3 wt% SiO2) magnetite overgrowths or magnetite grains that have a recrystallization texture. In contrast, lowest δ18O values were measured from magnetite that contains less than 1 wt% SiO2. Individual magnetite grains can have up to 6 ‰ variation in δ18O values between low-Si core and Si-rich overgrowth. Iron

  4. Identifying Fossil Biosignatures and Minerals in Mars Analog Materials Using Time-Resolved Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Shkolyar, S.; Farmer, J.; Alerstam, E.; Maruyama, Y.; Blacksberg, J.

    2013-12-01

    Mars sample return has been identified as a top priority in the planetary science decadal survey. A Mars sample selection and caching mission would be the likely first step in this endeavor. Such a mission would aim to select and prioritize for return to Earth aqueously formed geological samples present at a selected site on Mars, based upon their potential for biosignature capture and preservation. If evidence of past life exists and is found, it is likely to come via the identification of fossilized carbonaceous matter of biological origin (kerogen) found in the selected samples analyzed in laboratories after return to Earth. Raman spectroscopy is considered one of the primary techniques for analyzing materials in situ and selecting the most promising samples for Earth return. We have previously performed a pilot study to better understand the complexities of identifying kerogen using Raman spectroscopy. For the study, we examined a variety of Mars analog materials representing a broad range of mineral compositions and kerogen maturities. The study revealed that kerogen identification in many of the most promising lithologies is often impeded by background fluorescence that originates from long (>10 ns to ms) and short (<1 ns) lifetime fluorophores in both the mineral matrixes and preserved organic matter in the samples. This work explores the potential for time-gated Raman spectroscopy to enable clear kerogen and mineral identifications in such samples. The JPL time-resolved Raman system uses time gating to reduce background fluorescence. It uses a custom-built SPAD (single photon avalanche diode) detector, featuring a 1-ns time-gate, and electronically variable gate delay. Results for a range of fluorescent samples show that the JPL system reduces fluorescence, allowing the identification of both kerogen and mineral components more successfully than with conventional Raman systems. In some of the most challenging samples, the detection of organic matter is

  5. The asymmetrical structure of Golgi apparatus membranes revealed by in situ atomic force microscope.

    PubMed

    Xu, Haijiao; Su, Weiheng; Cai, Mingjun; Jiang, Junguang; Zeng, Xianlu; Wang, Hongda

    2013-01-01

    The Golgi apparatus has attracted intense attentions due to its fascinating morphology and vital role as the pivot of cellular secretory pathway since its discovery. However, its complex structure at the molecular level remains elusive due to limited approaches. In this study, the structure of Golgi apparatus, including the Golgi stack, cisternal structure, relevant tubules and vesicles, were directly visualized by high-resolution atomic force microscope. We imaged both sides of Golgi apparatus membranes and revealed that the outer leaflet of Golgi membranes is relatively smooth while the inner membrane leaflet is rough and covered by dense proteins. With the treatment of methyl-β-cyclodextrin and Triton X-100, we confirmed the existence of lipid rafts in Golgi apparatus membrane, which are mostly in the size of 20 nm -200 nm and appear irregular in shape. Our results may be of significance to reveal the structure-function relationship of the Golgi complex and pave the way for visualizing the endomembrane system in mammalian cells at the molecular level.

  6. The Asymmetrical Structure of Golgi Apparatus Membranes Revealed by In situ Atomic Force Microscope

    PubMed Central

    Xu, Haijiao; Su, Weiheng; Cai, Mingjun; Jiang, Junguang; Zeng, Xianlu; Wang, Hongda

    2013-01-01

    The Golgi apparatus has attracted intense attentions due to its fascinating morphology and vital role as the pivot of cellular secretory pathway since its discovery. However, its complex structure at the molecular level remains elusive due to limited approaches. In this study, the structure of Golgi apparatus, including the Golgi stack, cisternal structure, relevant tubules and vesicles, were directly visualized by high-resolution atomic force microscope. We imaged both sides of Golgi apparatus membranes and revealed that the outer leaflet of Golgi membranes is relatively smooth while the inner membrane leaflet is rough and covered by dense proteins. With the treatment of methyl-β-cyclodextrin and Triton X-100, we confirmed the existence of lipid rafts in Golgi apparatus membrane, which are mostly in the size of 20 nm –200 nm and appear irregular in shape. Our results may be of significance to reveal the structure-function relationship of the Golgi complex and pave the way for visualizing the endomembrane system in mammalian cells at the molecular level. PMID:23613878

  7. In-situ time resolved synchrotron powder diffraction studies of synthesis and chemical reactions

    SciTech Connect

    Norby, P.

    1995-09-01

    Equipment for time and temperature dependent powder diffraction has been developed, especially in order to be able to study hydrothermal syntheses of zeolites. The system is very versatile and has so far been used to study e.g. hydrothermal syntheses of zeolites and aluminophosphates, syntheses of layered phosphates, formation of Sorel cements, dehydration and phase transformations of zeolites, solid state synthesis of lanthanum manganites, ion exchange of zeolites using molten salt, and oxidation/reduction of lanthanum manganites at high temperatures. The sample is contained in quartz capillaries and is heated using a stream of hot air. External pressure can be applied allowing hydrothermal syntheses at temperatures up to 200 C to be performed. Controlled atmosphere is obtained by flowing gas or a mixture of gases through the capillary.

  8. Apoptotic DNA fragmentation can be revealed in situ: an ultrastructural approach.

    PubMed

    Burattini, Sabrina; Ferri, Paola; Battistelli, Michela; D'Emilio, Alessandra; Biagiotti, Laura; Sestili, Piero; Rocchi, Marco B L; Falcieri, Elisabetta

    2009-12-01

    A common pattern of apoptotic death is DNA cleavage, initially producing large fragments (50 kbp), followed by the production of nucleosomic/oligonucleosomic fragments. Nevertheless, apoptosis without DNA fragmentation, at least of the nucleosomic type, has been reported. To investigate the spatial relationship between DNA cleavage and chromatin condensation, we applied the TUNEL technique to the ultrastructural analysis of apoptotic cells. A modified method, utilizing a gold-conjugated antidigoxigenin antibody, was carried out on U937 versus Molt-4 cells, both exposed to UVB radiation or staurosporine treatment. Gold particle density in the different domains of apoptotic cells was evaluated by a four-way ANOVA test. Gold labelling was more strongly localised in condensed chromatin than in the diffuse chromatin. U937 cells, which evidenced in vitro oligonucleosomic fragmentation after both UVB and staurosporine treatments, revealed a significantly higher gold particle density, when compared with Molt-4, which did not show, on the other hand, oligonucleosomic cleavage even in the presence of < or = 50 kbp cleavage. Thus, a correlation between DNA fragment sizes and gold particle density appears. TUNEL applied to electron microscopy is an effective approach to study the relationship between apoptotic chromatin condensation and DNA cleavage. Both these events indeed appear in the apoptotic nucleus, but their reciprocal correlation is still greatly unknown. Microsc. Res. Tech. 2009. (c) 2009 Wiley-Liss, Inc.

  9. Variable chromatin structure revealed by in situ spatially correlated DNA cleavage mapping.

    PubMed

    Risca, Viviana I; Denny, Sarah K; Straight, Aaron F; Greenleaf, William J

    2017-01-12

    Chromatin structure at the length scale encompassing local nucleosome-nucleosome interactions is thought to play a crucial role in regulating transcription and access to DNA. However, this secondary structure of chromatin remains poorly understood compared with the primary structure of single nucleosomes or the tertiary structure of long-range looping interactions. Here we report the first genome-wide map of chromatin conformation in human cells at the 1-3 nucleosome (50-500 bp) scale, obtained using ionizing radiation-induced spatially correlated cleavage of DNA with sequencing (RICC-seq) to identify DNA-DNA contacts that are spatially proximal. Unbiased analysis of RICC-seq signal reveals regional enrichment of DNA fragments characteristic of alternating rather than adjacent nucleosome interactions in tri-nucleosome units, particularly in H3K9me3-marked heterochromatin. We infer differences in the likelihood of nucleosome-nucleosome contacts among open chromatin, H3K27me3-marked, and H3K9me3-marked repressed chromatin regions. After calibrating RICC-seq signal to three-dimensional distances, we show that compact two-start helical fibre structures with stacked alternating nucleosomes are consistent with RICC-seq fragmentation patterns from H3K9me3-marked chromatin, while non-compact structures and solenoid structures are consistent with open chromatin. Our data support a model of chromatin architecture in intact interphase nuclei consistent with variable longitudinal compaction of two-start helical fibres.

  10. Native architecture of the Chlamydomonas chloroplast revealed by in situ cryo-electron tomography

    PubMed Central

    Engel, Benjamin D; Schaffer, Miroslava; Kuhn Cuellar, Luis; Villa, Elizabeth; Plitzko, Jürgen M; Baumeister, Wolfgang

    2015-01-01

    Chloroplast function is orchestrated by the organelle's intricate architecture. By combining cryo-focused ion beam milling of vitreous Chlamydomonas cells with cryo-electron tomography, we acquired three-dimensional structures of the chloroplast in its native state within the cell. Chloroplast envelope inner membrane invaginations were frequently found in close association with thylakoid tips, and the tips of multiple thylakoid stacks converged at dynamic sites on the chloroplast envelope, implicating lipid transport in thylakoid biogenesis. Subtomogram averaging and nearest neighbor analysis revealed that RuBisCO complexes were hexagonally packed within the pyrenoid, with ∼15 nm between their centers. Thylakoid stacks and the pyrenoid were connected by cylindrical pyrenoid tubules, physically bridging the sites of light-dependent photosynthesis and light-independent carbon fixation. Multiple parallel minitubules were bundled within each pyrenoid tubule, possibly serving as conduits for the targeted one-dimensional diffusion of small molecules such as ATP and sugars between the chloroplast stroma and the pyrenoid matrix. DOI: http://dx.doi.org/10.7554/eLife.04889.001 PMID:25584625

  11. Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip

    NASA Astrophysics Data System (ADS)

    Navin, Chelliah V.; Krishna, Katla Sai; Theegala, Chandra S.; Kumar, Challa S. S. R.

    2016-03-01

    Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors.Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06752a

  12. Time-resolved crystallography and protein design: signalling photoreceptors and optogenetics.

    PubMed

    Moffat, Keith

    2014-07-17

    Time-resolved X-ray crystallography and solution scattering have been successfully conducted on proteins on time-scales down to around 100 ps, set by the duration of the hard X-ray pulses emitted by synchrotron sources. The advent of hard X-ray free-electron lasers (FELs), which emit extremely intense, very brief, coherent X-ray pulses, opens the exciting possibility of time-resolved experiments with femtosecond time resolution on macromolecular structure, in both single crystals and solution. The X-ray pulses emitted by an FEL differ greatly in many properties from those emitted by a synchrotron, in ways that at first glance make time-resolved measurements of X-ray scattering with the required accuracy extremely challenging. This opens up several questions which I consider in this brief overview. Are there likely to be chemically and biologically interesting structural changes to be revealed on the femtosecond time-scale? How shall time-resolved experiments best be designed and conducted to exploit the properties of FELs and overcome challenges that they pose? To date, fast time-resolved reactions have been initiated by a brief laser pulse, which obviously requires that the system under study be light-sensitive. Although this is true for proteins of the visual system and for signalling photoreceptors, it is not naturally the case for most interesting biological systems. To generate more biological targets for time-resolved study, can this limitation be overcome by optogenetic, chemical or other means? © 2014 The Author(s) Published by the Royal Society. All rights reserved.

  13. Protein-ligand interactions probed by time-resolved crystallography

    SciTech Connect

    Schmidt, M.; Ihee, H.; Pahl, R.; Srajer, V.

    2005-03-09

    Time-resolved (TR) crystallography is a unique method for determining the structures of intermediates in biomolecular reactions. The technique reached its mature stage with the development of the powerful third-generation synchrotron X-ray sources, and the advances in data processing and analysis of time-resolved Laue crystallographic data. A time resolution of 100 ps has been achieved and relatively small structural changes can be detected even from only partial reaction initiation. The remaining challenge facing the application of this technique to a broad range of biological systems is to find an efficient and rapid, system-specific method for the reaction initiation in the crystal. Other frontiers for the technique involve the continued improvement in time resolution and further advances in methods for determining intermediate structures and reaction mechanisms. The time-resolved technique, combined with trapping methods and computational approaches, holds the promise for a complete structure-based description of biomolecular reactions.

  14. A time-resolved image sensor for tubeless streak cameras

    NASA Astrophysics Data System (ADS)

    Yasutomi, Keita; Han, SangMan; Seo, Min-Woong; Takasawa, Taishi; Kagawa, Keiichiro; Kawahito, Shoji

    2014-03-01

    This paper presents a time-resolved CMOS image sensor with draining-only modulation (DOM) pixels for tube-less streak cameras. Although the conventional streak camera has high time resolution, the device requires high voltage and bulky system due to the structure with a vacuum tube. The proposed time-resolved imager with a simple optics realize a streak camera without any vacuum tubes. The proposed image sensor has DOM pixels, a delay-based pulse generator, and a readout circuitry. The delay-based pulse generator in combination with an in-pixel logic allows us to create and to provide a short gating clock to the pixel array. A prototype time-resolved CMOS image sensor with the proposed pixel is designed and implemented using 0.11um CMOS image sensor technology. The image array has 30(Vertical) x 128(Memory length) pixels with the pixel pitch of 22.4um. .

  15. Melting depths associated with Jack Hills zircons crystallization as revealed by in situ trace element measurements

    NASA Astrophysics Data System (ADS)

    Profeta, L.; Ducea, M. N.; Gehrels, G. E.

    2016-12-01

    The Jack Hills zircons hosted within the Narryer Gneiss Complex, Yilgarn craton have ages from 4.4 Ga up to Mesoarchean. These zircons crystallized from low temperature granitoid magmas (Harrison, 2009). Here, we use trace element measurements obtained simultaneously with U-Pb ages using LA-ICP-MS on 276 Jack Hills zircons in order to estimate the depth of melting. La/Yb are converted to whole rock equivalent values using newly determined REE -whole rock partition coefficients (Chapman et al., 2016). La/Yb are subsequently transformed into depth estimates using the correlation between whole rock La/Yb and crustal thickness put forward in Profeta et al. (2015) for modern arcs. Our data pertains to 4.2 to 3.2 Ga zircons, which are supplemented with previously published data on 4.4.-4.3 Ga zircons (Peck et al. 2001). Depth estimates are averaged over 100 Ma bins, revealing a remarkably constant trend throughout the investigated period with values around 50 ± 10 km. We interpret that these depths may not be the result of a thick continental crust, as is the case for modern arcs, but rather the existence of different melting conditions during the Hadean and Paleoarchean due to elevated thermal regimes within the mantle. The high La/Yb whole rock ratios (with computed values greater than 10) coupled with elevated mantle temperatures point towards granitoid generation from partial melting of hydrated basalts (e.g. Martin et al., 2014). [1] Harrison, T.M., Annu. Rev. Earth Planet. Sci. 37, 479-505 (2009). [2] Chapman, J. B. et al., Chem. Geol. 439, 59-70 (2016). doi: 10.1016/j.chemgeo.2016.06.014. [3] Profeta, L. et al., Sci. Rep. 5, 17786 (2015). doi: 10.1038/srep17786 [4] Peck, W. et al., Cosmochim. Acta 65, 4215-4229 (2001). doi: 10.1016/S0016-7037(01)00711-6 [5] Martin, H. et al. Lithos 198, 1-13 (2014). doi: 10.1016/j.lithos.2014.02.017

  16. Time-Resolved X-Ray Crystallography of Heme Proteins

    SciTech Connect

    Srajer, Vukica; Royer, Jr., William E.

    2008-04-29

    Heme proteins, with their natural photosensitivity, are excellent systems for the application of time-resolved crystallographic methods. Ligand dissociation can be readily initiated by a short laser pulse with global structural changes probed at the atomic level by X-rays in real time. Third-generation synchrotrons provide 100-ps X-ray pulses of sufficient intensity for monitoring very fast processes. Successful application of such time-resolved crystallographic experiments requires that the structural changes being monitored are compatible with the crystal lattice. These techniques have recently permitted observing for the first time allosteric transitions in real time for a cooperative dimeric hemoglobin.

  17. Time-resolved x-ray crystallography of heme proteins

    PubMed Central

    Royer, William E.

    2012-01-01

    Heme proteins, with their natural photosensitivity, are excellent systems for the application of time-resolved crystallographic methods. Ligand dissociation can be readily initiated by a short laser pulse with global structural changes probed at the atomic level by X-rays in real time. Third generation synchrotrons provide 100ps X-ray pulses of sufficient intensity for monitoring very fast processes. Successful application of such time-resolved crystallographic experiments requires that the structural changes being monitored are compatible with the crystal lattice. These techniques have permitted observing allosteric transitions in real time for a cooperative dimeric hemoglobin. PMID:18433638

  18. Time-resolved photon emission from layered turbid media

    NASA Astrophysics Data System (ADS)

    Hielscher, Andreas H.; Liu, Hanli; Chance, Britton; Tittel, Frank K.; Jacques, Steven L.

    1996-02-01

    We present numerical and experimental results of time-resolved emission profiles from various layered turbid media. Numerical solutions determined by time-resolved Monte Carlo simulations are compared with measurements on layered-tissue phantoms made from gelatin. In particular, we show that in certain cases the effects of the upper layers can be eliminated. As a practical example, these results are used to analyze in vivo measurements on the human head. This demonstrates the influence of skin, skull, and meninges on the determination of the blood oxygenation in the brain.

  19. Time-resolved photon emission from layered turbid media

    SciTech Connect

    Hielscher, A.H.; Liu, H.; Chance, B.; Tittel, F.K.; Jacques, S.L.

    1996-02-01

    We present numerical and experimental results of time-resolved emission profiles from various layered turbid media. Numerical solutions determined by time-resolved Monte Carlo simulations are compared with measurements on layered-tissue phantoms made from gelatin. In particular, we show that in certain cases the effects of the upper layers can be eliminated. As a practical example, these results are used to analyze {ital in} {ital vivo} measurements on the human head. This demonstrates the influence of skin, skull, and meninges on the determination of the blood oxygenation in the brain. {copyright} {ital 1996 Optical Society of America.}

  20. Mid-infrared time-resolved photoconduction in black phosphorus

    NASA Astrophysics Data System (ADS)

    Suess, Ryan J.; Leong, Edward; Garrett, Joseph L.; Zhou, Tong; Salem, Reza; Munday, Jeremy N.; Murphy, Thomas E.; Mittendorff, Martin

    2016-12-01

    Black phosphorus has attracted interest as a material for use in optoelectronic devices due to many favorable properties such as a high carrier mobility, field-effect, and a direct bandgap that can range from 0.3 eV in its bulk crystalline form to 1.7-2.0 eV for a single atomic layer. The low bandgap energy for multilayer black phosphorus consisting of more than approximately five atomic layers allows for direct transition photoabsorption that enables detection of light out to mid-infrared frequencies. In this work, we characterize the room temperature optical response of a black phosphorus photoconductive detector at wavelengths ranging from 1.56 to 3.75 μm. Pulsed autocorrelation measurements in the near-infrared regime reveal a strong, sub-linear photocurrent nonlinearity with a response time of 1 ns, indicating that gigahertz electrical bandwidth is feasible. Time resolved photoconduction measurements covering near- and mid-infrared frequencies show a fast 65 ps rise time, followed by a carrier relaxation with a time scale that matches the intrinsic limit determined by autocorrelation. The sublinear photoresponse is shown to be caused by a reduction in the carrier relaxation time as more energy is absorbed in the black phosphorus flake and is well described by a carrier recombination model that is nonlinear with excess carrier density. The device exhibits a measured noise-equivalent power of 530 pW Hz-1/2, which is the value expected for Johnson noise limited performance. The fast and sensitive room temperature photoresponse demonstrates that black phosphorus is a promising new material for mid-infrared optoelectronics.

  1. Revealing the surface and bulk regimes of isothermal graphene growth on Ni with in situ kinetic measurements and modeling

    SciTech Connect

    Puretzky, Alexander A; Merkulov, Igor A; Rouleau, Christopher M; Eres, Gyula; Geohegan, David B

    2014-01-01

    In situ optical diagnostics are used to reveal the isothermal nucleation and growth mechanisms of graphene on Ni across a wide temperature range (560 C < T < 840 C) by chemical vapor deposition from single, sub-second pulses of acetylene. An abrupt, two-orders of magnitude change in growth times (~ 100s to 1s) is revealed at T = 680 C. Below and above this temperature, similar sigmoidal kinetics are measured and attributed to autocatalytic growth reactions but by two different mechanisms, surface assembly and dissolution/precipitation, respectively. These data are used to develop a simple and general kinetic model for graphene growth that includes the nucleation phase and includes the effects of carbon solubility in metals, describes delayed nucleation, and allows the interpretation of the competition between surface and bulk growth modes. The sharp transition in growth kinetics at T = 680 C is explained by a change in defect site density required for nucleation due to a transition in the carbon-induced mobility of the Ni surface. The easily-implemented optical reflectivity diagnostics and the simple kinetic model described here allow a pathway to optimize the growth of graphene on metals with arbitrary carbon solubility.

  2. Sequential electrochemical unzipping of single-walled carbon nanotubes to graphene ribbons revealed by in situ Raman spectroscopy and imaging.

    PubMed

    John, Robin; Shinde, Dhanraj B; Liu, Lili; Ding, Feng; Xu, Zhiping; Vijayan, Cherianath; Pillai, Vijayamohanan K; Pradeep, Thalappil

    2014-01-28

    We report an in situ Raman spectroscopic and microscopic investigation of the electrochemical unzipping of single-walled carbon nanotubes (SWNTs). Observations of the radial breathing modes (RBMs) using Raman spectral mapping reveal that metallic SWNTs are opened up rapidly followed by gradual unzipping of semiconducting SWNTs. Consideration of the resonant Raman scattering theory suggests that two metallic SWNTs with chiralities (10, 4) and (12, 0) get unzipped first at a lower electrode potential (0.36 V) followed by the gradual unzipping of another two metallic tubes, (9, 3) and (10, 1), at a relatively higher potential (1.16 V). The semiconducting SWNTs with chiralities (11, 7) and (12, 5), however, get open up gradually at ±1.66 V. A rapid decrease followed by a subsequent gradual decrease in the metallicity of the SWNT ensemble as revealed from a remarkable variation of the peak width of the G band complies well with the variations of RBM. Cyclic voltammetry also gives direct evidence for unzipping in terms of improved capacitance after oxidation followed by more important removal of oxygen functionalities during the reduction step, as reflected in subtle changes of the morphology confirming the formation of graphene nanoribbons. The density functional-based tight binding calculations show additional dependence of chirality and diameter of nanotubes on the epoxide binding energies, which is in agreement with the Raman spectroscopic results and suggests a possible mechanism of unzipping determined by combined effects of the structural characteristics of SWNTs and applied field.

  3. Similarities and differences in the nuclear genome organization within Pooideae species revealed by comparative genomic in situ hybridization (GISH).

    PubMed

    Majka, Joanna; Majka, Maciej; Kwiatek, Michał; Wiśniewska, Halina

    2016-10-14

    In this paper, we highlight the affinity between the genomes of key representatives of the Pooideae subfamily, revealed at the chromosomal level by genomic in situ hybridization (GISH). The analyses were conducted using labeled probes from each species to hybridize with chromosomes of every species used in this study based on a "round robin" rule. As a result, the whole chromosomes or chromosome regions were distinguished or variable types of signals were visualized to prove the different levels of the relationships between genomes used in this study. We observed the unexpected lack of signals in secondary constrictions of rye (RR) chromosomes probed by triticale (AABBRR) genomic DNA. We have also identified unlabeled chromosome regions, which point to species-specific sequences connected with disparate pathways of chromosome differentiation. Our results revealed a conservative character of coding sequence of 35S rDNA among selected species of the genera Aegilops, Brachypodium, Festuca, Hordeum, Lolium, Secale, and Triticum. In summary, we showed strong relationships in genomic DNA sequences between species which have been previously reported to be phylogenetically distant.

  4. A Flow-through Reaction Cell that Couples Time-resolved X-ray Diffraction with Stable Isotope Analysis

    SciTech Connect

    Hanson, J.C.; Wall, A.J.; Heaney, P.J.; Mathur, R.; Post, J.E.; Eng, P.J.

    2011-04-01

    A non-metallic flow-through reaction cell is described, designed for in situ time-resolved X-ray diffraction coupled with stable isotope analysis. The experimental setup allows the correlation of Cu isotope fractionation with changes in crystal structure during copper sulfide dissolution. This flow-through cell can be applied to many classes of fluid-mineral reactions that involve dissolution or ion exchange.

  5. Time-Resolved Emission Spectroscopy of Field Reversed Configuration Thruster

    DTIC Science & Technology

    2016-08-31

    Field Reversed Configuration (FRC) thrusters are candidates for next generation high -powered electric propulsion (EP) • Advantages over competing...16468 Introduction • Field Reversed Configuration (FRC) thrusters are candidates for next generation high -powered electric propulsion (EP) • Advantages...Briefing Charts 3. DATES COVERED (From - To) 06 September 2016 - 01 November 2016 4. TITLE AND SUBTITLE Time-Resolved Emission Spectroscopy of Field

  6. Time-resolved imaging of cavitation effects during laser lithotripsy

    NASA Astrophysics Data System (ADS)

    Siano, Salvatore; Pini, Roberto; Salimbeni, Renzo; Vannini, Matteo

    1995-01-01

    We devised a diagnostic technique based on a pump-and-probe scheme that provided time- resolved imaging of photofragmentation effects during laser lithotripsy. The evolution of the cavitation bubble induced on kidney stone samples by underwater irradiation with a XeCl excimer laser is presented and analyzed.

  7. Fluorescent in situ hybridization (FISH) and high resolution karyotype analysis reveal a novel inversion duplication of 10q

    SciTech Connect

    Czarnecki, P.; Dyke, D.L. Van; Dowling, P.K.

    1994-09-01

    A white male born with dysmorphic features, including upslanting palpebral fissures, bilateral simian creases, posteriorly rotated ears, bitemporal narrowing, frontal bossing, camptodactyly and head circumference and weight less than the 5th percentile was found to have a de novo add(10)(q26.1). High resolution karyotype analysis revealed a novel chromosomal abnormality: 46,XY,inv dup(10)(q26.3-q25.1). Fluorescent in situ hybridization using a chromosome 10-specific painting probe (Oncor, Inc.) confirmed that the extra material was derived from chromosome 10. Duplication of 10q24 or 10q25 is associated with characteristic craniofacial malformations, minor malformations of the hands and feet, major malformations of the heart, skeleton, and kidneys and severe mental retardation. Our patient, currently 7 months old, has many of the skeletal and craniofacial manifestations of other patients, but is developmentally normal at this early age. This is the first FISH confirmation of a 10q duplication and demonstrates the utility of this technology in addition to karyotype analysis. Molecular studies to determine the parental origin and extent of the duplication are in progress, since the apparent lack of developmental delay was unexpected. Identification of the origin of duplicated material will help assist in genetic counseling by further delineating new genetic syndromes.

  8. Atomic-Scale Mechanism on Nucleation and Growth of Mo2C Nanoparticles Revealed by in Situ Transmission Electron Microscopy.

    PubMed

    Fei, Linfeng; Ng, Sheung Mei; Lu, Wei; Xu, Ming; Shu, Longlong; Zhang, Wei-Bing; Yong, Zehui; Sun, Tieyu; Lam, Chi Hang; Leung, Chi Wah; Mak, Chee Leung; Wang, Yu

    2016-12-14

    With a similar electronic structure as that of platinum, molybdenum carbide (Mo2C) holds significant potential as a high performance catalyst across many chemical reactions. Empirically, the precise control of particle size, shape, and surface nature during synthesis largely determines the catalytic performance of nanoparticles, giving rise to the need of clarifying the underlying growth characteristics in the nucleation and growth of Mo2C. However, the high-temperature annealing involved during the growth of carbides makes it difficult to directly observe and understand the nucleation and growth processes. Here, we report on the use of advanced in situ transmission electron microscopy with atomic resolution to reveal a three-stage mechanism during the growth of Mo2C nanoparticles over a wide temperature range: initial nucleation via a mechanism consistent with spinodal decomposition, subsequent particle coalescence and monomer attachment, and final surface faceting to well-defined particles with minimum surface energy. These microscopic observations made under a heating atmosphere offer new perspectives toward the design of carbide-based catalysts, as well as the tuning of their catalytic performances.

  9. In situ hybridization and sequence analysis reveal an association of Plasmodium spp. with mortalities in wild passerine birds in Austria.

    PubMed

    Dinhopl, Nora; Nedorost, Nora; Mostegl, Meike M; Weissenbacher-Lang, Christiane; Weissenböck, Herbert

    2015-04-01

    Native European passerine birds are frequently clinically inapparent carriers of haemosporidian parasites of the genus Plasmodium. Clinical disease and death are only exceptionally reported. In the present study, tissue samples of 233 wild passerine birds found dead in Eastern Austria were examined by in situ hybridization (ISH) and partial cytochrome B gene sequence analysis for the presence, abundance and taxonomic assignment of Plasmodium spp. In 34 cases (14.6%), ISH yielded a positive result with large numbers of developmental stages in different cell types of the spleen, liver, brain and lung. The abundance of the tissue stages, which was comparable to fatal cases of avian malaria in penguins, suggested a major contribution to the cause of death. Genetic analysis revealed infections with representatives of three different valid species of Plasmodium, Plasmodium elongatum, Plasmodium lutzi and Plasmodium vaughani. Genetically identical parasite lineages had been found in a previous study in penguins kept in the Vienna zoo, providing evidence for the role of wild birds as reservoir hosts. Further, this study provides evidence that several species of Plasmodium are able to abundantly proliferate in endemic wild birds ultimately resulting in mortalities.

  10. Germanium as a Sodium Ion Battery Material: In Situ TEM Reveals Fast Sodiation Kinetics with High Capacity

    SciTech Connect

    Lu, Xiaotang; Adkins, Emily R.; He, Yang; Zhong, Li; Luo, Langli; Mao, Scott X.; Wang, Chong M.; Korgel, Brian A.

    2016-01-29

    Amorphous germanium (a-Ge) nanowires have great potential for application as anodes in Na-ion batteries. However, the Na-Ge reaction is much less studied and understood compared with other metal alloy anodes. Here, in situ transmission electron microscopy (TEM) is used to study the sodiation/desodiation behavior of a-Ge nanowires. Unexpectedly, our experiments revealed that a-Ge nanowires can be charged at a very fast rate and the final sodiation product, with over 300% volume expansion, is close to Na3Ge instead of NaGe which was considered as the ultimate sodiation state that Ge could achieve. Porous structure was observed in desodiation and, in contrast to delithiation, Na extraction is more likely to create pores in the nanowires due to the much larger radius of the Na ion. This porous structure has demonstrated excellent robustness upon cycling: it could recover flawlessly from the giant pores that were created during experimentation. These results show that the potential of a-Ge for Na-ion battery applications may have been previously underestimated.

  11. Kinetic and Conformational Insights of Protein Adsorption onto Montmorillonite Revealed Using in Situ ATR-FTIR/2D-COS.

    PubMed

    Schmidt, Michael P; Martínez, Carmen Enid

    2016-08-09

    Protein adsorption onto clay minerals is a process with wide-ranging impacts on the environmental cycling of nutrients and contaminants. This process is influenced by kinetic and conformational factors that are often challenging to probe in situ. This study represents an in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic investigation of the adsorption of a model protein (bovine serum albumin (BSA)) onto a clay mineral (montmorillonite) at four concentrations (1.50, 3.75, 7.50, and 15.0 μM) under environmentally relevant conditions. At all concentrations probed, FTIR spectra show that BSA readily adsorbs onto montmorillonite. Adsorption kinetics follow an Elovich model, suggesting that primary limitations on adsorption rates are surface-related heterogeneous energetic restrictions associated with protein rearrangement and lateral protein-protein interaction. BSA adsorption onto montmorillonite fits the Langmuir model, yielding K = 5.97 × 10(5) M(-1). Deconvolution and curve fitting of the amide I band at the end of the adsorption process (∼120 min) shows a large extent of BSA unfolding upon adsorption at 1.50 μM, with extended chains and turns increasing at the expense of α-helices. At higher concentrations/surface coverages, BSA unfolding is less pronounced and a more compact structure is assumed. Two-dimensional correlation spectroscopic (2D-COS) analysis reveals three different pathways corresponding to adsorbed conformations. At 1.50 μM, adsorption increases extended chains, followed by a loss in α-helices and a subsequent increase in turns. At 3.75 μM, extended chains decrease and then aggregated strands increase and side chains decrease, followed by a decrease in turns. With 7.50 and 15.0 μM BSA, the loss of side-chain vibrations is followed by an increase in aggregated strands and a subsequent decrease in turns and extended chains. Overall, the BSA concentration and resultant surface coverage have a profound

  12. Elucidating low-frequency vibrational dynamics in calcite and water with time-resolved third-harmonic generation spectroscopy.

    PubMed

    Wang, Liang; Liu, Weimin; Fang, Chong

    2015-07-14

    Low-frequency vibrations are foundational for material properties including thermal conductivity and chemical reactivity. To resolve the intrinsic molecular conformational dynamics in condensed phase, we implement time-resolved third-harmonic generation (TRTHG) spectroscopy to unravel collective skeletal motions in calcite, water, and aqueous salt solution in situ. The lifetime of three Raman-active modes in polycrystalline calcite at 155, 282 and 703 cm(-1) is found to be ca. 1.6 ps, 1.3 ps and 250 fs, respectively. The lifetime difference is due to crystallographic defects and anharmonic effects. By incorporating a home-built wire-guided liquid jet, we apply TRTHG to investigate pure water and ZnCl2 aqueous solution, revealing ultrafast dynamics of water intermolecular stretching and librational bands below 500 cm(-1) and a characteristic 280 cm(-1) vibrational mode in the ZnCl4(H2O)2(2-) complex. TRTHG proves to be a compact and versatile technique that directly uses the 800 nm fundamental laser pulse output to capture ultrafast low-frequency vibrational motion snapshots in condensed-phase materials including the omnipresent water, which provides the important time dimension to spectral characterization of molecular structure-function relationships.

  13. Time-resolved spectroscopy of the pulsating CV GW Lib

    NASA Astrophysics Data System (ADS)

    van Spaandonk, L.; Steeghs, D.; Marsh, T. R.; Torres, M. A. P.

    2010-01-01

    We present time-resolved optical spectroscopy of the dwarf nova GW Librae during its rare 2007 April superoutburst and compare these with quiescent epochs. The data provide the first opportunity to track the evolution of the principal spectral features. In the early stages of the outburst, the optically thick disc dominates the optical and the line components show clear orbital radial velocity excursions. In the course of several weeks, optically thin regions become more prominent as strong emission lines replace the broad disc absorption. Post-outburst spectroscopy covering the I band illustrates the advantages of CaII relative to the commonly used Balmer lines when attempting to constrain binary parameters. Due to the lower ionization energy combined with smaller thermal and shear broadening of these lines, a sharp emission component is seen to be moving in between the accretion disc peaks in the CaII line. No such component is visible in the Balmer lines. We interpret this as an emission component originating on the hitherto unseen mass donor star. This emission component has a mean velocity of ~ -15 +/- 5 kms-1 which is associated with the systemic velocity γ, and a velocity semi-amplitude of Kem = 82.2 +/- 4.9 kms-1. Doppler tomography reveals an asymmetric accretion disc, with the S-wave mapping to a sharp spot in the tomogram with a velocity consistent to what is obtained with line profile fitting. A centre of symmetry analysis of the disc component suggests a very small value for the WD orbital velocity K1 as is also inferred from double Gaussian fits to the spectral lines. While our conservative dynamical limits place a hard upper limit on the binary mass ratio of q < 0.23, we favour a significantly lower value near q ~ 0.06. Pulsation modelling suggests a white dwarf mass ~1Msolar. This, paired with a low-mass donor, near the empirical sequence of an evolved cataclysmic variable close to the period bounce, appears to be consistent with all the

  14. Ultrafast time-resolved spectroscopy of xanthophylls at low temperature.

    PubMed

    Cong, Hong; Niedzwiedzki, Dariusz M; Gibson, George N; Frank, Harry A

    2008-03-20

    Many of the spectroscopic features and photophysical properties of xanthophylls and their role in energy transfer to chlorophyll can be accounted for on the basis of a three-state model. The characteristically strong visible absorption of xanthophylls is associated with a transition from the ground state S0 (1(1)Ag-) to the S2 (1(1)Bu+) excited state. The lowest lying singlet state denoted S1 (2(1)Ag-), is a state into which absorption from the ground state is symmetry forbidden. Ultrafast optical spectroscopic studies and quantum computations have suggested the presence of additional excited singlet states in the vicinity of S1 (2(1)Ag-) and S2 (1(1)Bu+). One of these is denoted S* and has been suggested in previous work to be associated with a twisted molecular conformation of the molecule in the S1 (2(1)Ag-) state. In this work, we present the results of a spectroscopic investigation of three major xanthophylls from higher plants: violaxanthin, lutein, and zeaxanthin. These molecules have systematically increasing extents of pi-electron conjugation from nine to eleven conjugated carbon-carbon double bonds. All-trans isomers of the molecules were purified by high-performance liquid chromatography (HPLC) and studied by steady-state and ultrafast time-resolved optical spectroscopy at 77 K. Analysis of the data using global fitting techniques has revealed the inherent spectral properties and ultrafast dynamics of the excited singlet states of each of the molecules. Five different global fitting models were tested, and it was found that the data are best explained using a kinetic model whereby photoexcitation results in the promotion of the molecule into the S2 (1(1)Bu+) state that subsequently undergoes decay to a vibrationally hot S1 (1(1)Ag-) state and with the exception of violaxanthin also to the S* state. The vibrationally hot S1 (1(1)Ag-) state then cools to a vibrationally relaxed S1 (2(1)Ag-) state in less than a picosecond. It was also found that a portion

  15. In situ monitoring of H and O stable isotopes in soil water reveals ecohydrologic dynamics in managed soil systems [Urban ecohydrologic dynamics revealed by in situ monitoring of H and O stable isotopes in soil water

    DOE PAGES

    Oerter, Erik J.; Bowen, Gabriel

    2017-04-12

    The water cycle in urban and hydrologically managed settings is subject to perturbations that are dynamic on small spatial and temporal scales; the effects of which may be especially profound in soils. We deploy a membrane inlet-based laser spectroscopy system in conjunction with soil moisture and temperature sensors to monitor soil water dynamics and H and O stable isotope ratios (δ2H and δ18O values) in a seasonally irrigated urban-landscaped garden soil over the course of 9 months between the cessation of irrigation in the autumn and the onset of irrigation through the summer. Here, we find that soil water δ2Hmore » and δ18O values predominately reflect seasonal precipitation and irrigation inputs. A comparison of total soil water by cryogenic extraction and mobile soil water measured by in situ water vapor probes reveals that initial infiltration events after long periods of soil drying (the autumn season in this case) emplace water into the soil matrix that is not easily replaced by, or mixed with, successive pulses of infiltrating soil water. Tree stem xylem water H and O stable isotope composition did not match that of available water sources. Our findings suggest that partitioning of soil water into mobile and immobile “pools” and resulting ecohydrologic separation may occur in engineered and hydrologically managed soils and not be limited to natural settings. Furthermore, the laser spectroscopy method detailed here has potential to yield insights in a variety of critical zone and vadose zone studies, potential that is heightened by the simplicity and portability of the system.« less

  16. Plasticity mechanisms in ultrafine grained freestanding aluminum thin films revealed by in-situ transmission electron microscopy nanomechanical testing

    SciTech Connect

    Idrissi, Hosni; Kobler, Aaron; Amin-Ahmadi, Behnam; Schryvers, Dominique; Coulombier, Michael; Pardoen, Thomas; Galceran, Montserrat; Godet, Stéphane; Kübel, Christian

    2014-03-10

    In-situ bright field transmission electron microscopy (TEM) nanomechanical tensile testing and in-situ automated crystallographic orientation mapping in TEM were combined to unravel the elementary mechanisms controlling the plasticity of ultrafine grained Aluminum freestanding thin films. The characterizations demonstrate that deformation proceeds with a transition from grain rotation to intragranular dislocation glide and starvation plasticity mechanism at about 1% deformation. The grain rotation is not affected by the character of the grain boundaries. No grain growth or twinning is detected.

  17. Time-Resolved Rayleigh Scattering Measurements in Hot Gas Flows

    NASA Technical Reports Server (NTRS)

    Mielke, Amy F.; Elam, Kristie A.; Sung, Chih-Jen

    2008-01-01

    A molecular Rayleigh scattering technique is developed to measure time-resolved gas velocity, temperature, and density in unseeded gas flows at sampling rates up to 32 kHz. A high power continuous-wave laser beam is focused at a point in an air flow field and Rayleigh scattered light is collected and fiber-optically transmitted to the spectral analysis and detection equipment. The spectrum of the light, which contains information about the temperature and velocity of the flow, is analyzed using a Fabry-Perot interferometer. Photomultipler tubes operated in the photon counting mode allow high frequency sampling of the circular interference pattern to provide time-resolved flow property measurements. Mean and rms velocity and temperature fluctuation measurements in both an electrically-heated jet facility with a 10-mm diameter nozzle and also in a hydrogen-combustor heated jet facility with a 50.8-mm diameter nozzle at NASA Glenn Research Center are presented.

  18. Benchtop time-resolved magneto-optical Kerr magnetometer.

    PubMed

    Barman, Anjan; Kimura, T; Otani, Y; Fukuma, Y; Akahane, K; Meguro, S

    2008-12-01

    We present here the construction and application of a compact benchtop time-resolved Kerr magnetometer to measure the magnetization precession in magnetic thin films and lithographically patterned elements. As opposed to very expensive femtosecond lasers this system is built upon a picosecond pulsed injection diode laser and electronic pulse and delay generators. The precession is triggered by the electronic pulses of controlled duration and shape, which is launched onto the sample by a microstrip line. We used polarized optical pulses synchronous to the electronic pulses to measure the magneto-optical Kerr rotation. The system is integrated in a conventional upright microscope configuration with separate illumination, imaging, and magneto-optical probe paths. The system offers high stability, relative ease of alignment, sample changing, and a long range of time delay. We demonstrate the measurements of time-resolved dynamics of a Permalloy microwire and microdot using this system, which showed dynamics at two different time scales.

  19. Time-resolved single dopant charge dynamics in silicon

    NASA Astrophysics Data System (ADS)

    Rashidi, Mohammad; Burgess, Jacob A. J.; Taucer, Marco; Achal, Roshan; Pitters, Jason L.; Loth, Sebastian; Wolkow, Robert A.

    2016-10-01

    As the ultimate miniaturization of semiconductor devices approaches, it is imperative that the effects of single dopants be clarified. Beyond providing insight into functions and limitations of conventional devices, such information enables identification of new device concepts. Investigating single dopants requires sub-nanometre spatial resolution, making scanning tunnelling microscopy an ideal tool. However, dopant dynamics involve processes occurring at nanosecond timescales, posing a significant challenge to experiment. Here we use time-resolved scanning tunnelling microscopy and spectroscopy to probe and study transport through a dangling bond on silicon before the system relaxes or adjusts to accommodate an applied electric field. Atomically resolved, electronic pump-probe scanning tunnelling microscopy permits unprecedented, quantitative measurement of time-resolved single dopant ionization dynamics. Tunnelling through the surface dangling bond makes measurement of a signal that would otherwise be too weak to detect feasible. Distinct ionization and neutralization rates of a single dopant are measured and the physical process controlling those are identified.

  20. The RATIO method for time-resolved Laue crystallography

    PubMed Central

    Coppens, Philip; Pitak, Mateusz; Gembicky, Milan; Messerschmidt, Marc; Scheins, Stephan; Benedict, Jason; Adachi, Shin-ichi; Sato, Tokushi; Nozawa, Shunsuke; Ichiyanagi, Kohei; Chollet, Matthieu; Koshihara, Shin-ya

    2009-01-01

    A RATIO method for analysis of intensity changes in time-resolved pump–probe Laue diffraction experiments is described. The method eliminates the need for scaling the data with a wavelength curve representing the spectral distribution of the source and removes the effect of possible anisotropic absorption. It does not require relative scaling of series of frames and removes errors due to all but very short term fluctuations in the synchrotron beam. PMID:19240334

  1. Ultrafast Time-Resolved Electron Diffraction with Megavolt Electron Beams

    SciTech Connect

    Hastings, J.B.; Rudakov, F.M.; Dowell, D.H.; Schmerge, J.F.; Cardoza, J.D.; Castro, J.M.; Gierman, S.M.; Loos, H.; Weber, P.M.; /Brown U.

    2006-10-24

    An rf photocathode electron gun is used as an electron source for ultrafast time-resolved pump-probe electron diffraction. We observed single-shot diffraction patterns from a 160 nm Al foil using the 5.4 MeV electron beam from the Gun Test Facility at the Stanford Linear Accelerator. Excellent agreement with simulations suggests that single-shot diffraction experiments with a time resolution approaching 100 fs are possible.

  2. Time-resolved studies of a rolled-up semiconductor microtube laser

    NASA Astrophysics Data System (ADS)

    Strelow, Ch.; Sauer, M.; Fehringer, S.; Korn, T.; Schüller, C.; Stemmann, A.; Heyn, Ch.; Heitmann, D.; Kipp, T.

    2009-11-01

    We report on lasing in rolled-up microtube resonators. Time-resolved studies on these semiconductor lasers containing GaAs quantum wells as optical gain material reveal particularly fast turn-on times and short pulse emissions above the threshold. We observe a strong redshift of the laser mode during the pulse emission which is compared to the time evolution of the charge-carrier density calculated by rate equations.

  3. Detection of colorectal cancer using time-resolved autofluorescence spectrometer

    NASA Astrophysics Data System (ADS)

    Fu, Sheng; Kwek, Leong-Chuan; Chia, Teck-Chee; Lim, Chu-Sing; Tang, Choong-Leong; Ang, Wuan-Suan; Zhou, Miao-Chang; Loke, Po-Ling

    2006-04-01

    As we know Quantum mechanics is a mathematical theory that can describe the behavior of objects that are at microscopic level. Time-resolved autofluorescence spectrometer monitors events that occur during the lifetime of the excited state. This time ranges from a few picoseconds to hundreds of nanoseconds. That is an extremely important advance as it allows environmental parameters to be monitored in a spatially defined manner in the specimen under study. This technique is based on the application of Quantum Mechanics. This principle is applied in our project as we are trying to use different fluorescence spectra to detect biological molecules commonly found in cancerous colorectal tissue and thereby differentiate the cancerous and non-cancerous colorectal polyps more accurately and specifically. In this paper, we use Fluorescence Lifetime Spectrometer (Edinburgh Instruments FL920) to measure decay time of autofluorescence of colorectal cancerous and normal tissue sample. All specimens are from Department of Colorectal Surgery, Singapore General Hospital. The tissues are placed in the time-resolved autofluorescence instrument, which records and calculates the decay time of the autofluorescence in the tissue sample at the excitation and emission wavelengths pre-determined from a conventional spectrometer. By studying the decay time,τ, etc. for cancerous and normal tissue, we aim to present time-resolved autofluorescence as a feasible technique for earlier detection of malignant colorectal tissues. By using this concept, we try to contribute an algorithm even an application tool for real time early diagnosis of colorectal cancer for clinical services.

  4. Nanoscale diffusion in the synaptic cleft and beyond measured with time-resolved fluorescence anisotropy imaging

    PubMed Central

    Zheng, Kaiyu; Jensen, Thomas P.; Savtchenko, Leonid P.; Levitt, James A.; Suhling, Klaus; Rusakov, Dmitri A.

    2017-01-01

    Neural activity relies on molecular diffusion within nanoscopic spaces outside and inside nerve cells, such as synaptic clefts or dendritic spines. Measuring diffusion on this small scale in situ has not hitherto been possible, yet this knowledge is critical for understanding the dynamics of molecular events and electric currents that shape physiological signals throughout the brain. Here we advance time-resolved fluorescence anisotropy imaging combined with two-photon excitation microscopy to map nanoscale diffusivity in ex vivo brain slices. We find that in the brain interstitial gaps small molecules move on average ~30% slower than in a free medium whereas inside neuronal dendrites this retardation is ~70%. In the synaptic cleft free nanodiffusion is decelerated by ~46%. These quantities provide previously unattainable basic constrains for the receptor actions of released neurotransmitters, the electrical conductance of the brain interstitial space and the limiting rate of molecular interactions or conformational changes in the synaptic microenvironment. PMID:28181535

  5. Thin film growth studies using time-resolved x-ray scattering

    NASA Astrophysics Data System (ADS)

    Kowarik, Stefan

    2017-02-01

    Thin-film growth is important for novel functional materials and new generations of devices. The non-equilibrium growth physics involved is very challenging, because the energy landscape for atomic scale processes is determined by many parameters, such as the diffusion and Ehrlich-Schwoebel barriers. We review the in situ real-time techniques of x-ray diffraction (XRD), x-ray growth oscillations and diffuse x-ray scattering (GISAXS) for the determination of structure and morphology on length scales from Å to µm. We give examples of time resolved growth experiments mainly from molecular thin film growth, but also highlight growth of inorganic materials using molecular beam epitaxy (MBE) and electrochemical deposition from liquids. We discuss how scaling parameters of rate equation models and fundamental energy barriers in kinetic Monte Carlo methods can be determined from fits of the real-time x-ray data.

  6. Space and time-resolved probing of heterogeneous catalysis reactions using lab-on-a-chip.

    PubMed

    Navin, Chelliah V; Krishna, Katla Sai; Theegala, Chandra S; Kumar, Challa S S R

    2016-03-14

    Probing catalytic reactions on a catalyst surface in real time is a major challenge. Herein, we demonstrate the utility of a continuous flow millifluidic chip reactor coated with a nanostructured gold catalyst as an effective platform for in situ investigation of the kinetics of catalytic reactions by taking 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) conversion as a model reaction. The idea conceptualized in this paper can not only dramatically change the ability to probe the time-resolved kinetics of heterogeneous catalysis reactions but also used for investigating other chemical and biological catalytic processes, thereby making this a broad platform for probing reactions as they occur within continuous flow reactors.

  7. Time-resolved WAXD studies on the crystallization of semicrystalline/graphene nanocomposites

    NASA Astrophysics Data System (ADS)

    Endoh, Maya; Nishitsuji, Shotaro; Koga, Tad; Rafailovich, Mirian

    Graphene is one layer of carbon atoms, which has good electronic, thermal conductivity, and mechanical properties. By adding graphene to semicrystalline polymers such as polyethylene (PE) and isotactic polypropylene (iPP), the mechanical and electrical properties of the polymers are significantly improved. To further achieve high performance of semicrystalline polymer/graphene nanocomposites, it is important to investigate the relationship between the crystalline structure of the polymer and the mechanical property of the nanocomposites. In this study, the effect of graphene on the crystallization behavior of PE and iPP was investigated by using time-resolved wide angle X-ray diffraction (WAXD). The in situ WAXD results on the melt-crystallization process showed that the crystalline structures of all the samples remained the same as the pure bulk, while both the rate and degree of the crystallinity increased. We will discuss the detailed structure information along with DSC and mechanical test results.

  8. Relationship between time-resolved and non-time-resolved Beer-Lambert law in turbid media.

    PubMed

    Nomura, Y; Hazeki, O; Tamura, M

    1997-06-01

    The time-resolved Beer-Lambert law proposed for oxygen monitoring using pulsed light was extended to the non-time-resolved case in a scattered medium such as living tissues with continuous illumination. The time-resolved Beer-Lambert law was valid for the phantom model and living tissues in the visible and near-infrared regions. The absolute concentration and oxygen saturation of haemoglobin in rat brain and thigh muscle could be determined. The temporal profile of rat brain was reproduced by Monte Carlo simulation. When the temporal profiles of rat brain under different oxygenation states were integrated with time, the absorbance difference was linearly related to changes in the absorption coefficient. When the simulated profiles were integrated, there was a linear relationship within the absorption coefficient which was predicted for fractional inspiratory oxygen concentration from 10 to 100% and, in the case beyond the range of the absorption coefficient, the deviation from linearity was slight. We concluded that an optical pathlength which is independent of changes in the absorption coefficient is a good approximation for near-infrared oxygen monitoring.

  9. Watching a protein as it functions with 150-ps time-resolved x-ray crystallography.

    PubMed

    Schotte, Friedrich; Lim, Manho; Jackson, Timothy A; Smirnov, Aleksandr V; Soman, Jayashree; Olson, John S; Phillips, George N; Wulff, Michael; Anfinrud, Philip A

    2003-06-20

    We report picosecond time-resolved x-ray diffraction from the myoglobin (Mb) mutant in which Leu29 is replaced by Phe (L29Fmutant). The frame-by-frame structural evolution, resolved to 1.8 angstroms, allows one to literally "watch" the protein as it executes its function. Time-resolved mid-infrared spectroscopy of flash-photolyzed L29F MbCO revealed a short-lived CO intermediate whose 140-ps lifetime is shorter than that found in wild-type protein by a factor of 1000. The electron density maps of the protein unveil transient conformational changes far more dramatic than the structural differences between the carboxy and deoxy states and depict the correlated side-chain motion responsible for rapidly sweeping CO away from its primary docking site.

  10. Ultrafast Dynamics of a Charge Density Wave via Time-Resolved Resonant Diffraction

    NASA Astrophysics Data System (ADS)

    Moore, R. G.

    2012-02-01

    Understanding the emergence of collective behavior in correlated electron systems remains at the forefront of modern condensed matter physics. The key to such an understanding is unraveling the contributions from the coupling degrees of freedom in exotic many body states. Density waves, both of charge and spin, have been studied for decades and a wealth of information and insight has been gained. However, there are still open questions that need to be solved for a complete description of the phenomena as there are several existing density wave systems that exhibit prototypical behavior while violating traditional theory. Ultrafast dynamics of such a system, TbTe3, has been investigated via time-resolved resonant diffraction at the SXR endstation at LCLS. Oscillations of the amplitude mode and coherent phonons have been observed previously in time resolved photoemission and reflectivity measurement but, here we reveal a direct observation of the lattice response via resonant diffraction. Watching dynamics of the two dimensional Te plane density wave diffraction peak at a resonant energy of a bystander Tb atom reveals new insights into the coupling responsible for the formation of the state. Results and comparison with previous time resolved measurements will be discussed.

  11. Lucas-Kanade fluid trajectories for time-resolved PIV

    NASA Astrophysics Data System (ADS)

    Yegavian, Robin; Leclaire, Benjamin; Champagnat, Frédéric; Illoul, Cédric; Losfeld, Gilles

    2016-08-01

    We introduce a new method for estimating fluid trajectories in time-resolved PIV. It relies on a Lucas-Kanade paradigm and consists in a simple and direct extension of a two-frame estimation with FOLKI-PIV (Champagnat et al 2011 Exp. Fluids 50 1169-82). The so-called Lucas-Kanade Fluid Trajectories (LKFT) are assumed to be polynomial in time, and are found as the minimizer of a global functional, in which displacements are sought so as to match the intensities of a series of images pairs in the sequence, in the least-squares sense. All pairs involve the central image, similar to other recent time-resolved approaches (FTC (Lynch and Scarano 2013 Meas. Sci. Technol. 24 035305) and FTEE (Jeon et al 2014 Exp. Fluids 55 1-16)). As switching from a two-frame to a time-resolved objective simply amounts to adding terms in a functional, no significant additional algorithmic element is required. Similar to FOLKI-PIV the method is very well suited for GPU acceleration, which is an important feature as computational complexity increases with the image sequence size. Tests on synthetic data exhibiting peak-locking show that increasing the image sequence size strongly reduces both associated bias and random error, and that LKFT has a remaining total error comparable to that of FTEE on this case. Results on case B of the third PIV challenge (Stanislas et al 2008 Exp. Fluids 45 27-71) also show its ability to drastically reduce the error in situations with low signal-to-noise ratio. These results are finally confirmed on experimental images acquired in the near-field of a low Reynolds number jet. Strong reductions in peak-locking, spatial and temporal noise compared to two-frame estimation are also observed, on the displacement components themselves, as well as on spatial or temporal derivatives, such as vorticity and material acceleration.

  12. Time resolved spectral behavior of bright BATSE precursors

    NASA Astrophysics Data System (ADS)

    Burlon, D.; Ghirlanda, G.; Ghisellini, G.; Greiner, J.; Celotti, A.

    2009-10-01

    Aims: Gamma ray bursts (GRBs) are sometimes preceded by dimmer emission episodes, called “precursors”, whose nature is still a puzzle: they could either have the same origin as the main emission episode or they could be due to another mechanism. We investigate if precursors have some spectral distinctive feature with respect to the main GRB episodes. Methods: To this aim we compare the spectral evolution of the precursor with that of the main GRB event. We also study if and how the spectral parameters, and in particular the peak of the ν Fν spectrum of time resolved spectra, correlates with the flux. This allows us to test if the spectra of the precursor and of the main event belong to the same correlation (if any). We searched GRBs with precursor activity in the complete sample of 2704 bursts detected by BATSE finding that 12% of GRBs have one or more precursors. Among these we considered the bursts with time resolved spectral analysis performed by Kaneko et al. ( 2006, ApJS, 166, 298), selecting those having at least two time resolved spectra for the precursor. Results: We find that precursors and main events have very similar spectral properties. The spectral evolution within precursors has similar trends as the spectral evolution observed in the subsequent peaks. Also the typical spectral parameters of the precursors are similar to those of the main GRB events. Moreover, in several cases we find that within the precursors the peak energy of the spectrum is correlated with the flux similarly to what happens in the main GRB event. This strongly favors models in which the precursor is due to the same fireball physics of the main emission episodes. Figures 8 to 41 are only available in electronic form at http://www.aanda.org

  13. Time-resolved resonance Raman spectroscopy: exploring reactive intermediates.

    PubMed

    Sahoo, Sangram Keshari; Umapathy, Siva; Parker, Anthony W

    2011-10-01

    The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single "do-it-all" technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-μs) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy. © 2011 Society for Applied Spectroscopy

  14. Time-resolved fluorescence decay measurements for flowing particles

    DOEpatents

    Deka, C.; Steinkamp, J.A.

    1999-06-01

    Time-resolved fluorescence decay measurements are disclosed for flowing particles. An apparatus and method for the measurement and analysis of fluorescence for individual cells and particles in flow are described, wherein the rapid measurement capabilities of flow cytometry and the robust measurement and analysis procedures of time-domain fluorescence lifetime spectroscopy are combined. A pulse-modulated CW laser is employed for excitation of the particles. The characteristics and the repetition rate of the excitation pulses can be readily adjusted to accommodate for fluorescence decays having a wide range of lifetimes. 12 figs.

  15. Time-resolved fluorescence decay measurements for flowing particles

    DOEpatents

    Deka, Chiranjit; Steinkamp, John A.

    1999-01-01

    Time-resolved fluorescence decay measurements for flowing particles. An apparatus and method for the measurement and analysis of fluorescence for individual cells and particles in flow are described, wherein the rapid measurement capabilities of flow cytometry and the robust measurement and analysis procedures of time-domain fluorescence lifetime spectroscopy are combined. A pulse-modulated cw laser is employed for excitation of the particles. The characteristics and the repetition rate of the excitation pulses can be readily adjusted to accommodate for fluorescence decays having a wide range of lifetimes.

  16. Picosecond time-resolved measurements of dense plasma line shifts

    DOE PAGES

    Stillman, C. R.; Nilson, P. M.; Ivancic, S. T.; ...

    2017-06-13

    Picosecond time-resolved x-ray spectroscopy is used to measure the spectral line shift of the 1s2p–1s2 transition in He-like Al ions as a function of the instantaneous plasma conditions. The plasma temperature and density are inferred from the Al Heα complex using a nonlocal-thermodynamic-equilibrium atomic physics model. The experimental spectra show a linearly increasing red shift for electron densities of 1 to 5 × 1023 cm–3. Furthermore, the measured line shifts are broadly consistent with a generalized analytic line-shift model based on calculations of a self-consistent field ion sphere model.

  17. Time-resolved SERS for characterizing extracellular vesicles

    NASA Astrophysics Data System (ADS)

    Rojalin, Tatu; Saari, Heikki; Somersalo, Petter; Laitinen, Saara; Turunen, Mikko; Viitala, Tapani; Wachsmann-Hogiu, Sebastian; Smith, Zachary J.; Yliperttula, Marjo

    2017-02-01

    The aim of this work is to develop a platform for characterizing extracellular vesicles (EV) by using gold-polymer nanopillar SERS arrays simultaneously circumventing the photoluminescence-related disadvantages of Raman with a time-resolved approach. EVs are rich of biochemical information reporting of, for example, diseased state of the biological system. Currently, straightforward, label-free and fast EV characterization methods with low sample consumption are warranted. In this study, SERS spectra of red blood cell and platelet derived EVs were successfully measured and their biochemical contents analyzed using multivariate data analysis techniques. The developed platform could be conveniently used for EV analytics in general.

  18. A compact electron gun for time-resolved electron diffraction

    SciTech Connect

    Robinson, Matthew S.; Lane, Paul D.; Wann, Derek A.

    2015-01-15

    A novel compact time-resolved electron diffractometer has been built with the primary goal of studying the ultrafast molecular dynamics of photoexcited gas-phase molecules. Here, we discuss the design of the electron gun, which is triggered by a Ti:Sapphire laser, before detailing a series of calibration experiments relating to the electron-beam properties. As a further test of the apparatus, initial diffraction patterns have been collected for thin, polycrystalline platinum samples, which have been shown to match theoretical patterns. The data collected demonstrate the focusing effects of the magnetic lens on the electron beam, and how this relates to the spatial resolution of the diffraction pattern.

  19. Time Resolved Phonon Spectroscopy, Version 1.0

    SciTech Connect

    Goett, Johnny; Zhu, Brian

    2016-12-22

    TRPS code was developed for the project "Time Resolved Phonon Spectroscopy". Routines contained in this piece of software were specially created to model phonon generation and tracking within materials that interact with ionizing radiation, particularly applicable to the modeling of cryogenic radiation detectors for dark matter and neutrino research. These routines were created to link seamlessly with the open source Geant4 framework for the modeling of radiation transport in matter, with the explicit intent of open sourcing them for eventual integration into that code base.

  20. Time resolved structural dynamics of butadiyne-linked porphyrin dimers

    PubMed Central

    Camargo, Franco V. A.; Hall, Christopher R.; Anderson, Harry L.; Meech, Stephen R.; Heisler, Ismael A.

    2016-01-01

    In this work, the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump/broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through the addition of a ligand, provides conclusive evidence for the twisting motion performed by the porphyrin dimer in solution. PMID:26798839

  1. Sensitive, time-resolved, broadband spectroscopy of single transient processes

    NASA Astrophysics Data System (ADS)

    Fjodorow, Peter; Baev, Ivan; Hellmig, Ortwin; Sengstock, Klaus; Baev, Valery M.

    2015-09-01

    Intracavity absorption spectroscopy with a broadband Er3+-doped fiber laser is applied to time-resolved measurements of transient gain and absorption in electrically excited Xe and Kr plasmas. The achieved time resolution for broadband spectral recording of a single process is 25 µs. For pulsed-periodic processes, the time resolution is limited by the laser pulse duration, which is set here to 3 µs. This pulse duration also predefines the effective absorption path length, which amounts to 900 m. The presented technique can be applied to multicomponent analysis of single transient processes such as shock tube experiments, pulse detonation engines, or explosives.

  2. Time resolved cryogenic cooling analysis of the Cornell Injector Cryomodule

    NASA Astrophysics Data System (ADS)

    Eichhorn, R.; Markham, S.; Smith, E.; Quigley, P.

    2015-12-01

    Managing parallel cryogenic flows has become a key challenge in designing efficient and smart cryo-modules for particle accelerators. In analysing the heating dynamics of the Cornell high current injector module a computational tool has been set-up allowing time resolved analysis and optimization. We describe the computational methods and data sets we have used, report the results and compare them to measured data from the module being in good agreement. Mitigation strategies developed on basis of this model have helped us in pushing the operational limitations.

  3. Femtosecond time-resolved electronic relaxation dynamics in tetrathiafulvalene

    SciTech Connect

    Staedter, D.; Polizzi, L.; Thiré, N.; Mairesse, Y.; Mayer, P.; Blanchet, V.

    2015-05-21

    In the present paper, the ultrafast electronic relaxation of tetrathiafulvalene (TTF) initiated around 4 eV is studied by femtosecond time-resolved velocity-map imaging. The goal is to investigate the broad double structure observed in the absorption spectrum at this energy. By monitoring the transients of the parent cation and its fragments and by varying the pump and the probe wavelengths, two internal conversions and intramolecular vibrational relaxation are detected both on the order of a few hundred of femtoseconds. Photoelectron images permit the assignment of a dark electronic state involved in the relaxation. In addition, the formation of the dimer of TTF has been observed.

  4. Coherent state statistics from time-resolved photon counting

    NASA Astrophysics Data System (ADS)

    Ravi, Harish; Prabhakar, Anil

    2011-01-01

    Time resolved photon counting was used to separate the different photon states emitted from a strongly attenuated laser source. We first describe a method to quantify the efficiency of our gated avalanche photo-detector, by relying on known Poissonian statistics. The detector was then optimized under different temperature and bias voltage conditions using the noise equivalent power as a metric. Finally, coherent pulses are sent into a ring cavity, such that the tapped output from the cavity forms a series of time multiplexed pulses, which then yield the photon counting statistics. We observed good agreement between theoretical estimates and experimental observations, to as low as 0.01% probability of detection.

  5. Picosecond time-resolved measurements of dense plasma line shifts

    NASA Astrophysics Data System (ADS)

    Stillman, C. R.; Nilson, P. M.; Ivancic, S. T.; Golovkin, I. E.; Mileham, C.; Begishev, I. A.; Froula, D. H.

    2017-06-01

    Picosecond time-resolved x-ray spectroscopy is used to measure the spectral line shift of the 1 s 2 p -1 s2 transition in He-like Al ions as a function of the instantaneous plasma conditions. The plasma temperature and density are inferred from the Al H eα complex using a nonlocal-thermodynamic-equilibrium atomic physics model. The experimental spectra show a linearly increasing redshift for electron densities of 1 -5 ×1023c m-3 . The measured line shifts are broadly consistent with a generalized analytic line-shift model based on calculations of a self-consistent field ion-sphere model.

  6. Systematic analysis of the in situ crosstalk of tyrosine modifications reveals no additional natural selection on multiply modified residues

    PubMed Central

    Pan, Zhicheng; Liu, Zexian; Cheng, Han; Wang, Yongbo; Gao, Tianshun; Ullah, Shahid; Ren, Jian; Xue, Yu

    2014-01-01

    Recent studies have indicated that different post-translational modifications (PTMs) synergistically orchestrate specific biological processes by crosstalks. However, the preference of the crosstalk among different PTMs and the evolutionary constraint on the PTM crosstalk need further dissections. In this study, the in situ crosstalk at the same positions among three tyrosine PTMs including sulfation, nitration and phosphorylation were systematically analyzed. The experimentally identified sulfation, nitration and phosphorylation sites were collected and integrated with reliable predictions to perform large-scale analyses of in situ crosstalks. From the results, we observed that the in situ crosstalk between sulfation and nitration is significantly under-represented, whereas both sulfation and nitration prefer to co-occupy with phosphorylation at same tyrosines. Further analyses suggested that sulfation and nitration preferentially co-occur with phosphorylation at specific positions in proteins, and participate in distinct biological processes and functions. More interestingly, the long-term evolutionary analysis indicated that multi-PTM targeting tyrosines didn't show any higher conservation than singly modified ones. Also, the analysis of human genetic variations demonstrated that there is no additional functional constraint on inherited disease, cancer or rare mutations of multiply modified tyrosines. Taken together, our systematic analyses provided a better understanding of the in situ crosstalk among PTMs. PMID:25476580

  7. Miniaturized time-resolved Raman spectrometer for planetary science based on a fast single photon avalanche diode detector array.

    PubMed

    Blacksberg, Jordana; Alerstam, Erik; Maruyama, Yuki; Cochrane, Corey J; Rossman, George R

    2016-02-01

    We present recent developments in time-resolved Raman spectroscopy instrumentation and measurement techniques for in situ planetary surface exploration, leading to improved performance and identification of minerals and organics. The time-resolved Raman spectrometer uses a 532 nm pulsed microchip laser source synchronized with a single photon avalanche diode array to achieve sub-nanosecond time resolution. This instrument can detect Raman spectral signatures from a wide variety of minerals and organics relevant to planetary science while eliminating pervasive background interference caused by fluorescence. We present an overview of the instrument design and operation and demonstrate high signal-to-noise ratio Raman spectra for several relevant samples of sulfates, clays, and polycyclic aromatic hydrocarbons. Finally, we present an instrument design suitable for operation on a rover or lander and discuss future directions that promise great advancement in capability.

  8. Experimental Time Resolved Electron Beam Temperature Measurements Using Bremsstrahlung Diagnostics

    SciTech Connect

    Menge, P.R.; Maenchen, J.E.; Mazarakis, M.G.; Rosenthal, S.E.

    1999-06-25

    Electron beam temperature, {beta}{perpendicular} (= v{perpendicular}/v), is important to control for the development of high dose flash radiographic bremsstrahlung sources. At high voltage (> 5 MV) increasing electron beam temperature has a serious deleterious effect on dose production. The average and time resolved behavior of beam temperature was measured during radiographic experiments on the HERMES III accelerator (10 MV, 50 kA, 70 ns). A linear array of thermoluminescent dosimeters (TLDs) were used to estimate the time integrated average of beam temperature. On and off-axis photoconducting diamond (PCD) detectors were used to measure the time resolved bremsstrahlung dose rate, which is dependent on beam energy and temperature. The beam temperature can be determined by correlating PCD response with accelerator voltage and current and also by analyzing the ratio of PCD amplitudes on and off axis. This ratio is insensitive to voltage and current and thus, is more reliable than utilizing absolute dose rate. The data is unfolded using comparisons with Monte Carlo simulations to obtain absolute beam temperatures. The data taken on HERMES III show abrupt increases in {beta}{perpendicular} midway through the pulse indicating rapid onset of beam instability.

  9. Time-resolved videothermography at above-frame-rate frequencies

    NASA Astrophysics Data System (ADS)

    Shepard, Steven M.; Sass, David T.; Imirowicz, Thomas P.; Meng, A.

    1991-03-01

    Temporal aliasing is a problem common all video imaging systems. IR video systems are particularly susceptible because of the relatively low (30 Hz) RS-170 frame rate. We have developed a system which compensates for the effects of aliasing, and allows images of repetitive thermal phenomena at frequencies up to 4 kHz to be acquired. The system utilizes an unmodified commercial imager (Inframetrics IR 600) and a microcomputer. Data is acquired selectively using a 'line-by-line' scheme which compares the motion of the camera's horizontal scanning mirror to a reference signal correlated to the event of interest. Only those horizontal lines that have a user-specified phase relationship to the reference signal are acquired. The resulting images have an effective integration time of 125 microseconds. This ability to acquire 'time-resolved' IR images allows investigation of phenomena not possible with a conventional RS-170 IR imaging system. For example, a conventional thermal image of an integrated circuit operating at several kilohertz yields no temporal information whatsoever. By comparison, we have acquired time-resolved images which show the AC heating and cooling of the circuit, so that we may identify AC hot spots. The system has also been applied to a running internal combustion engine. The imager views the piston head through an IR transparent (ZnS) window. Acquired images clearly show the motion of the flame front through the combustion chamber, and the subsequent heating and cooling of the piston head.

  10. Time-resolved fluorescence study of all-trans-retinal

    NASA Astrophysics Data System (ADS)

    Erez, Yuval; Presiado, Itay; Gepshtein, Rinat; Simkovitch, Ron; Huppert, Dan

    2014-11-01

    UV-vis steady-state and time-resolved emission techniques were employed to study the ultrafast relaxation path of all-trans-retinal. We found that the steady-state emission spectrum consists mainly of two bands that we assign to the allowed transition from the ? state and the forbidden transition from the ?(ππ*) state. The time-resolved emission signal is dependent on the excitation wavelength, and is composed of three decay components. The short-time component of less than 80 fs, irrespective of the solvent, is assigned to the transition from the ? state. The intermediate-time decay component is assigned to the transition from the ?(ππ*) state, depends on the solvent's polarity and not on the existence of hydrogen bonds between the solute and the solvent or the viscosity of the latter. It has a lifetime of ~1 ps in polar solvents, and of 0.6 and 0.4 ps in the non-polar solvents n-octane and cyclohexane, respectively.

  11. Time-resolved luminescent lateral flow assay technology.

    PubMed

    Song, Xuedong; Knotts, Michael

    2008-09-26

    We here report a detection technology that integrates highly sensitive time-resolved luminescence technique into lateral flow assay platform to achieve excellent detection performance with low cost. We have developed very bright, surface-functionalized and mono-dispersed phosphorescent nanoparticles of long lifetime under ambient conditions. The phosphorescent nanoparticles have been used to conjugate with monoclonal antibody for C-reactive protein (CRP), an inflammatory biomarker. Lateral flow immunoassay devices have been developed using the conjugate for highly sensitive detection of CRP. The CRP assay can achieve a detection sensitivity of <0.2 ngmL(-1) in serum with a linear response from 0.2 to 200 ngmL(-1) CRP. We have also developed a low cost time-resolved luminescence reader for the lateral flow immunoassay (LFIA) devices. The reader does not use expensive band pass filter and still provide very low detection background and high detection sensitivity on solid substrates such as nitrocellulose membranes. The reader can detect less than 2.5 ng phosphorescent particles captured on a nitrocellulose membrane strip with more than three orders of magnitude linear detection dynamic range. The technology should find a number of applications, ranging from clinical diagnostics, detection of chemical and biological warfare agents, to food and environmental monitoring.

  12. Time-resolved quasielastic neutron scattering studies of native photosystems.

    PubMed

    Pieper, Jörg

    2010-01-01

    The internal molecular dynamics of proteins plays an important role in a number of functional processes in native photosystems. Prominent examples include the photocycle of bacteriorhodopsin and electron transfer in the reaction center of plant photosystem II. In this regard, the recently developed technique of time-resolved quasielastic neutron scattering with laser excitation opens up new perspectives for the study of protein/membrane dynamics in specific functional states of even complex systems. The first direct observation of a functionally modulated protein dynamics has just recently been reported for the model system bacteriorhodopsin (Pieper et al., Phys. Rev. Lett. 100, 2008, 228103.), where a transient softening of the protein was observed on a timescale of approximately 1 ms along with the large-scale structural change in the M-intermediate of bacteriorhodopsin. In contrast, photosystem II membrane fragments with inhibited electron transfer show a suppression of protein dynamics approximately 160 mus after the actinic laser flash (Pieper and Renger, Biochemistry 48, 2009, 6111). This effect may reflect aggregation-like conformational changes capable of dissipation of excess excitation energy to prevent photodamage in the absence of Q(A)-->Q(B) electron transfer. These findings indicate that proteins exhibit a remarkable flexibility to accommodate different functional processes. This contribution will discuss methodical aspects, challenges, and recent applications of laser-excited, time-resolved quasielastic neutron scattering.

  13. Time Resolved FTIR Analysis of Tailpipe Exhaust for Several Automobiles

    NASA Astrophysics Data System (ADS)

    White, Allen R.; Allen, James; Devasher, Rebecca B.

    2011-06-01

    The automotive catalytic converter reduces or eliminates the emission of various chemical species (e.g. CO, hydrocarbons, etc.) that are the products of combustion from automobile exhaust. However, these units are only effective once they have reached operating temperature. The design and placement of catalytic converters has changed in order to reduce both the quantity of emissions and the time that is required for the converter to be effective. In order to compare the effectiveness of catalytic converters, time-resolved measurements were performed on several vehicles, including a 2010 Toyota Prius, a 2010 Honda Fit, a 1994 Honda Civic, and a 1967 Oldsmobile 442 (which is not equipped with a catalytic converter but is used as a baseline). The newer vehicles demonstrate bot a reduced overall level of CO and hydrocarbon emissions but are also effective more quickly than older units. The time-resolved emissions will be discussed along with the impact of catalytic converter design and location on the measured emissions.

  14. Structural kinetics of myosin by transient time-resolved FRET

    PubMed Central

    Nesmelov, Yuri E.; Agafonov, Roman V.; Negrashov, Igor V.; Blakely, Sarah E.; Titus, Margaret A.; Thomas, David D.

    2011-01-01

    For many proteins, especially for molecular motors and other enzymes, the functional mechanisms remain unsolved due to a gap between static structural data and kinetics. We have filled this gap by detecting structure and kinetics simultaneously. This structural kinetics experiment is made possible by a new technique, (TR)2FRET (transient time-resolved FRET), which resolves protein structural states on the submillisecond timescale during the transient phase of a biochemical reaction. (TR)2FRET is accomplished with a fluorescence instrument that uses a pulsed laser and direct waveform recording to acquire an accurate subnanosecond time-resolved fluorescence decay every 0.1 ms after stopped flow. To apply this method to myosin, we labeled the force-generating region site specifically with two probes, mixed rapidly with ATP to initiate the recovery stroke, and measured the interprobe distance by (TR)2FRET with high resolution in both space and time. We found that the relay helix bends during the recovery stroke, most of which occurs before ATP is hydrolyzed, and two structural states (relay helix straight and bent) are resolved in each nucleotide-bound biochemical state. Thus the structural transition of the force-generating region of myosin is only loosely coupled to the ATPase reaction, with conformational selection driving the motor mechanism. PMID:21245357

  15. Time resolved fluorescence of cow and goat milk powder

    NASA Astrophysics Data System (ADS)

    Brandao, Mariana P.; de Carvalho dos Anjos, Virgílio; Bell., Maria José V.

    2017-01-01

    Milk powder is an international dairy commodity. Goat and cow milk powders are significant sources of nutrients and the investigation of the authenticity and classification of milk powder is particularly important. The use of time-resolved fluorescence techniques to distinguish chemical composition and structure modifications could assist develop a portable and non-destructive methodology to perform milk powder classification and determine composition. This study goal is to differentiate milk powder samples from cows and goats using fluorescence lifetimes. The samples were excited at 315 nm and the fluorescence intensity decay registered at 468 nm. We observed fluorescence lifetimes of 1.5 ± 0.3, 6.4 ± 0.4 and 18.7 ± 2.5 ns for goat milk powder; and 1.7 ± 0.3, 6.9 ± 0.2 and 29.9 ± 1.6 ns for cow's milk powder. We discriminate goat and cow powder milk by analysis of variance using Fisher's method. In addition, we employed quadratic discriminant analysis to differentiate the milk samples with accuracy of 100%. Our results suggest that time-resolved fluorescence can provide a new method to the analysis of powder milk and its composition.

  16. Time-resolved multispectral imaging of combustion reaction

    NASA Astrophysics Data System (ADS)

    Huot, Alexandrine; Gagnon, Marc-André; Jahjah, Karl-Alexandre; Tremblay, Pierre; Savary, Simon; Farley, Vincent; Lagueux, Philippe; Guyot, Éric; Chamberland, Martin; Marcotte, Fréderick

    2015-05-01

    Thermal infrared imaging is a field of science that evolves rapidly. Scientists have used for years the simplest tool: thermal broadband cameras. This allows to perform target characterization in both the longwave (LWIR) and midwave (MWIR) infrared spectral range. Infrared thermal imaging is used for a wide range of applications, especially in the combustion domain. For example, it can be used to follow combustion reactions, in order to characterize the injection and the ignition in a combustion chamber or even to observe gases produced by a flare or smokestack. Most combustion gases such as carbon dioxide (CO2) selectively absorb/emit infrared radiation at discrete energies, i.e. over a very narrow spectral range. Therefore, temperatures derived from broadband imaging are not reliable without prior knowledge about spectral emissivity. This information is not directly available from broadband images. However, spectral information is available using spectral filters. In this work, combustion analysis was carried out using Telops MS-IR MW camera which allows multispectral imaging at a high frame rate. A motorized filter wheel allowing synchronized acquisitions on eight (8) different channels was used to provide time-resolved multispectral imaging of combustion products of a candle in which black powder has been burnt to create a burst. It was then possible to estimate the temperature by modeling spectral profile derived from information obtained with the different spectral filters. Comparison with temperatures obtained using conventional broadband imaging illustrates the benefits of time-resolved multispectral imaging for the characterization of combustion processes.

  17. Time-resolved multispectral imaging of combustion reactions

    NASA Astrophysics Data System (ADS)

    Huot, Alexandrine; Gagnon, Marc-André; Jahjah, Karl-Alexandre; Tremblay, Pierre; Savary, Simon; Farley, Vincent; Lagueux, Philippe; Guyot, Éric; Chamberland, Martin; Marcotte, Frédérick

    2015-10-01

    Thermal infrared imaging is a field of science that evolves rapidly. Scientists have used for years the simplest tool: thermal broadband cameras. These allow to perform target characterization in both the longwave (LWIR) and midwave (MWIR) infrared spectral range. Infrared thermal imaging is used for a wide range of applications, especially in the combustion domain. For example, it can be used to follow combustion reactions, in order to characterize the injection and the ignition in a combustion chamber or even to observe gases produced by a flare or smokestack. Most combustion gases, such as carbon dioxide (CO2), selectively absorb/emit infrared radiation at discrete energies, i.e. over a very narrow spectral range. Therefore, temperatures derived from broadband imaging are not reliable without prior knowledge of spectral emissivity. This information is not directly available from broadband images. However, spectral information is available using spectral filters. In this work, combustion analysis was carried out using a Telops MS-IR MW camera, which allows multispectral imaging at a high frame rate. A motorized filter wheel allowing synchronized acquisitions on eight (8) different channels was used to provide time-resolved multispectral imaging of combustion products of a candle in which black powder has been burnt to create a burst. It was then possible to estimate the temperature by modeling spectral profiles derived from information obtained with the different spectral filters. Comparison with temperatures obtained using conventional broadband imaging illustrates the benefits of time-resolved multispectral imaging for the characterization of combustion processes.

  18. Time-resolved single dopant charge dynamics in silicon

    PubMed Central

    Rashidi, Mohammad; Burgess, Jacob A. J.; Taucer, Marco; Achal, Roshan; Pitters, Jason L.; Loth, Sebastian; Wolkow, Robert A.

    2016-01-01

    As the ultimate miniaturization of semiconductor devices approaches, it is imperative that the effects of single dopants be clarified. Beyond providing insight into functions and limitations of conventional devices, such information enables identification of new device concepts. Investigating single dopants requires sub-nanometre spatial resolution, making scanning tunnelling microscopy an ideal tool. However, dopant dynamics involve processes occurring at nanosecond timescales, posing a significant challenge to experiment. Here we use time-resolved scanning tunnelling microscopy and spectroscopy to probe and study transport through a dangling bond on silicon before the system relaxes or adjusts to accommodate an applied electric field. Atomically resolved, electronic pump-probe scanning tunnelling microscopy permits unprecedented, quantitative measurement of time-resolved single dopant ionization dynamics. Tunnelling through the surface dangling bond makes measurement of a signal that would otherwise be too weak to detect feasible. Distinct ionization and neutralization rates of a single dopant are measured and the physical process controlling those are identified. PMID:27782125

  19. Time resolved imaging microscopy. Phosphorescence and delayed fluorescence imaging.

    PubMed Central

    Marriott, G; Clegg, R M; Arndt-Jovin, D J; Jovin, T M

    1991-01-01

    An optical microscope capable of measuring time resolved luminescence (phosphorescence and delayed fluorescence) images has been developed. The technique employs two phase-locked mechanical choppers and a slow-scan scientific CCD camera attached to a normal fluorescence microscope. The sample is illuminated by a periodic train of light pulses and the image is recorded within a defined time interval after the end of each excitation period. The time resolution discriminates completely against light scattering, reflection, autofluorescence, and extraneous prompt fluorescence, which ordinarily decrease contrast in normal fluorescence microscopy measurements. Time resolved image microscopy produces a high contrast image and particular structures can be emphasized by displaying a new parameter, the ratio of the phosphorescence to fluorescence. Objects differing in luminescence decay rates are easily resolved. The lifetime of the long lived luminescence can be measured at each pixel of the microscope image by analyzing a series of images that differ by a variable time delay. The distribution of luminescence decay rates is displayed directly as an image. Several examples demonstrate the utility of the instrument and the complementarity it offers to conventional fluorescence microscopy. Images FIGURE 2 FIGURE 3 FIGURE 4 FIGURE 5 FIGURE 6 PMID:1723311

  20. Motor Oil Classification Based on Time-Resolved Fluorescence

    PubMed Central

    Mu, Taotao; Chen, Siying; Zhang, Yinchao; Guo, Pan; Chen, He; Meng, Fandong

    2014-01-01

    A time-resolved fluorescence (TRF) technique is presented for classifying motor oils. The system is constructed with a third harmonic Nd:YAG laser, a spectrometer, and an intensified charge coupled device (ICCD) camera. Steady-state and time-resolved fluorescence (TRF) measurements are reported for several motor oils. It is found that steady-state fluorescence is insufficient to distinguish the motor oil samples. Then contour diagrams of TRF intensities (CDTRFIs) are acquired to serve as unique fingerprints to identify motor oils by using the distinct TRF of motor oils. CDTRFIs are preferable to steady-state fluorescence spectra for classifying different motor oils, making CDTRFIs a particularly choice for the development of fluorescence-based methods for the discrimination and characterization of motor oils. The two-dimensional fluorescence contour diagrams contain more information, not only the changing shapes of the LIF spectra but also the relative intensity. The results indicate that motor oils can be differentiated based on the new proposed method, which provides reliable methods for analyzing and classifying motor oils. PMID:24988439

  1. Nonadiabatic and Time-Resolved Photoelectron Spectroscopy for Molecular Systems.

    PubMed

    Flick, Johannes; Appel, Heiko; Rubio, Angel

    2014-04-08

    We quantify the nonadiabatic contributions to the vibronic sidebands of equilibrium and explicitly time-resolved nonequilibrium photoelectron spectra for a vibronic model system of trans-polyacetylene. Using exact diagonalization, we directly evaluate the sum-over-states expressions for the linear-response photocurrent. We show that spurious peaks appear in the Born-Oppenheimer approximation for the vibronic spectral function, which are not present in the exact spectral function of the system. The effect can be traced back to the factorized nature of the Born-Oppenheimer initial and final photoemission states and also persists when either only initial or final states are replaced by correlated vibronic states. Only when correlated initial and final vibronic states are taken into account are the spurious spectral weights of the Born-Oppenheimer approximation suppressed. In the nonequilibrium case, we illustrate for an initial Franck-Condon excitation and an explicit pump-pulse excitation how the vibronic wavepacket motion of the system can be traced in the time-resolved photoelectron spectra as a function of the pump-probe delay.

  2. Revealing Chemical Processes Involved in Electrochemical (De)Lithiation of Al with in Situ Neutron Depth Profiling and X-ray Diffraction.

    PubMed

    Liu, Danny X; Co, Anne C

    2016-01-13

    Herein we report a direct measurement of Li transport in real-time during charge and discharge process within an Al matrix using neutron depth profiling (NDP). In situ NDP was used to reveal and quantify parasitic losses during the first 25 mAhr/g of lithiation, followed by the formation of LiAl protrusions from the surface of pristine Al. Evidence of Li entrapment is also reported during delithiation. Subsequent lithiation and delithiation showed electrochemical charge passed to be equivalent to the amount of lithium incorporated into the Al matrix with negligible difference, suggesting that the parasitic losses including the formation of the solid electrolyte layer may be confined to the first lithiation. Parallel in situ XRD measurements also confirm the transformation of β-LiAl from a solid solution of α-LiAl, revealing solid solution-mediated crystallization of β-LiAl.

  3. Synthesis and time-resolved structural characterization of framework and mineral sulfides

    NASA Astrophysics Data System (ADS)

    Cahill, Christopher Langley

    A new class of open-framework organic/inorganic hybrid materials based on In-S chemistry has been discovered. The compounds therein exhibit unprecedented structural diversity compared to known porous sulfides, primarily due to variation in framework building units. Further, large increases in pore dimensions (vs. zeolites, for example) are observed as these materials consist of comer and edge linked clusters, e.g. In10S20, In9S17, In4S10 and In6S 15. Choice of organic structure directing agents (templates) and careful control of reaction conditions (temperature, pH) both in the In-S and Ge-S systems is shown not only to dictate which building unit will form, but also to direct the resulting framework topology. Several of the compounds described herein crystallize either as powders, or as crystals too small for standard in-house X-ray structural analysis. Diffraction experiments have thus required synchrotron based single crystal techniques for structure determination. Further, certain reaction mixture compositions result in multi-phase end products, the formation pathways of which have been studied with time resolved, in situ synchrotron powder diffraction. An extension of the applicability of the in situ techniques investigated the role of oxygen in hydrothermal systems. Oxidation state is proposed to dictate speciation in the Ni-Ge-S system and to promote phase transformations in the Fe-S mineral system.

  4. Time-Resolved Chemical Mapping in Light-Emitting Electrochemical Cells.

    PubMed

    Jafari, Mohammad Javad; Liu, Jiang; Engquist, Isak; Ederth, Thomas

    2017-01-25

    An understanding of the doping and ion distributions in light-emitting electrochemical cells (LECs) is required to approach a realistic conduction model which can precisely explain the electrochemical reactions, p-n junction formation, and ion dynamics in the active layer and to provide relevant information about LECs for systematic improvement of function and manufacture. Here, Fourier-transform infrared (FTIR) microscopy is used to monitor anion density profile and polymer structure in situ and for time-resolved mapping of electrochemical doping in an LEC under bias. The results are in very good agreement with the electrochemical doping model with respect to ion redistribution and formation of a dynamic p-n junction in the active layer. We also physically slow ions by decreasing the working temperature and study frozen-junction formation and immobilization of ions in a fixed-junction LEC device by FTIR imaging. The obtained results show irreversibility of the ion redistribution and polymer doping in a fixed-junction device. In addition, we demonstrate that infrared microscopy is a useful tool for in situ characterization of electroactive organic materials.

  5. Dynamic structural evolution of supported palladium-ceria core-shell catalysts revealed by in situ electron microscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Shuyi; Chen, Chen; Cargnello, Matteo; Fornasiero, Paolo; Gorte, Raymond J.; Graham, George W.; Pan, Xiaoqing

    2015-07-01

    The exceptional activity for methane combustion of modular palladium-ceria core-shell subunits on silicon-functionalized alumina that was recently reported has created renewed interest in the potential of core-shell structures as catalysts. Here we report on our use of advanced ex situ and in situ electron microscopy with atomic resolution to show that the modular palladium-ceria core-shell subunits undergo structural evolution over a wide temperature range. In situ observations performed in an atmospheric gas cell within this temperature range provide real-time evidence that the palladium and ceria nanoparticle constituents of the palladium-ceria core-shell participate in a dynamical process that leads to the formation of an unanticipated structure comprised of an intimate mixture of palladium, cerium, silicon and oxygen, with very high dispersion. This finding may open new perspectives about the origin of the activity of this catalyst.

  6. In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism

    NASA Astrophysics Data System (ADS)

    Kirshenbaum, Kevin; Bock, David C.; Lee, Chia-Ying; Zhong, Zhong; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

    2015-01-01

    The functional capacity of a battery is observed to decrease, often quite dramatically, as discharge rate demands increase. These capacity losses have been attributed to limited ion access and low electrical conductivity, resulting in incomplete electrode use. A strategy to improve electronic conductivity is the design of bimetallic materials that generate a silver matrix in situ during cathode reduction. Ex situ x-ray absorption spectroscopy coupled with in situ energy-dispersive x-ray diffraction measurements on intact lithium/silver vanadium diphosphate (Li/Ag2VP2O8) electrochemical cells demonstrate that the metal center preferentially reduced and its location in the bimetallic cathode are rate-dependent, affecting cell impedance. This work illustrates that spatial imaging as a function of discharge rate can provide needed insights toward improving realizable capacity of bimetallic cathode systems.

  7. Dynamic structural evolution of supported palladium-ceria core-shell catalysts revealed by in situ electron microscopy.

    PubMed

    Zhang, Shuyi; Chen, Chen; Cargnello, Matteo; Fornasiero, Paolo; Gorte, Raymond J; Graham, George W; Pan, Xiaoqing

    2015-07-10

    The exceptional activity for methane combustion of modular palladium-ceria core-shell subunits on silicon-functionalized alumina that was recently reported has created renewed interest in the potential of core-shell structures as catalysts. Here we report on our use of advanced ex situ and in situ electron microscopy with atomic resolution to show that the modular palladium-ceria core-shell subunits undergo structural evolution over a wide temperature range. In situ observations performed in an atmospheric gas cell within this temperature range provide real-time evidence that the palladium and ceria nanoparticle constituents of the palladium-ceria core-shell participate in a dynamical process that leads to the formation of an unanticipated structure comprised of an intimate mixture of palladium, cerium, silicon and oxygen, with very high dispersion. This finding may open new perspectives about the origin of the activity of this catalyst.

  8. Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy

    PubMed Central

    Liu, Xiaosong; Wang, Dongdong; Liu, Gao; Srinivasan, Venkat; Liu, Zhi; Hussain, Zahid; Yang, Wanli

    2013-01-01

    Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co1/3Ni1/3Mn1/3)O2 and LiFePO4 cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO4 is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries. PMID:24100759

  9. Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy.

    PubMed

    Liu, Xiaosong; Wang, Dongdong; Liu, Gao; Srinivasan, Venkat; Liu, Zhi; Hussain, Zahid; Yang, Wanli

    2013-01-01

    Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co(¹/₃)Ni(¹/₃)Mn(¹/₃))O₂ and LiFePO₄ cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO₄ is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries.

  10. Highly sensitive detection of human papillomavirus type 16 DNA using time-resolved fluorescence microscopy and long lifetime probes

    NASA Astrophysics Data System (ADS)

    Wang, Xue F.; Periasamy, Ammasi; Wodnicki, Pawel; Siadat-Pajouh, M.; Herman, Brian

    1995-04-01

    We have been interested in the role of Human Papillomavirus (HPV) in cervical cancer and its diagnosis; to that end we have been developing microscopic imaging and fluorescent in situ hybridization (FISH) techniques to genotype and quantitate the amount of HPV present at a single cell level in cervical PAP smears. However, we have found that low levels of HPV DNA are difficult to detect accurately because theoretically obtainable sensitivity is never achieved due to nonspecific autofluorescence, fixative induced fluorescence of cells and tissues, and autofluorescence of the optical components in the microscopic system. In addition, the absorption stains used for PAP smears are intensely autofluorescent. Autofluorescence is a rapidly decaying process with lifetimes in the range of 1-100 nsec, whereas phosphorescence and delayed fluorescence have lifetimes in the range of 1 microsecond(s) ec-10 msec. The ability to discriminate between specific fluorescence and autofluorescence in the time-domain has improved the sensitivity of diagnostic test such that they perform comparably to, or even more sensitive than radioisotopic assays. We have developed a novel time-resolved fluorescence microscope to improve the sensitivity of detection of specific molecules of interest in slide based specimens. This time-resolved fluorescence microscope is based on our recently developed fluorescence lifetime imaging microscopy (FILM) in conjunction with the use of long lifetime fluorescent labels. By using fluorescence in situ hybridization and the long lifetime probe (europium), we have demonstrated the utility of this technique for detection of HPV DNA in cervicovaginal cells. Our results indicate that the use of time-resolved fluorescence microscopy and long lifetime probes increases the sensitivity of detection by removing autofluorescence and will thus lead to improved early diagnosis of cervical cancer. Since the highly sensitive detection of DNA in clinical samples using

  11. Singlet internal conversion processes in the order of 1Bu+→3Ag-→1Bu-→2Ag-→1Ag- in all- trans-spheroidene and lycopene as revealed by subpicosecond time-resolved Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Rondonuwu, Ferdy S.; Kakitani, Yoshinori; Tamura, Hiroshi; Koyama, Yasushi

    2006-09-01

    Key Raman lines ascribable to the 1Bu+, 3Ag-, 1Bu- and 2Ag- states were identified in the subpicosecond time-resolved Raman spectra of spheroidene and lycopene having 10 and 11 conjugated double bonds, respectively. The sequential rise-and-decay of the key Raman lines showed the internal conversion processes of 1Bu+→3Ag-→1Bu-→2Ag-→1Ag- (ground). The time constant in each step of internal conversion reflects the energy gap between the relevant states that had been determined by measurement of resonance - Raman excitation profiles [K. Furuichi, T. Sashima, Y. Koyama, Chem. Phys. Lett. 356 (2002) 547].

  12. Spectral characteristics of time resolved magnonic spin Seebeck effect

    SciTech Connect

    Etesami, S. R.; Chotorlishvili, L.; Berakdar, J.

    2015-09-28

    Spin Seebeck effect (SSE) holds promise for new spintronic devices with low-energy consumption. The underlying physics, essential for a further progress, is yet to be fully clarified. This study of the time resolved longitudinal SSE in the magnetic insulator yttrium iron garnet concludes that a substantial contribution to the spin current stems from small wave-vector subthermal exchange magnons. Our finding is in line with the recent experiment by S. R. Boona and J. P. Heremans [Phys. Rev. B 90, 064421 (2014)]. Technically, the spin-current dynamics is treated based on the Landau-Lifshitz-Gilbert equation also including magnons back-action on thermal bath, while the formation of the time dependent thermal gradient is described self-consistently via the heat equation coupled to the magnetization dynamics.

  13. Time-resolved thermal transport in compositionally modulated metal films

    SciTech Connect

    Clemens, B.M.; Eesley, G.L.; Paddock, C.A.

    1988-01-15

    We report on investigations of one-dimensional thermal transport in compositionally modulated metal films produced with a systematic variation in atomic lattice mismatch. In the case of Ni-Cu, Ni-Mo, Ni-Ti, and Ni-Zr, we observe the relative effects of interfacial disorder on thermal diffusion. Our observations demonstrate the thermal impedance of a single metal-metal interface and indicate that thermal diffusion in a bilayer film is strongly influenced by the interface between contacting metal pairs. This study is made possible by picosecond time-resolved thermoreflectance measurements which probe thermal transport perpendicular to the film plane. This technique can impact on our understanding of electron scattering and transport across metallic boundaries, and it provides a means of inferring electrical transport properties.

  14. Photon-Counting Arrays for Time-Resolved Imaging

    PubMed Central

    Antolovic, I. Michel; Burri, Samuel; Hoebe, Ron A.; Maruyama, Yuki; Bruschini, Claudio; Charbon, Edoardo

    2016-01-01

    The paper presents a camera comprising 512 × 128 pixels capable of single-photon detection and gating with a maximum frame rate of 156 kfps. The photon capture is performed through a gated single-photon avalanche diode that generates a digital pulse upon photon detection and through a digital one-bit counter. Gray levels are obtained through multiple counting and accumulation, while time-resolved imaging is achieved through a 4-ns gating window controlled with subnanosecond accuracy by a field-programmable gate array. The sensor, which is equipped with microlenses to enhance its effective fill factor, was electro-optically characterized in terms of sensitivity and uniformity. Several examples of capture of fast events are shown to demonstrate the suitability of the approach. PMID:27367697

  15. Multidimensional Time-Resolved Spectroscopy of Vibrational Coherence in Biopolyenes

    NASA Astrophysics Data System (ADS)

    Buckup, Tiago; Motzkus, Marcus

    2014-04-01

    Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm-1 to over 2,000 cm-1 and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all-trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence.

  16. Nonselective and polarization effects in time-resolved optogalvanic spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhechev, D.; Steflekova, V.

    2016-02-01

    Three interfering effects in optogalvanic (OG) spectroscopy are identified in a hollow cathode discharge (HCD) - OG detector. The laser beam is found to generate two nonselective processes, namely photoelectron emission (PE) from the cathode surface with a sub-breakdown bias applied, and nonresonant space ionization. The convolution of these galvanic contributions was determined experimentally as an instrumental function and a deconvolution procedure to determine the actual OG signal was developed. Specific plasma conductance is detected dependent on the polarization of the laser beam irradiating. Linearly/circularly polarized light beam is found to induce OG signals differ in amplitude (and their shape parameters in the time-resolved OG signals (TROGS)). The phenomena coherence and specific conductance are found to be in causal relationship. The additional conductance due to coherent states of atoms manifests itself as an intrinsic instrumental property of OG detector.

  17. FXR LIA Optimization - Time-resolved OTR Emittance Measurement

    SciTech Connect

    Jacob, J; Ong, M; Wargo, P; LeSage, G

    2005-07-21

    The Flash X-Ray Radiography (FXR) facility at Lawrence Livermore National Laboratory utilizes a high current, long pulse linear induction accelerator to produce high doses of x-ray radiation. Accurate characterization of the transverse beam emittance is required in order to facilitate accelerator modeling and tuning efforts and, ultimately, to optimize the final focus spot size, yielding higher resolution radiographs. In addition to conventional magnet scan, pepper-pot, and multiple screen techniques, optical transition radiation (OTR) has been proven as a useful emittance measurement diagnostic and is particularly well suited to the FXR accelerator. We shall discuss the time-resolved emittance characterization of an induction linac electron beam using OTR, and we will present our experimental apparatus and analysis software. We shall also develop the theoretical background of beam emittance and transition radiation.

  18. Examining Electron-Boson Coupling Using Time-Resolved Spectroscopy

    SciTech Connect

    Sentef, Michael; Kemper, Alexander F.; Moritz, Brian; Freericks, James K.; Shen, Zhi-Xun; Devereaux, Thomas P.

    2013-12-26

    Nonequilibrium pump-probe time-domain spectroscopies can become an important tool to disentangle degrees of freedom whose coupling leads to broad structures in the frequency domain. Here, using the time-resolved solution of a model photoexcited electron-phonon system, we show that the relaxational dynamics are directly governed by the equilibrium self-energy so that the phonon frequency sets a window for “slow” versus “fast” recovery. The overall temporal structure of this relaxation spectroscopy allows for a reliable and quantitative extraction of the electron-phonon coupling strength without requiring an effective temperature model or making strong assumptions about the underlying bare electronic band dispersion.

  19. Towards time-resolved serial crystallography in a microfluidic device

    PubMed Central

    Pawate, Ashtamurthy S.; Šrajer, Vukica; Schieferstein, Jeremy; Guha, Sudipto; Henning, Robert; Kosheleva, Irina; Schmidt, Marius; Ren, Zhong; Kenis, Paul J. A.; Perry, Sarah L.

    2015-01-01

    Serial methods for crystallography have the potential to enable dynamic structural studies of protein targets that have been resistant to single-crystal strategies. The use of serial data-collection strategies can circumvent challenges associated with radiation damage and repeated reaction initiation. This work utilizes a microfluidic crystallization platform for the serial time-resolved Laue diffraction analysis of macroscopic crystals of photoactive yellow protein (PYP). Reaction initiation was achieved via pulsed laser illumination, and the resultant electron-density difference maps clearly depict the expected pR1/pRE46Q and pR2/pRCW states at 10 µs and the pB1 intermediate at 1 ms. The strategies presented here have tremendous potential for extension to chemical triggering methods for reaction initiation and for extension to dynamic, multivariable analyses. PMID:26144226

  20. Fast Time-Resolved Aerosol Collector: Proof of Concept

    SciTech Connect

    Yu, Xiao-Ying; Cowin, James P.; Iedema, Martin J.; Ali, Hashim M.

    2010-10-12

    Atmospheric particles can be collected in the field on substrates for subsequent laboratory analysis via chemically sensitive single particle methods such as scanning electron microscopy with energy dispersed x-ray analysis. With moving substrates one can achieve time resolution of seconds to minutes. We demonstrate how to increase the time resolution to a few milliseconds to provide real-time information in this paper. Our fast time-resolved aerosol collector (“Fast-TRAC”) microscopically observes the particle collection on substrate and record an on-line video. Particle arrivals are resolved to within a single frame (17 to 4 ms in this setup), and the spatial locations are matched to the subsequent single particle analysis. This approach provides real-time information on particle size and number concentration. Applications are expected in airborne studies of cloud microstructure, pollution plumes, and long term site monitoring.

  1. Spectral characteristics of time resolved magnonic spin Seebeck effect

    NASA Astrophysics Data System (ADS)

    Etesami, S. R.; Chotorlishvili, L.; Berakdar, J.

    2015-09-01

    Spin Seebeck effect (SSE) holds promise for new spintronic devices with low-energy consumption. The underlying physics, essential for a further progress, is yet to be fully clarified. This study of the time resolved longitudinal SSE in the magnetic insulator yttrium iron garnet concludes that a substantial contribution to the spin current stems from small wave-vector subthermal exchange magnons. Our finding is in line with the recent experiment by S. R. Boona and J. P. Heremans [Phys. Rev. B 90, 064421 (2014)]. Technically, the spin-current dynamics is treated based on the Landau-Lifshitz-Gilbert equation also including magnons back-action on thermal bath, while the formation of the time dependent thermal gradient is described self-consistently via the heat equation coupled to the magnetization dynamics.

  2. Time-resolved measurements of equilibrium profiles in MST

    NASA Astrophysics Data System (ADS)

    Deng, B. H.; Brower, D. L.; Ding, W. X.; Yates, T. F.; Anderson, J. K.; Caspary, K.; McCollam, K. J.; Prager, S. C.; Reusch, J. A.; Sarff, J. S.; Craig, D.

    2007-11-01

    Based on the high-speed, three-wave, far-infrared polarimeter-interferometer measurement of Bpol profiles and external coil measurements of Btave and Btw, a new method is developed to derive Btor and other equilibrium profiles (J// and q) with high time resolution. Using Faraday's law, the inductive electric field (E//) profile is also deduced from the temporal derivatives of the time-resolved magnetic field profiles. The derived B(0) values have excellent agreement with direct measurements using a Motional Stark Effect (MSE) diagnostic. Evolution of equilibrium profiles during single sawtooth events in MST, both the slow linear ramp and crash phases, are presented. Profile scaling with plasma current Ip and reversal parameter F is also explored. MHD stability is tested from the spatial gradients of the J// and q profiles, and correlation with fluctuation mode amplitude is investigated. Future improvements to equilibrium reconstruction are expected by measuring Btor(r,t) directly via Cotton-Mouton interferometry.

  3. Time-resolved phase-sensitive second harmonic generation spectroscopy

    NASA Astrophysics Data System (ADS)

    Nowakowski, Paweł J.; Woods, David A.; Bain, Colin D.; Verlet, Jan R. R.

    2015-02-01

    A methodology based on time-resolved, phase-sensitive second harmonic generation (SHG) for probing the excited state dynamics of species at interfaces is presented. It is based on an interference measurement between the SHG from the sample and a local oscillator generated at a reference together with a lock-in measurement to remove the large constant offset from the interference. The technique is characterized by measuring the phase and excited state dynamics of the dye malachite green at the water/air interface. The key attributes of the technique are that the observed signal is directly proportional to sample concentration, in contrast to the quadratic dependence from non-phase sensitive SHG, and that the real and imaginary parts of the 2nd order non-linear susceptibility can be determined independently. We show that the method is highly sensitive and can provide high quality excited state dynamics in short data acquisition times.

  4. Time-resolve study of the photooxygenation of 3-hydroxyflavone

    SciTech Connect

    Studer, S.L.; Brewer, W.E.; Martinez, M.L.; Chou, Pi-Tai )

    1989-09-13

    3-hydroxyflavones are prototype molecules for studying the dynamics of the proton-transfer reaction in the excited state as well as in the ground state. Their lasing action has been reported with a high efficiency of laser gain. Unfortunately, a major obstruction to the practical application of 3-hydroxy-flavones as laser dyes is due to a photochemical reaction possibly involving molecular oxygen. In this communication we report a direct time-resolved study of the photooxygenation of 3-hydroxyflavone (3HF) in the normal state as well as in the tau-tomer state. Our results not only provide a detailed mechanism of the photooxygenation reaction but also give indirect evidence to support the role of the triplet state in the reverse proton-transfer reaction.

  5. Time-resolved spectroscopy of low-dimensional semiconductor structures

    NASA Astrophysics Data System (ADS)

    Murphy, Joseph R.

    This dissertation is a survey of ultrafast time-resolved optical measurements conducted on a variety of low-dimensional semiconductor systems to further the understanding of the dynamic behavior in the following systems: ZnMnTe/ZnSe quantum dots, ZnTe/ZnMnSe quantum dots, InGaAs quantum wells, CdMnSe colloidal quantum dots, multi-shell CdSe/CdMnS/CdS colloidal nanoplatelets, and graphene and graphene-related solutions and films. Using time-resolved photoluminescence to study epitaxially-grown ZnTe and ZnMnTe quantum dots in corresponding ZnMnSe and ZnSe matrices, the location dependence of manganese ions in respect to magnetic polaron formation is shown. The structure with manganese ions located in the matrix exhibited magnetic polaron behavior consistent with previous literature, whereas the structure with the magnetic ions located within the quantum dots exhibited unconventional magnetic polaron properties. These properties, including temperature and magnetic field insensitivity, were explained through the use of a model that predicted an increased internal magnetic field due to a decreased effective volume of the magnetic polaron and a higher effective temperature due to laser heating. Magneto-time-resolved photoluminescence measurements on a system of colloidal CdMnSe quantum dots show that the magnetic polaron properties differ significantly from the epitaxially grown quantum dots. First the timescales at which the magnetic polaron forms and the polarization saturates are different by more than an order of magnitude, and second, the magnetic polaron energy exhibited step-like behavior as the strength of the externally applied magnetic field is increased. The field dependent MP formation energy that is observed experimentally is explained as due to the breaking of the antiferromagnetic coupling of Mn dimers within the QDs. This model is further verified by the observation of quantized behavior in the Zeeman energy splitting. Through the use of magneto

  6. Towards time-resolved serial crystallography in a microfluidic device.

    PubMed

    Pawate, Ashtamurthy S; Šrajer, Vukica; Schieferstein, Jeremy; Guha, Sudipto; Henning, Robert; Kosheleva, Irina; Schmidt, Marius; Ren, Zhong; Kenis, Paul J A; Perry, Sarah L

    2015-07-01

    Serial methods for crystallography have the potential to enable dynamic structural studies of protein targets that have been resistant to single-crystal strategies. The use of serial data-collection strategies can circumvent challenges associated with radiation damage and repeated reaction initiation. This work utilizes a microfluidic crystallization platform for the serial time-resolved Laue diffraction analysis of macroscopic crystals of photoactive yellow protein (PYP). Reaction initiation was achieved via pulsed laser illumination, and the resultant electron-density difference maps clearly depict the expected pR(1)/pR(E46Q) and pR(2)/pR(CW) states at 10 µs and the pB1 intermediate at 1 ms. The strategies presented here have tremendous potential for extension to chemical triggering methods for reaction initiation and for extension to dynamic, multivariable analyses.

  7. Femtosecond time-resolved ERE-CARS of PM650

    NASA Astrophysics Data System (ADS)

    He, Ping; Fan, Rongwei; Chen, Deying; Li, Xiaohui; Xia, Yuanqin; Yu, Xin; Wang, Jialing; Jiang, Yugang

    2012-07-01

    We utilize femtosecond time-resolved electronic resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS) to investigate new information for pyrromethene 650 (PM650) dye molecules. For this purpose, the vibrational properties of PM650 are registered in diluted solutions of several organisms. We observe a strong Raman vibrational mode with a wavenumber difference of about 48 cm- 1 in its organic solutions. This may be linked to the intramolecular electron transfer (ICT) process from the aromatic ring to the cyano group in PM650. The influence of the solvent effects on the vibrational dynamics of PM650 is also investigated. The vibrational properties of PM650 dye molecules diluted in polar organic solutions are light solvent-dependent.

  8. Time-Resolved Infrared (TRIR) Studies of Oxycarbonylnitrenes.

    PubMed

    Chavez, Tyler A; Liu, Yonglin; Toscano, John P

    2016-08-05

    N-Ethyloxycarbonyl-S,S-dibenzothiphene sulfilimine and N-t-butyloxycarbonyl-S,S-dibenzothiphene sulfilimine have been utilized as precursors to ethoxycarbonylnitrene and t-butyloxycarbonylnitrene. B3LYP/6-31G(d) calculations predict triplet ground states for both oxycarbonylnitrenes, albeit by small margins. Triplet ethoxycarbonylnitrene and triplet t-butyloxycarbonylnitrene have been observed following photolysis of these sulfilimine precursors by time-resolved infrared (TRIR) spectroscopy. Kinetic studies show that ethoxycarbonylnitrene reacts with solvents such as acetonitrile and cyclohexane, while t-butyloxycarbonylnitrene undergoes an intramolecular insertion reaction to produce 5,5-dimethyl oxazolidinone. Product analysis following photolysis of N-t-butyloxycarbonyl-S,S-dibenzothiphene sulfilimine confirms that the oxazolidinone is the major product with an estimated yield of 90%. The products from these two nitrenes are derived from the corresponding singlet nitrene, either directly or via thermal repopulation of the singlet from the lower-energy triplet nitrene.

  9. Theoretical Studies of Time-Resolved Photoelectron Spectra of IBr^-

    NASA Astrophysics Data System (ADS)

    Horvath, Samantha; McCoy, Anne B.; Pitzer, Russell M.

    2009-06-01

    In the present study, we examine the time-resolved photoelectron spectra of IBr^-. In the photodetachment studies performed by Sanov and co-workers and Lineberger and co-workers, the anionic species, prepared in its electronic ground state (^2Σ_{1/2}^+), is excited to either its \\Atilde' (^2Π_{3/2}) or \\Btilde (^2Σ_{1/2}^+) excited state, before electron photodetachment and dissociation on the \\Ctilde (^1Π_1) or higher-lying excited states of the neutral species, respectively. In this work, we use the electronic structure program Columbus to calculate the six lowest electronic states of IBr^- and the ten lowest Σ states of IBr at the MR-SO-CISD/aug-cc-pVDZ level of theory/basis, using relativistic core potentials for I and Br. Experimentally determined electronic states of IBr are also used. Vibrational eigenstates for these electronic states are calculated in a discrete variable representation, and propagation of the thermally populated \\Xtilde-state vibrational wave functions on either the \\Atilde' or \\Btilde electronic states of the anion is performed using a Lanczos scheme. We then take time-dependent overlaps between these propagated states and the vibrational eigenstates of the neutral surface. Results for IBr^- show good agreement with the experimental time-resolved spectra. Extensions to IBr^-(CO_2)_n (n < 2) will also be discussed. R. Mabbs, K. Pichugin, and A. Sanov, J. Chem. Phys., 2005 122, 174305 Leonid Sheps, Elisa M. Miller, and W. C. Lineberger (private communication) E. Wrede, S. Laubach, S. Schulenburg, A. Brown, E. R. Wouters, A. J. Orr-Ewing, and M. N. R. Ashfold, J. Chem. Phys., 2001, 114(6), 2629. D. T. Colbert and W. H. Miller, J. Chem. Phys., 1992, 96(3), 1982

  10. Time Resolved Phase Transitions via Dynamic Transmission Electron Microscopy

    SciTech Connect

    Reed, B W; Armstrong, M R; Blobaum, K J; Browning, N D; Burnham, A K; Campbell, G H; Gee, R; Kim, J S; King, W E; Maiti, A; Piggott, W T; Torralva, B R

    2007-02-22

    The Dynamic Transmission Electron Microscope (DTEM) project is developing an in situ electron microscope with nanometer- and nanosecond-scale resolution for the study of rapid laser-driven processes in materials. We report on the results obtained in a year-long LDRD-supported effort to develop DTEM techniques and results for phase transitions in molecular crystals, reactive multilayer foils, and melting and resolidification of bismuth. We report the first in situ TEM observation of the HMX {beta}-{delta} phase transformation in sub-{micro}m crystals, computational results suggesting the importance of voids and free surfaces in the HMX transformation kinetics, and the first electron diffraction patterns of intermediate states in fast multilayer foil reactions. This project developed techniques which are applicable to many materials systems and will continue to be employed within the larger DTEM effort.

  11. Time-resolved pump-probe spectroscopy of intraband absorption by a semiconductor nanorod

    NASA Astrophysics Data System (ADS)

    Leonov, Mikhail Y.; Rukhlenko, Ivan D.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2013-09-01

    We develop a theory of time-resolved pump-probe optical spectroscopy of intraband absorption of a probe pulse inside an anisotropic semiconductor nanorod. The absorption is preceded by the absorption of the pump pulse resonant to an interband transition. It is assumed that the resonantly exited states of the nanorod are interrelated via the relaxation induced by their interaction with a bath. We reveal the conditions for which the absorption of the probe's pulse is governed by a simple formula regardless of the pulse's shape. This formula is useful for the analysis of the experimental data containing information on the relaxation parameters of the nanorod's electronic subsystem.

  12. Atomic motion of resonantly vibrating quartz crystal visualized by time-resolved X-ray diffraction

    SciTech Connect

    Aoyagi, Shinobu; Osawa, Hitoshi; Sugimoto, Kunihisa; Fujiwara, Akihiko

    2015-11-16

    Transient atomic displacements during a resonant thickness-shear vibration of AT-cut α-quartz are revealed by time-resolved X-ray diffraction under an alternating electric field. The lattice strain resonantly amplified by the alternating electric field is ∼10{sup 4} times larger than that induced by a static electric field. The resonantly amplified lattice strain is achieved by fast displacements of oxygen anions and collateral resilient deformation of Si−O−Si angles bridging rigid SiO{sub 4} tetrahedra, which efficiently transduce electric energy into elastic energy.

  13. Attosecond time-resolved imaging of molecular structure by photoelectron holography.

    PubMed

    Bian, Xue-Bin; Bandrauk, André D

    2012-06-29

    Dynamic imaging of the molecular structure of H(2)(+) is investigated by attosecond photoelectron holography. The interference between direct (reference) and backward rescattered (signal) photoelectrons in attosecond photoelectron holography reveals the birth time of both channels and the spatial information of molecular structure. This is confirmed by simulations with a semiclassical model and numerical solutions of the corresponding time-dependent Schrödinger equation, suggesting an attosecond time-resolved way of imaging molecular structure obtained from laser induced rescattering of ionized electrons. It is shown that both short and long rescattered electron trajectories can be imaged from the momentum distribution.

  14. Time-resolved infrared absorption studies applied to the study of radical plus molecule reactions

    SciTech Connect

    Bethardy, G.A.; Macdonald, R.G.; Northrup, F.J.

    1994-02-01

    Reaction of the cyano radical (CN) with ethane (C{sub 2}H{sub 6}) was studied using time resolved infrared absorption to monitor the product hydrogen cyanide (HCN) in individual to-vibrational states. Pulse laser photolysis was used to provide an initial excess of the CN radical and the time dependence of individual ro-vibrational states of the high frequency anti-symmetric stretching mode of HCN (0,0,v{sub 3}) was followed. These experiments reveal that the initial product state distribution of HCN is not highly excited in the HCN(0,0,{sub 3}) vibrational manifold.

  15. Mating behavior of a deep-sea squid revealed by in situ videography and the study of archived specimens.

    PubMed

    Hoving, H J T; Vecchione, M

    2012-12-01

    The mating behavior of deep-sea squids is shrouded in mystery. The squids for which mating has been observed use a hectocotylus, a modified arm, for the transfer of sperm packets called spermatophores. However, many deep-sea squid species lack a hectocotylus. We present the first in situ observations of mating behavior in a deep-sea squid that has no hectocotylus but instead uses an elongated terminal organ for the transfer of spermatangia, which are released from the spermatophores and burrow deeply into the female tissue. With remotely operated vehicles (ROVs), we observed two mating pairs of the deep-sea squid Pholidoteuthis adami in the Gulf of Mexico. The male adopted a peculiar position during mating, with its ventral side up and its posterior mantle above the female’s head. While the male held the female in what looked like a firm grip, we observed the long terminal organ extending through the funnel of the male, contacting the female dorsal mantle. Examinations of museum specimens show that spermatangia burrow from the outer dorsal mantle into the inner dorsal mantle. This combination of serendipitous in situ observations and archived specimens can be a powerful tool for understanding the behavior of deep-sea animals.

  16. Hydrogen-enhanced cracking revealed by in situ micro-cantilever bending test inside environmental scanning electron microscope.

    PubMed

    Deng, Yun; Hajilou, Tarlan; Barnoush, Afrooz

    2017-07-28

    To evaluate the hydrogen (H)-induced embrittlement in iron aluminium intermetallics, especially the one with stoichiometric composition of 50 at.% Al, a novel in situ micro-cantilever bending test was applied within an environmental scanning electron microscope (ESEM), which provides both a full process monitoring and a clean, in situ H-charging condition. Two sets of cantilevers were analysed in this work: one set of un-notched cantilevers, and the other set with focused ion beam-milled notch laying on two crystallographic planes: (010) and (110). The cantilevers were tested under two environmental conditions: vacuum (approximately 5 × 10(-4) Pa) and ESEM (450 Pa water vapour). Crack initiation at stress-concentrated locations and propagation to cause catastrophic failure were observed when cantilevers were tested in the presence of H; while no cracking occurred when tested in vacuum. Both the bending strength for un-notched beams and the fracture toughness for notched beams were reduced under H exposure. The hydrogen embrittlement (HE) susceptibility was found to be orientation dependent: the (010) crystallographic plane was more fragile to HE than the (110) plane.This article is part of the themed issue 'The challenges of hydrogen and metals'. © 2017 The Author(s).

  17. Hydrogen-enhanced cracking revealed by in situ micro-cantilever bending test inside environmental scanning electron microscope

    NASA Astrophysics Data System (ADS)

    Deng, Yun; Hajilou, Tarlan; Barnoush, Afrooz

    2017-06-01

    To evaluate the hydrogen (H)-induced embrittlement in iron aluminium intermetallics, especially the one with stoichiometric composition of 50 at.% Al, a novel in situ micro-cantilever bending test was applied within an environmental scanning electron microscope (ESEM), which provides both a full process monitoring and a clean, in situ H-charging condition. Two sets of cantilevers were analysed in this work: one set of un-notched cantilevers, and the other set with focused ion beam-milled notch laying on two crystallographic planes: (010) and (110). The cantilevers were tested under two environmental conditions: vacuum (approximately 5 × 10-4 Pa) and ESEM (450 Pa water vapour). Crack initiation at stress-concentrated locations and propagation to cause catastrophic failure were observed when cantilevers were tested in the presence of H; while no cracking occurred when tested in vacuum. Both the bending strength for un-notched beams and the fracture toughness for notched beams were reduced under H exposure. The hydrogen embrittlement (HE) susceptibility was found to be orientation dependent: the (010) crystallographic plane was more fragile to HE than the (110) plane. This article is part of the themed issue 'The challenges of hydrogen and metals'.

  18. In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors.

    PubMed

    Griffin, John M; Forse, Alexander C; Tsai, Wan-Yu; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P

    2015-08-01

    Supercapacitors store charge through the electrosorption of ions on microporous electrodes. Despite major efforts to understand this phenomenon, a molecular-level picture of the electrical double layer in working devices is still lacking as few techniques can selectively observe the ionic species at the electrode/electrolyte interface. Here, we use in situ NMR to directly quantify the populations of anionic and cationic species within a working microporous carbon supercapacitor electrode. Our results show that charge storage mechanisms are different for positively and negatively polarized electrodes for the electrolyte tetraethylphosphonium tetrafluoroborate in acetonitrile; for positive polarization charging proceeds by exchange of the cations for anions, whereas for negative polarization, cation adsorption dominates. In situ electrochemical quartz crystal microbalance measurements support the NMR results and indicate that adsorbed ions are only partially solvated. These results provide new molecular-level insight, with the methodology offering exciting possibilities for the study of pore/ion size, desolvation and other effects on charge storage in supercapacitors.

  19. Time-Resolved Photoluminescence Spectroscopy and Imaging: New Approaches to the Analysis of Cultural Heritage and Its Degradation

    PubMed Central

    Nevin, Austin; Cesaratto, Anna; Bellei, Sara; D'Andrea, Cosimo; Toniolo, Lucia; Valentini, Gianluca; Comelli, Daniela

    2014-01-01

    Applications of time-resolved photoluminescence spectroscopy (TRPL) and fluorescence lifetime imaging (FLIM) to the analysis of cultural heritage are presented. Examples range from historic wall paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested. PMID:24699285

  20. Time-resolved spectral imaging: better photon economy, higher accuracy

    NASA Astrophysics Data System (ADS)

    Fereidouni, Farzad; Reitsma, Keimpe; Blab, Gerhard A.; Gerritsen, Hans C.

    2015-03-01

    Lifetime and spectral imaging are complementary techniques that offer a non-invasive solution for monitoring metabolic processes, identifying biochemical compounds, and characterizing their interactions in biological tissues, among other tasks. Newly developed instruments that perform time-resolved spectral imaging can provide even more information and reach higher sensitivity than either modality alone. Here we report a multispectral lifetime imaging system based on a field-programmable gate array (FPGA), capable of operating at high photon count rates (12 MHz) per spectral detection channel, and with time resolution of 200 ps. We performed error analyses to investigate the effect of gate width and spectral-channel width on the accuracy of estimated lifetimes and spectral widths. Temporal and spectral phasors were used for analysis of recorded data, and we demonstrated blind un-mixing of the fluorescent components using information from both modalities. Fractional intensities, spectra, and decay curves of components were extracted without need for prior information. We further tested this approach with fluorescently doubly-labeled DNA, and demonstrated its suitability for accurately estimating FRET efficiency in the presence of either non-interacting or interacting donor molecules.

  1. Monitoring tissue metabolism via time-resolved laser fluorescence

    NASA Astrophysics Data System (ADS)

    Maerz, Holger K.; Buchholz, Rainer; Emmrich, Frank; Fink, Frank; Geddes, Clive L.; Pfeifer, Lutz; Raabe, Ferdinand; Marx, Uwe

    1999-05-01

    Most assays for drug screening are monitoring the metabolism of cells by detecting the NADH content, which symbolize its metabolic activity, indirectly. Nowadays, the performance of a LASER enables us to monitor the metabolic state of mammalian cells directly and on-line by using time-resolved autofluorescence detection. Therefore, we developed in combination with tissue engineering, an assay for monitoring minor toxic effects of volatile organic compounds (VOC), which are accused of inducing Sick Building Syndrome (SBS). Furthermore, we used the Laserfluoroscope (LF) for pharmacological studies on human bone marrow in vitro with special interest in chemotherapy simulation. In cancer research and therapy, the effect of chemostatica in vitro in the so-called oncobiogram is being tested; up to now without great success. However, it showed among other things that tissue structure plays a vital role. Consequently, we succeeded in simulating a chemotherapy in vitro on human bone marrow. Furthermore, after tumor ektomy we were able to distinguish between tumoric and its surrounding healthy tissue by using the LF. With its sensitive detection of metabolic changes in tissues the LF enables a wide range of applications in biotechnology, e.g. for quality control in artificial organ engineering or biocompatability testing.

  2. Fielding of a time-resolved tomographic diagnostic

    SciTech Connect

    Daniel Frayer, Brian Cox, Wendi Dreesen, Douglas Johnson, Morris Kaufman

    2008-03-01

    A diagnostic instrument has been developed for the acquisition of high-speed time-resolved images at the Dual-Axis Radiographic Hydrodynamic Test (DARHT) Facility at Los Alamos National Laboratory. The instrument was developed in order to create time histories of the electron beam. Four discrete optical subsystems view Cerenkov light generated at an X-ray target inside of a vacuum envelope. Each system employs cylindrical optics to image light in one direction and collapse light in the orthogonal direction. Each of the four systems images and collapses in unique axes, thereby capturing unique information. Light along the imaging axis is relayed via optical fiber to streak cameras. A computer is used to reconstruct the original image from the four optically collapsed images. Due to DARHT’s adverse environment, the instrument can be operated remotely to adjust optical parameters and contains a subsystem for remote calibration. The instrument was deployed and calibrated, and has been used to capture and reconstruct images. Matters of alignment, calibration, control, resolution, adverse conditions and maintenance will be discussed.

  3. Chopper system for time resolved experiments with synchrotron radiation.

    PubMed

    Cammarata, Marco; Eybert, Laurent; Ewald, Friederike; Reichenbach, Wolfgang; Wulff, Michael; Anfinrud, Philip; Schotte, Friedrich; Plech, Anton; Kong, Qingyu; Lorenc, Maciej; Lindenau, Bernd; Räbiger, Jürgen; Polachowski, Stephan

    2009-01-01

    A chopper system for time resolved pump-probe experiments with x-ray beams from a synchrotron is described. The system has three parts: a water-cooled heatload chopper, a high-speed chopper, and a millisecond shutter. The chopper system, which is installed in beamline ID09B at the European Synchrotron Radiation Facility, provides short x-ray pulses for pump-probe experiments with ultrafast lasers. The chopper system can produce x-ray pulses as short as 200 ns in a continuous beam and repeat at frequencies from 0 to 3 kHz. For bunch filling patterns of the synchrotron with pulse separations greater than 100 ns, the high-speed chopper can isolate single 100 ps x-ray pulses that are used for the highest time resolution. A new rotor in the high-speed chopper is presented with a single pulse (100 ps) and long pulse (10 micros) option. In white beam experiments, the heatload of the (noncooled) high-speed chopper is lowered by a heatload chopper, which absorbs 95% of the incoming power without affecting the pulses selected by the high speed chopper.

  4. Time-Resolved Hard X-Ray Spectrometer

    SciTech Connect

    Kenneth Moya; Ian McKennaa; Thomas Keenana; Michael Cuneob

    2007-03-01

    Wired array studies are being conducted at the SNL Z accelerator to maximize the x-ray generation for inertial confinement fusion targets and high energy density physics experiments. An integral component of these studies is the characterization of the time-resolved spectral content of the x-rays. Due to potential spatial anisotropy in the emitted radiation, it is also critical to diagnose the time-evolved spectral content in a space-resolved manner. To accomplish these two measurement goals, we developed an x-ray spectrometer using a set of high-speed detectors (silicon PIN diodes) with a collimated field-of-view that converged on a 1-cm-diameter spot at the pinch axis. Spectral discrimination is achieved by placing high Z absorbers in front of these detectors. We built two spectrometers to permit simultaneous different angular views of the emitted radiation. Spectral data have been acquired from recent Z shots for the radial and polar views. UNSPEC1 has been adapted to analyze and unfold the measured data to reconstruct the x-ray spectrum. The unfold operator code, UFO2, is being adapted for a more comprehensive spectral unfolding treatment.

  5. Time resolved spectroscopic NMR imaging using hyperpolarized 129Xe

    NASA Astrophysics Data System (ADS)

    Han, S.; Kühn, H.; Häsing, F. W.; Münnemann, K.; Blümich, B.; Appelt, S.

    2004-04-01

    We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized 129Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.

  6. Femtosecond time-resolved MeV electron diffraction

    DOE PAGES

    Zhu, Pengfei; Zhu, Y.; Hidaka, Y.; ...

    2015-06-02

    We report the experimental demonstration of femtosecond electron diffraction using high-brightness MeV electron beams. High-quality, single-shot electron diffraction patterns for both polycrystalline aluminum and single-crystal 1T-TaS2 are obtained utilizing a 5 fC (~3 × 104 electrons) pulse of electrons at 2.8 MeV. The high quality of the electron diffraction patterns confirms that electron beam has a normalized emittance of ~50 nm rad. The transverse and longitudinal coherence length is ~11 and ~2.5 nm, respectively. The timing jitter between the pump laser and probe electron beam was found to be ~100 fs (rms). The temporal resolution is demonstrated by observing themore » evolution of Bragg and superlattice peaks of 1T-TaS2 following an 800 nm optical pump and was found to be 130 fs. Lastly, our results demonstrate the advantages of MeV electrons, including large elastic differential scattering cross-section and access to high-order reflections, and the feasibility of ultimately realizing below 10 fs time-resolved electron diffraction.« less

  7. Time-Resolved Synchronous Fluorescence for Biomedical Diagnosis

    PubMed Central

    Zhang, Xiaofeng; Fales, Andrew; Vo-Dinh, Tuan

    2015-01-01

    This article presents our most recent advances in synchronous fluorescence (SF) methodology for biomedical diagnostics. The SF method is characterized by simultaneously scanning both the excitation and emission wavelengths while keeping a constant wavelength interval between them. Compared to conventional fluorescence spectroscopy, the SF method simplifies the emission spectrum while enabling greater selectivity, and has been successfully used to detect subtle differences in the fluorescence emission signatures of biochemical species in cells and tissues. The SF method can be used in imaging to analyze dysplastic cells in vitro and tissue in vivo. Based on the SF method, here we demonstrate the feasibility of a time-resolved synchronous fluorescence (TRSF) method, which incorporates the intrinsic fluorescent decay characteristics of the fluorophores. Our prototype TRSF system has clearly shown its advantage in spectro-temporal separation of the fluorophores that were otherwise difficult to spectrally separate in SF spectroscopy. We envision that our previously-tested SF imaging and the newly-developed TRSF methods will combine their proven diagnostic potentials in cancer diagnosis to further improve the efficacy of SF-based biomedical diagnostics. PMID:26404289

  8. Time resolved EUV spectra from Zpinching capillary discharge plasma

    NASA Astrophysics Data System (ADS)

    Jancarek, Alexandr; Nevrkla, Michal; Nawaz, Fahad

    2015-09-01

    We developed symmetrically charged driver to obtain high voltage, high current Z-pinching capillary discharge. Plasma is created by up to 70 kA, 29 ns risetime current pulse passing through a 5 mm inner diameter, 224 mm long capillary filled with gas to initial pressure in the range of 1 kPa. Due to the low inductance design of the driver, the pinch is observable directly from the measured current curve. Time-integrated and time-resolved spectra of discharge plasma radiation are recorded together with the capillary current and analyzed. The most encouraging spectra were captured in the wavelength range 8.3 ÷ 14 nm. This spectral region contains nitrogen Balmer series lines including potentially lasing NVII 2 - 3 transition. Spectral lines are identified in the NIST database using the FLY kinetic code. The line of 13.38 nm wavelength, transition NVII 2 - 3, was observed in gated, and also in time-integrated spectra for currents >60 kA. This work has been supported by the Ministry of Education, Youth and Sports of the Czech Republic grants LG13029.

  9. Time-resolved infrared spectroscopic techniques as applied to channelrhodopsin

    PubMed Central

    Ritter, Eglof; Puskar, Ljiljana; Bartl, Franz J.; Aziz, Emad F.; Hegemann, Peter; Schade, Ulrich

    2015-01-01

    Among optogenetic tools, channelrhodopsins, the light gated ion channels of the plasma membrane from green algae, play the most important role. Properties like channel selectivity, timing parameters or color can be influenced by the exchange of selected amino acids. Although widely used, in the field of neurosciences for example, there is still little known about their photocycles and the mechanism of ion channel gating and conductance. One of the preferred methods for these studies is infrared spectroscopy since it allows observation of proteins and their function at a molecular level and in near-native environment. The absorption of a photon in channelrhodopsin leads to retinal isomerization within femtoseconds, the conductive states are reached in the microsecond time scale and the return into the fully dark-adapted state may take more than minutes. To be able to cover all these time regimes, a range of different spectroscopical approaches are necessary. This mini-review focuses on time-resolved applications of the infrared technique to study channelrhodopsins and other light triggered proteins. We will discuss the approaches with respect to their suitability to the investigation of channelrhodopsin and related proteins. PMID:26217670

  10. Femtosecond time-resolved MeV electron diffraction

    SciTech Connect

    Zhu, Pengfei; Zhu, Y.; Hidaka, Y.; Wu, L.; Cao, J.; Berger, H.; Geck, J.; Kraus, R.; Pjerov, S.; Shen, Y.; Tobey, R. I.; Hill, J. P.; Wang, X. J.

    2015-06-02

    We report the experimental demonstration of femtosecond electron diffraction using high-brightness MeV electron beams. High-quality, single-shot electron diffraction patterns for both polycrystalline aluminum and single-crystal 1T-TaS2 are obtained utilizing a 5 fC (~3 × 104 electrons) pulse of electrons at 2.8 MeV. The high quality of the electron diffraction patterns confirms that electron beam has a normalized emittance of ~50 nm rad. The transverse and longitudinal coherence length is ~11 and ~2.5 nm, respectively. The timing jitter between the pump laser and probe electron beam was found to be ~100 fs (rms). The temporal resolution is demonstrated by observing the evolution of Bragg and superlattice peaks of 1T-TaS2 following an 800 nm optical pump and was found to be 130 fs. Lastly, our results demonstrate the advantages of MeV electrons, including large elastic differential scattering cross-section and access to high-order reflections, and the feasibility of ultimately realizing below 10 fs time-resolved electron diffraction.

  11. Fielding of a Time-Resolved Tomographic Diagnostic

    SciTech Connect

    Daniel Frayer, Brian Cox, Wendi Dreesen, Douglas Johnson, Mike Jones, Morris Kaufman

    2008-09-11

    A diagnostic instrument has been developed for the acquisition of high-speed time-resolved images at the Dual-Axis Radiographic Hydrodynamic Test (DARHT) Facility at Los Alamos National Laboratory. The instrument was developed in order to create time histories of the electron beam. Four discrete optical subsystems view Cerenkov light generated at an x-ray target inside of a vacuum envelope. Each system employs cylindrical optics to image light in one direction and collapse light in the orthogonal direction. Each of the four systems images and collapses in unique axes, thereby capturing unique information. Light along the imaging axis is relayed via optical fiber to streak cameras. A computer is used to reconstruct the original image from the four optically collapsed images. Due to DARHT’s adverse environment, the instrument can be operated remotely to adjust optical parameters and contains a subsystem for remote calibration. The instrument was deployed and calibrated, and has been used to capture and reconstruct images. Matters of alignment, calibration, control, resolution, and adverse conditions will be discussed.

  12. Time-resolved pump-probe experiments at the LCLS

    SciTech Connect

    Glownia, James; Cryan, J.; Andreasson, J.; Belkacem, A.; Berrah, N.; Blaga, C.L.; Bostedt, C.; Bozek, J.; DiMauro, L.F.; Fang, L.; Frisch, J.; Gessner, O.; Guhr, M.; Hajdu, J.; Hertlein, M.P.; Hoener, M.; Huang, G.; Kornilov, O.; Marangos, J.P.; March, A.M.; McFarland, B.K.; /SLAC /Stanford U., Phys. Dept. /SLAC /IRAMIS, Saclay /Stanford U., Phys. Dept. /Georgia Tech /Argonne /Kansas State U. /SLAC /Stanford U., Phys. Dept. /SLAC /Stanford U., Appl. Phys. Dept. /Stanford U., Appl. Phys. Dept. /SLAC /LBNL /Argonne /SLAC /SLAC /Stanford U., Appl. Phys. Dept. /Stanford U., Phys. Dept.

    2011-08-12

    The first time-resolved x-ray/optical pump-probe experiments at the SLAC Linac Coherent Light Source (LCLS) used a combination of feedback methods and post-analysis binning techniques to synchronize an ultrafast optical laser to the linac-based x-ray laser. Transient molecular nitrogen alignment revival features were resolved in time-dependent x-ray-induced fragmentation spectra. These alignment features were used to find the temporal overlap of the pump and probe pulses. The strong-field dissociation of x-ray generated quasi-bound molecular dications was used to establish the residual timing jitter. This analysis shows that the relative arrival time of the Ti:Sapphire laser and the x-ray pulses had a distribution with a standard deviation of approximately 120 fs. The largest contribution to the jitter noise spectrum was the locking of the laser oscillator to the reference RF of the accelerator, which suggests that simple technical improvements could reduce the jitter to better than 50 fs.

  13. Time-resolved pump-probe experiments at the LCLS.

    PubMed

    Glownia, James M; Cryan, J; Andreasson, J; Belkacem, A; Berrah, N; Blaga, C I; Bostedt, C; Bozek, J; DiMauro, L F; Fang, L; Frisch, J; Gessner, O; Gühr, M; Hajdu, J; Hertlein, M P; Hoener, M; Huang, G; Kornilov, O; Marangos, J P; March, A M; McFarland, B K; Merdji, H; Petrovic, V S; Raman, C; Ray, D; Reis, D A; Trigo, M; White, J L; White, W; Wilcox, R; Young, L; Coffee, R N; Bucksbaum, P H

    2010-08-16

    The first time-resolved x-ray/optical pump-probe experiments at the SLAC Linac Coherent Light Source (LCLS) used a combination of feedback methods and post-analysis binning techniques to synchronize an ultrafast optical laser to the linac-based x-ray laser. Transient molecular nitrogen alignment revival features were resolved in time-dependent x-ray-induced fragmentation spectra. These alignment features were used to find the temporal overlap of the pump and probe pulses. The strong-field dissociation of x-ray generated quasi-bound molecular dications was used to establish the residual timing jitter. This analysis shows that the relative arrival time of the Ti:Sapphire laser and the x-ray pulses had a distribution with a standard deviation of approximately 120 fs. The largest contribution to the jitter noise spectrum was the locking of the laser oscillator to the reference RF of the accelerator, which suggests that simple technical improvements could reduce the jitter to better than 50 fs.

  14. Time-resolved spectral analysis of Radachlorin luminescence in water

    NASA Astrophysics Data System (ADS)

    Belik, V. P.; Gadzhiev, I. M.; Semenova, I. V.; Vasyutinskii, O. S.

    2017-05-01

    We report results of spectral- and time-resolved study of Radachlorin photosensitizer luminescence in water in the spectral range of 950-1350nm and for determination of the photosensitizer triplet state and the singlet oxygen lifetimes responsible for singlet oxygen generation and degradation. At any wavelength within the explored spectral range the luminescence decay contained two major contributions: a fast decay at the ns time scale and a slow evolution at the μs time scale. The fast decay was attributed to electric dipole fluorescence transitions in photosensitizer molecules and the slow evolution to intercombination phosphorescence transitions in singlet oxygen and photosensitizer molecules. Relatively high-amplitude ns peak observed at all wavelengths suggests that singlet oxygen monitoring with spectral isolation methods alone, without additional temporal resolution can be controversial. In the applied experimental conditions the total phosphorescence signal at any wavelength contained a contribution from the photosensitizer triplet state decay, while at 1274nm the singlet oxygen phosphorescence dominated. The results obtained can be used for optimization of the methods of singlet oxygen monitoring and imaging.

  15. Time-resolved spectral analysis of Radachlorin luminescence in water.

    PubMed

    Belik, V P; Gadzhiev, I M; Semenova, I V; Vasyutinskii, O S

    2017-05-05

    We report results of spectral- and time-resolved study of Radachlorin photosensitizer luminescence in water in the spectral range of 950-1350nm and for determination of the photosensitizer triplet state and the singlet oxygen lifetimes responsible for singlet oxygen generation and degradation. At any wavelength within the explored spectral range the luminescence decay contained two major contributions: a fast decay at the ns time scale and a slow evolution at the μs time scale. The fast decay was attributed to electric dipole fluorescence transitions in photosensitizer molecules and the slow evolution to intercombination phosphorescence transitions in singlet oxygen and photosensitizer molecules. Relatively high-amplitude ns peak observed at all wavelengths suggests that singlet oxygen monitoring with spectral isolation methods alone, without additional temporal resolution can be controversial. In the applied experimental conditions the total phosphorescence signal at any wavelength contained a contribution from the photosensitizer triplet state decay, while at 1274nm the singlet oxygen phosphorescence dominated. The results obtained can be used for optimization of the methods of singlet oxygen monitoring and imaging. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. A Multi-Enzyme Bioluminescent Time-Resolved Pyrophosphate Assay

    PubMed Central

    Sun, Ye; Jacobson, K. Bruce; Golovlev, Val

    2009-01-01

    We have developed a high-sensitivity assay for measurement of inorganic pyrophosphate (PPi) in adenosine 5′-triphosphate (ATP) contaminated samples. The assay is based on time-resolved measurements of the luminescence kinetics and implements multiple enzymes to convert PPi to ATP that is, in turn, utilized to produce light; and to hydrolyze PPi for measurement of the steady-state background luminescence. A theoretical model for describing luminescence kinetics and optimizing composition of the assay detection mixture is presented. We found the model is in excellent agreement with the experimental results. We have developed and evaluated two algorithms for PPi measurement from luminescence kinetics acquired from ATP-contaminated samples. The first algorithm is considered to be the method of choice for analysis of long, i.e., 3-5 min, kinetics. The activity of enzymes is controlled during the experiment; the sensitivity of PPi detection is about 7 pg/ml or 15 pM of PPi in ATP-contaminated samples. The second algorithm is designed for analysis of short, i.e., less than 1-min luminescence kinetics. It has about 20 pM PPi detection sensitivity and may be the better choice for assays in microplate format, where a short measurement time is required. The PPi assay is primarily developed for RNA expression analysis, but it also can be used in various applications, which require high sensitivity PPi detection in ATP-contaminated samples. PMID:17540325

  17. Time-resolved multiphoton imaging of basal cell carcinoma

    NASA Astrophysics Data System (ADS)

    Cicchi, R.; Sestini, S.; De Giorgi, V.; Stambouli, D.; Carli, P.; Massi, D.; Pavone, F. S.

    2007-02-01

    We investigated human cutaneous basal cell carcinoma ex-vivo samples by combined time resolved two photon intrinsic fluorescence and second harmonic generation microscopy. Morphological and spectroscopic differences were found between malignant skin and corresponding healthy skin tissues. In comparison with normal healthy skin, cancer tissue showed a different morphology and a mean fluorescence lifetime distribution slightly shifted towards higher values. Topical application of delta-aminolevulinic acid to the lesion four hours before excision resulted in an enhancement of the fluorescence signal arising from malignant tissue, due to the accumulation of protoporphyrines inside tumor cells. Contrast enhancement was prevalent at tumor borders by both two photon fluorescence microscopy and fluorescence lifetime imaging. Fluorescence-based images showed a good correlation with conventional histopathological analysis, thereby supporting the diagnostic accuracy of this novel method. Combined morphological and lifetime analysis in the study of ex-vivo skin samples discriminated benign from malignant tissues, thus offering a reliable, non-invasive tool for the in-vivo analysis of inflammatory and neoplastic skin lesions.

  18. Development of ultrafast time-resolved dual-comb spectroscopy

    NASA Astrophysics Data System (ADS)

    Asahara, Akifumi; Minoshima, Kaoru

    2017-04-01

    Ultrafast time-resolved dual-comb spectroscopy (TR-DCS) has been demonstrated, which enables direct observations of transient responses of complex optical spectra by combining dual-comb spectroscopy with the pump-probe method. TR-DCS achieves two-dimensional spectroscopy with a wide dynamic range for both the temporal and frequency axes. As a demonstration, we investigated the femtosecond relaxation dynamics of a photo-excited InGaAs saturable absorber in the near-infrared frequency region. The transient response of the interferogram was successfully obtained, and both the amplitude and phase spectra of the dynamic complex transmittance were independently deduced without using the Kramers-Kronig relations. A high phase resolution in the order of milliradian was achieved by suppressing the effect from the slow phase drift caused in the experimental system. Our proof-of-principle experiment promotes a pathway to coherent, highly accurate, and multi-dimensional pump-probe spectroscopy using the optical frequency comb technology.

  19. Time-resolved local strain tracking microscopy for cell mechanics

    NASA Astrophysics Data System (ADS)

    Aydin, O.; Aksoy, B.; Akalin, O. B.; Bayraktar, H.; Alaca, B. E.

    2016-02-01

    A uniaxial cell stretching technique to measure time-resolved local substrate strain while simultaneously imaging adherent cells is presented. The experimental setup comprises a uniaxial stretcher platform compatible with inverted microscopy and transparent elastomer samples with embedded fluorescent beads. This integration enables the acquisition of real-time spatiotemporal data, which is then processed using a single-particle tracking algorithm to track the positions of fluorescent beads for the subsequent computation of local strain. The present local strain tracking method is demonstrated using polydimethylsiloxane (PDMS) samples of rectangular and dogbone geometries. The comparison of experimental results and finite element simulations for the two sample geometries illustrates the capability of the present system to accurately quantify local deformation even when the strain distribution is non-uniform over the sample. For a regular dogbone sample, the experimentally obtained value of local strain at the center of the sample is 77%, while the average strain calculated using the applied cross-head displacement is 48%. This observation indicates that considerable errors may arise when cross-head measurement is utilized to estimate strain in the case of non-uniform sample geometry. Finally, the compatibility of the proposed platform with biological samples is tested using a unibody PDMS sample with a well to contain cells and culture media. HeLa S3 cells are plated on collagen-coated samples and cell adhesion and proliferation are observed. Samples with adherent cells are then stretched to demonstrate simultaneous cell imaging and tracking of embedded fluorescent beads.

  20. Time-resolved shadowgraphy of optical breakdown in fused silica

    NASA Astrophysics Data System (ADS)

    Tran, K. A.; Grigorov, Y. V.; Nguyen, V. H.; Rehman, Z. U.; Le, N. T.; Janulewicz, K. A.

    2015-07-01

    Dynamics of a laser-induced optical breakdown in the bulk of fused silica initiated by a sub-nanosecond laser pulse of an energy fluence as high as 8.7 kJ/cm2 was investigated by using femtosecond time-resolved shadowgraphy. Plasma ignition, growth of the damaged region and accompanying hydrodynamic motion were recorded from the moment directly before the arrival of the driving laser pulse, in the time steps adapted to the rate of the occurring processes. The growth rate of the plasma channel, curvature radii and velocities of the wave fronts were extracted from the shadowgrams. It was found that the plasma channel develops with a supersonic velocity and the first observed shock front tends to transform itself from the initial bowl-like shape to the final spherical one characterising an acoustic wave. Appearance of multiple fronts accompanying the main shock front was registered and used in more detailed analysis of the optical breakdown dynamics in the transparent dielectrics.

  1. Time-resolved hard x-ray spectrometer

    NASA Astrophysics Data System (ADS)

    Moy, Kenneth; Cuneo, Michael; McKenna, Ian; Keenan, Thomas; Sanford, Thomas; Mock, Ray

    2006-08-01

    Wired array studies are being conducted at the SNL Z accelerator to maximize the x-ray generation for inertial confinement fusion targets and high energy density physics experiments. An integral component of these studies is the characterization of the time-resolved spectral content of the x-rays. Due to potential spatial anisotropy in the emitted radiation, it is also critical to diagnose the time-evolved spectral content in a space-resolved manner. To accomplish these two measurement goals, we developed an x-ray spectrometer using a set of high-speed detectors (silicon PIN diodes) with a collimated field-of-view that converged on a 1-cm-diameter spot at the pinch axis. Spectral discrimination is achieved by placing high Z absorbers in front of these detectors. We built two spectrometers to permit simultaneous different angular views of the emitted radiation. Spectral data have been acquired from recent Z shots for the radial and axial (polar) views. UNSPEC 1 has been adapted to analyze and unfold the measured data to reconstruct the x-ray spectrum. The unfold operator code, UFO2, is being adapted for a more comprehensive spectral unfolding treatment.

  2. In-Situ Incubation of Iron-Sulfide Mineral in Seawater Reveals Colonization by Iron-Oxidizing Gammaproteobacteria and Zetaproteobacteria.

    NASA Astrophysics Data System (ADS)

    Barco, R. A.; Ramírez, G. A.; Sylvan, J. B.; Edwards, K. J.

    2015-12-01

    Sulfide mineral precipitation occurs at mid-ocean ridge (MOR) spreading centers, both in the form of plume particles and massive sulfide structures. A common constituent of MOR sulfide mineral is pyrrhotite (Fe1-xS). This mineral was chosen as a substrate for in-situ incubation studies in the shallow waters of Catalina Islands, CA to investigate the colonization of iron-oxidizing bacteria. Gammaproteobacteria and Alphaproteobacteria largely dominated the bacterial community on pyrrhotite samples incubated in the water column. Pyrrhotite samples incubated at the sediment/water column interface showed more even dominance by Gammaproteobacteria, Alphaproteobacteria, Deltaproteobacteria and Bacteroidetes. Cultivations that originated from these pyrrhotite samples resulted in the enrichment of Zetaproteobacteria with either twisted-stalks (Mariprofundus) or sheath structures. Additionally, a candidate novel Gammaproteobacterium was isolated and shown to grow autotrophically via the oxidation of iron.

  3. Segmental duplications within the Glycine max genome revealed by fluorescence in situ hybridization of bacterial artificial chromosomes.

    PubMed

    Pagel, Janice; Walling, Jason G; Young, Nevin D; Shoemaker, Randy C; Jackson, Scott A

    2004-08-01

    Soybean (Glycine max L. Merr.) is presumed to be an ancient polyploid based on chromosome number and multiple RFLP fragments in genetic mapping. Direct cytogenetic observation of duplicated regions within the soybean genome has not heretofore been reported. Employing fluorescence in situ hybridization (FISH) of genetically anchored bacterial artificial chromosomes (BACs) in soybean, we were able to observe that the distal ends of molecular linkage group E had duplicated regions on linkage groups A2 and B2. Further, using fiber-FISH, it was possible to measure the molecular size and organization of one of the duplicated regions. As FISH did not require repetitive DNA for blocking fluorescence signals, we assume that the 200-kb genome region is relatively low in repetitive sequences. This observation, along with the observation that the BACs are located in distal euchromatin regions, has implications for genome structure/evolution and the approach used to sequence the soybean genome.

  4. In vivo expression of mRNA for the Ca++-binding protein SPARC (osteonectin) revealed by in situ hybridization

    PubMed Central

    1987-01-01

    In situ hybridization is used to survey the tissue-specific and developmental expression of the cloned mouse gene Sparc, coding for a protein homologous to the bovine Ca++-binding protein, osteonectin. High levels of SPARC RNA are found in osteoblasts and odontoblasts. In addition, high grain counts are associated with a variety of other cell types in the embryo and newborn mouse, including parietal endoderm, deciduum, whisker follicles (connective tissue sheath), peripheral nerve trunk, skin (dermis), and stomach (submucosa). Spatially restricted but high levels of SPARC mRNA are also seen in the adult adrenal glands, testis, and ovary. This pattern of differential gene expression demands a reassessment of the function originally proposed for osteonectin, and predicts a much wider role for the protein in a variety of biological processes. PMID:2440898

  5. Molecular orientation of molybdate ions adsorbed on goethite nanoparticles revealed by polarized in situ ATR-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Davantès, Athénaïs; Lefèvre, Grégory

    2016-11-01

    The speciation of species adsorbed on nanoparticles is a major concern for several fields, as environmental pollution and remediation, surface functionalization, or catalysis. Attenuated total reflectance infrared spectroscopy (ATR-IR) was amongst the rare methods able to give in situ information about the geometry of surface complexes on nanoparticles. A new possibility using this technique is illustrated here with the MoO42 -/goethite system. Using deuterated goethite to avoid spectral interferences, adsorption of molybdate ions on a spontaneous oriented film of nanoparticles has been followed using a polarized infrared beam. From the decomposition of spectra in the x, y and z directions, a monodentate surface complex on the {101} faces has been found as the most probable geometry. This result demonstrates that polarized ATR-IR allows to characterize in more details adsorption mode at the atomic scale, in comparison with usual ATR-IR spectroscopy.

  6. Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy.

    PubMed

    Smeets, Paul J M; Cho, Kang Rae; Kempen, Ralph G E; Sommerdijk, Nico A J M; De Yoreo, James J

    2015-04-01

    The characteristic shapes, structures and properties of biominerals arise from their interplay with a macromolecular matrix. The developing mineral interacts with acidic macromolecules, which are either dissolved in the crystallization medium or associated with insoluble matrix polymers, that affect growth habits and phase selection or completely inhibit precipitation in solution. Yet little is known about the role of matrix-immobilized acidic macromolecules in directing mineralization. Here, by using in situ liquid-phase electron microscopy to visualize the nucleation and growth of CaCO3 in a matrix of polystyrene sulphonate (PSS), we show that the binding of calcium ions to form Ca-PSS globules is a key step in the formation of metastable amorphous calcium carbonate (ACC), an important precursor phase in many biomineralization systems. Our findings demonstrate that ion binding can play a significant role in directing nucleation, independently of any control over the free-energy barrier to nucleation.

  7. In situ SUMOylation analysis reveals a modulatory role of RanBP2 in the nuclear rim and PML bodies

    SciTech Connect

    Saitoh, Noriko . E-mail: hisa@gpo.kumamoto-u.ac.jp; Uchimura, Yasuhiro; Tachibana, Taro; Sugahara, Satoko; Saitoh, Hisato; Nakao, Mitsuyoshi . E-mail: mnakao@gpo.kumamoto-u.ac.jp

    2006-05-01

    SUMO modification plays a critical role in a number of cellular functions including nucleocytoplasmic transport, gene expression, cell cycle and formation of subnuclear structures such as promyelocytic leukemia (PML) bodies. In order to identify the sites where SUMOylation takes place in the cell, we developed an in situ SUMOylation assay using a semi-intact cell system and subsequently combined it with siRNA-based knockdown of nucleoporin RanBP2, also known as Nup358, which is one of the known SUMO E3 proteins. With the in situ SUMOylation assay, we found that both nuclear rim and PML bodies, besides mitotic apparatuses, are major targets for active SUMOylation. The ability to analyze possible SUMO conjugation sites would be a valuable tool to investigate where SUMO E3-like activities and/or SUMO substrates exist in the cell. Specific knockdown of RanBP2 completely abolished SUMOylation along the nuclear rim and dislocated RanGAP1 from the nuclear pore complexes. Interestingly, the loss of RanBP2 markedly reduced the number of PML bodies, in contrast to other, normal-appearing nuclear compartments including the nuclear lamina, nucleolus and chromatin, suggesting a novel link between RanBP2 and PML bodies. SUMOylation facilitated by RanBP2 at the nuclear rim may be a key step for the formation of a particular subnuclear organization. Our data imply that SUMO E3 proteins like RanBP2 facilitate spatio-temporal SUMOylation for certain nuclear structure and function.

  8. Static and time-resolved spectroscopic studies of low-symmetry Ru(II) polypyridyl complexes

    SciTech Connect

    Curtright, A.E.; McCusker, J.K.

    1999-09-02

    The spectroscopic and electrochemical properties of a series of four Ru{sup II} polypyridyl complexes are reported. Compounds of the form [Ru(dmb){sub x}(dea){sub 3{minus}x}]{sup 2+} (x = 0--3), where dmb is 4,4{prime}-dimethyl-2,2{prime}-bipyridine and dea is 4,4{prime}-bis(diethylamino)-2,2{prime}-bipyridine, have been prepared and studied using static and time-resolved electronic and vibrational spectroscopies as a prelude to femtosecond spectroscopic studies of excited-state dynamics. Static electronic spectra in CH{sub 3}CN solution reveal a systematic shift of the MLCT absorption envelope from a maximum of 458 nm in the case of [Ru(dmb){sub 3}]{sup 2+} to 518 nm for [Ru(dea){sub 3}]{sup 2+} with successive substitutions of dea for dmb, suggesting a dea-based chromophore as the lowest-energy species. However, analysis of static and time-resolved emission data indicates an energy gap ordering of [Ru(dmb){sub 3}]{sup 2+} > [Ru(dmb){sub 2}(dea)]{sup 2+} > [Ru(dea){sub 3}]{sup 2+} > [Ru(dmb)(DEA){sub 2}]{sup 2+}, at variance with the electronic structures inferred from the absorption spectra. Nanosecond time-resolved electronic absorption and time-resolved step-scan infrared data are used to resolve this apparent conflict and confirm localization of the long-lived {sup 3}MLCT state on dmb in all three complexes where this ligand is present, thus making the dea-based excited state unique to [Ru(dea){sub 3}]{sup 2+}. Electrochemical studies further reveal the origin of this result, where a strong influence of the dea ligand on the oxidative Ru{sup II/III} couple, due to {pi} donation from the diethylamino substituent, is observed. The electronic absorption spectra are then reexamined in light of the now well-determined excited-state electronic structure. The results serve to underscore the importance of complete characterization of the electronic structures of transition metal complexes before embarking on ultrafast studies of their excited-state properties.

  9. Persistent luminescence nanoprobe for biosensing and lifetime imaging of cell apoptosis via time-resolved fluorescence resonance energy transfer.

    PubMed

    Zhang, Lei; Lei, Jianping; Liu, Jintong; Ma, Fengjiao; Ju, Huangxian

    2015-10-01

    Time-resolved fluorescence technique can reduce the short-lived background luminescence and auto-fluorescence interference from cells and tissues by exerting the delay time between pulsed excitation light and signal acquisition. Here, we prepared persistent luminescence nanoparticles (PLNPs) to design a universal time-resolved fluorescence resonance energy transfer (TR-FRET) platform for biosensing, lifetime imaging of cell apoptosis and in situ lifetime quantification of intracellular caspase-3. Three kinds of PLNPs-based nanoprobes are assembled by covalently binding dye-labeled peptides or DNA to carboxyl-functionalized PLNPs for the efficient detection of caspase-3, microRNA and protein. The peptides-functionalized nanoprobe is also employed for fluorescence lifetime imaging to monitor cell apoptosis, which shows a dependence of cellular fluorescence lifetime on caspase-3 activity and thus leads to an in situ quantification method. This work provides a proof-of-concept for PLNPs-based TR-FRET analysis and demonstrates its potential in exploring dynamical information of life process. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Time-Resolved Langmuir Probe Measurements in an Ionized PVD System

    NASA Astrophysics Data System (ADS)

    Juliano, D. R.; Hayden, D. B.; Ruzic, D. N.

    1997-10-01

    The experimental apparatus consists of a commercial-scale magnetron (Donated by Materials Research Corporation) with an RF coil between the target and substrate holder. This coil creates a secondary inductive plasma that ionizes a significant portion of the sputter flux en route from target to substrate. Ionization of the metal atoms that make up the sputter flux is highly sensitive to the high energy tail of the electron energy distribution, which in turn is highly dependent on the background gas mixture. Since there is some capacitive coupling from the coil this high energy population could change through the RF cycle. Time-averaged Langmuir probe measurements would not reveal either the extent of this high energy population or its time dependence. Further, if the probe voltage were held constant for such time-resolved measurements, they would yield incorrect results. At probe voltages above the plasma potential minimum the sheath is disrupted so that at points in the phase for which the probe voltage is below plasma potential the data is invalid. Therefore in order to take valid measurements at all phase points, it is necessary for the probe voltage to follow the RF variation in plasma potential. Using such a system, we have made time-resolved Langmuir probe measurements. Current-voltage traces as a function of phase then reveal plasma parameters as a function of time over the RF cycle for various background gases and operating parameters.

  11. New Pathways and Time-resolved Vibrational Dynamics of Surface Reactions

    NASA Astrophysics Data System (ADS)

    Wolf, Martin

    2000-03-01

    We discuss recent results of femtosecond laser-induced reactions and time-resolved vibrational spectroscopy at metal surfaces which provide detailed insights into the microscopic reaction mechanism and the rate of energy flow between the adsorbate and the underlying substrate. We demonstrate that fs laser excitation allows to access new reaction pathways which cannot be induced with conventional thermal activation: Heating of a Ru(001) surface on which CO and atomic oxygen are co-adsorbed leads exclusively to desorption of CO. In contrast, excitation with intense fs laser pulses enables also the formation of CO_2, in addition to CO desorption. Thus a new reaction path is opened upon fs laser excitation. Time-resolved two-pulse-correlation and isotope substitution experiments as well as density functional calculations reveal that this novel reaction pathway is initiated by laser heated hot substrate electrons which populate an antibonding unoccupied state of the O-Ru bond. The vibrationally activated oxygen reacts with co-adsorbed CO on an ultrashort time scale. On the other hand, desorption of CO molecules is caused by coupling of the adsorbate to the phonon bath of the substrate, which occurs much slower than the hot electron driven CO2 formation. Thus under fs excitation the process of CO desorption is outpaced, but prevails for conventional thermal heating due to a lower activation energy. In a further set of experiments the technique of fs infrared-visible sum-frequency generation (SFG) has been used as a time-resolved molecule specific 'probe' to analyze the transient changes of the CO stretching mode on Ru(001) after excitation with an intense fs 'pump' pulse. At low CO coverages the broadband infrared laser pulses also allow to excite the overtones of the CO stretch.

  12. Time resolved studies of bond activation by organometallic complexes

    SciTech Connect

    Wilkens, Matthew J.

    1998-05-01

    In 1971, Jetz and Graham discovered that the silicon-hydrogen bond in silanes could be broken under mild photochemical conditions in the presence of certain transition metal carbonyls. Such reactions fall within the class of oxidative addition. A decade later, similar reactivity was discovered in alkanes. In these cases a C-H bond in non-functionalized alkanes was broken through the oxidative addition of Cp*Ir(H)2L (Cp* = (CH3)5C5, L = PPh3, Ph = C6H5) to form Cp*ML(R)(H) or of Cp*Ir(CO)2 to form Cp*Ir(CO)(R)(H). These discoveries opened an entirely new field of research, one which naturally included mechanistic studies aimed at elucidating the various paths involved in these and related reactions. Much was learned from these experiments but they shared the disadvantage of studying under highly non-standard conditions a system which is of interest largely because of its characteristics under standard conditions. Ultrafast time-resolved IR spectroscopy provides an ideal solution to this problem; because it allows the resolution of chemical events taking place on the femto-through picosecond time scale, it is possible to study this important class of reactions under the ambient conditions which are most of interest to the practicing synthetic chemist. Certain of the molecules in question are particularly well-suited to study using the ultrafast IR spectrophotometer described in the experimental section because they contain one or more carbonyl ligands.

  13. Time-Resolved Bandgap Reflectivity of Photoexcited Cadmium-Selenium

    NASA Astrophysics Data System (ADS)

    Frigo, Nicholas John

    The first time-resolved bandgap reflectivity measurements of CdSe are presented. The time resolution was in the ten picosecond range and was attained by using a two-pulse pump-probe technique. Carriers were created by the absorption of the pump pulse and the reflectivity of the probe pulse was measured as a function of the probe's wavelength and its time delay relative to the pump. Specifically, the excitonic reflectivity was the feature monitored in these experiments. In order to perform the experiments, a new type of two-wavelength picosecond dye laser was developed. Its novel intersecting cavity configuration permitted the high flux levels, wide tuning range, spectral location, and pulse synchronization needed for creating high electron -hole densities and measuring the reflectivity near the bandgap of CdSe. The reflectivity results were surprising. A rapid recovery of the screened excitonic reflectivity was seen that was unanticipated by earlier experimental results and theoretical estimates. Attempts to explain the data by electron-hole liquid formation, surface recombination, or bimolecular recombination were unable to agree with the data. To explain the unusual speed of the recovery a model was developed which emphasized carrier diffusion against impurity scattering. The carrier diffusion model gave estimates of the recovery time in substantial agreement with the reflectivity measurements. In addition, the model's predictions agreed well with a wide range of other reported experiments ranging from picosecond to nanosecond time scales in CdS, CdSe, and GaAs using gain and luminescence measurements. Approximate solutions in closed form were presented that duplicated the major features of the model. Preliminary evidence against electron-hole liquid formation was presented; a low power experiment failed to give the expected signature. This result is unexpected since the temperature of these experiments is estimated to be lower than the temperature of the

  14. Time-resolved diagnostics for concrete target response

    SciTech Connect

    Baum, D.W.; Kuklo, R.M.; Reaugh, J.E.; Simonson, S.C.

    1996-05-01

    In order to facilitate the design of advanced penetrating weapons for defeating land targets, the interaction of concrete with high-velocity penetrators needs to be better characterized. To aid in this effort, three new types of time-resolved diagnostics are being developed and have been used in two experiments and one demonstration: fiber optic arrays to localize penetrators in space and time, Fabry-Perot velocimetry to record the concrete particle velocity, which is related to the pressure, at specific locations within concrete targets, and micropower impulse radar to provide a non-intrusive measure of the penetrator position-time history in a target. The two experiments used the fiber optic array and the Fabry-Perot velocimeter to diagnose the response of concrete to penetration by a Viper shaped charge jet. The results were analyzed using the CALE continuum mechanics simulation program, for which a preliminary model of the material properties of concrete was developed. The fiber optic arrays recorded the bow shock at locations 6.4 and 16.9 cm from the front surfaces. The Fabry-Perot velocimeter measured a free-surface velocity of 0.13 km/s at a distance of 3 cm and obliquity 70{degree} from the jet, which was moving at an interface velocity of 4.0 km/s at a depth of 29 cm. These values imply a pressure of about 6.6 kbar at that location. The demonstration used micropower impulse radar with a pulse repetition frequency of 0.25 MHz and a cell size of 30 ps to detect and record the motion of a metal penetrator simulant moving inside a cylindrical concrete target.

  15. Microsecond Time-Resolved Circular Dichroism of Rhodopsin Photointermediates†

    PubMed Central

    Thomas, Yiren Gu; Szundi, Istvan; Lewis, James W.; Kliger, David S.

    2009-01-01

    Time-resolved circular dichroism measurements, over a spectral range from 300 to 700 nm, were made at delays of 5, 100 and 500 μs after room temperature photoexcitation of bovine rhodopsin in lauryl maltoside suspension. The purpose was to provide more structural information about intermediate states in the activation of rhodopsin and other G protein-coupled receptors. In particular, information was sought about photointermediates that are isochromic or nearly isochromic in their unpolarized absorbance. The circular dichroism spectrum of lumirhodopsin, obtained after correcting the 5 μs difference CD data for the rhodopsin bleached, was in reasonable agreement with the lumirhodopsin CD spectrum obtained previously by thermal trapping at -76°C. Similarly, the metarhodopsin II spectrum obtained at 500 μs delay was also in agreement with the results of previous work on the temperature trapped form of metarhodopsin II. However, the CD of the mixture formed at 100 μs delay after photoexcitation, whose only visible absorbing component is lumirhodopsin, could not be accounted for near 480 nm in terms of the initially formed, 5 μs lumirhodopsin CD spectrum. Thus, the CD spectrum of lumirhodopsin changes on the time scale from 5 to 100 μs, showing reduced rotational strength in its visible band, possibly associated with either a process responsible for a small spectral shift that occurs in the lumirhodopsin absorbance spectrum at earlier times or the Schiff base deprotonation-reprotonation which occurs during equilibration of lumirhodopsin with the Meta I380 photointermediate. Either explanation suggests a chromophore conformation change closely associated with deprotonation which could be the earliest direct trigger of activation. PMID:19905009

  16. Time-resolved study of Higgs mode in superconductors

    NASA Astrophysics Data System (ADS)

    Shimano, Ryo

    The behavior of superconductors far from equilibrium has been intensively studied over decades. Goals of these studies are the elucidation of bosonic fluctuations essential for the pairing mechanisms, the manifestation of competing orders or hidden phases, and the optical manipulation of superconductivity. The study of collective modes is crucially important for these perspectives as it provides the information on the dynamics of order parameters in non-equilibirium states. Generally, collective modes in ordered phases associated with spontaneous symmetry breaking are classified into 1) gapless phase modes and 2) gapped amplitude modes. In superconductors, the phase mode is eaten by gauge field, according to the Anderson-Higgs mechanism. The remaining amplitude mode is recently termed as Higgs mode from its analogy to the Higgs boson in particle physics. Despite its long history of investigation, unambiguous observation of Higgs mode has remained elusive. This is because the Higgs mode does not have a charge nor electric dipole and therefore it does not couple directly to the electromagnetic field. Here we report on our recent observation of Higgs mode in s-wave superconductors by using THz-pump and THz-probe spectroscopy technique. After nonadiabatic excitation near the superconducting gap energy with monocycle THz pulses, Higgs mode was observed as oscillations in the transmission of THz probe pulse. The resonant nonlinear coupling between the Higgs mode and coherent radiation field was also discovered, resulting in an efficient third order harmonic generation of the incident THz radiation. The extension of experiments to multiband superconductors and unconventional superconductors will be discussed. Time-resolved study of Higgs mode in superconductors.

  17. Taking the pulse of snowmelt: in situ sensors reveal seasonal, event and diurnal patterns of nitrate and dissolved organic matter variability in an upland forest stream

    USGS Publications Warehouse

    Pellerin, Brian A.; Saraceno, John Franco; Shanley, James B.; Sebestyen, Stephen D.; Aiken, George R.; Wollheim, Wilfred M.; Bergamaschi, Brian A.

    2011-01-01

    Highly resolved time series data are useful to accurately identify the timing, rate, and magnitude of solute transport in streams during hydrologically dynamic periods such as snowmelt. We used in situ optical sensors for nitrate (NO3-) and chromophoric dissolved organic matter fluorescence (FDOM) to measure surface water concentrations at 30 min intervals over the snowmelt period (March 21–May 13, 2009) at a 40.5 hectare forested watershed at Sleepers River, Vermont. We also collected discrete samples for laboratory absorbance and fluorescence as well as δ18O–NO3- isotopes to help interpret the drivers of variable NO3- and FDOM concentrations measured in situ. In situ data revealed seasonal, event and diurnal patterns associated with hydrological and biogeochemical processes regulating stream NO3- and FDOM concentrations. An observed decrease in NO3- concentrations after peak snowmelt runoff and muted response to spring rainfall was consistent with the flushing of a limited supply of NO3- (mainly from nitrification) from source areas in surficial soils. Stream FDOM concentrations were coupled with flow throughout the study period, suggesting a strong hydrologic control on DOM concentrations in the stream. However, higher FDOM concentrations per unit streamflow after snowmelt likely reflected a greater hydraulic connectivity of the stream to leachable DOM sources in upland soils. We also observed diurnal NO3- variability of 1–2 μmol l-1 after snowpack ablation, presumably due to in-stream uptake prior to leafout. A comparison of NO3- and dissolved organic carbon yields (DOC, measured by FDOM proxy) calculated from weekly discrete samples and in situ data sub-sampled daily resulted in small to moderate differences over the entire study period (-4 to 1% for NO3- and -3 to -14% for DOC), but resulted in much larger differences for daily yields (-66 to +27% for NO3- and -88 to +47% for DOC, respectively). Despite challenges inherent in in situ sensor

  18. Application of singular value decomposition analysis to time-dependent powder diffraction data of an in-situ photodimerization reaction

    PubMed Central

    Mabied, Ahmed F.; Nozawa, Shunsuke; Hoshino, Manabu; Tomita, Ayana; Sato, Tokushi; Adachi, Shin-ichi

    2014-01-01

    Singular value decomposition (SVD) analysis has important applications for time-dependent crystallographic data, extracting significant information. Herein, a successful application of SVD analysis of time-resolved powder diffraction data over the course of an in-situ photodimerization reaction of anthracene derivatives is introduced. SVD revealed significant results in the case of 9-methylanthracene and 1-chloroanthracene. The results support the formation of the 9-methylanthracene stable dimer phase and suggest the existence of an excimer state. PMID:24763645

  19. Deformation mechanisms in a precipitation-strengthened ferritic superalloy revealed by in situ neutron diffraction studies at elevated temperatures

    DOE PAGES

    Huang, Shenyan; Gao, Yanfei; An, Ke; ...

    2014-10-22

    In this study, the ferritic superalloy Fe–10Ni–6.5Al–10Cr–3.4Mo strengthened by ordered (Ni,Fe)Al B2-type precipitates is a candidate material for ultra-supercritical steam turbine applications above 923 K. Despite earlier success in improving its room-temperature ductility, the creep resistance of this material at high temperatures needs to be further improved, which requires a fundamental understanding of the high-temperature deformation mechanisms at the scales of individual phases and grains. In situ neutron diffraction has been utilized to investigate the lattice strain evolution and the microscopic load-sharing mechanisms during tensile deformation of this ferritic superalloy at elevated temperatures. Finite-element simulations based on the crystal plasticitymore » theory are employed and compared with the experimental results, both qualitatively and quantitatively. Based on these interphase and intergranular load-partitioning studies, it is found that the deformation mechanisms change from dislocation slip to those related to dislocation climb, diffusional flow and possibly grain boundary sliding, below and above 873 K, respectively. Insights into microstructural design for enhancing creep resistance are also discussed.« less

  20. Concerted growth and ordering of cobalt nanorod arrays as revealed by tandem in situ SAXS-XAS studies

    SciTech Connect

    Cormary, Benoit; Li, Tao; Liakakos, Nikos; Peres, Laurent; Fazzini, Pier -Francesco; Blon, Thomas; Respaud, Marc; Kropf, A. Jeremy; Chaudret, Bruno; Miller, Jeffrey T.; Mader, Elizabeth A.; Soulantica, Katerina

    2016-06-14

    The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray Absorption Spectroscopy – Small Angle X-ray Scattering (XAS - SAXS). The super-crystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long chain amine and a long chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism, and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom by atom anisotropic growth and a slower oriented attach-ment process that continues well after cobalt reduction is complete. As a result, smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized super-lattices, which can be regarded as mesocrystals.

  1. Homoeologous chromosome pairing between the A and B genomes of Musa spp. revealed by genomic in situ hybridization.

    PubMed

    Jeridi, Mouna; Bakry, Frédéric; Escoute, Jacques; Fondi, Emmanuel; Carreel, Françoise; Ferchichi, Ali; D'Hont, Angélique; Rodier-Goud, Marguerite

    2011-10-01

    Most cooking banana and several desert bananas are interspecific triploid hybrids between Musa acuminata (A genome) and Musa balbisiana (B genome). In addition, M. balbisiana has agronomical characteristics such as resistance to biotic and abiotic stresses that could be useful to improve monospecific acuminata cultivars. To develop efficient breeding strategies for improving Musa cultivars, it is therefore important to understand the possibility of chromosome exchange between these two species. A protocol was developed to prepare chromosome at meiosis metaphase I suitable for genomic in situ hybridization. A series of technical challenges were encountered, the main ones being the hardness of the cell wall and the density of the microsporocyte's cytoplasm, which hampers accessibility of the probes to the chromosomes. Key parameters in solving these problems were addition of macerozyme in the enzyme mix, the duration of digestion and temperature during the spreading phase. This method was applied to analyse chromosome pairing in metaphase from triploid interspecific cultivars, and it was clearly demonstrated that interspecific recombinations between M. acuminata and M. balbisiana chromosomes do occur and may be frequent in triploid hybrids. These results provide new insight into Musa cultivar evolution and have important implications for breeding.

  2. Homoeologous chromosome pairing between the A and B genomes of Musa spp. revealed by genomic in situ hybridization

    PubMed Central

    Jeridi, Mouna; Bakry, Frédéric; Escoute, Jacques; Fondi, Emmanuel; Carreel, Françoise; Ferchichi, Ali; D'Hont, Angélique; Rodier-Goud, Marguerite

    2011-01-01

    Background and Aims Most cooking banana and several desert bananas are interspecific triploid hybrids between Musa acuminata (A genome) and Musa balbisiana (B genome). In addition, M. balbisiana has agronomical characteristics such as resistance to biotic and abiotic stresses that could be useful to improve monospecific acuminata cultivars. To develop efficient breeding strategies for improving Musa cultivars, it is therefore important to understand the possibility of chromosome exchange between these two species. Methods A protocol was developed to prepare chromosome at meiosis metaphase I suitable for genomic in situ hybridization. A series of technical challenges were encountered, the main ones being the hardness of the cell wall and the density of the microsporocyte's cytoplasm, which hampers accessibility of the probes to the chromosomes. Key parameters in solving these problems were addition of macerozyme in the enzyme mix, the duration of digestion and temperature during the spreading phase. Results and Conclusions This method was applied to analyse chromosome pairing in metaphase from triploid interspecific cultivars, and it was clearly demonstrated that interspecific recombinations between M. acuminata and M. balbisiana chromosomes do occur and may be frequent in triploid hybrids. These results provide new insight into Musa cultivar evolution and have important implications for breeding. PMID:21835815

  3. Concerted growth and ordering of cobalt nanorod arrays as revealed by tandem in situ SAXS-XAS studies

    SciTech Connect

    Cormary, Benoit; Li, Tao; Liakakos, Nikos; Peres, Laurent; Fazzini, Pier -Francesco; Blon, Thomas; Respaud, Marc; Kropf, A. Jeremy; Chaudret, Bruno; Miller, Jeffrey T.; Mader, Elizabeth A.; Soulantica, Katerina

    2016-06-14

    The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray Absorption Spectroscopy – Small Angle X-ray Scattering (XAS - SAXS). The super-crystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long chain amine and a long chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism, and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom by atom anisotropic growth and a slower oriented attach-ment process that continues well after cobalt reduction is complete. As a result, smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized super-lattices, which can be regarded as mesocrystals.

  4. Concerted growth and ordering of cobalt nanorod arrays as revealed by tandem in situ SAXS-XAS studies

    DOE PAGES

    Cormary, Benoit; Li, Tao; Liakakos, Nikos; ...

    2016-06-14

    The molecular and ensemble dynamics for the growth of hierarchical supercrystals of cobalt nanorods have been studied by in situ tandem X-ray Absorption Spectroscopy – Small Angle X-ray Scattering (XAS - SAXS). The super-crystals were obtained by reducing a Co(II) precursor under H2 in the presence of a long chain amine and a long chain carboxylic acid. Complementary time-dependent ex situ TEM studies were also performed. The experimental data provide critical insights into the nanorod growth mechanism, and unequivocal evidence for a concerted growth-organization process. Nanorod formation involves cobalt nucleation, a fast atom by atom anisotropic growth and a slowermore » oriented attach-ment process that continues well after cobalt reduction is complete. As a result, smectic-like ordering of the nanorods appears very early in the process, as soon as nanoparticle elongation appears, and nanorod growth takes place inside organized super-lattices, which can be regarded as mesocrystals.« less

  5. First in situ observations of the deep-sea squid Grimalditeuthis bonplandi reveal unique use of tentacles.

    PubMed

    Hoving, Hendrik J T; Zeidberg, Louis D; Benfield, Mark C; Bush, Stephanie L; Robison, Bruce H; Vecchione, Michael

    2013-10-22

    The deep-sea squid Grimalditeuthis bonplandi has tentacles unique among known squids. The elastic stalk is extremely thin and fragile, whereas the clubs bear no suckers, hooks or photophores. It is unknown whether and how these tentacles are used in prey capture and handling. We present, to our knowledge, the first in situ observations of this species obtained by remotely operated vehicles (ROVs) in the Atlantic and North Pacific. Unexpectedly, G. bonplandi is unable to rapidly extend and retract the tentacle stalk as do other squids, but instead manoeuvres the tentacles by undulation and flapping of the clubs' trabecular protective membranes. These tentacle club movements superficially resemble the movements of small marine organisms and suggest the possibility that G. bonplandi uses aggressive mimicry by the tentacle clubs to lure prey, which we find to consist of crustaceans and cephalopods. In the darkness of the meso- and bathypelagic zones the flapping and undulatory movements of the tentacle may: (i) stimulate bioluminescence in the surrounding water, (ii) create low-frequency vibrations and/or (iii) produce a hydrodynamic wake. Potential prey of G. bonplandi may be attracted to one or more of these as signals. This singular use of the tentacle adds to the diverse foraging and feeding strategies known in deep-sea cephalopods.

  6. First in situ observations of the deep-sea squid Grimalditeuthis bonplandi reveal unique use of tentacles

    PubMed Central

    Hoving, Hendrik J. T.; Zeidberg, Louis D.; Benfield, Mark C.; Bush, Stephanie L.; Robison, Bruce H.; Vecchione, Michael

    2013-01-01

    The deep-sea squid Grimalditeuthis bonplandi has tentacles unique among known squids. The elastic stalk is extremely thin and fragile, whereas the clubs bear no suckers, hooks or photophores. It is unknown whether and how these tentacles are used in prey capture and handling. We present, to our knowledge, the first in situ observations of this species obtained by remotely operated vehicles (ROVs) in the Atlantic and North Pacific. Unexpectedly, G. bonplandi is unable to rapidly extend and retract the tentacle stalk as do other squids, but instead manoeuvres the tentacles by undulation and flapping of the clubs’ trabecular protective membranes. These tentacle club movements superficially resemble the movements of small marine organisms and suggest the possibility that G. bonplandi uses aggressive mimicry by the tentacle clubs to lure prey, which we find to consist of crustaceans and cephalopods. In the darkness of the meso- and bathypelagic zones the flapping and undulatory movements of the tentacle may: (i) stimulate bioluminescence in the surrounding water, (ii) create low-frequency vibrations and/or (iii) produce a hydrodynamic wake. Potential prey of G. bonplandi may be attracted to one or more of these as signals. This singular use of the tentacle adds to the diverse foraging and feeding strategies known in deep-sea cephalopods. PMID:23986106

  7. Deep-sea in situ observations of gonatid squid and their prey reveal high occurrence of cannibalism

    NASA Astrophysics Data System (ADS)

    Hoving, H. J. T.; Robison, B. H.

    2016-10-01

    In situ observations are rarely applied in food web studies of deep-sea organisms. Using deep-sea observations obtained by remotely operated vehicles in the Monterey Submarine Canyon, we examined the prey choices of more than 100 individual squids of the genus Gonatus. Off the California coast, these squids are abundant, semelparous (one reproductive cycle) oceanic predators but their diet has remained virtually unknown. Gonatus onyx and Gonatus berryi were observed to feed on mesopelagic fishes (in particular the myctophid Stenobrachius leucopsarus) as often as on squids but inter-specific differences in feeding were apparent. Gonatids were the most common squid prey and while cannibalism occurred in both species it was particularly high in Gonatus onyx (42% of all prey items). Typically, the size of prey was similar to the size of the predator but the squids were also seen to take much larger prey. Postjuvenile gonatids are opportunistic predators that consume nektonic members of the meso-and bathypelagic communities, including their own species. Such voracious feeding is likely necessary to support the high energetic demands associated with the single reproductive event; and for females the long brooding period during which they must depend on stored resources.

  8. Deformation mechanisms in a precipitation-strengthened ferritic superalloy revealed by in situ neutron diffraction studies at elevated temperatures

    SciTech Connect

    Huang, Shenyan; Gao, Yanfei; An, Ke; Zheng, Lili; Wu, Wei; Teng, Zhenke; Liaw, Peter K

    2014-10-22

    In this study, the ferritic superalloy Fe–10Ni–6.5Al–10Cr–3.4Mo strengthened by ordered (Ni,Fe)Al B2-type precipitates is a candidate material for ultra-supercritical steam turbine applications above 923 K. Despite earlier success in improving its room-temperature ductility, the creep resistance of this material at high temperatures needs to be further improved, which requires a fundamental understanding of the high-temperature deformation mechanisms at the scales of individual phases and grains. In situ neutron diffraction has been utilized to investigate the lattice strain evolution and the microscopic load-sharing mechanisms during tensile deformation of this ferritic superalloy at elevated temperatures. Finite-element simulations based on the crystal plasticity theory are employed and compared with the experimental results, both qualitatively and quantitatively. Based on these interphase and intergranular load-partitioning studies, it is found that the deformation mechanisms change from dislocation slip to those related to dislocation climb, diffusional flow and possibly grain boundary sliding, below and above 873 K, respectively. Insights into microstructural design for enhancing creep resistance are also discussed.

  9. Dissolution Kinetics of Oxidative Etching of Cubic and Icosahedral Platinum Nanoparticles Revealed by in Situ Liquid Transmission Electron Microscopy.

    PubMed

    Wu, Jianbo; Gao, Wenpei; Yang, Hong; Zuo, Jian-Min

    2017-02-28

    Dissolution due to atom-level etching is a major factor for the degradation of Pt-based electrocatalysts used in low-temperature polymer electrolyte membrane fuel cells. Selective surface etching is also used to precisely control shapes of nanoparticles. Dissolution kinetics of faceted metal nanoparticles in solution however is poorly understood despite considerable progress in understanding etching of two-dimensional surfaces. We report here the application of in situ liquid transmission electron microscopy for quantitative analysis of oxidative etching of cubic and icosahedral Pt nanoparticles. The experiment was carried out using a liquid flow cell containing aqueous HAuCl4 solution. The data show that oxidative etching of these faceted nanocrystals depends on the location of atoms on the surface, which evolves with time. A quantitative kinetic model was developed to account for the mass lost in electrolyte solutions over time, showing the dissolutions followed the power law relationship for Pt nanocrystals of different shapes. Dissolution coefficients of different surface sites were obtained based on the models developed in this study.

  10. In situ observations of the basal angiosperm Amborella trichopoda reveal a long fruiting cycle overlapping two annual flowering periods.

    PubMed

    Fourcade, Fanny; Pouteau, Robin; Jaffré, Tanguy; Marmey, Philippe

    2015-09-01

    Amborella trichopoda is the sole living angiosperm species belonging to the sister lineage of all other extant flowering plants. In the last decade, the species has been the focus of many phylogenetic, genomic and reproductive biology studies, bringing new highlights regarding the evolution of flowering plants. However, little attention has been paid to in situ A. trichopoda populations, particularly to their fruiting cycle. In this study, an A. trichopoda population was observed during three annual flowering cycles. Individuals and branches were labeled in order to monitor the fruiting cycle precisely, from the flowering stage until the abscission of the fruit. Fruit exocarp was green during the first 9 months following flowering, turned red when the next flowering started a year later then remained on the branch during another year, between fruit ripping and abscission. Presence of fruits with two stages of maturity on shrubs was always noticed. Germination tests showed that seeds acquired their germination capacity 1 year after flowering, when fruits changed color. A. trichopoda's fruiting cycle is a long process overlapping two annual flowering periods. These results introduce a new model for flowering and fruiting cycles. The availability of mature seeds on shrubs for more than 1 year is likely to maximize opportunities to be dispersed, thus promoting the survival of this basal angiosperm.

  11. Deformation mechanisms in a precipitation-strengthened ferritic super alloy revealed by in situ neutron dffraction studies at elevated temperatures

    SciTech Connect

    Huang, Shenyan; Gao, Yanfei; An, Ke; Zheng, Lili; Teng, Zhenke; Wu, Wei; Liaw, Peter K.

    2015-01-01

    The ferritic superalloy Fe–10Ni–6.5Al–10Cr–3.4Mo strengthened by ordered (Ni,Fe)AlB2-type precipitates is a candidate material for ultra-supercritical steam turbine applications above 923 K. Despite earlier success in improving its room-temperature ductility, the creep resistance of this material at high temperatures needs to be further improved, which requires a fundamental understanding of the high-temperature deformation mechanisms at the scales of individual phases and grains. In situ neutron diffraction has been utilized to investigate the lattice strain evolution and the microscopic load-sharing mechanisms during tensile deformation of this ferritic superalloy at elevated temperatures. Finite-element simulations based on the crystal plasticity theory are employed and compared with the experimental results, both qualitatively and quantitatively. Based on these interphase and intergranular load-partitioning studies, it is found that the deformation mechanisms change from dislocation slip to those related to dislocation climb, diffusional flow and possibly grain boundary sliding, below and above 873 K, respectively. Insights into microstructural design for enhancing creep resistance are also discussed.

  12. In Situ Experiments To Reveal the Role of Surface Feature Sidewalls in the Cassie–Wenzel Transition

    PubMed Central

    2014-01-01

    Waterproof and self-cleaning surfaces continue to attract much attention as they can be instrumental in various different technologies. Such surfaces are typically rough, allowing liquids to contact only the outermost tops of their asperities, with air being entrapped underneath. The formed solid–liquid–air interface is metastable and, hence, can be forced into a completely wetted solid surface. A detailed understanding of the wetting barrier and the dynamics of this transition is critically important for the practical use of the related surfaces. Toward this aim, wetting transitions were studied in situ at a set of patterned perfluoropolyether dimethacrylate (PFPEdma) polymer surfaces exhibiting surface features with different types of sidewall profiles. PFPEdma is intrinsically hydrophobic and exhibits a refractive index very similar to water. Upon immersion of the patterned surfaces into water, incident light was differently scattered at the solid–liquid–air and solid–liquid interface, which allows for distinguishing between both wetting states by dark-field microscopy. The wetting transition observed with this methodology was found to be determined by the sidewall profiles of the patterned structures. Partial recovery of the wetting was demonstrated to be induced by abrupt and continuous pressure reductions. A theoretical model based on Laplace’s law was developed and applied, allowing for the analytical calculation of the transition barrier and the potential to revert the wetting upon pressure reduction. PMID:25496232

  13. Anomalous Resistance Hysteresis in Oxide ReRAM: Oxygen Evolution and Reincorporation Revealed by In Situ TEM.

    PubMed

    Cooper, David; Baeumer, Christoph; Bernier, Nicolas; Marchewka, Astrid; La Torre, Camilla; Dunin-Borkowski, Rafal E; Menzel, Stephan; Waser, Rainer; Dittmann, Regina

    2017-06-01

    The control and rational design of redox-based memristive devices, which are highly attractive candidates for next-generation nonvolatile memory and logic applications, is complicated by competing and poorly understood switching mechanisms, which can result in two coexisting resistance hystereses that have opposite voltage polarity. These competing processes can be defined as regular and anomalous resistive switching. Despite significant characterization efforts, the complex nanoscale redox processes that drive anomalous resistive switching and their implications for current transport remain poorly understood. Here, lateral and vertical mapping of O vacancy concentrations is used during the operation of such devices in situ in an aberration corrected transmission electron microscope to explain the anomalous switching mechanism. It is found that an increase (decrease) in the overall O vacancy concentration within the device after positive (negative) biasing of the Schottky-type electrode is associated with the electrocatalytic release and reincorporation of oxygen at the electrode/oxide interface and is responsible for the resistance change. This fundamental insight presents a novel perspective on resistive switching processes and opens up new technological opportunities for the implementation of memristive devices, as anomalous switching can now be suppressed selectively or used deliberately to achieve the desirable so-called deep Reset. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. [Characterization of Time-Resolved Laser-Induced Fluorescence from Crude Oil Samples].

    PubMed

    Liu, De-qing; Luan, Xiao-ning; Han, Xiao-shuang; Guo, Jin-jia; An, Ju-bai; Zheng, Rong-er

    2015-06-01

    To evaluate the feasibility of laser induced time-resolved fluorescence technique for in-situ detection of underwater suspended oil spill, extensive investigations have been carried out with different densities of crude oil samples from six different wells of Shengli Oilfield in this work. It was found that the fluorescence emission durations of these crude oil samples were almost the same, the Gate Pulse Delay of DDG (Digital Delay Generator) in the ICCD started at 52ns and ended at 82ns with a width (FWHM) of 10 ns. It appears that the peak location and lifetime of fluorescence for different crude oil samples varied with their densities, and those with similar densities shared a similar lifespan with the closer peak locations of fluorescence. It is also observed that the peak of fluorescence remained the same location before reaching the maximum intensity, subsequently shift to longer wavelength as fluorescence attenuated from maximum intensity with a red shift among 17-30 nm varied with samples. This demonstrated that the decay rate of fluorescent components in the crude oils was different, and energy transfer between these components might exist. It is hoped that those obtained results and characteristics could be the useful information for identification of suspended spilled-oil underwater.

  15. Time-resolved x-ray diffraction techniques for bulk polycrystalline materials under dynamic loading.

    PubMed

    Lambert, P K; Hustedt, C J; Vecchio, K S; Huskins, E L; Casem, D T; Gruner, S M; Tate, M W; Philipp, H T; Woll, A R; Purohit, P; Weiss, J T; Kannan, V; Ramesh, K T; Kenesei, P; Okasinski, J S; Almer, J; Zhao, M; Ananiadis, A G; Hufnagel, T C

    2014-09-01

    We have developed two techniques for time-resolved x-ray diffraction from bulk polycrystalline materials during dynamic loading. In the first technique, we synchronize a fast detector with loading of samples at strain rates of ~10(3)-10(4) s(-1) in a compression Kolsky bar (split Hopkinson pressure bar) apparatus to obtain in situ diffraction patterns with exposures as short as 70 ns. This approach employs moderate x-ray energies (10-20 keV) and is well suited to weakly absorbing materials such as magnesium alloys. The second technique is useful for more strongly absorbing materials, and uses high-energy x-rays (86 keV) and a fast shutter synchronized with the Kolsky bar to produce short (~40 μs) pulses timed with the arrival of the strain pulse at the specimen, recording the diffraction pattern on a large-format amorphous silicon detector. For both techniques we present sample data demonstrating the ability of these techniques to characterize elastic strains and polycrystalline texture as a function of time during high-rate deformation.

  16. On-chip time resolved detection of quantum dot emission using integrated superconducting single photon detectors

    PubMed Central

    Reithmaier, G.; Lichtmannecker, S.; Reichert, T.; Hasch, P.; Müller, K.; Bichler, M.; Gross, R.; Finley, J. J.

    2013-01-01

    We report the routing of quantum light emitted by self-assembled InGaAs quantum dots (QDs) into the optical modes of a GaAs ridge waveguide and its efficient detection on-chip via evanescent coupling to NbN superconducting nanowire single photon detectors (SSPDs). The waveguide coupled SSPDs primarily detect QD luminescence, with scattered photons from the excitation laser onto the proximal detector being negligible by comparison. The SSPD detection efficiency from the evanescently coupled waveguide modes is shown to be two orders of magnitude larger when compared with operation under normal incidence illumination, due to the much longer optical interaction length. Furthermore, in-situ time resolved measurements performed using the integrated detector show an average QD spontaneous emission lifetime of 0.95 ns, measured with a timing jitter of only 72 ps. The performance metrics of the SSPD integrated directly onto GaAs nano-photonic hardware confirms the strong potential for on-chip few-photon quantum optics using such semiconductor-superconductor hybrid systems. PMID:23712624

  17. Time-resolved monitoring of biofouling development on a flat sheet membrane using optical coherence tomography.

    PubMed

    Fortunato, Luca; Jeong, Sanghyun; Leiknes, TorOve

    2017-12-01

    Biofouling on a membrane leads to significant performance decrease in filtration processes. In this study, an optical coherence tomography (OCT) was used to perform a time-resolved analysis of dynamic biofouling development on a submerged membrane under continuous operation. A real-time change in the biofouling morphology was calculated through the image analysis of OCT scans. Three videos were generated through the acquisition of serial static images. This is the first study that displays the dynamic biofouling formation process as a video. The acquisition of OCT cross-sectional scans of the biofouling allowed to evaluate the time-lapsed evolution for three different time periods (early stage, double layers and long-term). Firstly, at the early filtration stage, membrane coverage and average biofouling layer thickness were found to be linearly correlated with the permeate flux pattern. Secondly, after 3 d of operation, an anomalous morphology was observed, constituted by a double-layered biofouling structure: denser on the bottom and looser on the top. In a long-term operation, the biofouling structure underwent a dynamic evolution over time, resulting in a multi-layered structure. The biofouling formation information was closely associated with filtration performance (i.e. flux) indicating the suitability of OCT as real-time and in-situ biofouling monitoring technique.

  18. On-chip time resolved detection of quantum dot emission using integrated superconducting single photon detectors.

    PubMed

    Reithmaier, G; Lichtmannecker, S; Reichert, T; Hasch, P; Müller, K; Bichler, M; Gross, R; Finley, J J

    2013-01-01

    We report the routing of quantum light emitted by self-assembled InGaAs quantum dots (QDs) into the optical modes of a GaAs ridge waveguide and its efficient detection on-chip via evanescent coupling to NbN superconducting nanowire single photon detectors (SSPDs). The waveguide coupled SSPDs primarily detect QD luminescence, with scattered photons from the excitation laser onto the proximal detector being negligible by comparison. The SSPD detection efficiency from the evanescently coupled waveguide modes is shown to be two orders of magnitude larger when compared with operation under normal incidence illumination, due to the much longer optical interaction length. Furthermore, in-situ time resolved measurements performed using the integrated detector show an average QD spontaneous emission lifetime of 0.95 ns, measured with a timing jitter of only 72 ps. The performance metrics of the SSPD integrated directly onto GaAs nano-photonic hardware confirms the strong potential for on-chip few-photon quantum optics using such semiconductor-superconductor hybrid systems.

  19. Time-resolved WAXD studies on the crystallization of isotactic polypropylene/graphene nanocomposites

    NASA Astrophysics Data System (ADS)

    Nishitsuji, Shotaro; Endoh, Maya; Guo, Yichen; Rafailovich, Miriam; Koga, Tadanori

    2015-03-01

    Graphene is one layer of carbon atoms, which has good electronic, thermal conductivity and mechanical properties. By adding graphene to isotactic polypropylene (iPP), the mechanical and electrical properties of the polymer are significantly improved. To further achieve high performance of iPP/graphene nanocomposites (``NCs''), it is important to investigate the relationship between the crystalline structure of iPP and the mechanical property of the iPP/graphene NCs. In this study, the effect of the graphene on the crystallization behavior of the polymer was investigated by using time-resolved wide angle X-ray diffraction (WAXD). The iPP/graphene NCs with different weight ratios of graphene were prepared by using a twin screw extruder. After temperature jump from 210 °C (>Tm) to 170 °C, the melt-crystallization process was observed by in situ WAXD. The results showed that the crystalline structure of all the samples was still α-form that is the same as the neat PP, while the ratios of the diffraction peaks are quite different from those of the neat PP. We will discuss the detailed structure in this presentation.

  20. Time-resolved x-ray diffraction techniques for bulk polycrystalline materials under dynamic loading

    PubMed Central

    Lambert, P. K.; Hustedt, C. J.; Vecchio, K. S.; Huskins, E. L.; Casem, D. T.; Gruner, S. M.; Tate, M. W.; Philipp, H. T.; Woll, A. R.; Purohit, P.; Weiss, J. T.; Kannan, V.; Ramesh, K. T.; Kenesei, P.; Okasinski, J. S.; Almer, J.; Zhao, M.; Ananiadis, A. G.; Hufnagel, T. C.

    2014-01-01

    We have developed two techniques for time-resolved x-ray diffraction from bulk polycrystalline materials during dynamic loading. In the first technique, we synchronize a fast detector with loading of samples at strain rates of ∼103–104 s−1 in a compression Kolsky bar (split Hopkinson pressure bar) apparatus to obtain in situ diffraction patterns with exposures as short as 70 ns. This approach employs moderate x-ray energies (10–20 keV) and is well suited to weakly absorbing materials such as magnesium alloys. The second technique is useful for more strongly absorbing materials, and uses high-energy x-rays (86 keV) and a fast shutter synchronized with the Kolsky bar to produce short (∼40 μs) pulses timed with the arrival of the strain pulse at the specimen, recording the diffraction pattern on a large-format amorphous silicon detector. For both techniques we present sample data demonstrating the ability of these techniques to characterize elastic strains and polycrystalline texture as a function of time during high-rate deformation. PMID:25273733

  1. Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

    PubMed

    Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

    2011-01-01

    Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry.

  2. Evaporation of ethanol and ethanol-water mixtures studied by time-resolved infrared spectroscopy.

    PubMed

    Innocenzi, Plinio; Malfatti, Luca; Costacurta, Stefano; Kidchob, Tongjit; Piccinini, Massimo; Marcelli, Augusto

    2008-07-24

    The knowledge of the physics and the chemistry behind the evaporation of solvents is very important for the development of several technologies, especially in the fabrication of thin films from liquid phase and the organization of nanostructures by evaporation-induced self-assembly. Ethanol, in particular, is one of the most common solvents in sol-gel and evaporation-induced self-assembly processing of thin films, and a detailed understanding of its role during these processes is of fundamental importance. Rapid scan time-resolved infrared spectroscopy has been applied to study in situ the evaporation of ethanol and ethanol-water droplets on a ZnSe substrate. Whereas the evaporation rate of ethanol remains constant during the process, water is adsorbed by the ethanol droplet from the external environment and evaporates in three stages that are characterized by different evaporation rates. The adsorption and evaporation process of water in an ethanol droplet has been observed to follow a complex behavior: due to this reason, it has been analyzed by two-dimensional infrared correlation. Three different components in the water bending band have been resolved.

  3. Time-resolved x-ray diffraction techniques for bulk polycrystalline materials under dynamic loading

    SciTech Connect

    Lambert, P. K.; Hustedt, C. J.; Zhao, M.; Ananiadis, A. G.; Hufnagel, T. C.; Vecchio, K. S.; Huskins, E. L.; Casem, D. T.; Gruner, S. M.; Tate, M. W.; Philipp, H. T.; Purohit, P.; Weiss, J. T.; Woll, A. R.; Kannan, V.; Ramesh, K. T.; Kenesei, P.; Okasinski, J. S.; Almer, J.

    2014-09-15

    We have developed two techniques for time-resolved x-ray diffraction from bulk polycrystalline materials during dynamic loading. In the first technique, we synchronize a fast detector with loading of samples at strain rates of ∼10{sup 3}–10{sup 4} s{sup −1} in a compression Kolsky bar (split Hopkinson pressure bar) apparatus to obtain in situ diffraction patterns with exposures as short as 70 ns. This approach employs moderate x-ray energies (10–20 keV) and is well suited to weakly absorbing materials such as magnesium alloys. The second technique is useful for more strongly absorbing materials, and uses high-energy x-rays (86 keV) and a fast shutter synchronized with the Kolsky bar to produce short (∼40 μs) pulses timed with the arrival of the strain pulse at the specimen, recording the diffraction pattern on a large-format amorphous silicon detector. For both techniques we present sample data demonstrating the ability of these techniques to characterize elastic strains and polycrystalline texture as a function of time during high-rate deformation.

  4. Time resolved studies on pulsed fluorocarbon plasmas using chirped quantum cascade lasers

    NASA Astrophysics Data System (ADS)

    Welzel, S.; Stepanov, S.; Meichsner, J.; Röpcke, J.

    2010-03-01

    The kinetics of stable species has been studied in situ in pulsed CF4/H2 radio frequency discharges by means of time resolved quantum cascade laser absorption spectroscopy. The absorption spectra were usually recorded with a time resolution of 5 ms and required a multi-species analysis, because of interfering complex absorption features of CF4 and C3F8. For this reason, measurements were carried out at two different spectral positions. High resolution spectroscopic data were established by calibrating effective absorption cross sections and their relative temperature dependences for the relevant low pressure conditions (10 Pa). During the discharge a decrease in the CF4 density by ~12% was observed. The off-phase was characterized mainly by the gas exchange. The C3F8 density in the off-phase was found to be of the order of the detection limit (3 × 1013 cm-3). Spectra acquired during the plasma-on phase showed a rapid temperature-induced increase in the absorption signal and, additionally, suggested the influence of a short-lived broadband absorbing species. The reasonable assumption of the presence of CF4 hotbands has not yet enabled a further quantification.

  5. Time-Resolved Cell Culture Assay Analyser (TReCCA Analyser) for the Analysis of On-Line Data: Data Integration—Sensor Correction—Time-Resolved IC50 Determination

    PubMed Central

    Werner, Tobias; Wölfl, Stefan

    2015-01-01

    Time-resolved cell culture assays circumvent the need to set arbitrary end-points and reveal the dynamics of quality controlled experiments. However, they lead to the generation of large data sets, which can represent a complexity barrier to their use. We therefore developed the Time-Resolved Cell Culture Assay (TReCCA) Analyser program to perform standard cell assay analyses efficiently and make sophisticated in-depth analyses easily available. The functions of the program include data normalising and averaging, as well as smoothing and slope calculation, pin-pointing exact change time points. A time-resolved IC50/EC50 calculation provides a better understanding of drug toxicity over time and a more accurate drug to drug comparison. Finally the logarithmic sensor recalibration function, for sensors with an exponential calibration curve, homogenises the sensor output and enables the detection of low-scale changes. To illustrate the capabilities of the TReCCA Analyser, we performed on-line monitoring of dissolved oxygen in the culture media of the breast cancer cell line MCF-7 treated with different concentrations of the anti-cancer drug Cisplatin. The TReCCA Analyser is freely available at www.uni-heidelberg.de/fakultaeten/biowissenschaften/ipmb/biologie/woelfl/Research.html. By introducing the program, we hope to encourage more systematic use of time-resolved assays and lead researchers to fully exploit their data. PMID:26110644

  6. Time-Resolved Photoluminescence Studies of InGaN/AlGaN Multiple Quantum Wells

    NASA Astrophysics Data System (ADS)

    Zeng, K. C.; Smith, M.; Lin, J. Y.; Jiang, H. X.; Robert, J. C.; Piner, E. L.; McIntosh, F. G.; Bahbahani, M.; Bedair, S. M.; Zavada, J.

    1997-03-01

    Picosecond time-resolved photoluminescence (PL) spectroscopy has been employed to study the dynamic processes of optical transitions in InGaN/AlGaN multiple quantum wells (MQW) grown by metal-organic chemical vapor deposition (MOCVD). The dynamical behavior of the PL emission reveals that the main emission line in these MQW is the combination of the localized exciton and a band-to-impurity emission lines. The spectral lineshape and the recombination dynamics of the localized exciton and of the band-to-impurity transitions have been systematically investigated at different temperatures and excitation intensities and for MQW with different structures and growth conditions. From these studies, important parameters, including the localization energy and the recombination lifetimes of the localized excitons in InGaN/AlGaN quantum wells, the well width fluctuation, alloy compositions in the well and the barrier materials, and the band offset between InGaN and AlGaN can be deduced. Comparing with time-resolved PL results of InGaN/GaN and GaN/AlGaN MQW, important effects of interface on the optical properties of the III-nitride MQW have been evaluated. Implications of our results to device applications will be discussed.

  7. Time-resolved studies of impact-initiated combustion in aluminum powder compacts

    NASA Astrophysics Data System (ADS)

    Breidenich, Jennifer; Dixon, Sean; Aydelotte, Brady; Thadhani, Naresh

    2011-06-01

    The mechanisms of combustion reaction occurring under impact loading of aluminum powder compacts are studied using UV/Vis spectroscopy to gain time-resolved chemical information. Impact experiments performed on aluminum powder compacts reveal light emission due to reaction at velocities greater than 400m/s in air, while no reaction is observed in a vacuum (50mTorr). Light emission and reaction occurrence is also sensitive to the density of the Al powder compacts. Upon combustion, wavelengths indicative of the well-known reaction Al +O2 --> AlO + O , a sharp doublet at 398 nm and multiple broad peaks between 420 and 500 nm, are observed. Microsecond time-resolved chemical information is gained through analysis of these wavelengths using a spectrometer coupled with an electron multiplier CCD camera. The impact initiated reaction is also monitored by high speed imaging of transient deformation profiles which are compared to those predicted using numerical simulations employing ANSYS-AUTODYN-3D computer code. The insight obtained from the combination of these analyses of impact-initiated combustion reaction in aluminum powder compacts will be presented. Funded by DTRA, Grant No. HDTRA1-10-1-0038

  8. Time-resolved fluorescence studies of nucleotide flipping by restriction enzymes.

    PubMed

    Neely, Robert K; Tamulaitis, Gintautas; Chen, Kai; Kubala, Marta; Siksnys, Virginijus; Jones, Anita C

    2009-11-01

    Restriction enzymes Ecl18kI, PspGI and EcoRII-C, specific for interrupted 5-bp target sequences, flip the central base pair of these sequences into their protein pockets to facilitate sequence recognition and adjust the DNA cleavage pattern. We have used time-resolved fluorescence spectroscopy of 2-aminopurine-labelled DNA in complex with each of these enzymes in solution to explore the nucleotide flipping mechanism and to obtain a detailed picture of the molecular environment of the extrahelical bases. We also report the first study of the 7-bp cutter, PfoI, whose recognition sequence (T/CCNGGA) overlaps with that of the Ecl18kI-type enzymes, and for which the crystal structure is unknown. The time-resolved fluorescence experiments reveal that PfoI also uses base flipping as part of its DNA recognition mechanism and that the extrahelical bases are captured by PfoI in binding pockets whose structures are quite different to those of the structurally characterized enzymes Ecl18kI, PspGI and EcoRII-C. The fluorescence decay parameters of all the enzyme-DNA complexes are interpreted to provide insight into the mechanisms used by these four restriction enzymes to flip and recognize bases and the relationship between nucleotide flipping and DNA cleavage.

  9. Time-resolved luminescence detection of spleen tyrosine kinase activity through terbium sensitization.

    PubMed

    Lipchik, Andrew M; Parker, Laurie L

    2013-03-05

    Disruption of regulatory protein phosphorylation can lead to disease and is particularly prevalent in cancers. Inhibitors that target deregulated kinases are therefore a major focus of chemotherapeutic development. Achieving sensitivity and specificity in high-throughput compatible kinase assays is key to successful inhibitor development. Here, we describe the application of time-resolved luminescence detection to the direct sensing of spleen tyrosine kinase (Syk) activity and inhibition using a novel peptide substrate. Chelation and luminescence sensitization of Tb(3+) allowed the direct detection of peptide phosphorylation without any antibodies or other labeling reagents. Characterizing the Tb(3+) coordination properties of the phosphorylated vs unphosphorylated form of the peptide revealed that an inner-sphere water was displaced upon phosphorylation, which likely was responsible for both enhancing the luminescence intensity and also extending the lifetime, which enabled gating of the luminescence signal to improve the dynamic range. Furthermore, a shift in the optimal absorbance maximum for excitation was observed, from 275 nm (for the unphosphorylated tyrosine peptide) to 266 nm (for the phosphorylated tyrosine peptide). Accordingly, time-resolved measurements with excitation at 266 nm via a monochromator enabled a 16-fold improvement in base signal-to-noise for distinguishing phosphopeptide from unphosphorylated peptide. This led to a high degree of sensitivity and quantitative reproducibility, demonstrating the amenability of this method to both research laboratory and high-throughput applications.

  10. Fluorescence imaging and time-resolved spectroscopy of steroid using confocal synchrotron radiation microscopy

    NASA Astrophysics Data System (ADS)

    Gerritsen, Hans C.; van der Oord, C. J. R.; Levine, Yehudi K.; Munro, Ian H.; Jones, Gareth R.; Shaw, D. A.; Rommerts, Fokko F.

    1994-08-01

    The Confocal Synchrotron Radiation Microscope at Daresbury was used in a study of the transport and distribution of the steroid Coumestrol in single Leydig cells. The broad spectrum of synchrotron radiation in combination with UV compatible microscope optics affords the extension of confocal microscopy from the visible to the UV region down to about 200 nm. Consequently fluorescent molecules with absorption bands in the UV can be imaged. In addition the pulsed nature of the light source allows us to perform time-resolved fluorescence spectroscopy experiments on microscopic volumes. Coumestrol is a naturally fluorescing plant steroid exhibiting estrogenic activity. In physiological environments it has an absorption peak in the UV at 340 nm and it emits around 440 nm. First results indicate that the Coumestrol transport through the cell membrane is diffusion limited. The weak fluorescence observed in the nuclei of the Leydig cells may be due to fluorescence quenching arising from the interaction of the Coumesterol with nuclear components. However, micro-volume time-resolved fluorescence spectroscopy experiments on cell nuclei have revealed the same decay behavior for Coumesterol in both the cytoplasm and nucleus of the cells.

  11. Time-Resolved Luminescence Detection of Syk Kinase Activity Through Terbium Sensitization

    PubMed Central

    Lipchik, Andrew M.; Parker, Laurie L.

    2013-01-01

    Disruption of regulatory protein phosphorylation can lead to disease, and is particularly prevalent in cancers. Inhibitors that target deregulated kinases are therefore a major focus of chemotherapeutic development. Achieving sensitivity and specificity in high-throughput compatible kinase assays is key to successful inhibitor development. Here we describe the application of time-resolved luminescence detection to the direct sensing of Syk kinase activity and inhibition using a novel peptide substrate. Chelation and luminescence sensitization of Tb3+ allowed the direct detection of peptide phosphorylation without any antibodies or other labeling reagents. Characterizing the Tb3+ coordination properties of the phosphorylated vs. unphosphorylated form of the peptide revealed that an inner-sphere water was displaced upon phosphorylation, which likely was responsible for both enhancing the luminescence intensity and also extending the lifetime, which enabled gating of the luminescence signal to improve the dynamic range. Furthermore, a shift in the optimal absorbance maximum for excitation was observed, from 275 nm (for the unphosphorylated tyrosine peptide) to 266 nm (for the phosphorylated tyrosine peptide). Accordingly, time-resolved measurements with excitation at 266 nm via a monochromator enabled a 16-fold improvement in base signal to noise for distinguishing phosphopeptide from unphosphorylated peptide. This led to a high degree of sensitivity and quantitative reproducibility, demonstrating the amenability of this method to both research laboratory and high-throughput applications. PMID:23414415

  12. Time resolved dosimetry of human brain exposed to low frequency pulsed magnetic fields

    NASA Astrophysics Data System (ADS)

    Paffi, Alessandra; Camera, Francesca; Lucano, Elena; Apollonio, Francesca; Liberti, Micaela

    2016-06-01

    An accurate dosimetry is a key issue to understanding brain stimulation and related interaction mechanisms with neuronal tissues at the basis of the increasing amount of literature revealing the effects on human brain induced by low-level, low frequency pulsed magnetic fields (PMFs). Most literature on brain dosimetry estimates the maximum E field value reached inside the tissue without considering its time pattern or tissue dispersivity. Nevertheless a time-resolved dosimetry, accounting for dispersive tissues behavior, becomes necessary considering that the threshold for an effect onset may vary depending on the pulse waveform and that tissues may filter the applied stimulatory fields altering the predicted stimulatory waveform’s size and shape. In this paper a time-resolved dosimetry has been applied on a realistic brain model exposed to the signal presented in Capone et al (2009 J. Neural Transm. 116 257-65), accounting for the broadband dispersivity of brain tissues up to several kHz, to accurately reconstruct electric field and current density waveforms inside different brain tissues. The results obtained by exposing the Duke’s brain model to this PMF signal show that the E peak in the brain is considerably underestimated if a simple monochromatic dosimetry is carried out at the pulse repetition frequency of 75 Hz.

  13. Simulation of time resolved photoelectron spectra with Stieltjes imaging illustrated on ultrafast internal conversion in pyrazine.

    PubMed

    Werner, Ute; Mitrić, Roland; Bonacić-Koutecký, Vlasta

    2010-05-07

    We present an approach for the simulation of time resolved photoelectron spectra based on the combination of the ab initio nonadiabatic molecular dynamics "on the fly" with the Stieltjes imaging method utilizing discrete neutral states above the ionization limit for the approximate description of the ionization continuum. Our approach has been implemented in the framework of the time-dependent density functional theory and has been applied to interrogate the ultrafast internal conversion between the S(2) and S(1) states in pyrazine. The simulations reveal that, parallel to the S(2)-->S(1) internal conversion, a change in the dominant ionization process (S(2)-->D(1) versus S(1)-->D(0)) occurs on the time scale of 20 fs such that no significant change in the photoelectron kinetic energy distribution is observed. The presented results are in full agreement with the experimental results presented in the accompanying paper [Suzuki et al., J. Chem. Phys. 132, 174302 (2010)] and provide an insight into the interplay between the nonradiative relaxation and the photoionization process in pyrazine as reflected in the time resolved photoelectron spectrum. Our approach represents a general tool for the investigation of ultrafast photoionization processes in complex systems and thus can be used to investigate the ultrafast femtochemistry of complex molecular systems including all degrees of freedom.

  14. Simulation of time resolved photoelectron spectra with Stieltjes imaging illustrated on ultrafast internal conversion in pyrazine

    NASA Astrophysics Data System (ADS)

    Werner, Ute; Mitrić, Roland; Bonačić-Koutecký, Vlasta

    2010-05-01

    We present an approach for the simulation of time resolved photoelectron spectra based on the combination of the ab initio nonadiabatic molecular dynamics "on the fly" with the Stieltjes imaging method utilizing discrete neutral states above the ionization limit for the approximate description of the ionization continuum. Our approach has been implemented in the framework of the time-dependent density functional theory and has been applied to interrogate the ultrafast internal conversion between the S2 and S1 states in pyrazine. The simulations reveal that, parallel to the S2→S1 internal conversion, a change in the dominant ionization process (S2→D1 versus S1→D0) occurs on the time scale of 20 fs such that no significant change in the photoelectron kinetic energy distribution is observed. The presented results are in full agreement with the experimental results presented in the accompanying paper [Suzuki et al., J. Chem. Phys. 132, 174302 (2010)] and provide an insight into the interplay between the nonradiative relaxation and the photoionization process in pyrazine as reflected in the time resolved photoelectron spectrum. Our approach represents a general tool for the investigation of ultrafast photoionization processes in complex systems and thus can be used to investigate the ultrafast femtochemistry of complex molecular systems including all degrees of freedom.

  15. The time-resolved natural flow field of a fluidic oscillator

    NASA Astrophysics Data System (ADS)

    Woszidlo, Rene; Ostermann, Florian; Nayeri, C. N.; Paschereit, C. O.

    2015-06-01

    The internal and external flow field of a fluidic oscillator with two feedback channels are examined experimentally within the incompressible flow regime. A scaled-up device with a square outlet nozzle is supplied with pressurized air and emits a spatially oscillating jet into quiescent environment. Time-resolved information are obtained by phase-averaging pressure and PIV data based on an internal reference signal. The temporal resolution is better than a phase angle of 3°. A detailed analysis of the internal dynamics reveals that the oscillation mechanism is based on fluid feeding into a separation bubble between the jet and mixing chamber wall which pushes the jet to the opposite side. The total volume of fluid transported through one feedback channel during one oscillation cycle matches the total growth of the separation bubble from its initial size to its maximum extent. Although the oscillation frequency increases linearly with supply rate, sudden changes in the internal dynamics are observed. These changes are caused by a growth in reversed flow through the feedback channels. The time-resolved properties of the emitted jet such as instantaneous jet width and exit velocity are found to oscillate substantially during one oscillation cycle. Furthermore, the results infer that the jet's oscillation pattern is approximately sinusoidal with comparable residence and switching times.

  16. Time-resolved Optical Spectroscopy of the Cataclysmic Variable PG 0859+415

    NASA Astrophysics Data System (ADS)

    Hoard, D. W.; Szkody, Paula

    1996-10-01

    We present time-resolved, high-resolution (2 Å) spectra of the nova-like cataclysmic variable (CV) PG 0859+415. The average optical spectrum of this star displays a continuum slope that is steeper than expected for a steady state accretion disk this is attributed to the presence of a hot spot with T ˜ 12,000 K at the impact site of the accretion stream. As first observed by Grauer et al., the time- resolved spectra exhibit a transient central absorption feature in the Balmer lines that appears near φ = 0.6 and lasts into the (partial) eclipse, and the radial velocity solution of the Balmer lines shows a phase offset of Δφ = -0.1 from the photometric phasing. System parameters are estimated from the radial velocity solution to the He II lines (which is consistent with an origin close to the white dwarf primary star). Doppler tomograms constructed from the Balmer emission lines reveal the presence of a region of enhanced emission at a location consistent with the expected impact site of the accretion stream with the edge of the disk. Finally, the similarities between PG 0859+415 and the recently identified SW Sextantis subclass of CV is discussed, and a qualitative model for the system is proposed to explain the observational results.

  17. The Time-Resolved Flow Field of a Spatially Oscillating Jet in Crossflow

    NASA Astrophysics Data System (ADS)

    Ostermann, F.; Woszidlo, R.; Nayeri, C. N.; Paschereit, C. O.

    2016-11-01

    Spatially oscillating jets in crossflow emitted by fluidic oscillators have been proven beneficial for flow control applications in recent studies. However, the driving mechanism behind the efficacy remains unknown. The presented study examines the fundamental, time-resolved flow field of a spatially oscillating jet in crossflow. The inclination angle between oscillation plane and crossflow is 90°. The underlying experimental dataset is acquired plane-by-plane by a traversable stereoscopic particle image velocimetry system. Phase-averaging reduces stochastic noise, compensates low sampling rates, and allows combining the individual planes to a time-resolved three-dimensional flow field. The trajectory of the oscillating jet is much shallower than a steady jet. Two counter-rotating streamwise vortices are revealed. The sense of rotation is opposite to that of the counter-rotating vortex pair of steady jets in crossflow. This sense of rotation enables the vortices to prevail far downstream because they push each other toward the wall. The strength of the vortices is alternating. This vortex pair is a promising candidate to be the driving mechanism behind the high efficacy in separation control. PhD Student.

  18. In situ Spectroscopy Reveals that Microorganisms in Different Phyla Use Different Electron Transfer Biomolecules to Respire Aerobically on Soluble Iron

    PubMed Central

    Blake II, Robert C.; Anthony, Micah D.; Bates, Jordan D.; Hudson, Theresa; Hunter, Kamilya M.; King, Brionna J.; Landry, Bria L.; Lewis, Megan L.; Painter, Richard G.

    2016-01-01

    Absorbance spectra were collected on 12 different live microorganisms, representing six phyla, as they respired aerobically on soluble iron at pH 1.5. A novel integrating cavity absorption meter was employed that permitted accurate absorbance measurements in turbid suspensions that scattered light. Illumination of each microorganism yielded a characteristic spectrum of electrochemically reduced colored prosthetic groups. A total of six different patterns of reduced-minus-oxidized difference spectra were observed. Three different spectra were obtained with members of the Gram-negative eubacteria. Acidithiobacillus, representing Proteobacteria, yielded a spectrum in which cytochromes a and c and a blue copper protein were all prominent. Acidihalobacter, also representing the Proteobacteria, yielded a spectrum in which both cytochrome b and a long-wavelength cytochrome a were clearly visible. Two species of Leptospirillum, representing the Nitrospirae, both yielded spectra that were dominated by a cytochrome with a reduced peak at 579 nm. Sulfobacillus and Alicyclobacillus, representing the Gram-positive Firmicutes, both yielded spectra dominated by a-type cytochromes. Acidimicrobium and Ferrimicrobium, representing the Gram-positive Actinobacteria, also yielded spectra dominated by a-type cytochromes. Acidiplasma and Ferroplasma, representing the Euryarchaeota, both yielded spectra dominated by a ba3-type of cytochrome. Metallosphaera and Sulfolobus, representing the Crenarchaeota, both yielded spectra dominated by the same novel cytochrome as that observed in the Nitrospirae and a new, heretofore unrecognized redox-active prosthetic group with a reduced peak at around 485 nm. These observations are consistent with the hypothesis that individual acidophilic microorganisms that respire aerobically on iron utilize one of at least six different types of electron transfer pathways that are characterized by different redox-active prosthetic groups. In situ absorbance

  19. High frequency measurements using in situ sensors in a coupled watershed-estuary reveal factors driving DOC variability

    NASA Astrophysics Data System (ADS)

    Mulukutla, G. K.; Carey, R. O.; Wollheim, W. M.; Salisbury, J.

    2012-12-01

    Estuaries are recipients of large inputs of organic matter and nutrients from coastal river systems and together form a vital link between two of the largest pools of carbon, the terrestrial and ocean environment, at the same time actively cycling carbon. The Great Bay situated in New Hampshire/Maine is a nitrogen(N)-impaired estuary with a suburbanizing watershed of the Lamprey River its largest source of DOC. Long term deployment of continuously monitoring sensors are changing the way biogeochemical studies of rivers, streams and estuaries are conducted. We linked simultaneous and continuous in situ measurements of CDOM and associated measures of DOC quality (e.g. absorption coefficient, spectral slope ) in both the Great Bay estuary and its largest source of DOC the Lamprey River between April and December 2011. These sensors allowed us to examine the continuous dynamics of CDOM from inland to the coastal waters not only in short-term hydrologically varying (storm pulses) conditions, but also the longer term seasonal variability. We also collected a suite of other relevant parameters in both the watershed and estuary, including NO3, PO4, Turbidity, Chlorophyll, Conductivity/Salinity to help understand the dynamics of DOC in the river and estuary. Preliminary time series analysis indicates that DOC in the Great Bay estuary co-varies with discharge of the Lamprey River, especially in spring and fall. Freshwater discharges and its variations explained the variability in estuarine DOC. UV- absorbance at 254 nm (the precursor to SUVA) co-varies in periods of high flow during spring and fall, consistent with the bulk DOC results This suggests that hydrology is the more important driver of variability of coastal CDOM. In light of climate change, suburbanization and changing land use patterns this emphasizes the need to examine continuous measurements of DOC quantity and quality in coupled watershed-estuarine systems.

  20. The allocation of assimilated carbon to shoot growth: in situ assessment in natural grasslands reveals nitrogen effects and interspecific differences.

    PubMed

    Gong, Xiao Ying; Berone, Germán Darío; Agnusdei, Mónica Graciela; Palma, Ricardo Manuel Rodríguez; Schäufele, Rudi; Lattanzi, Fernando Alfredo

    2014-04-01

    In grasslands, sustained nitrogen loading would increase the proportion of assimilated carbon allocated to shoot growth (A shoot), because it would decrease allocation to roots and also encourage the contribution of species with inherently high A shoot. However, in situ measurements of carbon allocation are scarce. Therefore, it is unclear to what extent species that coexist in grasslands actually differ in their allocation strategy or in their response to nitrogen. We used a mobile facility to perform steady-state (13)C-labeling of field stands to quantify, in winter and autumn, the daily relative photosynthesis rate (RPR~tracer assimilated over one light-period) and A shoot (~tracer remaining in shoots after a 100 degree days chase period) in four individual species with contrasting morpho-physiological characteristics coexisting in a temperate grassland of Argentina, either fertilized or not with nitrogen, and either cut intermittently or grazed continuously. Plasticity in response to nitrogen was substantial in most species, as indicated by positive correlations between A shoot and shoot nitrogen concentration. There was a notable interspecific difference: productive species with higher RPR, enhanced by fertilization and characterized by faster leaf turnover rate, allocated ~20% less of the assimilated carbon to shoot growth than species of lower productivity (and quality) characterized by longer leaf life spans and phyllochrons. These results imply that, opposite to the expected response, sustained nitrogen loading would change little the A shoot of grassland communities if increases at the species-level are offset by decreases associated with replacement of 'low RPR-high A shoot' species by 'high RPR-low A shoot' species.

  1. Microbial diversity in an in situ reactor system treating monochlorobenzene contaminated groundwater as revealed by 16S ribosomal DNA analysis.

    PubMed

    Alfreider, Albin; Vogt, Carsten; Babel, Wolfgang

    2002-08-01

    A molecular approach based on the construction of 16S ribosomal DNA clone libraries was used to investigate the microbial diversity of an underground in situ reactor system filled with the original aquifer sediments. After chemical steady state was reached in the monochlorobenzene concentration between the original inflowing groundwater and the reactor outflow, samples from different reactor locations and from inflowing and outflowing groundwater were taken for DNA extraction. Small-subunit rRNA genes were PCR-amplified with primers specific for Bacteria, subsequently cloned and screened for variation by restriction fragment length polymorphism (RFLP). A total of 87 bacterial 16S rDNA genes were sequenced and subjected to phylogenetic analysis. The original groundwater was found to be dominated by a bacterial consortium affiliated with various members of the class of Proteobacteria, by phylotypes not affiliated with currently recognized bacterial phyla, and also by sporulating and non-sporulating sulfate-reducing bacteria. The most occurring clone types obtained from the sediment samples of the reactor were related to the beta-Proteobacteria, dominated by sequences almost identical to the widespread bacterium Alcaligenes faecalis, to low G+C gram-positive bacteria and to Acidithiobacillus ferrooxidans (formerly Thiobacillus ferrooxidans) within the gamma subclass of Proteobacteria in the upper reactor sector. Although bacterial phylotypes originating from the groundwater outflow of the reactors also grouped within different subdivisions of Proteobacteria and low G+C gram-positive bacteria, most of the 16S rDNA sequences were not associated with the sequence types observed in the reactor samples. Our results suggest that the different environments were inhabited by distinct microbial communities in respect to their taxonomic diversity, particular pronounced between sediment attached microbial communities from the reactor samples and free-living bacteria from the

  2. Time-Resolved Spectroscopy of Active Binary Stars

    NASA Technical Reports Server (NTRS)

    Brown, Alexander

    2000-01-01

    This NASA grant covered EUVE observing and data analysis programs during EUVE Cycle 5 GO observing. The research involved a single Guest Observer project 97-EUVE-061 "Time-Resolved Spectroscopy of Active Binary Stars". The grant provided funding that covered 1.25 months of the PI's salary. The activities undertaken included observation planning and data analysis (both temporal and spectral). This project was awarded 910 ksec of observing time to study seven active binary stars, all but one of which were actually observed. Lambda-And was observed on 1997 Jul 30 - Aug 3 and Aug 7-14 for a total of 297 ksec; these observations showed two large complex flares that were analyzed by Osten & Brown (1999). AR Psc, observed for 350 ksec on 1997 Aug 27 - Sep 13, showed only relatively small flares that were also discussed by Osten & Brown (1999). EUVE observations of El Eri were obtained on 1994 August 24-28, simultaneous with ASCA X-ray spectra. Four flares were detected by EUVE with one of these also observed simultaneously, by ASCA. The other three EUVE observations were of the stars BY Dra (1997 Sep 22-28), V478 Lyr (1998 May 18-27), and sigma Gem (1998 Dec 10-22). The first two stars showed a few small flares. The sigma Gem data shows a beautiful complete flare with a factor of ten peak brightness compared to quiescence. The flare rise and almost all the decay phase are observed. Unfortunately no observations in other spectral regions were obtained for these stars. Analysis of the lambda-And and AR Psc observations is complete and the results were published in Osten & Brown (1999). Analysis of the BY Dra, V478 Lyr and sigma Gem EUVE data is complete and will be published in Osten (2000, in prep.). The El Eri EUV analysis is also completed and the simultaneous EUV/X-ray study will be published in Osten et al. (2000, in prep.). Both these latter papers will be submitted in summer 2000. All these results will form part of Rachel Osten's PhD thesis.

  3. Time-resolved optical spectroscopy measurements of shocked liquid deuterium

    NASA Astrophysics Data System (ADS)

    Bailey, J. E.; Knudson, M. D.; Carlson, A. L.; Dunham, G. S.; Desjarlais, M. P.; Hanson, D. L.; Asay, J. R.

    2008-10-01

    Time-resolved optical spectroscopy has been used to measure the shock pressure steadiness, emissivity, and temperature of liquid deuterium shocked to 22-90 GPa. The shock was produced using magnetically accelerated flyer plate impact, and spectra were acquired with a suite of four fiber-optic-coupled spectrometers with streak camera detectors. The shock pressure changes by an average of -1.2% over the 10-30 ns cell transit time, determined from the relative changes in the shock front self-emission with time. The shock front reflectivity was measured from 5140Å and 5320Å laser light reflected from the D2 shock. The emissivity inferred from the reflectivity measurements was in reasonably good agreement with quantum molecular dynamics simulation predictions. The spectral radiance wavelength dependence was found to agree well (average normalized χ2=1.6 ) with a Planckian multiplied by the emissivity. The shock front temperature was determined from the emissivity and the wavelength-dependent shock self-emission. Thirty-seven temperature measurements spanning the 22-90 GPa range were accumulated. The large number of temperature measurements enables a comparison of the scatter in the data with expectations for a Gaussian distribution. This facilitates determination of uncertainties that incorporate both apparatus contributions and otherwise unquantified systematic effects that cause self-emission variations from one experiment to another. Agreement between temperatures determined from the absolute spectral radiance and from the relative shape of the spectrum further substantiates the absence of systematic biases. The weighted mean temperature uncertainties were as low as ±3-4% , enabling the discrimination between competing models for the D2 equation of state (EOS). The temperature results agree well with models that predict a maximum compression of ˜4.4 . Softer models that predict approximately sixfold compression are inconsistent with the data to a very high

  4. Time-Resolved Fluorescent Immunochromatography of Aflatoxin B1 in Soybean Sauce: A Rapid and Sensitive Quantitative Analysis

    PubMed Central

    Wang, Du; Zhang, Zhaowei; Li, Peiwu; Zhang, Qi; Zhang, Wen

    2016-01-01

    Rapid and quantitative sensing of aflatoxin B1 with high sensitivity and specificity has drawn increased attention of studies investigating soybean sauce. A sensitive and rapid quantitative immunochromatographic sensing method was developed for the detection of aflatoxin B1 based on time-resolved fluorescence. It combines the advantages of time-resolved fluorescent sensing and immunochromatography. The dynamic range of a competitive and portable immunoassay was 0.3–10.0 µg·kg−1, with a limit of detection (LOD) of 0.1 µg·kg−1 and recoveries of 87.2%–114.3%, within 10 min. The results showed good correlation (R2 > 0.99) between time-resolved fluorescent immunochromatographic strip test and high performance liquid chromatography (HPLC). Soybean sauce samples analyzed using time-resolved fluorescent immunochromatographic strip test revealed that 64.2% of samples contained aflatoxin B1 at levels ranging from 0.31 to 12.5 µg·kg−1. The strip test is a rapid, sensitive, quantitative, and cost-effective on-site screening technique in food safety analysis. PMID:27428975

  5. Immunotoxicity risks associated with land-treatment of petrochemical wastes revealed using an in situ rodent model.

    PubMed

    Rafferty, D P; Lochmiller, R L; McBee, K; Qualls, C W; Basta, N T

    2001-01-01

    Land-treatment of petrochemical wastes is a widely used method to dispose of hazardous and non-hazardous waste by biodegradation. However, no comprehensive assessment of the impact of such disposal techniques on terrestrial ecosystems has been conducted. Despite the presence of suspected immunotoxicants in the soil, wild rodents frequently reside on these waste sites after closure or abandonment. We explored the seasonal sensitivity of the immune system of the hispid cotton rat (Sigmodon hispidus) to in situ exposures on sites land-treated with petrochemical wastes. Animals were monitored on five contaminated land-treatment sites and five ecologically matched-reference sites in Oklahoma, USA, over two seasons (summer and winter). Most hematological parameters were not adversely affected by land-treatment; however, platelet counts were 26% greater in cotton rats from land-treatment sites compared to reference sites in winter. Significant treatment-related differences were observed in total serum protein concentrations, organ mass and organ cellularity, but these differences were not consistent across the five land-treatment units. Lymphoproliferative responses of cotton rat splenocytes stimulated in vitro were elevated for a T-cell mitogen and depressed for a B-cell mitogen in animals from land-treatment compared to reference sites. The ability of splenocytes to proliferate in response to interleukin-2 receptor-binding was not influenced by treatment. Total yields of peritoneal cells, yield of peritoneal macrophages, and yield of peritoneal lymphocytes were influenced to varying degrees by land-treatment. Functionally, in vitro metabolic activity of peritoneal macrophages was 114% greater in cotton rats from land-treatment sites compared to reference sites during summer. These results indicate that petrochemical wastes applied to soils on these five land-treatment sites had variable immunomodulatory effects in resident cotton rats. Immune alterations for some assays

  6. Resistive switching mechanism in the one diode-one resistor memory based on p(+)-Si/n-ZnO heterostructure revealed by in-situ TEM.

    PubMed

    Zhang, Lei; Zhu, Liang; Li, Xiaomei; Xu, Zhi; Wang, Wenlong; Bai, Xuedong

    2017-03-21

    One diode-one resistor (1D1R) memory is an effective architecture to suppress the crosstalk interference, realizing the crossbar network integration of resistive random access memory (RRAM). Herein, we designed a p(+)-Si/n-ZnO heterostructure with 1D1R function. Compared with the conventional multilayer 1D1R devices, the structure and fabrication technique can be largely simplified. The real-time imaging of formation/rupture process of conductive filament (CF) process demonstrated the RS mechanism by in-situ transmission electron microscopy (TEM). Meanwhile, we observed that the formed CF is only confined to the outside of depletion region of Si/ZnO pn junction, and the formation of CF does not degrade the diode performance, which allows the coexistence of RS and rectifying behaviors, revealing the 1D1R switching model. Furthermore, it has been confirmed that the CF is consisting of the oxygen vacancy by in-situ TEM characterization.

  7. Resistive switching mechanism in the one diode-one resistor memory based on p+-Si/n-ZnO heterostructure revealed by in-situ TEM

    PubMed Central

    Zhang, Lei; Zhu, Liang; Li, Xiaomei; Xu, Zhi; Wang, Wenlong; Bai, Xuedong

    2017-01-01

    One diode-one resistor (1D1R) memory is an effective architecture to suppress the crosstalk interference, realizing the crossbar network integration of resistive random access memory (RRAM). Herein, we designed a p+-Si/n-ZnO heterostructure with 1D1R function. Compared with the conventional multilayer 1D1R devices, the structure and fabrication technique can be largely simplified. The real-time imaging of formation/rupture process of conductive filament (CF) process demonstrated the RS mechanism by in-situ transmission electron microscopy (TEM). Meanwhile, we observed that the formed CF is only confined to the outside of depletion region of Si/ZnO pn junction, and the formation of CF does not degrade the diode performance, which allows the coexistence of RS and rectifying behaviors, revealing the 1D1R switching model. Furthermore, it has been confirmed that the CF is consisting of the oxygen vacancy by in-situ TEM characterization. PMID:28322336

  8. Resistive switching mechanism in the one diode-one resistor memory based on p+-Si/n-ZnO heterostructure revealed by in-situ TEM

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zhu, Liang; Li, Xiaomei; Xu, Zhi; Wang, Wenlong; Bai, Xuedong

    2017-03-01

    One diode-one resistor (1D1R) memory is an effective architecture to suppress the crosstalk interference, realizing the crossbar network integration of resistive random access memory (RRAM). Herein, we designed a p+-Si/n-ZnO heterostructure with 1D1R function. Compared with the conventional multilayer 1D1R devices, the structure and fabrication technique can be largely simplified. The real-time imaging of formation/rupture process of conductive filament (CF) process demonstrated the RS mechanism by in-situ transmission electron microscopy (TEM). Meanwhile, we observed that the formed CF is only confined to the outside of depletion region of Si/ZnO pn junction, and the formation of CF does not degrade the diode performance, which allows the coexistence of RS and rectifying behaviors, revealing the 1D1R switching model. Furthermore, it has been confirmed that the CF is consisting of the oxygen vacancy by in-situ TEM characterization.

  9. A Time-Resolved Study on Nanodisc-to-Vesicle Transformation

    NASA Astrophysics Data System (ADS)

    Nieh, Mu-Ping; Mahabir, Suanne; Wan, Wan Kei; Kastaras, John

    2011-03-01

    Structural phase diagram of a phospholipid mixture composed of dimyristoyl phosphatidylcholine (DMPC), dihexanoyl phosphatidylcholine (DHPC) and dimyristoyl phosphatidylglycerol (DMPG) contains many rich morphologies, e.g., nanodiscs also known as ``bicelles'', bilayered ribbons, unilamellar vesicles (ULVs), multi-lamellar vesicles (MLVs) and perforated lamellae. In this report, we will present time-resolved small angle neutron scattering and dynamic light scattering measurements of the structural transformation from nanodiscs to ULVs as a function of temperature, lipid concentration and charge density. The result will reveal the growth rate of nanodiscs and all the intermediate structures along the transformation process. Through the understanding of the kinetic pathway, the size and polydispersity of the self-assembled nano-size ULVs can be well-controlled. These ULVs can be used as a carrier for therapeutics or imaging probes.

  10. The time resolved measurement of ultrashort terahertz-band electric fields without an ultrashort probe

    NASA Astrophysics Data System (ADS)

    Walsh, D. A.; Snedden, E. W.; Jamison, S. P.

    2015-05-01

    The time-resolved detection of ultrashort pulsed THz-band electric field temporal profiles without an ultrashort laser probe is demonstrated. A non-linear interaction between a narrow-bandwidth optical probe and the THz pulse transposes the THz spectral intensity and phase information to the optical region, thereby generating an optical pulse whose temporal electric field envelope replicates the temporal profile of the real THz electric field. This optical envelope is characterised via an autocorrelation based FROG (frequency resolved optical gating) measurement, hence revealing the THz temporal profile. The combination of a narrow-bandwidth, long duration, optical probe, and self-referenced FROG makes the technique inherently immune to timing jitter between the optical probe and THz pulse and may find particular application where the THz field is not initially generated via ultrashort laser methods, such as the measurement of longitudinal electron bunch profiles in particle accelerators.

  11. The time resolved measurement of ultrashort terahertz-band electric fields without an ultrashort probe

    SciTech Connect

    Walsh, D. A. Snedden, E. W.; Jamison, S. P.

    2015-05-04

    The time-resolved detection of ultrashort pulsed THz-band electric field temporal profiles without an ultrashort laser probe is demonstrated. A non-linear interaction between a narrow-bandwidth optical probe and the THz pulse transposes the THz spectral intensity and phase information to the optical region, thereby generating an optical pulse whose temporal electric field envelope replicates the temporal profile of the real THz electric field. This optical envelope is characterised via an autocorrelation based FROG (frequency resolved optical gating) measurement, hence revealing the THz temporal profile. The combination of a narrow-bandwidth, long duration, optical probe, and self-referenced FROG makes the technique inherently immune to timing jitter between the optical probe and THz pulse and may find particular application where the THz field is not initially generated via ultrashort laser methods, such as the measurement of longitudinal electron bunch profiles in particle accelerators.

  12. Revisiting the photophysics of 9-fluorenone: Ultrafast time-resolved fluorescence and theoretical studies

    NASA Astrophysics Data System (ADS)

    Chang, Chih-Wei; Sølling, Theis I.; Diau, Eric Wei-Guang

    2017-10-01

    Ultrafast intersystem crossing dynamics of fluorenone in gas and condensed phases were investigated by time-resolved mass spectrometry and fluorescence up-conversion spectroscopy. The former shows the ultrafast Franck-Condon relaxation and the internal conversion dynamics of isolated fluorenone in the gas phase. The latter reveals that the vibrational relaxation time is 2.2 ps and a 110 ps fluorescence lifetime of fluorenone in hexane. The fluorescence lifetime in acetonitrile and dimethylsulfoxide is 16 ns and 15.1 ns, respectively. The potential energy surface along the Cdbnd O out of plane bending motion shows that this coordinate is important for ISC in both polar and non-polar solvents.

  13. Cluster-surface interaction studied by time-resolved two-photon photoemission

    NASA Astrophysics Data System (ADS)

    Busolt, U.; Cottancin, E.; Röhr, H.; Socaciu, L.; Leisner, T.; Wöste, L.

    We use time-resolved two-photon photoemission to study the stability of size selected Agn+ clusters (n=2-9)deposited onto highly oriented pyrolytic graphite (HOPG) substrates at liquid nitrogen temperatures. The deposition was carried out with variable kinetic energies of the clusters. Clusters deposited with high kinetic energy (up to 60 eV/cluster) become fragmented upon impact. For low deposition energies (1-4 eV/cluster) the size dependence of the photoelectron spectra reveals a pronounced odd/even effect, which is well known for gas phase silver clusters. This indicates that the soft deposited clusters retain their size and identity on the sample. The phase of the odd/even effect suggests that transient negatively charged cluster ions serve as an intermediate step in the two-photon photoemission process. The lifetime of the anions rises with cluster size. This is attributed to an increasing electronic density of states for larger clusters.

  14. Protein analysis by time-resolved measurements with an electro-switchable DNA chip

    PubMed Central

    Langer, Andreas; Hampel, Paul A.; Kaiser, Wolfgang; Knezevic, Jelena; Welte, Thomas; Villa, Valentina; Maruyama, Makiko; Svejda, Matej; Jähner, Simone; Fischer, Frank; Strasser, Ralf; Rant, Ulrich

    2013-01-01

    Measurements in stationary or mobile phases are fundamental principles in protein analysis. Although the immobilization of molecules on solid supports allows for the parallel analysis of interactions, properties like size or shape are usually inferred from the molecular mobility under the influence of external forces. However, as these principles are mutually exclusive, a comprehensive characterization of proteins usually involves a multi-step workflow. Here we show how these measurement modalities can be reconciled by tethering proteins to a surface via dynamically actuated nanolevers. Short DNA strands, which are switched by alternating electric fields, are employed as capture probes to bind target proteins. By swaying the proteins over nanometre amplitudes and comparing their motional dynamics to a theoretical model, the protein diameter can be quantified with Angström accuracy. Alterations in the tertiary protein structure (folding) and conformational changes are readily detected, and even post-translational modifications are revealed by time-resolved molecular dynamics measurements. PMID:23839273

  15. Time-resolved scanning Kerr microscopy of flux beam formation in hard disk write heads

    NASA Astrophysics Data System (ADS)

    Valkass, Robert A. J.; Spicer, Timothy M.; Burgos Parra, Erick; Hicken, Robert J.; Bashir, Muhammad A.; Gubbins, Mark A.; Czoschke, Peter J.; Lopusnik, Radek

    2016-06-01

    To meet growing data storage needs, the density of data stored on hard disk drives must increase. In pursuit of this aim, the magnetodynamics of the hard disk write head must be characterized and understood, particularly the process of "flux beaming." In this study, seven different configurations of perpendicular magnetic recording (PMR) write heads were imaged using time-resolved scanning Kerr microscopy, revealing their detailed dynamic magnetic state during the write process. It was found that the precise position and number of driving coils can significantly alter the formation of flux beams during the write process. These results are applicable to the design and understanding of current PMR and next-generation heat-assisted magnetic recording devices, as well as being relevant to other magnetic devices.

  16. Femtosecond time-resolved EUV photoion imaging studies of pure helium nanodroplets

    NASA Astrophysics Data System (ADS)

    Buenermann, Oliver; Kornilov, Oleg; Gessner, Oliver; Leone, Stephen R.; Neumark, Daniel M.

    2010-03-01

    Helium nanodroplets provide a cryogenic, weakly interacting matrix for the isolation and spectroscopy of molecules and clusters. The relaxation dynamics of electronically excited helium nanodroplets are investigated by femtosecond time resolved photoion imaging studies. The droplets are excited into a broad absorption band centered at 23.8 eV. The electronic and nuclear dynamics following this excitation are monitored by photoionization with a 785nm probe pulse. A Wiley-McLaren time of flight spectrometer equipped with a time- and position sensitive delay line detector facilitates the measurement of mass selective ion kinetic energy distributions. First measurements reveal differences in the kinetic energy release of the Helium monomer, dimer and trimer ions. Furthermore, the pump-probe time-delay dependent ion spectra exhibit several features evolving on various timescales. The combination of these results with previously recorded photoelectron imaging measurements allows for a new level of insight into the electronic and nuclear dynamics of electronically excited helium nanodroplets.

  17. Time-resolved transmittance: a comparison of the diffusion model approach with Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Rothfischer, Ramona; Grosenick, Dirk; Macdonald, Rainer

    2015-07-01

    We discuss the determination of optical properties of thick scattering media from measurements of time-resolved transmittance by diffusion theory using Monte Carlo simulations as a gold standard to model photon migration. Our theoretical and experimental investigations reveal differences between calculated distributions of times of flight (DTOFs) of photons from both models which result in an overestimation of the absorption and the reduced scattering coefficient by diffusion theory which becomes larger for small scattering coefficients. By introducing a temporal shift in the DTOFs obtained with the diffusion model as additional fit parameter, the deviation in the absorption coefficient can be compensated almost completely. If the scattering medium is additionally covered by transparent layers (e.g. glass plates) the deviation between the DTOFs from both models is even larger which mainly effects the determination of the reduced scattering coefficient by diffusion theory. A temporal shift improves the accuracy of the optical properties derived by diffusion theory in this case as well.

  18. Hydrogen-Mediated Electron Doping of Gold Clusters As Revealed by In Situ X-ray and UV-vis Absorption Spectroscopy.

    PubMed

    Ishida, Ryo; Hayashi, Shun; Yamazoe, Seiji; Kato, Kazuo; Tsukuda, Tatsuya

    2017-06-01

    We previously reported that small (∼1.2 nm) gold clusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) exhibited a localized surface plasmon resonance (LSPR) band at ∼520 nm in the presence of NaBH4. To reveal the mechanism of this phenomenon, the electronic structure of Au:PVP during the reaction with NaBH4 in air was examined by means of in situ X-ray absorption spectroscopy at Au L3-edge and UV-vis spectroscopy. These measurements indicated that the appearance of the LSPR band is not associated with the growth in size but is ascribed to electron doping to the Au sp band by the adsorbed H atoms.

  19. Laser scanning confocal microscopy and quantitative microscopy with a charge coupled device camera improve detection of human papillomavirus DNA revealed by fluorescence in situ hybridization.

    PubMed

    Lizard, G; Chignol, M C; Souchier, C; Schmitt, D; Chardonnet, Y

    1994-04-01

    Epithelial cervical CaSki, SiHa and HeLa cells containing respectively 600 copies of human papillomavirus (HPV) DNA type 16, 1-2 copies of HPV DNA type 16 and 10-50 copies of HPV DNA type 18 were used as model to detect different quantities of integrated HPV genome. The HPV DNA was identified on cell deposits with specific biotinylated DNA probes either by enzymatic in situ hybridization (EISH) or fluorescence in situ hybridization (FISH) involving successively a rabbit anti-biotin antibody, a biotinylated goat anti-rabbit antibody and streptavidin-alkaline phosphatase complex or streptavidin-fluorescein isothiocyanate complex. With brightfield microscopy and EISH, hybridization spots were observed in CaSki and HeLa cells but hardly any in SiHa cells. With fluorescence microscopy and FISH, hybridization spots were clearly seen only on CaSki cell nuclei. In an attempt to improve the detection of low quantities of HPV DNA signals revealed by FISH, laser scanning confocal microscopy (LSCM) and quantitative microscopy with an intensified charge coupled device (CCD) camera were used. With both LSCM and quantitative microscopy, as few as 1-2 copies of HPV DNA were detected and found to be confined to cell nuclei counterstained with propidium iodide. Under Nomarski phase contrast, a good preservation of the cell structure was observed. With quantitative microscopy, differences in the number, size, total area and integrated fluorescence intensity of hybridization spots per nucleus were revealed between CaSki, SiHa and HeLa cells.(ABSTRACT TRUNCATED AT 250 WORDS)

  20. In-situ atomic force microscopy observation revealing gel-like plasticity on a metallic glass surface

    NASA Astrophysics Data System (ADS)

    Lu, Y. M.; Zeng, J. F.; Huang, J. C.; Kuan, S. Y.; Nieh, T. G.; Wang, W. H.; Pan, M. X.; Liu, C. T.; Yang, Y.

    2017-03-01

    It has been decade-long and enduring efforts to decipher the structural mechanism of plasticity in metallic glasses; however, it still remains a challenge to directly reveal the structural change, if any, that precedes; and dominant plastics flow in them. Here, by using the dynamic atomic force microscope as an "imaging" as well as a "forcing" tool, we unfold a real-time sequence of structural evolution occurring on the surface of an Au-Si thin film metallic glass. In sharp contrast to the common notion that plasticity comes along with mechanical softening in bulk metallic glasses, our experimental results directly reveal three types of nano-sized surface regions, which undergo plasticity but exhibit different characters of structural evolution following the local plasticity events, including stochastic structural rearrangement, unusual local relaxation and rejuvenation. As such, yielding on the metallic-glass surface manifests as a dynamic equilibrium between local relaxation and rejuvenation as opposed to shear instability in bulk metallic-glasses. Our finding demonstrates that plasticity on the metallic glass surface of Au-Si metallic glass bears much resemblance to that of the colloidal gels, of which nonlinear rheology rather than shear instability governs the constitutive behavior of plasticity.

  1. Calcium Triggered Lα-H2 Phase Transition Monitored by Combined Rapid Mixing and Time-Resolved Synchrotron SAXS

    PubMed Central

    Yaghmur, Anan; Laggner, Peter; Sartori, Barbara; Rappolt, Michael

    2008-01-01

    Background Awad et al. [1] reported on the Ca2+-induced transitions of dioleoyl-phosphatidylglycerol (DOPG)/monoolein (MO) vesicles to bicontinuous cubic phases at equilibrium conditions. In the present study, the combination of rapid mixing and time-resolved synchrotron small-angle X-ray scattering (SAXS) was applied for the in-situ investigations of fast structural transitions of diluted DOPG/MO vesicles into well-ordered nanostructures by the addition of low concentrated Ca2+ solutions. Methodology/Principal Findings Under static conditions and the in absence of the divalent cations, the DOPG/MO system forms large vesicles composed of weakly correlated bilayers with a d-spacing of ∼140 Å (Lα-phase). The utilization of a stopped-flow apparatus allowed mixing these DOPG/MO vesicles with a solution of Ca2+ ions within 10 milliseconds (ms). In such a way the dynamics of negatively charged PG to divalent cation interactions, and the kinetics of the induced structural transitions were studied. Ca2+ ions have a very strong impact on the lipidic nanostructures. Intriguingly, already at low salt concentrations (DOPG/Ca2+>2), Ca2+ ions trigger the transformation from bilayers to monolayer nanotubes (inverted hexagonal phase, H2). Our results reveal that a binding ratio of 1 Ca2+ per 8 DOPG is sufficient for the formation of the H2 phase. At 50°C a direct transition from the vesicles to the H2 phase was observed, whereas at ambient temperature (20°C) a short lived intermediate phase (possibly the cubic Pn3m phase) coexisting with the H2 phase was detected. Conclusions/Significance The strong binding of the divalent cations to the negatively charged DOPG molecules enhances the negative spontaneous curvature of the monolayers and causes a rapid collapsing of the vesicles. The rapid loss of the bilayer stability and the reorganization of the lipid molecules within ms support the argument that the transition mechanism is based on a leaky fusion of the vesicles. PMID

  2. In situ microscopy analysis reveals local innate immune response developed around Brucella infected cells in resistant and susceptible mice.

    PubMed

    Copin, Richard; Vitry, Marie-Alice; Hanot Mambres, Delphine; Machelart, Arnaud; De Trez, Carl; Vanderwinden, Jean-Marie; Magez, Stefan; Akira, Shizuo; Ryffel, Bernhard; Carlier, Yves; Letesson, Jean-Jacques; Muraille, Eric

    2012-01-01

    Brucella are facultative intracellular bacteria that chronically infect humans and animals causing brucellosis. Brucella are able to invade and replicate in a broad range of cell lines in vitro, however the cells supporting bacterial growth in vivo are largely unknown. In order to identify these, we used a Brucella melitensis strain stably expressing mCherry fluorescent protein to determine the phenotype of infected cells in spleen and liver, two major sites of B. melitensis growth in mice. In both tissues, the majority of primary infected cells expressed the F4/80 myeloid marker. The peak of infection correlated with granuloma development. These structures were mainly composed of CD11b⁺ F4/80⁺ MHC-II⁺ cells expressing iNOS/NOS2 enzyme. A fraction of these cells also expressed CD11c marker and appeared similar to inflammatory dendritic cells (DCs). Analysis of genetically deficient mice revealed that differentiation of iNOS⁺ inflammatory DC, granuloma formation and control of bacterial growth were deeply affected by the absence of MyD88, IL-12p35 and IFN-γ molecules. During chronic phase of infection in susceptible mice, we identified a particular subset of DC expressing both CD11c and CD205, serving as a reservoir for the bacteria. Taken together, our results describe the cellular nature of immune effectors involved during Brucella infection and reveal a previously unappreciated role for DC subsets, both as effectors and reservoir cells, in the pathogenesis of brucellosis.

  3. In-situ analysis of fruit anthocyanins by means of total internal reflectance, continuous wave and time-resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Zude, Manuela; Spinelli, Lorenzo; Dosche, Carsten; Torricelli, Alessandro

    2009-08-01

    In sweet cherry (Prunus avium), the red pigmentation is correlated with the fruit maturity stage and can be measured by non-invasive spectroscopy. In the present study, the influence of varying fruit scattering coefficients on the fruit remittance spectrum (cw) were corrected with the effective pathlength and refractive index in the fruit tissue obtained with distribution of time-of-flight (DTOF) readings and total internal reflection fluorescence (TIRF) analysis, respectively. The approach was validated on fruits providing variation in the scattering coefficient outside the calibration sample set. In the validation, the measuring uncertainty when non-invasively analyzing fruits with cw method in comparison with combined application of cw, DTOF, and TIRF measurements showed an increase in r2 up to 22.7 % with, however, high errors in all approaches.

  4. In-situ, time resolved monitoring of uranium in BFS:OPC grout. Part 1: Corrosion in water vapour.

    PubMed

    Stitt, C A; Paraskevoulakos, C; Banos, A; Harker, N J; Hallam, K R; Davenport, A; Street, S; Scott, T B

    2017-08-11

    Uranium encapsulated in grout was exposed to water vapour for extended periods of time. Through synchrotron x-ray powder diffraction and tomography measurements, uranium dioxide was determined the dominant corrosion product over a 50-week time period. The oxide growth rate initiated rapidly, with rates comparable to the U + H2O reaction. Over time, the reaction rate decreased and eventually plateaued to a rate similar to the U + H2O + O2 reaction. This behaviour was not attributed to oxygen ingress, but instead the decreasing permeability of the grout, limiting oxidising species access to the metal surface.

  5. Zoo-fluorescence in situ hybridization analysis of human and Indian muntjac karyotypes (Muntiacus muntjak vaginalis) reveals satellite DNA clusters at the margins of conserved syntenic segments.

    PubMed

    Frönicke, L; Scherthan, H

    1997-06-01

    Zoo-fluorescence in situ hybridization (FISH) with human whole chromosome-specific paint probes revealed extensive homoeologies between Indian muntjac (2n=6, 7 female, male) and human karyotypes (2n=46). Forty-two conserved syntenic segments, corresponding to all human chromosomes except the Y chromosome, produced a near-complete coverage of the muntjac complement and revealed margins of interspecific segmental homoeology. To test the hypothesis that interstitial satellite DNA loci, illuminated by a Chinese muntjac C5-satellite probe in Indian muntjac chromosome arms, mark ancestral fusion points (Lin CC, Sasi R, Fan YS, Chen Z-Q (1991) New evidence for tandem chromosome fusions in the karyotypic evolution of the Asian muntjacs. Chromosoma 101: 19-24), we combined Zoo-FISH with C5 satellite mapping. Twenty-six interstitial satellite DNA loci were detected in the haploid Indian muntjac genome and were found to co-localize with the margins of conserved human/Indian muntjac syntenic segments. These results were confirmed by two-colour FISH and are in accordance with the tandem fusion hypothesis for Indian muntjac chromosomes. Furthermore, conserved syntenic segment combinations detected in pig, cattle and Indian muntjac Zoo-FISH maps reveal ancestral artiodactyl chromosomes.

  6. Lateral association and elongation of vimentin intermediate filament proteins: A time-resolved light-scattering study

    NASA Astrophysics Data System (ADS)

    Lopez, Carlos G.; Saldanha, Oliva; Huber, Klaus; Köster, Sarah

    2016-10-01

    Vimentin intermediate filaments (IFs) are part of a family of proteins that constitute one of the three filament systems in the cytoskeleton, a major contributor to cell mechanics. One property that distinguishes IFs from the other cytoskeletal filament types, actin filaments and microtubules, is their highly hierarchical assembly pathway, where a lateral association step is followed by elongation. Here we present an innovative technique to follow the elongation reaction in solution and in situ by time-resolved static and dynamic light scattering, thereby precisely capturing the relevant time and length scales of seconds to minutes and 60-600 nm, respectively. We apply a quantitative model to our data and succeed in consistently describing the entire set of data, including particle mass, radius of gyration, and hydrodynamic radius during longitudinal association.

  7. Time-resolved x-ray diffraction and electrical resistance measurements of structural phase transitions in zirconium

    DOE PAGES

    Velisavljevic, N.; Sinogeikin, S.; Saavedra, R.; ...

    2014-05-07

    Here, we have designed a portable pressure controller module to tune compression rates and maximum pressures attainable in a standard gas-membrane diamond anvil cell (DAC). During preliminary experiments, performed on zirconium (Zr) metal sample, pressure jumps of up to 80 GPa were systematically obtained in less than 0.2s (resulting in compression rate of few GPa/s up to more than 400 GPa/s). In-situ x-ray diffraction and electrical resistance measurements were performed simultaneously during this rapid pressure increase to provide the first time resolved data on α → ω → β structural evolution in Zr at high pressures. Direct control of compressionmore » rates and peak pressures, which can be held for prolonged time, allows for investigation of structural evolution and kinetics of structural phase transitions of materials under previously unexplored compression rate-pressure conditions that bridge traditional static and shock/dynamic experimental platforms.« less

  8. Lateral association and elongation of vimentin intermediate filament proteins: A time-resolved light-scattering study

    PubMed Central

    Saldanha, Oliva; Huber, Klaus; Köster, Sarah

    2016-01-01

    Vimentin intermediate filaments (IFs) are part of a family of proteins that constitute one of the three filament systems in the cytoskeleton, a major contributor to cell mechanics. One property that distinguishes IFs from the other cytoskeletal filament types, actin filaments and microtubules, is their highly hierarchical assembly pathway, where a lateral association step is followed by elongation. Here we present an innovative technique to follow the elongation reaction in solution and in situ by time-resolved static and dynamic light scattering, thereby precisely capturing the relevant time and length scales of seconds to minutes and 60–600 nm, respectively. We apply a quantitative model to our data and succeed in consistently describing the entire set of data, including particle mass, radius of gyration, and hydrodynamic radius during longitudinal association. PMID:27655889

  9. Time-resolved x-ray diffraction and electrical resistance measurements of structural phase transitions in zirconium

    SciTech Connect

    Velisavljevic, N.; Sinogeikin, S.; Saavedra, R.; Chellappa, R. S.; Rothkirch, A.; Dattelbaum, D. M.; Konopkova, Z.; Liermann, H. -P.; Bishop, M.; Tsoi, G. M.; Vohra, Y. K.

    2014-05-07

    Here, we have designed a portable pressure controller module to tune compression rates and maximum pressures attainable in a standard gas-membrane diamond anvil cell (DAC). During preliminary experiments, performed on zirconium (Zr) metal sample, pressure jumps of up to 80 GPa were systematically obtained in less than 0.2s (resulting in compression rate of few GPa/s up to more than 400 GPa/s). In-situ x-ray diffraction and electrical resistance measurements were performed simultaneously during this rapid pressure increase to provide the first time resolved data on α → ω → β structural evolution in Zr at high pressures. Direct control of compression rates and peak pressures, which can be held for prolonged time, allows for investigation of structural evolution and kinetics of structural phase transitions of materials under previously unexplored compression rate-pressure conditions that bridge traditional static and shock/dynamic experimental platforms.

  10. An Analysis of Shock-Compression in Mo-Si Powder Mixtures Using Recovery and Time-Resolved Measurements

    NASA Astrophysics Data System (ADS)

    Vandersall, Kevin S.; Thadhani, Naresh N.

    1999-06-01

    The densification and reaction characteristics in the Mo-Si system were investigated utilizing recovery experiments as well as time resolved measurements with in-situ stress gages. The starting sample in all cases consisted of statically pressed Mo + 2 Si powder mixtures ( ~55% TMD). The recovery experiments were performed using the Sandia Momma Bear and Momma Bear A fixtures with baratol and composition B explosives respectively. The instrumented experiments were performed in a capsule design similar to that of the Momma Bear, but modified to incorporate poly-vinyl di-flouride (PVDF) stress gages at the front and rear surfaces of the powder. These experiments were performed using a single stage gas gun in the velocity range of 500 m/s to 1 km/s. The instrumented experiments allow the crush strength, densification history, and reaction threshold to be mapped at increasing pressure to correlate with reaction observed in the recovery experiments.

  11. Portable double-sided pulsed laser heating system for time-resolved geoscience and materials science applications

    NASA Astrophysics Data System (ADS)

    Aprilis, G.; Strohm, C.; Kupenko, I.; Linhardt, S.; Laskin, A.; Vasiukov, D. M.; Cerantola, V.; Koemets, E. G.; McCammon, C.; Kurnosov, A.; Chumakov, A. I.; Rüffer, R.; Dubrovinskaia, N.; Dubrovinsky, L.

    2017-08-01

    A portable double-sided pulsed laser heating system for diamond anvil cells has been developed that is able to stably produce laser pulses as short as a few microseconds with repetition frequencies up to 100 kHz. In situ temperature determination is possible by collecting and fitting the thermal radiation spectrum for a specific wavelength range (particularly, between 650 nm and 850 nm) to the Planck radiation function. Surface temperature information can also be time-resolved by using a gated detector that is synchronized with the laser pulse modulation and space-resolved with the implementation of a multi-point thermal radiation collection technique. The system can be easily coupled with equipment at synchrotron facilities, particularly for nuclear resonance spectroscopy experiments. Examples of applications include investigations of high-pressure high-temperature behavior of iron oxides, both in house and at the European Synchrotron Radiation Facility using the synchrotron Mössbauer source and nuclear inelastic scattering.

  12. Pyrosequencing reveals high-temperature cellulolytic microbial consortia in Great Boiling Spring after in situ lignocellulose enrichment.

    PubMed

    Peacock, Joseph P; Cole, Jessica K; Murugapiran, Senthil K; Dodsworth, Jeremy A; Fisher, Jenny C; Moser, Duane P; Hedlund, Brian P

    2013-01-01

    To characterize high-temperature cellulolytic microbial communities, two lignocellulosic substrates, ammonia fiber-explosion-treated corn stover and aspen shavings, were incubated at average temperatures of 77 and 85°C in the sediment and water column of Great Boiling Spring, Nevada. Comparison of 109,941 quality-filtered 16S rRNA gene pyrosequences (pyrotags) from eight enrichments to 37,057 quality-filtered pyrotags from corresponding natural samples revealed distinct enriched communities dominated by phylotypes related to cellulolytic and hemicellulolytic Thermotoga and Dictyoglomus, cellulolytic and sugar-fermenting Desulfurococcales, and sugar-fermenting and hydrogenotrophic Archaeoglobales. Minor enriched populations included close relatives of hydrogenotrophic Thermodesulfobacteria, the candidate bacterial phylum OP9, and candidate archaeal groups C2 and DHVE3. Enrichment temperature was the major factor influencing community composition, with a negative correlation between temperature and richness, followed by lignocellulosic substrate composition. This study establishes the importance of these groups in the natural degradation of lignocellulose at high temperatures and suggests that a substantial portion of the diversity of thermophiles contributing to consortial cellulolysis may be contained within lineages that have representatives in pure culture.

  13. Pyrosequencing Reveals High-Temperature Cellulolytic Microbial Consortia in Great Boiling Spring after In Situ Lignocellulose Enrichment

    PubMed Central

    Peacock, Joseph P.; Cole, Jessica K.; Murugapiran, Senthil K.; Dodsworth, Jeremy A.; Fisher, Jenny C.; Moser, Duane P.; Hedlund, Brian P.

    2013-01-01

    To characterize high-temperature cellulolytic microbial communities, two lignocellulosic substrates, ammonia fiber-explosion-treated corn stover and aspen shavings, were incubated at average temperatures of 77 and 85°C in the sediment and water column of Great Boiling Spring, Nevada. Comparison of 109,941 quality-filtered 16S rRNA gene pyrosequences (pyrotags) from eight enrichments to 37,057 quality-filtered pyrotags from corresponding natural samples revealed distinct enriched communities dominated by phylotypes related to cellulolytic and hemicellulolytic Thermotoga and Dictyoglomus, cellulolytic and sugar-fermenting Desulfurococcales, and sugar-fermenting and hydrogenotrophic Archaeoglobales. Minor enriched populations included close relatives of hydrogenotrophic Thermodesulfobacteria, the candidate bacterial phylum OP9, and candidate archaeal groups C2 and DHVE3. Enrichment temperature was the major factor influencing community composition, with a negative correlation between temperature and richness, followed by lignocellulosic substrate composition. This study establishes the importance of these groups in the natural degradation of lignocellulose at high temperatures and suggests that a substantial portion of the diversity of thermophiles contributing to consortial cellulolysis may be contained within lineages that have representatives in pure culture. PMID:23555835

  14. In situ analysis of the bacterial community associated with the reindeer lichen Cladonia arbuscula reveals predominance of Alphaproteobacteria.

    PubMed

    Cardinale, Massimiliano; Vieira de Castro, João; Müller, Henry; Berg, Gabriele; Grube, Martin

    2008-10-01

    The diversity and spatial pattern of the bacterial community hosted by the shrub-like reindeer lichen Cladonia arbuscula were investigated by general DNA staining and FISH, coupled with confocal laser scanning microscopy (CLSM). Using an optimized protocol for FISH using cryosections of small lichen fragments, we found about 6 x 10(7) bacteria g(-1) of C. arbuscula. Approximately 86% of acridine orange-stained cells were also stained by the universal FISH probe EUB338. Using group-specific FISH probes, we detected a dominance of Alphaproteobacteria (more than 60% of all bacteria), while the abundance of Actinobacteria and Betaproteobacteria was much lower (<10%). Firmicutes were rarely detected, and no Gammaproteobacteria were present. Bacterial cells of different taxonomic groups are embedded in a biofilm-like, continuous layer on the internal surface of the C. arbuscula podetia, mainly occurring in small colonies of a few to a few hundred cells. The other parts of the lichen showed a lower bacterial colonization. alpha-proteobacterial 16S rRNA genes were amplified using total DNA extracts from C. arbuscula and separated by single-strand conformation polymorphism (SSCP). Sequencing of excised bands revealed the dominance of Acetobacteraceae.

  15. Standoff Time-Resolved Laser-Based Spectroscopy Tools for Sample Characterization and Biosignature Detection

    NASA Astrophysics Data System (ADS)

    Gasda, P. J.; Acosta-Maeda, T.; Lucey, P. G.; Misra, A. K.; Sharma, S. K.; Taylor, J.

    2014-12-01

    The NASA Mars2020 rover will be searching for signs of past habitability and past life on Mars. Additionally, the rover mission will prepare a cache of highly significant samples for a future sample return mission. NASA requires these samples to be well characterized; the instruments on the rover must be capable of fine-scale in situ mineralogical or elemental analysis with emphasis on biosignature detection or characterization. We have been developing multiple standoff laser-based instruments at the University of Hawaii, Manoa that are capable of fine-scale in situ chemical analysis and biosignatures detection. By employing a time-resolved spectroscopy, we can perform elemental analysis with Laser-Induced Breakdown Spectroscopy (LIBS), mineral and organic analysis with Raman spectroscopy, and biosignature detection with Laser-Induced Fluorescence (LIF). Each of these techniques share the same optics and detection equipment, allowing us to integrate them into a single, compact instrument. High time-resolution (~100 ns/pulse) is the key to this instrument; with it, the detector only records data when the signal is the brightest. Spectra can be taken during the day, LIBS can be measured without a plasma light background, and the Raman signal can be separated from the mineral fluorescence signal. Since bio-organics have very short fluorescence lifetimes, the new instrument can be used to unambiguously detect bio-organics. The prototype uses a low power (0.5 mJ/pulse) 532 nm laser with a detection limit of < 30 ppm of organics in a sample of Antarctica Dry Valley soil measured from 8 m. Another LIF instrument under development in our lab, called the Biofinder, takes advantage of the extremely intense fluorescence signal produced by organics by using a wide laser spot and a camera to produce LIF images of wide area (25 cm area from 2 m distance with 2 mm/pixel resolution). The Biofinder can quickly assess the area around the rover (at 10 frames/s) by imaging sample

  16. Dynamic changes in the higher-level chromatin organization of specific sequences revealed by in situ hybridization to nuclear halos

    PubMed Central

    1994-01-01

    A novel approach to study the higher level packaging of specific DNA sequences has been developed by coupling high-resolution fluorescence hybridization with biochemical fractionation to remove histones and distend DNA loops to form morphologically reproducible nuclear "halos." Results demonstrate consistent differences in the organization of specific sequences, and further suggest a relationship to functional activity. Pulse-incorporated bromodeoxyuridine representing nascent replicating DNA localized with the base of the chromatin loops in discrete clustered patterns characteristic of intact cells, whereas at increasing chase times, the replicated DNA was consistently found further out on the extended region of the halo. Fluorescence hybridization to unique loci for four transcriptionally inactive sequences produced long strings of signal extending out onto the DNA halo or "loop," whereas four transcriptionally active sequences remained tightly condensed as single spots within the residual nucleus. In contrast, in non-extracted cells, all sequences studied typically remained condensed as single spots of fluorescence signal. Interestingly, two transcriptionally active, tandemly repeated gene clusters exhibited strikingly different packaging by this assay. Analysis of specific genes in single cells during the cell cycle revealed changes in packaging between S-phase and non S-phase cells, and further suggested a dramatic difference in the structural associations in mitotic and interphase chromatin. These results are consistent with and suggestive of a loop domain organization of chromatin packaging involving both stable and transient structural associations, and provide precedent for an approach whereby different biochemical fractionation methods may be used to unravel various aspects of the complex higher-level organization of the genome. PMID:8034736

  17. Studies of Minerals, Organic and Biogenic Materials through Time-Resolved Raman Spectroscopy

    NASA Technical Reports Server (NTRS)

    Garcia, Christopher S.; Abedin, M. Nurul; Ismail, Syed; Sharma, Shiv K.; Misra, Anupam K.; Nyugen, Trac; Elsayed-Ali, hani

    2009-01-01

    A compact remote Raman spectroscopy system was developed at NASA Langley Research center and was previously demonstrated for its ability to identify chemical composition of various rocks and minerals. In this study, the Raman sensor was utilized to perform time-resolved Raman studies of various samples such as minerals and rocks, Azalea leaves and a few fossil samples. The Raman sensor utilizes a pulsed 532 nm Nd:YAG laser as excitation source, a 4-inch telescope to collect the Raman-scattered signal from a sample several meters away, a spectrograph equipped with a holographic grating, and a gated intensified CCD (ICCD) camera system. Time resolved Raman measurements were carried out by varying the gate delay with fixed short gate width of the ICCD camera, allowing measurement of both Raman signals and fluorescence signals. Rocks and mineral samples were characterized including marble, which contain CaCO3. Analysis of the results reveals the short (approx.10-13 s) lifetime of the Raman process, and shows that Raman spectra of some mineral samples contain fluorescence emission due to organic impurities. Also analyzed were a green (pristine) and a yellow (decayed) sample of Gardenia leaves. It was observed that the fluorescence signals from the green and yellow leaf samples showed stronger signals compared to the Raman lines. Moreover, it was also observed that the fluorescence of the green leaf was more intense and had a shorter lifetime than that of the yellow leaf. For the fossil samples, Raman shifted lines could not be observed due the presence of very strong short-lived fluorescence.

  18. Exploring ultrafast dynamics of pyrazine by time-resolved photoelectron imaging.

    PubMed

    Tomasello, Gaia; Humeniuk, Alexander; Mitrić, Roland

    2014-09-18

    We present the simulation of time-resolved photoelectron imaging spectra of pyrazine in the gas phase. The approach we have adopted is based on the combination of the ab initio nonadiabatic molecular dynamics "on the fly" with an approximate treatment of the photoionization process using Dyson orbitals and Coulomb functions to describe the bound and ionized states of the photoelectron. The method has been implemented (Humeniuk, A.; et al. J. Chem. Phys 2013, 139, 134104) in the framework of the time-dependent density functional theory and has been applied here to interrogate the ultrafast internal conversion between the S2 and S1 states in pyrazine. Conventional time-resolved photoelectron spectra without angular resolution fail to locate the S2 → S1 internal conversion, because the ionization potentials relevant for the photoionization channels S2 → D1 (π(-1)) and S1 → D0 (n(-1)) are almost identical. Introducing the angular resolution in the photoelectron spectra reveals evidence of such ultrafast internal conversion and provides a more detailed picture of the overall dynamics. The simulated time- and energy-dependent anisotropy map obtained within the Dyson/time-dependent density functional theory approach is in good agreement with its experimental counterpart provided by Horio et al. (Horio, T.; et al. J. Am. Chem. Soc. 2009, 131, 10932). Our theoretical approach represents a general tool for mapping the time- and angle-resolved photoelectron spectra in complex systems and thus can be used to investigate the ultrafast relaxation processes occurring in isolated molecules.

  19. Spatially complex distribution of dissolved manganese in a fjord as revealed by high-resolution in situ sensing using the autonomous underwater vehicle Autosub.

    PubMed

    Statham, P J; Connelly, D P; German, C R; Brand, T; Overnell, J O; Bulukin, E; Millard, N; McPhail, S; Pebody, M; Perrett, J; Squire, M; Stevenson, P; Webb, A

    2005-12-15

    Loch Etive is a fjordic system on the west coast of Scotland. The deep waters of the upper basin are periodically isolated, and during these periods oxygen is lost through benthic respiration and concentrations of dissolved manganese increase. In April 2000 the autonomous underwater vehicle (AUV) Autosub was fitted with an in situ dissolved manganese analyzer and was used to study the spatial variability of this element together with oxygen, salinity, and temperature throughout the basin. Six along-loch transects were completed at either constant height above the seafloor or at constant depth below the surface. The ca. 4000 in situ 10-s-average dissolved Mn (Mnd) data points obtained provide a new quasi-synoptic and highly detailed view of the distribution of manganese in this fjordic environment not possible using conventional (water bottle) sampling. There is substantial variability in concentrations (<25 to >600 nM) and distributions of Mnd. Surface waters are characteristically low in Mnd reflecting mixing of riverine and marine end-member waters, both of which are low in Mnd. The deeper waters are enriched in Mnd, and as the water column always contains some oxygen, this must reflect primarily benthic inputs of reduced dissolved Mn. However, this enrichment of Mnd is spatially very variable, presumably as a result of variability in release of Mn coupled with mixing of water in the loch and removal processes. This work demonstrates how AUVs coupled with chemical sensors can reveal substantial small-scale variability of distributions of chemical species in coastal environments that would not be resolved by conventional sampling approaches. Such information is essential if we are to improve our understanding of the nature and significance of the underlying processes leading to this variability.

  20. Individual boron nanowire has ultra-high specific Young's modulus and fracture strength as revealed by in situ transmission electron microscopy.

    PubMed

    Liu, Fei; Tang, Dai-Ming; Gan, Haibo; Mo, Xiaoshu; Chen, Jun; Deng, Shaozhi; Xu, Ningsheng; Bando, Yoshio; Golberg, Dmitri

    2013-11-26

    Boron nanowires (BNWs) may have potential applications as reinforcing materials because B fibers are widely known for their excellent mechanical performance. However until now, there have been only few reports on the mechanical properties of individual BNW, and in situ transmission electron microscopy (TEM) investigations shining a light on their fracture mechanism have not been performed. In this paper, we applied in situ high-resolution TEM (HRTEM) technique to study the mechanical properties of individual BNWs using three loading schemes. The mean fracture strength and the maximum strain of individual BNWs were measured to be 10.4 GPa and 4.1%, respectively, during the tensile tests. And the averaged Young's modulus was calculated to be 308.2 GPa under tensile and compression tests. Bending experiments for the first time performed on individual BNWs revealed that their maximum bending strain could reach 9.9% and their ultimate bending stress arrived at 36.2 GPa. These figures are much higher than those of Si and ZnO nanowires known for their high bending strength. Moreover, the BNWs exhibited very high specific fracture strength (3.9 (GPa·cm(3))/g) and specific elastic modulus (130.6 (GPa·cm(3))/g), which are several dozens of times larger compared to many nanostructures known for their superb mechanical behaviors. At last, the effect of surface oxide layer on the Young's modulus, fracture strength and maximum bending strength of individual BNWs was elucidated to extract their intrinsic mechanical parameters using calculated corrections. All experimental results suggest that the present BNW are a bright promise as lightweight reinforcing fillers.

  1. Optimization and comprehensive characterization of metal hydride based hydrogen storage systems using in-situ Neutron Radiography

    NASA Astrophysics Data System (ADS)

    Börries, S.; Metz, O.; Pranzas, P. K.; Bellosta von Colbe, J. M.; Bücherl, T.; Dornheim, M.; Klassen, T.; Schreyer, A.

    2016-10-01

    For the storage of hydrogen, complex metal hydrides are considered as highly promising with respect to capacity, reversibility and safety. The optimization of corresponding storage tanks demands a precise and time-resolved investigation of the hydrogen distribution in scaled-up metal hydride beds. In this study it is shown that in situ fission Neutron Radiography provides unique insights into the spatial distribution of hydrogen even for scaled-up compacts and therewith enables a direct study of hydrogen storage tanks. A technique is introduced for the precise quantification of both time-resolved data and a priori material distribution, allowing inter alia for an optimization of compacts manufacturing process. For the first time, several macroscopic fields are combined which elucidates the great potential of Neutron Imaging for investigations of metal hydrides by going further than solely 'imaging' the system: A combination of in-situ Neutron Radiography, IR-Thermography and thermodynamic quantities can reveal the interdependency of different driving forces for a scaled-up sodium alanate pellet by means of a multi-correlation analysis. A decisive and time-resolved, complex influence of material packing density is derived. The results of this study enable a variety of new investigation possibilities that provide essential information on the optimization of future hydrogen storage tanks.

  2. Micromechanics of ultra-toughened electrospun PMMA/PEO fibres as revealed by in-situ tensile testing in an electron microscope

    NASA Astrophysics Data System (ADS)

    Andersson, Richard L.; Ström, Valter; Gedde, Ulf W.; Mallon, Peter E.; Hedenqvist, Mikael S.; Olsson, Richard T.

    2014-09-01

    A missing cornerstone in the development of tough micro/nano fibre systems is an understanding of the fibre failure mechanisms, which stems from the limitation in observing the fracture of objects with dimensions one hundredth of the width of a hair strand. Tensile testing in the electron microscope is herein adopted to reveal the fracture behaviour of a novel type of toughened electrospun poly(methyl methacrylate)/poly(ethylene oxide) fibre mats for biomedical applications. These fibres showed a toughness more than two orders of magnitude greater than that of pristine PMMA fibres. The in-situ microscopy revealed that the toughness were not only dependent on the initial molecular alignment after spinning, but also on the polymer formulation that could promote further molecular orientation during the formation of micro/nano-necking. The true fibre strength was greater than 150 MPa, which was considerably higher than that of the unmodified PMMA (17 MPa). This necking phenomenon was prohibited by high aspect ratio cellulose nanocrystal fillers in the ultra-tough fibres, leading to a decrease in toughness by more than one order of magnitude. The reported necking mechanism may have broad implications also within more traditional melt-spinning research.

  3. Micromechanics of ultra-toughened electrospun PMMA/PEO fibres as revealed by in-situ tensile testing in an electron microscope

    PubMed Central

    Andersson, Richard L.; Ström, Valter; Gedde, Ulf W.; Mallon, Peter E.; Hedenqvist, Mikael S.; Olsson, Richard T.

    2014-01-01

    A missing cornerstone in the development of tough micro/nano fibre systems is an understanding of the fibre failure mechanisms, which stems from the limitation in observing the fracture of objects with dimensions one hundredth of the width of a hair strand. Tensile testing in the electron microscope is herein adopted to reveal the fracture behaviour of a novel type of toughened electrospun poly(methyl methacrylate)/poly(ethylene oxide) fibre mats for biomedical applications. These fibres showed a toughness more than two orders of magnitude greater than that of pristine PMMA fibres. The in-situ microscopy revealed that the toughness were not only dependent on the initial molecular alignment after spinning, but also on the polymer formulation that could promote further molecular orientation during the formation of micro/nano-necking. The true fibre strength was greater than 150 MPa, which was considerably higher than that of the unmodified PMMA (17 MPa). This necking phenomenon was prohibited by high aspect ratio cellulose nanocrystal fillers in the ultra–tough fibres, leading to a decrease in toughness by more than one order of magnitude. The reported necking mechanism may have broad implications also within more traditional melt–spinning research. PMID:25208692

  4. Spatial heterogeneity of dechlorinating bacteria and limiting factors for in situ trichloroethene dechlorination revealed by analyses of sediment cores from a polluted field site.

    PubMed

    Dowideit, Kerstin; Scholz-Muramatsu, Heidrun; Miethling-Graff, Rona; Vigelahn, Lothar; Freygang, Martina; Dohrmann, Anja B; Tebbe, Christoph C

    2010-03-01

    Microbiological analyses of sediment samples were conducted to explore potentials and limitations for bioremediation of field sites polluted with chlorinated ethenes. Intact sediment cores, collected by direct push probing from a 35-ha contaminated area, were analyzed in horizontal layers. Cultivation-independent PCR revealed Dehalococcoides to be the most abundant 16S rRNA gene phylotype with a suspected potential for reductive dechlorination of the major contaminant trichloroethene (TCE). In declining abundances, Desulfitobacterium, Desulfuromonas and Dehalobacter were also detected. In TCE-amended sediment slurry incubations, 66% of 121 sediment samples were dechlorinating, among them one-third completely and the rest incompletely (end product cis-1,2-dichloroethene; cDCE). Both PCR and slurry analyses revealed highly heterogeneous horizontal and vertical distributions of the dechlorination potentials in the sediments. Complete reductive TCE dechlorination correlated with the presence of Dehalococcoides, accompanied by Acetobacterium and a relative of Trichococcus pasteurii. Sediment incubations under close to in situ conditions showed that a low TCE dechlorination activity could be stimulated by 7 mg L(-1) dissolved carbon for cDCE formation and by an additional 36 mg carbon (lactate) L(-1) for further dechlorination. The study demonstrates that the highly heterogeneous distribution of TCE degraders and their specific requirements for carbon and electrons are key issues for TCE degradation in contaminated sites.

  5. The time-resolved transcriptome of C. elegans

    PubMed Central

    Boeck, Max E.; Huynh, Chau; Gevirtzman, Lou; Thompson, Owen A.; Wang, Guilin; Kasper, Dionna M.; Reinke, Valerie; Hillier, LaDeana W.; Waterston, Robert H.

    2016-01-01

    We generated detailed RNA-seq data for the nematode Caenorhabditis elegans with high temporal resolution in the embryo as well as representative samples from post-embryonic stages across the life cycle. The data reveal that early and late embryogenesis is accompanied by large numbers of genes changing expression, whereas fewer genes are changing in mid-embryogenesis. This lull in genes changing expression correlates with a period during which histone mRNAs produce almost 40% of the RNA-seq reads. We find evidence for many more splice junctions than are annotated in WormBase, with many of these suggesting alternative splice forms, often with differential usage over the life cycle. We annotated internal promoter usage in operons using SL1 and SL2 data. We also uncovered correlated transcriptional programs that span >80 kb. These data provide detailed annotation of the C. elegans transcriptome. PMID:27531719

  6. Time-Resolved Imaging of Single HIV-1 Uncoating In Vitro and in Living Cells

    PubMed Central

    Francis, Ashwanth C.; Marin, Mariana; Shi, Jiong; Aiken, Christopher; Melikyan, Gregory B.

    2016-01-01

    Disassembly of the cone-shaped HIV-1 capsid in target cells is a prerequisite for establishing a life-long infection. This step in HIV-1 entry, referred to as uncoating, is critical yet poorly understood. Here we report a novel strategy to visualize HIV-1 uncoating using a fluorescently tagged oligomeric form of a capsid-binding host protein cyclophilin A (CypA-DsRed), which is specifically packaged into virions through the high-avidity binding to capsid (CA). Single virus imaging reveals that CypA-DsRed remains associated with cores after permeabilization/removal of the viral membrane and that CypA-DsRed and CA are lost concomitantly from the cores in vitro and in living cells. The rate of loss is modulated by the core stability and is accelerated upon the initiation of reverse transcription. We show that the majority of single cores lose CypA-DsRed shortly after viral fusion, while a small fraction remains intact for several hours. Single particle tracking at late times post-infection reveals a gradual loss of CypA-DsRed which is dependent on reverse transcription. Uncoating occurs both in the cytoplasm and at the nuclear membrane. Our novel imaging assay thus enables time-resolved visualization of single HIV-1 uncoating in living cells, and reveals the previously unappreciated spatio-temporal features of this incompletely understood process. PMID:27322072

  7. Time-Resolved Spectral Analysis of Blazar 0716+714

    NASA Astrophysics Data System (ADS)

    Diaz, Rosamaria; Harp, Gerald

    2016-01-01

    As electromagnetic (EM) waves from sources such as blazars travel through the intergalactic medium (IGM), they are slowed by electrons; a phenomenon called dispersion delay [2]. We study the propagation effects in emissions of EM waves from blazar source BL 0716+714 by estimating the average electron density, or dispersion measure (DM), of the IGM on a line of sight to the blazar. Measuring the variations in these effects with time allow us to understand the properties of the intervening material. Toward this goal we analyzed months of archived observations of BL 0716+714 taken by the Allen Telescope Array (ATA). The ATA's correlator produces cross-power vs. frequency spectra for every baseline (distance between a pair of antennas) in ten-second intervals. To reduce this immense load of data we used a technique based on interferometry called bispectrum, which does not depend on complicated array calibration and simplifies our work. The bispectrum multiplies baselines, three at a time, so that they form a closed loop, then the cube root of spectra are averaged [1]. This technique is independent of phase errors associated with any individual antenna and has a better SNR ratio than simply taking the average of all the baselines. We developed a numerical analysis program that takes in archived blazar files containing correlation data, computes the bispectrum, and outputs FITS images for each day of observations. The results show that our observations do not have sufficient sensitivity to reveal blazar variations in the frequency ranges that were studied. It is suggested that future observations at higher frequencies and/or with another telescope having greater sensitivity would reveal the time/frequency dependence of emission structure that would allow measurements of electron content. This work shows that but bispectrum is a useful tool for rapid characterization of interferometer data that does not require interferometer caclibration which could introduce artifacts

  8. Polar plot representation of time-resolved fluorescence.

    PubMed

    Eichorst, John Paul; Wen Teng, Kai; Clegg, Robert M

    2014-01-01

    Measuring changes in a molecule's fluorescence emission is a common technique to study complex biological systems such as cells and tissues. Although the steady-state fluorescence intensity is frequently used, measuring the average amount of time that a molecule spends in the excited state (the fluorescence lifetime) reveals more detailed information about its local environment. The lifetime is measured in the time domain by detecting directly the decay of fluorescence following excitation by short pulse of light. The lifetime can also be measured in the frequency domain by recording the phase and amplitude of oscillation in the emitted fluorescence of the sample in response to repetitively modulated excitation light. In either the time or frequency domain, the analysis of data to extract lifetimes can be computationally intensive. For example, a variety of iterative fitting algorithms already exist to determine lifetimes from samples that contain multiple fluorescing species. However, recently a method of analysis referred to as the polar plot (or phasor plot) is a graphical tool that projects the time-dependent features of the sample's fluorescence in either the time or frequency domain into the Cartesian plane to characterize the sample's lifetime. The coordinate transformations of the polar plot require only the raw data, and hence, there are no uncertainties from extensive corrections or time-consuming fitting in this analysis. In this chapter, the history and mathematical background of the polar plot will be presented along with examples that highlight how it can be used in both cuvette-based and imaging applications.

  9. Time-resolved study on dynamic chemical state conversion of SiO2-supported Co species by means of dispersive XAFS technique

    NASA Astrophysics Data System (ADS)

    Chotiwan, S.; Tomiga, H.; Yamashita, S.; Katayama, M.; Inada, Y.

    2016-05-01

    The chemical state conversion of the Co species supported on SiO2 was investigated using the in-situ and the time-resolved XAFS techniques. The supported Co3O4 species was finally reduced to metallic Co with the stable intermediate state of CoO for both the temperature-programmed and time-course processes. The oxidation of Co0 traced the reverse route to Co3O4, whereas the relative stability of the Co3O4 species to the CoO intermediate under the oxidative environment diminished the composition of CoO. The time-resolved measurement for the oxidation reaction showed an additional intermediate at the early stage of the CoO intermediate formation suggesting the Co0 particle dispersion.

  10. Time-resolved oxygen production by PSII: chasing chemical intermediates.

    PubMed

    Clausen, Jürgen; Debus, Richard J; Junge, Wolfgang

    2004-04-12

    Photosystem II (PSII) produces dioxygen from water in a four-stepped process, which is driven by four quanta of light and catalysed by a Mn-cluster and tyrosine Z. Oxygen is liberated during one step, coined S(3)=>S(0). Chemical intermediates on the way from reversibly bound water to dioxygen have not yet been tracked, however, a break in the Arrhenius plot of the oxygen-evolving step has been taken as evidence for its existence. We scrutinised the temperature dependence of (i) UV-absorption transients attributable to the reduction of the Mn-cluster and tyrosine Z by water, and (ii) polarographic transients attributable to the release of dioxygen. Using a centrifugatable and kinetically competent Pt-electrode, we observed no deviation from a linear Arrhenius plot of oxygen release in the temperature range from -2 to 32 degrees C, and hence no evidence, by this approach, for a sufficiently long-lived chemical intermediate. The half-rise times of oxygen release differed between Synechocystis WT* (at 20 degrees C: 1.35 ms) and a point mutant (D1-D61N: 13.1 ms), and the activation energies differed between species (Spinacia oleracea, 30 kJ/mol versus Synechocystis, 41 kJ/mol) and preparations (PSII membranes, 41 kJ/mol versus core complexes, 33 kJ/mol, Synechocystis). Correction for polarographic artefacts revealed, for the first time, a temperature-dependent lag-phase of the polarographic transient (duration at 20 degrees C: 0.45 ms, activation energy: 31 kJ/mol), which was indicative of a short-lived intermediate. It was, however, not apparent in the UV-transients. Thus the "intermediate" was probably newly formed and transiently bound oxygen.

  11. Time-resolved structural studies of protein reaction dynamics: a smorgasbord of X-ray approaches

    SciTech Connect

    Westenhoff, Sebastian; Nazarenko, Elena; Malmerberg, Erik; Davidsson, Jan; Katona, Gergely; Neutze, Richard

    2010-03-01

    Time-resolved structural studies of proteins have undergone several significant developments during the last decade. Recent developments using time-resolved X-ray methods, such as time-resolved Laue diffraction, low-temperature intermediate trapping, time-resolved wide-angle X-ray scattering and time-resolved X-ray absorption spectroscopy, are reviewed. Proteins undergo conformational changes during their biological function. As such, a high-resolution structure of a protein’s resting conformation provides a starting point for elucidating its reaction mechanism, but provides no direct information concerning the protein’s conformational dynamics. Several X-ray methods have been developed to elucidate those conformational changes that occur during a protein’s reaction, including time-resolved Laue diffraction and intermediate trapping studies on three-dimensional protein crystals, and time-resolved wide-angle X-ray scattering and X-ray absorption studies on proteins in the solution phase. This review emphasizes the scope and limitations of these complementary experimental approaches when seeking to understand protein conformational dynamics. These methods are illustrated using a limited set of examples including myoglobin and haemoglobin in complex with carbon monoxide, the simple light-driven proton pump bacteriorhodopsin, and the superoxide scavenger superoxide reductase. In conclusion, likely future developments of these methods at synchrotron X-ray sources and the potential impact of emerging X-ray free-electron laser facilities are speculated upon.

  12. Characterization of type I, II, III, IV, and V collagens by time-resolved laser-induced fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Marcu, Laura; Cohen, David; Maarek, Jean-Michel I.; Grundfest, Warren S.

    2000-04-01

    The relative proportions of genetically distinct collagen types in connective tissues vary with tissue type and change during disease progression, development, wound healing, aging. This study aims to 1) characterize the spectro- temporal fluorescence emission of fiber different types of collagen and 2) assess the ability of time-resolved laser- induced fluorescence spectroscopy to distinguish between collagen types. Fluorescence emission of commercially available purified samples was induced with nitrogen laser excitation pulses and detected with a MCP-PMT connected to a digital storage oscilloscope. The recorded time-resolved emission spectra displayed distinct fluorescence emission characteristics for each collagen type. The time domain information complemented the spectral domain intensity data for improved discrimination between different collagen types. Our results reveal that analysis of the fluorescence emission can be used to characterize different species of collagen. Also, the results suggest that time-resolved spectroscopy can be used for monitoring of connective tissue matrix composition changes due to various pathological and non-pathological conditions.

  13. Steady state and time resolved optical characterization studies of Zn2SnO4 nanowires for solar cell applications

    NASA Astrophysics Data System (ADS)

    Yakami, Baichhabi R.; Poudyal, Uma; Nandyala, Shashank R.; Rimal, Gaurab; Cooper, Jason K.; Zhang, Xuejie; Wang, Jing; Wang, Wenyong; Pikal, Jon M.

    2016-10-01

    Nanowires are a promising option for sensitized solar cells, sensors, and display technology. Most of the work thus far has focused on binary oxides for these nanowires, but ternary oxides have advantages in additional control of optical and electronic properties. Here, we report on the diffuse reflectance, Low Temperature and Room Temperature Photoluminescence (PL), PL excitation spectrum, and Time Resolved PL (TRPL) of Zinc Tin Oxide (ZTO) nanowires grown by Chemical Vapor Deposition. The PL from the ZTO nanowires does not exhibit any band gap or near gap emission, and the diffuse reflectance measurement confirms that these ZTO nanowires have a direct forbidden transition. The broad PL spectrum reveals two Gaussian peaks centered at 1.86 eV (red) and 2.81 eV (blue), representing two distinct defect states or complexes. The PL spectra were further studied by the Time Resolved Emission Spectrum and intensity dependent PL and TRPL. The time resolved measurements show complex non-exponential decays at all wavelengths, indicative of defect to defect transitions, and the red emissive states decay much slower than the blue emissive states. The effects of annealing in air and vacuum are studied to investigate the origin of the defect states in the nanowires, showing that the blue states are related to oxygen vacancies. We propose an energy band model for the nanowires containing defect states within the band gap and the associated transitions between these states that are consistent with our measurements.