Time-dependent first-principles study of angle-resolved secondary electron emission from atomic sheets

NASA Astrophysics Data System (ADS)

Ueda, Yoshihiro; Suzuki, Yasumitsu; Watanabe, Kazuyuki

2018-02-01

Angle-resolved secondary electron emission (ARSEE) spectra were analyzed for two-dimensional atomic sheets using a time-dependent first-principles simulation of electron scattering. We demonstrate that the calculated ARSEE spectra capture the unoccupied band structure of the atomic sheets. The excitation dynamics that lead to SEE have also been revealed by the time-dependent Kohn-Sham decomposition scheme. In the present study, the mechanism for the experimentally observed ARSEE from atomic sheets is elucidated with respect to both energetics and the dynamical aspects of SEE.

"Structure and dynamics in complex chemical systems: Gaining new insights through recent advances in time-resolved spectroscopies.” ACS Division of Physical Chemistry Symposium presented at the Fall National ACS Meeting in Boston, MA, August 2015

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

Crawford, Daniel

8-Session Symposium on STRUCTURE AND DYNAMICS IN COMPLEX CHEMICAL SYSTEMS: GAINING NEW INSIGHTS THROUGH RECENT ADVANCES IN TIME-RESOLVED SPECTROSCOPIES. The intricacy of most chemical, biochemical, and material processes and their applications are underscored by the complex nature of the environments in which they occur. Substantial challenges for building a global understanding of a heterogeneous system include (1) identifying unique signatures associated with specific structural motifs within the heterogeneous distribution, and (2) resolving the significance of each of multiple time scales involved in both small- and large-scale nuclear reorganization. This symposium focuses on the progress in our understanding of dynamics inmore » complex systems driven by recent innovations in time-resolved spectroscopies and theoretical developments. Such advancement is critical for driving discovery at the molecular level facilitating new applications. Broad areas of interest include: Structural relaxation and the impact of structure on dynamics in liquids, interfaces, biochemical systems, materials, and other heterogeneous environments.« less

Study on the conformation changes of Lysozyme induced by Hypocrellin A: The mechanism investigation

NASA Astrophysics Data System (ADS)

Ma, Fei; Huang, He-Yong; Zhou, Lin; Yang, Chao; Zhou, Jia-Hong; Liu, Zheng-Ming

2012-11-01

The interactions between Lysozyme and Hypocrellin A are investigated in details using time-resolved fluorescence, fourier transform infrared spectroscopy (FTIR), circular dichroism spectroscopy (CD), three-dimensional fluorescence spectra, and thermal gravimetric analysis (TGA) techniques. The results of time-resolved fluorescence suggest that the quenching mechanism is static quenching. FTIR and CD spectroscopy provide evidences of the reducing of α-helix after interaction. Hypocrellin A could change the micro-environmental of Lysozyme according to hydrophobic interaction between the aromatic ring and the hydrophobic amino acid residues, and the altered polypeptide backbone structures induce the reduction of α-helical structures. Moreover, TGA study further demonstrates the structure changes of Lysozyme on the effect of Hypocrellin A. This study could provide some important information for the derivatives of HA in pharmacy, pharmacology and biochemistry.

Ultrafast Structural Dynamics in Combustion Relevant Model Systems

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

Weber, Peter M.

2014-03-31

The research project explored the time resolved structural dynamics of important model reaction system using an array of novel methods that were developed specifically for this purpose. They include time resolved electron diffraction, time resolved relativistic electron diffraction, and time resolved Rydberg fingerprint spectroscopy. Toward the end of the funding period, we also developed time-resolved x-ray diffraction, which uses ultrafast x-ray pulses at LCLS. Those experiments are just now blossoming, as the funding period expired. In the following, the time resolved Rydberg Fingerprint Spectroscopy is discussed in some detail, as it has been a very productive method. The binding energymore » of an electron in a Rydberg state, that is, the energy difference between the Rydberg level and the ground state of the molecular ion, has been found to be a uniquely powerful tool to characterize the molecular structure. To rationalize the structure sensitivity we invoke a picture from electron diffraction: when it passes the molecular ion core, the Rydberg electron experiences a phase shift compared to an electron in a hydrogen atom. This phase shift requires an adjustment of the binding energy of the electron, which is measurable. As in electron diffraction, the phase shift depends on the molecular, geometrical structure, so that a measurement of the electron binding energy can be interpreted as a measurement of the molecule’s structure. Building on this insight, we have developed a structurally sensitive spectroscopy: the molecule is first elevated to the Rydberg state, and the binding energy is then measured using photoelectron spectroscopy. The molecule’s structure is read out as the binding energy spectrum. Since the photoionization can be done with ultrafast laser pulses, the technique is inherently capable of a time resolution in the femtosecond regime. For the purpose of identifying the structures of molecules during chemical reactions, and for the analysis of molecular species in the hot environments of combustion processes, there are several features that make the Rydberg ionization spectroscopy uniquely useful. First, the Rydberg electron’s orbit is quite large and covers the entire molecule for most molecular structures of combustion interest. Secondly, the ionization does not change vibrational quantum numbers, so that even complicated and large molecules can be observed with fairly well resolved spectra. In fact, the spectroscopy is blind to vibrational excitation of the molecule. This has the interesting consequence for the study of chemical dynamics, where the molecules are invariably very energetic, that the molecular structures are observed unobstructed by the vibrational congestion that dominates other spectroscopies. This implies also that, as a tool to probe the time-dependent structural dynamics of chemically interesting molecules, Rydberg spectroscopy may well be better suited than electron or x-ray diffraction. With recent progress in calculating Rydberg binding energy spectra, we are approaching the point where the method can be evolved into a structure determination method. To implement the Rydberg ionization spectroscopy we use a molecular beam based, time-resolved pump-probe multi-photon ionization/photoelectron scheme in which a first laser pulse excites the molecule to a Rydberg state, and a probe pulse ionizes the molecule. A time-of-flight detector measures the kinetic energy spectrum of the photoelectrons. The photoelectron spectrum directly provides the binding energy of the electron, and thereby reveals the molecule’s time-dependent structural fingerprint. Only the duration of the laser pulses limits the time resolution. With a new laser system, we have now reached time resolutions better than 100 fs, although very deep UV wavelengths (down to 190 nm) have slightly longer instrument functions. The structural dynamics of molecules in Rydberg-excited states is obtained by delaying the probe ionization photon from the pump photon; the structural dynamics of molecules in their ground state or excited valence states is measured by inducing the dynamics using a near UV laser pulse, and employing a multi-photon ionization scheme via the Rydberg states as a probe process. Thus, the technique is capable of measuring the reaction dynamics in any electronic state of neutral molecules.« less

Gamma Knife surgery for arteriovenous malformations in the brain: integration of time-resolved contrast-enhanced magnetic resonance angiography into dosimetry planning. Technical note.

PubMed

Taschner, Christian A; Le Thuc, Vianney; Reyns, Nicolas; Gieseke, Juergen; Gauvrit, Jean-Yves; Pruvo, Jean-Pierre; Leclerc, Xavier

2007-10-01

The aim of this study was to develop an algorithm for the integration of time-resolved contrast-enhanced magnetic resonance (MR) angiography into dosimetry planning for Gamma Knife surgery (GKS) of arteriovenous malformations (AVMs) in the brain. Twelve patients harboring brain AVMs referred for GKS underwent intraarterial digital subtraction (DS) angiography and time-resolved MR angiography while wearing an externally applied cranial stereotactic frame. Time-resolved MR angiography was performed on a 1.5-tesla MR unit (Achieva, Philips Medical Systems) using contrast-enhanced 3D fast field echo sequencing with stochastic central k-space ordering. Postprocessing with interactive data language (Research Systems, Inc.) produced hybrid data sets containing dynamic angiographic information and the MR markers necessary for stereotactic transformation. Image files were sent to the Leksell GammaPlan system (Elekta) for dosimetry planning. Stereotactic transformation of the hybrid data sets containing the time-resolved MR angiography information with automatic detection of the MR markers was possible in all 12 cases. The stereotactic coordinates of vascular structures predefined from time-resolved MR angiography matched with DS angiography data in all cases. In 10 patients dosimetry planning could be performed based on time-resolved MR angiography data. In two patients, time-resolved MR angiography data alone were considered insufficient. The target volumes showed a notable shift of centers between modalities. Integration of time-resolved MR angiography data into the Leksell GammaPlan system for patients with brain AVMs is feasible. The proposed algorithm seems concise and sufficiently robust for clinical application. The quality of the time-resolved MR angiography sequencing needs further improvement.

Time-resolved infrared and resonance Raman studies of benzil. Vibrational analysis and structures of the excited states

NASA Astrophysics Data System (ADS)

Mizuno, Misao; Iwata, Koichi; Takahashi, Hiroaki

2003-12-01

Structures of the S 1 and T 1 states of benzil are examined based on the experimental results from nanosecond time-resolved infrared spectroscopy and picosecond time-resolved Raman spectroscopy. Nanosecond time-resolved infrared spectra of the T 1 state of benzil as well as its three isotopically substituted analogues were measured in carbon tetrachloride. The observed infrared bands of T 1 benzil were assigned based on the frequency shifts on isotopic ( 18O, and deuteration) substitutions. The infrared band at 1312 cm -1 is assigned to the CO anti-symmetric stretch vibration. An infrared band that has large contribution from the central C-C stretch is not observed. Picosecond time-resolved resonance Raman spectra of the S 1 state of benzil were also measured. It has been reported that after the photoexcitation, the benzil molecule shows an ultrafast conformational change in the S 1 state. The observed resonance Raman bands are attributable to the vibrations of the relaxed form of the S 1 state. By comparing the Raman and infrared spectra of the S 0, S 1, and T 1 states of benzil, the structures of benzil in the excited states are discussed. Upon going from the S 0 state to the S 1 or T 1 state, the bond order of the CO bond decreases while that of the central C-C bond increases. Although several ground-state bands appear in both the infrared and Raman spectra, there is no band observed simultaneously in the infrared and Raman spectra of the T 1 state, except for bands attributable to the phenyl ring vibrations. We conclude that T 1 benzil has the inversion center that arises from the trans-planar structure. The spectral pattern of the resonance Raman scattering of the relaxed S 1 state is very similar to that of the T 1 state. This implies that the molecular structure of the relaxed S 1 state is similar to that of the T 1 state. The structure of the relaxed form of the S 1 state is also considered to be trans-planar.

In Situ X-Ray Studies of Crystallization Kinetics and Ordering in Functional Organic and Hybrid Materials

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

Yang, Bin; Keum, Jong K.; Geohegan, David B.

In-Situ and time-resolved X-ray scattering and diffraction is dedicated to yielding the change of structural information as the materials are processed or grown in a controlled environment. In this chapter, we introduce the use of in situ and time-resolved X-ray techniques to understand molecular packing, crystal orientation, and phase transformation during the synthesis and processing of functional organic semiconductors, organic nanowires, and hybrid perovskite materials.

Structure and dynamics of water in nonionic reverse micelles: a combined time-resolved infrared and small angle x-ray scattering study.

PubMed

van der Loop, Tibert H; Panman, Matthijs R; Lotze, Stephan; Zhang, Jing; Vad, Thomas; Bakker, Huib J; Sager, Wiebke F C; Woutersen, Sander

2012-07-28

We study the structure and reorientation dynamics of nanometer-sized water droplets inside nonionic reverse micelles (water/Igepal-CO-520/cyclohexane) with time-resolved mid-infrared pump-probe spectroscopy and small angle x-ray scattering. In the time-resolved experiments, we probe the vibrational and orientational dynamics of the O-D bonds of dilute HDO:H(2)O mixtures in Igepal reverse micelles as a function of temperature and micelle size. We find that even small micelles contain a large fraction of water that reorients at the same rate as water in the bulk, which indicates that the polyethylene oxide chains of the surfactant do not penetrate into the water volume. We also observe that the confinement affects the reorientation dynamics of only the first hydration layer. From the temperature dependent surface-water dynamics, we estimate an activation enthalpy for reorientation of 45 ± 9 kJ mol(-1) (11 ± 2 kcal mol(-1)), which is close to the activation energy of the reorientation of water molecules in ice.

Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

NASA Astrophysics Data System (ADS)

Brauße, Felix; Goldsztejn, Gildas; Amini, Kasra; Boll, Rebecca; Bari, Sadia; Bomme, Cédric; Brouard, Mark; Burt, Michael; de Miranda, Barbara Cunha; Düsterer, Stefan; Erk, Benjamin; Géléoc, Marie; Geneaux, Romain; Gentleman, Alexander S.; Guillemin, Renaud; Ismail, Iyas; Johnsson, Per; Journel, Loïc; Kierspel, Thomas; Köckert, Hansjochen; Küpper, Jochen; Lablanquie, Pascal; Lahl, Jan; Lee, Jason W. L.; Mackenzie, Stuart R.; Maclot, Sylvain; Manschwetus, Bastian; Mereshchenko, Andrey S.; Mullins, Terence; Olshin, Pavel K.; Palaudoux, Jérôme; Patchkovskii, Serguei; Penent, Francis; Piancastelli, Maria Novella; Rompotis, Dimitrios; Ruchon, Thierry; Rudenko, Artem; Savelyev, Evgeny; Schirmel, Nora; Techert, Simone; Travnikova, Oksana; Trippel, Sebastian; Underwood, Jonathan G.; Vallance, Claire; Wiese, Joss; Simon, Marc; Holland, David M. P.; Marchenko, Tatiana; Rouzée, Arnaud; Rolles, Daniel

2018-04-01

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I ) is investigated by ionization above the iodine 4 d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

Lipidic cubic phase injector is a viable crystal delivery system for time-resolved serial crystallography

DOE PAGES

Nogly, Przemyslaw; Panneels, Valerie; Nelson, Garrett; ...

2016-08-22

Serial femtosecond crystallography (SFX) using X-ray free-electron laser sources is an emerging method with considerable potential for time-resolved pump-probe experiments. Here we present a lipidic cubic phase SFX structure of the light-driven proton pump bacteriorhodopsin (bR) to 2.3 Å resolution and a method to investigate protein dynamics with modest sample requirement. Time-resolved SFX (TR-SFX) with a pump-probe delay of 1 ms yields difference Fourier maps compatible with the dark to M state transition of bR. Importantly, the method is very sample efficient and reduces sample consumption to about 1 mg per collected time point. Accumulation of M intermediate within themore » crystal lattice is confirmed by time-resolved visible absorption spectroscopy. Furthermore, this study provides an important step towards characterizing the complete photocycle dynamics of retinal proteins and demonstrates the feasibility of a sample efficient viscous medium jet for TR-SFX.« less

Lipidic cubic phase injector is a viable crystal delivery system for time-resolved serial crystallography

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

Nogly, Przemyslaw; Panneels, Valerie; Nelson, Garrett

Serial femtosecond crystallography (SFX) using X-ray free-electron laser sources is an emerging method with considerable potential for time-resolved pump-probe experiments. Here we present a lipidic cubic phase SFX structure of the light-driven proton pump bacteriorhodopsin (bR) to 2.3 Å resolution and a method to investigate protein dynamics with modest sample requirement. Time-resolved SFX (TR-SFX) with a pump-probe delay of 1 ms yields difference Fourier maps compatible with the dark to M state transition of bR. Importantly, the method is very sample efficient and reduces sample consumption to about 1 mg per collected time point. Accumulation of M intermediate within themore » crystal lattice is confirmed by time-resolved visible absorption spectroscopy. Furthermore, this study provides an important step towards characterizing the complete photocycle dynamics of retinal proteins and demonstrates the feasibility of a sample efficient viscous medium jet for TR-SFX.« less

Lipidic cubic phase injector is a viable crystal delivery system for time-resolved serial crystallography

PubMed Central

Nogly, Przemyslaw; Panneels, Valerie; Nelson, Garrett; Gati, Cornelius; Kimura, Tetsunari; Milne, Christopher; Milathianaki, Despina; Kubo, Minoru; Wu, Wenting; Conrad, Chelsie; Coe, Jesse; Bean, Richard; Zhao, Yun; Båth, Petra; Dods, Robert; Harimoorthy, Rajiv; Beyerlein, Kenneth R.; Rheinberger, Jan; James, Daniel; DePonte, Daniel; Li, Chufeng; Sala, Leonardo; Williams, Garth J.; Hunter, Mark S.; Koglin, Jason E.; Berntsen, Peter; Nango, Eriko; Iwata, So; Chapman, Henry N.; Fromme, Petra; Frank, Matthias; Abela, Rafael; Boutet, Sébastien; Barty, Anton; White, Thomas A.; Weierstall, Uwe; Spence, John; Neutze, Richard; Schertler, Gebhard; Standfuss, Jörg

2016-01-01

Serial femtosecond crystallography (SFX) using X-ray free-electron laser sources is an emerging method with considerable potential for time-resolved pump-probe experiments. Here we present a lipidic cubic phase SFX structure of the light-driven proton pump bacteriorhodopsin (bR) to 2.3 Å resolution and a method to investigate protein dynamics with modest sample requirement. Time-resolved SFX (TR-SFX) with a pump-probe delay of 1 ms yields difference Fourier maps compatible with the dark to M state transition of bR. Importantly, the method is very sample efficient and reduces sample consumption to about 1 mg per collected time point. Accumulation of M intermediate within the crystal lattice is confirmed by time-resolved visible absorption spectroscopy. This study provides an important step towards characterizing the complete photocycle dynamics of retinal proteins and demonstrates the feasibility of a sample efficient viscous medium jet for TR-SFX. PMID:27545823

Driving force behind adsorption-induced protein unfolding: a time-resolved X-ray reflectivity study on lysozyme adsorbed at an air/water interface.

PubMed

Yano, Yohko F; Uruga, Tomoya; Tanida, Hajime; Toyokawa, Hidenori; Terada, Yasuko; Takagaki, Masafumi; Yamada, Hironari

2009-01-06

Time-resolved X-ray reflectivity measurements for lysozyme (LSZ) adsorbed at an air/water interface were performed to study the mechanism of adsorption-induced protein unfolding. The time dependence of the density profile at the air/water interface revealed that the molecular conformation changed significantly during adsorption. Taking into account previous work using Fourier transform infrared (FTIR) spectroscopy, we propose that the LSZ molecules initially adsorbed on the air/water interface have a flat unfolded structure, forming antiparallel beta-sheets as a result of hydrophobic interactions with the gas phase. In contrast, as adsorption continues, a second layer forms in which the molecules have a very loose structure having random coils as a result of hydrophilic interactions with the hydrophilic groups that protrude from the first layer.

Exploring the structural changes on excitation of a luminescent organic bromine-substituted complex by in-house time-resolved pump-probe diffraction

DOE PAGES

Basuroy, Krishnayan; Chen, Yang; Sarkar, Sounak; ...

2017-03-09

The structural changes accompanying the excitation of the luminescent dibromobenzene derivative, 1,4-dibromo-2,5-bis(octyloxy)benzene, have been measured by in-house monochromatic time-resolved (TR) diffraction at 90 K. Results show an increment of the very short intermolecular Br•••Br contact distance from 3.290 Å to 3.380 Å. These calculations show the Br…Br interaction to be strongly repulsive in both the Ground and Excited states but significantly relaxed by the lengthening of the contact distance on excitation. The stability of the crystals is attributed to the many weak C-H···Br and C-H···π intermolecular interactions. Our study described is the first practical application of In-House Time-Resolved diffraction, mademore » possible by the continuing increase in the brightness of X-ray sources and the sensitivity of our detectors.« less

Exploring the structural changes on excitation of a luminescent organic bromine-substituted complex by in-house time-resolved pump-probe diffraction

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

Basuroy, Krishnayan; Chen, Yang; Sarkar, Sounak

The structural changes accompanying the excitation of the luminescent dibromobenzene derivative, 1,4-dibromo-2,5-bis(octyloxy)benzene, have been measured by in-house monochromatic time-resolved (TR) diffraction at 90 K. Results show an increment of the very short intermolecular Br•••Br contact distance from 3.290 Å to 3.380 Å. These calculations show the Br…Br interaction to be strongly repulsive in both the Ground and Excited states but significantly relaxed by the lengthening of the contact distance on excitation. The stability of the crystals is attributed to the many weak C-H···Br and C-H···π intermolecular interactions. Our study described is the first practical application of In-House Time-Resolved diffraction, mademore » possible by the continuing increase in the brightness of X-ray sources and the sensitivity of our detectors.« less

Entering an era of dynamic structural biology….

PubMed

Orville, Allen M

2018-05-31

A recent paper in BMC Biology presents a general method for mix-and-inject serial crystallography, to facilitate the visualization of enzyme intermediates via time-resolved serial femtosecond crystallography (tr-SFX). They apply their method to resolve in near atomic detail the cleavage and inactivation of the antibiotic ceftriaxone by a β-lactamase enzyme from Mycobacterium tuberculosis. Their work demonstrates the general applicability of time-resolved crystallography, from which dynamic structures, at atomic resolution, can be obtained.See research article: https://bmcbiol.biomedcentral.com/articles/10.1186/s12915-018-0524-5 .

Time-resolved serial crystallography captures high-resolution intermediates of photoactive yellow protein

DOE PAGES

Tenboer, Jason; Basu, Shibom; Zatsepin, Nadia; ...

2014-12-05

We report that serial femtosecond crystallography using ultrashort pulses from X-ray Free Electron Lasers (XFELs) offers the possibility to study light-triggered dynamics of biomolecules. Using microcrystals of the blue light photoreceptor, photoactive yellow protein, as a model system, we present high resolution, time-resolved difference electron density maps of excellent quality with strong features, which allow the determination of structures of reaction intermediates to 1.6 Å resolution. These results open the way to the study of reversible and non-reversible biological reactions on time scales as short as femtoseconds under conditions which maximize the extent of reaction initiation throughout the crystal.

SVD-aided pseudo principal-component analysis: A new method to speed up and improve determination of the optimum kinetic model from time-resolved data

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

Oang, Key Young; Yang, Cheolhee; Muniyappan, Srinivasan

Determination of the optimum kinetic model is an essential prerequisite for characterizing dynamics and mechanism of a reaction. Here, we propose a simple method, termed as singular value decomposition-aided pseudo principal-component analysis (SAPPA), to facilitate determination of the optimum kinetic model from time-resolved data by bypassing any need to examine candidate kinetic models. We demonstrate the wide applicability of SAPPA by examining three different sets of experimental time-resolved data and show that SAPPA can efficiently determine the optimum kinetic model. In addition, the results of SAPPA for both time-resolved X-ray solution scattering (TRXSS) and transient absorption (TA) data of themore » same protein reveal that global structural changes of protein, which is probed by TRXSS, may occur more slowly than local structural changes around the chromophore, which is probed by TA spectroscopy.« less

Capturing Structural Dynamics in Crystalline Silicon Using Chirped Electrons from a Laser Wakefield Accelerator

PubMed Central

He, Z.-H.; Beaurepaire, B.; Nees, J. A.; Gallé, G.; Scott, S. A.; Pérez, J. R. Sánchez; Lagally, M. G.; Krushelnick, K.; Thomas, A. G. R.; Faure, J.

2016-01-01

Recent progress in laser wakefield acceleration has led to the emergence of a new generation of electron and X-ray sources that may have enormous benefits for ultrafast science. These novel sources promise to become indispensable tools for the investigation of structural dynamics on the femtosecond time scale, with spatial resolution on the atomic scale. Here, we demonstrate the use of laser-wakefield-accelerated electron bunches for time-resolved electron diffraction measurements of the structural dynamics of single-crystal silicon nano-membranes pumped by an ultrafast laser pulse. In our proof-of-concept study, we resolve the silicon lattice dynamics on a picosecond time scale by deflecting the momentum-time correlated electrons in the diffraction peaks with a static magnetic field to obtain the time-dependent diffraction efficiency. Further improvements may lead to femtosecond temporal resolution, with negligible pump-probe jitter being possible with future laser-wakefield-accelerator ultrafast-electron-diffraction schemes. PMID:27824086

Capturing Structural Dynamics in Crystalline Silicon Using Chirped Electrons from a Laser Wakefield Accelerator

DOE PAGES

He, Z. -H.; Beaurepaire, B.; Nees, J. A.; ...

2016-11-08

Recent progress in laser wakefield acceleration has led to the emergence of a new generation of electron and X-ray sources that may have enormous benefits for ultrafast science. These novel sources promise to become indispensable tools for the investigation of structural dynamics on the femtosecond time scale, with spatial resolution on the atomic scale. Here in this paper, we demonstrate the use of laser-wakefield-accelerated electron bunches for time-resolved electron diffraction measurements of the structural dynamics of single-crystal silicon nano-membranes pumped by an ultrafast laser pulse. In our proof-of-concept study, we resolve the silicon lattice dynamics on a picosecond time scalemore » by deflecting the momentum-time correlated electrons in the diffraction peaks with a static magnetic field to obtain the time-dependent diffraction efficiency. Further improvements may lead to femtosecond temporal resolution, with negligible pump-probe jitter being possible with future laser-wakefield-accelerator ultrafast-electron-diffraction schemes.« less

Structural dynamics of ribosome subunit association studied by mixing-spraying time-resolved cryo-EM

PubMed Central

Chen, Bo; Kaledhonkar, Sandip; Sun, Ming; Shen, Bingxin; Lu, Zonghuan; Barnard, David; Lu, Toh-Ming; Gonzalez, Ruben L.; Frank, Joachim

2015-01-01

Ribosomal subunit association is a key checkpoint in translation initiation, but its structural dynamics are poorly understood. Here, we used a recently developed mixing-spraying, time-resolved, cryogenic electron microscopy (cryo-EM) method to study ribosomal subunit association in the sub-second time range. We have improved this method and increased the cryo-EM data yield by tenfold. Pre-equilibrium states of the association reaction were captured by reacting the mixture of ribosomal subunits for 60 ms and 140 ms. We also identified three distinct ribosome conformations in the associated ribosomes. The observed proportions of these conformations are the same in these two time points, suggesting that ribosomes equilibrate among the three conformations within less than 60 ms upon formation. Our results demonstrate that the mixing-spraying method can capture multiple states of macromolecules during a sub-second reaction. Other fast processes, such as translation initiation, decoding and ribosome recycling, are amenable to study with this method. PMID:26004440

Time-Resolved Macromolecular Crystallography at Modern X-Ray Sources.

PubMed

Schmidt, Marius

2017-01-01

Time-resolved macromolecular crystallography unifies protein structure determination with chemical kinetics. With the advent of fourth generation X-ray sources the time-resolution can be on the order of 10-40 fs, which opens the ultrafast time scale to structure determination. Fundamental motions and transitions associated with chemical reactions in proteins can now be observed. Moreover, new experimental approaches at synchrotrons allow for the straightforward investigation of all kind of reactions in biological macromolecules. Here, recent developments in the field are reviewed.

ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

NASA Astrophysics Data System (ADS)

Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

2005-05-01

Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

Elucidating the Nature of the Excited State of a Heteroleptic Copper Photosensitizer by using Time-Resolved X-ray Absorption Spectroscopy.

PubMed

Moonshiram, Dooshaye; Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Picón, Antonio; Liu, Cunming; Zhang, Xiaoyi; Karnahl, Michael; Llobet, Antoni

2018-04-25

We report the light-induced electronic and geometric changes taking place within a heteroleptic Cu I photosensitizer, namely [(xant)Cu(Me 2 phenPh 2 )]PF 6 (xant=xantphos, Me 2 phenPh 2 =bathocuproine), by time-resolved X-ray absorption spectroscopy in the ps-μs time regime. Time-resolved X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis enabled the elucidation of the electronic and structural configuration of the copper center in the excited state as well as its decay dynamics in different solvent conditions with and without triethylamine acting as a sacrificial electron donor. A three-fold decrease in the decay lifetime of the excited state is observed in the presence of triethylamine, showing the feasibility of the reductive quenching pathway in the latter case. A prominent pre-edge feature is observed in the XANES spectrum of the excited state upon metal to charge ligand transfer transition, showing an increased hybridization of the 3d states with the ligand p orbitals in the tetrahedron around the Cu center. EXAFS and density functional theory illustrate a significant shortening of the Cu-N and an elongation of the Cu-P bonds together with a decrease in the torsional angle between the xantphos and bathocuproine ligand. This study provides mechanistic time-resolved understanding for the development of improved heteroleptic Cu I photosensitizers, which can be used for the light-driven production of hydrogen from water. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal and Denaturation Studies of the Time-Resolved Fluorescence Decay of Human Superoxide Dismutase

NASA Astrophysics Data System (ADS)

Silva, Norberto De Jesus

Previous studies have shown that time-resolved fluorescence decay of various single tryptophan proteins is best described by a distribution of fluorescence lifetimes rather than one or two lifetimes. The thermal dependence of the lifetime distributions is consistent with the hypothesis that proteins fluctuate between a hierarchy of many conformational substates. With this scenario as a theoretical framework, the correlations between protein dynamic and structure are investigated by studying the time-resolved fluorescence and anisotropy decay of the single tryptophan (Trp) residue of human superoxide dismutase (HSOD) over a wide range of temperatures and at different denaturant concentrations. First, it is demonstrated that the center of the lifetime distribution can characterize the average deactivation environment of the excited Trp-protein system. A qualitative model is introduced to explain the time-resolved fluorescence decay of HSOD in 80% glycerol over a wide range of temperatures. The dynamical model features isoenergetic conformational substates separated by a hierarchy of energy barriers. The HSOD system is also investigated as a function of denaturant concentration in aqueous solution. As a function of guanidine hydrochloride (GdHCl), the width of the fluorescence lifetime distribution of HSOD displays a maximum which is not coincident with the fully denatured form of HSOD at 6.5M GdHCl. Furthermore, the width for the fully denatured form of HSOD is greater than that of the native form. This is consistent with the scenario that more conformational substates are being created upon denaturation of HSOD. HSOD is a dimeric protein and it was observed that the width of the lifetime distribution of HSOD at intermediate GdHCl concentrations increased with decreasing protein concentration. In addition, the secondary structure of HSOD at intermediate GdHCl concentration does not change with protein concentration. These results suggest that HSOD display structural microheterogeneity which is consistent with the hypothesis of conformational substates. Further analysis show that, during denaturation, the monomeric form of HSOD is an intermediate which displays native-like secondary structure and fluctuating tertiary structure; i.e., the monomeric form of HSOD is a molten globule.

Direct Observation of Insulin Association Dynamics with Time-Resolved X-ray Scattering

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

Rimmerman, Dolev; Leshchev, Denis; Hsu, Darren J.

Biological functions frequently require protein-protein interactions that involve secondary and tertiary structural perturbation. Here we study protein-protein dissociation and reassociation dynamics in insulin, a model system for protein oligomerization. Insulin dimer dissociation into monomers was induced by a nanosecond temperature-jump (T-jump) of ~8 °C in aqueous solution, and the resulting protein and solvent dynamics were tracked by time-resolved X-ray solution scattering (TRXSS) on time scales of 10 ns to 100 ms. The protein scattering signals revealed the formation of five distinguishable transient species during the association process that deviate from simple two state kinetics. Our results show that the combinationmore » of T-jump pump coupled to TRXSS probe allows for direct tracking of structural dynamics in nonphotoactive proteins.« less

Development of soft x-ray time-resolved photoemission spectroscopy system with a two-dimensional angle-resolved time-of-flight analyzer at SPring-8 BL07LSU

NASA Astrophysics Data System (ADS)

Ogawa, Manami; Yamamoto, Susumu; Kousa, Yuka; Nakamura, Fumitaka; Yukawa, Ryu; Fukushima, Akiko; Harasawa, Ayumi; Kondoh, Hiroshi; Tanaka, Yoshihito; Kakizaki, Akito; Matsuda, Iwao

2012-02-01

We have developed a soft x-ray time-resolved photoemission spectroscopy system using synchrotron radiation (SR) at SPring-8 BL07LSU and an ultrashort pulse laser system. Two-dimensional angle-resolved measurements were performed with a time-of-flight-type analyzer. The photoemission spectroscopy system is synchronized to light pulses of SR and laser using a time control unit. The performance of the instrument is demonstrated by mapping the band structure of a Si(111) crystal over the surface Brillouin zones and observing relaxation of the surface photo-voltage effect using the pump (laser) and probe (SR) method.

Development of soft x-ray time-resolved photoemission spectroscopy system with a two-dimensional angle-resolved time-of-flight analyzer at SPring-8 BL07LSU.

PubMed

Ogawa, Manami; Yamamoto, Susumu; Kousa, Yuka; Nakamura, Fumitaka; Yukawa, Ryu; Fukushima, Akiko; Harasawa, Ayumi; Kondoh, Hiroshi; Tanaka, Yoshihito; Kakizaki, Akito; Matsuda, Iwao

2012-02-01

We have developed a soft x-ray time-resolved photoemission spectroscopy system using synchrotron radiation (SR) at SPring-8 BL07LSU and an ultrashort pulse laser system. Two-dimensional angle-resolved measurements were performed with a time-of-flight-type analyzer. The photoemission spectroscopy system is synchronized to light pulses of SR and laser using a time control unit. The performance of the instrument is demonstrated by mapping the band structure of a Si(111) crystal over the surface Brillouin zones and observing relaxation of the surface photo-voltage effect using the pump (laser) and probe (SR) method.

Evaluating scintillator performance in time-resolved hard X-ray studies at synchrotron light sources.

PubMed

Rutherford, Michael E; Chapman, David J; White, Thomas G; Drakopoulos, Michael; Rack, Alexander; Eakins, Daniel E

2016-05-01

The short pulse duration, small effective source size and high flux of synchrotron radiation is ideally suited for probing a wide range of transient deformation processes in materials under extreme conditions. In this paper, the challenges of high-resolution time-resolved indirect X-ray detection are reviewed in the context of dynamic synchrotron experiments. In particular, the discussion is targeted at two-dimensional integrating detector methods, such as those focused on dynamic radiography and diffraction experiments. The response of a scintillator to periodic synchrotron X-ray excitation is modelled and validated against experimental data collected at the Diamond Light Source (DLS) and European Synchrotron Radiation Facility (ESRF). An upper bound on the dynamic range accessible in a time-resolved experiment for a given bunch separation is calculated for a range of scintillators. New bunch structures are suggested for DLS and ESRF using the highest-performing commercially available crystal LYSO:Ce, allowing time-resolved experiments with an interframe time of 189 ns and a maximum dynamic range of 98 (6.6 bits).

Evaluating scintillator performance in time-resolved hard X-ray studies at synchrotron light sources

PubMed Central

Rutherford, Michael E.; Chapman, David J.; White, Thomas G.; Drakopoulos, Michael; Rack, Alexander; Eakins, Daniel E.

2016-01-01

The short pulse duration, small effective source size and high flux of synchrotron radiation is ideally suited for probing a wide range of transient deformation processes in materials under extreme conditions. In this paper, the challenges of high-resolution time-resolved indirect X-ray detection are reviewed in the context of dynamic synchrotron experiments. In particular, the discussion is targeted at two-dimensional integrating detector methods, such as those focused on dynamic radiography and diffraction experiments. The response of a scintillator to periodic synchrotron X-ray excitation is modelled and validated against experimental data collected at the Diamond Light Source (DLS) and European Synchrotron Radiation Facility (ESRF). An upper bound on the dynamic range accessible in a time-resolved experiment for a given bunch separation is calculated for a range of scintillators. New bunch structures are suggested for DLS and ESRF using the highest-performing commercially available crystal LYSO:Ce, allowing time-resolved experiments with an interframe time of 189 ns and a maximum dynamic range of 98 (6.6 bits). PMID:27140147

Interferometry in the era of time-domain astronomy

NASA Astrophysics Data System (ADS)

Schaefer, Gail H.; Cassan, Arnaud; Gallenne, Alexandre; Roettenbacher, Rachael M.; Schneider, Jean

2018-04-01

The physical nature of time variable objects is often inferred from photometric light-curves and spectroscopic variations. Long-baseline optical interferometry has the power to resolve the spatial structure of time variable sources directly in order to measure their physical properties and test the physics of the underlying models. Recent interferometric studies of variable objects include measuring the angular expansion and spatial structure during the early stages of novae outbursts, studying the transits and tidal distortions of the components in eclipsing and interacting binaries, measuring the radial pulsations in Cepheid variables, monitoring changes in the circumstellar discs around rapidly rotating massive stars, and imaging starspots. Future applications include measuring the image size and centroid displacements in gravitational microlensing events, and imaging the transits of exoplanets. Ongoing and upcoming photometric surveys will dramatically increase the number of time-variable objects detected each year, providing many potential targets to observe interferometrically. For short-lived transient events, it is critical for interferometric arrays to have the flexibility to respond rapidly to targets of opportunity and optimize the selection of baselines and beam combiners to provide the necessary resolution and sensitivity to resolve the source as its brightness and size change. We discuss the science opportunities made possible by resolving variable sources using long baseline optical interferometry.

Time-resolved structural studies with serial crystallography: A new light on retinal proteins

PubMed Central

Panneels, Valérie; Wu, Wenting; Tsai, Ching-Ju; Nogly, Przemek; Rheinberger, Jan; Jaeger, Kathrin; Cicchetti, Gregor; Gati, Cornelius; Kick, Leonhard M.; Sala, Leonardo; Capitani, Guido; Milne, Chris; Padeste, Celestino; Pedrini, Bill; Li, Xiao-Dan; Standfuss, Jörg; Abela, Rafael; Schertler, Gebhard

2015-01-01

Structural information of the different conformational states of the two prototypical light-sensitive membrane proteins, bacteriorhodopsin and rhodopsin, has been obtained in the past by X-ray cryo-crystallography and cryo-electron microscopy. However, these methods do not allow for the structure determination of most intermediate conformations. Recently, the potential of X-Ray Free Electron Lasers (X-FELs) for tracking the dynamics of light-triggered processes by pump-probe serial femtosecond crystallography has been demonstrated using 3D-micron-sized crystals. In addition, X-FELs provide new opportunities for protein 2D-crystal diffraction, which would allow to observe the course of conformational changes of membrane proteins in a close-to-physiological lipid bilayer environment. Here, we describe the strategies towards structural dynamic studies of retinal proteins at room temperature, using injector or fixed-target based serial femtosecond crystallography at X-FELs. Thanks to recent progress especially in sample delivery methods, serial crystallography is now also feasible at synchrotron X-ray sources, thus expanding the possibilities for time-resolved structure determination. PMID:26798817

Biosonar resolving power: echo-acoustic perception of surface structures in the submillimeter range.

PubMed

Simon, Ralph; Knörnschild, Mirjam; Tschapka, Marco; Schneider, Annkathrin; Passauer, Nadine; Kalko, Elisabeth K V; von Helversen, Otto

2014-01-01

The minimum distance for which two points still can be separated from each other defines the resolving power of a visual system. In an echo-acoustic context, the resolving power is usually measured as the smallest perceivable distance of two reflecting surfaces on the range axis and is found to be around half a millimeter for bats employing frequency modulated (FM) echolocation calls. Only few studies measured such thresholds with physical objects, most often bats were trained on virtual echoes i.e., echoes generated and played back by a computer; moreover, bats were sitting while they received the stimuli. In these studies differences in structure depth between 200 and 340 μm were found. However, these low thresholds were never verified for free-flying bats and real physical objects. Here, we show behavioral evidence that the echo-acoustic resolving power for surface structures in fact can be as low as measured for computer generated echoes and even lower, sometimes below 100 μm. We found this exceptional fine discrimination ability only when one of the targets showed spectral interferences in the frequency range of the bats' echolocation call while the other target did not. This result indicates that surface structure is likely to be perceived as a spectral quality rather than being perceived strictly in the time domain. Further, it points out that sonar resolving power directly depends on the highest frequency/shortest wavelength of the signal employed.

Biosonar resolving power: echo-acoustic perception of surface structures in the submillimeter range

PubMed Central

Simon, Ralph; Knörnschild, Mirjam; Tschapka, Marco; Schneider, Annkathrin; Passauer, Nadine; Kalko, Elisabeth K. V.; von Helversen, Otto

2014-01-01

The minimum distance for which two points still can be separated from each other defines the resolving power of a visual system. In an echo-acoustic context, the resolving power is usually measured as the smallest perceivable distance of two reflecting surfaces on the range axis and is found to be around half a millimeter for bats employing frequency modulated (FM) echolocation calls. Only few studies measured such thresholds with physical objects, most often bats were trained on virtual echoes i.e., echoes generated and played back by a computer; moreover, bats were sitting while they received the stimuli. In these studies differences in structure depth between 200 and 340 μm were found. However, these low thresholds were never verified for free-flying bats and real physical objects. Here, we show behavioral evidence that the echo-acoustic resolving power for surface structures in fact can be as low as measured for computer generated echoes and even lower, sometimes below 100 μm. We found this exceptional fine discrimination ability only when one of the targets showed spectral interferences in the frequency range of the bats′ echolocation call while the other target did not. This result indicates that surface structure is likely to be perceived as a spectral quality rather than being perceived strictly in the time domain. Further, it points out that sonar resolving power directly depends on the highest frequency/shortest wavelength of the signal employed. PMID:24616703

Effect of the N-terminal residues on the quaternary dynamics of human adult hemoglobin

NASA Astrophysics Data System (ADS)

Chang, Shanyan; Mizuno, Misao; Ishikawa, Haruto; Mizutani, Yasuhisa

2016-05-01

The protein dynamics of human hemoglobin following ligand photolysis was studied by time-resolved resonance Raman spectroscopy. The time-resolved spectra of two kinds of recombinant hemoglobin expressed in Escherichia coli, normal recombinant hemoglobin and the α(V1M)/β(V1M) double mutant, were compared with those of human adult hemoglobin (HbA) purified from blood. A frequency shift of the iron-histidine stretching [ν(Fe-His)] band was observed in the time-resolved spectra of all three hemoglobin samples, indicative of tertiary and quaternary changes in the protein following photolysis. The spectral changes of the α(V1M)/β(V1M) double mutant were distinct from those of HbA in the tens of microseconds region, whereas the spectral changes of normal recombinant hemoglobin were similar to those of HbA isolated from blood. These results demonstrated that a structural change in the N-termini is involved in the second step of the quaternary structure change of hemoglobin. We discuss the implications of these results for understanding the allosteric pathway of HbA.

Identifying Coherent Structures in a 3-Stream Supersonic Jet Flow using Time-Resolved Schlieren Imaging

NASA Astrophysics Data System (ADS)

Tenney, Andrew; Coleman, Thomas; Berry, Matthew; Magstadt, Andy; Gogineni, Sivaram; Kiel, Barry

2015-11-01

Shock cells and large scale structures present in a three-stream non-axisymmetric jet are studied both qualitatively and quantitatively. Large Eddy Simulation is utilized first to gain an understanding of the underlying physics of the flow and direct the focus of the physical experiment. The flow in the experiment is visualized using long exposure Schlieren photography, with time resolved Schlieren photography also a possibility. Velocity derivative diagnostics are calculated from the grey-scale Schlieren images are analyzed using continuous wavelet transforms. Pressure signals are also captured in the near-field of the jet to correlate with the velocity derivative diagnostics and assist in unraveling this complex flow. We acknowledge the support of AFRL through an SBIR grant.

Time-resolved fluorescence spectroscopic study of flavin fluorescence in purified enzymes of bioluminescent bacteria

NASA Astrophysics Data System (ADS)

Vetrova, Elena; Kudryasheva, N.; Cheng, K.

2006-10-01

Time-resolved fluorescence intensity and anisotropy decay measurements have been used to study the environment and rotational mobility of endogenous flavin in two purified enzymes of bioluminescent bacteria, Luciferase from Photobacterium leiognathi and NAD(P)H:FMN-oxidoreductase from Vibrio fischeri. We compared the time-resolved fluorescence parameters, intensity decay lifetimes, rotational correlation times, and their fractional contribution, of the endogeneous flavin fluorescence in each of the two enzymes in the presence or absence of quinones of different structures and redox potentials. The endogeneous flavin exhibited multi-exponential decay characteristics as compared to a single decay lifetime of around 5 ns for free flavin, suggesting a complex and heterogeneous environment of flavin bound to the enzyme. In addition, a significant increase in the rotational correlation time and a certain degree of ordering of the molecule were observed for endogenous flavin when compared to a single and fast rotational correlation time of 150 ps of free flavin. Quinone significantly altered both the lifetime and rotational characteristics of endogenous flavin suggesting specific interactions of quinones to the endogeneous flavin in the bacterial enzyme.

Time-resolved optical studies of wide-gap II-VI semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Wang, Hong

ZnSe and ZnSe-based quantum well and superlattice structures are potential candidates for light emitting devices and other optical devices such as switches and modulators working in the blue-green wavelength range. Carrier dynamics studies of these structures are important in evaluating device performance as well as understanding the underlying physical processes. In this thesis, a carrier dynamics investigation is conducted for temperature from 77K to 295K on CdZnSSe/ZnSSe single quantum well structure (SQW) and ZnSe/ZnSTe superlattice fabricated by molecular beam epitaxy (MBE). Two experimental techniques with femtosecond time resolution are used in this work: up-conversion technique for time- resolved photoluminescence (PL) and pump-probe technique for time-resolved differential absorption studies. For both heterostructures, the radiative recombination is dominated by exciton transition due to the large exciton binding energy as a result of quantum confinement effect. The measured decay time of free exciton PL in CdZnSSe/ZnSSe SQW increases linearly with increasing temperature which agrees with the theoretical prediction by considering the conservation of momentum requirement for radiative recombination. However, the recombination of free carriers is also observed in CdZnSSe/ZnSSe SQW for the whole temperature range studied. On the other hand, in ZnSe/ZnSTe superlattice structures, the non- radiative recombination processes are non-negligible even at 77K and become more important in higher temperature range. The relaxation processes such as spectral hole burning, carrier thermalization and hot-carrier cooling are observed in ZnSe/ZnSTe superlattices at room temperature (295K) by the femtosecond pump-probe measurements. A rapid cooling of the thermalized hot- carrier from 763K to 450K within 4ps is deduced. A large optical nonlinearity (i.e., the induced absorption change) around the heavy-hole exciton energy is also obtained.

Low pressure-induced secondary structure transitions of regenerated silk fibroin in its wet film studied by time-resolved infrared spectroscopy.

PubMed

He, Zhipeng; Liu, Zhao; Zhou, Xiaofeng; Huang, He

2018-06-01

The secondary structure transitions of regenerated silk fibroin (RSF) under different external perturbations have been studied extensively, except for pressure. In this work, time-resolved infrared spectroscopy with the attenuated total reflectance (ATR) accessory was employed to follow the secondary structure transitions of RSF in its wet film under low pressure. It has been found that pressure alone is favorable only to the formation of β-sheet structure. Under constant pressure there is an optimum amount of D 2 O in the wet film (D 2 O : film = 2:1) so as to provide the optimal condition for the reorganization of the secondary structure and to have the largest formation of β-sheet structure. Under constant amount of D 2 O and constant pressure, the secondary structure transitions of RSF in its wet film can be divided into three stages along with time. In the first stage, random coil, α-helix, and β-turn were quickly transformed into β-sheet. In the second stage, random coil and β-turn were relatively slowly transformed into β-sheet and α-helix, and the content of α-helix was recovered to the value prior to the application of pressure. In the third and final stage, no measurable changes can be found for each secondary structure. This study may be helpful to understand the secondary structure changes of silk fibroin in silkworm's glands under hydrostatic pressure. © 2018 Wiley Periodicals, Inc.

Simulating pump-probe photoelectron and absorption spectroscopy on the attosecond timescale with time-dependent density functional theory.

PubMed

De Giovannini, Umberto; Brunetto, Gustavo; Castro, Alberto; Walkenhorst, Jessica; Rubio, Angel

2013-05-10

Molecular absorption and photoelectron spectra can be efficiently predicted with real-time time-dependent density functional theory. We show herein how these techniques can be easily extended to study time-resolved pump-probe experiments, in which a system response (absorption or electron emission) to a probe pulse is measured in an excited state. This simulation tool helps with the interpretation of fast-evolving attosecond time-resolved spectroscopic experiments, in which electronic motion must be followed at its natural timescale. We show how the extra degrees of freedom (pump-pulse duration, intensity, frequency, and time delay), which are absent in a conventional steady-state experiment, provide additional information about electronic structure and dynamics that improve characterization of a system. As an extension of this approach, time-dependent 2D spectroscopy can also be simulated, in principle, for large-scale structures and extended systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radial Growth of Self-Catalyzed GaAs Nanowires and the Evolution of the Liquid Ga-Droplet Studied by Time-Resolved in Situ X-ray Diffraction.

PubMed

Schroth, Philipp; Jakob, Julian; Feigl, Ludwig; Mostafavi Kashani, Seyed Mohammad; Vogel, Jonas; Strempfer, Jörg; Keller, Thomas F; Pietsch, Ullrich; Baumbach, Tilo

2018-01-10

We report on a growth study of self-catalyzed GaAs nanowires based on time-resolved in situ X-ray structure characterization during molecular-beam-epitaxy in combination with ex situ scanning-electron-microscopy. We reveal the evolution of nanowire radius and polytypism and distinguish radial growth processes responsible for tapering and side-wall growth. We interpret our results using a model for diameter self-stabilization processes during growth of self-catalyzed GaAs nanowires including the shape of the liquid Ga-droplet and its evolution during growth.

Plastique: A synchrotron radiation beamline for time resolved fluorescence in the frequency domain

NASA Astrophysics Data System (ADS)

De Stasio, Gelsomina; Zema, N.; Antonangeli, F.; Savoia, A.; Parasassi, T.; Rosato, N.

1991-06-01

PLASTIQUE is the only synchrotron radiation beamline in the world that performs time resolved fluorescence experiments in frequency domain. These experiments are extremely valuable sources of information on the structure and dynamics of molecules. We describe the beamline and some initial data.

Structural evolution of detonation carbon in Composition B-3 by X-ray scattering

NASA Astrophysics Data System (ADS)

Firestone, Millicent; Dattelbaum, Dana; Gustavsen, Richard; Podlesak, David; Jensen, Brian; Watkins, Erik; Ringstrand, Bryan; Willey, Trevor; Lauderbach, Lisa; Hodgin, Ralph; Bagge-Hansen, Michael; van Buuren, Tony; Graber, Tim

2015-06-01

High explosive detonation products are primarily composed of solid carbon products. Prior electron microscopy studies have revealed that detonation carbon can contain a variety of unique carbon particles possessing novel morphologies, including core-shell, onions and ribbons. Despite these observations very little is known on what conditions leads to the production of novel carbon nanoparticles. A fuller understanding on conditions that generate such novel carbon materials would greatly benefit from time-resolved studies that probe particle formation and evolution through and beyond the chemical reaction zone. Here, we report initial experiments employing time-resolved X-ray scattering measurements to monitor the detonation carbon products formed from Composition B-3 (60% TNT, 40% RDX). Time-resolved SAXS (TRSAXS) studies were performed at the Dynamic Compression Sector (DCS, Sector 35) at the Advanced Photon Source (Argonne National Laboratory). In-situ formation of solid carbon behind the detonation front was probed on the nanosecond time scale. Analysis of the scattering patterns using model independent methods (Porod and Guinier) yielded insights into particle morphology and interfaces.

Wake losses from averaged and time-resolved power measurements at full scale wind turbines

NASA Astrophysics Data System (ADS)

Castellani, Francesco; Astolfi, Davide; Mana, Matteo; Becchetti, Matteo; Segalini, Antonio

2017-05-01

This work deals with the experimental analysis of wake losses fluctuations at full-scale wind turbines. The test case is a wind farm sited on a moderately complex terrain: 4 turbines are installed, having 2 MW of rated power each. The sources of information are the time-resolved data, as collected from the OPC server, and the 10-minutes averaged SCADA data. The objective is to compare the statistical distributions of wake losses for far and middle wakes, as can be observed through the “fast” lens of time-resolved data, for certain selected test-case time series, and through the “slow” lens of SCADA data, on a much longer time basis that allow to set the standards of the mean wake losses along the wind farm. Further, time-resolved data are used for an insight into the spectral properties of wake fluctuations, highlighting the role of the wind turbine as low-pass filter. Summarizing, the wind rose, the layout of the site and the structure of the data sets at disposal allow to study middle and far wake behavior, with a “slow” and “fast” perspective.

Time-Resolved Study of Nanomorphology and Nanomechanic Change of Early-Stage Mineralized Electrospun Poly(lactic acid) Fiber by Scanning Electron Microscopy, Raman Spectroscopy and Atomic Force Microscopy

PubMed Central

Wang, Mengmeng; Cai, Yin; Zhao, Bo; Zhu, Peizhi

2017-01-01

In this study, scanning electron microscopy (SEM), Raman spectroscopy and high-resolution atomic force microscopy (AFM) were used to reveal the early-stage change of nanomorphology and nanomechanical properties of poly(lactic acid) (PLA) fibers in a time-resolved manner during the mineralization process. Electrospun PLA nanofibers were soaked in simulated body fluid (SBF) for different periods of time (0, 1, 3, 5, 7 and 21 days) at 10 °C, much lower than the conventional 37 °C, to simulate the slow biomineralization process. Time-resolved Raman spectroscopy analysis can confirm that apatites were deposited on PLA nanofibers after 21 days of mineralization. However, there is no significant signal change among several Raman spectra before 21 days. SEM images can reveal the mineral deposit on PLA nanofibers during the process of mineralization. In this work, for the first time, time-resolved AFM was used to monitor early-stage nanomorphology and nanomechanical changes of PLA nanofibers. The Surface Roughness and Young’s Modulus of the PLA nanofiber quantitatively increased with the time of mineralization. The electrospun PLA nanofibers with delicate porous structure could mimic the extracellular matrix (ECM) and serve as a model to study the early-stage mineralization. Tested by the mode of PLA nanofibers, we demonstrated that AFM technique could be developed as a potential diagnostic tool to monitor the early onset of pathologic mineralization of soft tissues. PMID:28817096

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

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

Ren, Zhong; Šrajer, Vukica; Knapp, James 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 ormore » 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.« less

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Time resolved flow-field measurements of a turbulent mixing layer over a rectangular cavity

NASA Astrophysics Data System (ADS)

Bian, Shiyao; Driscoll, James F.; Elbing, Brian R.; Ceccio, Steven L.

2011-07-01

High Reynolds number, low Mach number, turbulent shear flow past a rectangular, shallow cavity has been experimentally investigated with the use of dual-camera cinematographic particle image velocimetry (CPIV). The CPIV had a 3 kHz sampling rate, which was sufficient to monitor the time evolution of large-scale vortices as they formed, evolved downstream and impinged on the downstream cavity wall. The time-averaged flow properties (velocity and vorticity fields, streamwise velocity profiles and momentum and vorticity thickness) were in agreement with previous cavity flow studies under similar operating conditions. The time-resolved results show that the separated shear layer quickly rolled-up and formed eddies immediately downstream of the separation point. The vortices convect downstream at approximately half the free-stream speed. Vorticity strength intermittency as the structures approach the downstream edge suggests an increase in the three-dimensionality of the flow. Time-resolved correlations reveal that the in-plane coherence of the vortices decays within 2-3 structure diameters, and quasi-periodic flow features are present with a vortex passage frequency of ~1 kHz. The power spectra of the vertical velocity fluctuations within the shear layer revealed a peak at a non-dimensional frequency corresponding to that predicted using linear, inviscid instability theory.

High-resolution structure, interactions, and dynamics of self-assembled virus-like partilces

NASA Astrophysics Data System (ADS)

Raviv, Uri; Asor, R.; Ben-Shaul, O.; Oppenheim, A.; Schlicksup, L. C.; Seltzer, L.; Jarrold, M. F.; Zlotnick, A.

Using SAXS, in combination with Monte Carlo simulations, and our unique solution x-ray scattering data analysis program, we resolved at high spatial resolution, the manner by which wtSV40 packages its 5.2kb circular DNA about 20 histone octamers in the virus capsid (Figure 1). This structure, known as a mini-chromosome, is highly dynamic and could not be resolved by microscopy methods. Using time-resolved solution SAXS, stopped-flow, and flow-through setups the assembly process of VP1, the major caspid protein of the SV40 virus, with RNA or DNA to form virus-like particles (VLPs) was studied in msec temporal resolution. By mixing the nucleotides and the capsid protein, virus-like particles formed within 35 msec, in the case of RNA that formed T =1 particles, and within 15 seconds in the case of DNA that formed T =7 particles, similar to wt SV40. The structural changes leading to the particle formation were followed in detail. More recently, we have extended this work to study the assembly of HBV virus-like particles.

Time-resolved rhodopsin activation currents in a unicellular expression system.

PubMed Central

Sullivan, J M; Shukla, P

1999-01-01

The early receptor current (ERC) is the charge redistribution occurring in plasma membrane rhodopsin during light activation of photoreceptors. Both the molecular mechanism of the ERC and its relationship to rhodopsin conformational activation are unknown. To investigate whether the ERC could be a time-resolved assay of rhodopsin structure-function relationships, the distinct sensitivity of modern electrophysiological tools was employed to test for flash-activated ERC signals in cells stably expressing normal human rod opsin after regeneration with 11-cis-retinal. ERCs are similar in waveform and kinetics to those found in photoreceptors. The action spectrum of the major R(2) charge motion is consistent with a rhodopsin photopigment. The R(1) phase is not kinetically resolvable and the R(2) phase, which overlaps metarhodopsin-II formation, has a rapid risetime and complex multiexponential decay. These experiments demonstrate, for the first time, kinetically resolved electrical state transitions during activation of expressed visual pigment in a unicellular environment (single or fused giant cells) containing only 6 x 10(6)-8 x 10(7) molecules of rhodopsin. This method improves measurement sensitivity 7 to 8 orders of magnitude compared to other time-resolved techniques applied to rhodopsin to study the role particular amino acids play in conformational activation and the forces that govern those transitions. PMID:10465746

Structure of Quasar Continuum Emission Regions and Cosmology from Optical and X-Ray Microlensing in Gravitationally Lensed Quasars

DTIC Science & Technology

2008-05-02

information is estimated to average 1 hour per response, including g the time for reviewing instructions, searching existing data sources, gathering...their central engines cannot be resolved with ordinary telescopes. Gravitational telescopes, however, provide the necessary resolution to study the...structure of the continuum emission regions at optical and X-ray wavelengths and make time delay estimates in the systems in which sufficient data were

Application of Mythen detector: In-situ XRD study on the thermal expansion behavior of metal indium

NASA Astrophysics Data System (ADS)

Du, Rong; Chen, ZhongJun; Cai, Quan; Fu, JianLong; Gong, Yu; Wu, ZhongHua

2016-07-01

A Mythen detector has been equipped at the beamline 4B9A of Beijing Synchrotron Radiation Facility (BSRF), which is expected to enable BSRF to perform time-resolved measurement of X-ray diffraction (XRD) full-profiles. In this paper, the thermal expansion behavior of metal indium has been studied by using the in-situ XRD technique with the Mythen detector. The indium was heated from 303 to 433 K with a heating rate of 2 K/min. The in-situ XRD full-profiles were collected with a rate of one profile per 10 seconds. Rietveld refinement was used to extract the structural parameters. The results demonstrate that these collected quasi-real-time XRD profiles can be well used for structural analysis. The metal indium was found to have a nonlinear thermal expansion behavior from room temperature to the melting point (429.65 K). The a-axis of the tetragonal unit cell expands with a biquadratic dependency on temperature, while the c-axis contracts with a cubic dependency on temperature. By the time-resolved XRD measurements, it was observed that the [200] preferred orientation can maintain to about 403.15 K. While (110) is the last and detectable crystal plane just before melting of the polycrystalline indium foil. This study is not only beneficial to the application of metal indium, but also exhibits the capacity of in-situ time-resolved XRD measurements at the X-ray diffraction station of BSRF.

Ultrafast photodimerization dynamics in α-cyano-4-hydroxycinnamic and sinapinic acid crystals

NASA Astrophysics Data System (ADS)

Hoyer, Theo; Tuszynski, Wilfried; Lienau, Christoph

2007-07-01

We report a sub-picosecond time-resolved fluorescence spectroscopic study of different cinnamic acid crystals, model systems for solid-state photodimerization reactions. For α-cyano-4-hydroxycinnamic acid (α-CHC), we identify the emission spectra of both monomers and dimers, allowing us to directly probe the photoinduced dynamics of both species. The dimerization occurs on a timescale of 10 ps and results in a long-lived dimer product, stable for hours. For sinapinic acid, we find an extremely fast, sub-picosecond dimerization reaction and a short-lived dimer. This first sub-picosecond time-resolved dimerization study in cinnamic acid crystals provides a new basis for relating their structural properties and microscopic reaction dynamics.

Non-Destructive Study of Bulk Crystallinity and Elemental Composition of Natural Gold Single Crystal Samples by Energy-Resolved Neutron Imaging

PubMed Central

Tremsin, Anton S.; Rakovan, John; Shinohara, Takenao; Kockelmann, Winfried; Losko, Adrian S.; Vogel, Sven C.

2017-01-01

Energy-resolved neutron imaging enables non-destructive analyses of bulk structure and elemental composition, which can be resolved with high spatial resolution at bright pulsed spallation neutron sources due to recent developments and improvements of neutron counting detectors. This technique, suitable for many applications, is demonstrated here with a specific study of ~5–10 mm thick natural gold samples. Through the analysis of neutron absorption resonances the spatial distribution of palladium (with average elemental concentration of ~0.4 atom% and ~5 atom%) is mapped within the gold samples. At the same time, the analysis of coherent neutron scattering in the thermal and cold energy regimes reveals which samples have a single-crystalline bulk structure through the entire sample volume. A spatially resolved analysis is possible because neutron transmission spectra are measured simultaneously on each detector pixel in the epithermal, thermal and cold energy ranges. With a pixel size of 55 μm and a detector-area of 512 by 512 pixels, a total of 262,144 neutron transmission spectra are measured concurrently. The results of our experiments indicate that high resolution energy-resolved neutron imaging is a very attractive analytical technique in cases where other conventional non-destructive methods are ineffective due to sample opacity. PMID:28102285

Resolving Structural Isomers of Monosaccharide Methyl Glycosides Using Drift Tube and Traveling Wave Ion Mobility Mass Spectrometry

PubMed Central

Li, Hongli; Giles, Kevin; Bendiak, Brad; Kaplan, Kimberly; Siems, William F.; Hill, Herbert H.

2013-01-01

Monosaccharide structural isomers including sixteen methyl-D-glycopyranosides and four methyl-N-acetylhexosamines were subjected to ion mobility measurements by electrospray ion mobility mass spectrometry. Two ion mobility-MS systems were employed: atmospheric pressure drift tube ion mobility time-of-flight mass spectrometry and a Synapt G2 HDMS system which incorporates a low pressure traveling wave ion mobility separator. All the compounds were investigated as [M+Na]+ ions in the positive mode. A majority of the monosaccharide structural isomers exhibited different mobility drift times in either system, depending on differences in their anomeric and stereochemical configurations. In general, drift time patterns (relative drift times of isomers) matched between the two instruments. Higher resolving power was observed using the atmospheric pressure drift tube. Collision cross section values of monosaccharide structural isomers were directly calculated from the atmospheric pressure ion mobility experiments and a collision cross section calibration curve was made for the traveling wave ion mobility instrument. Overall, it was demonstrated that ion mobility-mass spectrometry using either drift tube or traveling wave ion mobility is a valuable technique for resolving subtle variations in stereochemistry among the sodium adducts of monosaccharide methyl glycosides. PMID:22339760

Pulsed-High Field/High-Frequency EPR Spectroscopy

NASA Astrophysics Data System (ADS)

Fuhs, Michael; Moebius, Klaus

Pulsed high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is used to disentangle many kinds of different effects often obscured in continuous wave (cw) EPR spectra at lower magnetic fields/microwave frequencies. While the high magnetic field increases the resolution of G tensors and of nuclear Larmor frequencies, the high frequencies allow for higher time resolution for molecular dynamics as well as for transient paramagnetic intermediates studied with time-resolved EPR. Pulsed EPR methods are used for example for relaxation-time studies, and pulsed Electron Nuclear DOuble Resonance (ENDOR) is used to resolve unresolved hyperfine structure hidden in inhomogeneous linewidths. In the present article we introduce the basic concepts and selected applications to structure and mobility studies on electron transfer systems, reaction centers of photosynthesis as well as biomimetic models. The article concludes with an introduction to stochastic EPR which makes use of an other concept for investigating resonance systems in order to increase the excitation bandwidth of pulsed EPR. The limited excitation bandwidth of pulses at high frequency is one of the main limitations which, so far, made Fourier transform methods hardly feasible.

Surface and interface effects on non-radiative exciton recombination and relaxation dynamics in CdSe/Cd,Zn,S nanocrystals

NASA Astrophysics Data System (ADS)

Walsh, Brenna R.; Saari, Jonathan I.; Krause, Michael M.; Nick, Robert; Coe-Sullivan, Seth; Kambhampati, Patanjali

2016-06-01

Excitonic state-resolved pump/probe spectroscopy and time correlate single photon counting were used to study exciton dynamics from the femtosecond to nanosecond time scales in CdSe/Cd,Zn,S nanocrystals. These measurements reveal the role of the core/shell interface as well as surface on non-radiative excitonic processes over three time regimes. Time resolved photoluminescence reports on how the interface controls slow non-radiative processes that dictate emission at the single excitonic level. Heterogeneity in decay is minimized by interfacial structure. Pump/probe measurements explore the non-radiative multiexcitonic recombination processes on the picosecond timescale. These Auger based non-radiative processes dictate lifetimes of multiexcitonic states. Finally state-resolved pump/probe measurements on the femtosecond timescale reveal the influence of the interface on electron and hole relaxation dynamics. We find that the interface has a profound influence on all three types of non-radiative processes which ultimately control light emission from nanocrystals.

Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL

PubMed Central

Obara, Yuki; Ito, Hironori; Ito, Terumasa; Kurahashi, Naoya; Thürmer, Stephan; Tanaka, Hiroki; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yamamoto, Yo-ichi; Karashima, Shutaro; Nishitani, Junichi; Yabashi, Makina; Suzuki, Toshinori; Misawa, Kazuhiko

2017-01-01

The charge-carrier dynamics of anatase TiO2 nanoparticles in an aqueous solution were studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser in combination with a synchronized ultraviolet femtosecond laser (268 nm). Using an arrival time monitor for the X-ray pulses, we obtained a temporal resolution of 170 fs. The transient X-ray absorption spectra revealed an ultrafast Ti K-edge shift and a subsequent growth of a pre-edge structure. The edge shift occurred in ca. 100 fs and is ascribed to reduction of Ti by localization of generated conduction band electrons into shallow traps of self-trapped polarons or deep traps at penta-coordinate Ti sites. Growth of the pre-edge feature and reduction of the above-edge peak intensity occur with similar time constants of 300–400 fs, which we assign to the structural distortion dynamics near the surface. PMID:28713842

Structural phase transitions and time-resolved dynamics of solid-supported interfacial methanol observed by reflection electron diffraction

NASA Astrophysics Data System (ADS)

Yang, Ding-Shyue; He, Xing; Wu, Chengyi

Due to their large scattering cross sections with matter, electrons are suitable for contactless probing of solid-supported surface assemblies, especially in a reflection geometry. Direct visualization of assembly structures through electron diffraction further enables studies of ultrafast structural dynamics through the pump-probe scheme as well as discoveries of hidden phase changes in equilibrium that have been obscure in spectroscopic measurements. In this presentation, we report our first observation of unique two-stage transformations of interfacial methanol on smooth hydrophobic surfaces. The finding may reconcile the inconsistent previous reports of the crystallization temperature using various indirect methods. Dynamically, energy transfer across a solid-molecule interface following photoexcitation of the substrate is found to be highly dependent on the structure of interfacial methanol. If it is only 2-dimensionally ordered, as the film thickness increases, a prolonged time in the decrease of diffraction intensity is seen, signifying an inefficient vibrational coupling in the surface normal direction. Implications of the dynamics results and an outlook of interfacial studies using time-resolved and averaged electron diffraction will be discussed. We gratefully acknowledge the support from the R. A. Welch Foundation (Grant No. E-1860), the Donors of the American Chemical Society Petroleum Research Fund (ACS-PRF), and the University of Houston.

Spectro-Interferometry Studies of Velocity-Related Phenomena at the Surface of Stars: Pulsation and Rotation

NASA Astrophysics Data System (ADS)

Mérand, Antoine; Patru, Fabien; Aufdenberg, Jason

We illustrate here two applications of spectro-interferometry to the study of velocity fields at the surface of stars: pulsation and rotation. Stellar pulsation has been resolved spectroscopically for a long time, and interferometry has resolved stellar diameters variations due to pulsation. Combining the two provides unique insights to the study of Cepheids, in particular regarding the structure of the photosphere or investigating the infamous projection factor which biases distances measured by the Baade-Wesselink method. On the other hand, resolving the surface velocity field of rotating stars offers a unique opportunity to potentially study differential rotation in other cases than for the Sun. We also present the model we have implemented recently, as well as two applications to VLTI/AMBER Data: the pulsation of Cepheids and the rotation of intermediate mass main sequence stars.

Time-resolved fluorescence spectroscopy of human brain tumors

NASA Astrophysics Data System (ADS)

Marcu, Laura; Thompson, Reid C.; Garde, Smita; Sedrak, Mark; Black, Keith L.; Yong, William H.

2002-05-01

Fluorescence spectroscopy of the endogenous emission of brain tumors has been researched as a potentially important method for the intraoperative localization of brain tumor margins. In this study, we investigate the use of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) for demarcation of primary brain tumors by studying the time-resolved spectra of gliomas of different histologic grades. Time-resolved fluorescence (3 ns, 337 nm excitation) from excised human brain tumor show differences between the time-resolved emission of malignant glioma and normal brain tissue (gray and white matter). Our findings suggest that brain tumors can be differentiated from normal brain tissue based upon unique time-resolved fluorescence signature.

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

Kim, Jeongho; Kim, Kyung Hwan; Oang, Key Young

Characterization of transient molecular structures formed during chemical and biological processes is essential for understanding their mechanisms and functions. Over the last decade, time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TRXAS) have emerged as powerful techniques for molecular and electronic structural analysis of photoinduced reactions in the solution phase. Both techniques make use of a pump–probe scheme that consists of (1) an optical pump pulse to initiate a photoinduced process and (2) an X-ray probe pulse to monitor changes in the molecular structure as a function of time delay between pump and probe pulses. TRXL is sensitive tomore » changes in the global molecular structure and therefore can be used to elucidate structural changes of reacting solute molecules as well as the collective response of solvent molecules. On the other hand, TRXAS can be used to probe changes in both local geometrical and electronic structures of specific X-ray-absorbing atoms due to the element-specific nature of core-level transitions. These techniques are complementary to each other and a combination of the two methods will enhance the capability of accurately obtaining structural changes induced by photoexcitation. Here we review the principles of TRXL and TRXAS and present recent application examples of the two methods for studying chemical and biological processes in solution. Furthermore, we briefly discuss the prospect of using X-ray free electron lasers for the two techniques, which will allow us to keep track of structural dynamics on femtosecond time scales in various solution-phase molecular reactions.« less

An algorithm for localization of optical disturbances in turbid media using time-resolved diffuse optical tomography

NASA Astrophysics Data System (ADS)

Potlov, A. Yu.; Frolov, S. V.; Proskurin, S. G.

2018-04-01

Optical structure disturbances localization algorithm for time-resolved diffuse optical tomography of biological objects is described. The key features of the presented algorithm are: the initial approximation for the spatial distribution of the optical characteristics based on the Homogeneity Index and the assumption that all the absorbing and scattering inhomogeneities in an investigated object are spherical and have the same absorption and scattering coefficients. The described algorithm can be used in the brain structures diagnosis, in traumatology and optical mammography.

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. .

Photogenerated radical intermediates of vitamin K 1: a time-resolved resonance Raman study

NASA Astrophysics Data System (ADS)

Balakrishnan, G.; Umapathy, S.

1999-01-01

Quinones play a vital role in the process of electron transfer in bacterial photosynthetic reaction centers. It is of interest to investigate the photochemical reactions involving quinones with a view to elucidating the structure-function relationships in the biological processes. Resonance Raman spectra of radical anions and the time-resolved resonance Raman spectra of vitamin K 1 (model compound for Q A in Rhodopseudomonas viridis, a bacterial photosynthetic reception center) are presented. The photochemical intermediates of vitamin K 1, viz. radical anion, ketyl radical and o-quinone methide have been identified. The vibrational assignments of all these intermediates are made on the basis of comparison with our earlier TR3 studies on radical anions of naphthoquinone and menaquinone.

Time resolved PIV and flow visualization of 3D sheet cavitation

NASA Astrophysics Data System (ADS)

Foeth, E. J.; van Doorne, C. W. H.; van Terwisga, T.; Wieneke, B.

2006-04-01

Time-resolved PIV was applied to study fully developed sheet cavitation on a hydrofoil with a spanwise varying angle of attack. The hydrofoil was designed to have a three-dimensional cavitation pattern closely related to propeller cavitation, studied for its adverse effects as vibration, noise, and erosion production. For the PIV measurements, fluorescent tracer particles were applied in combination with an optical filter, in order to remove the reflections of the laser lightsheet by the cavitation. An adaptive mask was developed to find the interface between the vapor and liquid phase. The velocity at the interface of the cavity was found to be very close to the velocity predicted by a simple streamline model. For a visualization of the global flow dynamics, the laser beam was expanded and used to illuminate the entire hydrofoil and cavitation structure. The time-resolved recordings reveal the growth of the attached cavity and the cloud shedding. Our investigation proves the viability of accurate PIV measurements around developed sheet cavitation. The presented results will further be made available as a benchmark for the validation of numerical simulations of this complicated flow.

Assessment of swirl spray interaction in lab scale combustor using time-resolved measurements

NASA Astrophysics Data System (ADS)

Rajamanickam, Kuppuraj; Jain, Manish; Basu, Saptarshi

2017-11-01

Liquid fuel injection in highly turbulent swirling flows becomes common practice in gas turbine combustors to improve the flame stabilization. It is well known that the vortex bubble breakdown (VBB) phenomenon in strong swirling jets exhibits complicated flow structures in the spatial domain. In this study, the interaction of hollow cone liquid sheet with such coaxial swirling flow field has been studied experimentally using time-resolved measurements. In particular, much attention is focused towards the near field breakup mechanism (i.e. primary atomization) of liquid sheet. The detailed swirling gas flow field characterization is carried out using time-resolved PIV ( 3.5 kHz). Furthermore, the complicated breakup mechanisms and interaction of the liquid sheet are imaged with the help of high-speed shadow imaging system. Subsequently, proper orthogonal decomposition (POD) and dynamic mode decomposition (DMD) is implemented over the instantaneous data sets to retrieve the modal information associated with the interaction dynamics. This helps to delineate more quantitative nature of interaction process between the liquid sheet and swirling gas phase flow field.

Simulation of multi-photon emission isotopes using time-resolved SimSET multiple photon history generator

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

Chiang, Chih-Chieh; Lin, Hsin-Hon; Lin, Chang-Shiun

Abstract-Multiple-photon emitters, such as In-111 or Se-75, have enormous potential in the field of nuclear medicine imaging. For example, Se-75 can be used to investigate the bile acid malabsorption and measure the bile acid pool loss. The simulation system for emission tomography (SimSET) is a well-known Monte Carlo simulation (MCS) code in nuclear medicine for its high computational efficiency. However, current SimSET cannot simulate these isotopes due to the lack of modeling of complex decay scheme and the time-dependent decay process. To extend the versatility of SimSET for simulation of those multi-photon emission isotopes, a time-resolved multiple photon history generatormore » based on SimSET codes is developed in present study. For developing the time-resolved SimSET (trSimSET) with radionuclide decay process, the new MCS model introduce new features, including decay time information and photon time-of-flight information, into this new code. The half-life of energy states were tabulated from the Evaluated Nuclear Structure Data File (ENSDF) database. The MCS results indicate that the overall percent difference is less than 8.5% for all simulation trials as compared to GATE. To sum up, we demonstrated that time-resolved SimSET multiple photon history generator can have comparable accuracy with GATE and keeping better computational efficiency. The new MCS code is very useful to study the multi-photon imaging of novel isotopes that needs the simulation of lifetime and the time-of-fight measurements. (authors)« less

Unravelling the mysteries of sub-second biochemical processes using time-resolved mass spectrometry.

PubMed

Lento, Cristina; Wilson, Derek J

2017-05-21

Many important chemical and biochemical phenomena proceed on sub-second time scales before entering equilibrium. In this mini-review, we explore the history and recent advancements of time-resolved mass spectrometry (TRMS) for the characterization of millisecond time-scale chemical reactions and biochemical processes. TRMS allows for the simultaneous tracking of multiple reactants, intermediates and products with no chromophoric species required, high sensitivity and temporal resolution. The method has most recently been used for the characterization of several short-lived reaction intermediates in rapid chemical reactions. Most of the reactions that occur in living organisms are accelerated by enzymes, with pre-steady state kinetics only attainable using time-resolved methods. TRMS has been increasingly used to monitor the conversion of substrates to products and the resulting changes to the enzyme during catalytic turnover. Early events in protein folding systems have also been elucidated, along with the characterization of dynamics and transient secondary structures in intrinsically disordered proteins. In this review, we will highlight representative examples where TRMS has been applied to study these phenomena.

Capturing Structural Snapshots during Photochemical Reactions with Ultrafast Raman Spectroscopy: From Materials Transformation to Biosensor Responses.

PubMed

Fang, Chong; Tang, Longteng; Oscar, Breland G; Chen, Cheng

2018-06-21

Chemistry studies the composition, structure, properties, and transformation of matter. A mechanistic understanding of the pertinent processes is required to translate fundamental knowledge into practical applications. The current development of ultrafast Raman as a powerful time-resolved vibrational technique, particularly femtosecond stimulated Raman spectroscopy (FSRS), has shed light on the structure-energy-function relationships of various photosensitive systems. This Perspective reviews recent work incorporating optical innovations, including the broad-band up-converted multicolor array (BUMA) into a tunable FSRS setup, and demonstrates its resolving power to watch metal speciation and photolysis, leading to high-quality thin films, and fluorescence modulation of chimeric protein biosensors for calcium ion imaging. We discuss advantages of performing FSRS in the mixed time-frequency domain and present strategies to delineate mechanisms by tracking low-frequency modes and systematically modifying chemical structures with specific functional groups. These unique insights at the chemical-bond level have started to enable the rational design and precise control of functional molecular machines in optical, materials, energy, and life sciences.

Fast Fenton footprinting: a laboratory-based method for the time-resolved analysis of DNA, RNA and proteins

PubMed Central

Shcherbakova, Inna; Mitra, Somdeb; Beer, Robert H.; Brenowitz, Michael

2006-01-01

‘Footprinting’ describes assays in which ligand binding or structure formation protects polymers such as nucleic acids and proteins from either cleavage or modification; footprinting allows the accessibility of individual residues to be mapped in solution. Equilibrium and time-dependent footprinting links site-specific structural information with thermodynamic and kinetic transitions. The hydroxyl radical (·OH) is a particularly valuable footprinting probe by virtue of it being among the most reactive of chemical oxidants; it reports the solvent accessibility of reactive sites on macromolecules with as fine as a single residue resolution. A novel method of millisecond time-resolved ·OH footprinting has been developed based on the Fenton reaction, Fe(II) + H2O2 → Fe(III) + ·OH + OH−. This method can be implemented in laboratories using widely available three-syringe quench flow mixers and inexpensive reagents to study local changes in the solvent accessibility of DNA, RNA and proteins associated with their biological function. PMID:16582097

Low temperature time resolved photoluminescence in ordered and disordered Cu2ZnSnS4 single crystals

NASA Astrophysics Data System (ADS)

Raadik, Taavi; Krustok, Jüri; Kauk-Kuusik, M.; Timmo, K.; Grossberg, M.; Ernits, K.; Bleuse, J.

2017-03-01

In this work we performed time-resolved micro-photoluminescence (TRPL) studies of Cu2ZnSnS4 (CZTS) single crystals grown in molten KI salt. The order/disorder degree of CZTS was varied by the thermal post treatment temperature. Photoluminescence spectra measured at T=8 K showed an asymmetric band with a peak position of 1.33 eV and 1.27 eV for partially ordered and disordered structures, respectively. Thermal activation energies were found to be ET (PO) =65±9 meV for partially ordered and ET (PD) =27±4 meV for partially disordered. These low activation energy values indicating to the defect cluster recombination model for both partially ordered and disordered structures. TRPL was measured for both crystals and their decay curves were fitted with a stretched exponential function, in order to describe the charge carriers' recombination dynamics at low temperature.

New developments in laser-based photoemission spectroscopy and its scientific applications: a key issues review

NASA Astrophysics Data System (ADS)

Zhou, Xingjiang; He, Shaolong; Liu, Guodong; Zhao, Lin; Yu, Li; Zhang, Wentao

2018-06-01

The significant progress in angle-resolved photoemission spectroscopy (ARPES) in last three decades has elevated it from a traditional band mapping tool to a precise probe of many-body interactions and dynamics of quasiparticles in complex quantum systems. The recent developments of deep ultraviolet (DUV, including ultraviolet and vacuum ultraviolet) laser-based ARPES have further pushed this technique to a new level. In this paper, we review some latest developments in DUV laser-based photoemission systems, including the super-high energy and momentum resolution ARPES, the spin-resolved ARPES, the time-of-flight ARPES, and the time-resolved ARPES. We also highlight some scientific applications in the study of electronic structure in unconventional superconductors and topological materials using these state-of-the-art DUV laser-based ARPES. Finally we provide our perspectives on the future directions in the development of laser-based photoemission systems.

A near-infrared, optical, and ultraviolet polarimetric and timing investigation of complex equatorial dusty structures

NASA Astrophysics Data System (ADS)

Marin, F.; Rojas Lobos, P. A.; Hameury, J. M.; Goosmann, R. W.

2018-05-01

Context. From stars to active galactic nuclei, many astrophysical systems are surrounded by an equatorial distribution of dusty material that is, in a number of cases, spatially unresolved even with cutting edge facilities. Aims: In this paper, we investigate if and how one can determine the unresolved and heterogeneous morphology of dust distribution around a central bright source using time-resolved polarimetric observations. Methods: We used polarized radiative transfer simulations to study a sample of circumnuclear dusty morphologies. We explored a grid of geometrically variable models that are uniform, fragmented, and density stratified in the near-infrared, optical, and ultraviolet bands, and we present their distinctive time-dependent polarimetric signatures. Results: As expected, varying the structure of the obscuring equatorial disk has a deep impact on the inclination-dependent flux, polarization degree and angle, and time lags we observe. We find that stratified media are distinguishable by time-resolved polarimetric observations, and that the expected polarization is much higher in the infrared band than in the ultraviolet. However, because of the physical scales imposed by dust sublimation, the average time lags of months to years between the total and polarized fluxes are important; these time lags lengthens the observational campaigns necessary to break more sophisticated, and therefore also more degenerated, models. In the ultraviolet band, time lags are slightly shorter than in the infrared or optical bands, and, coupled to lower diluting starlight fluxes, time-resolved polarimetry in the UV appears more promising for future campaigns. Conclusions: Equatorial dusty disks differ in terms of inclination-dependent photometric, polarimetric, and timing observables, but only the coupling of these different markers can lead to inclination-independent constraints on the unresolved structures. Even though it is complex and time consuming, polarized reverberation mapping in the ultraviolet-blue band is probably the best technique to rely on in this field.

Watching a signaling protein function in real time via 100-ps time-resolved Laue crystallography

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

Schotte, Friedrich; Cho, Hyun Sun; Kaila, Ville R.I.

2012-11-06

To understand how signaling proteins function, it is necessary to know the time-ordered sequence of events that lead to the signaling state. We recently developed on the BioCARS 14-IDB beamline at the Advanced Photon Source the infrastructure required to characterize structural changes in protein crystals with near-atomic spatial resolution and 150-ps time resolution, and have used this capability to track the reversible photocycle of photoactive yellow protein (PYP) following trans-to-cis photoisomerization of its p-coumaric acid (pCA) chromophore over 10 decades of time. The first of four major intermediates characterized in this study is highly contorted, with the pCA carbonyl rotatedmore » nearly 90° out of the plane of the phenolate. A hydrogen bond between the pCA carbonyl and the Cys69 backbone constrains the chromophore in this unusual twisted conformation. Density functional theory calculations confirm that this structure is chemically plausible and corresponds to a strained cis intermediate. This unique structure is short-lived (~600 ps), has not been observed in prior cryocrystallography experiments, and is the progenitor of intermediates characterized in previous nanosecond time-resolved Laue crystallography studies. The structural transitions unveiled during the PYP photocycle include trans/cis isomerization, the breaking and making of hydrogen bonds, formation/relaxation of strain, and gated water penetration into the interior of the protein. This mechanistically detailed, near-atomic resolution description of the complete PYP photocycle provides a framework for understanding signal transduction in proteins, and for assessing and validating theoretical/computational approaches in protein biophysics.« less

Time Resolved Spectroscopic Studies on a Novel Synthesized Photo-Switchable Organic Dyad and Its Nanocomposite Form in Order to Develop Light Energy Conversion Devices.

PubMed

Dutta Pal, Gopa; Paul, Abhijit; Yadav, Somnath; Bardhan, Munmun; De, Asish; Chowdhury, Joydeep; Jana, Aindrila; Ganguly, Tapan

2015-08-01

UV-vis absorption, steady state and time resolved spectroscopic investigations in pico and nanosecond time domain were made in the different environments on a novel synthesized dyad, 3-(2-methoxynaphthalen-1-yl)-1-(4-methoxyphenyl)prop-2-en-1-one (MNTMA) in its pristine form and when combined with gold (Au) nanoparticles i.e., in its nanocomposite structure. Both steady state and time resolved measurements coupled with the DFT calculations performed by using Gaussian 03 suit of software operated in the linux operating system show that though the dyad exhibits mainly the folded conformation in the ground state but on photoexcitation the nanocomposite form of dyad prefers to be in elongated structure in the excited state indicating its photoswitchable nature. Due to the predominancy of elongated isomeric form of the dyad in the excited state in presence of Au Nps, it appears that the dyad MNTMA may behave as a good light energy converter specially in its nanocomposite form. As larger charge separation rate (kcs ~ 4 x 10(8) s-1) is found relative to the rate associated with the energy wasting charge recombination processes (kcR ~ 3 x 10(5) s-1) in the nanocomposite form of the dyad, it demonstrates the suitability of constructing the efficient light energy conversion devices with Au-dyad hybrid nanomaterials.

On the Resolvability of Steam Assisted Gravity Drainage Reservoirs Using Time-Lapse Gravity Gradiometry

NASA Astrophysics Data System (ADS)

Elliott, E. Judith; Braun, Alexander

2017-11-01

Unconventional heavy oil resource plays are important contributors to oil and gas production, as well as controversial for posing environmental hazards. Monitoring those reservoirs before, during, and after operations would assist both the optimization of economic benefits and the mitigation of potential environmental hazards. This study investigates how gravity gradiometry using superconducting gravimeters could resolve depletion areas in steam assisted gravity drainage (SAGD) reservoirs. This is achieved through modelling of a SAGD reservoir at 1.25 and 5 years of operation. Specifically, the density change structure identified from geological, petrological, and seismic observations is forward modelled for gravity and gradients. Three main parameters have an impact on the resolvability of bitumen depletion volumes and are varied through a suitable parameter space: well pair separation, depth to the well pairs, and survey grid sampling. The results include a resolvability matrix, which identifies reservoirs that could benefit from time-lapse gravity gradiometry monitoring. After 1.25 years of operation, during the rising phase, the resolvable maximum reservoir depth ranges between the surface and 230 m, considering a well pair separation between 80 and 200 m. After 5 years of production, during the spreading phase, the resolvability of depletion volumes around single well pairs is greatly compromised as the depletion volume is closer to the surface, which translates to a larger portion of the gravity signal. The modelled resolvability matrices were derived from visual inspection and spectral analysis of the gravity gradient signatures and can be used to assess the applicability of time-lapse gradiometry to monitor reservoir density changes.

Possibilities for serial femtosecond crystallography sample delivery at future light sourcesa)

PubMed Central

Chavas, L. M. G.; Gumprecht, L.; Chapman, H. N.

2015-01-01

Serial femtosecond crystallography (SFX) uses X-ray pulses from free-electron laser (FEL) sources that can outrun radiation damage and thereby overcome long-standing limits in the structure determination of macromolecular crystals. Intense X-ray FEL pulses of sufficiently short duration allow the collection of damage-free data at room temperature and give the opportunity to study irreversible time-resolved events. SFX may open the way to determine the structure of biological molecules that fail to crystallize readily into large well-diffracting crystals. Taking advantage of FELs with high pulse repetition rates could lead to short measurement times of just minutes. Automated delivery of sample suspensions for SFX experiments could potentially give rise to a much higher rate of obtaining complete measurements than at today's third generation synchrotron radiation facilities, as no crystal alignment or complex robotic motions are required. This capability will also open up extensive time-resolved structural studies. New challenges arise from the resulting high rate of data collection, and in providing reliable sample delivery. Various developments for fully automated high-throughput SFX experiments are being considered for evaluation, including new implementations for a reliable yet flexible sample environment setup. Here, we review the different methods developed so far that best achieve sample delivery for X-ray FEL experiments and present some considerations towards the goal of high-throughput structure determination with X-ray FELs. PMID:26798808

Microscopic observation of carrier-transport dynamics in quantum-structure solar cells using a time-of-flight technique

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

Toprasertpong, Kasidit; Fujii, Hiromasa; Sugiyama, Masakazu

2015-07-27

In this study, we propose a carrier time-of-flight technique to evaluate the carrier transport time across a quantum structure in an active region of solar cells. By observing the time-resolved photoluminescence signal with a quantum-well probe inserted under the quantum structure at forward bias, the carrier transport time can be efficiently determined at room temperature. The averaged drift velocity shows linear dependence on the internal field, allowing us to estimate the quantum structure as a quasi-bulk material with low effective mobility containing the information of carrier dynamics. We show that this direct and real-time observation is more sensitive to carriermore » transport than other conventional techniques, providing better insights into microscopic carrier transport dynamics to overcome a device design difficulty.« less

Time-Resolved X-Ray Magnetic Circular Dichroism - A Selective Probe of Magnetization Dynamics on Nanosecond Timescales

NASA Astrophysics Data System (ADS)

Pizzini, Stefania; Vogel, Jan; Bonfim, Marlio; Fontaine, Alain

Many synchrotron radiation techniques have been developed in the last 15 years for studying the magnetic properties of thin-film materials. The most attractive properties of synchrotron radiation are its energy tunability and its time structure. The first property allows measurements in resonant conditions at an absorption edge of each of the magnetic elements constituting the probed sample, and the latter allows time-resolved measurements on subnanosecond timescales. In this review, we introduce some of the synchrotron-based techniques used for magnetic investigations. We then describe in detail X-ray magnetic circular dichroism (XMCD) and how time-resolved XMCD studies can be carried out in the pump-probe mode. Finally, we illustrate some applications to magnetization reversal dynamics in spin valves and tunnel junctions, using fast magnetic field pulses applied along the easy magnetization axis of the samples. Thanks to the element-selectivity of X-ray absorption spectroscopy, the magnetization dynamics of the soft (Permalloy) and the hard (cobalt) layers can be studied independently. In the case of spin valves, this allowed us to show that two magnetic layers that are strongly coupled in a static regime can become uncoupled on nanosecond timescales.Present address: Universidade Federal do Paraná, Centro Politécnico CP 19011, Curitiba - PR CEP 81531-990, Brazil

Time-resolved x-ray diffraction and Raman studies of the phase transition mechanisms of methane hydrate

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

Hirai, Hisako, E-mail: hirai@sci.ehime-u.ac.jp; Kadobayashi, Hirokazu; Hirao, Naohisa

The mechanisms by which methane hydrate transforms from an sI to sH structure and from an sH to filled-ice Ih structure were examined using time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device camera observation under fixed pressure conditions. The XRD data obtained for the sI–sH transition at 0.8 GPa revealed an inverse correlation between sI and sH, suggesting that the sI structure is replaced by sH. Meanwhile, the Raman analysis demonstrated that although the 12-hedra of sI are retained, the 14-hedra are replaced sequentially by additional 12-hedra, modified 12-hedra, and 20-hedra cages of sH. With themore » sH to filled-ice Ih transition at 1.8 GPa, both the XRD and Raman data showed that this occurs through a sudden collapse of the sH structure and subsequent release of solid and fluid methane that is gradually incorporated into the filled-ice Ih to complete its structure. This therefore represents a typical reconstructive transition mechanism.« less

Time Resolved Digital PIV Measurements of Flow Field Cyclic Variation in an Optical IC Engine

NASA Astrophysics Data System (ADS)

Jarvis, S.; Justham, T.; Clarke, A.; Garner, C. P.; Hargrave, G. K.; Halliwell, N. A.

2006-07-01

Time resolved digital particle image velocimetry (DPIV) experimental data is presented for the in-cylinder flow field development of a motored four stroke spark ignition (SI) optical internal combustion (IC) engine. A high speed DPIV system was employed to quantify the velocity field development during the intake and compression stroke at an engine speed of 1500 rpm. The results map the spatial and temporal development of the in-cylinder flow field structure allowing comparison between traditional ensemble average and cycle average flow field structures. Conclusions are drawn with respect to engine flow field cyclic variations.

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

DOE PAGES

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro; ...

2017-02-08

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Elucidating light-induced charge accumulation in an artificial analogue of methane monooxygenase enzymes using time-resolved X-ray absorption spectroscopy

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

Moonshiram, Dooshaye; Picon, Antonio; Vazquez-Mayagoitia, Alvaro

Here, we report the use of time-resolved X-ray absorption spectroscopy in the ns–μs time scale to track the light induced two electron transfer processes in a multi-component photocatalytic system, consisting of [Ru(bpy) 3] 2+/ a diiron(III,III) model/triethylamine. EXAFS analysis with DFT calculations confirms the structural configurations of the diiron(III,III) and reduced diiron(II,II) states.

Quasiparticle dynamics across the full Brillouin zone of Bi 2Sr 2CaCu 2O 8+δ traced with ultrafast time and angle-resolved photoemission spectroscopy

DOE PAGES

Dakovski, Georgi L.; Durakiewicz, Tomasz; Zhu, Jian-Xin; ...

2015-10-12

A hallmark in the cuprate family of high-temperature superconductors is the nodal-antinodal dichotomy. In this regard, angle-resolved photoemission spectroscopy (ARPES) has proven especially powerful, providing band structure information directly in energy-momentum space. Time-resolved ARPES (trARPES) holds great promise of adding ultrafast temporal information, in an attempt to identify different interaction channels in the time domain. Previous studies of the cuprates using trARPES were handicapped by the low probing energy which significantly limits the accessible momentum space. Using 20.15eV, 12 fs pulses we show for the first time the evolution of quasiparticles in the antinodal region of Bi 2Sr 2CaCu 2Omore » 8+δ and demonstrate that nonmonotonic relaxation dynamics dominates above a certain fluence threshold. The dynamics is heavily influenced by transient modification of the electron-phonon interaction and phase space restrictions, in severe contrast to the monotonic relaxation in the nodal and off-nodal regions.« less

Spectral and time-resolved studies on ocular structures

NASA Astrophysics Data System (ADS)

Schweitzer, D.; Jentsch, S.; Schenke, S.; Hammer, M.; Biskup, C.; Gaillard, E.

2007-07-01

Measurements of endogeous fluorophores open the possibility for evaluation of metabolic state at the eye. For interpretation of 2-dimensional measurements of time-resolved auto fluorescence in 2 separate spectral ranges at the human eye, comparing measurements were performed on porcine eyes. Determining excitation and emission spectra, attention was drawn of proof of coenzymes NADH and FAD in isolated anatomical structures cornea, aqueous humor, lens, vitreous, neuronal retina, retinal pigment epithelium (RPE), choroid, and sclera. All these structures exhibit auto fluorescence, highest in lens. Excitation at 350 nm results in local fluorescence maxima at 460 nm, corresponding to NADH, in all structures. This short-wave excitation allows metabolic studies only at the anterior eye, because of the limited transmission of the ocular media. During excitation at 446 nm the existence of FAD is expressed by local fluorescence maxima at 530 nm. The composition fluorescence spectra allow no discrimination between single ocular structures. Approximating the dynamic fluorescence by a double exponential function, the shortest lifetimes were detected in RPE and neuronal retina. The histograms of mean lifetime t M cover each other on lens with cornea and also on sclera with choroid. Despite the lifetimes are close between RPE and neuronal retina, the relative contributions Q I are wide different. The gradient of trend lines in cluster diagrams of amplitudes α II vs. α I allows a discrimination of ocular structures.

Deactivation of Zeolite Catalyst H-ZSM-5 during Conversion of Methanol to Gasoline: Operando Time- and Space-Resolved X-ray Diffraction.

PubMed

Rojo-Gama, Daniel; Mentel, Lukasz; Kalantzopoulos, Georgios N; Pappas, Dimitrios K; Dovgaliuk, Iurii; Olsbye, Unni; Lillerud, Karl Petter; Beato, Pablo; Lundegaard, Lars F; Wragg, David S; Svelle, Stian

2018-03-15

The deactivation of zeolite catalyst H-ZSM-5 by coking during the conversion of methanol to hydrocarbons was monitored by high-energy space- and time-resolved operando X-ray diffraction (XRD) . Space resolution was achieved by continuous scanning along the axial length of a capillary fixed bed reactor with a time resolution of 10 s per scan. Using real structural parameters obtained from XRD, we can track the development of coke at different points in the reactor and link this to a kinetic model to correlate catalyst deactivation with structural changes occurring in the material. The "burning cigar" model of catalyst bed deactivation is directly observed in real time.

Tracking reaction dynamics in solution by pump-probe X-ray absorption spectroscopy and X-ray liquidography (solution scattering).

PubMed

Kim, Jeongho; Kim, Kyung Hwan; Oang, Key Young; Lee, Jae Hyuk; Hong, Kiryong; Cho, Hana; Huse, Nils; Schoenlein, Robert W; Kim, Tae Kyu; Ihee, Hyotcherl

2016-03-07

Characterization of transient molecular structures formed during chemical and biological processes is essential for understanding their mechanisms and functions. Over the last decade, time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TRXAS) have emerged as powerful techniques for molecular and electronic structural analysis of photoinduced reactions in the solution phase. Both techniques make use of a pump-probe scheme that consists of (1) an optical pump pulse to initiate a photoinduced process and (2) an X-ray probe pulse to monitor changes in the molecular structure as a function of time delay between pump and probe pulses. TRXL is sensitive to changes in the global molecular structure and therefore can be used to elucidate structural changes of reacting solute molecules as well as the collective response of solvent molecules. On the other hand, TRXAS can be used to probe changes in both local geometrical and electronic structures of specific X-ray-absorbing atoms due to the element-specific nature of core-level transitions. These techniques are complementary to each other and a combination of the two methods will enhance the capability of accurately obtaining structural changes induced by photoexcitation. Here we review the principles of TRXL and TRXAS and present recent application examples of the two methods for studying chemical and biological processes in solution. Furthermore, we briefly discuss the prospect of using X-ray free electron lasers for the two techniques, which will allow us to keep track of structural dynamics on femtosecond time scales in various solution-phase molecular reactions.

Protein structural dynamics in solution unveiled via 100-ps time-resolved x-ray scattering

PubMed Central

Anfinrud, Philip

2010-01-01

We have developed a time-resolved x-ray scattering diffractometer capable of probing structural dynamics of proteins in solution with 100-ps time resolution. This diffractometer, developed on the ID14B BioCARS (Consortium for Advanced Radiation Sources) beamline at the Advanced Photon Source, records x-ray scattering snapshots over a broad range of q spanning 0.02–2.5 Å-1, thereby providing simultaneous coverage of the small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) regions. To demonstrate its capabilities, we have tracked structural changes in myoglobin as it undergoes a photolysis-induced transition from its carbon monoxy form (MbCO) to its deoxy form (Mb). Though the differences between the MbCO and Mb crystal structures are small (rmsd < 0.2 Å), time-resolved x-ray scattering differences recorded over 8 decades of time from 100 ps to 10 ms are rich in structure, illustrating the sensitivity of this technique. A strong, negative-going feature in the SAXS region appears promptly and corresponds to a sudden > 22 Å3 volume expansion of the protein. The ensuing conformational relaxation causes the protein to contract to a volume ∼2 Å3 larger than MbCO within ∼10 ns. On the timescale for CO escape from the primary docking site, another change in the SAXS/WAXS fingerprint appears, demonstrating sensitivity to the location of the dissociated CO. Global analysis of the SAXS/WAXS patterns recovered time-independent scattering fingerprints for four intermediate states of Mb. These SAXS/WAXS fingerprints provide stringent constraints for putative models of conformational states and structural transitions between them. PMID:20406909

Protein structural dynamics in solution unveiled via 100-ps time-resolved x-ray scattering.

PubMed

Cho, Hyun Sun; Dashdorj, Naranbaatar; Schotte, Friedrich; Graber, Timothy; Henning, Robert; Anfinrud, Philip

2010-04-20

We have developed a time-resolved x-ray scattering diffractometer capable of probing structural dynamics of proteins in solution with 100-ps time resolution. This diffractometer, developed on the ID14B BioCARS (Consortium for Advanced Radiation Sources) beamline at the Advanced Photon Source, records x-ray scattering snapshots over a broad range of q spanning 0.02-2.5 A(-1), thereby providing simultaneous coverage of the small-angle x-ray scattering (SAXS) and wide-angle x-ray scattering (WAXS) regions. To demonstrate its capabilities, we have tracked structural changes in myoglobin as it undergoes a photolysis-induced transition from its carbon monoxy form (MbCO) to its deoxy form (Mb). Though the differences between the MbCO and Mb crystal structures are small (rmsd < 0.2 A), time-resolved x-ray scattering differences recorded over 8 decades of time from 100 ps to 10 ms are rich in structure, illustrating the sensitivity of this technique. A strong, negative-going feature in the SAXS region appears promptly and corresponds to a sudden > 22 A(3) volume expansion of the protein. The ensuing conformational relaxation causes the protein to contract to a volume approximately 2 A(3) larger than MbCO within approximately 10 ns. On the timescale for CO escape from the primary docking site, another change in the SAXS/WAXS fingerprint appears, demonstrating sensitivity to the location of the dissociated CO. Global analysis of the SAXS/WAXS patterns recovered time-independent scattering fingerprints for four intermediate states of Mb. These SAXS/WAXS fingerprints provide stringent constraints for putative models of conformational states and structural transitions between them.

Spatial and Temporal Extent of Ion Spectral Structures at the Inner Edge of the Plasma Sheet

NASA Astrophysics Data System (ADS)

Ferradas, C.; Reeves, G. D.; Zhang, J.; Spence, H. E.; Kistler, L. M.; Larsen, B.; Skoug, R. M.; Funsten, H. O.

2017-12-01

Several ion spectral structures are observed near the inner edge of the plasma sheet and constitute the signatures of ion drift and loss in the highly dynamic environment of the inner magnetosphere. Their study helps us understand ion access and losses in this region. Several studies have found that these structures vary with geomagnetic activity, local time, and ion species, but their spatial and temporal extent remain undetermined. We use data from the Helium, Oxygen, Proton, and Electron (HOPE) mass spectrometers onboard the Van Allen Probes to analyze the spectral structures in the energy range of 1- 50 keV. HOPE measurements on both Van Allen Probes spacecraft enable us to resolve the extent of these ion structures in space and time. As the structures respond to changes in the convection electric field on a variety of time scales, the lapping of the two spacecraft on time scales of minutes to hours helps determine their spatial and temporal evolution.

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

Steele, Amy; Hughes, A. Meredith; Carpenter, John

The presence of debris disks around young main-sequence stars hints at the existence and structure of planetary systems. Millimeter-wavelength observations probe large grains that trace the location of planetesimal belts. The Formation and Evolution of Planetary Systems Spitzer Legacy survey of nearby young solar analogues yielded a sample of five debris disk-hosting stars with millimeter flux suitable for interferometric follow-up. We present observations with the Submillimeter Array (SMA) and the Combined Array for Research in Millimeter-wave Astronomy at ∼2″ resolution that spatially resolve the debris disks around these nearby (d ∼ 50 pc) stars. Two of the five disks (HDmore » 377, HD 8907) are spatially resolved for the first time and one (HD 104860) is resolved at millimeter wavelengths for the first time. We combine our new observations with archival SMA and Atacama Large Millimeter/Submillimeter Array data to enable a uniform analysis of the full five-object sample. We simultaneously model the broadband photometric data and resolved millimeter visibilities to constrain the dust temperatures and disk morphologies, and perform a Markov Chain Monte Carlo analysis to fit for basic structural parameters. We find that the radii and widths of the cold outer belts exhibit properties consistent with scaled-up versions of the Solar System's Kuiper Belt. All the disks exhibit characteristic grain sizes comparable to the blowout size, and all the resolved observations of emission from large dust grains are consistent with an axisymmetric dust distribution to within the uncertainties. These results are consistent with comparable studies carried out at infrared wavelengths.« less

Vibrational structure of the S 2 (1B u) excited state of diphenyloctatetraene observed by femtosecond stimulated Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kukura, Philipp; McCamant, David W.; Davis, Paul H.; Mathies, Richard A.

2003-11-01

Femtosecond time-resolved stimulated Raman spectroscopy (FSRS) is used to study the vibrational structure and dynamics of the S 2 state of diphenyloctatetraene. Strong vibrational features at 1184, 1259 and 1578 cm -1 whose linewidths are determined by the S 2 electronic lifetime are observed at early times after photoexcitation at 397 nm. Kinetic analysis of the integrated Raman intensities as well as the transient absorption reveals an exponential decay of the S 2 state on the order of 100 fs. These results demonstrate the ability of FSRS to study the vibrational structure of excited state and chemical reaction dynamics on the femtosecond timescale.

Ultrafast Time-Resolved Hard X-Ray Emission Spectroscopy on a Tabletop

NASA Astrophysics Data System (ADS)

Miaja-Avila, Luis; O'Neil, Galen C.; Joe, Young I.; Alpert, Bradley K.; Damrauer, Niels H.; Doriese, William B.; Fatur, Steven M.; Fowler, Joseph W.; Hilton, Gene C.; Jimenez, Ralph; Reintsema, Carl D.; Schmidt, Daniel R.; Silverman, Kevin L.; Swetz, Daniel S.; Tatsuno, Hideyuki; Ullom, Joel N.

2016-07-01

Experimental tools capable of monitoring both atomic and electronic structure on ultrafast (femtosecond to picosecond) time scales are needed for investigating photophysical processes fundamental to light harvesting, photocatalysis, energy and data storage, and optical display technologies. Time-resolved hard x-ray (>3 keV ) spectroscopies have proven valuable for these measurements due to their elemental specificity and sensitivity to geometric and electronic structures. Here, we present the first tabletop apparatus capable of performing time-resolved x-ray emission spectroscopy. The time resolution of the apparatus is better than 6 ps. By combining a compact laser-driven plasma source with a highly efficient array of microcalorimeter x-ray detectors, we are able to observe photoinduced spin changes in an archetypal polypyridyl iron complex [Fe (2 ,2'-bipyridine)3]2 + and accurately measure the lifetime of the quintet spin state. Our results demonstrate that ultrafast hard x-ray emission spectroscopy is no longer confined to large facilities and now can be performed in conventional laboratories with 10 times better time resolution than at synchrotrons. Our results are enabled, in part, by a 100- to 1000-fold increase in x-ray collection efficiency compared to current techniques.

Watching proteins function with picosecond X-ray crystallography and molecular dynamics simulations.

NASA Astrophysics Data System (ADS)

Anfinrud, Philip

2006-03-01

Time-resolved electron density maps of myoglobin, a ligand-binding heme protein, have been stitched together into movies that unveil with < 2-å spatial resolution and 150-ps time-resolution the correlated protein motions that accompany and/or mediate ligand migration within the hydrophobic interior of a protein. A joint analysis of all-atom molecular dynamics (MD) calculations and picosecond time-resolved X-ray structures provides single-molecule insights into mechanisms of protein function. Ensemble-averaged MD simulations of the L29F mutant of myoglobin following ligand dissociation reproduce the direction, amplitude, and timescales of crystallographically-determined structural changes. This close agreement with experiments at comparable resolution in space and time validates the individual MD trajectories, which identify and structurally characterize a conformational switch that directs dissociated ligands to one of two nearby protein cavities. This unique combination of simulation and experiment unveils functional protein motions and illustrates at an atomic level relationships among protein structure, dynamics, and function. In collaboration with Friedrich Schotte and Gerhard Hummer, NIH.

Observing Holliday junction branch migration one step at a time

NASA Astrophysics Data System (ADS)

Ha, Taekjip

2004-03-01

During genetic recombination, two homologous DNA molecules undergo strand exchange to form a four-way DNA (Holliday) junction and the recognition and processing of this species by branch migration and junction resolving enzymes determine the outcome. We have used single molecule fluorescence techniques to study two intrinsic structural dynamics of the Holliday junction, stacking conformer transitions and spontaneous branch migration. Our studies show that the dynamics of branch migration, resolved with one base pair resolution, is determined by the stability of conformers which in turn depends on the local DNA sequences. Therefore, the energy landscape of Holliday junction branch migation is not uniform, but is rugged.

A stretch/compress scheme for a high temporal resolution detector for the magnetic recoil spectrometer time (MRSt)

DOE PAGES

Hilsabeck, T. J.; Frenje, J. A.; Hares, J. D.; ...

2016-08-02

Here we present a time-resolved detector concept for the magnetic recoil spectrometer for time-resolved measurements of the NIF neutron spectrum. The measurement is challenging due to the time spreading of the recoil protons (or deuterons) as they transit an energy dispersing magnet system. Ions arrive at the focal plane of the magnetic spectrometer over an interval of tens of nanoseconds. We seek to measure the time-resolved neutron spectrum with 20 ps precision by manipulating an electron signal derived from the ions. A stretch-compress scheme is employed to remove transit time skewing while simultaneously reducing the bandwidth requirements for signal recording.more » Simulation results are presented along with design concepts for structures capable of establishing the required electromagnetic fields.« less

A stretch/compress scheme for a high temporal resolution detector for the magnetic recoil spectrometer time (MRSt)

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

Hilsabeck, T. J.; Frenje, J. A.; Hares, J. D.

Here we present a time-resolved detector concept for the magnetic recoil spectrometer for time-resolved measurements of the NIF neutron spectrum. The measurement is challenging due to the time spreading of the recoil protons (or deuterons) as they transit an energy dispersing magnet system. Ions arrive at the focal plane of the magnetic spectrometer over an interval of tens of nanoseconds. We seek to measure the time-resolved neutron spectrum with 20 ps precision by manipulating an electron signal derived from the ions. A stretch-compress scheme is employed to remove transit time skewing while simultaneously reducing the bandwidth requirements for signal recording.more » Simulation results are presented along with design concepts for structures capable of establishing the required electromagnetic fields.« less

Mesoscopic structural phase progression in photo-excited VO 2 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 VO 2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation ismore » 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 VO 2 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 VO 2. Lastly, the direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.« less

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.

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.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction

NASA Astrophysics Data System (ADS)

Minitti, M. P.; Budarz, J. M.; Kirrander, A.; Robinson, J. S.; Ratner, D.; Lane, T. J.; Zhu, D.; Glownia, J. M.; Kozina, M.; Lemke, H. T.; Sikorski, M.; Feng, Y.; Nelson, S.; Saita, K.; Stankus, B.; Northey, T.; Hastings, J. B.; Weber, P. M.

2015-06-01

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction.

PubMed

Minitti, M P; Budarz, J M; Kirrander, A; Robinson, J S; Ratner, D; Lane, T J; Zhu, D; Glownia, J M; Kozina, M; Lemke, H T; Sikorski, M; Feng, Y; Nelson, S; Saita, K; Stankus, B; Northey, T; Hastings, J B; Weber, P M

2015-06-26

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

Resolved Dual-Frequency Observations of the Debris Disk Around AU Mic: Strengths of Bodies in the Collisional Cascade

NASA Astrophysics Data System (ADS)

Carter, Evan; Hughes, A. Meredith; Daley, Cail; Flaherty, Kevin; Pan, Margaret; Schlichting, Hilke; Chiang, Eugene; MacGregor, Meredith Ann; Wilner, David; Dent, Bill; Carpenter, John; Andrews, Sean; Moor, Attila; Kospal, Agnes

2018-01-01

Debris disks are hallmarks of mature planetary systems, with second-generation dust produced via collisions between pluto-like planetesimals. The vertical structure of a debris disk encodes unique information about the dynamical state of the system, particularly at millimeter wavelengths where gravitational effects dominate over the effects of stellar radiation. We present 450 μm Atacama Large Millimeter/sub-millimeter Array (ALMA) observations of the edge-on debris disk around AU Mic, a nearby (d = 9.91 ± 0.10 pc) M1-type star. The 0.3'' angular resolution of the data allows us to spatially resolve the scale height of the disk, complementing previous observations at a wavelength of 1.3 mm. By resolving the vertical structure of the disk at these two widely-separated frequencies, we are able to spatially resolve the spectral index and study variations in the grain size distribution as a function of disk radius. The comparison of scale heights for two different wavelengths and therefore particle sizes also constrains the velocity dispersion as a function of grain size, which allows us to probe the strengths of bodies in the collisional cascade for the first time outside the Solar System.

Imaging Magnetization Structure and Dynamics in Ultrathin Y3Fe5O12/Pt Bilayers with High Sensitivity Using the Time-Resolved Longitudinal Spin Seebeck Effect

NASA Astrophysics Data System (ADS)

Bartell, Jason M.; Jermain, Colin L.; Aradhya, Sriharsha V.; Brangham, Jack T.; Yang, Fengyuan; Ralph, Daniel C.; Fuchs, Gregory D.

2017-04-01

We demonstrate an instrument for time-resolved magnetic imaging that is highly sensitive to the in-plane magnetization state and dynamics of thin-film bilayers of yttrium iron garnet [Y3Fe5O12(YIG )]/Pt : the time-resolved longitudinal spin Seebeck (TRLSSE) effect microscope. We detect the local in-plane magnetic orientation within the YIG by focusing a picosecond laser to generate thermally driven spin current from the YIG into the Pt by the spin Seebeck effect and then use the inverse spin Hall effect in the Pt to transduce this spin current to an output voltage. To establish the time resolution of TRLSSE, we show that pulsed optical heating of patterned YIG (20 nm )/Pt (6 nm )/Ru (2 nm ) wires generates a magnetization-dependent voltage pulse of less than 100 ps. We demonstrate TRLSSE microscopy to image both static magnetic structure and gigahertz-frequency magnetic resonance dynamics with submicron spatial resolution and a sensitivity to magnetic orientation below 0.3 °/√{H z } in ultrathin YIG.

Interplay of superconductivity and bosonic coupling in the peak-dip-hump structure of Bi2Sr2CaCu2O8 +δ

NASA Astrophysics Data System (ADS)

Miller, Tristan L.; Zhang, Wentao; Ma, Jonathan; Eisaki, Hiroshi; Moore, Joel E.; Lanzara, Alessandra

2018-04-01

Because of the important role of electron-boson interactions in conventional superconductivity, it has long been asked whether any similar mechanism is at play in high-temperature cuprate superconductors. Evidence for strong electron-boson coupling is observed in cuprates with angle-resolved photoemission spectroscopy (ARPES), in the form of a dispersion kink and peak-dip-hump structure. What is missing is evidence of a causal relation to superconductivity. Here we revisit the problem using the technique of time-resolved ARPES on Bi2Sr2CaCu2O8 +δ . We focus on the peak-dip-hump structure, and show that laser pulses shift spectral weight into the dip as superconductivity is destroyed on picosecond time scales. We compare our results to simulations of Eliashberg theory in a superconductor with an Einstein boson, and find that the magnitude of the shift in spectral weight depends on the degree to which the bosonic mode contributes to superconductivity. Further study could address one of the longstanding mysteries of high-temperature superconductivity.

Time-resolved ESR spectra of the α-hydroxybenzyl-amine complex

NASA Astrophysics Data System (ADS)

Kawai, Akio; Kobori, Yasuhiro; Obi, Kinichi

1993-11-01

Time-resolved ESR spectra of the α-hydroxybenzyl radical were measured in benzene and 2-propanol solutions by the photo-dissociation of benzoin. The hyperfine structure (hfs) of α-hydroxybenzyl depends on the solvents. In a benzene solution containing triethylamine, two species with different hyperfine structure appeared simultaneously. As the ratio of intensity for the two species depends on the concentration of triethylamine, one of them is assigned to the bare α-hydroxybenzyl and the other to the 1:1 complex of α-hydroxybenzyl and triethylamine. The equilibrium constant of complex formation was estimated to be about 450 M -1 from the analysis of CIDEP intensities.

Analysis of multicrystal pump–probe data sets. I. Expressions for the RATIO model

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

Fournier, Bertrand; Coppens, Philip

2014-08-30

The RATIO method in time-resolved crystallography [Coppenset al.(2009).J. Synchrotron Rad.16, 226–230] was developed for use with Laue pump–probe diffraction data to avoid complex corrections due to wavelength dependence of the intensities. The application of the RATIO method in processing/analysis prior to structure refinement requires an appropriate ratio model for modeling the light response. The assessment of the accuracy of pump–probe time-resolved structure refinements based on the observed ratios was discussed in a previous paper. In the current paper, a detailed ratio model is discussed, taking into account both geometric and thermal light-induced changes.

Long-Time Variation of Magnetic Structure in (Pr xLa 1-x)Co 2Si 2: Coexistence of Slow and Fast Processes in Magnetic Phase Transition

DOE PAGES

Motoya, Kiyoichiro; Hagihala, Masato; Shigeoka, Toru; ...

2017-03-14

In this paper, long-time variations of the magnetic structure in PrCo 2Si 2 and (Pr 0.98La 0.02)Co 2Si 2 were studied by magnetization and time-resolved neutron scattering measurements. The amplitudes of magnetic Bragg peaks showed marked time variations after cooling or heating across the magnetic transition temperature T 1 between two different antiferromagnetic phases. However, the amplitude of the time variation decreased rapidly with increasing distance from T 1. Finally, we analyzed the results on the basis of a phase transition model that includes the coexistence of fast and slow processes.

Single shot near edge x-ray absorption fine structure spectroscopy in the laboratory

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

Mantouvalou, I., E-mail: ioanna.mantouvalou@tu-berlin.de; Witte, K.; Martyanov, W.

With the help of adapted off-axis reflection zone plates, near edge X-ray absorption fine structure spectra at the C and N K-absorption edge have been recorded using a single 1.2 ns long soft X-ray pulse. The transmission experiments were performed with a laser-produced plasma source in the laboratory rendering time resolved measurements feasible independent on large scale facilities. A resolving power of E/ΔE ∼ 950 at the respective edges could be demonstrated. A comparison of single shot spectra with those collected with longer measuring time proves that all features of the used reference samples (silicon nitrate and polyimide) can be resolved in 1.2 ns.more » Hence, investigations of radiation sensitive biological specimen become possible due to the high efficiency of the optical elements enabling low dose experiments.« less

4D blood flow mapping using SPIM-microPIV in the developing zebrafish heart

NASA Astrophysics Data System (ADS)

Zickus, Vytautas; Taylor, Jonathan M.

2018-02-01

Fluid-structure interaction in the developing heart is an active area of research in developmental biology. However, investigation of heart dynamics is mostly limited to computational uid dynamics simulations using heart wall structure information only, or single plane blood ow information - so there is a need for 3D + time resolved data to fully understand cardiac function. We present an imaging platform combining selective plane illumination microscopy (SPIM) with micro particle image velocimetry (μPIV) to enable 3D-resolved flow mapping in a microscopic environment, free from many of the sources of error and bias present in traditional epi uorescence-based μPIV systems. By using our new system in conjunction with optical heart beat synchronization, we demonstrate the ability obtain non-invasive 3D + time resolved blood flow measurements in the heart of a living zebrafish embryo.

Structural evolution of detonation carbon in composition B by X-ray scattering

NASA Astrophysics Data System (ADS)

Firestone, Millicent A.; Dattelbaum, Dana M.; Podlesak, David W.; Gustavsen, Richard L.; Huber, Rachel C.; Ringstrand, Bryan S.; Watkins, Erik B.; Jensen, Brian; Willey, Trevor; Lauderbauch, Lisa; Hodgin, Ralph; Bagge-Hansen, Michael; van Buuren, Tony; Seifert, Sönke; Graber, Timothy

2017-01-01

Products evolved during the detonation of high explosives are primarily a collection of molecular gases and solid carbon condensates. Electron microscopy studies have revealed that detonation carbon (soot) can contain a variety of unique carbon particles possessing novel morphologies, such as carbon onions and ribbons. Despite these observations very little is known about the conditions that leads to the production of these novel carbon nanoparticles. A fuller understanding on conditions that generate such nanoparticles would greatly benefit from time-resolved studies that probe particle formation and evolution through and beyond the chemical reaction zone. Herein, we report initial results employing time-resolved X-ray scattering (TRSAXS) measurements to monitor nanosecond time-scale carbon products formed from detonating Composition B (60% TNT, 40% RDX). These studies were performed at the Dynamic Compression Sector (DCS, Sector 35) at the Advanced Photon Source (Argonne National Laboratory). Analysis of the collected scattering patterns reveals the presence of fractal multi-layered carbon condensates.

Diagnosis of vulnerable atherosclerotic plaques by time-resolved fluorescence spectroscopy and ultrasound imaging.

PubMed

Jo, J A; Fang, Q; Papaioannou, T; Qiao, J H; Fishbein, M C; Beseth, B; Dorafshar, A H; Reil, T; Baker, D; Freischlag, J; Shung, K K; Sun, L; Marcu, L

2006-01-01

In this study, time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) and ultrasonography were applied to detect vulnerable (high-risk) atherosclerotic plaque. A total of 813 TR-LIFS measurements were taken from carotid plaques of 65 patients, and subsequently analyzed using the Laguerre deconvolution technique. The investigated spots were classified by histopathology as thin, fibrotic, calcified, low-inflamed, inflamed and necrotic lesions. Spectral and time-resolved parameters (normalized intensity values and Laguerre expansion coefficients) were extracted from the TR-LIFS data. Feature selection for classification was performed by either analysis of variance (ANOVA) or principal component analysis (PCA). A stepwise linear discriminant analysis algorithm was developed for detecting inflamed and necrotic lesion, representing the most vulnerable plaques. These vulnerable plaques were detected with high sensitivity (>80%) and specificity (>90%). Ultrasound (US) imaging was obtained in 4 carotid plaques in addition to TR-LIFS examination. Preliminary results indicate that US provides important structural information of the plaques that could be combined with the compositional information obtained by TR-LIFS, to obtain a more accurate diagnosis of vulnerable atherosclerotic plaque.

In Situ, Time-Resolved, and Mechanistic Studies of Metal–Organic Framework Nucleation and Growth

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

Van Vleet, Mary J.; Weng, Tingting; Li, Xinyi

The vast chemical and structural diversity of metal–organic frameworks (MOFs) opens up the exciting possibility of “crystal engineering” MOFs tailored for particular catalytic or separation applications. Yet the process of reaction discovery, optimization, and scale-up of MOF synthesis remains extremely challenging, presenting significant obstacles to the synthetic realization of many otherwise promising MOF structures. Recently, significant new insights into the fundamental processes governing MOF nucleation and growth, as well as the relationship between reaction parameters and synthetic outcome, have been derived using powerful in situ, time-resolved and/or mechanistic studies of MOF crystallization. This Review provides a summary and associated criticalmore » analysis of the results of these and other related “direct” studies of MOF nucleation and growth, with a particular emphasis on the recent advances in instrument technologies that have enabled such studies and on the major hypotheses, theories, and models that have been used to explain MOF formation. We conclude with a summary of the major insights that have been gained from the work summarized in this Review, outlining our own perspective on potential fruitful new directions for investigation.« less

In Situ, Time-Resolved, and Mechanistic Studies of Metal–Organic Framework Nucleation and Growth

DOE PAGES

Van Vleet, Mary J.; Weng, Tingting; Li, Xinyi; ...

2018-03-07

The vast chemical and structural diversity of metal–organic frameworks (MOFs) opens up the exciting possibility of “crystal engineering” MOFs tailored for particular catalytic or separation applications. Yet the process of reaction discovery, optimization, and scale-up of MOF synthesis remains extremely challenging, presenting significant obstacles to the synthetic realization of many otherwise promising MOF structures. Recently, significant new insights into the fundamental processes governing MOF nucleation and growth, as well as the relationship between reaction parameters and synthetic outcome, have been derived using powerful in situ, time-resolved and/or mechanistic studies of MOF crystallization. This Review provides a summary and associated criticalmore » analysis of the results of these and other related “direct” studies of MOF nucleation and growth, with a particular emphasis on the recent advances in instrument technologies that have enabled such studies and on the major hypotheses, theories, and models that have been used to explain MOF formation. We conclude with a summary of the major insights that have been gained from the work summarized in this Review, outlining our own perspective on potential fruitful new directions for investigation.« less

Resolving the detailed structure of cortical and thalamic neurons in the adult rat brain with refined biotinylated dextran amine labeling.

PubMed

Ling, Changying; Hendrickson, Michael L; Kalil, Ronald E

2012-01-01

Biotinylated dextran amine (BDA) has been used frequently for both anterograde and retrograde pathway tracing in the central nervous system. Typically, BDA labels axons and cell somas in sufficient detail to identify their topographical location accurately. However, BDA labeling often has proved to be inadequate to resolve the fine structural details of axon arbors or the dendrites of neurons at a distance from the site of BDA injection. To overcome this limitation, we varied several experimental parameters associated with the BDA labeling of neurons in the adult rat brain in order to improve the sensitivity of the method. Specifically, we compared the effect on labeling sensitivity of: (a) using 3,000 or 10,000 MW BDA; (b) injecting different volumes of BDA; (c) co-injecting BDA with NMDA; and (d) employing various post-injection survival times. Following the extracellular injection of BDA into the visual cortex, labeled cells and axons were observed in both cortical and thalamic areas of all animals studied. However, the detailed morphology of axon arbors and distal dendrites was evident only under optimal conditions for BDA labeling that take into account the: molecular weight of the BDA used, concentration and volume of BDA injected, post-injection survival time, and toning of the resolved BDA with gold and silver. In these instances, anterogradely labeled axons and retrogradely labeled dendrites were resolved in fine detail, approximating that which can be achieved with intracellularly injected compounds such as biocytin or fluorescent dyes.

Nonlinear Optical Spectroscopy in the Time Domain: Studies of Ultrafast Molecular Processes in the Condensed Phase.

NASA Astrophysics Data System (ADS)

Joo, Taiha

Ultrafast molecular processes in the condensed phase at room temperature are studied in the time domain by four wave mixing spectroscopy. The structure/dynamics of various quantum states can be studied by varying the time ordering of the incident fields, their polarization, their colors, etc. In one, time-resolved coherent Stokes Raman spectroscopy of benzene is investigated at room temperature. The reorientational correlation time of benzene as well as the T_2 time of the nu _1 ring-breathing mode have been measured by using two different polarization geometries. Bohr frequency difference beats have also been resolved between the nu_1 modes of ^ {12}C_6H_6 and ^{12}C_5^{13 }CH_6.. The dephasing dynamics of the nu _1 ring-breathing mode of neat benzene is studied by time-resolved coherent anti-Stokes Raman scattering. Ultrafast time resolution reveals deviation from the conventional exponential decay. The correlation time, tau _{rm c}, and the rms magnitude, Delta, of the Bohr frequency modulation are determined for the process responsible for the vibrational dephasing by Kubo dephasing function analysis. The electronic dephasing of two oxazine dyes in ethylene glycol at room temperature is investigated by photon echo experiments. It was found that at least two stochastic processes are responsible for the observed electronic dephasing. Both fast (homogeneous) and slow (inhomogeneous) dynamics are recovered using Kubo line shape analysis. Moreover, the slow dynamics is found to spectrally diffuse over the inhomogeneous distribution on the time scale around a picosecond. Time-resolved degenerate four wave mixing signal of dyes in a population measurement geometry is reported. The vibrational coherences both in the ground and excited electronic states produced strong oscillations in the signal together with the usual population decay from the excited electronic state. Absolute frequencies and their dephasing times of the vibrational modes at ~590 cm^{-1} are obtained. Finally, a new inverse transform procedure is presented that calculates the absorption band (ABS) from an experimental Raman excitation profile (REP). An iterative solution is sought for an integral Hilbert transform relation. An exact ABS is recovered regardless of the starting ABS when sufficient iterations are performed.

Multimodal imaging of vascular grafts using time-resolved fluorescence and ultrasound

NASA Astrophysics Data System (ADS)

Fatakdawala, Hussain; Griffiths, Leigh G.; Wong, Maelene L.; Humphrey, Sterling; Marcu, Laura

2015-02-01

The translation of engineered tissues into clinic requires robust monitoring of tissue development, both in vitro and in vivo. Traditional methods for the same are destructive, inefficient in time and cost and do not allow time-lapse measurements from the same sample or animal. This study reports on the ability of time-resolved fluorescence and ultrasound measurements for non-destructive characterization of explanted tissue engineered vascular grafts. Results show that TRFS and FLIm are able to assess alterations in luminal composition namely elastin, collagen and cellular (hyperplasia) content via changes in fluorescence lifetime values between normal and grafted tissue. These observations are complemented by structural changes observed in UBM pertaining to graft integration and intimal thickness over the grafted region. These results encourage the future application of a catheter-based technique that combines these imaging modalities for non-destructive characterization of vascular grafts in vivo.

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.

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

PubMed

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.

Software defined photon counting system for time resolved x-ray experiments.

PubMed

Acremann, Y; Chembrolu, V; Strachan, J P; Tyliszczak, T; Stöhr, J

2007-01-01

The time structure of synchrotron radiation allows time resolved experiments with sub-100 ps temporal resolution using a pump-probe approach. However, the relaxation time of the samples may require a lower repetition rate of the pump pulse compared to the full repetition rate of the x-ray pulses from the synchrotron. The use of only the x-ray pulse immediately following the pump pulse is not efficient and often requires special operation modes where only a few buckets of the storage ring are filled. We designed a novel software defined photon counting system that allows to implement a variety of pump-probe schemes at the full repetition rate. The high number of photon counters allows to detect the response of the sample at multiple time delays simultaneously, thus improving the efficiency of the experiment. The system has been successfully applied to time resolved scanning transmission x-ray microscopy. However, this technique is applicable more generally.

Electronic structure of p-type transparent conducting oxide CuAlO2

NASA Astrophysics Data System (ADS)

Mo, Sung-Kwan; Yoon, Joonseok; Liu, Xiaosong; Yang, Wanli; Mun, Bongjin; Ju, Honglyoul

2014-03-01

CuAlO2 is a prototypical p-type transparent conducting oxide. Despite its importance for potential applications and number of studies on its band structure and gap characteristics, experimental study on the momentum-resolved electronic structure has been lacking. We present angle-resolved photoemission data on single crystalline CuAlO2 using synchrotron light source to reveal complete band structure. Complemented by the x-ray absorption and emission spectra, we also study band gap characteristics and compare them with theory.

Exact Time-Dependent Exchange-Correlation Potential in Electron Scattering Processes

NASA Astrophysics Data System (ADS)

Suzuki, Yasumitsu; Lacombe, Lionel; Watanabe, Kazuyuki; Maitra, Neepa T.

2017-12-01

We identify peak and valley structures in the exact exchange-correlation potential of time-dependent density functional theory that are crucial for time-resolved electron scattering in a model one-dimensional system. These structures are completely missed by adiabatic approximations that, consequently, significantly underestimate the scattering probability. A recently proposed nonadiabatic approximation is shown to correctly capture the approach of the electron to the target when the initial Kohn-Sham state is chosen judiciously, and it is more accurate than standard adiabatic functionals but ultimately fails to accurately capture reflection. These results may explain the underestimation of scattering probabilities in some recent studies on molecules and surfaces.

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

Mediation of donor–acceptor distance in an enzymatic methyl transfer reaction

PubMed Central

Zhang, Jianyu; Kulik, Heather J.; Martinez, Todd J.; Klinman, Judith P.

2015-01-01

Enzymatic methyl transfer, catalyzed by catechol-O-methyltransferase (COMT), is investigated using binding isotope effects (BIEs), time-resolved fluorescence lifetimes, Stokes shifts, and extended graphics processing unit (GPU)-based quantum mechanics/molecular mechanics (QM/MM) approaches. The WT enzyme is compared with mutants at Tyr68, a conserved residue that is located behind the reactive sulfur of cofactor. Small (>1) BIEs are observed for an S-adenosylmethionine (AdoMet)-binary and abortive ternary complex containing 8-hydroxyquinoline, and contrast with previously reported inverse (<1) kinetic isotope effects (KIEs). Extended GPU-based computational studies of a ternary complex containing catecholate show a clear trend in ground state structures, from noncanonical bond lengths for WT toward solution values with mutants. Structural and dynamical differences that are sensitive to Tyr68 have also been detected using time-resolved Stokes shift measurements and molecular dynamics. These experimental and computational results are discussed in the context of active site compaction that requires an ionization of substrate within the enzyme ternary complex. PMID:26080432

Luminescence lifetime enhanced by exciton-plasmon couple in hybrid CsPbBr3 perovskite/Pt nanostructure

NASA Astrophysics Data System (ADS)

Liu, Chunxu; Zhang, Jisen; Chen, Yongyi; Jing, Pengtao; Zhang, Ligong; Zhao, Haifeng; Fu, Xihong; Wang, Lijun

2018-02-01

Photoluminescence (PL) and time-resolved spectroscopic studies on plasmonically coupled semiconductor nanoparticles (SNPs) have demonstrated the PL quenched and lifetime enhanced of SNPs in the presence of metal nanoparticles (MNPs). The hybrid colloidal CsPbBr3 perovskite SNPs/Pt MNPs (S-M) structures exhibit novel optical properties due to the synergetic interaction between the individual components. In hybrid S-M nanostructures colloidal chemistry incorporates SNP and MNP into a single unit resulting in the formation of plexciton (or excimon) which has now been established in a series of hybrid structures. The experimental results of femtosecond transient absorption (TA) spectroscopy based on the time-resolved pump-probe confirm the transformation from excitons to plexcitons. It was found that the experimental data can’t be well described by the theory based on conventional Fӧster resonance energy transfer (FRET). The differences between theory and experiment may be due to the missing some PbBr2 PL peaks, the reason will be revealed further.

The 7BM beamline at the APS: a facility for time-resolved fluid dynamics measurements

PubMed Central

Kastengren, Alan; Powell, Christopher F.; Arms, Dohn; Dufresne, Eric M.; Gibson, Harold; Wang, Jin

2012-01-01

In recent years, X-ray radiography has been used to probe the internal structure of dense sprays with microsecond time resolution and a spatial resolution of 15 µm even in high-pressure environments. Recently, the 7BM beamline at the Advanced Photon Source (APS) has been commissioned to focus on the needs of X-ray spray radiography measurements. The spatial resolution and X-ray intensity at this beamline represent a significant improvement over previous time-resolved X-ray radiography measurements at the APS. PMID:22713903

Site-Resolved Imaging with the Fermi Gas Microscope

NASA Astrophysics Data System (ADS)

Huber, Florian Gerhard

The recent development of quantum gas microscopy for bosonic rubidium atoms trapped in optical lattices has made it possible to study local structure and correlations in quantum many-body systems. Quantum gas microscopes are a perfect platform to perform quantum simulation of condensed matter systems, offering unprecedented control over both internal and external degrees of freedom at a single-site level. In this thesis, this technique is extended to fermionic particles, paving the way to fermionic quantum simulation, which emulate electrons in real solids. Our implementation uses lithium, the lightest atom amenable to laser cooling. The absolute timescales of dynamics in optical lattices are inversely proportional to the mass. Therefore, experiments are more than six times faster than for the only other fermionic alkali atom, potassium, and more then fourteen times faster than an equivalent rubidium experiment. Scattering and collecting a sufficient number of photons with our high-resolution imaging system requires continuous cooling of the atoms during the fluorescence imaging. The lack of a resolved excited hyperfine structure on the D2 line of lithium prevents efficient conventional sub-Doppler cooling. To address this challenge we have applied a Raman sideband cooling scheme and achieved the first site-resolved imaging of ultracold fermions in an optical lattice.

Rapid high-resolution spin- and angle-resolved photoemission spectroscopy with pulsed laser source and time-of-flight spectrometer

NASA Astrophysics Data System (ADS)

Gotlieb, K.; Hussain, Z.; Bostwick, A.; Lanzara, A.; Jozwiak, C.

2013-09-01

A high-efficiency spin- and angle-resolved photoemission spectroscopy (spin-ARPES) spectrometer is coupled with a laboratory-based laser for rapid high-resolution measurements. The spectrometer combines time-of-flight (TOF) energy measurements with low-energy exchange scattering spin polarimetry for high detection efficiencies. Samples are irradiated with fourth harmonic photons generated from a cavity-dumped Ti:sapphire laser that provides high photon flux in a narrow bandwidth, with a pulse timing structure ideally matched to the needs of the TOF spectrometer. The overall efficiency of the combined system results in near-EF spin-resolved ARPES measurements with an unprecedented combination of energy resolution and acquisition speed. This allows high-resolution spin measurements with a large number of data points spanning multiple dimensions of interest (energy, momentum, photon polarization, etc.) and thus enables experiments not otherwise possible. The system is demonstrated with spin-resolved energy and momentum mapping of the L-gap Au(111) surface states, a prototypical Rashba system. The successful integration of the spectrometer with the pulsed laser system demonstrates its potential for simultaneous spin- and time-resolved ARPES with pump-probe based measurements.

Time-resolved observation of protein allosteric communication

PubMed Central

Buchenberg, Sebastian; Sittel, Florian; Stock, Gerhard

2017-01-01

Allostery represents a fundamental mechanism of biological regulation that is mediated via long-range communication between distant protein sites. Although little is known about the underlying dynamical process, recent time-resolved infrared spectroscopy experiments on a photoswitchable PDZ domain (PDZ2S) have indicated that the allosteric transition occurs on multiple timescales. Here, using extensive nonequilibrium molecular dynamics simulations, a time-dependent picture of the allosteric communication in PDZ2S is developed. The simulations reveal that allostery amounts to the propagation of structural and dynamical changes that are genuinely nonlinear and can occur in a nonlocal fashion. A dynamic network model is constructed that illustrates the hierarchy and exceeding structural heterogeneity of the process. In compelling agreement with experiment, three physically distinct phases of the time evolution are identified, describing elastic response (≲0.1 ns), inelastic reorganization (∼100 ns), and structural relaxation (≳1μs). Issues such as the similarity to downhill folding as well as the interpretation of allosteric pathways are discussed. PMID:28760989

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE PAGES

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.; ...

2017-02-20

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

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

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Time-resolved measurement of single pulse femtosecond laser-induced periodic surface structure formation induced by a pre-fabricated surface groove.

PubMed

Kafka, K R P; Austin, D R; Li, H; Yi, A Y; Cheng, J; Chowdhury, E A

2015-07-27

Time-resolved diffraction microscopy technique has been used to observe the formation of laser-induced periodic surface structures (LIPSS) from the interaction of a single femtosecond laser pulse (pump) with a nano-scale groove mechanically formed on a single-crystal Cu substrate. The interaction dynamics (0-1200 ps) was captured by diffracting a time-delayed, frequency-doubled pulse (probe) from nascent LIPSS formation induced by the pump with an infinity-conjugate microscopy setup. The LIPSS ripples are observed to form asynchronously, with the first one forming after 50 ps and others forming sequentially outward from the groove edge at larger time delays. A 1-D analytical model of electron heating including both the laser pulse and surface plasmon polariton excitation at the groove edge predicts ripple period, melt spot diameter, and qualitatively explains the asynchronous time-evolution of LIPSS formation.

Femtosecond characterization of vibrational optical activity of chiral molecules.

PubMed

Rhee, Hanju; June, Young-Gun; Lee, Jang-Soo; Lee, Kyung-Koo; Ha, Jeong-Hyon; Kim, Zee Hwan; Jeon, Seung-Joon; Cho, Minhaeng

2009-03-19

Optical activity is the result of chiral molecules interacting differently with left versus right circularly polarized light. Because of this intrinsic link to molecular structure, the determination of optical activity through circular dichroism (CD) spectroscopy has long served as a routine method for obtaining structural information about chemical and biological systems in condensed phases. A recent development is time-resolved CD spectroscopy, which can in principle map the structural changes associated with biomolecular function and thus lead to mechanistic insights into fundamental biological processes. But implementing time-resolved CD measurements is experimentally challenging because CD is a notoriously weak effect (a factor of 10(-4)-10(-6) smaller than absorption). In fact, this problem has so far prevented time-resolved vibrational CD experiments. Here we show that vibrational CD spectroscopy with femtosecond time resolution can be realized when using heterodyned spectral interferometry to detect the phase and amplitude of the infrared optical activity free-induction-decay field in time (much like in a pulsed NMR experiment). We show that we can detect extremely weak signals in the presence of large achiral background contributions, by simultaneously measuring with a femtosecond laser pulse the vibrational CD and optical rotatory dispersion spectra of dissolved chiral limonene molecules. We have so far only targeted molecules in equilibrium, but it would be straightforward to extend the method for the observation of ultrafast structural changes such as those occurring during protein folding or asymmetric chemical reactions. That is, we should now be in a position to produce 'molecular motion pictures' of fundamental molecular processes from a chiral perspective.

Structure and function of proteins investigated by crystallographic and spectroscopic time-resolved methods

NASA Astrophysics Data System (ADS)

Purwar, Namrta

Biomolecules play an essential role in performing the necessary functions for life. The goal of this thesis is to contribute to an understanding of how biological systems work on the molecular level. We used two biological systems, beef liver catalase (BLC) and photoactive yellow protein (PYP). BLC is a metalloprotein that protects living cells from the harmful effects of reactive oxygen species by converting H2O2 into water and oxygen. By binding nitric oxide (NO) to the catalase, a complex was generated that mimics the Cat-H2O2 adduct, a crucial intermediate in the reaction promoted by the catalase. The Cat-NO complex is obtained by using a convenient NO generator (1-(N,N-diethylamino)diazen-1-ium-1,2-diolate). Concentrations up to 100˜200 mM are reached by using a specially designed glass cavity. With this glass apparatus and DEANO, sufficient NO occupation is achieved and structure determination of the catalase with NO bound to the heme iron becomes possible. Structural changes upon NO binding are minute. NO has a slightly bent geometry with respect to the heme normal, which results in a substantial overlap of the NO orbitals with the iron-porphyrin molecular orbitals. From the structure of the iron-NO complex, conclusions on the electronic properties of the heme iron can be drawn that ultimately lead to an insight into the catalytic properties of this enzyme. Enzyme kinetics is affected by additional parameters such as temperature and pH. Additionally, in crystallography, the absorbed X-ray dose may impair protein function. To address the effect of these parameters, we performed time-resolved crystallographic experiments on a model system, PYP. By collecting multiple time-series on PYP at increasing X-ray dose levels, we determined a kinetic dose limit up to which kinetically meaningful X-ray data sets can be collected. From this, we conclude that comprehensive time-series spanning up to 12 orders of magnitude in time can be collected from a single PYP crystal. Time-resolved X-ray data collected at pH's of 4, 7 and 9 demonstrate that pH alters the kinetics of the PYP photocycle dramatically. At pH 4 the photocycle lasts almost one order of magnitude longer in time compared to pH 7. The final intermediate that accumulates at both pH 7 and pH 4 is absent at pH 9. Results from the dose- and the pH-dependent time-resolved crystallographic experiments show that it is imperative to carefully control the conditions under which time-resolved data are collected. With these considerations we collected a comprehensive time-series from nanoseconds to seconds at 14 different temperature settings from -40 °C to 70 °C. Results from time-resolved crystallography are corroborated by employing time-resolved absorption spectroscopy. For this, absorption spectra on crystals and solution are collected by a fast micro-spectrophotometer custom-designed in our lab. We identify kinetic phases of the PYP photocycle at all 14 temperature settings. Relaxation times associated with these phases are temperature-dependent and can be fit by the Van't Hoff-Arrhenius equation. Kinetic modeling yields entropy and enthalpy values at the barriers of the activation solely from the time-resolved crystallographic data. With this, we advance crystallography to a new frontier: the determination of free energy surfaces. Investigating enzymatic reactions can be challenging, because they are non-cyclic. After one turnover product must be washed away and substrate must be reloaded. A promising approach for routine application can be envisioned at the new 4th generation X-ray sources, such as X-ray free electron lasers (XFELs). With our results we set the scene to comprehensively investigate all kinds of enzymatic reactions with these instruments.

Two-site ionic labeling with pyranine: implications for structural dynamics studies of polymers and polypeptides by time-resolved fluorescence anisotropy.

PubMed

Sharma, Jai; Tleugabulova, Dina; Czardybon, Wojciech; Brennan, John D

2006-04-26

Time-resolved fluorescence anisotropy (TRFA) is widely used to study dynamic motions of biomolecules in a variety of environments. However, depolarization due to rapid side chain motions often complicates the interpretation of anisotropy decay data and interferes with the accurate observation of segmental motions. Here, we demonstrate a new method for two-point ionic labeling of polymers and biomolecules that have appropriately spaced amino groups using the fluorescent probe 8-hydroxyl-1,3,6-trisulfonated pyrene (pyranine). TRFA analysis shows that such labeling provides a more rigid attachment of the fluorophore to the macromolecule than the covalent or single-point ionic labeling of amino groups, leading to time-resolved anisotropy decays that better reflect the backbone motion of the labeled polymer segment. Optimal coupling of pyranine to biomolecule dynamics is shown to be obtained for appropriately spaced Arg groups, and in such cases the ionic binding is stable up to 150 mM ionic strength. TRFA was used to monitor the behavior of pyranine-labeled poly(allylamine) (PAM) and poly-d-lysine (PL) in sodium silicate derived sol-gel materials and revealed significant restriction of backbone motion upon entrapment for both polymers, an observation that was not readily apparent in a previous study with entrapped fluorescein-labeled PAM and PL. The implications of these findings for fluorescence studies of polymer and biomolecule dynamics are discussed.

X-ray absorption spectroscopy with time-tagged photon counting: application to study the structure of a Co(i) intermediate of H2 evolving photo-catalyst.

PubMed

Smolentsev, Grigory; Guda, Alexander A; Janousch, Markus; Frieh, Cristophe; Jud, Gaudenz; Zamponi, Flavio; Chavarot-Kerlidou, Murielle; Artero, Vincent; van Bokhoven, Jeroen A; Nachtegaal, Maarten

2014-01-01

In order to probe the structure of reaction intermediates of photochemical reactions a new setup for laser-initiated time-resolved X-ray absorption (XAS) measurements has been developed. With this approach the arrival time of each photon in respect to the laser pulse is measured and therefore full kinetic information is obtained. All X-rays that reach the detector are used to measure this kinetic information and therefore the detection efficiency of this method is high. The newly developed setup is optimized for time-resolved experiments in the microsecond range for samples with relatively low metal concentration (∼1mM). This setup has been applied to study a multicomponent photocatalytic system with a Co(dmgBF(2))(2) catalyst (dmg(2-) = dimethylglyoximato dianion), [Ru(bpy)(3)](2+) chromophore (bpy = 2,2'-bipyridine) and methyl viologen as the electron relay. On the basis of the analysis of hundreds of Co K-edge XAS spectra corresponding to different delay times after the laser excitation of the chromophore, the presence of a Co(i) intermediate is confirmed. The calculated X-ray transient signal for a model of Co(i) state with a 0.14 Å displacement of Co out of the dmg ligand plane and with the closest solvent molecule at a distance of 2.06 Å gives reasonable agreement with the experimental data.

Depth- and momentum- resolved electronic structure at buried oxide interfaces from standing-wave angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Fadley, Charles

2015-03-01

It is clear that interfaces in complex oxide heterostructures often represent emergent materials that possess surprising properties not associated with the parent oxides, such as two-dimensional electron gases (2DEGs), superconductivity, and magnetism. A detailed knowledge of the composition, atomic structure, and electronic structure through such interfaces is thus critical. Photomission (PES) and angle-resolved photoemission (ARPES) represent techniques of choice for such studies, but have certain limitations in being too surface sensitive and in not being able to focus specifically on buried interfaces or heterostructure layers. In this talk, I will discuss combining two newer elements of PES/ARPES to deal with this challenge: - the use of soft x-rays in the ca. few hundred-to-2000 eV regime, or even into the true hard x-ray regime, to probe more deeply into the structure, and - tailoring of the x-ray intensity profile into a strong standing wave (SW) through reflection from a multilayer heterostructure to provide much enhanced depth resolution. The relative advantages of soft/hard x-ray PES and ARPES and their complementarity to conventional VUV ARPES in the ca. 5-150 eV regime will be considered. As illustrative examples, by combining SW-PES and SW-ARPES, it has been possible to measure for the first time the detailed concentration profiles and momentum-resolved electronic structure at the SrTiO3/La0.67Sr0.33MnO3 interface and to directly measure the depth profile of the 2DEG at SrTiO3/GdTiO3 interfaces. Future directions for such measurements will also be discussed. Supported by US DOE Contract No. DE-AC02-05CH11231, ARO-MURI Grant W911-NF-09-1-0398, and the PALM-APTCOM Project (France).

X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

DOE PAGES

Yin, Panchao; Wu, Bin; Mamontov, Eugene; ...

2016-02-05

A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo 72Fe 30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types ofmore » water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo 72Fe 30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.« less

Relationship of D'' structure with the velocity variations near the inner-core boundary

NASA Astrophysics Data System (ADS)

Luo, Sheng-Nian; Ni, Sidao; Helmberger, Don

2002-06-01

Variations in regional differential times between PKiKP (i) and PKIKP (I) have been attributed to hemispheric P-velocity variations of about 1% in the upper 100 km of the inner core (referred to as HIC). The top of the inner core appears relatively fast beneath Asia where D'' is also fast. An alternative interpretation could be the lateral variation in P velocity at the lowermost outer core (HOC) producing the same differential times. To resolve this issue, we introduce the diffracted PKP phase near the B caustic (Bdiff) in the range of 139-145° epicenter distances, and the corresponding differential times between Bdiff and PKiKP and PKIKP as observed on broadband arrays. Due to the long-wavelength nature of Bdiff, we scaled the S-wave tomography model with k values (k ≡ dlnVs/dlnVp) to obtain large-scale P-wave velocity structure in the lower mantle as proposed by earlier studies. Waveform synthetics of Bdiff constructed with small k's predict complex waveforms not commonly observed, confirming the validity of large scaling factor k. With P-velocity in lower mantle constrained at large scale, the extra travel-time constraint imposed by Bdiff helps to resolve the HOC-HIC issue. Our preliminary results suggest k > 2 for the lowermost mantle and support HIC hypothesis. An important implication is that there appears to be a relationship of D'' velocity structures with the structures near the inner core boundary via core dynamics.

Ultrafast time-resolved spectroscopy of lead halide perovskite films

NASA Astrophysics Data System (ADS)

Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

2015-09-01

Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

DOE PAGES

Hassan, Asra; Zhang, Xiaoyi; Liu, Xiaohan; ...

2017-08-28

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopantmore » oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.« less

Conformational States of the Rapana thomasiana Hemocyanin and Its Substructures Studied by Dynamic Light Scattering and Time-Resolved Fluorescence Spectroscopy

PubMed Central

Georgieva, Dessislava; Schwark, Daniel; Nikolov, Peter; Idakieva, Krassimira; Parvanova, Katja; Dierks, Karsten; Genov, Nicolay; Betzel, Christian

2005-01-01

Hemocyanins are dioxygen-transporting proteins freely dissolved in the hemolymph of mollusks and arthropods. Dynamic light scattering and time-resolved fluorescence measurements show that the oxygenated and apo-forms of the Rapana thomasiana hemocyanin, its structural subunits RtH1 and RtH2, and those of the functional unit RtH2e, exist in different conformations. The oxygenated respiratory proteins are less compact and more asymmetric than the respective apo-forms. Different conformational states were also observed for the R. thomasiana hemocyanin in the absence and presence of an allosteric regulator. The results are in agreement with a molecular mechanism for cooperative dioxygen binding in molluscan hemocyanins including transfer of conformational changes from one functional unit to another. PMID:15533921

Charge Carriers Modulate the Bonding of Semiconductor Nanoparticle Dopants As Revealed by Time-Resolved X-ray Spectroscopy

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

Hassan, Asra; Zhang, Xiaoyi; Liu, Xiaohan

Understanding the electronic structure of doped semiconductors is essential to realize advancements in electronics and in the rational design of nanoscale devices. Here, we report the results of time-resolved X-ray absorption studies on copper-doped cadmium sulfide nanoparticles that provide an explicit description of the electronic dynamics of the dopants. The interaction of a dopant ion and an excess charge carrier is unambiguously observed via monitoring the oxidation state. The experimental data combined with DFT calculations demonstrate that dopant bonding to the host matrix is modulated by its interaction with charge carriers. Additionally, the transient photoluminescence and the kinetics of dopantmore » oxidation reveal the presence of two types of surface-bound ions that create mid-gap states.« less

Cloudy Skies over AGN: Observations with Simbol-X

NASA Astrophysics Data System (ADS)

Salvati, M.; Risaliti, G.

2009-05-01

Recent time-resolved spectroscopic X-ray studies of bright obscured AGN show that column density variability on time scales of hours/days may be common, at least for sources with NH>1023 cm-2. This opens new oppurtunities in the analysis of the structure of the circumnuclear medium and of the X-ray source: resolving the variations due to single clouds covering/uncovering the X-ray source provides tight constraints on the source size, the clouds' size and distance, and their average number, density and column density. We show how Simbol-X will provide a breakthrough in this field, thanks to its broad band coverage, allowing (a) to precisely disentangle the continuum and NH variations, and (2) to extend the NH variability analysis to column densities >1023 cm-2.

Levels in N 12 via the N 14 ( p ,   t ) reaction using the JENSA gas-jet target

DOE PAGES

Chipps, K. A.; Pain, S. D.; Greife, U.; ...

2015-09-25

As one of a series of physics cases to demonstrate the unique benefit of the new Jet Experiments in Nuclear Structure and Astrophysics gas-jet target for enabling next-generation transfer reaction studies, the ¹⁴N (p, t)¹²N reaction was studied for the first time, using a pure jet of nitrogen, in an attempt to resolve conflicting information on the structure of ¹²N. A new level at 4.561-MeV excitation energy in ¹²N was found.

Pressure-induced kinetics of the α to ω transition in zirconium

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

Jacobsen, M. K.; Velisavljevic, N., E-mail: nenad@lanl.gov; Sinogeikin, S. V.

Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformationsmore » and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.« less

Pressure-induced kinetics of the α to ω transition in zirconium

DOE PAGES

Jacobsen, M. K.; Velisavljevic, N.; Sinogeikin, S. V.

2015-07-13

Diamond anvil cells (DAC) coupled with x-ray diffraction (XRD) measurements are one of the primary techniques for investigating structural stability of materials at high pressure-temperature (P-T) conditions. DAC-XRD has been predominantly used to resolve structural information at set P-T conditions and, consequently, provides P-T phase diagram information on a broad range of materials. With advances in large scale synchrotron x-ray facilities and corresponding x-ray diagnostic capabilities, it is now becoming possible to perform sub-second time resolved measurements on micron sized DAC samples. As a result, there is an opportunity to gain valuable information about the kinetics of structural phase transformationsmore » and extend our understanding of material behavior at high P-T conditions. Using DAC-XRD time resolved measurements, we have investigated the kinetics of the α to ω transformation in zirconium. We observe a clear time and pressure dependence in the martensitic α-ω transition as a function of pressure-jump, i.e., drive pressure. The resulting data are fit using available kinetics models, which can provide further insight into transformation mechanism that influence transformation kinetics. Our results help shed light on the discrepancies observed in previous measurements of the α-ω transition pressure in zirconium.« less

Time-resolved measurements of coherent structures in the turbulent boundary layer

NASA Astrophysics Data System (ADS)

LeHew, J. A.; Guala, M.; McKeon, B. J.

2013-04-01

Time-resolved particle image velocimetry was used to examine the structure and evolution of swirling coherent structure (SCS), one interpretation of which is a marker for a three-dimensional coherent vortex structure, in wall-parallel planes of a turbulent boundary layer with a large field of view, 4.3 δ × 2.2 δ. Measurements were taken at four different wall-normal locations ranging from y/ δ = 0.08-0.48 at a friction Reynolds number, Re τ = 410. The data set yielded statistically converged results over a larger field of view than typically observed in the literature. The method for identifying and tracking swirling coherent structure is discussed, and the resulting trajectories, convection velocities, and lifespan of these structures are analyzed at each wall-normal location. The ability of a model in which the entirety of an individual SCS travels at a single convection velocity, consistent with the attached eddy hypothesis of Townsend (The structure of turbulent shear flows. Cambridge University Press, Cambridge, 1976), to describe the data is investigated. A methodology for determining whether such structures are "attached" or "detached" from the wall is also proposed and used to measure the lifespan and convection velocity distributions of these different structures. SCS were found to persist for longer periods of time further from the wall, particularly those inferred to be "detached" from the wall, which could be tracked for longer than 5 eddy turnover times.

Pathways of energy transfer in LHCII revealed by room-temperature 2D electronic spectroscopy.

PubMed

Wells, Kym L; Lambrev, Petar H; Zhang, Zhengyang; Garab, Gyözö; Tan, Howe-Siang

2014-06-21

We present here the first room-temperature 2D electronic spectroscopy study of energy transfer in the plant light-harvesting complex II, LHCII. Two-dimensional electronic spectroscopy has been used to study energy transfer dynamics in LHCII trimers from the chlorophyll b Qy band to the chlorophyll a Qy band. Observing cross-peak regions corresponding to couplings between different excitonic states reveals partially resolved fine structure at the exciton level that cannot be isolated by pump-probe or linear spectroscopy measurements alone. Global analysis of the data has been performed to identify the pathways and time constants of energy transfer. The measured waiting time (Tw) dependent 2D spectra are found to be composed of 2D decay-associated spectra with three timescales (0.3 ps, 2.3 ps and >20 ps). Direct and multistep cascading pathways from the high-energy chlorophyll b states to the lowest-energy chlorophyll a states have been resolved occurring on time scales of hundreds of femtoseconds to picoseconds.

Dynamics of a pulsed laser generated tin plasma expanding in an oxygen atmosphere

NASA Astrophysics Data System (ADS)

Barreca, F.; Fazio, E.; Neri, F.; Barletta, E.; Trusso, S.; Fazio, B.

2005-10-01

Semiconducting tin oxide can be successfully deposited by means of the laser ablation technique. In particular by ablating metallic tin in a controlled oxygen atmosphere, thin films of SnOx have been deposited. The partial oxygen pressure at which the films are deposited strongly influences both the stoichiometry and the structural properties of the films. In this work, we present a study of the expansion dynamics of the plasma generated by ablating a tin target by means of a pulsed laser using time and space resolved optical emission spectroscopy and fast photography imaging of the expanding plasma. Both Sn I and Sn II optical emission lines have been observed from the time-integrated spectroscopy. Time resolved-measurements revealed the dynamics of the expanding plasma in the ambient oxygen atmosphere. Stoichiometry of the films has been determined by means of X-ray photoelectron spectroscopy and correlated to the expansion dynamics of the plasma.

Compressive hyperspectral time-resolved wide-field fluorescence lifetime imaging

NASA Astrophysics Data System (ADS)

Pian, Qi; Yao, Ruoyang; Sinsuebphon, Nattawut; Intes, Xavier

2017-07-01

Spectrally resolved fluorescence lifetime imaging and spatial multiplexing have offered information content and collection-efficiency boosts in microscopy, but efficient implementations for macroscopic applications are still lacking. An imaging platform based on time-resolved structured light and hyperspectral single-pixel detection has been developed to perform quantitative macroscopic fluorescence lifetime imaging (MFLI) over a large field of view (FOV) and multiple spectral bands simultaneously. The system makes use of three digital micromirror device (DMD)-based spatial light modulators (SLMs) to generate spatial optical bases and reconstruct N by N images over 16 spectral channels with a time-resolved capability (∼40 ps temporal resolution) using fewer than N2 optical measurements. We demonstrate the potential of this new imaging platform by quantitatively imaging near-infrared (NIR) Förster resonance energy transfer (FRET) both in vitro and in vivo. The technique is well suited for quantitative hyperspectral lifetime imaging with a high sensitivity and paves the way for many important biomedical applications.

Recent Advances in 3D Time-Resolved Contrast-Enhanced MR Angiography

PubMed Central

Riederer, Stephen J.; Haider, Clifton R.; Borisch, Eric A.; Weavers, Paul T.; Young, Phillip M.

2015-01-01

Contrast-enhanced MR angiography (CE-MRA) was first introduced for clinical studies approximately 20 years ago. Early work provided 3 to 4 mm spatial resolution with acquisition times in the 30 sec range. Since that time there has been continuing effort to provide improved spatial resolution with reduced acquisition time, allowing high resolution three-dimensional (3D) time-resolved studies. The purpose of this work is to describe how this has been accomplished. Specific technical enablers have been: improved gradients allowing reduced repetition times, improved k-space sampling and reconstruction methods, parallel acquisition particularly in two directions, and improved and higher count receiver coil arrays. These have collectively made high resolution time-resolved studies readily available for many anatomic regions. Depending on the application, approximate 1 mm isotropic resolution is now possible with frame times of several seconds. Clinical applications of time-resolved CE-MRA are briefly reviewed. PMID:26032598

Transition mechanism of sH to filled-ice Ih structure of methane hydrate under fixed pressure condition

NASA Astrophysics Data System (ADS)

Kadobayashi, H.; Hirai, H.; Ohfuji, H.; Kojima, Y.; Ohishi, Y.; Hirao, N.; Ohtake, M.; Yamamoto, Y.

2017-10-01

The phase transition mechanism of methane hydrate from sH to filled-ice Ih structure was examined using a combination of time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device (CCD) camera observation under fixed pressure conditions. Prior to time-resolved Raman experiments, the typical C-H vibration modes and their pressure dependence of three methane hydrate structures, fluid methane and solid methane were measured using Raman spectroscopy to distinguish the phase transitions of methane hydrates from decomposition to solid methane and ice VI or VII. Experimental results by XRD, Raman spectroscopy and CCD camera observation revealed that the structural transition of sH to filled-ice Ih occurs through a collapse of the sH framework followed by the release of fluid methane that is then gradually incorporated into the filled-ice Ih to reconstruct its structure. These observations suggest that the phase transition of sH to filled-ice Ih takes place by a typical reconstructive mechanism.

Time-resolved x-ray absorption spectroscopy: Watching atoms dance

NASA Astrophysics Data System (ADS)

Milne, Chris J.; Pham, Van-Thai; Gawelda, Wojciech; van der Veen, Renske M.; El Nahhas, Amal; Johnson, Steven L.; Beaud, Paul; Ingold, Gerhard; Lima, Frederico; Vithanage, Dimali A.; Benfatto, Maurizio; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Hauser, Andreas; Abela, Rafael; Bressler, Christian; Chergui, Majed

2009-11-01

The introduction of pump-probe techniques to the field of x-ray absorption spectroscopy (XAS) has allowed the monitoring of both structural and electronic dynamics of disordered systems in the condensed phase with unprecedented accuracy, both in time and in space. We present results on the electronically excited high-spin state structure of an Fe(II) molecular species, [FeII(bpy)3]2+, in aqueous solution, resolving the Fe-N bond distance elongation as 0.2 Å. In addition an analysis technique using the reduced χ2 goodness of fit between FEFF EXAFS simulations and the experimental transient absorption signal in energy space has been successfully tested as a function of excited state population and chemical shift, demonstrating its applicability in situations where the fractional excited state population cannot be determined through other measurements. Finally by using a novel ultrafast hard x-ray 'slicing' source the question of how the molecule relaxes after optical excitation has been successfully resolved using femtosecond XANES.

Resolving the Detailed Structure of Cortical and Thalamic Neurons in the Adult Rat Brain with Refined Biotinylated Dextran Amine Labeling

PubMed Central

Ling, Changying; Hendrickson, Michael L.; Kalil, Ronald E.

2012-01-01

Biotinylated dextran amine (BDA) has been used frequently for both anterograde and retrograde pathway tracing in the central nervous system. Typically, BDA labels axons and cell somas in sufficient detail to identify their topographical location accurately. However, BDA labeling often has proved to be inadequate to resolve the fine structural details of axon arbors or the dendrites of neurons at a distance from the site of BDA injection. To overcome this limitation, we varied several experimental parameters associated with the BDA labeling of neurons in the adult rat brain in order to improve the sensitivity of the method. Specifically, we compared the effect on labeling sensitivity of: (a) using 3,000 or 10,000 MW BDA; (b) injecting different volumes of BDA; (c) co-injecting BDA with NMDA; and (d) employing various post-injection survival times. Following the extracellular injection of BDA into the visual cortex, labeled cells and axons were observed in both cortical and thalamic areas of all animals studied. However, the detailed morphology of axon arbors and distal dendrites was evident only under optimal conditions for BDA labeling that take into account the: molecular weight of the BDA used, concentration and volume of BDA injected, post-injection survival time, and toning of the resolved BDA with gold and silver. In these instances, anterogradely labeled axons and retrogradely labeled dendrites were resolved in fine detail, approximating that which can be achieved with intracellularly injected compounds such as biocytin or fluorescent dyes. PMID:23144777

Watching hydrogen-bond dynamics in a β-turn by transient two-dimensional infrared spectroscopy

NASA Astrophysics Data System (ADS)

Kolano, Christoph; Helbing, Jan; Kozinski, Mariusz; Sander, Wolfram; Hamm, Peter

2006-11-01

X-ray crystallography and nuclear magnetic resonance measurements provide us with atomically resolved structures of an ever-growing number of biomolecules. These static structural snapshots are important to our understanding of biomolecular function, but real biomolecules are dynamic entities that often exploit conformational changes and transient molecular interactions to perform their tasks. Nuclear magnetic resonance methods can follow such structural changes, but only on millisecond timescales under non-equilibrium conditions. Time-resolved X-ray crystallography has recently been used to monitor the photodissociation of CO from myoglobin on a subnanosecond timescale, yet remains challenging to apply more widely. In contrast, two-dimensional infrared spectroscopy, which maps vibrational coupling between molecular groups and hence their relative positions and orientations, is now routinely used to study equilibrium processes on picosecond timescales. Here we show that the extension of this method into the non-equilibrium regime allows us to observe in real time in a short peptide the weakening of an intramolecular hydrogen bond and concomitant opening of a β-turn. We find that the rate of this process is two orders of magnitude faster than the `folding speed limit' established for contact formation between protein side chains.

The crustal structures from Wuyi-Yunkai orogen to Taiwan orogen: the onshore-offshore wide-angle seismic experiment of TAIGER and ATSEE projects

NASA Astrophysics Data System (ADS)

Kuochen, H.; Kuo, N. Y. W.; Wang, C. Y.; Jin, X.; Cai, H. T.; Lin, J. Y.; Wu, F. T.; Yen, H. Y.; Huang, B. S.; Liang, W. T.; Okaya, D. A.; Brown, L. D.

2015-12-01

The crustal structure is key information for understanding the tectonic framework and geological evolution in the southeastern China and its adjacent area. In this study, we integrated the data sets from the TAIGER and ATSEE projects to resolve onshore-offshore deep crustal seismic profiles from the Wuyi-Yunkai orogen to the Taiwan orogen in southeastern China. Totally, there are three seismic profiles resolved and the longest profile is 850 km. Unlike 2D and 3D first arrival travel-time tomography from previous studies, we used both refracted and reflected phases (Pg, Pn, PcP, and PmP) to model the crustal structures and the crustal reflectors. 40 shots, 2 earthquakes, and about 1,950 stations were used and 15,319 arrivals were picked among three transects. As a result, the complex crustal evolution since Paleozoic era are shown, which involved the closed Paleozoic rifted basin in central Fujian, the Cenozoic extension due to South China sea opening beneath the coastline of southern Fujian, and the on-going collision of the Taiwan orogen.

Effect of enzymatic hydrolysis on native starch granule structure.

PubMed

Blazek, Jaroslav; Gilbert, Elliot Paul

2010-12-13

Enzymatic digestion of six starches of different botanical origin was studied in real time by in situ time-resolved small-angle neutron scattering (SANS) and complemented by the analysis of native and digested material by X-ray diffraction, differential scanning calorimetry, small-angle X-ray scattering, and scanning electron microscopy with the aim of following changes in starch granule nanostructure during enzymatic digestion. This range of techniques enables coverage over five orders of length-scale, as is necessary for this hierarchically structured material. Starches studied varied in their digestibility and displayed structural differences in the course of enzymatic digestion. The use of time-resolved SANS showed that solvent-drying of digested residues does not induce any structural artifacts on the length scale followed by small-angle scattering. In the course of digestion, the lamellar peak intensity gradually decreased and low-q scattering increased. These trends were more substantial for A-type than for B-type starches. These observations were explained by preferential digestion of the amorphous growth rings. Hydrolysis of the semicrystalline growth rings was explained on the basis of a liquid-crystalline model for starch considering differences between A-type and B-type starches in the length and rigidity of amylopectin spacers and branches. As evidenced by differing morphologies of enzymatic attack among varieties, the existence of granular pores and channels and physical penetrability of the amorphous growth ring affect the accessibility of the enzyme to the substrate. The combined effects of the granule microstructure and the nanostructure of the growth rings influence the opportunity of the enzyme to access its substrate; as a consequence, these structures determine the enzymatic digestibility of granular starches more than the absolute physical densities of the amorphous growth rings and amorphous and crystalline regions of the semicrystalline growth rings.

Exploring Nuclear Photorelaxation of Pyranine in Aqueous Solution: an Integrated Ab-Initio Molecular Dynamics and Time Resolved Vibrational Analysis Approach.

PubMed

Chiariello, Maria Gabriella; Rega, Nadia

2018-03-22

Advances in time-resolved vibrational spectroscopy techniques provided a new stimulus for understanding the transient molecular dynamics triggered by the electronic excitation. The detailed interpretation of such time-dependent spectroscopic signals is a challenging task from both experimental and theoretical points of view. We simulated and analyzed the transient photorelaxation of the pyranine photoacid in aqueous solution, with special focus on structural parameters and low frequency skeleton modes that are possibly preparatory for the photoreaction occurring at later time, as suggested by experimental spectroscopic studies. To this aim, we adopted an accurate computational protocol that combines excited state ab initio molecular dynamics within an hybrid quantum mechanical/molecular mechanics framework and a time-resolved vibrational analysis based on the Wavelet transform. According to our results, the main nuclear relaxation on the excited potential energy surface is completed in about 500 fs, in agreement with experimental data. The rearrangement of C-C bonds occurs according to a complex vibrational dynamics, showing oscillatory patterns that are out of phase and modulated by modes below 200 cm -1 . We also analyzed in both the ground and the excited state the evolution of some structural parameters involved in excited state proton transfer reaction, namely, those involving the pyranine and the water molecule hydrogen bonded to the phenolic O-H group. Both the hydrogen bond distance and the intermolecular orientation are optimized in the excited state, resulting in a tighter proton donor-acceptor couple. Indeed, we found evidence that collective low frequency skeleton modes, such as the out of plane wagging at 108 cm -1 and the deformation at 280 cm -1 , are photoactivated by the ultrafast part of the relaxation and modulate the pyranine-water molecule rearrangement, favoring the preparatory step for the photoreactivity.

Ultrafast nuclear dynamics in halomethanes studied with time-resolved Coulomb explosion imaging and channel-selective Fourier spectroscopy

NASA Astrophysics Data System (ADS)

Malakar, Y.; Kaderiya, B.; Pearson, W. L.; Ziaee, F.; Kanaka Raju, P.; Zohrabi, M.; Jensen, K.; Rajput, J.; Ben-Itzhak, I.; Rolles, D.; Rudenko, A.

2016-05-01

Halomethanes have recently attracted considerable attention since they often serve as prototype systems for laser-controlled chemistry (e.g., selective bond breaking or concerted elimination reactions), and are important molecules in atmospheric chemistry. Here we combine a femtosecond laser pump-probe setup with coincident 3D ion momentum imaging apparatus to study strong-field induced nuclear dynamics in methane and several of its halogenated derivatives (CH3 I, CH2 I2, CH2 ICl). We apply a time-resolved Coulomb explosion imaging technique to map the nuclear motion on both, bound and continuum potential surfaces, disentangle different fragmentation pathways and, for halogenated molecules, observe clear signatures of vibrational wave packets in neutral or ionized states. Channel-selective and kinetic-energy resolved Fourier analysis of these data allows for unique identification of different electronic states and vibrational modes responsible for a particular structure. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. DOE. K. R. P. and W. L. P. supported by NSF Award No. IIA-143049. K.J. supported by the NSF-REU Grant No. PHYS-1461251.

Investigations on the interactions of aurintricarboxylic acid with bovine serum albumin: Steady state/time resolved spectroscopic and docking studies.

PubMed

Bardhan, Munmun; Chowdhury, Joydeep; Ganguly, Tapan

2011-01-10

In this paper, the nature of the interactions between bovine serum albumin (BSA) and aurintricarboxylic acid (ATA) has been investigated by measuring steady state and time-resolved fluorescence, circular dichroism (CD), FT-IR and fluorescence anisotropy in protein environment under physiological conditions. From the analysis of the steady state and time-resolved fluorescence quenching of BSA in aqueous solution in presence of ATA it has been inferred that the nature of the quenching originates from the combined effect of static and dynamic modes. From the determination of the thermodynamic parameters obtained from temperature-dependent changes in K(b) (binding constant) it was apparent that the combined effect of hydrophobic association and electrostatic attraction is responsible for the interaction of ATA with BSA. The effect of ATA on the conformation of BSA has been examined by analyzing CD spectrum. Though the observed results demonstrate some conformational changes in BSA in presence of ATA but the secondary structure of BSA, predominantly of α-helix, is found to retain its identity. Molecular docking of ATA with BSA also indicates that ATA docks through hydrophobic interaction. Copyright © 2010 Elsevier B.V. All rights reserved.

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.

Time Resolved X-ray Surface Diffraction Study of Surface Transport During Pulsed Laser Deposition of SrTiO_3

NASA Astrophysics Data System (ADS)

Tischler, J. Z.; Larson, B. C.; Eres, Gyula; Rouleau, D. H.; Lowndes, D. H.; Zschack, P.

2003-03-01

Time-resolved, phin-situ, surface x-ray diffraction measurements at the UNICAT beamline at the Advanced Photon Source were used to study the early stages of growth during pulsed laser deposition of SrTiO_3. Crystal truncation rod (CTR) intensity oscillations observed at anti-Bragg positions indicated layer by layer growth in the broad temperature range of 350^oC to 850^oC. The structure of the CTR intensities between laser pulses shows two time scales, a prompt (< 1 msec) response when the laser ablation plume arrives at the substrate followed by a slower ( ˜1-10 sec) intensity response. The fast time scale is attributed to a prompt ˜μ s transfer of newly arrived species to a lower level, and the slower to material transfer delayed by the evolution of small islands. We present analyses of the CTR intensties in terms of the fraction of the deposited material that promptly changes level and the kinetics of the delayed transfer as a function of surface coverage.

Degradation of CMOS image sensors in deep-submicron technology due to γ-irradiation

NASA Astrophysics Data System (ADS)

Rao, Padmakumar R.; Wang, Xinyang; Theuwissen, Albert J. P.

2008-09-01

In this work, radiation induced damage mechanisms in deep submicron technology is resolved using finger gated-diodes (FGDs) as a radiation sensitive tool. It is found that these structures are simple yet efficient structures to resolve radiation induced damage in advanced CMOS processes. The degradation of the CMOS image sensors in deep-submicron technology due to γ-ray irradiation is studied by developing a model for the spectral response of the sensor and also by the dark-signal degradation as a function of STI (shallow-trench isolation) parameters. It is found that threshold shifts in the gate-oxide/silicon interface as well as minority carrier life-time variations in the silicon bulk are minimal. The top-layer material properties and the photodiode Si-SiO2 interface quality are degraded due to γ-ray irradiation. Results further suggest that p-well passivated structures are inevitable for radiation-hard designs. It was found that high electrical fields in submicron technologies pose a threat to high quality imaging in harsh environments.

Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites.

PubMed

Wu, Xiaoxi; Tan, Liang Z; Shen, Xiaozhe; Hu, Te; Miyata, Kiyoshi; Trinh, M Tuan; Li, Renkai; Coffee, Ryan; Liu, Shi; Egger, David A; Makasyuk, Igor; Zheng, Qiang; Fry, Alan; Robinson, Joseph S; Smith, Matthew D; Guzelturk, Burak; Karunadasa, Hemamala I; Wang, Xijie; Zhu, Xiaoyang; Kronik, Leeor; Rappe, Andrew M; Lindenberg, Aaron M

2017-07-01

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. This work shows the important role of light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.

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

Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. Here, this work shows the important role ofmore » light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.« less

Time-resolved structural dynamics of thin metal films heated with femtosecond optical pulses.

PubMed

Chen, Jie; Chen, Wei-Kan; Tang, Jau; Rentzepis, Peter M

2011-11-22

We utilize 100 fs optical pulses to induce ultrafast disorder of 35- to 150-nm thick single Au(111) crystals and observe the subsequent structural evolution using 0.6-ps, 8.04-keV X-ray pulses. Monitoring the picosecond time-dependent modulation of the X-ray diffraction intensity, width, and shift, we have measured directly electron/phonon coupling, phonon/lattice interaction, and a histogram of the lattice disorder evolution, such as lattice breath due to a pressure wave propagating at sonic velocity, lattice melting, and recrystallization, including mosaic formation. Results of theoretical simulations agree and support the experimental data of the lattice/liquid phase transition process. These time-resolved X-ray diffraction data provide a detailed description of all the significant processes induced by ultrafast laser pulses impinging on thin metallic single crystals.

Cluster Morphology-Polymer Dynamics Correlations in Sulfonated Polystyrene Melts: Computational Study

DOE PAGES

Agrawal, Anupriya; Perahia, Dvora; Grest, Gary S.

2016-04-11

Reaching exceptionally long times up to 500 ns in equilibrium and nonequilibrium molecular dynamics simulations studies, we have attained a fundamental molecular understanding of the correlation of ionomer clusters structure and multiscale dynamics, providing new insight into one critical, long-standing challenge in ionic polymer physics. The cluster structure in melts of sulfonated polystyrene with Na + and Mg 2+ counterions are resolved and correlated with the dynamics on multiple length and time scales extracted from measurements of the dynamic structure factor and shear rheology. We find that as the morphology of the ionic clusters changes from ladderlike for Na +more » to disordered structures for Mg 2+, the dynamic structure factor is affected on the length scale corresponding to the ionic clusters. Lastly, rheology studies show that the viscosity for Mg 2+ melts is higher than for Na + ones for all shear rates, which is well correlated with the larger ionic clusters’ size for the Mg 2+ melts.« less

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.

4D Magnetic Resonance Velocimetry in a 3D printed brain aneurysm

NASA Astrophysics Data System (ADS)

Amili, Omid; Schiavazzi, Daniele; Coletti, Filippo

2016-11-01

Cerebral aneurysms are of great clinical importance. It is believed that hemodynamics play a critical role in the development, growth, and rupture of brain arteries with such condition. The flow structure in the aneurysm sac is complex, unsteady, and three-dimensional. Therefore the time-resolved measurement of the three-dimensional three-component velocity field is crucial to predict the clinical outcome. In this study magnetic resonance velocimetry is used to assess the fluid dynamics inside a 3D printed model of a giant intracranial aneurysm. We reach sub-millimeter resolution while resolving sixteen instances within the cardiac cycle. The physiological flow waveform is imposed using an in-house built pump in a flow circuit where the cardiovascular impedance is matched. The flow evolution over time is reconstructed in detail. The complex flow structure is characterized by vortical and helical motions that reside in the aneurysm for most part of the cycle. The 4D pressured distribution is also reconstructed from the velocity field. The present case study was used in a previous CFD challenge, therefore these results may provide useful experimental comparison for simulations performed by other research groups.

Time-resolved X-ray diffraction microprobe studies of the conversion of cellulose I to ethylenediamine-cellulose I

PubMed Central

Nishiyama, Yoshiharu; Wada, Masahisa; Hanson, B. Leif

2012-01-01

Structural changes during the treatment of films of highly crystalline microfibers of Cladophora cellulose with ethylenediamine (EDA) have been studied by time-resolved X-ray microprobe diffraction methods. As EDA penetrates the sample and converts cellulose I to EDA-cellulose I, the measured profile widths of reflections reveal changes in the shapes and average dimensions of cellulose I and EDA-cellulose I crystals. The (200) direction of cellulose I is most resistant to EDA penetration, with EDA penetrating most effectively at the hydrophilic edges of the hydrogen bonded sheets of cellulose chains. Most of the cellulose chains in the initial crystals of cellulose I are incorporated into crystals of EDA-cellulose I. The size of the emerging EDA-cellulose I crystals is limited to about half of their size in cellulose I, most likely due to strains introduced by the penetration of EDA molecules. There is no evidence of any gradual structural transition from cellulose I to EDA-cellulose I involving a continuously changing intermediate phase. Rather, the results point to a rapid transition to EDA-cellulose I in regions of the microfibrils that have been penetrated by EDA. PMID:22693365

Visualizing electron dynamics in organic materials: Charge transport through molecules and angular resolved photoemission

NASA Astrophysics Data System (ADS)

Kümmel, Stephan

Being able to visualize the dynamics of electrons in organic materials is a fascinating perspective. Simulations based on time-dependent density functional theory allow to realize this hope, as they visualize the flow of charge through molecular structures in real-space and real-time. We here present results on two fundamental processes: Photoemission from organic semiconductor molecules and charge transport through molecular structures. In the first part we demonstrate that angular resolved photoemission intensities - from both theory and experiment - can often be interpreted as a visualization of molecular orbitals. However, counter-intuitive quantum-mechanical electron dynamics such as emission perpendicular to the direction of the electrical field can substantially alter the picture, adding surprising features to the molecular orbital interpretation. In a second study we calculate the flow of charge through conjugated molecules. The calculations show in real time how breaks in the conjugation can lead to a local buildup of charge and the formation of local electrical dipoles. These can interact with neighboring molecular chains. As a consequence, collections of ''molecular electrical wires'' can show distinctly different characteristics than ''classical electrical wires''. German Science Foundation GRK 1640.

Contrast-enhanced time-resolved MRA for follow-up of intracranial aneurysms treated with the pipeline embolization device.

PubMed

Boddu, S R; Tong, F C; Dehkharghani, S; Dion, J E; Saindane, A M

2014-01-01

Endovascular reconstruction and flow diversion by using the Pipeline Embolization Device is an effective treatment for complex cerebral aneurysms. Accurate noninvasive alternatives to DSA for follow-up after Pipeline Embolization Device treatment are desirable. This study evaluated the accuracy of contrast-enhanced time-resolved MRA for this purpose, hypothesizing that contrast-enhanced time-resolved MRA will be comparable with DSA and superior to 3D-TOF MRA. During a 24-month period, 37 Pipeline Embolization Device-treated intracranial aneurysms in 26 patients underwent initial follow-up by using 3D-TOF MRA, contrast-enhanced time-resolved MRA, and DSA. MRA was performed on a 1.5T unit by using 3D-TOF and time-resolved imaging of contrast kinetics. All patients underwent DSA a median of 0 days (range, 0-68) after MRA. Studies were evaluated for aneurysm occlusion, quality of visualization of the reconstructed artery, and measurable luminal diameter of the Pipeline Embolization Device, with DSA used as the reference standard. The sensitivity, specificity, and positive and negative predictive values of contrast-enhanced time-resolved MRA relative to DSA for posttreatment aneurysm occlusion were 96%, 85%, 92%, and 92%. Contrast-enhanced time-resolved MRA demonstrated superior quality of visualization (P = .0001) and a higher measurable luminal diameter (P = .0001) of the reconstructed artery compared with 3D-TOF MRA but no significant difference compared with DSA. Contrast-enhanced time-resolved MRA underestimated the luminal diameter of the reconstructed artery by 0.965 ± 0.497 mm (27% ± 13%) relative to DSA. Contrast-enhanced time-resolved MRA is a reliable noninvasive method for monitoring intracranial aneurysms following flow diversion and vessel reconstruction by using the Pipeline Embolization Device. © 2014 by American Journal of Neuroradiology.

Ultrafast carrier dynamics in a GaN/Al 0.18Ga0.82N superlattice

NASA Astrophysics Data System (ADS)

Mahler, Felix; Tomm, Jens W.; Reimann, Klaus; Woerner, Michael; Elsaesser, Thomas; Flytzanis, Christos; Hoffmann, Veit; Weyers, Markus

2018-04-01

Relaxation processes of photoexcited carriers in a GaN /Al0.18Ga0.82N superlattice are studied in femtosecond spectrally resolved reflectivity measurements at ambient temperature. The transient reflectivity reveals electron trapping into defect states close to the conduction-band minimum with a 150-200 fs time constant, followed by few-picosecond carrier cooling. A second slower trapping process into a different manifold of defect states is observed on a time scale of approximately 10 ps. Our results establish the prominent role of structural defects and disorder for ultrafast carrier dynamics in nitride semiconductor structures.

An inexpensive technique for the time resolved laser induced plasma spectroscopy

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

Ahmed, Rizwan, E-mail: rizwan.ahmed@ncp.edu.pk; Ahmed, Nasar; Iqbal, J.

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 informationmore » 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.« less

Structurally Resolved Abundances and Depletions in the Rho OPH Cloud

NASA Astrophysics Data System (ADS)

Seab, C.

1995-07-01

The mechanism that determines the pattern of depletion ofelements in the interstellar medium has been a problem for along time. It is clear that some of the most refractoryelements such as Si, Fe, and Mg, are heavily depleted onto theinterstellar grains. On the other hand, some elements such asS and Zn are normally either undepleted or very lightlydepleted. The difference between the two cases is notunderstood. We propose to address this question with adetailed study of the depletion patterns in the Rho Ophiuchicloud. This study is strongly based on a combination of thecapabilities of two modern instruments: the GHRS for high-resolution UV data, and the Ultra High Resolution Facility(UHRF) of the AAT. This instrument has been used to obtain NaI line profiles in the Rho Oph cloud with a resolution ofR=1,000,000. The combination of these two types of data willbe used to resolve the velocity structure of the elementdepletions in the cloud.

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

Time-resolved experiments in the frequency domain using synchrotron radiation (invited)

NASA Astrophysics Data System (ADS)

De Stasio, Gelsomina; Giusti, A. M.; Parasassi, T.; Ravagnan, G.; Sapora, O.

1992-01-01

PLASTIQUE is the only synchrotron radiation beam line in the world that performs time-resolved fluorescence experiments in frequency domain. These experiments are extremely valuable sources of information on the structure and the dynamics of molecules. This technique measures fluorescence lifetimes with picosecond resolution in the near UV spectral range. Such accurate measurements are rendered possible by taking phase and modulation data, and by the advantages of the cross-correlation technique. A successful experiment demonstrated the radiation damage induced by low doses of radiation on rabbit blood cell membranes.

Implementation of Time-Resolved Step-Scan Fourier Transform Infrared (FT-IR) Spectroscopy Using a kHz Repetition Rate Pump Laser

PubMed Central

MAGANA, DONNY; PARUL, DZMITRY; DYER, R. BRIAN; SHREVE, ANDREW P.

2011-01-01

Time-resolved step-scan Fourier transform infrared (FT-IR) spectroscopy has been shown to be invaluable for studying excited-state structures and dynamics in both biological and inorganic systems. Despite the established utility of this method, technical challenges continue to limit the data quality and more wide ranging applications. A critical problem has been the low laser repetition rate and interferometer stepping rate (both are typically 10 Hz) used for data acquisition. Here we demonstrate significant improvement in the quality of time-resolved spectra through the use of a kHz repetition rate laser to achieve kHz excitation and data collection rates while stepping the spectrometer at 200 Hz. We have studied the metal-to-ligand charge transfer excited state of Ru(bipyridine)3Cl2 in deuterated acetonitrile to test and optimize high repetition rate data collection. Comparison of different interferometer stepping rates reveals an optimum rate of 200 Hz due to minimization of long-term baseline drift. With the improved collection efficiency and signal-to-noise ratio, better assignments of the MLCT excited-state bands can be made. Using optimized parameters, carbonmonoxy myoglobin in deuterated buffer is also studied by observing the infrared signatures of carbon monoxide photolysis upon excitation of the heme. We conclude from these studies that a substantial increase in performance of ss-FT-IR instrumentation is achieved by coupling commercial infrared benches with kHz repetition rate lasers. PMID:21513597

Interpretation of measurements of dynamic fluorescence of the eye

NASA Astrophysics Data System (ADS)

Schweitzer, Dietrich; Hammer, Martin; Jentsch, Susanne; Schenke, Stefan

2007-09-01

First pathological alterations occur at cellular level, most in metabolism. An indirect estimation of metabolic activity in cells is measurement of microcirculation. Measurements of tissue autofluorescence are potentially suited for direct investigation of cellular metabolism. Besides redox pairs of co-enzymes (NADH-NAD, FADH2-FAD) several other fluorophores are excited in tissue. In addition, a number of anatomical structures are simultaneously excited, when investigating the eye-ground. In this study, spectral and time resolved comparison was performed between purified substances, single ocular structures and in vivo measurements of the time-resolved autofluorescence at the human eye. In human eyes, the ageing pigment lipofuscin covers other fluorophores at the fundus in long - wave visible range. Applying lifetime measurements, weakly emitting fluorophores can be detected, when the lifetimes are different from the strongly emitting fluorophore. For this, the autofluorescence was excited at 468 nm and detected in two spectral ranges (500 nm-560 nm, 560 nm-700 nm). In tri-exponential fitting, the short lifetime corresponds to retinal pigment epithelium, the mean lifetime corresponds probably to neural retina and the long lifetime is caused by fluorescence of connective tissue.

Time-resolved studies define the nature of toxic IAPP intermediates, providing insight for anti-amyloidosis therapeutics

PubMed Central

Abedini, Andisheh; Plesner, Annette; Cao, Ping; Ridgway, Zachary; Zhang, Jinghua; Tu, Ling-Hsien; Middleton, Chris T; Chao, Brian; Sartori, Daniel J; Meng, Fanling; Wang, Hui; Wong, Amy G; Zanni, Martin T; Verchere, C Bruce; Raleigh, Daniel P; Schmidt, Ann Marie

2016-01-01

Islet amyloidosis by IAPP contributes to pancreatic β-cell death in diabetes, but the nature of toxic IAPP species remains elusive. Using concurrent time-resolved biophysical and biological measurements, we define the toxic species produced during IAPP amyloid formation and link their properties to induction of rat INS-1 β-cell and murine islet toxicity. These globally flexible, low order oligomers upregulate pro-inflammatory markers and induce reactive oxygen species. They do not bind 1-anilnonaphthalene-8-sulphonic acid and lack extensive β-sheet structure. Aromatic interactions modulate, but are not required for toxicity. Not all IAPP oligomers are toxic; toxicity depends on their partially structured conformational states. Some anti-amyloid agents paradoxically prolong cytotoxicity by prolonging the lifetime of the toxic species. The data highlight the distinguishing properties of toxic IAPP oligomers and the common features that they share with toxic species reported for other amyloidogenic polypeptides, providing information for rational drug design to treat IAPP induced β-cell death. DOI: http://dx.doi.org/10.7554/eLife.12977.001 PMID:27213520

From Supercomputer Modeling to Highest Mass Resolution in FT-ICR.

PubMed

N Nikolaev, Evgene; N Vladimirov, Gleb; Jertz, Roland; Baykut, Gökhan

2013-01-01

Understanding of behavior of ion ensembles inside FT-ICR cell based on the computer simulation of ion motion gives rise to the new ideas of cell designs. The recently introduced novel FT-ICR cell based on a Penning ion trap with specially shaped excitation and detection electrodes prevents distortion of ion cyclotron motion phases (normally caused by non-ideal electric trapping fields) by averaging the trapping DC electric field during the ion motion in the ICR cell. Detection times of 5 min resulting in resolving power close to 40,000,000 have been reached for reserpine at m/z 609 at a magnetic field of only 7 Tesla. Fine structures of resolved 13Cn isotopic cluster groups could be measured for molecular masses up to 5.7 kDa (insulin) with resolving power of 4,000,000 at 7 Tesla. Based on resolved fine structure patterns atomic compositions can be directly determined using a new developed algorithm for fine structure processing. Mass spectra of proteins and multimers of proteins reaching masses up to 186 kDa (enolase tetramer) could be measured with isotopic resolution. For instance, at 7 Tesla resolving power of 800,000 was achieved for enolase dimer (96 kDa) and 500,000 for molecular masses above 100 kDa. Experimental data indicate that there is practically no limit for the resolving power of this ICR cell except by collisional damping in the ultrahigh vacuum chamber.

X-ray absorption spectroscopy with time-tagged photon counting: Application to study the structure of Co(I) intermediate of H2 evolving photo-catalyst

PubMed Central

Smolentsev, Grigory; Guda, Alexander; Janousch, Markus; Frieh, Cristophe; Jud, Gaudenz; Zamponi, Flavio; Chavarot-Kerlidou, Murielle; Artero, Vincent; van Bokhoven, Jeroen A.; Nachtegaal, Maarten

2015-01-01

In order to probe the structure of reaction intermediates of photochemical reactions a new setup for laser-initiated time-resolved X-ray absorption (XAS) measurements has been developed. With this approach the arrival time of each photon in respect to the laser pulse is measured and therefore full kinetic information is obtained. All X-rays that reach the detector are used to measure this kinetic information and therefore the detection efficiency of this method is high. The newly developed setup is optimized for time-resolved experiments in the microsecond range for samples with relatively low metal concentration (~1mM). This setup has been applied to study a multicomponent photocatalytic system with a Co(dmgBF2)2 catalyst (dmg2− = dimethylglyoximato dianion), [Ru(bpy)3]2+ chromophore (bpy=2,2′-bipyridine) and methyl viologen as the electron relay. On the basis of analysis of hundreds of Co K-edge XAS spectra corresponding to different delay times after the laser excitation of the chromophore, the presence of a Co(I) intermediate is confirmed. The calculated X-ray transient signal for a model of Co(I) state with a 0.14 Å displacement of Co out of the dmg ligand plane and with the closest solvent molecule at a distance of 2.06 Å gives reasonable agreement with the experimental data. PMID:25415460

Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

PubMed

Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

2018-03-06

Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To scrutinize this intriguing and challenging scientific issue, expanded porphyrins have been utilized as the ideal testing platform for investigating aromaticity because they show distinct aromatic and antiaromatic characters with aromaticity-specific spectroscopic features. Expanded porphyrins exhibit perfect aromatic and antiaromatic congener pairs having the same molecular framework but different numbers of π electrons, which facilitates the study of the pure effect of aromaticity by comparative analyses. On the basis of the characteristics of expanded porphyrins, time-resolved electronic and vibrational absorption spectroscopies capture the changes in electronic structure and molecular conformations driven by the change in aromaticity and provide clear evidence for aromaticity reversal in the excited states. The approaches described in this Account pave the way for the development of new and alternative experimental indices for the evaluation of excited-state aromaticity, which will enable overarching and fundamental comprehension of the role of (anti)aromaticity in the stability, dynamics, and reactivity in the excited states with possible implications for practical applications.

Spectrally- and Time-Resolved Sum Frequency Generation (STiR-SFG): a new tool for ultrafast hydrogen bond dynamics at interfaces.

NASA Astrophysics Data System (ADS)

Benderskii, Alexander; Bordenyuk, Andrey; Weeraman, Champika

2006-03-01

The recently developed spectrally- and time-resolved Sum Frequency Generation (STiR-SFG) is a surface-selective 3-wave mixing (IR+visible) spectroscopic technique capable of measuring ultrafast spectral evolution of vibrational coherences. A detailed description of this measurement will be presented, and a noniterative method or deconvolving the laser pulses will be introduced to obtain the molecular response function. STiR-SFG, combined with the frequency-domain SFG spectroscopy, was applied to study hydrogen bonding dynamics at aqueous interfaces (D2O/CaF2). Spectral dynamics of the OD-stretch on the 50-150 fs time scale provides real-time observation of ultrafast H-bond rearrangement. Tuning the IR wavelength to the blue or red side of the OD-stretch transition, we selectively monitor the dynamics of different sub-ensembles in the distribution of the H-bond structures. The blue-side excitation (weaker H-bonding) shows monotonic red-shift of the OD-frequency. In contrast, the red-side excitation (stronger H-bonding structures) produces a blue-shift and a recursion, which may indicate the presence of an underdamped intermolecular mode of interfacial water. Effect of electrolyte concentration on the H-bond dynamics will be discussed.

Probing the solvation structure and dynamics in ionic liquids by time-resolved infrared spectroscopy of 4-(dimethylamino)benzonitrile.

PubMed

Ando, Rômulo A; Brown-Xu, Samantha E; Nguyen, Lisa N Q; Gustafson, Terry L

2017-09-20

In this work we demonstrate the use of the push-pull model system 4-(dimethylamino)benzonitrile (DMABN) as a convenient molecular probe to investigate the local solvation structure and dynamics by means of time-resolved infrared spectroscopy (TRIR). The photochemical features associated with this system provide several advantages due to the high charge separation between the ground and charge transfer states involving the characteristic nitrile bond, and an excited state lifetime that is long enough to observe the slow solvation dynamics in organic solvents and ionic liquids. The conversion from a locally excited state to an intramolecular charge transfer state (LE-ICT) in ionic liquids shows similar kinetic lifetimes in comparison to organic solvents. This similarity confirms that such conversion depends solely on the intramolecular reorganization of DMABN in the excited state, and not by the dynamics of solvation. In contrast, the relative shift of the ν(CN) vibration during the relaxation of the ICT state reveals two distinct lifetimes that are sensitive to the solvent environment. This study reveals a fast time component which is attributed to the dipolar relaxation of the solvent and a slower time component related to the rotation of the dimethylamino group of DMABN.

A Low-Cost Time-Resolved Spectrometer for the Study of Ruby Emission

ERIC Educational Resources Information Center

McBane, George C.; Cannella, Christian; Schaertel, Stephanie

2018-01-01

A low-cost time-resolved emission spectrometer optimized for ruby emission is presented. The use of a Class II diode laser module as the excitation source reduces costs and hazards. The design presented here can facilitate the inclusion of time-resolved emission spectroscopy with laser excitation sources in the undergraduate laboratory curriculum.…

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy)2]2+

PubMed Central

2015-01-01

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations. PMID:25838847

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

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

Vankó, György; Bordage, Amélie; Pápai, Mátyás

2015-03-19

Theoretical predictions show that depending on the populations of the Fe 3dxy, 3dxz, and 3dyz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy)2]2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the lightmore » excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy)2]2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy)2]2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe-ligand bond-length variations with unprecedented bondlength accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)-high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.« less

Detailed Characterization of a Nanosecond-Lived Excited State: X-ray and Theoretical Investigation of the Quintet State in Photoexcited [Fe(terpy) 2 ] 2+

DOE PAGES

Vanko, Gyorgy; Bordage, Amelie; Papai, Matyas; ...

2015-03-19

Theoretical predictions show that depending on the populations of the Fe 3d xy, 3d xz, and 3d yz orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe(terpy) 2] 2+. The differences in the structure and molecular properties of these 5B2 and 5E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in themore » transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe(terpy) 2] 2+ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe(terpy) 2] 2+ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With ab initio calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as 5E, in agreement with our theoretical expectations.« less

A Q-switched Ho:YAG laser assisted nanosecond time-resolved T-jump transient mid-IR absorbance spectroscopy with high sensitivity

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

Li, Deyong; Li, Yunliang; Li, Hao

2015-05-15

Knowledge of dynamical structure of protein is an important clue to understand its biological function in vivo. Temperature-jump (T-jump) time-resolved transient mid-IR absorbance spectroscopy is a powerful tool in elucidating the protein dynamical structures and the folding/unfolding kinetics of proteins in solution. A home-built setup of T-jump time-resolved transient mid-IR absorbance spectroscopy with high sensitivity is developed, which is composed of a Q-switched Cr, Tm, Ho:YAG laser with an output wavelength at 2.09 μm as the T-jump heating source, and a continuous working CO laser tunable from 1580 to 1980 cm{sup −1} as the IR probe. The results demonstrate thatmore » this system has a sensitivity of 1 × 10{sup −4} ΔOD for a single wavelength detection, and 2 × 10{sup −4} ΔOD for spectral detection in amide I′ region, as well as a temporal resolution of 20 ns. Moreover, the data quality coming from the CO laser is comparable to the one using the commercial quantum cascade laser.« less

Multi-fluid Dynamics for Supersonic Jet-and-Crossflows and Liquid Plug Rupture

NASA Astrophysics Data System (ADS)

Hassan, Ezeldin A.

Multi-fluid dynamics simulations require appropriate numerical treatments based on the main flow characteristics, such as flow speed, turbulence, thermodynamic state, and time and length scales. In this thesis, two distinct problems are investigated: supersonic jet and crossflow interactions; and liquid plug propagation and rupture in an airway. Gaseous non-reactive ethylene jet and air crossflow simulation represents essential physics for fuel injection in SCRAMJET engines. The regime is highly unsteady, involving shocks, turbulent mixing, and large-scale vortical structures. An eddy-viscosity-based multi-scale turbulence model is proposed to resolve turbulent structures consistent with grid resolution and turbulence length scales. Predictions of the time-averaged fuel concentration from the multi-scale model is improved over Reynolds-averaged Navier-Stokes models originally derived from stationary flow. The response to the multi-scale model alone is, however, limited, in cases where the vortical structures are small and scattered thus requiring prohibitively expensive grids in order to resolve the flow field accurately. Statistical information related to turbulent fluctuations is utilized to estimate an effective turbulent Schmidt number, which is shown to be highly varying in space. Accordingly, an adaptive turbulent Schmidt number approach is proposed, by allowing the resolved field to adaptively influence the value of turbulent Schmidt number in the multi-scale turbulence model. The proposed model estimates a time-averaged turbulent Schmidt number adapted to the computed flowfield, instead of the constant value common to the eddy-viscosity-based Navier-Stokes models. This approach is assessed using a grid-refinement study for the normal injection case, and tested with 30 degree injection, showing improved results over the constant turbulent Schmidt model both in mean and variance of fuel concentration predictions. For the incompressible liquid plug propagation and rupture study, numerical simulations are conducted using an Eulerian-Lagrangian approach with a continuous-interface method. A reconstruction scheme is developed to allow topological changes during plug rupture by altering the connectivity information of the interface mesh. Rupture time is shown to be delayed as the initial precursor film thickness increases. During the plug rupture process, a sudden increase of mechanical stresses on the tube wall is recorded, which can cause tissue damage.

Cluster Analysis of Time-Dependent Crystallographic Data: Direct Identification of Time-Independent Structural Intermediates

PubMed Central

Kostov, Konstantin S.; Moffat, Keith

2011-01-01

The initial output of a time-resolved macromolecular crystallography experiment is a time-dependent series of difference electron density maps that displays the time-dependent changes in underlying structure as a reaction progresses. The goal is to interpret such data in terms of a small number of crystallographically refinable, time-independent structures, each associated with a reaction intermediate; to establish the pathways and rate coefficients by which these intermediates interconvert; and thereby to elucidate a chemical kinetic mechanism. One strategy toward achieving this goal is to use cluster analysis, a statistical method that groups objects based on their similarity. If the difference electron density at a particular voxel in the time-dependent difference electron density (TDED) maps is sensitive to the presence of one and only one intermediate, then its temporal evolution will exactly parallel the concentration profile of that intermediate with time. The rationale is therefore to cluster voxels with respect to the shapes of their TDEDs, so that each group or cluster of voxels corresponds to one structural intermediate. Clusters of voxels whose TDEDs reflect the presence of two or more specific intermediates can also be identified. From such groupings one can then infer the number of intermediates, obtain their time-independent difference density characteristics, and refine the structure of each intermediate. We review the principles of cluster analysis and clustering algorithms in a crystallographic context, and describe the application of the method to simulated and experimental time-resolved crystallographic data for the photocycle of photoactive yellow protein. PMID:21244840

Long-time variation in magnetic structure of CeIr 3Si 2: Observation of a nucleation-and-growth process of magnetic domains

DOE PAGES

Motoya, Kiyoichiro; Hagihala, Masato; Takabatake, Toshiro; ...

2016-02-29

CeIr 3Si 2 is the first three-dimensional uniform magnet in which the long-time variation in magnetic structure was observed. To clarify the microscopic mechanism of this magnetic structural change, time-resolved neutron scattering measurements have been reinvestigated. Clear time variations in the line widths as well as the amplitudes of magnetic Bragg diffractions have been observed in this improved instrumentation. On the notion of this observation, a nucleation-and-growth model of magnetic structural change has been presented. The numerical calculation with this model reproduces well the observation.

Long-time variation in magnetic structure of CeIr 3Si 2: Observation of a nucleation-and-growth process of magnetic domains

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

Motoya, Kiyoichiro; Hagihala, Masato; Takabatake, Toshiro

CeIr 3Si 2 is the first three-dimensional uniform magnet in which the long-time variation in magnetic structure was observed. To clarify the microscopic mechanism of this magnetic structural change, time-resolved neutron scattering measurements have been reinvestigated. Clear time variations in the line widths as well as the amplitudes of magnetic Bragg diffractions have been observed in this improved instrumentation. On the notion of this observation, a nucleation-and-growth model of magnetic structural change has been presented. The numerical calculation with this model reproduces well the observation.

Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites

DOE PAGES

Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe; ...

2017-07-26

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. Here, this work shows the important role ofmore » light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.« less

A direct electron detector for time-resolved MeV electron microscopy

DOE PAGES

Vecchione, T.; Denes, P.; Jobe, R. K.; ...

2017-03-15

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here in this paper, we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μm spatial resolution and less than 20 analogue-to-digital converter count RMS pixelmore » noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

A direct electron detector for time-resolved MeV electron microscopy

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

Vecchione, T.; Denes, P.; Jobe, R. K.

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μmμm spatial resolution and less than 20 analogue-to-digital converter count RMS pixel noise. The uniquemore » capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

A direct electron detector for time-resolved MeV electron microscopy

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

Vecchione, T.; Denes, P.; Jobe, R. K.

The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here in this paper, we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μm spatial resolution and less than 20 analogue-to-digital converter count RMS pixelmore » noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.« less

Combining Graphical and Analytical Methods with Molecular Simulations To Analyze Time-Resolved FRET Measurements of Labeled Macromolecules Accurately

PubMed Central

2017-01-01

Förster resonance energy transfer (FRET) measurements from a donor, D, to an acceptor, A, fluorophore are frequently used in vitro and in live cells to reveal information on the structure and dynamics of DA labeled macromolecules. Accurate descriptions of FRET measurements by molecular models are complicated because the fluorophores are usually coupled to the macromolecule via flexible long linkers allowing for diffusional exchange between multiple states with different fluorescence properties caused by distinct environmental quenching, dye mobilities, and variable DA distances. It is often assumed for the analysis of fluorescence intensity decays that DA distances and D quenching are uncorrelated (homogeneous quenching by FRET) and that the exchange between distinct fluorophore states is slow (quasistatic). This allows us to introduce the FRET-induced donor decay, εD(t), a function solely depending on the species fraction distribution of the rate constants of energy transfer by FRET, for a convenient joint analysis of fluorescence decays of FRET and reference samples by integrated graphical and analytical procedures. Additionally, we developed a simulation toolkit to model dye diffusion, fluorescence quenching by the protein surface, and FRET. A benchmark study with simulated fluorescence decays of 500 protein structures demonstrates that the quasistatic homogeneous model works very well and recovers for single conformations the average DA distances with an accuracy of < 2%. For more complex cases, where proteins adopt multiple conformations with significantly different dye environments (heterogeneous case), we introduce a general analysis framework and evaluate its power in resolving heterogeneities in DA distances. The developed fast simulation methods, relying on Brownian dynamics of a coarse-grained dye in its sterically accessible volume, allow us to incorporate structural information in the decay analysis for heterogeneous cases by relating dye states with protein conformations to pave the way for fluorescence and FRET-based dynamic structural biology. Finally, we present theories and simulations to assess the accuracy and precision of steady-state and time-resolved FRET measurements in resolving DA distances on the single-molecule and ensemble level and provide a rigorous framework for estimating approximation, systematic, and statistical errors. PMID:28709377

Time-resolved x-ray diffraction and calorimetric studies at low scan rates

PubMed Central

Yao, Haruhiko; Hatta, Ichiro; Koynova, Rumiana; Tenchov, Boris

1992-01-01

The phase transitions of dipalmitoylphosphatidylethanolamine (DPPE) in excess water have been examined by low-angle time-resolved x-ray diffraction and calorimetry at low scan rates. The lamellar subgel/lamellar liquid-crystalline (Lc → Lα), lamellar gel/lamellar liquid-crystalline (Lβ → Lα), and lamellar liquid-crystalline/lamellar gel (Lα → Lβ) phase transitions proceed via coexistence of the initial and final phases with no detectable intermediates at scan rates 0.1 and 0.5°C/min. At constant temperature within the region of the Lβ → Lα transition the ratio of the two coexisting phases was found to be stable for over 30 min. The state of stable phase coexistence was preceded by a 150-s relaxation taking place at constant temperature after termination of the heating scan in the transition region. While no intermediate structures were present in the coexistence region, a well reproducible multipeak pattern, with at least four prominent heat capacity peaks separated in temperature by 0.4-0.5°C, has been observed in the cooling transition (Lα → Lβ) by calorimetry. The multipeak pattern became distinct with an increase of incubation time in the liquid-crystalline phase. It was also clearly resolved in the x-ray diffraction intensity versus temperature plots recorded at slow cooling rates. These data suggest that the equilibrium state of the Lα phase of hydrated DPPE is represented by a mixture of domains that differ in thermal behavior, but cannot be distinguished structurally by x-ray scattering. Imagesp689-aFIGURE 9 PMID:19431820

Reconstructing the regulatory network controlling commitment and sporulation in Physarum polycephalum based on hierarchical Petri Net modelling and simulation.

PubMed

Marwan, Wolfgang; Sujatha, Arumugam; Starostzik, Christine

2005-10-21

We reconstruct the regulatory network controlling commitment and sporulation of Physarum polycephalum from experimental results using a hierarchical Petri Net-based modelling and simulation framework. The stochastic Petri Net consistently describes the structure and simulates the dynamics of the molecular network as analysed by genetic, biochemical and physiological experiments within a single coherent model. The Petri Net then is extended to simulate time-resolved somatic complementation experiments performed by mixing the cytoplasms of mutants altered in the sporulation response, to systematically explore the network structure and to probe its dynamics. This reverse engineering approach presumably can be employed to explore other molecular or genetic signalling systems where the activity of genes or their products can be experimentally controlled in a time-resolved manner.

Micro-photoluminescence of GaAs/AlGaAs triple concentric quantum rings.

PubMed

Abbarchi, Marco; Cavigli, Lucia; Somaschini, Claudio; Bietti, Sergio; Gurioli, Massimo; Vinattieri, Anna; Sanguinetti, Stefano

2011-10-31

A systematic optical study, including micro, ensemble and time resolved photoluminescence of GaAs/AlGaAs triple concentric quantum rings, self-assembled via droplet epitaxy, is presented. Clear emission from localized states belonging to the ring structures is reported. The triple rings show a fast decay dynamics, around 40 ps, which is expected to be useful for ultrafast optical switching applications.

Resolving an 80-Yr-Old Controversy: The Beginning of the Modern Era of Renal Physiology

ERIC Educational Resources Information Center

Jamison, Rex L.

2014-01-01

Marcello Malpighi discovered the glomerulus that bears his name in the 17th century, but it was not until the middle of the 19th century, in 1842, that William Bowman in London published his studies of the histological structure of the glomerulus and proposed that urine formation begins with glomerular secretion. At nearly the same time in…

Free radical and overtone spectroscopy

NASA Technical Reports Server (NTRS)

Reilly, James P.

1991-01-01

In the fall of 1987 during a photoacoustic study of hydrogen peroxide's fourth vibrational overtone band, the remarkably clear and well resolved spectrum was observed. Its periodicity and K subband structure suggested that the spectrum was not of hydrogen peroxide but of a smaller near-prolate symmetric top molecule. Furthermore, the time dependent behavior of the signal indicated that chemical changes were taking place within the photoacoustic apparatus.

Mapping atomic motions with ultrabright electrons: towards fundamental limits in space-time resolution.

PubMed

Manz, Stephanie; Casandruc, Albert; Zhang, Dongfang; Zhong, Yinpeng; Loch, Rolf A; Marx, Alexander; Hasegawa, Taisuke; Liu, Lai Chung; Bayesteh, Shima; Delsim-Hashemi, Hossein; Hoffmann, Matthias; Felber, Matthias; Hachmann, Max; Mayet, Frank; Hirscht, Julian; Keskin, Sercan; Hada, Masaki; Epp, Sascha W; Flöttmann, Klaus; Miller, R J Dwayne

2015-01-01

The long held objective of directly observing atomic motions during the defining moments of chemistry has been achieved based on ultrabright electron sources that have given rise to a new field of atomically resolved structural dynamics. This class of experiments requires not only simultaneous sub-atomic spatial resolution with temporal resolution on the 100 femtosecond time scale but also has brightness requirements approaching single shot atomic resolution conditions. The brightness condition is in recognition that chemistry leads generally to irreversible changes in structure during the experimental conditions and that the nanoscale thin samples needed for electron structural probes pose upper limits to the available sample or "film" for atomic movies. Even in the case of reversible systems, the degree of excitation and thermal effects require the brightest sources possible for a given space-time resolution to observe the structural changes above background. Further progress in the field, particularly to the study of biological systems and solution reaction chemistry, requires increased brightness and spatial coherence, as well as an ability to tune the electron scattering cross-section to meet sample constraints. The electron bunch density or intensity depends directly on the magnitude of the extraction field for photoemitted electron sources and electron energy distribution in the transverse and longitudinal planes of electron propagation. This work examines the fundamental limits to optimizing these parameters based on relativistic electron sources using re-bunching cavity concepts that are now capable of achieving 10 femtosecond time scale resolution to capture the fastest nuclear motions. This analysis is given for both diffraction and real space imaging of structural dynamics in which there are several orders of magnitude higher space-time resolution with diffraction methods. The first experimental results from the Relativistic Electron Gun for Atomic Exploration (REGAE) are given that show the significantly reduced multiple electron scattering problem in this regime, which opens up micron scale systems, notably solution phase chemistry, to atomically resolved structural dynamics.

Dual time-resolved temperature-jump fluorescence and infrared spectroscopy for the study of fast protein dynamics.

PubMed

Davis, Caitlin M; Reddish, Michael J; Dyer, R Brian

2017-05-05

Time-resolved temperature-jump (T-jump) coupled with fluorescence and infrared (IR) spectroscopy is a powerful technique for monitoring protein dynamics. Although IR spectroscopy of the polypeptide amide I mode is more technically challenging, it offers complementary information because it directly probes changes in the protein backbone, whereas, fluorescence spectroscopy is sensitive to the environment of specific side chains. With the advent of widely tunable quantum cascade lasers (QCL) it is possible to efficiently probe multiple IR frequencies with high sensitivity and reproducibility. Here we describe a dual time-resolved T-jump fluorescence and IR spectrometer and its application to study protein folding dynamics. A Q-switched Ho:YAG laser provides the T-jump source for both time-resolved IR and fluorescence spectroscopy, which are probed by a QCL and Ti:Sapphire laser, respectively. The Ho:YAG laser simultaneously pumps the time-resolved IR and fluorescence spectrometers. The instrument has high sensitivity, with an IR absorbance detection limit of <0.2mOD and a fluorescence sensitivity of 2% of the overall fluorescence intensity. Using a computer controlled QCL to rapidly tune the IR frequency it is possible to create a T-jump induced difference spectrum from 50ns to 0.5ms. This study demonstrates the power of the dual time-resolved T-jump fluorescence and IR spectroscopy to resolve complex folding mechanisms by complementary IR absorbance and fluorescence measurements of protein dynamics. Copyright © 2017 Elsevier B.V. All rights reserved.

Dual time-resolved temperature-jump fluorescence and infrared spectroscopy for the study of fast protein dynamics

NASA Astrophysics Data System (ADS)

Davis, Caitlin M.; Reddish, Michael J.; Dyer, R. Brian

2017-05-01

Time-resolved temperature-jump (T-jump) coupled with fluorescence and infrared (IR) spectroscopy is a powerful technique for monitoring protein dynamics. Although IR spectroscopy of the polypeptide amide I mode is more technically challenging, it offers complementary information because it directly probes changes in the protein backbone, whereas, fluorescence spectroscopy is sensitive to the environment of specific side chains. With the advent of widely tunable quantum cascade lasers (QCL) it is possible to efficiently probe multiple IR frequencies with high sensitivity and reproducibility. Here we describe a dual time-resolved T-jump fluorescence and IR spectrometer and its application to study protein folding dynamics. A Q-switched Ho:YAG laser provides the T-jump source for both time-resolved IR and fluorescence spectroscopy, which are probed by a QCL and Ti:Sapphire laser, respectively. The Ho:YAG laser simultaneously pumps the time-resolved IR and fluorescence spectrometers. The instrument has high sensitivity, with an IR absorbance detection limit of < 0.2 mOD and a fluorescence sensitivity of 2% of the overall fluorescence intensity. Using a computer controlled QCL to rapidly tune the IR frequency it is possible to create a T-jump induced difference spectrum from 50 ns to 0.5 ms. This study demonstrates the power of the dual time-resolved T-jump fluorescence and IR spectroscopy to resolve complex folding mechanisms by complementary IR absorbance and fluorescence measurements of protein dynamics.

Resolving plate structure across the seismogenic zone in Cascadia from onshore-offshore receiver function imaging

NASA Astrophysics Data System (ADS)

Audet, P.; Schaeffer, A. J.

2017-12-01

Studies of the forearc structure in the Cascadia subduction zone using teleseismic P-wave receiver function have resolved structures associated with deep fluid cycling, such as the basalt-to-eclogite reaction and fluid overpressure within the subducting oceanic crust, as well as the serpentinization of the forearc mantle wedge. Unfortunately, the updip extent of the over-pressured zone, and therefore the possible control on the transition from episodic slow slip to seismic slip, occurs offshore and is not resolved in those studies. The Cascadia Initiative (CI) has provided an opportunity to extend this work to the locked zone using teleseismic receiver functions from the deployment of a dense line of ocean-bottom seismograph stations offshore of Washington State, from the trench to the coastline. Here we calculate P-wave receiver functions using data from offshore (CI) and onshore (CAFE) broadband seismic stations. These data clearly show the various scattered phases associated with a dipping low-velocity layer that was identified in previous studies as the downgoing oceanic crust. These signals are difficult to untangle offshore because they arrive at similar times. We process receiver functions using a modified common-conversion point (CCP) stacking technique that uses a coherency filter to optimally stack images obtained from the three main scattered phases. The resulting image shows along-dip variations in the character of the seismic discontinuities associated with the top and bottom of the low-velocity layer. Combined with focal depth information of regular and low-frequency earthquakes, these variations may reflect changes in the material properties of the megathrust across the seismogenic zone in Cascadia.

Experimental Approaches for Solution X-Ray Scattering and Fiber Diffraction

PubMed Central

Irving, T. C.

2008-01-01

X-ray scattering and diffraction from non-crystalline systems have gained renewed interest in recent years, as focus shifts from the structural chemistry information gained by high-resolution studies to the context of structural physiology at larger length scales. Such techniques permit the study of isolated macromolecules as well as highly organized macromolecular assemblies as a whole under near-physiological conditions. Time-resolved approaches, made possible by advanced synchrotron instrumentation, add a critical dimension to many of these investigations. This article reviews experimental approaches in non-crystalline x-ray scattering and diffraction that may be used to illuminate important scientific questions such as protein/nucleic acid folding and structure-function relationships in large macromolecular assemblies. PMID:18801437

Femtosecond electron diffraction and spectroscopic studies of a solid state organic chemical reaction

NASA Astrophysics Data System (ADS)

Jean-Ruel, Hubert

Photochromic diarylethene molecules are excellent model systems for studying electrocyclic reactions, in addition to having important technological applications in optoelectronics. The photoinduced ring-closing reaction in a crystalline photochromic diarylethene derivative was fully resolved using the complementary techniques of transient absorption spectroscopy and femtosecond electron crystallography. These studies are detailed in this thesis, together with the associated technical developments which enabled them. Importantly, the time-resolved crystallographic investigation reported here represents a highly significant proof-of-principle experiment. It constitutes the first study directly probing the molecular structural changes associated with an organic chemical reaction with sub-picosecond temporal and atomic spatial resolution---to follow the primary motions directing chemistry. In terms of technological development, the most important advance reported is the implementation of a radio frequency rebunching system capable of producing femtosecond electron pulses of exceptional brightness. The temporal resolution of this newly developed electron source was fully characterized using laser ponderomotive scattering, confirming a 435 +/- 75 fs instrument response time with 0.20 pC bunches. The ultrafast spectroscopic and crystallographic measurements were both achieved by exploiting the photoreversibility of diarylethene. The transient absorption study was first performed, after developing a novel robust acquisition scheme for thermally irreversible reactions in the solid state. It revealed the formation of an open-ring excited state intermediate, following photoexcitation of the open-ring isomer with an ultraviolet laser pulse, with a time constant of approximately 200 fs. The actual ring closing was found to occur from this intermediate with a time constant of 5.3 +/- 0.3 ps. The femtosecond diffraction measurements were then performed using multiple crystal orientations and a large number of different samples. To analyse the results, an innovative method was developed in which the apparently complex ring-closing reaction is distilled down to a small number of basic rotations. Immediately following photoexcitation, sub-picosecond structural changes associated with the formation of the intermediate are observed. The rotation of the thiophene rings is identified as the key motion. Subsequently, on the few picosecond time scale, the time-resolved diffraction patterns are observed to converge towards those associated with the closed-ring photoproduct. The formation of the closed-ring molecule is thus unambiguously witnessed.

Energetics and dynamics through time-resolved measurements in mass spectrometry

NASA Astrophysics Data System (ADS)

Lifshitz, Chava

Results of recent work on time-resolved photoionization and electron ionization mass spectrometry carried out in Jerusalem are reviewed. Time-resolved photoionization mass spectrometry in the vacuum ultraviolet is applied to polycyclic aromatic hydrocarbons, for example naphthalene, pyrene and fluoranthene as well as to some bromo derivatives (bromonaphthalene and bromoanthracene). Time-resolved photoionization efficiency curves are modelled by Rice-Ramsperger-Kassel-Marcus QET rate-energy k ( E ) dependences of the unimolecular dissociative processes and by the rate process infrared radiative relaxation k . Experimental results are augmented by time-resolved photorad dissociation data for the same species, whenever available. Kinetic shifts, conventional and intrinsic (due to competition between dissociative and radiative decay), are evaluated. Activation parameters (activation energies and entropies) are deduced. Thermochemical information is obtained including bond energies and ionic heats of formation. Fullerenes, notably C , are studied by time-resolved electron ionization and a large intrinsic shift, due to competition with black-bodylike radiative decay in the visible is discussed.

Ultrafast excited-state dynamics of RNA and DNA C tracts

NASA Astrophysics Data System (ADS)

Cohen, Boiko; Larson, Matthew H.; Kohler, Bern

2008-06-01

The excited-state dynamics of the RNA homopolymer of cytosine and of the 18-mer (dC) 18 were studied by steady-state and time-resolved absorption and emission spectroscopy. At pH 6.8, excitation of poly(rC) by a femtosecond UV pump pulse produces excited states that decay up to one order of magnitude more slowly than the excited states formed in the mononucleotide cytidine 5'-monophosphate under the same conditions. Even slower relaxation is observed for the hemiprotonated, self-associated form of poly(rC), which is stable at acidic pH. Transient absorption and time-resolved fluorescence signals for (dC) 18 at pH 6.8 are similar to ones observed for poly(rC) near pH 4, indicating that hemiprotonated structures are found in DNA C tracts at neutral pH. In both systems, there is evidence for two kinds of emitting states with lifetimes of ˜100 ps and slightly more than 1 ns. The former states are responsible for the bulk of emission from the hemiprotonated structures. Evidence suggests that slow electronic relaxation in these self-complexes is the result of vertical base stacking. The similar signals from RNA and DNA C tracts suggest a common base-stacked structure, which may be identical with that of i-motif DNA.

Change in "resolved plans" and "suicidal ideation" factors of suicidality after participation in an intensive outpatient treatment program.

PubMed

Minnix, Jennifer A; Romero, Catherine; Joiner, Thomas E; Weinberg, Elizabeth F

2007-11-01

This study aims to investigate factors related to suicide in a unique clinical population with more chronic psychopathology than many outpatient samples. One hundred and five adult outpatients were included in the current study. We predicted that higher scores on the resolved plans and preparation (RPP) factor of the Beck Suicide Scale [Beck, A.T., Kovacs, M., Weissman, M., (1979). Assessment of suicidal intention: The scale for suicidal ideation. Journal of Consulting and Clinical Psychology 47, 343-352] would predict multiple attempter status even after accounting for co-morbid diagnoses and suicidal ideation (SI) factor scores. Additionally, we predicted that the scores on the RPP factor would decrease less over time than scores on the SI factor. Results were consistent with both hypotheses, suggesting that RPP factor scores were uniquely predictive of status as a multiple attempter and were more stable over time. Mental health diagnoses were rendered without the use of a structured interview and therefore no reliability data were collected.

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

PubMed

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

2015-08-28

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.

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

Future Directions of Structural Mass Spectrometry using Hydroxyl Radical Footprinting

PubMed Central

Kiselar, Janna G.; Chance, Mark R.

2010-01-01

Hydroxyl radical protein footprinting coupled to mass spectrometry has been developed over the last decade and has matured to a powerful method for analyzing protein structure and dynamics. It has been successfully applied in the analysis of protein structure, protein folding, protein dynamics, and protein-protein and protein-DNA interactions. Using synchrotron radiolysis, exposures of proteins to a “white” x-ray beam for milliseconds provide sufficient oxidative modifications to surface amino acid side chains that can be easily detected and quantified by mass spectrometry. Thus, conformational changes in proteins or protein complexes can be examined using a time-resolved approach, which would be a valuable method for the study of macromolecular dynamics. In this review, we describe a new application of hydroxyl radical protein footprinting to probe the time evolution of the calcium-dependent conformational changes of gelsolin on the millisecond timescale. The data suggest a cooperative transition as multiple sites in different molecular sub-domains have similar rates of conformational change. These findings demonstrate that time-resolved protein footprinting is suitable for studies of protein dynamics that occur over periods ranging from milliseconds to seconds. In this review we also show how the structural resolution and sensitivity of the technology can be improved as well. The hydroxyl radical varies in its reactivity to different side chains by over two orders of magnitude, thus oxidation of amino acid side chains of lower reactivity are more rarely observed in such experiments. Here we demonstrate that selected reaction monitoring (SRM)-based method can be utilized for quantification of oxidized species, improving the signal to noise ratio. This expansion of the set of oxidized residues of lower reactivity will improve the overall structural resolution of the technique. This approach is also suggested as a basis for developing hypothesis driven structural mass spectrometry experiments. PMID:20812376

Time-resolved fluorescence observation of di-tyrosine formation in horseradish peroxidase upon ultrasound treatment leading to enzyme inactivation

NASA Astrophysics Data System (ADS)

Tsikrika, Konstantina; Lemos, M. Adília; Chu, Boon-Seang; Bremner, David H.; Hungerford, Graham

2017-02-01

The application of ultrasound to a solution can induce cavitional phenomena and generate high localised temperatures and pressures. These are dependent of the frequency used and have enabled ultrasound application in areas such as synthetic, green and food chemistry. High frequency (100 kHz to 1 MHz) in particular is promising in food chemistry as a means to inactivate enzymes, replacing the need to use periods of high temperature. A plant enzyme, horseradish peroxidase, was studied using time-resolved fluorescence techniques as a means to assess the effect of high frequency (378 kHz and 583 kHz) ultrasound treatment at equivalent acoustic powers. This uncovered the fluorescence emission from a newly formed species, attributed to the formation of di-tyrosine within the horseradish peroxidase structure caused by auto-oxidation, and linked to enzyme inactivation.

Image potential states at transition metal oxide surfaces: A time-resolved two-photon photoemission study on ultrathin NiO films

NASA Astrophysics Data System (ADS)

Gillmeister, K.; Kiel, M.; Widdra, W.

2018-02-01

For well-ordered ultrathin films of NiO(001) on Ag(001), a series of unoccupied states below the vacuum level has been found. The states show a nearly free electron dispersion and binding energies which are typical for image potential states. By time-resolved two-photon photoemission (2PPE), the lifetimes of the first three states and their dependence on oxide film thickness are determined. For NiO film thicknesses between 2 and 4 monolayers (ML), the lifetime of the first state is in the range of 28-42 fs and shows an oscillatory behavior with increasing thickness. The values for the second state decrease monotonically from 88 fs for 2 ML to 33 fs for 4 ML. These differences are discussed in terms of coupling of the unoccupied states to the layer-dependent electronic structure of the growing NiO film.

Passive monitoring for near surface void detection using traffic as a seismic source

NASA Astrophysics Data System (ADS)

Zhao, Y.; Kuzma, H. A.; Rector, J.; Nazari, S.

2009-12-01

In this poster we present preliminary results based on our several field experiments in which we study seismic detection of voids using a passive array of surface geophones. The source of seismic excitation is vehicle traffic on nearby roads, which we model as a continuous line source of seismic energy. Our passive seismic technique is based on cross-correlation of surface wave fields and studying the resulting power spectra, looking for "shadows" caused by the scattering effect of a void. High frequency noise masks this effect in the time domain, so it is difficult to see on conventional traces. Our technique does not rely on phase distortions caused by small voids because they are generally too tiny to measure. Unlike traditional impulsive seismic sources which generate highly coherent broadband signals, perfect for resolving phase but too weak for resolving amplitude, vehicle traffic affords a high power signal a frequency range which is optimal for finding shallow structures. Our technique results in clear detections of an abandoned railroad tunnel and a septic tank. The ultimate goal of this project is to develop a technology for the simultaneous imaging of shallow underground structures and traffic monitoring near these structures.

Appropriate Minimal Dose of Gadobutrol for 3D Time-Resolved MRA of the Supra-Aortic Arteries: Comparison with Conventional Single-Phase High-Resolution 3D Contrast-Enhanced MRA.

PubMed

Bak, S H; Roh, H G; Moon, W-J; Choi, J W; An, H S

2017-07-01

The development of nephrogenic systemic fibrosis and neural tissue deposition is gadolinium dose-dependent. The purpose of this study was to determine the appropriate minimal dose of gadobutrol with time-resolved MRA to assess supra-aortic arterial stenosis with contrast-enhanced MRA as a reference standard. Four hundred sixty-two consecutive patients underwent both standard-dose contrast-enhanced MRA and low-dose time-resolved MRA and were classified into 3 groups; group A (a constant dose of 1 mL for time-resolved MRA), group B (2 mL), or group C (3 mL). All studies were independently evaluated by 2 radiologists for image quality by using a 5-point scale (from 0 = failure to 4 = excellent), grading of arterial stenosis (0 = normal, 1 = mild [<30%], 2 = moderate [30%-69%], 3 = severe to occlusion [≥70%]), and signal-to-noise ratio. The image quality of time-resolved MRA was similar to that of contrast-enhanced MRA in groups B and C, but it was inferior to contrast-enhanced MRA in group A. For the grading of arterial stenosis, there was an excellent correlation between contrast-enhanced MRA and time-resolved MRA ( R = 0.957 for group A, R = 0.988 for group B, R = 0.991 for group C). The SNR of time-resolved MRA tended to be lower than that of contrast-enhanced MRA in groups A and B. However, SNR was higher for time-resolved MRA compared with contrast-enhanced MRA in group C. Low-dose time-resolved MRA is feasible in the evaluation of supra-aortic stenosis and could be used as an alternative to contrast-enhanced MRA for a diagnostic technique in high-risk populations. © 2017 by American Journal of Neuroradiology.

Flow topologies and turbulence scales in a jet-in-cross-flow

DOE PAGES

Oefelein, Joseph C.; Ruiz, Anthony M.; Lacaze, Guilhem

2015-04-03

This study presents a detailed analysis of the flow topologies and turbulence scales in the jet-in-cross-flow experiment of [Su and Mungal JFM 2004]. The analysis is performed using the Large Eddy Simulation (LES) technique with a highly resolved grid and time-step and well controlled boundary conditions. This enables quantitative agreement with the first and second moments of turbulence statistics measured in the experiment. LES is used to perform the analysis since experimental measurements of time-resolved 3D fields are still in their infancy and because sampling periods are generally limited with direct numerical simulation. A major focal point is the comprehensivemore » characterization of the turbulence scales and their evolution. Time-resolved probes are used with long sampling periods to obtain maps of the integral scales, Taylor microscales, and turbulent kinetic energy spectra. Scalar-fluctuation scales are also quantified. In the near-field, coherent structures are clearly identified, both in physical and spectral space. Along the jet centerline, turbulence scales grow according to a classical one-third power law. However, the derived maps of turbulence scales reveal strong inhomogeneities in the flow. From the modeling perspective, these insights are useful to design optimized grids and improve numerical predictions in similar configurations.« less

The adsorption, stability and properties of Mn6Cr Single-Molecule-Magnets studied by means of nc-AFM, STM, XAS and Spin-resolved Photoelectron Spectroscopy

NASA Astrophysics Data System (ADS)

Heinzmann, U.; Gryzia, A.; Helmstedt, A.; Dohmeier, N.; Predatsch, H.; Brechling, A.; Müller, N.; Sacher, M.; Hoeke, V.; Krickemeyer, E.; Glaser, T.; Bouvron, S.; Fonin, M.; Neumann, M.

2012-11-01

The ionic single-molecule-magnet [MnIII6CrIII]3 with corresponding three counterions has been deposited on different surfaces and studied with respect to its structure and its electronic and magnetic properties. This is the first time that spin polarization of photoelectrons ejected by means of circularly polarized synchrotron radiation has been measured in a single-molecule-magnet.

Time-Resolved Small-Angle X-ray Scattering Reveals Millisecond Transitions of a DNA Origami Switch.

PubMed

Bruetzel, Linda K; Walker, Philipp U; Gerling, Thomas; Dietz, Hendrik; Lipfert, Jan

2018-04-11

Self-assembled DNA structures enable creation of specific shapes at the nanometer-micrometer scale with molecular resolution. The construction of functional DNA assemblies will likely require dynamic structures that can undergo controllable conformational changes. DNA devices based on shape complementary stacking interactions have been demonstrated to undergo reversible conformational changes triggered by changes in ionic environment or temperature. An experimentally unexplored aspect is how quickly conformational transitions of large synthetic DNA origami structures can actually occur. Here, we use time-resolved small-angle X-ray scattering to monitor large-scale conformational transitions of a two-state DNA origami switch in free solution. We show that the DNA device switches from its open to its closed conformation upon addition of MgCl 2 in milliseconds, which is close to the theoretical diffusive speed limit. In contrast, measurements of the dimerization of DNA origami bricks reveal much slower and concentration-dependent assembly kinetics. DNA brick dimerization occurs on a time scale of minutes to hours suggesting that the kinetics depend on local concentration and molecular alignment.

Real-time Crystal Growth Visualization and Quantification by Energy-Resolved Neutron Imaging.

PubMed

Tremsin, Anton S; Perrodin, Didier; Losko, Adrian S; Vogel, Sven C; Bourke, Mark A M; Bizarri, Gregory A; Bourret, Edith D

2017-04-20

Energy-resolved neutron imaging is investigated as a real-time diagnostic tool for visualization and in-situ measurements of "blind" processes. This technique is demonstrated for the Bridgman-type crystal growth enabling remote and direct measurements of growth parameters crucial for process optimization. The location and shape of the interface between liquid and solid phases are monitored in real-time, concurrently with the measurement of elemental distribution within the growth volume and with the identification of structural features with a ~100 μm spatial resolution. Such diagnostics can substantially reduce the development time between exploratory small scale growth of new materials and their subsequent commercial production. This technique is widely applicable and is not limited to crystal growth processes.

Real-time Crystal Growth Visualization and Quantification by Energy-Resolved Neutron Imaging

NASA Astrophysics Data System (ADS)

Tremsin, Anton S.; Perrodin, Didier; Losko, Adrian S.; Vogel, Sven C.; Bourke, Mark A. M.; Bizarri, Gregory A.; Bourret, Edith D.

2017-04-01

Energy-resolved neutron imaging is investigated as a real-time diagnostic tool for visualization and in-situ measurements of “blind” processes. This technique is demonstrated for the Bridgman-type crystal growth enabling remote and direct measurements of growth parameters crucial for process optimization. The location and shape of the interface between liquid and solid phases are monitored in real-time, concurrently with the measurement of elemental distribution within the growth volume and with the identification of structural features with a ~100 μm spatial resolution. Such diagnostics can substantially reduce the development time between exploratory small scale growth of new materials and their subsequent commercial production. This technique is widely applicable and is not limited to crystal growth processes.

Real-time Crystal Growth Visualization and Quantification by Energy-Resolved Neutron Imaging

PubMed Central

Tremsin, Anton S.; Perrodin, Didier; Losko, Adrian S.; Vogel, Sven C.; Bourke, Mark A.M.; Bizarri, Gregory A.; Bourret, Edith D.

2017-01-01

Energy-resolved neutron imaging is investigated as a real-time diagnostic tool for visualization and in-situ measurements of “blind” processes. This technique is demonstrated for the Bridgman-type crystal growth enabling remote and direct measurements of growth parameters crucial for process optimization. The location and shape of the interface between liquid and solid phases are monitored in real-time, concurrently with the measurement of elemental distribution within the growth volume and with the identification of structural features with a ~100 μm spatial resolution. Such diagnostics can substantially reduce the development time between exploratory small scale growth of new materials and their subsequent commercial production. This technique is widely applicable and is not limited to crystal growth processes. PMID:28425461

Micro-photoluminescence of GaAs/AlGaAs triple concentric quantum rings

PubMed Central

2011-01-01

A systematic optical study, including micro, ensemble and time resolved photoluminescence of GaAs/AlGaAs triple concentric quantum rings, self-assembled via droplet epitaxy, is presented. Clear emission from localized states belonging to the ring structures is reported. The triple rings show a fast decay dynamics, around 40 ps, which is expected to be useful for ultrafast optical switching applications. PMID:22039893

Industry-relevant magnetron sputtering and cathodic arc ultra-high vacuum deposition system for in situ x-ray diffraction studies of thin film growth using high energy synchrotron radiation.

PubMed

Schroeder, J L; Thomson, W; Howard, B; Schell, N; Näslund, L-Å; Rogström, L; Johansson-Jõesaar, M P; Ghafoor, N; Odén, M; Nothnagel, E; Shepard, A; Greer, J; Birch, J

2015-09-01

We present an industry-relevant, large-scale, ultra-high vacuum (UHV) magnetron sputtering and cathodic arc deposition system purposefully designed for time-resolved in situ thin film deposition/annealing studies using high-energy (>50 keV), high photon flux (>10(12) ph/s) synchrotron radiation. The high photon flux, combined with a fast-acquisition-time (<1 s) two-dimensional (2D) detector, permits time-resolved in situ structural analysis of thin film formation processes. The high-energy synchrotron-radiation based x-rays result in small scattering angles (<11°), allowing large areas of reciprocal space to be imaged with a 2D detector. The system has been designed for use on the 1-tonne, ultra-high load, high-resolution hexapod at the P07 High Energy Materials Science beamline at PETRA III at the Deutsches Elektronen-Synchrotron in Hamburg, Germany. The deposition system includes standard features of a typical UHV deposition system plus a range of special features suited for synchrotron radiation studies and industry-relevant processes. We openly encourage the materials research community to contact us for collaborative opportunities using this unique and versatile scientific instrument.

Computing Normal Shock-Isotropic Turbulence Interaction With Tetrahedral Meshes and the Space-Time CESE Method

NASA Astrophysics Data System (ADS)

Venkatachari, Balaji Shankar; Chang, Chau-Lyan

2016-11-01

The focus of this study is scale-resolving simulations of the canonical normal shock- isotropic turbulence interaction using unstructured tetrahedral meshes and the space-time conservation element solution element (CESE) method. Despite decades of development in unstructured mesh methods and its potential benefits of ease of mesh generation around complex geometries and mesh adaptation, direct numerical or large-eddy simulations of turbulent flows are predominantly carried out using structured hexahedral meshes. This is due to the lack of consistent multi-dimensional numerical formulations in conventional schemes for unstructured meshes that can resolve multiple physical scales and flow discontinuities simultaneously. The CESE method - due to its Riemann-solver-free shock capturing capabilities, non-dissipative baseline schemes, and flux conservation in time as well as space - has the potential to accurately simulate turbulent flows using tetrahedral meshes. As part of the study, various regimes of the shock-turbulence interaction (wrinkled and broken shock regimes) will be investigated along with a study on how adaptive refinement of tetrahedral meshes benefits this problem. The research funding for this paper has been provided by Revolutionary Computational Aerosciences (RCA) subproject under the NASA Transformative Aeronautics Concepts Program (TACP).

Time-resolved wide-field optically sectioned fluorescence microscopy

NASA Astrophysics Data System (ADS)

Dupuis, Guillaume; Benabdallah, Nadia; Chopinaud, Aurélien; Mayet, Céline; Lévêque-Fort, Sandrine

2013-02-01

We present the implementation of a fast wide-field optical sectioning technique called HiLo microscopy on a fluorescence lifetime imaging microscope. HiLo microscopy is based on the fusion of two images, one with structured illumination and another with uniform illumination. Optically sectioned images are then digitally generated thanks to a fusion algorithm. HiLo images are comparable in quality with confocal images but they can be acquired faster over larger fields of view. We obtain 4D imaging by combining HiLo optical sectioning, time-gated detection, and z-displacement. We characterize the performances of this set-up in terms of 3D spatial resolution and time-resolved capabilities in both fixed- and live-cell imaging modes.

Direct detection of time-resolved Rabi oscillations in a single quantum dot via resonance fluorescence

NASA Astrophysics Data System (ADS)

Schaibley, J. R.; Burgers, A. P.; McCracken, G. A.; Steel, D. G.; Bracker, A. S.; Gammon, D.; Sham, L. J.

2013-03-01

Optical Rabi oscillations are coherent population oscillations of a two-level system coupled by an electric dipole transition when driven by a strong nearly resonant optical field. In quantum dot structures, these measurements have typically been performed as a function of the total pulse area ∫Ω0(t)dt where the pulse area varies as a function of Rabi frequency. Here, we report direct detection of the time-resolved coherent transient response of the resonance fluorescence to measure the time evolution of the optical Rabi oscillations in a single charged InAs quantum dot. We extract a decoherence rate consistent with the limit from the excited state lifetime.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

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

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

An upwind method for the solution of the 3D Euler and Navier-Stokes equations on adaptively refined meshes

NASA Astrophysics Data System (ADS)

Aftosmis, Michael J.

1992-10-01

A new node based upwind scheme for the solution of the 3D Navier-Stokes equations on adaptively refined meshes is presented. The method uses a second-order upwind TVD scheme to integrate the convective terms, and discretizes the viscous terms with a new compact central difference technique. Grid adaptation is achieved through directional division of hexahedral cells in response to evolving features as the solution converges. The method is advanced in time with a multistage Runge-Kutta time stepping scheme. Two- and three-dimensional examples establish the accuracy of the inviscid and viscous discretization. These investigations highlight the ability of the method to produce crisp shocks, while accurately and economically resolving viscous layers. The representation of these and other structures is shown to be comparable to that obtained by structured methods. Further 3D examples demonstrate the ability of the adaptive algorithm to effectively locate and resolve multiple scale features in complex 3D flows with many interacting, viscous, and inviscid structures.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE PAGES

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; ...

2017-05-24

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Coherent convergent-beam time-resolved X-ray diffraction

PubMed Central

Spence, John C. H.; Zatsepin, Nadia A.; Li, Chufeng

2014-01-01

The use of coherent X-ray lasers for structural biology allows the use of nanometre diameter X-ray beams with large beam divergence. Their application to the structure analysis of protein nanocrystals and single particles raises new challenges and opportunities. We discuss the form of these coherent convergent-beam (CCB) hard X-ray diffraction patterns and their potential use for time-resolved crystallography, normally achieved by Laue (polychromatic) diffraction, for which the monochromatic laser radiation of a free-electron X-ray laser is unsuitable. We discuss the possibility of obtaining single-shot, angle-integrated rocking curves from CCB patterns, and the dependence of the resulting patterns on the focused beam coordinate when the beam diameter is larger or smaller than a nanocrystal, or smaller than one unit cell. We show how structure factor phase information is provided at overlapping interfering orders and how a common phase origin between different shots may be obtained. Their use in refinement of the phase-sensitive intensity between overlapping orders is suggested. PMID:24914153

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

NASA Astrophysics Data System (ADS)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; van Driel, Tim B.; Chollet, Matthieu; Glownia, James M.; Song, Sanghoon; Zhu, Diling; Pace, Elisabetta; Matar, Samir F.; Nielsen, Martin M.; Benfatto, Maurizio; Gaffney, Kelly J.; Collet, Eric; Cammarata, Marco

2017-05-01

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

Using resolvent analysis for the design of separation control on a NACA 0012 airfoil

NASA Astrophysics Data System (ADS)

Yeh, Chi-An; Taira, Kunihiko

2017-11-01

A combined effort based on large-eddy simulation and resolvent analysis on the separated flow over a NACA 0012 airfoil is conducted to design active flow control for suppression of separation. This study considers the the airfoil at 6 deg. angle-of-attack and Reynolds number of 23000. The response mode obtained from the resolvent analysis about the baseline turbulent mean flow reveals modal structures that can be categorized into three families when sweeping through the resonant frequency: (1) von Karman wake structure for low frequency; (2) Kelvin-Helmholtz structure in the separation bubble for high frequency; (3) blended structure of (1) and (2) for the intermediate frequency. Leveraging the insights from resolvent analysis, unsteady thermal actuation is introduced to the flow near the leading-edge to examine the use of the frequencies from three families for separation control in LES. As indicated by the resolvent response modes, we find that the use of intermediate frequencies are most effective in suppressing the flow separation, since the shear layer over the separation bubble and the wake are both receptive to the perturbation at the these frequencies. The resolvent-analysis-based control strategy achieves 35% drag reduction and 9% lift increase with effective frequency. This work was supported by Office of Naval Research (N00014-15-R-FO13) and Army Research Office (W911NF-14-1-0224).

Photoelectron Angular Distributions of Transition Metal Dioxide Anions - a joint experimental and theoretical study

NASA Astrophysics Data System (ADS)

Iordanov, Ivan; Gunaratne, Dasitha; Harmon, Christopher; Sofo, Jorge; Castleman, A. W., Jr.

2012-02-01

Angular-resolved photoelectron spectroscopy (PES) studies of the MO2- (M=Ti, Zr, Hf, Co, Rh) clusters are presented for the first time along with theoretical calculations of their properties. We confirm previously reported non-angular PES results for the vertical detachment energies (VDE), vibrational energies and geometric structures of these clusters and further explore the effect of the 'lanthanide contraction' on the MO2- clusters by comparing the electronic spectra of 4d and 5d transition metal dioxides. Angular-resolved PES provides the angular momentum contributions to the HOMO of these clusters and we use theoretical calculations to examine the HOMO and compare to our experimental results. First-principles calculations are done using both density functional theory (DFT) and the coupled-cluster, singles, doubles and triples (CCSD(T)) methods.

New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team

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

Meng, Yue; Hrubiak, Rostislav; Rod, Eric

An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. Furthermore, the new capabilities have demonstrated clear benefits and provide new opportunities in researchmore » areas including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.« less

New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team

DOE PAGES

Meng, Yue; Hrubiak, Rostislav; Rod, Eric; ...

2015-07-17

An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. Furthermore, the new capabilities have demonstrated clear benefits and provide new opportunities in researchmore » areas including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.« less

New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team

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

Meng, Yue; Hrubiak, Rostislav; Rod, Eric

An overview of the in situ laser heating system at the High Pressure Collaborative Access Team, with emphasis on newly developed capabilities, is presented. Since its establishment at the beamline 16-ID-B a decade ago, laser-heated diamond anvil cell coupled with in situ synchrotron x-ray diffraction has been widely used for studying the structural properties of materials under simultaneous high pressure and high temperature conditions. Recent developments in both continuous-wave and modulated heating techniques have been focusing on resolving technical issues of the most challenging research areas. The new capabilities have demonstrated clear benefits and provide new opportunities in research areasmore » including high-pressure melting, pressure-temperature-volume equations of state, chemical reaction, and time resolved studies.« less

Stimulated Emission Depletion Nanoscopy Reveals Time-Course of Human Immunodeficiency Virus Proteolytic Maturation.

PubMed

Hanne, Janina; Göttfert, Fabian; Schimer, Jiří; Anders-Össwein, Maria; Konvalinka, Jan; Engelhardt, Johann; Müller, Barbara; Hell, Stefan W; Kräusslich, Hans-Georg

2016-09-27

Concomitant with human immunodeficiency virus type 1 (HIV-1) budding from a host cell, cleavage of the structural Gag polyproteins by the viral protease (PR) triggers complete remodeling of virion architecture. This maturation process is essential for virus infectivity. Electron tomography provided structures of immature and mature HIV-1 with a diameter of 120-140 nm, but information about the sequence and dynamics of structural rearrangements is lacking. Here, we employed super-resolution STED (stimulated emission depletion) fluorescence nanoscopy of HIV-1 carrying labeled Gag to visualize the virion architecture. The incomplete Gag lattice of immature virions was clearly distinguishable from the condensed distribution of mature protein subunits. Synchronized activation of PR within purified particles by photocleavage of a caged PR inhibitor enabled time-resolved in situ observation of the induction of proteolysis and maturation by super-resolution microscopy. This study shows the rearrangement of subviral structures in a super-resolution light microscope over time, outwitting phototoxicity and fluorophore bleaching through synchronization of a biological process by an optical switch.

Probing Photoinduced Structural Phase Transitions by Fast or Ultra-Fast Time-Resolved X-Ray Diffraction

NASA Astrophysics Data System (ADS)

Cailleau, Hervé Collet, Eric; Buron-Le Cointe, Marylise; Lemée-Cailleau, Marie-Hélène Koshihara, Shin-Ya

A new frontier in the field of structural science is the emergence of the fast and ultra-fast X-ray science. Recent developments in time-resolved X-ray diffraction promise direct access to the dynamics of electronic, atomic and molecular motions in condensed matter triggered by a pulsed laser irradiation, i.e. to record "molecular movies" during the transformation of matter initiated by light pulse. These laser pump and X-ray probe techniques now provide an outstanding opportunity for the direct observation of a photoinduced structural phase transition as it takes place. The use of X-ray short-pulse of about 100ps around third-generation synchrotron sources allows structural investigations of fast photoinduced processes. Other new X-ray sources, such as laser-produced plasma ones, generate ultra-short pulses down to 100 fs. This opens the way to femtosecond X-ray crystallography, but with rather low X-ray intensities and more limited experimental possibilities at present. However this new ultra-fast science rapidly progresses around these sources and new large-scale projects exist. It is the aim of this contribution to overview the state of art and the perspectives of fast and ultra-fast X-ray scattering techniques to study photoinduced phase transitions (here, the word ultra-fast is used for sub-picosecond time resolution). In particular we would like to largely present the contribution of crystallographic methods in comparison with optical methods, such as pump-probe reflectivity measurements, the reader being not necessary familiar with X-ray scattering. Thus we want to present which type of physical information can be obtained from the positions of the Bragg peaks, their intensity and their shape, as well as from the diffuse scattering beyond Bragg peaks. An important physical feature is to take into consideration the difference in nature between a photoinduced phase transition and conventional homogeneous photoinduced chemical or biochemical processes where molecules transform in an independent way each other. Actually the photoinduced phase transition with the establishment of the new electronic and structural oscopic order is preceded by precursor co-operative phenomena due to the formation of nano-scale correlated objects. These are the counterpart of pre-transitional fluctuations at thermal equilibrium which take place above the transition temperature (short range order preceding long range one). Moreover ultra-fast X-ray scattering will play a central role within the fascinating field of manipulating coherence, for instance to directly observe coherent atomic motions induced by a light pulse, such as optical phonons. In the first part of this contribution we present what experimental features are accessible by X-ray scattering to describe the physical picture for a photoinduced structural phase transition. The second part shows how a time-resolved X-ray scattering experiment can be performed with regards to the different pulsed X-ray sources. The first time-resolved X-ray diffraction experiments on photoinduced phase transitions are described and discussed in the third part. Finally some challenges for future are briefly indicated in the conclusion.

Time-resolved contrast-enhanced MRA (TWIST) with gadofosveset trisodium in the classification of soft-tissue vascular anomalies in the head and neck in children following updated 2014 ISSVA classification: first report on systematic evaluation of MRI and TWIST in a cohort of 47 children.

PubMed

Higgins, L J; Koshy, J; Mitchell, S E; Weiss, C R; Carson, K A; Huisman, T A G M; Tekes, A

2016-01-01

To evaluate the relative accuracy of contrast-enhanced time-resolved angiography with interleaved stochastic trajectories versus conventional contrast-enhanced magnetic resonance imaging (MRI) following International Society for the Study of Vascular Anomalies updated 2014-based classification of soft-tissue vascular anomalies in the head and neck in children. Time-resolved angiography with interleaved stochastic trajectories versus conventional contrast-enhanced MRI of children with diagnosis of soft-tissue vascular anomalies in the head and neck referred for MRI between 2008 and 2014 were retrospectively reviewed. Forty-seven children (0-18 years) were evaluated. Two paediatric neuroradiologists evaluated time-resolved MRA and conventional MRI in two different sessions (30 days apart). Blood-pool endovascular MRI contrast agent gadofosveset trisodium was used. The present cohort had the following diagnoses: infantile haemangioma (n=6), venous malformation (VM; n=23), lymphatic malformation (LM; n=16), arteriovenous malformation (AVM; n=2). Time-resolved MRA alone accurately classified 38/47 (81%) and conventional MRI 42/47 (89%), respectively. Although time-resolved MRA alone is slightly superior to conventional MRI alone for diagnosis of infantile haemangioma, conventional MRI is slightly better for diagnosis of venous and LMs. Neither time-resolved MRA nor conventional MRI was sufficient for accurate diagnosis of AVM in this cohort. Conventional MRI combined with time-resolved MRA accurately classified 44/47 cases (94%). Time-resolved MRA using gadofosveset trisodium can accurately classify soft-tissue vascular anomalies in the head and neck in children. The addition of time-resolved MRA to existing conventional MRI protocols provides haemodynamic information, assisting the diagnosis of vascular anomalies in the paediatric population at one-third of the dose of other MRI contrast agents. Copyright © 2015 The Royal College of Radiologists. Published by Elsevier Ltd. All rights reserved.

Spatially resolved and time-resolved imaging of transport of indirect excitons in high magnetic fields

NASA Astrophysics Data System (ADS)

Dorow, C. J.; Hasling, M. W.; Calman, E. V.; Butov, L. V.; Wilkes, J.; Campman, K. L.; Gossard, A. C.

2017-06-01

We present the direct measurements of magnetoexciton transport. Excitons give the opportunity to realize the high magnetic-field regime for composite bosons with magnetic fields of a few tesla. Long lifetimes of indirect excitons allow the study of kinetics of magnetoexciton transport with time-resolved optical imaging of exciton photoluminescence. We performed spatially, spectrally, and time-resolved optical imaging of transport of indirect excitons in high magnetic fields. We observed that an increasing magnetic field slows down magnetoexciton transport. The time-resolved measurements of the magnetoexciton transport distance allowed for an experimental estimation of the magnetoexciton diffusion coefficient. An enhancement of the exciton photoluminescence energy at the laser excitation spot was found to anticorrelate with the exciton transport distance. A theoretical model of indirect magnetoexciton transport is presented and is in agreement with the experimental data.

Investigating the capability to resolve complex white matter structures with high b-value diffusion magnetic resonance imaging on the MGH-USC Connectom scanner.

PubMed

Fan, Qiuyun; Nummenmaa, Aapo; Witzel, Thomas; Zanzonico, Roberta; Keil, Boris; Cauley, Stephen; Polimeni, Jonathan R; Tisdall, Dylan; Van Dijk, Koene R A; Buckner, Randy L; Wedeen, Van J; Rosen, Bruce R; Wald, Lawrence L

2014-11-01

One of the major goals of the NIH Blueprint Human Connectome Project was to map and quantify the white matter connections in the brain using diffusion tractography. Given the prevalence of complex white matter structures, the capability of resolving local white matter geometries with multiple crossings in the diffusion magnetic resonance imaging (dMRI) data is critical. Increasing b-value has been suggested for delineation of the finer details of the orientation distribution function (ODF). Although increased gradient strength and duration increase sensitivity to highly restricted intra-axonal water, gradient strength limitations require longer echo times (TE) to accommodate the increased diffusion encoding times needed to achieve a higher b-value, exponentially lowering the signal-to-noise ratio of the acquisition. To mitigate this effect, the MGH-USC Connectom scanner was built with 300 mT/m gradients, which can significantly reduce the TE of high b-value diffusion imaging. Here we report comparisons performed across b-values based on q-ball ODF metrics to investigate whether high b-value diffusion imaging on the Connectom scanner can improve resolving complex white matter structures. The q-ball ODF features became sharper as the b-value increased, with increased power fraction in higher order spherical harmonic series of the ODF and increased peak heights relative to the overall size of the ODF. Crossing structures were detected in an increasingly larger fraction of white matter voxels and the spatial distribution of two-way and three-way crossing structures was largely consistent with known anatomy. Results indicate that dMRI with high diffusion encoding on the Connectom system is a promising tool to better characterize, and ultimately understand, the underlying structural organization and motifs in the human brain.

almaBTE : A solver of the space-time dependent Boltzmann transport equation for phonons in structured materials

NASA Astrophysics Data System (ADS)

Carrete, Jesús; Vermeersch, Bjorn; Katre, Ankita; van Roekeghem, Ambroise; Wang, Tao; Madsen, Georg K. H.; Mingo, Natalio

2017-11-01

almaBTE is a software package that solves the space- and time-dependent Boltzmann transport equation for phonons, using only ab-initio calculated quantities as inputs. The program can predictively tackle phonon transport in bulk crystals and alloys, thin films, superlattices, and multiscale structures with size features in the nm- μm range. Among many other quantities, the program can output thermal conductances and effective thermal conductivities, space-resolved average temperature profiles, and heat-current distributions resolved in frequency and space. Its first-principles character makes almaBTE especially well suited to investigate novel materials and structures. This article gives an overview of the program structure and presents illustrative examples for some of its uses. PROGRAM SUMMARY Program Title:almaBTE Program Files doi:http://dx.doi.org/10.17632/8tfzwgtp73.1 Licensing provisions: Apache License, version 2.0 Programming language: C++ External routines/libraries: BOOST, MPI, Eigen, HDF5, spglib Nature of problem: Calculation of temperature profiles, thermal flux distributions and effective thermal conductivities in structured systems where heat is carried by phonons Solution method: Solution of linearized phonon Boltzmann transport equation, Variance-reduced Monte Carlo

Structural changes in shock compressed silicon observed using time-resolved x-ray diffraction at the Dynamic Compression Sector

NASA Astrophysics Data System (ADS)

Turneaure, Stefan; Zdanowicz, E.; Sinclair, N.; Graber, T.; Gupta, Y. M.

2015-06-01

Structural changes in shock compressed silicon were observed directly using time-resolved x-ray diffraction (XRD) measurements at the Dynamic Compression Sector at the Advanced Photon Source. The silicon samples were impacted by polycarbonate impactors accelerated to velocities greater than 5 km/s using a two-stage light gas gun resulting in impact stresses of about 25 GPa. The 23.5 keV synchrotron x-ray beam passed through the polycarbonate impactor, the silicon sample, and an x-ray window (polycarbonate or LiF) at an angle of 30 degrees relative to the impact plane. Four XRD frames (~ 100 ps snapshots) were obtained with 153.4 ns between frames near the time of impact. The XRD measurements indicate that in the peak shocked state, the silicon samples completely transformed to a high-pressure phase. XRD results for both shocked polycrystalline silicon and single crystal silicon will be presented and compared. Work supported by DOE/NNSA.

Deployment Repeatability

DTIC Science & Technology

2016-08-31

photogrammetry to track a set of LEDS in two dimensions, a method that was able to resolve 2.2-mm lateral displacements of a 40-meter boom. This method... displacements . Sub-milliradian repeatability in MOIRE [This is a stand-in section for the MOIRE case study, which Dave Waller is getting through...The structure will most likely be under this stowed state for a long time under displacement paths and put this data into a computationally cheap 1

SU-F-J-190: Time Resolved Range Measurement System Using Scintillator and CCD Camera for the Slow Beam Extraction

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

Saotome, N; Furukawa, T; Mizushima, K

2016-06-15

Purpose: To investigate the time structure of the range, we have verified the rang shift due to the betatron tune shift with several synchrotron parameters. Methods: A cylindrical plastic scintillator block and a CCD camera were installed on the black box. Using image processing, the range was determined the 80 percent of distal dose of the depth light distribution. The root mean square error of the range measurement using the scintillator and CCD system is about 0.2 mm. Range measurement was performed at interval of 170 msec. The chromaticity of the synchrotron was changed in the range of plus ormore » minus 1% from reference chromaticity in this study. All of the particle inside the synchrotron ring were extracted with the output beam intensity 1.8×10{sup 8} and 5.0×10{sub 7} particle per sec. Results: The time strictures of the range were changed by changing of the chromaticity. The reproducibility of the measurement was sufficient to observe the time structures of the range. The range shift was depending on the number of the residual particle inside the synchrotron ring. Conclusion: In slow beam extraction for scanned carbon-ion therapy, the range shift is undesirable because it causes the dose uncertainty in the target. We introduced the time-resolved range measurement using scintillator and CCD system. The scintillator and CCD system have enabled to verify the range shift with sufficient spatial resolution and reproducibility.« less

Time-resolved imaging refractometry of microbicidal films using quantitative phase microscopy.

PubMed

Rinehart, Matthew T; Drake, Tyler K; Robles, Francisco E; Rohan, Lisa C; Katz, David; Wax, Adam

2011-12-01

Quantitative phase microscopy is applied to image temporal changes in the refractive index (RI) distributions of solutions created by microbicidal films undergoing hydration. We present a novel method of using an engineered polydimethylsiloxane structure as a static phase reference to facilitate calibration of the absolute RI across the entire field. We present a study of dynamic structural changes in microbicidal films during hydration and subsequent dissolution. With assumptions about the smoothness of the phase changes induced by these films, we calculate absolute changes in the percentage of film in regions across the field of view.

Time-resolved imaging refractometry of microbicidal films using quantitative phase microscopy

PubMed Central

Rinehart, Matthew T.; Drake, Tyler K.; Robles, Francisco E.; Rohan, Lisa C.; Katz, David; Wax, Adam

2011-01-01

Quantitative phase microscopy is applied to image temporal changes in the refractive index (RI) distributions of solutions created by microbicidal films undergoing hydration. We present a novel method of using an engineered polydimethylsiloxane structure as a static phase reference to facilitate calibration of the absolute RI across the entire field. We present a study of dynamic structural changes in microbicidal films during hydration and subsequent dissolution. With assumptions about the smoothness of the phase changes induced by these films, we calculate absolute changes in the percentage of film in regions across the field of view. PMID:22191912

Circularly polarized vacuum field in three-dimensional chiral photonic crystals probed by quantum dot emission

NASA Astrophysics Data System (ADS)

Takahashi, S.; Ota, Y.; Tajiri, T.; Tatebayashi, J.; Iwamoto, S.; Arakawa, Y.

2017-11-01

The modification of a circularly polarized vacuum field in three-dimensional chiral photonic crystals was measured by spontaneous emission from quantum dots in the structures. Due to the circularly polarized eigenmodes along the helical axis in the GaAs-based mirror-asymmetric structures we studied, we observed highly circularly polarized emission from the quantum dots. Both spectroscopic and time-resolved measurements confirmed that the obtained circularly polarized light was influenced by a large difference in the photonic density of states between the orthogonal components of the circular polarization in the vacuum field.

Optical investigation of carrier tunneling in semiconductor nanostructures

NASA Astrophysics Data System (ADS)

Emiliani, V.; Ceccherini, S.; Bogani, F.; Colocci, M.; Frova, A.; Shi, Song Stone

1997-08-01

The tunneling dynamics of excitons and free carriers in AlxGa1-xAs/GaAs asymmetric double quantum well and near-surface quantum well structures has been investigated by means of time-resolved optical techniques. The competing processes of carrier tunneling out of the quantum well and exciton formation and recombination inside the quantum well have been thoroughly studied in the range of the excitation densities relevant to device applications. A consistent picture capable of fully describing the carrier and exciton-tunneling mechanisms in both types of structures has been obtained and apparently contrasting results in the recent literature are clarified.

Femtosecond mega-electron-volt electron microdiffraction

DOE PAGES

Shen, X.; Li, R. K.; Lundstrom, U.; ...

2017-09-01

To understand and control the basic functions of physical, chemical and biological processes from micron to nano-meter scale, an instrument capable of visualizing transient structural changes of inhomogeneous materials with atomic spatial and temporal resolutions, is required. One such technique is femtosecond electron microdiffraction, in which a short electron pulse with femtosecond-scale duration is focused into a micron-scale spot and used to obtain diffraction images to resolve ultrafast structural dynamics over a localized crystalline domain. In this letter, we report the experimental demonstration of time-resolved mega-electron-volt electron microdiffraction which achieves a 5 μm root-mean-square (rms) beam size on the samplemore » and a 110 fs rms temporal resolution. Using pulses of 10k electrons at 4.2 MeV energy with a normalized emittance 3 nm-rad, we obtained high quality diffraction from a single 10 μm paraffin ( C 44 H 90) crystal. The phonon softening mode in optical-pumped polycrystalline Bi was also time-resolved, demonstrating the temporal resolution limits of the instrument. In conclusion, this new characterization capability will open many research opportunities in material and biological sciences.« less

Femtosecond mega-electron-volt electron microdiffraction

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

Shen, X.; Li, R. K.; Lundstrom, U.

To understand and control the basic functions of physical, chemical and biological processes from micron to nano-meter scale, an instrument capable of visualizing transient structural changes of inhomogeneous materials with atomic spatial and temporal resolutions, is required. One such technique is femtosecond electron microdiffraction, in which a short electron pulse with femtosecond-scale duration is focused into a micron-scale spot and used to obtain diffraction images to resolve ultrafast structural dynamics over a localized crystalline domain. In this letter, we report the experimental demonstration of time-resolved mega-electron-volt electron microdiffraction which achieves a 5 μm root-mean-square (rms) beam size on the samplemore » and a 110 fs rms temporal resolution. Using pulses of 10k electrons at 4.2 MeV energy with a normalized emittance 3 nm-rad, we obtained high quality diffraction from a single 10 μm paraffin ( C 44 H 90) crystal. The phonon softening mode in optical-pumped polycrystalline Bi was also time-resolved, demonstrating the temporal resolution limits of the instrument. In conclusion, this new characterization capability will open many research opportunities in material and biological sciences.« less

Time- and Space-Resolved SAXS Experiments Inform on Phase Transition Kinetics in Hydrated, Liquid-Crystalline Films of Polyion-Surfactant Ion "Complex Salts".

PubMed

Li, Joaquim; Gustavsson, Charlotte; Piculell, Lennart

2016-05-24

Detailed time- and space-resolved SAXS experiments show the variation with hydration of liquid crystalline structures in ethanol-cast 5-80 μm thick films of polyion-surfactant ion "complex salts" (CS). The CS were dodecyl- (C12) or hexadecyl- (C16) trimethylammonium surfactants with polyacrylate (DP 25 or 6000) counter-polyions. The experiments were carried out on vertical films in humid air above a movable water bath, so that gradients of hydration were generated, which could rapidly be altered. Scans over different positions along a film, kept fixed relative to the bath, showed that the surfactant aggregates of the various liquid-crystalline CS structures grow in cross-sectional area with decreasing hydration. This behavior is attributed to the low water content. Studies of films undergoing rapid dehydration, made possible by the original experimental setup, gave strong evidence that some of the investigated systems remain kinetically trapped for minutes in a nonequilibrium Pm3n micellar cubic phase before switching to the equilibrium P6mm 2D hexagonal phase. Both the length of the polyion and the length of the surfactant hydrocarbon "tail" affect the kinetics of the phase transition. The slowness of the cubic-to-hexagonal structural transition is attributed to the fact that it requires major rearrangements of the polyions and surfactant ions relative to each other. By contrast, other structure changes, such as between the hexagonal and rectangular phases, were observed to occur much more rapidly.

Nanosecond retinal structure changes in K-590 during the room-temperature bacteriorhodopsin photocycle: picosecond time-resolved coherent anti-stokes Raman spectroscopy.

PubMed

Weidlich, O; Ujj, L; Jäger, F; Atkinson, G H

1997-05-01

Time-resolved vibrational spectra are used to elucidate the structural changes in the retinal chromophore within the K-590 intermediate that precedes the formation of the L-550 intermediate in the room-temperature (RT) bacteriorhodopsin (BR) photocycle. Measured by picosecond time-resolved coherent anti-Stokes Raman scattering (PTR/CARS), these vibrational data are recorded within the 750 cm-1 to 1720 cm-1 spectral region and with time delays of 50-260 ns after the RT/BR photocycle is optically initiated by pulsed (< 3 ps, 1.75 nJ) excitation. Although K-590 remains structurally unchanged throughout the 50-ps to 1-ns time interval, distinct structural changes do appear over the 1-ns to 260-ns period. Specifically, comparisons of the 50-ps PTR/CARS spectra with those recorded with time delays of 1 ns to 260 ns reveal 1) three types of changes in the hydrogen-out-of-plane (HOOP) region: the appearance of a strong, new feature at 984 cm-1; intensity decreases for the bands at 957 cm-1, 952 cm-1, and 939 cm-1; and small changes intensity and/or frequency of bands at 855 cm-1 and 805 cm-1; and 2) two types of changes in the C-C stretching region: the intensity increase in the band at 1196 cm-1 and small intensity changes and/or frequency shifts for bands at 1300 cm-1 and 1362 cm-1. No changes are observed in the C = C stretching region, and no bands assignable to the Schiff base stretching mode (C = NH+) mode are found in any of the PTR/CARS spectra assignable to K-590. These PTR/CARS data are used, together with vibrational mode assignments derived from previous work, to characterize the retinal structural changes in K-590 as it evolves from its 3.5-ps formation (ps/K-590) through the nanosecond time regime (ns/K-590) that precedes the formation of L-550. The PTR/CARS data suggest that changes in the torsional modes near the C14-C15 = N bonds are directly associated with the appearance of ns/K-590, and perhaps with the KL intermediate proposed in earlier studies. These vibrational data can be primarily interpreted in terms of the degree of twisting of the C14-C15 retinal bond. Such twisting may be accompanied by changes in the adjacent protein. Other smaller, but nonetheless clear, spectral changes indicate that alterations along the retinal polyene chain also occur. The changes in the retinal structure are preliminary to the deprotonation of the Schiff base nitrogen during the formation of M-412. The time constant for the ps/ns K-590 transformation is estimated from the amplitude change of four vibrational bands in the HOOP region to be 40-70 ns.

AGN Space Telescope and Optical Reverberation Mapping Project. IV. Velocity-Delay Mapping of Broad Emission Lines in NGC 5548

NASA Astrophysics Data System (ADS)

Horne, Keith D.; Agn Storm Team

2015-01-01

Two-dimensional velocity-delay maps of AGN broad emission line regions can be recovered by modelling observations of reverberating emission-line profiles on the assumption that the line profile variations are driven by changes in ionising radiation from a compact source near the black hole. The observable light travel time delay resolves spatial structure on iso-delay paraboloids, while the doppler shift resolves kinematic structure along the observer's line-of-sight. Velocity-delay maps will be presented and briefly discussed for the Lyman alpha, CIV and Hbeta line profiles based on the HST and ground-based spectrophotometric monitoring of NGC 5548 during the 2014 AGN STORM campaign.

rf streak camera based ultrafast relativistic electron diffraction.

PubMed

Musumeci, P; Moody, J T; Scoby, C M; Gutierrez, M S; Tran, T

2009-01-01

We theoretically and experimentally investigate the possibility of using a rf streak camera to time resolve in a single shot structural changes at the sub-100 fs time scale via relativistic electron diffraction. We experimentally tested this novel concept at the UCLA Pegasus rf photoinjector. Time-resolved diffraction patterns from thin Al foil are recorded. Averaging over 50 shots is required in order to get statistics sufficient to uncover a variation in time of the diffraction patterns. In the absence of an external pump laser, this is explained as due to the energy chirp on the beam out of the electron gun. With further improvements to the electron source, rf streak camera based ultrafast electron diffraction has the potential to yield truly single shot measurements of ultrafast processes.

Real-time Crystal Growth Visualization and Quantification by Energy-Resolved Neutron Imaging

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

Tremsin, Anton S.; Perrodin, Didier; Losko, Adrian S.

Energy-resolved neutron imaging is investigated as a real-time diagnostic tool for visualization and in-situ measurements of "blind" processes. This technique is demonstrated for the Bridgman-type crystal growth enabling remote and direct measurements of growth parameters crucial for process optimization. The location and shape of the interface between liquid and solid phases are monitored in real-time, concurrently with the measurement of elemental distribution within the growth volume and with the identification of structural features with a ~100 μm spatial resolution. Such diagnostics can substantially reduce the development time between exploratory small scale growth of new materials and their subsequent commercial production.more » This technique is widely applicable and is not limited to crystal growth processes.« less

Real-time Crystal Growth Visualization and Quantification by Energy-Resolved Neutron Imaging

DOE PAGES

Tremsin, Anton S.; Perrodin, Didier; Losko, Adrian S.; ...

2017-04-20

Energy-resolved neutron imaging is investigated as a real-time diagnostic tool for visualization and in-situ measurements of "blind" processes. This technique is demonstrated for the Bridgman-type crystal growth enabling remote and direct measurements of growth parameters crucial for process optimization. The location and shape of the interface between liquid and solid phases are monitored in real-time, concurrently with the measurement of elemental distribution within the growth volume and with the identification of structural features with a ~100 μm spatial resolution. Such diagnostics can substantially reduce the development time between exploratory small scale growth of new materials and their subsequent commercial production.more » This technique is widely applicable and is not limited to crystal growth processes.« less

Understanding Unimer Exchange Processes in Block Copolymer Micelles using NMR Diffusometry, Time-Resolved NMR, and SANS

NASA Astrophysics Data System (ADS)

Madsen, Louis; Kidd, Bryce; Li, Xiuli; Miller, Katherine; Cooksey, Tyler; Robertson, Megan

Our team seeks to understand dynamic behaviors of block copolymer micelles and their interplay with encapsulated cargo molecules. Quantifying unimer and cargo exchange rates micelles can provide critical information for determining mechanisms of unimer exchange as well as designing systems for specific cargo release dynamics. We are exploring the utility of NMR spectroscopy and diffusometry techniques as complements to existing SANS and fluorescence methods. One promising new method involves time-resolved NMR spin relaxation measurements, wherein mixing of fully protonated and 2H-labeled PEO-b-PCL micelles solutions shows an increase in spin-lattice relaxation time (T1) with time after mixing. This is due to a weakening in magnetic environment surrounding 1H spins as 2H-bearing unimers join fully protonated micelles. We are measuring time constants for unimer exchange of minutes to hours, and we expect to resolve times of <1 min. This method can work on any solution NMR spectrometer and with minimal perturbation to chemical structure (as in dye-labelled fluorescence methods). Multimodal NMR can complement existing characterization tools, expanding and accelerating dynamics measurements for polymer micelle, nanogel, and nanoparticle developers.

Structured literature review of responses of cattle to viral and bacterial pathogens causing bovine respiratory disease complex.

PubMed

Grissett, G P; White, B J; Larson, R L

2015-01-01

Bovine respiratory disease (BRD) is an economically important disease of cattle and continues to be an intensely studied topic. However, literature summarizing the time between pathogen exposure and clinical signs, shedding, and seroconversion is minimal. A structured literature review of the published literature was performed to determine cattle responses (time from pathogen exposure to clinical signs, shedding, and seroconversion) in challenge models using common BRD viral and bacterial pathogens. After review a descriptive analysis of published studies using common BRD pathogen challenge studies was performed. Inclusion criteria were single pathogen challenge studies with no treatment or vaccination evaluating outcomes of interest: clinical signs, shedding, and seroconversion. Pathogens of interest included: bovine viral diarrhea virus (BVDV), bovine herpesvirus type 1 (BHV-1), parainfluenza-3 virus, bovine respiratory syncytial virus, Mannheimia haemolytica, Mycoplasma bovis, Pastuerella multocida, and Histophilus somni. Thirty-five studies and 64 trials were included for analysis. The median days to the resolution of clinical signs after BVDV challenge was 15 and shedding was not detected on day 12 postchallenge. Resolution of BHV-1 shedding resolved on day 12 and clinical signs on day 12 postchallenge. Bovine respiratory syncytial virus ceased shedding on day 9 and median time to resolution of clinical signs was on day 12 postchallenge. M. haemolytica resolved clinical signs 8 days postchallenge. This literature review and descriptive analysis can serve as a resource to assist in designing challenge model studies and potentially aid in estimation of duration of clinical disease and shedding after natural pathogen exposure. Copyright © 2015 The Authors. Journal of Veterinary Internal Medicine published by Wiley Periodicals, Inc. on behalf of the American College of Veterinary Internal Medicine.

Elasticity and Anelasticity of Materials from Time-Resolved X-ray Diffraction

NASA Astrophysics Data System (ADS)

Sinogeikin, S. V.; Smith, J.; Lin, C.; Bai, L.; Rod, E.; Shen, G.

2014-12-01

Recent advances in synchrotron sources, x-ray optics, area detectors, and sample environment control have enabled many time-resolved experimental techniques for studying materials at extreme pressure and temperature conditions. The High Pressure Collaborative Access Team (HPCAT) at the Advanced Photon Source has made a sustained effort to develop and assemble a powerful collection of high-pressure apparatus for time-resolved research, and considerable time has been invested in developing techniques for collecting high-quality time-resolved x-ray scattering data. In this talk we will outline recently developed capabilities at HPCAT for studying elasticity and anelasticity of minerals using fast compression and cyclic compression-decompression. A few recent studies will be highlighted. For example, with fast x-ray area detectors having millisecond time resolution, accurate thermal equations of state of materials at temperatures up to 1000K and megabar pressures can be collected in a matter of seconds using membrane-driven diamond anvil cells (DAC), yielding unprecedented time and pressure resolution of true isotherms. Short duration of the experiments eliminates temperature variation during the experiments and in general allows volume measurements at higher pressures and temperatures. Alternatively, high-frequency (kilohertz range) radial diffraction measurements in a panoramic DAC combined with fast, precise cyclic loading/unloading by piezo drive could provide the short time scale necessary for studying rheology of minerals from the elastic response and lattice relaxation as a function of pressure, temperature and strain rate. Finally, we consider some possible future applications for time-resolved high-pressure, high-temperature research of mantle minerals.

Energy research with neutrons (ErwiN) and installation of a fast neutron powder diffraction option at the MLZ, Germany1

PubMed Central

Mühlbauer, Martin J.

2018-01-01

The need for rapid data collection and studies of small sample volumes in the range of cubic millimetres are the main driving forces for the concept of a new high-throughput monochromatic diffraction instrument at the Heinz Maier-Leibnitz Zentrum (MLZ), Germany. A large region of reciprocal space will be accessed by a detector with sufficient dynamic range and microsecond time resolution, while allowing for a variety of complementary sample environments. The medium-resolution neutron powder diffraction option for ‘energy research with neutrons’ (ErwiN) at the high-flux FRM II neutron source at the MLZ is foreseen to meet future demand. ErwiN will address studies of energy-related systems and materials with respect to their structure and uniformity by means of bulk and spatially resolved neutron powder diffraction. A set of experimental options will be implemented, enabling time-resolved studies, rapid parametric measurements as a function of external parameters and studies of small samples using an adapted radial collimator. The proposed powder diffraction option ErwiN will bridge the gap in functionality between the high-resolution powder diffractometer SPODI and the time-of-flight diffractometers POWTEX and SAPHiR at the MLZ. PMID:29896055

Bandgap modulation in photoexcited topological insulator Bi{sub 2}Te{sub 3} via atomic displacements

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

Hada, Masaki, E-mail: hadamasaki@okayama-u.ac.jp; Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503; PRESTO, Japan Science and Technology Agency, Kawaguchi 332-0012

2016-07-14

The atomic and electronic dynamics in the topological insulator (TI) Bi{sub 2}Te{sub 3} under strong photoexcitation were characterized with time-resolved electron diffraction and time-resolved mid-infrared spectroscopy. Three-dimensional TIs characterized as bulk insulators with an electronic conduction surface band have shown a variety of exotic responses in terms of electronic transport when observed under conditions of applied pressure, magnetic field, or circularly polarized light. However, the atomic motions and their correlation between electronic systems in TIs under strong photoexcitation have not been explored. The artificial and transient modification of the electronic structures in TIs via photoinduced atomic motions represents a novelmore » mechanism for providing a comparable level of bandgap control. The results of time-domain crystallography indicate that photoexcitation induces two-step atomic motions: first bismuth and then tellurium center-symmetric displacements. These atomic motions in Bi{sub 2}Te{sub 3} trigger 10% bulk bandgap narrowing, which is consistent with the time-resolved mid-infrared spectroscopy results.« less

Pressure spectra from single-snapshot tomographic PIV

NASA Astrophysics Data System (ADS)

Schneiders, Jan F. G.; Avallone, Francesco; Pröbsting, Stefan; Ragni, Daniele; Scarano, Fulvio

2018-03-01

The power spectral density and coherence of temporal pressure fluctuations are obtained from low-repetition-rate tomographic PIV measurements. This is achieved by extension of recent single-snapshot pressure evaluation techniques based upon the Taylor's hypothesis (TH) of frozen turbulence and vortex-in-cell (VIC) simulation. Finite time marching of the measured instantaneous velocity fields is performed using TH and VIC. Pressure is calculated from the resulting velocity time series. Because of the theoretical limitations, the finite time marching can be performed until the measured flow structures are convected out of the measurement volume. This provides a lower limit of resolvable frequency range. An upper limit is given by the spatial resolution of the measurements. Finite time-marching approaches are applied to low-repetition-rate tomographic PIV data of the flow past a straight trailing edge at 10 m/s. Reference results of the power spectral density and coherence are obtained from surface pressure transducers. In addition, the results are compared to state-of-the-art experimental data obtained from time-resolved tomographic PIV performed at 10 kHz. The time-resolved approach suffers from low spatial resolution and limited maximum acquisition frequency because of hardware limitations. Additionally, these approaches strongly depend upon the time kernel length chosen for pressure evaluation. On the other hand, the finite time-marching approaches make use of low-repetition-rate tomographic PIV measurements that offer higher spatial resolution. Consequently, increased accuracy of the power spectral density and coherence of pressure fluctuations are obtained in the high-frequency range, in comparison to the time-resolved measurements. The approaches based on TH and VIC are found to perform similarly in the high-frequency range. At lower frequencies, TH is found to underestimate coherence and intensity of the pressure fluctuations in comparison to time-resolved PIV and the microphone reference data. The VIC-based approach, on the other hand, returns results on the order of the reference.

Novel laser gain and time-resolved FTIR studies of photochemistry

NASA Technical Reports Server (NTRS)

Leone, Stephen R.

1990-01-01

Several techniques are discussed which can be used to explore laboratory photochemical processes and kinetics relevant to planetary atmospheres; these include time-resolved laser gain-versus-absorption spectroscopy and time-resolved Fourier transform infrared (FTIR) emission studies. The laser gain-versus-absorption method employed tunable diode and F-center lasers to determine the yields of excited photofragments and their kinetics. The time-resolved FTIR technique synchronizes the sweep of a commercial FTIR with a pulsed source of light to obtain emission spectra of novel transient species in the infrared. These methods are presently being employed to investigate molecular photodissociation, the yields of excited states of fragments, their subsequent reaction kinetics, Doppler velocity distributions, and velocity-changing collisions of translationally fast atoms. Such techniques may be employed in future investigations of planetary atmospheres, for example to study polycyclic aromatic hydrocarbons related to cometary emissions, to analyze acetylene decomposition products and reactions, and to determine spectral features in the near infrared and infrared wavelength regions for planetary molecules and clusters.

Intense pumping and time- and frequency-resolved CARS for driving and tracking structural deformation and recovery of liquid nitromethane molecules

NASA Astrophysics Data System (ADS)

Wang, Chang; Wu, Hong-lin; Song, Yun-fei; He, Xing; Yang, Yan-qiang; Tan, Duo-wang

2015-11-01

A modified CARS technique with an intense nonresonant femtosecond laser is presented to drive the structural deformation of liquid nitromethane molecules and track their structural relaxation process. The CARS spectra reveal that the internal rotation of the molecule can couple with the CN symmetric stretching vibration and the molecules undergo ultrafast structural deformation of the CH3 groups from 'opened umbrella' to 'closed umbrella' shape, and then experience a structural recovery process within 720 fs.

Interaction of Merocyanine 540 with serum albumins: photophysical and binding studies.

PubMed

Banerjee, Mousumi; Pal, Uttam; Subudhhi, Arijita; Chakrabarti, Abhijit; Basu, Samita

2012-03-01

Photophysical studies on binding interactions of a negatively charged anti-tumor photosensitizer, Merocyanine 540 (MC 540), with serum proteins, bovine serum albumin (BSA) and human serum albumin (HSA), have been performed using absorption and steady-state as well as time-resolved fluorescence techniques. Formation of ground state complex has been confirmed from the detailed studies of absorption spectra of MC 540 in presence of SAs producing isosbestic points. Binding between the proteins and MC 540, which perturbs the existing equilibrium between the fluorescent monomer and its non-fluorescent dimer, induces a remarkable enhancement in fluorescence anisotropy and intensity of MC 540 along with a red shift of its maximum. The binding stoichiometry of MC 540 and SAs are more than 1.0 which depicts that two types of complexes, i.e., 1:1 and 2:1 are formed with addition of varied concentration of protein. Both the steady-state and time-resolved fluorescence results show that in 2:1 complex one of the MC 540 molecules is exposed towards aqueous environment with a greater extent when bound with HSA compared to BSA due to the structural flexibility of that protein. Thermodynamic analyses using van't Hoff plot indicate that the binding between MC 540 and individual SA is an entropy-driven phenomenon. The probable hydrophobic binding site has been located by denaturation of proteins, micropolarity measurement and Förster resonance energy transfer and that is further supported by molecular docking studies. Changes in circular dichroism spectra of BSA in presence of MC 540 depict secondary structural changes of the protein. The induced-CD shows that BSA due to its rigid structure generates chirality in MC 540 much more efficiently compared to HSA. Copyright © 2011 Elsevier B.V. All rights reserved.

PIV measurements and flow characteristics downstream of mangrove root models

NASA Astrophysics Data System (ADS)

Kazemi, Amirkhosro; Curet, Oscar

2016-11-01

Mangrove forests attracted attentions as a solution to protect coastal areas exposed to sea-level rising, frequent storms, and tsunamis. Mangrove forests found in tide-dominated flow regions are characterized by their massive and complex root systems, which play a prominent role in the structure of tidal flow currents. To understand the role of mangrove roots in flow structure, we modeled mangrove roots with rigid and flexible arrays of cylinders with different spacing between them as well as different configurations. In this work, we investigate the fluid dynamics downstream of the models using a 2-D time-resolved particle image velocimetry (PIV) and flow visualization. We carried out experiments for four different Reynolds number based on cylinder diameters ranges from 2200 to 12000. We present time-averaged and time-resolved flow parameters including velocity distribution, vorticity, streamline, Reynolds shear stress and turbulent kinetic energy. The results show that the flow structure has different vortex shedding downstream of the cylinders due to interactions of shear layers separating from cylinders surface. The spectral analysis of the measured velocity data is also performed to obtain Strouhal number of the unsteady flow in the cylinder wake.

Influence of magnetocrystalline anisotropy on the magnetization dynamics of magnetic microstructures.

PubMed

Kaiser, A; Wiemann, C; Cramm, S; Schneider, C M

2009-08-05

The study of magnetodynamics using stroboscopic time-resolved x-ray photoemission electron microscopy (TR-XPEEM) involves an intrinsic timescale provided by the pulse structure of the synchrotron radiation. In the usual multi-bunch operation mode, the time span between two subsequent light pulses is too short to allow a relaxation of the system into the ground state before the next pump-probe cycle starts. Using a deflection gating mechanism described in this paper we are able to pick the photoemission signal resulting from selected light pulses. Thus, PEEM measurements can be carried out in a flexible timing scheme with longer delays between two light pulses. Using this technique, the magnetodynamics of both Permalloy and iron structures have been investigated. The differences in the dynamic response on a short magnetic field pulse are discussed with respect to the magnetocrystalline anisotropy.

Time-resolved vibrational spectroscopy

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

Tokmakoff, Andrei; Champion, Paul; Heilweil, Edwin J.

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 ofmore » 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.« less

Anisotropy enhanced X-ray scattering from solvated transition metal complexes

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

Biasin, Elisa; van Driel, Tim B.; Levi, Gianluca

Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV–Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time-resolved X-ray scattering experiment. This method is applied on time-resolvedmore » X-ray scattering patterns measured upon photoexcitation of a solvated di-platinum complex at an XFEL, and the key parameters involved are explored. Here it is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute,i.e.the change in Pt—Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function.« less

Anisotropy enhanced X-ray scattering from solvated transition metal complexes

DOE PAGES

Biasin, Elisa; van Driel, Tim B.; Levi, Gianluca; ...

2018-02-13

Time-resolved X-ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X-ray free-electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV–Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X-ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time-resolved X-ray scattering experiment. This method is applied on time-resolvedmore » X-ray scattering patterns measured upon photoexcitation of a solvated di-platinum complex at an XFEL, and the key parameters involved are explored. Here it is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute,i.e.the change in Pt—Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function.« less

All-Atom Multiscale Molecular Dynamics Theory and Simulation of Self-Assembly, Energy Transfer and Structural Transition in Nanosystems

NASA Astrophysics Data System (ADS)

Espinosa Duran, John Michael

The study of nanosystems and their emergent properties requires the development of multiscale computational models, theories and methods that preserve atomic and femtosecond resolution, to reveal details that cannot be resolved experimentally today. Considering this, three long time scale phenomena were studied using molecular dynamics and multiscale methods: self-assembly of organic molecules on graphite, energy transfer in nanosystems, and structural transition in vault nanoparticles. Molecular dynamics simulations of the self-assembly of alkoxybenzonitriles with different tail lengths on graphite were performed to learn about intermolecular interactions and phases exhibited by self-organized materials. This is important for the design of ordered self-assembled organic photovoltaic materials with greater efficiency than the disordered blends. Simulations revealed surface dynamical behaviors that cannot be resolved experimentally today due to the lack of spatiotemporal resolution. Atom-resolved structures predicted by simulations agreed with scanning tunneling microscopy images and unit cell measurements. Then, a multiscale theory based on the energy density as a field variable is developed to study energy transfer in nanoscale systems. For applications like photothermal microscopy or cancer phototherapy is required to understand how the energy is transferred to/from nanosystems. This multiscale theory could be applied in this context and here is tested for cubic nanoparticles immersed in water for energy being transferred to/from the nanoparticle. The theory predicts the energy transfer dynamics and reveals phenomena that cannot be described by current phenomenological theories. Finally, temperature-triggered structural transitions were revealed for vault nanoparticles using molecular dynamics and multiscale simulations. Vault is a football-shaped supramolecular assembly very distinct from the commonly observed icosahedral viruses. It has very promising applications in drug delivery and has been extensively studied experimentally. Sub-microsecond multiscale simulations at 310 K on the vault revealed the opening and closing of fractures near the shoulder while preserving the overall structure. This fracture mechanism could explain the uptake and release of small drugs while maintaining the overall structure. Higher temperature simulations show the generation of large fractures near the waist, which enables interaction of the external medium with the inner vault residues. Simulation results agreed with microscopy and spectroscopy measurements, and revealed new structures and mechanisms.

Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2

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

Liu, Jue; Yu, Lei; Hu, Enyuan

Layered δ-MnO 2 (birnessites) are ubiquitous in nature and have also been reported to work as promising water oxidation catalysts or rechargeable alkali-ion battery cathodes when fabricated under appropriate conditions. Although tremendous effort has been spent on resolving the structure of natural/synthetic layered δ-MnO 2 in the last few decades, no conclusive result has been reached. In this Article, we report an environmentally friendly route to synthesizing homogeneous Cu-rich layered δ-MnO 2 nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered δ-MnO 2 has been successfully resolved from combined Mn/Cu K-edge extended X-ray fine structure spectroscopymore » and X-ray and neutron total scattering analysis. It is found that appreciable amounts (~8%) of Mn vacancies are present in the MnO 2 layer and Cu 2+ occupies the interlayer sites above/below the vacant Mn sites. Effective hydrogen bonding among the interlayer water molecules and adjacent layer O ions has also been observed for the first time. These hydrogen bonds are found to play the key role in maintaining the intermediate and long-range stacking coherence of MnO 2 layers. Quantitative analysis of the turbostratic stacking disorder in this compound was achieved using a supercell approach coupled with anisotropic particle-size-effect modeling. Furthermore, the present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.« less

Large-Scale Synthesis and Comprehensive Structure Study of δ-MnO 2

DOE PAGES

Liu, Jue; Yu, Lei; Hu, Enyuan; ...

2018-05-30

Layered δ-MnO 2 (birnessites) are ubiquitous in nature and have also been reported to work as promising water oxidation catalysts or rechargeable alkali-ion battery cathodes when fabricated under appropriate conditions. Although tremendous effort has been spent on resolving the structure of natural/synthetic layered δ-MnO 2 in the last few decades, no conclusive result has been reached. In this Article, we report an environmentally friendly route to synthesizing homogeneous Cu-rich layered δ-MnO 2 nanoflowers in large scale. The local and average structure of synthetic Cu-rich layered δ-MnO 2 has been successfully resolved from combined Mn/Cu K-edge extended X-ray fine structure spectroscopymore » and X-ray and neutron total scattering analysis. It is found that appreciable amounts (~8%) of Mn vacancies are present in the MnO 2 layer and Cu 2+ occupies the interlayer sites above/below the vacant Mn sites. Effective hydrogen bonding among the interlayer water molecules and adjacent layer O ions has also been observed for the first time. These hydrogen bonds are found to play the key role in maintaining the intermediate and long-range stacking coherence of MnO 2 layers. Quantitative analysis of the turbostratic stacking disorder in this compound was achieved using a supercell approach coupled with anisotropic particle-size-effect modeling. Furthermore, the present method is expected to be generally applicable to the structural study of other technologically important nanomaterials.« less

Femtosecond/picosecond time-resolved fluorescence study of hydrophilic polymer fine particles.

PubMed

Nanjo, Daisuke; Hosoi, Haruko; Fujino, Tatsuya; Tahara, Tahei; Korenaga, Takashi

2007-03-22

Femtosecond/picosecond time-resolved fluorescence study of hydrophilic polymer fine particles (polyacrylamide, PAAm) was reported. Ultrafast fluorescence dynamics of polymer/water solution was monitored using a fluorescent probe molecule (C153). In the femtosecond time-resolved fluorescence measurement at 480 nm, slowly decay components having lifetimes of tau(1) approximately 53 ps and tau(2) approximately 5 ns were observed in addition to rapid fluorescence decay. Picosecond time-resolved fluorescence spectra of C153/PAAm/H2O solution were also measured. In the time-resolved fluorescence spectra of C153/PAAm/H2O, a peak shift from 490 to 515 nm was measured, which can be assigned to the solvation dynamics of polymer fine particles. The fluorescence peak shift was related to the solvation response function and two time constants were determined (tau(3) approximately 50 ps and tau(4) approximately 467 ps). Therefore, the tau(1) component observed in the femtosecond time-resolved fluorescence measurement was assigned to the solvation dynamics that was observed only in the presence of polymer fine particles. Rotational diffusion measurements were also carried out on the basis of the picosecond time-resolved fluorescence spectra. In the C153/PAAm/H2O solution, anisotropy decay having two different time constants was also derived (tau(6) approximately 76 ps and tau(7) approximately 676 ps), indicating the presence of two different microscopic molecular environments around the polymer surface. Using the Stokes-Einstein-Debye (SED) equation, microscopic viscosity around the polymer surface was evaluated. For the area that gave a rotational diffusion time of tau(6) approximately 76 ps, the calculated viscosity is approximately 1.1 cP and for tau(7) approximately 676 ps, it is approximately 10 cP. The calculated viscosity values clearly revealed that there are two different molecular environments around the polyacrylamide fine particles.

Flow temporal reconstruction from non-time-resolved data part I: mathematic fundamentals

NASA Astrophysics Data System (ADS)

Legrand, Mathieu; Nogueira, José; Lecuona, Antonio

2011-10-01

At least two circumstances point to the need of postprocessing techniques to recover lost time information from non-time-resolved data: the increasing interest in identifying and tracking coherent structures in flows of industrial interest and the high data throughput of global measuring techniques, such as PIV, for the validation of computational fluid dynamics (CFD) codes. This paper offers the mathematic fundamentals of a space--time reconstruction technique from non-time-resolved, statistically independent data. An algorithm has been developed to identify and track traveling coherent structures in periodic flows. Phase-averaged flow fields are reconstructed with a correlation-based method, which uses information from the Proper Orthogonal Decomposition (POD). The theoretical background shows that the snapshot POD coefficients can be used to recover flow phase information. Once this information is recovered, the real snapshots are used to reconstruct the flow history and characteristics, avoiding neither the use of POD modes nor any associated artifact. The proposed time reconstruction algorithm is in agreement with the experimental evidence given by the practical implementation proposed in the second part of this work (Legrand et al. in Exp Fluids, 2011), using the coefficients corresponding to the first three POD modes. It also agrees with the results on similar issues by other authors (Ben Chiekh et al. in 9 Congrès Francophone de Vélocimétrie Laser, Bruxelles, Belgium, 2004; Van Oudheusden et al. in Exp Fluids 39-1:86-98, 2005; Meyer et al. in 7th International Symposium on Particle Image Velocimetry, Rome, Italy, 2007a; in J Fluid Mech 583:199-227, 2007b; Perrin et al. in Exp Fluids 43-2:341-355, 2007). Computer time to perform the reconstruction is relatively short, of the order of minutes with current PC technology.

Time-resolved fluorescence polarization spectroscopy of visible and near infrared dyes in picosecond dynamics

NASA Astrophysics Data System (ADS)

Pu, Yang; Alfano, Robert R.

2015-03-01

Near-infrared (NIR) dyes absorb and emit light within the range from 700 to 900 nm have several benefits in biological studies for one- and/or two-photon excitation for deeper penetration of tissues. These molecules undergo vibrational and rotational motion in the relaxation of the excited electronic states, Due to the less than ideal anisotropy behavior of NIR dyes stemming from the fluorophores elongated structures and short fluorescence lifetime in picosecond range, no significant efforts have been made to recognize the theory of these dyes in time-resolved polarization dynamics. In this study, the depolarization of the fluorescence due to emission from rotational deactivation in solution will be measured with the excitation of a linearly polarized femtosecond laser pulse and a streak camera. The theory, experiment and application of the ultrafast fluorescence polarization dynamics and anisotropy are illustrated with examples of two of the most important medical based dyes. One is NIR dye, namely Indocyanine Green (ICG) and is compared with Fluorescein which is in visible range with much longer lifetime. A set of first-order linear differential equations was developed to model fluorescence polarization dynamics of NIR dye in picosecond range. Using this model, the important parameters of ultrafast polarization spectroscopy were identified: risetime, initial time, fluorescence lifetime, and rotation times.

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

PubMed

Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

2018-05-30

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Combining Structural Probes in the Gas Phase - Ion Mobility- Resolved Action-FRET

NASA Astrophysics Data System (ADS)

Daly, Steven; MacAleese, Luke; Dugourd, Philippe; Chirot, Fabien

2018-01-01

In the context of native mass spectrometry, the development of gas-phase structural probes sensitive to the different levels of structuration of biomolecular assemblies is necessary to push forward conformational studies. In this paper, we provide the first example of the combination of ion mobility (IM) and Förster resonance energy transfer (FRET) measurements within the same experimental setup. The possibility to obtain mass- and mobility-resolved FRET measurements is demonstrated on a model peptide and applied to monitor the collision-induced unfolding of ubiquitin. [Figure not available: see fulltext.

Correlated full-field and pointwise temporally resolved measurements of thermomechanical stress inside an operating power transistor

NASA Astrophysics Data System (ADS)

Borza, Dan N.; Gautrelet, Christophe

2015-01-01

The paper describes a measurement system based on time-resolved speckle interferometry, able to record long series of thermally induced full-field deformation maps of die and wire bonds inside an operating power transistor. The origin of the deformation is the transistor heating during its normal operation. The full-field results consist in completely unwrapped deformation maps for out-of-plane displacements greater than 14 μm, with nanometer resolution, in presence of discontinuities due to structural and material inhomogeneity. These measurements are synchronized with the measurement of heatsink temperature and of base-emitter junction temperature, so as to provide data related to several interacting physical parameters. The temporal histories of the displacement are also accessible for any point. They are correlated with the thermal and electrical time series. Mechanical full-field curvatures may also be estimated, making these measurements useful for inspecting physical origins of thermomechanical stresses and for interacting with numerical models used in reliability-related studies.

Ultrafast Imaging of Chiral Surface Plasmon by Photoemission Electron Microscopy

NASA Astrophysics Data System (ADS)

Dai, Yanan; Dabrowski, Maciej; Petek, Hrvoje

We employ Time-Resolved Photoemission Electron Microscopy (TR-PEEM) to study surface plasmon polariton (SPP) wave packet dynamics launched by tunable (VIS-UV) femtosecond pulses of various linear and circular polarizations. The plasmonic structures are micron size single-crystalline Ag islands grown in situ on Si surfaces and characterized by Low Energy Electron Microscopy (LEEM). The local fields of plasmonic modes enhance two and three photon photoemission (2PP and 3PP) at the regions of strong field enhancement. Imaging of the photoemission signal with PEEM electron optics thus images the plasmonic fields excited in the samples. The observed PEEM images with left and right circularly polarized light show chiral images, which is a consequence of the transverse spin momentum of surface plasmon. By changing incident light polarization, the plasmon interference pattern shifts with light ellipticity indicating a polarization dependent excitation phase of SPP. In addition, interferometric-time resolved measurements record the asymmetric SPP wave packet motion in order to characterize the dynamical properties of chiral SPP wave packets.

Stall behavior of a scaled three-dimensional wind turbine blade

NASA Astrophysics Data System (ADS)

Mulleners, Karen; Melius, Matthew; Cal, Raul Bayoan

2014-11-01

The power generation of a wind turbine is influenced by many factors including the unsteady incoming flow characteristics, pitch regulation, and the geometry of the various turbine components. Within the framework of maximizing energy extraction, it is important to understand and tailor the aerodynamics of a wind turbine. In the interest of seeking further understanding into the complex flow over wind turbine blades, a three-dimensional scaled blade model has been designed and manufactured to be dynamically similar to a rotating full-scale NREL 5MW wind turbine blade. A wind tunnel experiment has been carried out in the 2.2 m × 1.8 m cross-section closed loop wind tunnel at DLR in Göttingen by means of time-resolved stereoscopic PIV. An extensive coherent structure analysis of the time-resolved velocity field over the suction side of the blade was performed to study stall characteristics under a geometrically induced pressure gradient. In particular, the radial extent and propagation of stalled flow regions were characterized for various static angles of attack.

Magneto-optical properties and recombination dynamics of isoelectronic bound excitons in ZnO

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

Chen, S. L.; Chen, W. M.; Buyanova, I. A.

2014-02-21

Magneto-optical and time-resolved photoluminescence (PL) spectroscopies are employed to evaluate electronic structure of a bound exciton (BX) responsible for the 3.364 eV line (labeled as I{sub 1}{sup *}) in bulk ZnO. From time-resolved PL spectroscopy, I{sub 1}{sup *} is concluded to originate from the exciton ground state. Based on performed magneto-PL studies, the g-factors of the involved electron and hole are determined as being g{sub e} = 1.98 and g{sub h}{sup ∥}(g{sub h}{sup ⊥}) = 1.2(1.62), respectively. These values are nearly identical to the reported g-factors for the I{sup *} line in ZnO (Phys. Rev. B 86, 235205 (2012)), which proves thatmore » I{sub 1}{sup *} should have a similar origin as I{sup *} and should arise from an exciton bound to an isoelectronic center with a hole-attractive potential.« less

Highly sensitive time-resolved thermography and multivariate image analysis of the cerebral cortex for intrasurgical diagnostics

NASA Astrophysics Data System (ADS)

Hollmach, Julia; Hoffmann, Nico; Schnabel, Christian; Küchler, Saskia; Sobottka, Stephan; Kirsch, Matthias; Schackert, Gabriele; Koch, Edmund; Steiner, Gerald

2013-03-01

Time-resolved thermography is a novel method to assess thermal variations and heterogeneities in tissue and blood. The recent generation of thermal cameras provides a sensitivity of less than mK. This high sensitivity in conjunction with non-invasive, label-free and radiation-free monitoring makes thermography a promising tool for intrasurgical diagnostics. In brain surgery, time-resolved thermography can be employed to distinguish between normal and anomalous tissue. In this study, we investigated and discussed the potential of time-resolved thermography in neurosurgery for the intraoperative detection and demarcation of tumor borders. Algorithms for segmentation, reduction of movement artifacts and image fusion were developed. The preprocessed image stacks were subjected to discrete wavelet transform to examine individual frequency components. K-means clustering was used for image evaluation to reveal similarities within the image sequence. The image evaluation shows significant differences for both types of tissue. Tumor and normal tissues have different time characteristics in heat production and transfer. Furthermore, tumor could be highlighted. These results demonstrate that time-resolved thermography is able to support the detection of tumors in a contactless manner without any side effects for the tissue. The intraoperative usage of time-resolved thermography improves the accuracy of tumor resections to prevent irreversible brain damage during surgery.

Novel physical chemistry approaches in biophysical researches with advanced application of lasers: Detection and manipulation.

PubMed

Iwata, Koichi; Terazima, Masahide; Masuhara, Hiroshi

2018-02-01

Novel methodologies utilizing pulsed or intense CW irradiation obtained from lasers have a major impact on biological sciences. In this article, recent development in biophysical researches fully utilizing the laser irradiation is described for three topics, time-resolved fluorescence spectroscopy, time-resolved thermodynamics, and manipulation of the biological assemblies by intense laser irradiation. First, experimental techniques for time-resolved fluorescence spectroscopy are concisely explained in Section 2. As an example of the recent application of time-resolved fluorescence spectroscopy to biological systems, evaluation of the viscosity of lipid bilayer membranes is described. The results of the spectroscopic experiments strongly suggest the presence of heterogeneous membrane structure with two different viscosity values in liposomes formed by a single phospholipid. Section 3 covers the time-resolved thermodynamics. Thermodynamical properties are important to characterize biomolecules. However, measurement of these quantities for short-lived intermediate species has been impossible by traditional thermodynamical techniques. Recently, development of a spectroscopic method based on the transient grating method enables us to measure these quantities and also to elucidate reaction kinetics which cannot be detected by other spectroscopic methods. The principle of the measurements and applications to some protein reactions are reviewed. Manipulation and fabrication of supramolecues, amino acids, proteins, and living cells by intense laser irradiation are described in Section 4. Unconventional assembly, crystallization and growth, amyloid fibril formation, and living cell manipulation are achieved by CW laser trapping and femtosecond laser-induced cavitation bubbling. Their spatio-temporal controllability is opening a new avenue in the relevant molecular and bioscience research fields. This article is part of a Special Issue entitled "Biophysical Exploration of Dynamical Ordering of Biomolecular Systems" edited by Dr. Koichi Kato. Copyright © 2017. Published by Elsevier B.V.

Characterization of ultrafast laser-ablation plasma plumes at various Ar ambient pressures

DOE PAGES

Diwakar, P. K.; Harilal, S. S.; Phillips, M. C.; ...

2015-07-30

Expansion dynamics and internal plume structures of fs laser ablated brass plasma in Ar at various pressure levels ranging from vacuum to atmospheric were studied using multitude of diagnostic tools including time resolved and time integrated 2-dimensional imaging, optical time of flight measurements and visible emission spectroscopy. Temporal evolution of excited Cu and Zn species in the plume were imaged using band pass interference filters and compared its hydrodynamic expansion features with spectrally integrated images of the plume. 2D imaging coupled with monochromatic line selection showed several interesting features at various pressure levels which include velocity differences among the plumemore » species, emission intensity distribution, plasma temperature, electron density etc. Plume confinement, enhanced signal intensity, and dual peak structures in time-of-flight profiles were observed at intermediate pressure range of ~10 Torr. Optimum signal to background ratio was also observed in this pressure range. As a result, possible mechanisms for observed changes in plume shape, optical emission intensity and dual peak structures in time-of-flight profiles were discussed.« less

Coherent Acoustic Vibration of Metal Nanoshells

NASA Astrophysics Data System (ADS)

Guillon, C.; Langot, P.; Del Fatti, N.; Vallée, F.; Kirakosyan, A. S.; Shahbazyan, T. V.; Cardinal, T.; Treguer, M.

2007-01-01

Using time-resolved pump-probe spectroscopy we have performed the first investigation of the vibrational modes of gold nanoshells. The fundamental isotropic mode launched by a femtosecond pump pulse manifests itself in a pronounced time-domain modulation of the differential transmission probed at the frequency of nanoshell surface plasmon resonance. The modulation amplitude is significantly stronger and the period is longer than in a gold nanoparticle of the same overall size, in agreement with theoretical calculations. This distinct acoustical signature of nanoshells provides a new and efficient method for identifying these versatile nanostructures and for studying their mechanical and structural properties.

On seismic resolution of lateral heterogeneity in the Earth's outermost core

NASA Astrophysics Data System (ADS)

Garnero, Edward J.; Helmberger, Donald V.

1995-03-01

Issues concerning resolution of seismically determined outermost core properties are presented with an example from three earthquakes in the Fiji-Tonga region. Travel time behavior of the commonly used family of S mKS waves, which travel as S in the mantle, P in the core, reflecting m - 1 times at the underside of the core-mantle boundary (CMB), are analyzed over a large distance range (125-165°). Data having wavepaths through an area of known D″ heterogeneity (±2%) exhibit systematic anomalies in S mKS differential times. Two-dimensional wave propagation experiments demonstrate how large-scale lower-mantle velocity perturbations can explain long-wavelength behavior of such anomalous S mKS times, though heterogeneity on smaller scales may be responsible for the observed scatter about these trends. If lower-mantle heterogeneity is not properly accounted for in deriving a core model, misfit of the mantle model maps directly into core structure. The existence of outermost core heterogeneity is difficult to resolve at present, owing to uncertainties in global lower-mantle structure. Resolving a one-dimensional chemically stratified outermost core also remains difficult, owing to the same uncertainties. Inclusion of the slowly accruing broadband data should help in this regard. Restricting study to higher multiples of S mKS ( m = 2, 3, 4) can help reduce the effect of mantle heterogeneity, because of the closeness of the mantle legs of the wavepaths. S mKS waves are ideal in providing additional information on the details of lower-mantle heterogeneity.

Angle-resolved diffraction grating biosensor based on porous silicon

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

Lv, Changwu; Li, Peng; Jia, Zhenhong, E-mail: jzhh@xju.edu.cn

2016-03-07

In this study, an optical biosensor based on a porous silicon composite structure was fabricated using a simple method. This structure consists of a thin, porous silicon surface diffraction grating and a one-dimensional porous silicon photonic crystal. An angle-resolved diffraction efficiency spectrum was obtained by measuring the diffraction efficiency at a range of incident angles. The angle-resolved diffraction efficiency of the 2nd and 3rd orders was studied experimentally and theoretically. The device was sensitive to the change of refractive index in the presence of a biomolecule indicated by the shift of the diffraction efficiency spectrum. The sensitivity of this sensormore » was investigated through use of an 8 base pair antifreeze protein DNA hybridization. The shifts of the angle-resolved diffraction efficiency spectrum showed a relationship with the change of the refractive index, and the detection limit of the biosensor reached 41.7 nM. This optical device is highly sensitive, inexpensive, and simple to fabricate. Using shifts in diffraction efficiency spectrum to detect biological molecules has not yet been explored, so this study establishes a foundation for future work.« less

Ultrafast kinetics of linkage isomerism in Na2[Fe(CN)5NO] aqueous solution revealed by time-resolved photoelectron spectroscopy

PubMed Central

Raheem, Azhr A.; Wilke, Martin; Borgwardt, Mario; Engel, Nicholas; Bokarev, Sergey I.; Grell, Gilbert; Aziz, Saadullah G.; Kühn, Oliver; Kiyan, Igor Yu.; Merschjann, Christoph; Aziz, Emad F.

2017-01-01

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na2[Fe(CN)5NO] as a model complex. The buildup of the metastable side-on configuration of the NO ligand, as well as the electronic energy levels of ground, excited, and metastable states, has been revealed by means of time-resolved extreme UV (XUV) photoelectron spectroscopy in aqueous solution, aided by theoretical calculations. Evidence of a short-lived intermediate state in the isomerization process and its nature are discussed, finding that the complete isomerization process occurs in less than 240 fs after photoexcitation. PMID:28713840

Ultrafast structural dynamics of boron nitride nanotubes studied using transmitted electrons.

PubMed

Li, Zhongwen; Sun, Shuaishuai; Li, Zi-An; Zhang, Ming; Cao, Gaolong; Tian, Huanfang; Yang, Huaixin; Li, Jianqi

2017-09-14

We investigate the ultrafast structural dynamics of multi-walled boron nitride nanotubes (BNNTs) upon femtosecond optical excitation using ultrafast electron diffraction in a transmission electron microscope. Analysis of the time-resolved (100) and (002) diffraction profiles reveals highly anisotropic lattice dynamics of BNNTs, which can be attributed to the distinct nature of the chemical bonds in the tubular structure. Moreover, the changes in (002) diffraction positions and intensities suggest that the lattice response of BNNTs to the femtosecond laser excitation involves a fast and a slow lattice dynamic process. The fast process with a time constant of about 8 picoseconds can be understood to be a result of electron-phonon coupling, while the slow process with a time constant of about 100 to 300 picoseconds depending on pump laser fluence is tentatively associated with an Auger recombination effect. In addition, we discuss the power-law relationship of a three-photon absorption process in the BNNT nanoscale system.

Dynamics of DNA/intercalator complexes

NASA Astrophysics Data System (ADS)

Schurr, J. M.; Wu, Pengguang; Fujimoto, Bryant S.

1990-05-01

Complexes of linear and supercoiled DNAs with different intercalating dyes are studied by time-resolved fluorescence polarization anisotropy using intercalated ethidium as the probe. Existing theory is generalized to take account of excitation transfer between intercalated ethidiums, and Forster theory is shown to be valid in this context. The effects of intercalated ethidium, 9-aminoacridine, and proflavine on the torsional rigidity of linear and supercoiled DNAs are studied up to rather high binding ratios. Evidence is presented that metastable secondary structure persists in dye-relaxed supercoiled DNAs, which contradicts the standard model of supercoiled DNAs.

Robustness of coevolution in resolving prisoner's dilemma games on interdependent networks subject to attack

NASA Astrophysics Data System (ADS)

Liu, Penghui; Liu, Jing

2017-08-01

Recently, coevolution between strategy and network structure has been established as a rule to resolve social dilemmas and reach optimal situations for cooperation. Many follow-up researches have focused on studying how coevolution helps networks reorganize to deter the defectors and many coevolution methods have been proposed. However, the robustness of the coevolution rules against attacks have not been studied much. Since attacks may directly influence the original evolutionary process of cooperation, the robustness should be an important index while evaluating the quality of a coevolution method. In this paper, we focus on investigating the robustness of an elementary coevolution method in resolving the prisoner's dilemma game upon the interdependent networks. Three different types of time-independent attacks, named as edge attacks, instigation attacks and node attacks have been employed to test its robustness. Through analyzing the simulation results obtained, we find this coevolution method is relatively robust against the edge attack and the node attack as it successfully maintains cooperation in the population over the entire attack range. However, when the instigation probability of the attacked individuals is large or the attack range of instigation attack is wide enough, coevolutionary rule finally fails in maintaining cooperation in the population.

High-pressure studies with x-rays using diamond anvil cells

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

Shen, Guoyin; Mao, Ho Kwang

2016-11-22

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials' properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. Thesemore » HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.« less

High-pressure studies with x-rays using diamond anvil cells

NASA Astrophysics Data System (ADS)

Shen, Guoyin; Mao, Ho Kwang

2017-01-01

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials’ properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. These HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.

Examination of Rotating Spoke Instability in a Cross-Field Discharge

DTIC Science & Technology

2013-07-08

leader), L. Balika, J. Vaudolon EMAU R. Schneider, K. Matyash PPPL Y. Raitses, A. Diallo, Y. Shi Distribution A: Approved for public...the spoke. The project was originally divided into three successive phases, namely: Phase 1: Time-averaged LIF study on the CHT at PPPL Phase 2...Time-resolved LIF study on the CHT at ICARE Phase 3: Time-resolved LIF study on a 2 kW HT at PPPL (Optional) Distribution A: Approved for public

Monolithic Microfluidic Mixing-Spraying Devices for Time-Resolved Cryo-Electron Microscopy

PubMed Central

Lu, Zonghuan; Shaikh, Tanvir R.; Barnard, David; Meng, Xing; Mohamed, Hisham; Yassin, Aymen; Mannella, Carmen A.; Agrawal, Rajendra K.; Lu, Toh-Ming

2009-01-01

The goal of time-resolved cryo-electron microscopy is to determine structural models for transient functional states of large macromolecular complexes such as ribosomes and viruses. The challenge of time-resolved cryo-electron microscopy is to rapidly mix reactants, and then, following a defined time interval, to rapidly deposit them as a thin film and freeze the sample to the vitreous state. Here we describe a methodology in which reaction components are mixed and allowed to react, and are then sprayed onto an EM grid as it is being plunged into cryogen. All steps are accomplished by a monolithic, microfabricated silicon device that incorporates a mixer, reaction channel, and pneumatic sprayer in a single chip. We have found that microdroplets produced by air atomization spread to sufficiently thin films on a millisecond time scale provided that the carbon supporting film is made suitably hydrophilic. The device incorporates two T-mixers flowing into a single channel of four butterfly-shaped mixing elements that ensure effective mixing, followed by a microfluidic reaction channel whose length can be varied to achieve the desired reaction time. The reaction channel is flanked by two ports connected to compressed humidified nitrogen gas (at 50 psi) to generate the spray. The monolithic mixer-sprayer is incorporated into a computer-controlled plunging apparatus. To test the mixing performance and the suitability of the device for preparation of biological macromolecules for cryo-EM, ribosomes and ferritin were mixed in the device and sprayed onto grids. Three-dimensional reconstructions of the ribosomes demonstrated retention of native structure, and 30S and 50S subunits were shown to be capable of reassociation into ribosomes after passage through the device. PMID:19683579

Bioinspired Non-iridescent Structural Color from Polymer Blend Thin Films

NASA Astrophysics Data System (ADS)

Nallapaneni, Asritha; Shawkey, Matthew; Karim, Alamgir

Colors exhibited in biological species are either due to natural pigments, sub-micron structural variation or both. Structural colors thus exhibited can be iridescent (ID) or non-iridescent (NID) in nature. NID colors originate due to interference and coherent scattering of light with quasi-ordered micro- and nano- structures. Specifically, in Eastern Bluebird (Sialia sialis) these nanostructures develop as a result of phase separation of β-keratin from cytoplasm present in cells. We replicate these structures via spinodal blend phase separation of PS-PMMA thin films. Colors of films vary from ultraviolet to blue. Scattering of UV-visible light from selectively leeched phase separated blends are studied in terms of varying domain spacing (200nm to 2 μm) of film. We control these parameters by tuning annealing time and temperature. Angle-resolved spectroscopy studies suggest that the films are weakly iridescent and scattering from phase-separated films is more diffused when compared to well-mixed films. This study offers solutions to several color-based application in paints and coatings industry.

Polychromatic microdiffraction characterization of defect gradients in severely deformed materials.

PubMed

Barabash, Rozaliya I; Ice, Gene E; Liu, Wenjun; Barabash, Oleg M

2009-01-01

This paper analyzes local lattice rotations introduced in severely deformed polycrystalline titanium by friction stir welding. Nondestructive three-dimensional (3D) spatially resolved polychromatic X-ray microdiffraction, is used to resolve the local crystal structure of the restructured surface from neighboring local structures in the sample material. The measurements reveal strong gradients of strain and geometrically necessary dislocations near the surface and illustrate the potential of polychromatic microdiffraction for the study of deformation in complex materials systems.

A non-uniformly sampled 4D HCC(CO)NH-TOCSY experiment processed using maximum entropy for rapid protein sidechain assignment

PubMed Central

Mobli, Mehdi; Stern, Alan S.; Bermel, Wolfgang; King, Glenn F.; Hoch, Jeffrey C.

2010-01-01

One of the stiffest challenges in structural studies of proteins using NMR is the assignment of sidechain resonances. Typically, a panel of lengthy 3D experiments are acquired in order to establish connectivities and resolve ambiguities due to overlap. We demonstrate that these experiments can be replaced by a single 4D experiment that is time-efficient, yields excellent resolution, and captures unique carbon-proton connectivity information. The approach is made practical by the use of non-uniform sampling in the three indirect time dimensions and maximum entropy reconstruction of the corresponding 3D frequency spectrum. This 4D method will facilitate automated resonance assignment procedures and it should be particularly beneficial for increasing throughput in NMR-based structural genomics initiatives. PMID:20299257

Time Resolved Tomographic PIV Measurements of Rough-Wall Turbulent Channel Flow

NASA Astrophysics Data System (ADS)

Miorini, Rinaldo; Zhang, Cao; Katz, Joseph

2013-11-01

Time resolved tomographic PIV is used to study flow structures in the outer region of a rough-wall turbulent boundary layer, focusing on imprints of the roughness on the outer layer. Measurements are performed in a transparent channel installed in the JHU optically index matched facility. The roughness consists of pyramids with height, k = 0.46 mm, and wavelength, λ = 3.2 mm, satisfying h/k = 55 (h = 25.4 mm is the channel half-height), k + = 64 and Re = 40000. The TPIV setup consists of four high-speed cameras operating at 3 kHz, which view the sample volume through acrylic prisms. The flow field is illuminated by an Nd:YLF laser. Following enhancement, calibration, and reconstruction, 643 voxels interrogation volumes with 0.75 overlap provide 3D velocity fields with spacing of 0.5883 mm3. Formation and transport of near-wall 3D U-shaped vortex structures, with base in front of the pyramids, and quasi-streamwise legs extending between pyramid crest lines are evident from the data. Extended streamwise regions of high wall-normal vorticity appear ``latched'' to the roughness elements close to the wall, but are transported downstream at higher elevations. Also evident are traveling streamwise low velocity streaks, which cover many roughness elements. Sponsored by NSF CBET and ONR.

How to measure separations and angles between intra-molecular fluorescent markers

NASA Astrophysics Data System (ADS)

Flyvbjerg, Henrik; Mortensen, Kim I.; Sung, Jongmin; Spudich, James A.

We demonstrate a novel, yet simple tool for the study of structure and function of biomolecules by extending two-colour co-localization microscopy to fluorescent molecules with fixed orientations and in intra-molecular proximity. From each color-separated microscope image in a time-lapse movie and using only simple means, we simultaneously determine both the relative (x,y)-separation of the fluorophores and their individual orientations in space with accuracy and precision. The positions and orientations of two domains of the same molecule are thus time-resolved. Using short double-stranded DNA molecules internally labelled with two fixed fluorophores, we demonstrate the accuracy and precision of our method using the known structure of double-stranded DNA as a benchmark, resolve 10-base-pair differences in fluorophore separations, and determine the unique 3D orientation of each DNA molecule, thereby establishing short, double-labelled DNA molecules as probes of 3D orientation of anything to which one can attach them firmly. This work was supported by a Lundbeck fellowship to K.I.M; a Stanford Bio-X fellowship to J.S. and Grants from the NIH (GM33289) to J.A.S. and the Human Frontier Science Program (GP0054/2009-C) to J.A.S. and H.F.

Shining X-rays on catalysts at work

NASA Astrophysics Data System (ADS)

Grunwaldt, J.-D.

2009-11-01

Structure-performance relationships gained by studying catalysts at work are considered the key to further development of catalysts underlined here by a brief overview on our research in this area. The partial oxidation of methane to hydrogen and carbon monoxide over Pt- and Rh-based catalysts and the total combustion of hydrocarbons demonstrate the importance of structural identification of catalysts in its working state and the measurement of the catalytic performance at the same time. Moreover, proper cell design is a key both here and in liquid phase reactions including preparation or high pressure reactions. In several cases structural changes during preparation, activation and reaction occur on a subminute scale or the catalyst structure varies inside a reactor as a result of temperature or concentration gradients. This, additionally, requires time and spatial resolution. Examples from time-resolved QEXAFS studies during the partial oxidation of methane over Pt- and Rh-based catalysts demonstrate some of the recent developments of the technique (use not only of Si(111) but also Si(311) crystals, angular encoder, full EXAFS spectra at subsecond recording time, and modulation excitation spectroscopy). In order to obtain spectroscopic information on the oxidation state inside a microreactor, scanning and full field X-ray microscopy with X-ray absorption spectroscopic contrast were achieved under reaction conditions. If a microbeam is applied, fast scanning techniques like QEXAFS are required. In this way, even X-ray absorption spectroscopic tomographic images of a slice of a microreactor were obtained. The studies were recently extended to spatiotemporal studies that give important insight into the dynamics of the catalyst structure in a spatial manner with subsecond time-resolution.

Structural signature of a brittle-to-ductile transition in self-assembled networks.

PubMed

Ramos, Laurence; Laperrousaz, Arnaud; Dieudonné, Philippe; Ligoure, Christian

2011-09-30

We study the nonlinear rheology of a novel class of transient networks, made of surfactant micelles of tunable morphology reversibly linked by block copolymers. We couple rheology and time-resolved structural measurements, using synchrotron radiation, to characterize the highly nonlinear viscoelastic regime. We propose the fluctuations of the degree of alignment of the micelles under shear as a probe to identify a fracture process. We show a clear signature of a brittle-to-ductile transition in transient gels, as the morphology of the micelles varies, and provide a parallel between the fracture of solids and the fracture under shear of viscoelastic fluids.

Femtosecond diffraction dynamics of laser-induced periodic surface structures on fused silica

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

Hoehm, S.; Rosenfeld, A.; Krueger, J.

2013-02-04

The formation of laser-induced periodic surface structures (LIPSS) on fused silica upon irradiation with linearly polarized fs-laser pulses (50 fs pulse duration, 800 nm center wavelength) is studied experimentally using a transillumination femtosecond time-resolved (0.1 ps-1 ns) pump-probe diffraction approach. This allows to reveal the generation dynamics of near-wavelength-sized LIPSS showing a transient diffraction at specific spatial frequencies even before a corresponding permanent surface relief was observed. The results confirm that the ultrafast energy deposition to the materials surface plays a key role and triggers subsequent physical mechanisms such as carrier scattering into self-trapped excitons.

Non-Intrusive, Time-Resolved Hall Thruster Near-Field Electron Temperature Measurements

DTIC Science & Technology

2011-08-01

With the growing interest in Hall thruster technology, comes the need to fully characterize the plasma dynamics that determine performance. Of...instabilities characteristic of Hall thruster behavior, time resolved techniques must be developed. This study presents a non-intrusive method of

The turbulent cascade of individual eddies

NASA Astrophysics Data System (ADS)

Huertas-Cerdeira, Cecilia; Lozano-Durán, Adrián; Jiménez, Javier

2014-11-01

The merging and splitting processes of Reynolds-stress carrying structures in the inertial range of scales are studied through their time-resolved evolution in channels at Reλ = 100 - 200 . Mergers and splits coexist during the whole life of the structures, and are responsible for a substantial part of their growth and decay. Each interaction involves two or more eddies and results in little overall volume loss or gain. Most of them involve a small eddy that merges with, or splits from, a significantly larger one. Accordingly, if merge and split indexes are respectively defined as the maximum number of times that a structure has merged from its birth or will split until its death, the mean eddy volume grows linearly with both indexes, suggesting an accretion process rather than a hierarchical fragmentation. However, a non-negligible number of interactions involve eddies of similar scale, with a second probability peak of the volume of the smaller parent or child at 0.3 times that of the resulting or preceding structure. Funded by the Multiflow project of the ERC.

Application of spectroscopy and super-resolution microscopy: Excited state

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

Bhattacharjee, Ujjal

Photophysics of inorganic materials and organic molecules in complex systems have been extensively studied with absorption and emission spectroscopy.1-4 Steady-state and time-resolved fluorescence studies are commonly carried out to characterize excited-state properties of fluorophores. Although steady-state fluorescence measurements are widely used for analytical applications, time-resolved fluorescence measurements provide more detailed information about excited-state properties and the environment in the vicinity of the fluorophore. Many photophysical processes, such as photoinduced electron transfer (PET), rotational reorientation, solvent relaxation, and energy transfer, occur on a nanosecond (10 -9 s) timescale, thus affecting the lifetime of the fluorophores. Moreover, time-resolved microscopy methods, such asmore » lifetimeimaging, combine the benefits of the microscopic measurement and information-rich, timeresolved data. Thus, time-resolved fluorescence spectroscopy combined with microscopy can be used to quantify these processes and to obtain a deeper understanding of the chemical surroundings of the fluorophore in a small area under investigation. This thesis discusses various photophysical and super-resolution microscopic studies of organic and inorganic materials, which have been outlined below.« less

Time-resolved fluorescence microscopy to study biologically related applications using sol-gel derived and cellular media

NASA Astrophysics Data System (ADS)

Toury, Marion; Chandler, Lin; Allison, Archie; Campbell, David; McLoskey, David; Holmes-Smith, A. Sheila; Hungerford, Graham

2011-03-01

Fluorescence microscopy provides a non-invasive means for visualising dynamic protein interactions. As well as allowing the calculation of kinetic processes via the use of time-resolved fluorescence, localisation of the protein within cells or model systems can be monitored. These fluorescence lifetime images (FLIM) have become the preferred technique for elucidating protein dynamics due to the fact that the fluorescence lifetime is an absolute measure, in the main independent of fluorophore concentration and intensity fluctuations caused by factors such as photobleaching. In this work we demonstrate the use of a time-resolved fluorescence microscopy, employing a high repetition rate laser excitation source applied to study the influence of a metal surface on fluorescence tagged protein and to elucidate viscosity using the fluorescence lifetime probe DASPMI. These were studied in a cellular environment (yeast) and in a model system based on a sol-gel derived material, in which silver nanostructures were formed in situ using irradiation from a semiconductor laser in CW mode incorporated on a compact time-resolved fluorescence microscope (HORIBA Scientific DeltaDiode and DynaMyc).

Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring.

PubMed

Kapuscinski, Martin; Agthe, Michael; Bergström, Lennart

2018-07-15

Self-assembly of nanoparticles into superlattices can be used to create hierarchically structured materials with tailored functions. We have used the surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) technique in combination with video microscopy (VM) to obtain time-resolved information on the mass increase and rheological properties of evaporation-induced self-assembly of nanocubes. We have recorded the frequency and dissipation shifts during growth and densification of superlattices formed by self-assembly of oleic acid capped, truncated iron oxide nanocubes and analyzed the time-resolved QCM-D data using a Kelvin-Voigt viscoelastic model. We show that the nanoparticles first assemble into solvent-containing arrays dominated by a viscous response followed by a solvent-releasing step that results in the formation of rigid and well-ordered superlattices. Our findings demonstrate that QCM-D can be successfully used to follow self-assembly and assist in the design of optimized routes to produce well-ordered superlattices. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Fast reconstruction of optical properties for complex segmentations in near infrared imaging

NASA Astrophysics Data System (ADS)

Jiang, Jingjing; Wolf, Martin; Sánchez Majos, Salvador

2017-04-01

The intrinsic ill-posed nature of the inverse problem in near infrared imaging makes the reconstruction of fine details of objects deeply embedded in turbid media challenging even for the large amounts of data provided by time-resolved cameras. In addition, most reconstruction algorithms for this type of measurements are only suitable for highly symmetric geometries and rely on a linear approximation to the diffusion equation since a numerical solution of the fully non-linear problem is computationally too expensive. In this paper, we will show that a problem of practical interest can be successfully addressed making efficient use of the totality of the information supplied by time-resolved cameras. We set aside the goal of achieving high spatial resolution for deep structures and focus on the reconstruction of complex arrangements of large regions. We show numerical results based on a combined approach of wavelength-normalized data and prior geometrical information, defining a fully parallelizable problem in arbitrary geometries for time-resolved measurements. Fast reconstructions are obtained using a diffusion approximation and Monte-Carlo simulations, parallelized in a multicore computer and a GPU respectively.

Validation of a time-resolved fluorescence spectroscopy apparatus in a rabbit atherosclerosis model

NASA Astrophysics Data System (ADS)

Fang, Qiyin; Jo, Javier A.; Papaioannou, Thanassis; Dorafshar, Amir; Reil, Todd; Qiao, Jian-Hua; Fishbein, Michael C.; Freischlag, Julie A.; Marcu, Laura

2004-07-01

Time-resolved laser-induced fluorescence spectroscopy (tr-LIFS) has been studied as a potential tool for in vivo diagnosis of atherosclerotic lesions. This study is to evaluate the potential of a compact fiber-optics based tr-LIFS instrument developed in our laboratory for in vivo analysis of atherosclerotic plaque composition. Time-resolved fluorescence spectroscopy studies were performed in vivo on fifteen New Zealand White rabbits (atherosclerotic: N=8, control: N=7). Time-resolved fluorescence spectra were acquired (range: 360-600 nm, increment: 5 nm, total acquisition time: 65 s) from normal aorta wall and lesions in the abdominal aorta. Data were analyzed in terms of fluorescence emission spectra and wavelength specific lifetimes. Following trichrome staining, tissue specimens were analyzed histopathologically in terms of intima/media thickness and biochemical composition (collagen, elastin, foam cells, and etc). Based on intimal thickness, the lesions were divided into thin and thick lesions. Each group was further separated into two categories: collagen rich lesions and foam cell rich lesions based on their biochemical composition. The obtained spectral and time domain fluorescence signatures were subsequently correlated to the histopathological findings. The results have shown that time-domain fluorescence spectral features can be used in vivo to separate atherosclerotic lesions from normal aorta wall as well discrimination within certain types of lesions.

Dynamics of photogenerated carriers near magnetic field driven quantum phase transition in aperiodic multiple quantum wells

NASA Astrophysics Data System (ADS)

Tito, M. A.; Pusep, Yu A.

2018-01-01

Time-resolved magneto-photoluminescence was employed to study the magnetic field induced quantum phase transition separating two phases with different distributions of electrons over quantum wells in an aperiodic multiple quantum well, embedded in a wide AlGaAs parabolic quantum well. Intensities, broadenings and recombination times attributed to the photoluminescence lines emitted from individual quantum wells of the multiple quantum well structure were measured as a function of the magnetic field near the transition. The presented data manifest themselves to the magnetic field driven migration of the free electrons between the quantum wells of the studied multiple quantum well structure. The observed charge transfer was found to influence the screening of the multiple quantum well and disorder potentials. Evidence of the localization of the electrons in the peripheral quantum wells in strong magnetic field is presented.

Effects of tissue optical properties on time-resolved fluorescence measurements from brain tumors: an experimental and computational study

NASA Astrophysics Data System (ADS)

Butte, Pramod V.; Vishwanath, Karthik; Pikul, Brian K.; Mycek, Mary-Ann; Marcu, Laura

2003-07-01

Time-Resolved Laser-Induced Fluorescence Spectroscopy (tr-LIFS) offers the potential for intra-operative diagnosis of primary brain tumors. However, both the intrinsic properties of endogenous fluorophores and the optical properties of brain tissue could affect the fluorescence measurements from brain. Scattering has been demonstrated to increase, for instance, detected lifetimes by 10-20% in media less scattering than the brain. The overall goal of this study is to investigate experimentally and computationally how optical properties of distinct types of brain tissue (normal porcine white and gray matter) affect the propagation of the excitation pulse and fluorescent transients and the detected fluorescence lifetime. A time-domain tr-LIFS apparatus (fast digitizer and gated detection) was employed to measure the propagation of ultra-short pulsed light through brain specimens (1-2.5-mm source-detector separation; 0.100-mm increment). A Monte Carlo model for semi-infinite turbid media was used to simulate time-resolved light propagation for arbitrary source-detector fiber geometries and optical fiber specifications; and to record spatially- and temporally resolved information. We determined a good correlation between experimental and computational results. Our findings provide means for quantification of time-resolved fluorescence spectra from healthy and diseased brain tissue.

Escherichia coli DNA polymerase I can disrupt G-quadruplex structures during DNA replication.

PubMed

Teng, Fang-Yuan; Hou, Xi-Miao; Fan, San-Hong; Rety, Stephane; Dou, Shuo-Xing; Xi, Xu-Guang

2017-12-01

Non-canonical four-stranded G-quadruplex (G4) DNA structures can form in G-rich sequences that are widely distributed throughout the genome. The presence of G4 structures can impair DNA replication by hindering the progress of replicative polymerases (Pols), and failure to resolve these structures can lead to genetic instability. In the present study, we combined different approaches to address the question of whether and how Escherichia coli Pol I resolves G4 obstacles during DNA replication and/or repair. We found that E. coli Pol I-catalyzed DNA synthesis could be arrested by G4 structures at low protein concentrations and the degree of inhibition was strongly dependent on the stability of the G4 structures. Interestingly, at high protein concentrations, E. coli Pol I was able to overcome some kinds of G4 obstacles without the involvement of other molecules and could achieve complete replication of G4 DNA. Mechanistic studies suggested that multiple Pol I proteins might be implicated in G4 unfolding, and the disruption of G4 structures requires energy derived from dNTP hydrolysis. The present work not only reveals an unrealized function of E. coli Pol I, but also presents a possible mechanism by which G4 structures can be resolved during DNA replication and/or repair in E. coli. © 2017 Federation of European Biochemical Societies.

Coherent acoustic vibrations of metal nanoshells

NASA Astrophysics Data System (ADS)

Kirakosyan, A. S.; Shahbazyan, T. V.; Guillon, C.; Langot, P.; Del Fatti, N.; Vallee, F.; Cardinal, T.; Treguer, M.

2007-03-01

We study vibrational modes of gold nanoshells grown on dielectric core by means of time-resolved pump-probe spectroscopy. The fundamental breathing mode launched by a femtosecond pump pulse manifests itself in a pronounced time-domain modulation of the differential transmission probed at the frequency of the nanoshell surface plasmon resonance. The modulation amplitude is significantly stronger while the period is longer than in a gold nanoparticle of the same overall size. A theoretical model describing breathing mode frequency and damping for a nanoshell in a medium is developed. A distinct acoustical signature of nanoshells provides a new and efficient method for identifying these versatile nanostructures and for studying their mechanical and structural properties.

Time-resolved autofluorescence imaging of human donor retina tissue from donors with significant extramacular drusen.

PubMed

Schweitzer, Dietrich; Gaillard, Elizabeth R; Dillon, James; Mullins, Robert F; Russell, Stephen; Hoffmann, Birgit; Peters, Sven; Hammer, Martin; Biskup, Christoph

2012-06-08

Time and spectrally resolved measurements of autofluorescence have the potential to monitor metabolism at the cellular level. Fluorophores that emit with the same fluorescence intensity can be discriminated from each other by decay time of fluorescence intensity after pulsed excitation. We performed time-resolved autofluorescence measurements on fundus samples from a donor with significant extramacular drusen. Tissue sections from two human donors were prepared and imaged with a laser scanning microscope. The sample was excited with a titanium-sapphire laser, which was tuned to 860 nm, and frequency doubled by a BBO crystal to 430 nm. The repetition rate was 76 MHz and the pulse width was 170 femtoseconds (fs). The time-resolved autofluorescence was recorded simultaneously in 16 spectral channels (445-605 nm) and bi-exponentially fitted. RPE can be discriminated clearly from Bruch's membrane, drusen, and choroidal connective tissue by fluorescence lifetime. In RPE, bright fluorescence of lipofuscin could be detected with a maximum at 510 nm and extending beyond 600 nm. The lifetime was 385 ps. Different types of drusen were found. Most of them did not contain lipofuscin and exhibited a weak fluorescence, with a maximum at 470 nm. The lifetime was 1785 picoseconds (ps). Also, brightly emitting lesions, presumably representing basal laminar deposits, with fluorescence lifetimes longer than those recorded in RPE could be detected. The demonstrated differentiation of fluorescent structures by their fluorescence decay time is important for interpretation of in vivo measurements by the new fluorescence lifetime imaging (FLIM) ophthalmoscopy on healthy subjects as well as on patients.

Femtosecond-laser-driven photoelectron-gun for time-resolved cathodoluminescence measurement of GaN.

PubMed

Onuma, T; Kagamitani, Y; Hazu, K; Ishiguro, T; Fukuda, T; Chichibu, S F

2012-04-01

A rear-excitation femtosecond-laser-driven photoelectron gun (PE-gun) is developed for measuring time-resolved cathodoluminescence (TRCL) spectrum of wide bandgap materials and structures such as semiconductors and phosphors. The maximum quantum efficiency of a 20-nm-thick Au photocathode excited using a frequency-tripled Al(2)O(3):Ti laser under a rear-excitation configuration is 3.6×10(-6), which is a reasonable value for a PE-gun. When the distance between the front edge of the PE-gun and the observation point is 10 mm, the narrowest electron-beam (e-beam) diameter is 19 μm, which corresponds to one tenth of the laser-beam diameter and is comparable to the initial e-beam diameter of a typical W hair-pin filament of thermionic electron-gun. From the results of TRCL measurements on the freestanding GaN grown by the ammonothermal method and a GaN homoepitaxial film grown by metalorganic vapor phase epitaxy, overall response time for the present TRCL system is estimated to be 8 ps. The value is the same as that of time-resolved photoluminescence measurement using the same excitation laser pulses, meaning that the time-resolution is simply limited by the streak-camera, not by the PE-gun performance. The result of numerical simulation on the temporal e-beam broadening caused by the space-charge-effect suggests that the present PE-gun can be used as a pulsed e-beam source for spatio-time-resolved cathodoluminescence, when equipped in a scanning electron microscope. © 2012 American Institute of Physics

Femtosecond-laser-driven photoelectron-gun for time-resolved cathodoluminescence measurement of GaN

NASA Astrophysics Data System (ADS)

Onuma, T.; Kagamitani, Y.; Hazu, K.; Ishiguro, T.; Fukuda, T.; Chichibu, S. F.

2012-04-01

A rear-excitation femtosecond-laser-driven photoelectron gun (PE-gun) is developed for measuring time-resolved cathodoluminescence (TRCL) spectrum of wide bandgap materials and structures such as semiconductors and phosphors. The maximum quantum efficiency of a 20-nm-thick Au photocathode excited using a frequency-tripled Al2O3:Ti laser under a rear-excitation configuration is 3.6×10-6, which is a reasonable value for a PE-gun. When the distance between the front edge of the PE-gun and the observation point is 10 mm, the narrowest electron-beam (e-beam) diameter is 19 μm, which corresponds to one tenth of the laser-beam diameter and is comparable to the initial e-beam diameter of a typical W hair-pin filament of thermionic electron-gun. From the results of TRCL measurements on the freestanding GaN grown by the ammonothermal method and a GaN homoepitaxial film grown by metalorganic vapor phase epitaxy, overall response time for the present TRCL system is estimated to be 8 ps. The value is the same as that of time-resolved photoluminescence measurement using the same excitation laser pulses, meaning that the time-resolution is simply limited by the streak-camera, not by the PE-gun performance. The result of numerical simulation on the temporal e-beam broadening caused by the space-charge-effect suggests that the present PE-gun can be used as a pulsed e-beam source for spatio-time-resolved cathodoluminescence, when equipped in a scanning electron microscope.

Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

PubMed

Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

2017-10-30

Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

The time resolved SBS and SRS research in heavy water and its application in CARS

NASA Astrophysics Data System (ADS)

Liu, Jinbo; Gai, Baodong; Yuan, Hong; Sun, Jianfeng; Zhou, Xin; Liu, Di; Xia, Xusheng; Wang, Pengyuan; Hu, Shu; Chen, Ying; Guo, Jingwei; Jin, Yuqi; Sang, Fengting

2018-05-01

We present the time-resolved character of stimulated Brillouin scattering (SBS) and backward stimulated Raman scattering (BSRS) in heavy water and its application in Coherent Anti-Stokes Raman Scattering (CARS) technique. A nanosecond laser from a frequency-doubled Nd: YAG laser is introduced into a heavy water cell, to generate SBS and BSRS beams. The SBS and BSRS beams are collinear, and their time resolved characters are studied by a streak camera, experiment show that they are ideal source for an alignment-free CARS system, and the time resolved property of SBS and BSRS beams could affect the CARS efficiency significantly. By inserting a Dye cuvette to the collinear beams, the time-overlapping of SBS and BSRS could be improved, and finally the CARS efficiency is increased, even though the SBS energy is decreased. Possible methods to improve the efficiency of this CARS system are discussed too.

Coherent manipulation of spin correlations in the Hubbard model

NASA Astrophysics Data System (ADS)

Wurz, N.; Chan, C. F.; Gall, M.; Drewes, J. H.; Cocchi, E.; Miller, L. A.; Pertot, D.; Brennecke, F.; Köhl, M.

2018-05-01

We coherently manipulate spin correlations in a two-component atomic Fermi gas loaded into an optical lattice using spatially and time-resolved Ramsey spectroscopy combined with high-resolution in situ imaging. This technique allows us not only to imprint spin patterns but also to probe the static magnetic structure factor at an arbitrary wave vector, in particular, the staggered structure factor. From a measurement along the diagonal of the first Brillouin zone of the optical lattice, we determine the magnetic correlation length and the individual spatial spin correlators. At half filling, the staggered magnetic structure factor serves as a sensitive thermometer, which we employ to study the equilibration in the spin and density sector during a slow quench of the lattice depth.

Synthesis and Study of Optical Characteristics of Ti0.91O2/CdS Hybrid Sphere Structures

NASA Astrophysics Data System (ADS)

Kong, Lingbin; Xu, Qinfeng; Zhang, Meng; Wang, Dehua; Liu, Mingliang; Zhang, Lei; Jiao, Mengmeng; Wang, Honggang; Yang, Chuanlu

2018-03-01

The optical properties of alternating ultrathin Ti0.91O2 nanosheets and CdS nanoparticle hybrid spherical structures designed by the layer-by-layer (LBL) assembly technique are investigated. From the photoluminescence (PL) spectral measurements on the hybrid spherical structures, a spectrum-shifted fluorescence emission occurs in this novel hybrid material. The time-resolved PL measurements exhibit a remarkably increased PL lifetime of 3.75 ns compared with only Ti0.91O2 spheres or CdS nanoparticles. The novel results were attributed to the enhanced electron-hole separation due to the new type II indirect optical transition mechanism between Ti0.91O2 and CdS in a charge-separated configuration.

Study on spin and optical polarization in a coupled InGaN/GaN quantum well and quantum dots structure.

PubMed

Yu, Jiadong; Wang, Lai; Di Yang; Zheng, Jiyuan; Xing, Yuchen; Hao, Zhibiao; Luo, Yi; Sun, Changzheng; Han, Yanjun; Xiong, Bing; Wang, Jian; Li, Hongtao

2016-10-19

The spin and optical polarization based on a coupled InGaN/GaN quantum well (QW) and quantum dots (QDs) structure is investigated. In this structure, spin-electrons can be temporarily stored in QW, and spin injection from the QW into QDs via spin-conserved tunneling is enabled. Spin relaxation can be suppressed owing to the small energy difference between the initial state in the QW and the final states in the QDs. Photoluminescence (PL) and time-resolved photoluminescence (TRPL) measurements are carried out on optical spin-injection and -detection. Owing to the coupled structure, spin-conserved tunneling mechanism plays a significant role in preventing spin relaxation process. As a result, a higher circular polarization degree (CPD) (~49.1%) is achieved compared with conventional single layer of QDs structure. Moreover, spin relaxation time is also extended to about 2.43 ns due to the weaker state-filling effect. This coupled structure is believed an appropriate candidate for realization of spin-polarized light source.

Feasibility experiments on time-resolved fluorosensing applied to oil slicks

NASA Technical Reports Server (NTRS)

Camagni, P.; Colombo, G.; Koechler, C.; Pedrini, A.; Omenetto, N.; Rossi, G.

1986-01-01

The introduction of time resolved observations can provide a very penetrating tool in the practice of laser fluorosensing. The investigations have demonstrated a relevance of multispectral, time resolved analysis for oil fingerprinting. By comparative studies on a variety of crude oils and their most significant fractions, it was found that the process of time decay in a composite oil is characterized by a few steps, which are associated with specific components in the medium light range. The average decay times of these pure fractions are markedly differentiated as to absolute values and spectral spread; as a consequence, the corresponding parameters in the resultant crude are quite sensitive to the particular mixture of these components. Measurements of the time response give then a finer discrimination between oil classes, depending on the relative content of certain fractions. Experiments were pursued with an improved fluorosensor facility, in order to test the application of time resolved fluorosensing to remote samples on water.

Epitaxial Growth and Electronic Structure of Half Heuslers Co1-xNixTiSb (001), Ni1-xCoxTiSn, and PtLuSb

DTIC Science & Technology

2016-01-09

studied in detail using scanning tunneling microscopy and angle resolved photoemission. For the doping levels achieved in cobalt titanium antimony, the...angle resolved photoemission. For the doping levels achieved in cobalt titanium antimony, the electron mobility at room temperature was comparable...scanning tunneling microscopy and angle resolved photoemission. For the doping levels achieved in cobalt titanium antimony, the electron mobility at room

A New Approach to Time-Resolved 3D-PTV

NASA Astrophysics Data System (ADS)

Boomsma, Aaron; Troolin, Dan; Bjorkquist, Dan; TSI Inc Team

2017-11-01

Volumetric three-component velocimetry via particle tracking is a powerful alternative to TomoPIV. It has been thoroughly documented that compared to TomoPIV, particle tracking velocimetry (PTV) methods (whether 2D or 3D) better resolve regions of high velocity gradient, identify fewer ghost particles, and are less computationally demanding, which results in shorter processing times. Recently, 3D-PTV has seen renewed interest in the PIV community with the availability of time-resolved data. Of course, advances in hardware are partly to thank for that availability-higher speed cameras, more effective memory management, and higher speed lasers. But in software, algorithms that utilize time resolved data to improve 3D particle reconstruction and particle tracking are also under development and advancing (e.g. shake-the-box, neighbor tracking reconstruction, etc.). .In the current study, we present a new 3D-PTV method that incorporates time-resolved data. We detail the method, its performance in terms of particle identification and reconstruction error and their relation to varying seeding densities, as well as computational performance.

Time-Resolved Fluorescent Immunochromatography of Aflatoxin B1 in Soybean Sauce: A Rapid and Sensitive Quantitative Analysis.

PubMed

Wang, Du; Zhang, Zhaowei; Li, Peiwu; Zhang, Qi; Zhang, Wen

2016-07-14

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.

Applications of Second Harmonic and Sum Frequency Generation to Graphite and Silica Type Interfaces.

DTIC Science & Technology

1994-08-01

investigated. The ultrafast barrierless isomerization of an organic dye, Malachite Green, has also been probed with femtosecond time resolution, enabling the... Malachite Green, has also been probed with femtosecond time resolution, enabling the structure of water at various aqueous interfaces to be probed. In...6G at air/aqueous interface ....................................... 7 6. Time-resolved SHG of Malachite Green at air and silica/aqueous interfaces

Photoelectron Spectroscopy of Substituted Phenylnitrenes

NASA Astrophysics Data System (ADS)

Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

2009-06-01

Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

Cold DUst around NEarby Stars (DUNES). First results. A resolved exo-Kuiper belt around the solar-like star ζ2 Ret

NASA Astrophysics Data System (ADS)

Eiroa, C.; Fedele, D.; Maldonado, J.; González-García, B. M.; Rodmann, J.; Heras, A. M.; Pilbratt, G. L.; Augereau, J.-Ch.; Mora, A.; Montesinos, B.; Ardila, D.; Bryden, G.; Liseau, R.; Stapelfeldt, K.; Launhardt, R.; Solano, E.; Bayo, A.; Absil, O.; Arévalo, M.; Barrado, D.; Beichmann, C.; Danchi, W.; Del Burgo, C.; Ertel, S.; Fridlund, M.; Fukagawa, M.; Gutiérrez, R.; Grün, E.; Kamp, I.; Krivov, A.; Lebreton, J.; Löhne, T.; Lorente, R.; Marshall, J.; Martínez-Arnáiz, R.; Meeus, G.; Montes, D.; Morbidelli, A.; Müller, S.; Mutschke, H.; Nakagawa, T.; Olofsson, G.; Ribas, I.; Roberge, A.; Sanz-Forcada, J.; Thébault, P.; Walker, H.; White, G. J.; Wolf, S.

2010-07-01

We present the first far-IR observations of the solar-type stars δ Pav, HR 8501, 51 Peg and ζ2 Ret, taken within the context of the DUNES Herschel open time key programme (OTKP). This project uses the PACS and SPIRE instruments with the objective of studying infrared excesses due to exo-Kuiper belts around nearby solar-type stars. The observed 100 μm fluxes from δ Pav, HR 8501, and 51 Peg agree with the predicted photospheric fluxes, excluding debris disks brighter than Ldust/Lstar 5 × 10-7 (1σ level) around those stars. A flattened, disk-like structure with a semi-major axis of 100 AU in size is detected around ζ2 Ret. The resolved structure suggests the presence of an eccentric dust ring, which we interpret as an exo-Kuiper belt with Ldust/Lstar ≈ 10-5. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Hydration behavior of casein micelles in thin film geometry: a GISANS study?

PubMed

Metwalli, E; Moulin, J F; Gebhardt, R; Cubitt, R; Tolkach, A; Kulozik, U; Müller-Buschbaum, P

2009-04-07

The water content of casein micelle films in water vapor atmosphere is investigated using time-resolved grazing incidence small-angle neutron scattering (GISANS). Initial dry casein films are prepared with a spin-coating method. At 30 degrees C, the formation of a water-equilibrated casein protein film is reached after 11 min with a total content of 0.36 g of water/g of protein. With increasing water vapor temperature up to 70 degrees C, an increase in the water content is found. With GISANS, lateral structures on the nanometer scale are resolved during the swelling experiment at different temperatures and modeled using two types of spheres: micelles and mini-micelles. Upon water uptake, molecular assemblies in the size range of 15 nm (mini-micelles) are attributed to the formation of a high-contrast D2O outer shell on the small objects that already exist in the protein film. For large objects (>100 nm), the mean size increases at high D2O vapor temperature because of possible aggregation between hydrated micelles. These results are discussed and compared with various proposed models for casein micelle structures.

Darius Kuciauskas | NREL

Science.gov Websites

, low-temperature and time-resolved photoluminescence spectrometers, and a microscope for time-resolved Diploma Physics, Vilnius University Featured Publications Kuciauskas et al., "Time-resolved ;Dependence of the minority-carrier lifetime on the stoichiometry of CdTe using time-resolved

Hyperfine Structure Constants of Energetically High-lying Levels of Odd Parity of Atomic Vanadium

NASA Astrophysics Data System (ADS)

Güzelçimen, F.; Yapıcı, B.; Demir, G.; Er, A.; Öztürk, I. K.; Başar, Gö.; Kröger, S.; Tamanis, M.; Ferber, R.; Docenko, D.; Başar, Gü.

2014-09-01

High-resolution Fourier transform spectra of a vanadium-argon plasma have been recorded in the wavelength range of 365-670 nm (15,000-27,400 cm-1). Optical bandpass filters were used in the experimental setup to enhance the sensitivity of the Fourier transform spectrometer. In total, 138 atomic vanadium spectral lines showing resolved or partially resolved hyperfine structure have been analyzed to determine the magnetic dipole hyperfine structure constants A of the involved energy levels. One of the investigated lines has not been previously classified. As a result, the magnetic dipole hyperfine structure constants A for 90 energy levels are presented: 35 of them belong to the configuration 3d 34s4p and 55 to the configuration 3d 44p. Of these 90 constants, 67 have been determined for the first time, with 23 corresponding to the configuration 3d 34s4p and 44 to 3d 44p.

Valence-band structure of organic radical p-CF3PNN investigated by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Anzai, Hiroaki; Takakura, Ryosuke; Ono, Yusuke; Ishihara, Suzuna; Sato, Hitoshi; Namatame, Hirofumi; Taniguchi, Masaki; Matsui, Toshiyuki; Noguchi, Satoru; Hosokoshi, Yuko

2018-05-01

We study the electronic structure of p-trifluoromethylphenyl nitronyl nitroxide (p-CF3PNN), which forms a one-dimensional alternating antiferromagnetic chain of molecules, using angle-resolved photoemission spectroscopy. A singly occupied molecular orbital (SOMO) is observed clearly at ∼ 2 eV in the valence-band spectra. The small band gap and the overlap between the SOMO orbitals in the NO groups are associated with the antiferromagnetic interaction between neighboring spins.

Looking inside jets: optical polarimetry as a probe of Gamma-Ray Bursts physics

NASA Astrophysics Data System (ADS)

Kopac, D.; Mundell, C.

2015-07-01

It is broadly accepted that gamma-ray bursts (GRBs) are powered by accretion of matter by black holes, formed during massive stellar collapse, which launch ultra-relativistic, collimated outflows or jets. The nature of the progenitor star, the structure of the jet, and thus the underlying mechanisms that drive the explosion and provide collimation, remain some of the key unanswered questions. To approach these problems, and in particular the role of magnetic fields in GRBs, early time-resolved polarimetry is the key, because it is the only direct probe of the magnetic fields structure. Using novel fast RINGO polarimeter developed for use on the 2-m robotic optical Liverpool Telescope, we have made the first measurements of optical linear polarization of the early optical afterglows of GRBs, finding linear percentage polarization as high as 30% and, for the first time, making time-resolved polarization measurements. I will present the past 8 years of RINGO observations, discuss how the results fit into the GRB theoretical picture, and highlight recent data, in particular high-time resolution multi-colour optical photometry performed during the prompt GRB phase, which also provides some limits on polarization.

Time-Resolved C-Arm Computed Tomographic Angiography Derived From Computed Tomographic Perfusion Acquisition: New Capability for One-Stop-Shop Acute Ischemic Stroke Treatment in the Angiosuite.

PubMed

Yang, Pengfei; Niu, Kai; Wu, Yijing; Struffert, Tobias; Dorfler, Arnd; Schafer, Sebastian; Royalty, Kevin; Strother, Charles; Chen, Guang-Hong

2015-12-01

Multimodal imaging using cone beam C-arm computed tomography (CT) may shorten the delay from ictus to revascularization for acute ischemic stroke patients with a large vessel occlusion. Largely because of limited temporal resolution, reconstruction of time-resolved CT angiography (CTA) from these systems has not yielded satisfactory results. We evaluated the image quality and diagnostic value of time-resolved C-arm CTA reconstructed using novel image processing algorithms. Studies were done under an Institutional Review Board approved protocol. Postprocessing of data from 21 C-arm CT dynamic perfusion acquisitions from 17 patients with acute ischemic stroke were done to derive time-resolved C-arm CTA images. Two observers independently evaluated image quality and diagnostic content for each case. ICC and receiver-operating characteristic analysis were performed to evaluate interobserver agreement and diagnostic value of this novel imaging modality. Time-resolved C-arm CTA images were successfully generated from 20 data sets (95.2%, 20/21). Two observers agreed well that the image quality for large cerebral arteries was good but was more limited for small cerebral arteries (distal to M1, A1, and P1). receiver-operating characteristic curves demonstrated excellent diagnostic value for detecting large vessel occlusions (area under the curve=0.987-1). Time-resolved CTAs derived from C-arm CT perfusion acquisitions provide high quality images that allowed accurate diagnosis of large vessel occlusions. Although image quality of smaller arteries in this study was not optimal ongoing modifications of the postprocessing algorithm will likely remove this limitation. Adding time-resolved C-arm CTAs to the capabilities of the angiography suite further enhances its suitability as a one-stop shop for care for patients with acute ischemic stroke. © 2015 American Heart Association, Inc.

Structural Changes in PEO-PPO-PEO Gels Induced by Methylparaben and Dexamethasone Observed Using Time-Resolved SAXS

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

Meznarich, Norman A.K.; Juggernauth, K Anne; Batzli, Kiersten M

2011-11-17

Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymers (commercially available as Pluronic surfactants) micellize and structurally arrange into cubic quasicrystalline lattices as their temperature is raised. This structural evolution is seen macroscopically as a gelation, and the presence of these ordered phases can be controlled through both polymer concentration and temperature. The presence of added solutes within the dispersions can also affect the onset and kinetics of structure formation. Here we investigate the structures formed in Pluronic F127 solutions ranging from 20 to 30% with two pharmaceutical additives [methylparaben (MP) and dexamethasone (DX)] using small-angle X-ray scattering (SAXS). We observe bothmore » the progressive evolution and breakdown of these structures as the temperature is increased from 0 to 80 °C. Additionally, we conducted time-resolved SAXS measurements to elucidate the kinetics of the structural evolution. On the basis of the evolution of scattering peaks as the samples were being heated, we suggest that added MP changes the nucleation behavior of fcc phases within the sample from a heterogeneous process to a more homogeneous distribution of nucleated species. MP and DX also stabilize the micelle lattices, allowing them to persevere at higher temperatures. We observed the unusual result that the presence of DX caused the primary peaks of the structure factor to be suppressed, while preserving the higher order peaks. The primary peaks reappeared at the highest temperatures tested.« less

Trion fine structure and coupled spin–valley dynamics in monolayer tungsten disulfide

PubMed Central

Plechinger, Gerd; Nagler, Philipp; Arora, Ashish; Schmidt, Robert; Chernikov, Alexey; del Águila, Andrés Granados; Christianen, Peter C.M.; Bratschitsch, Rudolf; Schüller, Christian; Korn, Tobias

2016-01-01

Monolayer transition-metal dichalcogenides have recently emerged as possible candidates for valleytronic applications, as the spin and valley pseudospin are directly coupled and stabilized by a large spin splitting. The optical properties of these two-dimensional crystals are dominated by tightly bound electron–hole pairs (excitons) and more complex quasiparticles such as charged excitons (trions). Here we investigate monolayer WS2 samples via photoluminescence and time-resolved Kerr rotation. In photoluminescence and in energy-dependent Kerr rotation measurements, we are able to resolve two different trion states, which we interpret as intravalley and intervalley trions. Using time-resolved Kerr rotation, we observe a rapid initial valley polarization decay for the A exciton and the trion states. Subsequently, we observe a crossover towards exciton–exciton interaction-related dynamics, consistent with the formation and decay of optically dark A excitons. By contrast, resonant excitation of the B exciton transition leads to a very slow decay of the Kerr signal. PMID:27586517

Prospective time-resolved LCA of fully electric supercap vehicles in Germany.

PubMed

Zimmermann, Benedikt M; Dura, Hanna; Baumann, Manuel J; Weil, Marcel R

2015-07-01

The ongoing transition of the German electricity supply toward a higher share of renewable and sustainable energy sources, called Energiewende in German, has led to dynamic changes in the environmental impact of electricity over the last few years. Prominent scenario studies predict that comparable dynamics will continue in the coming decades, which will further improve the environmental performance of Germany's electricity supply. Life cycle assessment (LCA) is the methodology commonly used to evaluate environmental performance. Previous LCA studies on electric vehicles have shown that the electricity supply for the vehicles' operation is responsible for the major part of their environmental impact. The core question of this study is how the prospective dynamic development of the German electricity mix will affect the impact of electric vehicles operated in Germany and how LCA can be adapted to analyze this impact in a more robust manner. The previously suggested approach of time-resolved LCA, which is located between static and dynamic LCA, is used in this study and compared with several static approaches. Furthermore, the uncertainty issue associated with scenario studies is addressed in general and in relation to time-resolved LCA. Two scenario studies relevant to policy making have been selected, but a moderate number of modifications have been necessary to adapt the data to the requirements of a life cycle inventory. A potential, fully electric vehicle powered by a supercapacitor energy storage system is used as a generic example. The results show that substantial improvements in the environmental repercussions of the electricity supply and, consequentially, of electric vehicles will be achieved between 2020 and 2031 on the basis of the energy mixes predicted in both studies. This study concludes that although scenarios might not be able to predict the future, they should nonetheless be used as data sources in prospective LCA studies, because in many cases historic data appears to be unsuitable for providing realistic information on the future. The time-resolved LCA approach improves the assessment's robustness substantially, especially when nonlinear developments are foreseen in the future scenarios. This allows for a reduction of bias in LCA-based decision making. However, a deeper integration of time-resolved data in the life cycle inventory and the implementation of a more suitable software framework are desirable. The study describes how life cycle assessment's (LCA) robustness can be improved by respecting prospective fluctuations, like the transition of the German electricity mix, in the modeling of the life cycle inventory. It presents a feasible and rather simple process to add time-resolved data to LCA. The study selects 2 different future scenarios from important German studies and processes their data systematically to make them compatible with the requirements of a life cycle inventory. The use of external scenarios as basis for future-oriented LCA is reflected critically. A case study on electric mobility is presented and used to compare historic, prospective static, and prospective time-resolved electricity mix modeling approaches. The case study emphasizes the benefits of time-resolved LCA in direct comparison with the currently used approaches. © 2015 SETAC.

Emission Enhancement in Quantum Emitters - Plasmonic Nanostructures Systems

NASA Astrophysics Data System (ADS)

Muqri, Aeshah; Suh, Jae Yong; Michogan Technological University Team

In this poster, the emission enhancement probed by spectroscopic and dynamic means will be presented. Systems composed of quantum emitters ensembles in the vicinity of plasmonic structures were fabricated. Their coupling strength were investigated by measuring the reflection, steady state photoluminescence, and time resolved fluorescence.

Duration of bubble rearrangements in a coarsening foam probed by time-resolved diffusing-wave spectroscopy: Impact of interfacial rigidity

NASA Astrophysics Data System (ADS)

Le Merrer, Marie; Cohen-Addad, Sylvie; Höhler, Reinhard

2013-08-01

In aqueous foams, the diffusive gas transfer among neighboring bubbles drives a coarsening process which is accompanied by intermittent rearrangements of the structure. Using time-resolved diffusing-wave spectroscopy, we probe the dynamics of these events as a function of the rigidity of the gas-liquid interfaces, liquid viscosity, bubble size, and confinement pressure. We present in detail two independent techniques for analyzing the light scattering data, from which we extract the rearrangement duration. Our results show that interfacial rheology has a major impact on this duration. In the case of low interfacial rigidity, the rearrangements strongly slow down as the pressure is decreased close to the value zero where the bubble packing unjams. In contrast, if the interfaces are rigid, rearrangement durations are independent of the confinement pressure in the same investigated range. Using scaling arguments, we discuss dissipation mechanisms that may explain the observed dependency of the rearrangement dynamics on foam structure, pressure, and physicochemical solution properties.

Enhanced ultrafast relaxation rate in the Weyl semimetal phase of MoTe2 measured by time- and angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Crepaldi, A.; Autès, G.; Gatti, G.; Roth, S.; Sterzi, A.; Manzoni, G.; Zacchigna, M.; Cacho, C.; Chapman, R. T.; Springate, E.; Seddon, E. A.; Bugnon, Ph.; Magrez, A.; Berger, H.; Vobornik, I.; Kalläne, M.; Quer, A.; Rossnagel, K.; Parmigiani, F.; Yazyev, O. V.; Grioni, M.

2017-12-01

MoTe2 has recently been shown to realize in its low-temperature phase the type-II Weyl semimetal (WSM). We investigated by time- and angle- resolved photoelectron spectroscopy (tr-ARPES) the possible influence of the Weyl points on the electron dynamics above the Fermi level EF, by comparing the ultrafast response of MoTe2 in the trivial and topological phases. In the low-temperature WSM phase, we report an enhanced relaxation rate of electrons optically excited to the conduction band, which we interpret as a fingerprint of the local gap closure when Weyl points form. By contrast, we find that the electron dynamics of the related compound WTe2 is slower and temperature independent, consistent with a topologically trivial nature of this material. Our results shows that tr-ARPES is sensitive to the small modifications of the unoccupied band structure accompanying the structural and topological phase transition of MoTe2.

Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy

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

Subramanian, Ganesh; Zhang, Xiaoyi; Kodis, Gerdenis

Cobalt-carbon bond cleavage is crucial to most natural and synthetic applications of the cobalamin class of compounds, and here we present the first direct electronic and geometric structural characteristics of intermediates formed following photoexcitation of methylcobalamin (MeCbl) using time-resolved X-ray absorption spectroscopy (XAS). We catch transients corresponding to two intermediates, in the hundreds of picoseconds and a few microseconds. Highlights of the picosecond intermediate, which is reduced in comparison to the ground state, are elongation of the upper axial Co-C bond and relaxation of the corrin ring. This is not so with the recombining photocleaved products captured at a fewmore » microseconds, where the Co-C bond almost (yet not entirely) reverts to its ground state configuration and a substantially elongated lower axial Co-NIm bond is observed. The reduced cobalt site here confirms formation of methyl radical as the photoproduct.« less

A fast 1-D detector for imaging and time resolved SAXS experiments

NASA Astrophysics Data System (ADS)

Menk, R. H.; Arfelli, F.; Bernstorff, S.; Pontoni, D.; Sarvestani, A.; Besch, H. J.; Walenta, A. H.

1999-02-01

A one-dimensional test detector on the principle of a highly segmented ionization chamber with shielding grid (Frisch grid) was developed to evaluate if this kind of detector is suitable for advanced small-angle X-ray scattering (SAXS) experiments. At present it consists of 128 pixels which can be read out within 0.2 ms with a noise floor of 2000 e-ENC. A quantum efficiency of 80% for a photon energy of 8 keV was achieved. This leads to DQE values of 80% for photon fluxes above 1000 photons/pixel and integration time. The shielding grid is based on the principles of the recently invented MCAT structure and the GEM structure which also allows electron amplification in the gas. In the case of the MCAT structure, an energy resolution of 20% at 5.9 keV was observed. The gas amplification mode enables imaging with this integrating detector on a subphoton noise level with respect to the integration time. Preliminary experiments of saturation behavior show that this kind of detector digests a photon flux density up to 10 12 photons/mm 2 s and operates linearly. A spatial resolution of at least three line pairs/mm was obtained. All these features show that this type of detector is well suited for time-resolved SAXS experiments as well as high flux imaging applications.

An innovative Yb-based ultrafast deep ultraviolet source for time-resolved photoemission experiments

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

Boschini, F.; Hedayat, H.; Dallera, C.

2014-12-15

Time- and angle-resolved photoemission spectroscopy is a powerful technique to study ultrafast electronic dynamics in solids. Here, an innovative optical setup based on a 100-kHz Yb laser source is presented. Exploiting non-collinear optical parametric amplification and sum-frequency generation, ultrashort pump (hν = 1.82 eV) and ultraviolet probe (hν = 6.05 eV) pulses are generated. Overall temporal and instrumental energy resolutions of, respectively, 85 fs and 50 meV are obtained. Time- and angle-resolved measurements on BiTeI semiconductor are presented to show the capabilities of the setup.

Time-resolved fluorescence and ultrafast energy transfer in a zinc (hydr)oxide-graphite oxide mesoporous composite

NASA Astrophysics Data System (ADS)

Secor, Jeff; Narinesingh, Veeshan; Seredych, Mykola; Giannakoudakis, Dimitrios A.; Bandosz, Teresa; Alfano, Robert R.

2015-01-01

Ultrafast energy decay kinetics of a zinc (hydr)oxide-graphite oxide (GO) composite is studied via time-resolved fluorescence spectroscopy. The time-resolved emission is spectrally decomposed into emission regions originating from the zinc (hydr)oxide optical gap, surface, and defect states of the composite material. The radiative lifetime of deep red emission becomes an order of magnitude longer than that of GO alone while the radiative lifetime of the zinc optical gap is shortened in the composite. An energy transfer scheme from the zinc (hydr)oxide to GO is considered.

Photo-multiplier Tube Based Hybrid MRI and Frequency Domain Fluorescence Tomography System for Small Animal Imaging

PubMed Central

Lin, Y; Ghijsen, M T; Gao, H; Liu, N; Nalcioglu, O; Gulsen, G

2014-01-01

Fluorescence tomography (FT) is a promising molecular imaging technique that can spatially resolve both fluorophore concentration and lifetime parameters. However, recovered fluorophore parameters highly depend on the size and depth of the object due to the ill-posedness of the FT inverse problem. Structural a priori information from another high spatial resolution imaging modality has been demonstrated to significantly improve FT reconstruction accuracy. In this study, we have constructed a combined magnetic resonance imaging (MRI) and FT system for small animal imaging. A photo-multiplier tube (PMT) is used as the detector to acquire frequency domain FT measurements. This is the first MR-compatible time-resolved FT system that can reconstruct both fluorescence concentration and lifetime maps simultaneously. The performance of the hybrid system is evaluated with phantom studies. Two different fluorophores, Indocyanine Green (ICG) and 3-3′ Diethylthiatricarbocyanine Iodide (DTTCI), which have similar excitation and emission spectra but different lifetimes, are utilized. The fluorescence concentration and lifetime maps are both reconstructed with and without the structural a priori information obtained from MRI for comparison. We show that the hybrid system can accurately recover both fluorescence intensity and lifetime within 10% error for two 4.2 mm-diameter cylindrical objects embedded in a 38 mm-diameter cylindrical phantom when MRI structural a priori information is utilized. PMID:21753235

Exploratory study on a statistical method to analyse time resolved data obtained during nanomaterial exposure measurements

NASA Astrophysics Data System (ADS)

Clerc, F.; Njiki-Menga, G.-H.; Witschger, O.

2013-04-01

Most of the measurement strategies that are suggested at the international level to assess workplace exposure to nanomaterials rely on devices measuring, in real time, airborne particles concentrations (according different metrics). Since none of the instruments to measure aerosols can distinguish a particle of interest to the background aerosol, the statistical analysis of time resolved data requires special attention. So far, very few approaches have been used for statistical analysis in the literature. This ranges from simple qualitative analysis of graphs to the implementation of more complex statistical models. To date, there is still no consensus on a particular approach and the current period is always looking for an appropriate and robust method. In this context, this exploratory study investigates a statistical method to analyse time resolved data based on a Bayesian probabilistic approach. To investigate and illustrate the use of the this statistical method, particle number concentration data from a workplace study that investigated the potential for exposure via inhalation from cleanout operations by sandpapering of a reactor producing nanocomposite thin films have been used. In this workplace study, the background issue has been addressed through the near-field and far-field approaches and several size integrated and time resolved devices have been used. The analysis of the results presented here focuses only on data obtained with two handheld condensation particle counters. While one was measuring at the source of the released particles, the other one was measuring in parallel far-field. The Bayesian probabilistic approach allows a probabilistic modelling of data series, and the observed task is modelled in the form of probability distributions. The probability distributions issuing from time resolved data obtained at the source can be compared with the probability distributions issuing from the time resolved data obtained far-field, leading in a quantitative estimation of the airborne particles released at the source when the task is performed. Beyond obtained results, this exploratory study indicates that the analysis of the results requires specific experience in statistics.

Study of Near-Surface Models in Large-Eddy Simulations of a Neutrally Stratified Atmospheric Boundary Layer

NASA Technical Reports Server (NTRS)

Senocak, I.; Ackerman, A. S.; Kirkpatrick, M. P.; Stevens, D. E.; Mansour, N. N.

2004-01-01

Large-eddy simulation (LES) is a widely used technique in armospheric modeling research. In LES, large, unsteady, three dimensional structures are resolved and small structures that are not resolved on the computational grid are modeled. A filtering operation is applied to distinguish between resolved and unresolved scales. We present two near-surface models that have found use in atmospheric modeling. We also suggest a simpler eddy viscosity model that adopts Prandtl's mixing length model (Prandtl 1925) in the vicinity of the surface and blends with the dynamic Smagotinsky model (Germano et al, 1991) away from the surface. We evaluate the performance of these surface models by simulating a neutraly stratified atmospheric boundary layer.

Following strain-induced mosaicity changes of ferroelectric thin films by ultrafast reciprocal space mapping.

PubMed

Schick, D; Bojahr, A; Herzog, M; Gaal, P; Vrejoiu, I; Bargheer, M

2013-03-01

We investigate coherent phonon propagation in a thin film of ferroelectric PbZr(0.2)Ti(0.8)O(3) (PZT) by ultrafast x-ray diffraction experiments, which are analyzed as time-resolved reciprocal space mapping in order to observe the in- and out-of-plane structural dynamics, simultaneously. The mosaic structure of the PZT leads to a coupling of the excited out-of-plane expansion to in-plane lattice dynamics on a picosecond time scale, which is not observed for out-of-plane compression.

Challenges in Scale-Resolving Simulations of turbulent wake flows with coherent structures

NASA Astrophysics Data System (ADS)

Pereira, Filipe S.; Eça, Luís; Vaz, Guilherme; Girimaji, Sharath S.

2018-06-01

The objective of this work is to investigate the challenges encountered in Scale-Resolving Simulations (SRS) of turbulent wake flows driven by spatially-developing coherent structures. SRS of practical interest are expressly intended for efficiently computing such flows by resolving only the most important features of the coherent structures and modelling the remainder as stochastic field. The success of SRS methods depends upon three important factors: i) ability to identify key flow mechanisms responsible for the generation of coherent structures; ii) determine the optimum range of resolution required to adequately capture key elements of coherent structures; and iii) ensure that the modelled part is comprised nearly exclusively of fully-developed stochastic turbulence. This study considers the canonical case of the flow around a circular cylinder to address the aforementioned three key issues. It is first demonstrated using experimental evidence that the vortex-shedding instability and flow-structure development involves four important stages. A series of SRS computations of progressively increasing resolution (decreasing cut-off length) are performed. An a priori basis for locating the origin of the coherent structures development is proposed and examined. The criterion is based on the fact that the coherent structures are generated by the Kelvin-Helmholtz (KH) instability. The most important finding is that the key aspects of coherent structures can be resolved only if the effective computational Reynolds number (based on total viscosity) exceeds the critical value of the KH instability in laminar flows. Finally, a quantitative criterion assessing the nature of the unresolved field based on the strain-rate ratio of mean and unresolved fields is examined. The two proposed conditions and rationale offer a quantitative basis for developing "good practice" guidelines for SRS of complex turbulent wake flows with coherent structures.

Synchrotron Powder X-ray Diffraction Study of the Structure and Dehydration Behavior of Sepiolite

NASA Astrophysics Data System (ADS)

Post, J. E.; Bish, D. L.; Heaney, P. J.

2006-05-01

Sepiolite is a hydrous Mg-silicate clay mineral with fibrous morphology that typically occurs as fine-grained, poorly crystalline masses. It occurs in a wide variety of geological environments and has been mined for centuries because of its many uses, e.g. in the pharmaceutical, fertilizer, and pesticide industries. Its versatile functionality derives from the large surface area and microporosity that are characteristic of the material. In recent years, sepiolite has received considerable attention with regard to the adsorption of organics, for use as a support for catalysts, as a molecular sieve, and as an inorganic membrane for ultrafiltration. Because of its fine-grained and poorly crystalline nature, it has not been possible to study sepiolite's crystal structure using single-crystal X-ray diffraction methods, and consequently many details of the structure are still not well known. In this study, Rietveld refinements using synchrotron powder X-ray diffraction data were used to investigate the crystal structure and dehydration behavior of sepiolite from Durango, Mexico. The room- temperature (RT) sepiolite structure in air compares well with previous models but reveals an additional zeolitic water site. The RT structure under vacuum retained only ~1/8 of the zeolitic water and the volume decreased 1.3%. Real-time, temperature-resolved synchrotron powder X-ray diffraction data and Rietveld refinements were used to investigate the behavior of the sepiolite structure from 300 to 925 K. Rietveld refinements revealed that most of the zeolitic water is lost by ~390 K, accompanied by a decrease in the a and c unit-cell parameters. Above ~600 K the sepiolite structure folds as one-half of the crystallographically bound water is lost. Rietveld refinements of the "anhydrous" sepiolite structure reveal that, in general, unit-cell parameters a, b, â and volume steadily decrease with increasing temperature; there is an obvious change in slope at ~820 K suggesting a phase transformation coinciding with the loss of the remaining bound water molecule. These temperature-resolved real-time powder X-ray diffraction studies provide the first comprehensive description of the sepiolite structure and the complex changes it undergoes as it dehydrates. Additional heating and cooling in situ powder X-ray diffraction experiments are underway in order to investigate the relative stabilities and rehydration behaviors of the partially-hydrated sepiolite phases. The results of these studies should provide a more robust model for predicting and modifying the properties and applications of this critical industrial material and environmentally important mineral.

Scale separation for multi-scale modeling of free-surface and two-phase flows with the conservative sharp interface method

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

Han, L.H., E-mail: Luhui.Han@tum.de; Hu, X.Y., E-mail: Xiangyu.Hu@tum.de; Adams, N.A., E-mail: Nikolaus.Adams@tum.de

In this paper we present a scale separation approach for multi-scale modeling of free-surface and two-phase flows with complex interface evolution. By performing a stimulus-response operation on the level-set function representing the interface, separation of resolvable and non-resolvable interface scales is achieved efficiently. Uniform positive and negative shifts of the level-set function are used to determine non-resolvable interface structures. Non-resolved interface structures are separated from the resolved ones and can be treated by a mixing model or a Lagrangian-particle model in order to preserve mass. Resolved interface structures are treated by the conservative sharp-interface model. Since the proposed scale separationmore » approach does not rely on topological information, unlike in previous work, it can be implemented in a straightforward fashion into a given level set based interface model. A number of two- and three-dimensional numerical tests demonstrate that the proposed method is able to cope with complex interface variations accurately and significantly increases robustness against underresolved interface structures.« less

Electronic structure investigation of MoS2 and MoSe2 using angle-resolved photoemission spectroscopy and ab initio band structure studies.

PubMed

Mahatha, S K; Patel, K D; Menon, Krishnakumar S R

2012-11-28

Angle-resolved photoemission spectroscopy (ARPES) and ab initio band structure calculations have been used to study the detailed valence band structure of molybdenite, MoS(2) and MoSe(2). The experimental band structure obtained from ARPES has been found to be in good agreement with the theoretical calculations performed using the linear augmented plane wave (LAPW) method. In going from MoS(2) to MoSe(2), the dispersion of the valence bands decreases along both k(parallel) and k(perpendicular), revealing the increased two-dimensional character which is attributed to the increasing interlayer distance or c/a ratio in these compounds. The width of the valence band and the band gap are also found to decrease, whereas the valence band maxima shift towards the higher binding energy from MoS(2) to MoSe(2).

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 the strong mineral fluorescence saturates the detector and Raman spectra are unattainable. This problem is overcome by using time resolved Raman where fluorescence is eliminated. [1]Frosch et al., Anal. Chem. 2007, 79, 1101-1108 [2]Bell, J.,ed, The Martian Surface: Composition, Mineralogy, and physical Properties, Cambridge University Press, 2008

Hemodynamics in a giant intracranial aneurysm characterized by in vitro 4D flow MRI

PubMed Central

Schiavazzi, Daniele; Moen, Sean; Jagadeesan, Bharathi; Van de Moortele, Pierre-François; Coletti, Filippo

2018-01-01

Experimental and computational data suggest that hemodynamics play a critical role in the development, growth, and rupture of cerebral aneurysms. The flow structure, especially in aneurysms with a large sac, is highly complex and three-dimensional. Therefore, volumetric and time-resolved measurements of the flow properties are crucial to fully characterize the hemodynamics. In this study, phase-contrast Magnetic Resonance Imaging is used to assess the fluid dynamics inside a 3D-printed replica of a giant intracranial aneurysm, whose hemodynamics was previously simulated by multiple research groups. The physiological inflow waveform is imposed in a flow circuit with realistic cardiovascular impedance. Measurements are acquired with sub-millimeter spatial resolution for 16 time steps over a cardiac cycle, allowing for the detailed reconstruction of the flow evolution. Moreover, the three-dimensional and time-resolved pressure distribution is calculated from the velocity field by integrating the fluid dynamics equations, and is validated against differential pressure measurements using precision transducers. The flow structure is characterized by vortical motions that persist within the aneurysm sac for most of the cardiac cycle. All the main flow statistics including velocity, vorticity, pressure, and wall shear stress suggest that the flow pattern is dictated by the aneurysm morphology and is largely independent of the pulsatility of the inflow, at least for the flow regimes investigated here. Comparisons are carried out with previous computational simulations that used the same geometry and inflow conditions, both in terms of cycle-averaged and systolic quantities. PMID:29300738

ESIPT and photodissociation of 3-hydroxychromone in solution: photoinduced processes studied by static and time-resolved UV/Vis, fluorescence, and IR spectroscopy.

PubMed

Chevalier, Katharina; Grün, Anneken; Stamm, Anke; Schmitt, Yvonne; Gerhards, Markus; Diller, Rolf

2013-11-07

The spectral properties of fluorescence sensors such as 3-hydroxychromone (3-HC) and its derivatives are sensitive to interaction with the surrounding medium as well as to substitution. 3-HC is a prototype system for other derivatives because it is the basic unit of all flavonoides undergoing ESIPT and is not perturbed by a substituent. In this study, the elementary processes and intermediate states in the photocycle of 3-HC as well as its anion were identified and characterized by the use of static and femtosecond time-resolved spectroscopy in different solvents (methylcyclohexane, acetonitrile, ethanol, and water at different pH). Electronic absorption and fluorescence spectra and lifetimes of the intermediate states were obtained for the normal, tautomer and anionic excited state, while mid-IR vibrational spectra yielded structural information on ground and excited states of 3-HC. A high sensitivity on hydrogen-bonding perturbations was observed, leading to photoinduced anion formation in water, while in organic solvents, different processes are suggested, including slow picosecond ESIPT and contribution of the trans-structure excited state or a different stable solvation state with different direction of OH. The formation of the latter could be favored by the lack of a substituent increasing contact points for specific solute-solvent interactions at the hydroxyl group compared to substituted derivatives. The effect of substituents has to be considered for the design of future fluorescence sensors based on 3-HC.

Ultrashort x-ray backlighters and applications

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

Umstadter, D., University of Michigan

Previously, using ultrashort laser pulses focused onto solid targets, we have experimentally studied a controllable ultrafast broadband radiation source in the extreme ultraviolet for time-resolved dynamical studies in ultrafast science [J. Workman, A. Maksimchuk, X. Llu, U. Ellenberger, J. S. Coe, C.-Y. Chien, and D. Umstadter, ``Control of Bright Picosecond X-Ray Emission from Intense Sub- Picosecond Laser-Plasma Interactions,`` Phys. Rev. Lett. 75, 2324 (1995)]. Once armed with a bright ultrafast broadband continuum x-ray source and appropriate detectors, we used the source as a backlighter to study a remotely produced plasma. The application of the source to a problem relevant tomore » high-density matter completes the triad: creating and controlling, efficiently detecting, and applying the source. This work represented the first use of an ultrafast laser- produced x-ray source as a time-resolving probe in an application relevant to atomic, plasma and high-energy-density matter physics. Using the x-ray source as a backlighter, we adopted a pump-probe geometry to investigate the dynamic changes in electronic structure of a thin metallic film as it is perturbed by an ultrashort laser pulse. Because the laser deposits its energy in a skin depth of about 100 {Angstrom} before expansion occurs, up to gigabar pressure shock waves lasting picosecond in duration have been predicted to form in these novel plasmas. This raises the possibility of studying high- energy-density matter relevant to inertial confinement fusion (ICF) and astrophysics in small-scale laboratory experiments. In the past, time-resolved measurements of K-edge shifts in plasmas driven by nanosecond pulses have been used to infer conditions in highly compressed materials. In this study, we used 100-fs laser pulses to impulsively drive shocks into a sample (an untamped 1000 {Angstrom} aluminum film on 2000 {Angstrom} of parylene-n), measuring L-edge shifts.« less

Depth resolved hyperspectral imaging spectrometer based on structured light illumination and Fourier transform interferometry

PubMed Central

Choi, Heejin; Wadduwage, Dushan; Matsudaira, Paul T.; So, Peter T.C.

2014-01-01

A depth resolved hyperspectral imaging spectrometer can provide depth resolved imaging both in the spatial and the spectral domain. Images acquired through a standard imaging Fourier transform spectrometer do not have the depth-resolution. By post processing the spectral cubes (x, y, λ) obtained through a Sagnac interferometer under uniform illumination and structured illumination, spectrally resolved images with depth resolution can be recovered using structured light illumination algorithms such as the HiLo method. The proposed scheme is validated with in vitro specimens including fluorescent solution and fluorescent beads with known spectra. The system is further demonstrated in quantifying spectra from 3D resolved features in biological specimens. The system has demonstrated depth resolution of 1.8 μm and spectral resolution of 7 nm respectively. PMID:25360367

Interaction of a vortex ring and a bubble

NASA Astrophysics Data System (ADS)

Jha, Narsing K.; Govardhan, Raghuraman N.

2014-11-01

Micro-bubble injection in to boundary layers is one possible method for reducing frictional drag of ships. Although this has been studied for some time, the physical mechanisms responsible for drag reduction using microbubbles in turbulent boundary layers is not yet fully understood. Previous studies suggest that bubble-vortical structure interaction seems to be one of the important physical mechanisms for frictional drag reduction using microbubbles. In the present work, we study a simplification of this problem, namely, the interaction of a single vortical structure, in particular a vortex ring, with a single bubble for better understanding of the physics. The vortex ring is generated using a piston-cylinder arrangement and the bubble is generated by connecting a capillary to an air pump. The bubble dynamics is directly visualized using a high speed camera, while the vorticity modification is measured using time resolved PIV. The results show that significant deformations can occur of both the bubble and the vortex ring. Effect of different non-dimensional parameters on the interaction will be presented in the meeting.

Numerical investigation of turbulent channel flow

NASA Technical Reports Server (NTRS)

Moin, P.; Kim, J.

1981-01-01

Fully developed turbulent channel flow was simulated numerically at Reynolds number 13800, based on centerline velocity and channel halt width. The large-scale flow field was obtained by directly integrating the filtered, three dimensional, time dependent, Navier-Stokes equations. The small-scale field motions were simulated through an eddy viscosity model. The calculations were carried out on the ILLIAC IV computer with up to 516,096 grid points. The computed flow field was used to study the statistical properties of the flow as well as its time dependent features. The agreement of the computed mean velocity profile, turbulence statistics, and detailed flow structures with experimental data is good. The resolvable portion of the statistical correlations appearing in the Reynolds stress equations are calculated. Particular attention is given to the examination of the flow structure in the vicinity of the wall.

Hot Carrier Dynamics in the X Valley in Si and Ge Measured by Pump-IR-Probe Absorption Spectroscopy

NASA Technical Reports Server (NTRS)

Wang, W. B.; Cavicchia, M. A.; Alfano, R. R.

1996-01-01

Si is the semiconductor of choice for nanoelectronic roadmap into the next century for computer and other nanodevices. With growing interest in Si, Ge, and Si(sub m)Ge(sub n) strained superlattices, knowledge of the carrier relaxation processes in these materials and structures has become increasingly important. The limited time resolution for earlier studies of carrier dynamics in Ge and Si, performed using Nd:glass lasers, was not sufficient to observe the fast cooling processes. In this paper, we present a direct measurement of hot carrier dynamics in the satellite X valley in Si and Ge by time-resolved infrared(IR) absorption spectroscopy, and show the potential of our technique to identify whether the X valley is the lowest conduction valley in semiconductor materials and structures.

A Bright Future for Serial Femtosecond Crystallography with XFELs.

PubMed

Johansson, Linda C; Stauch, Benjamin; Ishchenko, Andrii; Cherezov, Vadim

2017-09-01

X-ray free electron lasers (XFELs) have the potential to revolutionize macromolecular structural biology due to the unique combination of spatial coherence, extreme peak brilliance, and short duration of X-ray pulses. A recently emerged serial femtosecond (fs) crystallography (SFX) approach using XFEL radiation overcomes some of the biggest hurdles of traditional crystallography related to radiation damage through the diffraction-before-destruction principle. Intense fs XFEL pulses enable high-resolution room-temperature structure determination of difficult-to-crystallize biological macromolecules, while simultaneously opening a new era of time-resolved structural studies. Here, we review the latest developments in instrumentation, sample delivery, data analysis, crystallization methods, and applications of SFX to important biological questions, and conclude with brief insights into the bright future of structural biology using XFELs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Redox-dependent spatially resolved electrochemistry at graphene and graphite step edges.

PubMed

Güell, Aleix G; Cuharuc, Anatolii S; Kim, Yang-Rae; Zhang, Guohui; Tan, Sze-yin; Ebejer, Neil; Unwin, Patrick R

2015-04-28

The electrochemical (EC) behavior of mechanically exfoliated graphene and highly oriented pyrolytic graphite (HOPG) is studied at high spatial resolution in aqueous solutions using Ru(NH3)6(3+/2+) as a redox probe whose standard potential sits close to the intrinsic Fermi level of graphene and graphite. When scanning electrochemical cell microscopy (SECCM) data are coupled with that from complementary techniques (AFM, micro-Raman) applied to the same sample area, different time-dependent EC activity between the basal planes and step edges is revealed. In contrast, other redox couples (ferrocene derivatives) whose potential is further removed from the intrinsic Fermi level of graphene and graphite show uniform and high activity (close to diffusion-control). Macroscopic voltammetric measurements in different environments reveal that the time-dependent behavior after HOPG cleavage, peculiar to Ru(NH3)6(3+/2+), is not associated particularly with any surface contaminants but is reasonably attributed to the spontaneous delamination of the HOPG with time to create partially coupled graphene layers, further supported by conductive AFM measurements. This process has a major impact on the density of states of graphene and graphite edges, particularly at the intrinsic Fermi level to which Ru(NH3)6(3+/2+) is most sensitive. Through the use of an improved voltammetric mode of SECCM, we produce movies of potential-resolved and spatially resolved HOPG activity, revealing how enhanced activity at step edges is a subtle effect for Ru(NH3)6(3+/2+). These latter studies allow us to propose a microscopic model to interpret the EC response of graphene (basal plane and edges) and aged HOPG considering the nontrivial electronic band structure.

A Detailed Analysis of Frontal Precipitation in a Decadal Convection-Resolving Regional Climate Simulation over Europe

NASA Astrophysics Data System (ADS)

Ruedisuehli, S.; Sprenger, M.; Leutwyler, D.; Schar, C.; Wernli, H.

2017-12-01

We study fronts and precipitation in a decadal continental-scale convection-resolving (2.2 km) regional climate simulation over Europe, which has been conducted using a GPU-enabled version of the COSMO model. Resolving convection substantially improves the representation of precipitation, e.g., the diurnal cycle of summer convection or organization of convection along fronts, while the large domain is able to represent most synoptic fronts affecting Europe with their full spatial extent. Studying nine years of the simulation, we present climatological results of how precipitation relates to fronts both structurally and quantitatively, and address seasonal, regional, and diurnal effects. Cold and warm fronts are identified at hourly intervals based on horizontal gradients of equivalent potential temperature on 850 hPa. We track the frontal areas using a new feature tracking algorithm, which accounts for mergings and splittings and supports complex tracks.Based on track properties, we separate synoptic and local fronts. The latter mostly form along orography and coasts during summer. While the resulting front climatology is already valuable, we exploit the full potential of the simulation by relating fronts to precipitation. We subdivide the domain at every timestep into pre-, at-, post-, and non-frontal areas by considering at every grid point the time since the latest and until the next frontal passage (separately for cold and warm fronts). This allows, for the first time, to disaggregate the precipitation field into front-related components, and to quantify the influence of fronts on both regular and extreme precipitation throughout the domain. To investigate the average structure of precipitation across fronts, we composite precipitation relative to the time of frontal passage. This approach reveals characteristic properties of the precipitation distribution across fronts. The Figure shows the mean across-front distribution of precipitation, separated into intensity components, for all cold and warm fronts during JJA 2007. Precipitation amounts peak at the front for both front types, but the distribution around cold (warm) fronts is heavily tilted towards pre-frontal (post-frontal) precipitation. Post-frontal showers lead to a second increase behind many cold fronts, starting at around + 9 h.

A split-beam probe-pump-probe scheme for femtosecond time resolved protein X-ray crystallography

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

van Thor, Jasper J.; Madsen, Anders

In order to exploit the femtosecond pulse duration of X-ray Free-Electron Lasers (XFEL) operating in the hard X-ray regime for ultrafast time-resolved protein crystallography experiments, critical parameters that determine the crystallographic signal-to-noise (I/σI) must be addressed. For single-crystal studies under low absorbed dose conditions, it has been shown that the intrinsic pulse intensity stability as well as mode structure and jitter of this structure, significantly affect the crystallographic signal-to-noise. Here, geometrical parameters are theoretically explored for a three-beam scheme: X-ray probe, optical pump, X-ray probe (or “probe-pump-probe”) which will allow experimental determination of the photo-induced structure factor amplitude differences, ΔF,more » in a ratiometric manner, thereby internally referencing the intensity noise of the XFEL source. In addition to a non-collinear split-beam geometry which separates un-pumped and pumped diffraction patterns on an area detector, applying an additional convergence angle to both beams by focusing leads to integration over mosaic blocks in the case of well-ordered stationary protein crystals. Ray-tracing X-ray diffraction simulations are performed for an example using photoactive yellow protein crystals in order to explore the geometrical design parameters which would be needed. The specifications for an X-ray split and delay instrument that implements both an offset angle and focused beams are discussed, for implementation of a probe-pump-probe scheme at the European XFEL. We discuss possible extension of single crystal studies to serial femtosecond crystallography, particularly in view of the expected X-ray damage and ablation due to the first probe pulse.« less

A split-beam probe-pump-probe scheme for femtosecond time resolved protein X-ray crystallography

DOE PAGES

van Thor, Jasper J.; Madsen, Anders

2015-01-01

In order to exploit the femtosecond pulse duration of X-ray Free-Electron Lasers (XFEL) operating in the hard X-ray regime for ultrafast time-resolved protein crystallography experiments, critical parameters that determine the crystallographic signal-to-noise (I/σI) must be addressed. For single-crystal studies under low absorbed dose conditions, it has been shown that the intrinsic pulse intensity stability as well as mode structure and jitter of this structure, significantly affect the crystallographic signal-to-noise. Here, geometrical parameters are theoretically explored for a three-beam scheme: X-ray probe, optical pump, X-ray probe (or “probe-pump-probe”) which will allow experimental determination of the photo-induced structure factor amplitude differences, ΔF,more » in a ratiometric manner, thereby internally referencing the intensity noise of the XFEL source. In addition to a non-collinear split-beam geometry which separates un-pumped and pumped diffraction patterns on an area detector, applying an additional convergence angle to both beams by focusing leads to integration over mosaic blocks in the case of well-ordered stationary protein crystals. Ray-tracing X-ray diffraction simulations are performed for an example using photoactive yellow protein crystals in order to explore the geometrical design parameters which would be needed. The specifications for an X-ray split and delay instrument that implements both an offset angle and focused beams are discussed, for implementation of a probe-pump-probe scheme at the European XFEL. We discuss possible extension of single crystal studies to serial femtosecond crystallography, particularly in view of the expected X-ray damage and ablation due to the first probe pulse.« less

A split-beam probe-pump-probe scheme for femtosecond time resolved protein X-ray crystallography

PubMed Central

van Thor, Jasper J.; Madsen, Anders

2015-01-01

In order to exploit the femtosecond pulse duration of X-ray Free-Electron Lasers (XFEL) operating in the hard X-ray regime for ultrafast time-resolved protein crystallography experiments, critical parameters that determine the crystallographic signal-to-noise (I/σI) must be addressed. For single-crystal studies under low absorbed dose conditions, it has been shown that the intrinsic pulse intensity stability as well as mode structure and jitter of this structure, significantly affect the crystallographic signal-to-noise. Here, geometrical parameters are theoretically explored for a three-beam scheme: X-ray probe, optical pump, X-ray probe (or “probe-pump-probe”) which will allow experimental determination of the photo-induced structure factor amplitude differences, ΔF, in a ratiometric manner, thereby internally referencing the intensity noise of the XFEL source. In addition to a non-collinear split-beam geometry which separates un-pumped and pumped diffraction patterns on an area detector, applying an additional convergence angle to both beams by focusing leads to integration over mosaic blocks in the case of well-ordered stationary protein crystals. Ray-tracing X-ray diffraction simulations are performed for an example using photoactive yellow protein crystals in order to explore the geometrical design parameters which would be needed. The specifications for an X-ray split and delay instrument that implements both an offset angle and focused beams are discussed, for implementation of a probe-pump-probe scheme at the European XFEL. We discuss possible extension of single crystal studies to serial femtosecond crystallography, particularly in view of the expected X-ray damage and ablation due to the first probe pulse. PMID:26798786

Dynamical Study of Femtosecond-Laser-Ablated Liquid-Aluminum Nanoparticles Using Spatiotemporally Resolved X-Ray-Absorption Fine-Structure Spectroscopy

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

Oguri, Katsuya; Okano, Yasuaki; Nishikawa, Tadashi

2007-10-19

We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensedmore » liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.« less

[System of ns time-resolved spectroscopy diagnosis and radioprotection].

PubMed

Yao, Wei-Bo; Guo, Jian-Ming; Zhang, Yong-min; Tang, Jun-Ping; Cheng, Liang; Xu, Qi-fuo

2014-06-01

Cathode plasma of high current electron beam diode is an important research on high power microwave and strong pulsed radio accelerator. It is a reliable method to study cathode plasma by diagnosing the cathode plasma parameters with non-contact spectroscopy measurement system. The present paper introduced the work principle, system composition and performance of the nanosecond (ns) time-resolved spectroscopy diagnosis system. Furthermore, it introduced the implementing method and the temporal relation of lower jitter synchronous trigger system. Simultaneously, the authors designed electromagnetic and radio shield room to protect the diagnosis system due to the high electromagnetic and high X-ray and γ-ray radiation, which seriously interferes with the system. Time-resolved spectroscopy experiment on brass (H62) cathode shows that, the element and matter composition of cathode plasma is clearly increase with the increase in the diode pulsed voltage and current magnitude. The spectroscopy diagnosis system could be of up to 10 ns time resolve capability. It's least is 2 ns. Synchronous trigger system's jitter is less than 4 ns. The spectroscopy diagnosis system will open a new way to study the cathode emission mechanism in depth.

Optimal MRI sequence for identifying occlusion location in acute stroke: which value of time-resolved contrast-enhanced MRA?

PubMed

Le Bras, A; Raoult, H; Ferré, J-C; Ronzière, T; Gauvrit, J-Y

2015-06-01

Identifying occlusion location is crucial for determining the optimal therapeutic strategy during the acute phase of ischemic stroke. The purpose of this study was to assess the diagnostic efficacy of MR imaging, including conventional sequences plus time-resolved contrast-enhanced MRA in comparison with DSA for identifying arterial occlusion location. Thirty-two patients with 34 occlusion levels referred for thrombectomy during acute cerebral stroke events were consecutively included from August 2010 to December 2012. Before thrombectomy, we performed 3T MR imaging, including conventional 3D-TOF and gradient-echo T2 sequences, along with time-resolved contrast-enhanced MRA of the extra- and intracranial arteries. The 3D-TOF, gradient-echo T2, and time-resolved contrast-enhanced MRA results were consensually assessed by 2 neuroradiologists and compared with prethrombectomy DSA results in terms of occlusion location. The Wilcoxon test was used for statistical analysis to compare MR imaging sequences with DSA, and the κ coefficient was used to determine intermodality agreement. The occlusion level on the 3D-TOF and gradient-echo T2 images differed significantly from that of DSA (P < .001 and P = .002, respectively), while no significant difference was observed between DSA and time-resolved contrast-enhanced MRA (P = .125). κ coefficients for intermodality agreement with DSA (95% CI, percentage agreement) were 0.43 (0.3%-0.6; 62%), 0.32 (0.2%-0.5; 56%), and 0.81 (0.6%-1.0; 88%) for 3D-TOF, gradient-echo T2, and time-resolved contrast-enhanced MRA, respectively. The time-resolved contrast-enhanced MRA sequence proved reliable for identifying occlusion location in acute stroke with performance superior to that of 3D-TOF and gradient-echo T2 sequences. © 2015 by American Journal of Neuroradiology.

Numerical study of the small scale structures in Boussinesq convection

NASA Technical Reports Server (NTRS)

Weinan, E.; Shu, Chi-Wang

1992-01-01

Two-dimensional Boussinesq convection is studied numerically using two different methods: a filtered pseudospectral method and a high order accurate Essentially Nonoscillatory (ENO) scheme. The issue whether finite time singularity occurs for initially smooth flows is investigated. The numerical results suggest that the collapse of the bubble cap is unlikely to occur in resolved calculations. The strain rate corresponding to the intensification of the density gradient across the front saturates at the bubble cap. We also found that the cascade of energy to small scales is dominated by the formulation of thin and sharp fronts across which density jumps.

Ultrafast electron diffraction optimized for studying structural dynamics in thin films and monolayers

PubMed Central

Badali, D. S.; Gengler, R. Y. N.; Miller, R. J. D.

2016-01-01

A compact electron source specifically designed for time-resolved diffraction studies of free-standing thin films and monolayers is presented here. The sensitivity to thin samples is achieved by extending the established technique of ultrafast electron diffraction to the “medium” energy regime (1–10 kV). An extremely compact design, in combination with low bunch charges, allows for high quality diffraction in a lensless geometry. The measured and simulated characteristics of the experimental system reveal sub-picosecond temporal resolution, while demonstrating the ability to produce high quality diffraction patterns from atomically thin samples. PMID:27226978

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

NASA Astrophysics Data System (ADS)

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; Schirò, Giorgio; Adam, Virgile; Aquila, Andrew; Barends, Thomas R. M.; Boutet, Sébastien; Byrdin, Martin; Carbajo, Sergio; de La Mora, Eugenio; Doak, R. Bruce; Feliks, Mikolaj; Fieschi, Franck; Foucar, Lutz; Guillon, Virginia; Hilpert, Mario; Hunter, Mark S.; Jakobs, Stefan; Koglin, Jason E.; Kovacsova, Gabriela; Lane, Thomas J.; Lévy, Bernard; Liang, Mengning; Nass, Karol; Ridard, Jacqueline; Robinson, Joseph S.; Roome, Christopher M.; Ruckebusch, Cyril; Seaberg, Matthew; Thepaut, Michel; Cammarata, Marco; Demachy, Isabelle; Field, Martin; Shoeman, Robert L.; Bourgeois, Dominique; Colletier, Jacques-Philippe; Schlichting, Ilme; Weik, Martin

2018-01-01

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecond timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

DOE PAGES

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce; ...

2017-09-11

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Chromophore twisting in the excited state of a photoswitchable fluorescent protein captured by time-resolved serial femtosecond crystallography

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

Coquelle, Nicolas; Sliwa, Michel; Woodhouse, Joyce

Chromophores absorb light in photosensitive proteins and thereby initiate fundamental biological processes such as photosynthesis, vision and biofluorescence. An important goal in their understanding is the provision of detailed structural descriptions of the ultrafast photochemical events that they undergo, in particular of the excited states that connect chemistry to biological function. Here in this paper we report on the structures of two excited states in the reversibly photoswitchable fluorescent protein rsEGFP2. We populated the states through femtosecond illumination of rsEGFP2 in its non-fluorescent off state and observed their build-up (within less than one picosecond) and decay (on the several picosecondmore » timescale). Using an X-ray free-electron laser, we performed picosecond time-resolved crystallography and show that the hydroxybenzylidene imidazolinone chromophore in one of the excited states assumes a near-canonical twisted configuration halfway between the trans and cis isomers. This is in line with excited-state quantum mechanics/molecular mechanics and classical molecular dynamics simulations. Our new understanding of the structure around the twisted chromophore enabled the design of a mutant that displays a twofold increase in its off-to-on photoswitching quantum yield.« less

Galaxies as High-resolution Telescopes

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

Barnacka, Anna, E-mail: abarnacka@cfa.harvard.edu

Recent observations show a population of active galaxies with milliarcsecond offsets between optical and radio emission. Such offsets can be an indication of extreme phenomena associated with supermassive black holes including relativistic jets, binary supermassive black holes, or even recoiling supermassive black holes. However, the multi-wavelength structure of active galaxies at a few milliarcseconds cannot be resolved with direct observations. We propose using strong gravitational lensing to elucidate the multi-wavelength structure of sources. When sources are located close to the caustic of a lensing galaxy, even a small offset in the position of the sources results in a drastic differencemore » in the position and magnification of mirage images. We show that the angular offset in the position of the sources can be amplified more than 50 times in the observed position of mirage images. We find that at least 8% of the observed gravitationally lensed quasars will be in the caustic configuration. The synergy between SKA and Euclid will provide an ideal set of observations for thousands of gravitationally lensed sources in the caustic configuration, which will allow us to resolve the multi-wavelength structure for a large ensemble of sources and to study the physical origin of radio emissions, their connection to supermassive black holes, and their cosmic evolution.« less

Time-resolved diode laser infrared absorption spectroscopy of the nascent HCl in the infrared laser chemistry of 1,2-dichloro-1,1-difluoroethane

NASA Astrophysics Data System (ADS)

Dietrich, Peter; Quack, Martin; Seyfang, George

1990-04-01

The IR multiphoton excitation and the frequency, fluence and intensity dependence of the IR-laser chemical yields of CF 2ClCH 2Cl have been studied in the fluence range of 1 to 10 J cm -2 yielding a steady-state constant k(st)/ I=0.74×10 6 s -1 MW -1 cm 2 which is approximately independent of intensity. Time-resolved IR absorption spectroscopy with diode laser sources has been used to observe the nascent HCl during the first few 100 ns indicating a population inversion between the levels ν=1, J=4 and ν=2, J=5. At low reactant pressures ( p⩽10 Pa) the time-resolved measurement gives a steady-state rate constant consistent with the theoretical result adjusted to the static yield measurements. The capability of state-selective and time-resolved IR spectroscopy is thus demonstrated, giving real-time determinations of rate constants.

In vivo detection of macrophages in a rabbit atherosclerotic model by time-resolved laser-induced fluorescence spectroscopy

PubMed Central

Marcu, Laura; Fang, Qiyin; Jo, Javier A.; Papaioannou, Thanassis; Dorafshar, Amir; Reil, Todd; Qiao, Jian-Hua; Baker, J. Dennis; Freischlag, Julie A.; Fishbein, Michael C.

2007-01-01

Accumulation of numerous macrophages in the fibrous cap is a key identifying feature of plaque inflammation and vulnerability. This study investigates the use of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as a potential tool for detection of macrophage foam cells in the intima of atherosclerotic plaques. Experiments were conducted in vivo on 14 New Zealand rabbits (6 control, 8 hypercholesterolemic) following aortotomy to expose the intimal luminal surface of the aorta. Tissue autofluorescence was induced with a nitrogen pulse laser (337 nm, 1 ns). Lesions were histologically classified by the percent of collagen or macrophage foam cells as well as thickness of the intima. Using parameters derived from the time-resolved fluorescence emission of plaques, we determined that intima rich in macrophage foam cells can be distinguished from intima rich in collagen with high sensitivity (>85%) and specificity (>95%). This study demonstrates, for the first time, that a time-resolved fluorescence-based technique can differentiate and demark macrophage content versus collagen content in vivo. Our results suggest that TR-LIFS technique can be used in clinical applications for identification of inflammatory cells important in plaque formation and rupture. PMID:16039283

In vivo detection of macrophages in a rabbit atherosclerotic model by time-resolved laser-induced fluorescence spectroscopy.

PubMed

Marcu, Laura; Fang, Qiyin; Jo, Javier A; Papaioannou, Thanassis; Dorafshar, Amir; Reil, Todd; Qiao, Jian-Hua; Baker, J Dennis; Freischlag, Julie A; Fishbein, Michael C

2005-08-01

Accumulation of numerous macrophages in the fibrous cap is a key identifying feature of plaque inflammation and vulnerability. This study investigates the use of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as a potential tool for detection of macrophage foam cells in the intima of atherosclerotic plaques. Experiments were conducted in vivo on 14 New Zealand rabbits (6 control, 8 hypercholesterolemic) following aortotomy to expose the intimal luminal surface of the aorta. Tissue autofluorescence was induced with a nitrogen pulse laser (337 nm, 1 ns). Lesions were histologically classified by the percent of collagen or macrophage foam cells as well as thickness of the intima. Using parameters derived from the time-resolved fluorescence emission of plaques, we determined that intima rich in macrophage foam cells can be distinguished from intima rich in collagen with high sensitivity (>85%) and specificity (>95%). This study demonstrates, for the first time, that a time-resolved fluorescence-based technique can differentiate and demark macrophage content versus collagen content in vivo. Our results suggest that TR-LIFS technique can be used in clinical applications for identification of inflammatory cells important in plaque formation and rupture.

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.

Intermittent Fluorescence Oscillations in Lipid Droplets in a Live Normal and Lung Cancer Cell: Time-Resolved Confocal Microscopy.

PubMed

Chowdhury, Rajdeep; Amin, Md Asif; Bhattacharyya, Kankan

2015-08-27

Intermittent structural oscillation in the lipid droplets of live lung cells is monitored using time-resolved confocal microscopy. Significant differences are observed between the lung cancer cell (A549) and normal (nonmalignant) lung cell (WI38). For this study, the lipid droplets are covalently labeled with a fluorescent dye, coumarin maleimide (7-diethylamino-3-(4-maleimido-phenyl)-4-methylcoumarin, CPM). The number of lipid droplets in the cancer cell is found to be ∼20-fold higher than that in the normal (nonmalignant) cell. The fluctuation in the fluorescence intensity of the dye (CPM) is attributed to the red-ox processes and periodic formation/rupture of the S-CPM bond. The amount of reactive oxygen species (ROS) is much higher in a cancer cell. This is manifested in faster oscillations (0.9 ± 0.3 s) in cancer cells compared to that in the normal cells (2.8 ± 0.7 s). Solvation dynamics in the lipid droplets of cancer cells is slower compared to that in the normal cell.

Comparative studies of structural, thermal, optical, and electrochemical properties of azines with different end groups with their azomethine analogues toward application in (opto)electronics.

PubMed

Sek, Danuta; Siwy, Mariola; Bijak, Katarzyna; Grucela-Zajac, Marzena; Malecki, Grzegorz; Smolarek, Karolina; Bujak, Lukasz; Mackowski, Sebastian; Schab-Balcerzak, Ewa

2013-10-10

Two series of azines and their azomethine analogues were prepared via condensation reaction of benzaldehyde, 2-hydroxybenzaldehyde, 4-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde, and 4-(diphenylamino)benzaldehyde with hydrazine monohydrate and 1,4-phenylenediamine, respectively. The structures of given compounds were characterized by FTIR, (1)H NMR, and (13)C NMR spectroscopy as well as elemental analysis. Optical, electrochemical, and thermal properties of all compounds were investigated by means of differential scanning calorimetry (DSC), UV-vis spectroscopy, stationary and time-resolved photoluminescence spectroscopy, and cycling voltammetry (CV). Additionally, the electronic properties, that is, orbital energies and resulting energy gap were calculated theoretically by density functional theory (DFT). Influence of chemical structure of the compounds on their properties was analyzed.

Conformational dynamics of proanthocyanidins: physical and computational approaches

Treesearch

Fred L. Tobiason; Richard W. Hemingway; T. Hatano

1998-01-01

The interaction of plant polyphenols with proteins accounts for a good part of their commercial (e.g., leather manufacture) and biological (e.g., antimicrobial activity) significance. The interplay between observations of physical data such as crystal structure, NMR analyses, and time-resolved fluorescence with results of computational chemistry approaches has been...

Improvements in brain activation detection using time-resolved diffuse optical means

NASA Astrophysics Data System (ADS)

Montcel, Bruno; Chabrier, Renee; Poulet, Patrick

2005-08-01

An experimental method based on time-resolved absorbance difference is described. The absorbance difference is calculated over each temporal step of the optical signal with the time-resolved Beer-Lambert law. Finite element simulations show that each step corresponds to a different scanned zone and that cerebral contribution increases with the arrival time of photons. Experiments are conducted at 690 and 830 nm with a time-resolved system consisting of picosecond laser diodes, micro-channel plate photo-multiplier tube and photon counting modules. The hemodynamic response to a short finger tapping stimulus is measured over the motor cortex. Time-resolved absorbance difference maps show that variations in the optical signals are not localized in superficial regions of the head, which testify for their cerebral origin. Furthermore improvements in the detection of cerebral activation is achieved through the increase of variations in absorbance by a factor of almost 5 for time-resolved measurements as compared to non-time-resolved measurements.

Growth and development of the barnacle Amphibalanus amphitrite: time and spatially resolved structure and chemistry of the base plate

PubMed Central

Burden, Daniel K.; Spillmann, Christopher M.; Everett, Richard K.; Barlow, Daniel E.; Orihuela, Beatriz; Deschamps, Jeffrey R.; Fears, Kenan P.; Rittschof, Daniel; Wahl, Kathryn J.

2014-01-01

The radial growth and advancement of the adhesive interface to the substratum of many species of acorn barnacles occurs underwater and beneath an opaque, calcified shell. Here, the time-dependent growth processes involving various autofluorescent materials within the interface of live barnacles are imaged for the first time using 3D time-lapse confocal microscopy. Key features of the interface development in the striped barnacle, Amphibalanus (= Balanus) amphitrite were resolved in situ and include advancement of the barnacle/substratum interface, epicuticle membrane development, protein secretion, and calcification. Microscopic and spectroscopic techniques provide ex situ material identification of regions imaged by confocal microscopy. In situ and ex situ analysis of the interface support the hypothesis that barnacle interface development is a complex process coupling sequential, timed secretory events and morphological changes. This results in a multi-layered interface that concomitantly fulfills the roles of strongly adhering to a substratum while permitting continuous molting and radial growth at the periphery. PMID:25115515

Growth and development of the barnacle Amphibalanus amphitrite: time and spatially resolved structure and chemistry of the base plate.

PubMed

Burden, Daniel K; Spillmann, Christopher M; Everett, Richard K; Barlow, Daniel E; Orihuela, Beatriz; Deschamps, Jeffrey R; Fears, Kenan P; Rittschof, Daniel; Wahl, Kathryn J

2014-01-01

The radial growth and advancement of the adhesive interface to the substratum of many species of acorn barnacles occurs underwater and beneath an opaque, calcified shell. Here, the time-dependent growth processes involving various autofluorescent materials within the interface of live barnacles are imaged for the first time using 3D time-lapse confocal microscopy. Key features of the interface development in the striped barnacle, Amphibalanus (= Balanus) amphitrite were resolved in situ and include advancement of the barnacle/substratum interface, epicuticle membrane development, protein secretion, and calcification. Microscopic and spectroscopic techniques provide ex situ material identification of regions imaged by confocal microscopy. In situ and ex situ analysis of the interface support the hypothesis that barnacle interface development is a complex process coupling sequential, timed secretory events and morphological changes. This results in a multi-layered interface that concomitantly fulfills the roles of strongly adhering to a substratum while permitting continuous molting and radial growth at the periphery.

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.

Investigation and Characterization of Defects in Epitaxial Films for Ultraviolet Light Emitting Devices Using FUV Time-Resolved Photoluminescence, Time-Resolved Cathodoluminescence, and Spatio-Time-Resolved Cathodoluminescence Excited Using Femtosecond Laser Pulses

DTIC Science & Technology

2013-05-22

mole fraction AlxGa1-xN alloys, and GaN were studied in this project. For this purpose, we quantified the radiative lifetimes (R) and nonradiative ...61556;R) and nonradiative lifetimes (NR) for the near-band-edge (NBE) emission by measuring the luminescence lifetimes () and...that is a fraction of radiative rate over the sum of radiative and nonradiative rates; i. e. int=(1+R/NR)-1. To improve int of practical devices

Indium hydroxide to oxide decomposition observed in one nanocrystal during in situ transmission electron microscopy studies

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

Miehe, Gerhard; Lauterbach, Stefan; Kleebe, Hans-Joachim

The high-resolution transmission electron microscopy (HR-TEM) is used to study, in situ, spatially resolved decomposition in individual nanocrystals of metal hydroxides and oxyhydroxides. This case study reports on the decomposition of indium hydroxide (c-In(OH){sub 3}) to bixbyite-type indium oxide (c-In{sub 2}O{sub 3}). The electron beam is focused onto a single cube-shaped In(OH){sub 3} crystal of {l_brace}100{r_brace} morphology with ca. 35 nm edge length and a sequence of HR-TEM images was recorded during electron beam irradiation. The frame-by-frame analysis of video sequences allows for the in situ, time-resolved observation of the shape and orientation of the transformed crystals, which in turnmore » enables the evaluation of the kinetics of c-In{sub 2}O{sub 3} crystallization. Supplementary material (video of the transformation) related to this article can be found online at (10.1016/j.jssc.2012.09.022). After irradiation the shape of the parent cube-shaped crystal is preserved, however, its linear dimension (edge) is reduced by the factor 1.20. The corresponding spotted selected area electron diffraction (SAED) pattern representing zone [001] of c-In(OH){sub 3} is transformed to a diffuse strongly textured ring-like pattern of c-In{sub 2}O{sub 3} that indicates the transformed cube is no longer a single crystal but is disintegrated into individual c-In{sub 2}O{sub 3} domains with the size of about 5-10 nm. The induction time of approximately 15 s is estimated from the time-resolved Fourier transforms. The volume fraction of the transformed phase (c-In{sub 2}O{sub 3}), calculated from the shrinkage of the parent c-In(OH){sub 3} crystal in the recorded HR-TEM images, is used as a measure of the kinetics of c-In{sub 2}O{sub 3} crystallization within the framework of Avrami-Erofeev formalism. The Avrami exponent of {approx}3 is characteristic for a reaction mechanism with fast nucleation at the beginning of the reaction and subsequent three-dimensional growth of nuclei with a constant growth rate. The structural transformation path in reconstructive decomposition of c-In(OH){sub 3} to c-In{sub 2}O{sub 3} is discussed in terms of (i) the displacement of hydrogen atoms that lead to breaking the hydrogen bond between OH groups of [In(OH){sub 6}] octahedra and finally to their destabilization and (ii) transformation of the vertices-shared indium-oxygen octahedra in c-In(OH){sub 3} to vertices- and edge-shared octahedra in c-In{sub 2}O{sub 3}. - Graphical abstract: Frame-by-frame analysis of video sequences recorded of HR-TEM images reveals that a single cube-shaped In(OH){sub 3} nanocrystal with {l_brace}100{r_brace} morphology decomposes into bixbyite-type In{sub 2}O{sub 3} domains while being imaged. The mechanism of this decomposition is evaluated through the analysis of the structural relationship between initial (c-In(OH){sub 3}) and transformed (c-In{sub 2}O{sub 3}) phases and though the kinetics of the decomposition followed via the time-resolved shrinkage of the initial crystal of indium hydroxide. Highlights: Black-Right-Pointing-Pointer In-situ time-resolved High Resolution Transmission Electron Microscopy. Black-Right-Pointing-Pointer Crystallographic transformation path. Black-Right-Pointing-Pointer Kinetics of the decomposition in one nanocrystal.« less

The Andromeda Optical and Infrared Disk Survey

NASA Astrophysics Data System (ADS)

Sick, J.; Courteau, S.; Cuillandre, J.-C.

2014-03-01

The Andromeda Optical and Infrared Disk Survey has mapped M31 in u* g' r' i' JKs wavelengths out to R = 40 kpc using the MegaCam and WIRCam wide-field cameras on the Canada-France-Hawaii Telescope. Our survey is uniquely designed to simultaneously resolve stars while also carefully reproducing the surface brightness of M31, allowing us to study M31's global structure in the context of both resolved stellar populations and spectral energy distributions. We use the Elixir-LSB method to calibrate the optical u* g' r' i' images by building real-time maps of the sky background with sky-target nodding. These maps are stable to μg ≲ 28.5 mag arcsec-2 and reveal warps in the outer M31 disk in surface brightness. The equivalent WIRCam mapping in the near-infrared uses a combination of sky-target nodding and image-to-image sky offset optimization to produce stable surface brightnesses. This study enables a detailed analysis of the systematics of spectral energy distribution fitting with near-infrared bands where asymptotic giant branch stars impose a significant, but ill-constrained, contribution to the near-infrared light of a galaxy. Here we present panchromatic surface brightness maps and initial results from our near-infrared resolved stellar catalog.

Modeling and Laboratory Investigations of Radiative Shocks

NASA Astrophysics Data System (ADS)

Grun, Jacob; Laming, J. Martin; Manka, Charles; Moore, Christopher; Jones, Ted; Tam, Daniel

2001-10-01

Supernova remnants are often inhomogeneous, with knots or clumps of material expanding in ambient plasma. This structure may be initiated by hydrodynamic instabilities occurring during the explosion, but it may plausibly be amplified by instabilities of the expanding shocks such as, for example, corrugation instabilities described by D’yakov in 1954, Vishniac in 1983, and observed in the laboratory by Grun et al. in 1991. Shock instability can occur when radiation lowers the effective adiabatic index of the gas. In view of the difficulty of modeling radiation in non-equilibrium plasmas, and the dependence of shock instabilities on such radiation, we are performing a laboratory experiment to study radiative shocks. The shocks are generated in a miniature, laser-driven shock tube. The gas density inside the tube at any instant in time is measured using time and space-resolved interferometry, and the emission spectrum of the gas is measured with time-resolved spectroscopy. We simulate the experiment with a 1D code that models time dependent post-shock ionization and non-equilibrium radiative cooling. S. P. D’yakov, Zhurnal Eksperimentalnoi Teoreticheskoi Fiziki 27, 288 (1954); see also section 90 in L.D. Landau and E.M. Lifshitz, Fluid Mechanics (Butterworth-Heinemann 1987); E.T. Vishniac, Astrophys. J. 236, 880 (1983); J. Grun, et al., Phys. Rev. Lett., 66, 2738 (1991)

End-on soft x ray imaging of Field-Reversed Configurations (FRCs) on the Field-Reversal-C (FRX-C)/Large Scale Modification (LSM) experiment

NASA Astrophysics Data System (ADS)

Taggart, D. P.; Gribble, R. J.; Bailey, A. D., III; Sugimoto, S.

Recently, a prototype soft x ray pinhole camera was fielded on FRX-C/LSM at Los Alamos and TRX at Spectra Technology. The soft x ray FRC images obtained using this camera stand out in high contrast to their surroundings. It was particularly useful for studying the FRC during and shortly after formation when, at certain operating conditions, flute-like structures at the edge and internal structures of the FRC were observed which other diagnostics could not resolve. Building on this early experience, a new soft x ray pinhole camera was installed on FRX-C/LSM, which permits more rapid data acquisition and briefer exposures. It will be used to continue studying FRC formation and to look for internal structure later in time which could be a signature of instability. The initial operation of this camera is summarized.

Investigating plasma viscosity with fast framing photography in the ZaP-HD Flow Z-Pinch experiment

NASA Astrophysics Data System (ADS)

Weed, Jonathan Robert

The ZaP-HD Flow Z-Pinch experiment investigates the stabilizing effect of sheared axial flows while scaling toward a high-energy-density laboratory plasma (HEDLP > 100 GPa). Stabilizing flows may persist until viscous forces dissipate a sheared flow profile. Plasma viscosity is investigated by measuring scale lengths in turbulence intentionally introduced in the plasma flow. A boron nitride turbulence-tripping probe excites small scale length turbulence in the plasma, and fast framing optical cameras are used to study time-evolved turbulent structures and viscous dissipation. A Hadland Imacon 790 fast framing camera is modified for digital image capture, but features insufficient resolution to study turbulent structures. A Shimadzu HPV-X camera captures the evolution of turbulent structures with great spatial and temporal resolution, but is unable to resolve the anticipated Kolmogorov scale in ZaP-HD as predicted by a simplified pinch model.

Band-Edge Exciton Fine Structure and Recombination Dynamics in InP/ZnS Colloidal Nanocrystals.

PubMed

Biadala, Louis; Siebers, Benjamin; Beyazit, Yasin; Tessier, Mickaël D; Dupont, Dorian; Hens, Zeger; Yakovlev, Dmitri R; Bayer, Manfred

2016-03-22

We report on a temperature-, time-, and spectrally resolved study of the photoluminescence of type-I InP/ZnS colloidal nanocrystals with varying core size. By studying the exciton recombination dynamics we assess the exciton fine structure in these systems. In addition to the typical bright-dark doublet, the photoluminescence stems from an upper bright state in spite of its large energy splitting (∼100 meV). This striking observation results from dramatically lengthened thermalization processes among the fine structure levels and points to optical-phonon bottleneck effects in InP/ZnS nanocrystals. Furthermore, our data show that the radiative recombination of the dark exciton scales linearly with the bright-dark energy splitting for CdSe and InP nanocrystals. This finding strongly suggests a universal dangling bonds-assisted recombination of the dark exciton in colloidal nanostructures.

Vibrational and rotational energy transfers involving the CH B 2Σ- v=1 vibrational level in collisions with Ar, CO, and N2O

NASA Astrophysics Data System (ADS)

Huang, Hong-Yi; Tsai, Ming-Tsang; Lin, King-Chuen

2006-04-01

With photolysis-probe technique, we have studied vibrational and rotational energy transfers of CH involving the B Σ-2 (v =1, 0⩽N⩽6, F) state by collisions with Ar, CO, and N2O. For the vibrational energy transfer (VET) measurements, the time-resolved fluorescence of the B-X(0,0) band is monitored following the (1,0) band excitation. For the rotational energy transfer (RET) measurements, the laser-induced fluorescence of the initially populated state is dispersed using a step-scan Fourier transform spectrometer. The time-resolved spectra obtained in the nanosecond regime may yield the RET information under a single pressure of the collider. The rate constants of intramolecular energy transfers are evaluated with simulation of kinetic models. The VET lies in the range of 4×10-12to4×10-11cm3molecule-1s-1, with efficiency following the order of Ar

Time-resolved cathodoluminescence microscopy with sub-nanosecond beam blanking for direct evaluation of the local density of states.

PubMed

Moerland, Robert J; Weppelman, I Gerward C; Garming, Mathijs W H; Kruit, Pieter; Hoogenboom, Jacob P

2016-10-17

We show cathodoluminescence-based time-resolved electron beam spectroscopy in order to directly probe the spontaneous emission decay rate that is modified by the local density of states in a nanoscale environment. In contrast to dedicated laser-triggered electron-microscopy setups, we use commercial hardware in a standard SEM, which allows us to easily switch from pulsed to continuous operation of the SEM. Electron pulses of 80-90 ps duration are generated by conjugate blanking of a high-brightness electron beam, which allows probing emitters within a large range of decay rates. Moreover, we simultaneously attain a resolution better than λ/10, which ensures details at deep-subwavelength scales can be retrieved. As a proof-of-principle, we employ the pulsed electron beam to spatially measure excited-state lifetime modifications in a phosphor material across the edge of an aluminum half-plane, coated on top of the phosphor. The measured emission dynamics can be directly related to the structure of the sample by recording photon arrival histograms together with the secondary-electron signal. Our results show that time-resolved electron cathodoluminescence spectroscopy is a powerful tool of choice for nanophotonics, within reach of a large audience.

Scale-Resolving simulations (SRS): How much resolution do we really need?

NASA Astrophysics Data System (ADS)

Pereira, Filipe M. S.; Girimaji, Sharath

2017-11-01

Scale-resolving simulations (SRS) are emerging as the computational approach of choice for many engineering flows with coherent structures. The SRS methods seek to resolve only the most important features of the coherent structures and model the remainder of the flow field with canonical closures. With reference to a typical Large-Eddy Simulation (LES), practical SRS methods aim to resolve a considerably narrower range of scales (reduced physical resolution) to achieve an adequate degree of accuracy at reasonable computational effort. While the objective of SRS is well-founded, the criteria for establishing the optimal degree of resolution required to achieve an acceptable level of accuracy are not clear. This study considers the canonical case of the flow around a circular cylinder to address the issue of `optimal' resolution. Two important criteria are developed. The first condition addresses the issue of adequate resolution of the flow field. The second guideline provides an assessment of whether the modeled field is canonical (stochastic) turbulence amenable to closure-based computations.

Quasi-Steady-State Analysis based on Structural Modules and Timed Petri Net Predict System's Dynamics: The Life Cycle of the Insulin Receptor.

PubMed

Scheidel, Jennifer; Lindauer, Klaus; Ackermann, Jörg; Koch, Ina

2015-12-17

The insulin-dependent activation and recycling of the insulin receptor play an essential role in the regulation of the energy metabolism, leading to a special interest for pharmaceutical applications. Thus, the recycling of the insulin receptor has been intensively investigated, experimentally as well as theoretically. We developed a time-resolved, discrete model to describe stochastic dynamics and study the approximation of non-linear dynamics in the context of timed Petri nets. Additionally, using a graph-theoretical approach, we analyzed the structure of the regulatory system and demonstrated the close interrelation of structural network properties with the kinetic behavior. The transition invariants decomposed the model into overlapping subnetworks of various sizes, which represent basic functional modules. Moreover, we computed the quasi-steady states of these subnetworks and demonstrated that they are fundamental to understand the dynamic behavior of the system. The Petri net approach confirms the experimental results of insulin-stimulated degradation of the insulin receptor, which represents a common feature of insulin-resistant, hyperinsulinaemic states.

A Photoluminescence Study of the Changes Induced in the Zinc White Pigment by Formation of Zinc Complexes

PubMed Central

Artesani, Alessia; Gherardi, Francesca; Nevin, Austin; Valentini, Gianluca; Comelli, Daniela

2017-01-01

It is known that oil paintings containing zinc white are subject to rapid degradation. This is caused by the interaction between the active groups of binder and the metal ions of the pigment, which gives rise to the formation of new zinc complexes (metal soaps). Ongoing studies on zinc white paints have been limited to the chemical mechanisms that lead to the formation of zinc complexes. On the contrary, little is known of the photo-physical changes induced in the zinc oxide crystal structure following this interaction. Time-resolved photoluminescence spectroscopy has been applied to follow modifications in the luminescent zinc white pigment when mixed with binder. Significant changes in trap state photoluminescence emissions have been detected: the enhancement of a blue emission combined with a change of the decay kinetic of the well-known green emission. Complementary data from molecular analysis of paints using Fourier transform infrared spectroscopy confirms the formation of zinc carboxylates and corroborates the mechanism for zinc complexes formation. We support the hypothesis that zinc ions migrate into binder creating novel vacancies, affecting the photoluminescence intensity and lifetime properties of zinc oxide. Here, we further demonstrate the advantages of a time-resolved photoluminescence approach for studying defects in semiconductor pigments. PMID:28772700

Femtosecond Structural Dynamics Drives the Trans/Cis Isomerization in Photoactive Yellow Protein

PubMed Central

Pande, Kanupriya; Hutchison, Christopher D. M.; Groenhof, Gerrit; Aquila, Andy; Robinson, Josef S.; Tenboer, Jason; Basu, Shibom; Boutet, Sébastien; DePonte, Daniel P.; Liang, Mengning; White, Thomas A.; Zatsepin, Nadia A.; Yefanov, Oleksandr; Morozov, Dmitry; Oberthuer, Dominik; Gati, Cornelius; Subramanian, Ganesh; James, Daniel; Zhao, Yun; Koralek, Jake; Brayshaw, Jennifer; Kupitz, Christopher; Conrad, Chelsie; Roy-Chowdhury, Shatabdi; Coe, Jesse D.; Metz, Markus; Xavier, Paulraj Lourdu; Grant, Thomas D.; Koglin, Jason E.; Ketawala, Gihan; Fromme, Raimund; Šrajer, Vukica; Henning, Robert; Spence, John C. H.; Ourmazd, Abbas; Schwander, Peter; Weierstall, Uwe; Frank, Matthias; Fromme, Petra; Barty, Anton; Chapman, Henry N.; Moffat, Keith; van Thor, Jasper J.; Schmidt, Marius

2017-01-01

A variety of organisms have evolved mechanisms to detect and respond to light, in which the response is mediated by protein structural changes following photon absorption. The initial step is often the photo-isomerization of a conjugated chromophore. Isomerization occurs on ultrafast timescales, and is substantially influenced by the chromophore environment. Here we identify structural changes associated with the earliest steps in the trans to cis isomerization of the chromophore in photoactive yellow protein. Femtosecond, hard X-ray pulses emitted by the Linac Coherent Light Source were used to conduct time-resolved serial femtosecond crystallography on PYP microcrystals over the time range from 100 femtoseconds to 3 picoseconds to determine the structural dynamics of the photoisomerization reaction. PMID:27151871

Butterfly deformation modes in a photoexcited pyrazolate-bridged Pt complex measured by time-resolved x-ray scattering in solution

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

Haldrup, Kristoffer; Dohn, Asmus O.; Shelby, Megan L.

2016-08-27

Pyrazolate-bridged di-nuclear Pt complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet excited state has remained scarce. Using time-resolved wide angle X-ray scattering (WAXS), the molecular structure of the triplet excited state for one of the complexes [Pt(ppy)(μ-tBu 2pz)] 2 was obtained in a dilute (0.5 mM) toluene solution utilizing the monochromatic X-ray beamline 11IDD of the Advanced Photon Source. The excited state structural analysis was carried out based on the results frommore » both transient WAXS measurements and DFT calculations to shed light on the primary structural changes, in particular the Pt-Pt distance and ligand rotation taking place following the photo-excitation of [Pt(ppy)(μ-tBu 2pz)] 2 in toluene solution. We find that in the triplet excited state a pronounced contraction along the Pt-Pt axis has taken place accompanied by rotational motions of ppy ligands toward one another. Our results suggest that the contraction is larger than what has previously been reported, but are in good agreement with recent theoretical efforts and suggest the ppy moieties as targets for rational synthesis aimed at tuning the excited-state structure and properties« less

Evaluation of Collaterals and Clot Burden Using Time-Resolved C-Arm Conebeam CT Angiography in the Angiography Suite: A Feasibility Study.

PubMed

Yang, P; Niu, K; Wu, Y; Struffert, T; Doerfler, A; Holter, P; Aagaard-Kienitz, B; Strother, C; Chen, G-H

2017-04-01

The assessment of collaterals and clot burden in patients with acute ischemic stroke provides important information about treatment options and clinical outcome. Time-resolved C-arm conebeam CT angiography has the potential to provide accurate and reliable evaluations of collaterals and clot burden in the angiographic suite. Experience with this technique is extremely limited, and feasibility studies are needed to validate this technique. Our purpose was to present such a feasibility study. Ten C-arm conebeam CT perfusion datasets from 10 subjects with acute ischemic stroke acquired before endovascular treatment were retrospectively processed to generate time-resolved conebeam CTA. From time-resolved conebeam CTA, 2 experienced readers evaluated the clot burden and collateral flow in consensus by using previously reported scoring systems and assessed the clinical value of this novel imaging technique independently. Interobserver agreement was analyzed by using the intraclass correlation analysis method. Clot burden and collateral flow can be assessed by using the commonly accepted scoring systems for all eligible cases. Additional clinical information (eg, the quantitative dynamic information of collateral flow) can be obtained from this new imaging technique. Two readers agreed that time-revolved C-arm conebeam CTA is the preferred method for evaluating the clot burden and collateral flow compared with other conventional imaging methods. Comprehensive evaluations of clot burden and collateral flow are feasible by using time-resolved C-arm conebeam CTA data acquired in the angiography suite. This technique further enriches the imaging tools in the angiography suite to enable a "one-stop- shop" imaging workflow for patients with acute ischemic stroke. © 2017 by American Journal of Neuroradiology.

Flip-flop resolving time test circuit

NASA Technical Reports Server (NTRS)

Rosenberger, F.; Chaney, T. J.

1982-01-01

Integrated circuit (IC) flip-flop resolving time parameters are measured by wafer probing, without need of dicing or bonding, throught the incorporation of test structures on an IC together with the flip-flop to be measured. Several delays that are fabricated as part of the test circuit, including a voltage-controlled delay with a resolution of a few picosecs, are calibrated as part of the test procedure by integrating them into, and out of, the delay path of a ring oscillator. Each of the delay values is calculated by subtracting the period of the ring oscillator with the delay omitted from the period with the delay included. The delay measurement technique is sufficiently general for other applications. The technique is illustrated for the case of the flip-flop parameters of a 5-micron feature size NMOS circuit.

Time-resolved laser-induced incandescence characterization of metal nanoparticles

NASA Astrophysics Data System (ADS)

Sipkens, T. A.; Singh, N. R.; Daun, K. J.

2017-01-01

This paper presents a comparative analysis of time-resolved laser-induced incandescence measurements of iron, silver, and molybdenum aerosols. Both the variation of peak temperature with fluence and the temperature decay curves strongly depend on the melting point and latent heat of vaporization of the nanoparticles. Recovered nanoparticle sizes are consistent with ex situ analysis, while thermal accommodation coefficients follow expected trends with gas molecular mass and structure. Nevertheless, there remain several unanswered questions and unexplained behaviors: the radiative properties of laser-energized iron nanoparticles do not match those of bulk molten iron; the absorption cross sections of molten iron and silver at the excitation laser wavelength exceed theoretical predictions; and there is an unexplained feature in the temperature decay of laser-energized molybdenum nanoparticles immediately following the laser pulse.

Vibrationally resolved photoelectron angular distributions for H/sub 2/ in the range 17 eVless than or equal toh. nu. less than or equal to39 eV

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

Parr, A.C.; Hardis, J.E.; Southworth, S.H.

1988-01-15

Vibrationally resolved photoelectron angular distributions have been measured for photoionization of H/sub 2/ over the range 17 eVless than or equal toh..nu..less than or equal to39 eV using independent instrumentation at two synchro- tron radiation facilities. The present data greatly extend and add vibrational resolution to earlier variable-wavelength measurements. The average magnitude of the asymmetry parameter continues to lie lower than the best independent-electron calculations. Broad structure is observed for the first time, possibly indicating the effects of channel interaction with dissociative, doubly excited states of H/sub 2/. Neither the average magnitude nor the gross wavelength-dependent structure vary strongly withmore » the final vibrational channel.« less

Time Delays of Blazar Flares Observed at Different Wavebands

NASA Technical Reports Server (NTRS)

Marscher, Alan P.

2000-01-01

Correlated variability at different frequencies can probe the structure and physics of the jet of a blazar on size scales much smaller than can be resolved by telescopes and interferometers. I discuss some observations of frequency dependent time lags and how these place constraints on models for the nonthermal emission in blazars. The time lags can be either positive (high frequency variations leading those at lower frequencies) or negative, while simultaneous flares are also possible.

Detection of a Geostationary Satellite with the Navy Prototype Optical Interferometer

DTIC Science & Technology

2010-07-01

USA 86001 USA ABSTRACT We have detected a satellite via optical interferometry for the first time , using a 16 m baseline of the Navy Prototype Optical...available at the time of our observations, resolves out structures larger than ∼ 1.5 m at the geostationary distance, while a typical size for the solar... satellite via optical interferometry for the first time , using a 16 m baseline of the Navy Prototype Optical Interferometer (NPOI) to observe the

Revealing the distinct folding phases of an RNA three-helix junction.

PubMed

Plumridge, Alex; Katz, Andrea M; Calvey, George D; Elber, Ron; Kirmizialtin, Serdal; Pollack, Lois

2018-05-14

Remarkable new insight has emerged into the biological role of RNA in cells. RNA folding and dynamics enable many of these newly discovered functions, calling for an understanding of RNA self-assembly and conformational dynamics. Because RNAs pass through multiple structures as they fold, an ensemble perspective is required to visualize the flow through fleetingly populated sets of states. Here, we combine microfluidic mixing technology and small angle X-ray scattering (SAXS) to measure the Mg-induced folding of a small RNA domain, the tP5abc three helix junction. Our measurements are interpreted using ensemble optimization to select atomically detailed structures that recapitulate each experimental curve. Structural ensembles, derived at key stages in both time-resolved studies and equilibrium titrations, reproduce the features of known intermediates, and more importantly, offer a powerful new structural perspective on the time-progression of folding. Distinct collapse phases along the pathway appear to be orchestrated by specific interactions with Mg ions. These key interactions subsequently direct motions of the backbone that position the partners of tertiary contacts for later bonding, and demonstrate a remarkable synergy between Mg and RNA across numerous time-scales.

Transferring the entatic-state principle to copper photochemistry

NASA Astrophysics Data System (ADS)

Dicke, B.; Hoffmann, A.; Stanek, J.; Rampp, M. S.; Grimm-Lebsanft, B.; Biebl, F.; Rukser, D.; Maerz, B.; Göries, D.; Naumova, M.; Biednov, M.; Neuber, G.; Wetzel, A.; Hofmann, S. M.; Roedig, P.; Meents, A.; Bielecki, J.; Andreasson, J.; Beyerlein, K. R.; Chapman, H. N.; Bressler, C.; Zinth, W.; Rübhausen, M.; Herres-Pawlis, S.

2018-03-01

The entatic state denotes a distorted coordination geometry of a complex from its typical arrangement that generates an improvement to its function. The entatic-state principle has been observed to apply to copper electron-transfer proteins and it results in a lowering of the reorganization energy of the electron-transfer process. It is thus crucial for a multitude of biochemical processes, but its importance to photoactive complexes is unexplored. Here we study a copper complex—with a specifically designed constraining ligand geometry—that exhibits metal-to-ligand charge-transfer state lifetimes that are very short. The guanidine-quinoline ligand used here acts on the bis(chelated) copper(I) centre, allowing only small structural changes after photoexcitation that result in very fast structural dynamics. The data were collected using a multimethod approach that featured time-resolved ultraviolet-visible, infrared and X-ray absorption and optical emission spectroscopy. Through supporting density functional calculations, we deliver a detailed picture of the structural dynamics in the picosecond-to-nanosecond time range.

Nonlinear electron-phonon coupling in doped manganites

DOE PAGES

Esposito, Vincent; Fechner, M.; Mankowsky, R.; ...

2017-06-15

Here, we employ time-resolved resonant x-ray diffraction to study the melting of charge order and the associated insulator-to-metal transition in the doped manganite Pr 0.5Ca 0.5MnO 3 after resonant excitation of a high-frequency infrared-active lattice mode. We find that the charge order reduces promptly and highly nonlinearly as function of excitation fluence. Density-functional theory calculations suggest that direct anharmonic coupling between the excited lattice mode and the electronic structure drives these dynamics, highlighting a new avenue of nonlinear phonon control.

Nonlinear Electron-Phonon Coupling in Doped Manganites.

PubMed

Esposito, V; Fechner, M; Mankowsky, R; Lemke, H; Chollet, M; Glownia, J M; Nakamura, M; Kawasaki, M; Tokura, Y; Staub, U; Beaud, P; Först, M

2017-06-16

We employ time-resolved resonant x-ray diffraction to study the melting of charge order and the associated insulator-to-metal transition in the doped manganite Pr_{0.5}Ca_{0.5}MnO_{3} after resonant excitation of a high-frequency infrared-active lattice mode. We find that the charge order reduces promptly and highly nonlinearly as function of excitation fluence. Density-functional theory calculations suggest that direct anharmonic coupling between the excited lattice mode and the electronic structure drives these dynamics, highlighting a new avenue of nonlinear phonon control.

Interplay of coupling and superradiant emission in the optical response of a double quantum dot

NASA Astrophysics Data System (ADS)

Sitek, Anna; Machnikowski, Paweł

2009-09-01

We study theoretically the optical response of a double quantum dot structure to an ultrafast optical excitation. We show that the interplay of a specific type of coupling between the dots and their collective interaction with the radiative environment leads to very characteristic features in the time-resolved luminescence as well as in the absorption spectrum of the system. For a sufficiently strong coupling, these effects survive even if the transition energy mismatch between the two dots exceeds by far the emission linewidth.

Resolvability of regional density structure

NASA Astrophysics Data System (ADS)

Plonka, A.; Fichtner, A.

2016-12-01

Lateral density variations are the source of mass transport in the Earth at all scales, acting as drivers of convectivemotion. However, the density structure of the Earth remains largely unknown since classic seismic observables and gravityprovide only weak constraints with strong trade-offs. Current density models are therefore often based on velocity scaling,making strong assumptions on the origin of structural heterogeneities, which may not necessarily be correct. Our goal is to assessif 3D density structure may be resolvable with emerging full-waveform inversion techniques. We have previously quantified the impact of regional-scale crustal density structure on seismic waveforms with the conclusion that reasonably sized density variations within thecrust can leave a strong imprint on both travel times and amplitudes, and, while this can produce significant biases in velocity and Q estimates, the seismic waveform inversion for density may become feasible. In this study we performprincipal component analyses of sensitivity kernels for P velocity, S velocity, and density. This is intended to establish theextent to which these kernels are linearly independent, i.e. the extent to which the different parameters may be constrainedindependently. Since the density imprint we observe is not exclusively linked to travel times and amplitudes of specific phases,we consider waveform differences between complete seismograms. We test the method using a known smooth model of the crust and seismograms with clear Love and Rayleigh waves, showing that - as expected - the first principal kernel maximizes sensitivity to SH and SV velocity structure, respectively, and that the leakage between S velocity, P velocity and density parameter spaces is minimal in the chosen setup. Next, we apply the method to data from 81 events around the Iberian Penninsula, registered in total by 492 stations. The objective is to find a principal kernel which would maximize the sensitivity to density, potentially allowing for independent density resolution, and, as the final goal, for direct density inversion.

Silicon drift detectors as a tool for time-resolved fluorescence XAFS on low-concentrated samples in catalysis.

PubMed

Kappen, Peter; Tröger, Larc; Materlik, Gerhard; Reckleben, Christian; Hansen, Karsten; Grunwaldt, Jan-Dierk; Clausen, Bjerne S

2002-07-01

A silicon drift detector (SDD) was used for ex situ and time-resolved in situ fluorescence X-ray absorption fine structure (XAFS) on low-concentrated catalyst samples. For a single-element and a seven-element SDD the energy resolution and the peak-to-background ratio were verified at high count rates, sufficient for fluorescence XAFS. An experimental set-up including the seven-element SDD without any cooling and an in situ cell with gas supply and on-line gas analysis was developed. With this set-up the reduction and oxidation of a zeolite supported catalyst containing 0.3 wt% platinum was followed by fluorescence near-edge scans with a time resolution of 10 min each. From ex situ experiments on low-concentrated platinum- and gold-based catalysts fluorescence XAFS scans could be obtained with sufficient statistical quality for a quantitative analysis. Structural information on the gold and platinum particles could be extracted by both the Fourier transforms and the near-edge region of the XAFS spectra. Moreover, it was found that with the seven-element SDD concentrations of the element of interest as low as 100 ppm can be examined by fluorescence XAFS.

Ultrafast excited state deactivation of doped porous anodic alumina membranes

NASA Astrophysics Data System (ADS)

Makhal, Abhinandan; Sarkar, Soumik; Pal, Samir Kumar; Yan, Hongdan; Wulferding, Dirk; Cetin, Fatih; Lemmens, Peter

2012-08-01

Free-standing, bi-directionally permeable and ultra-thin anodic aluminum oxide (AAO) membranes establish attractive templates (host) for the synthesis of nano-dots and rods of various materials (guest). This is due to their chemical and structural integrity and high periodicity on length scales of 5-150 nm which are often used to host photoactive nano-materials for various device applications including dye-sensitized solar cells. In the present study, AAO membranes are synthesized by using electrochemical methods and a detailed structural characterization using FEG-SEM, XRD and TGA confirms the porosity and purity of the material. Defect-mediated photoluminescence quenching of the porous AAO membrane in the presence of an electron accepting guest organic molecule (benzoquinone) is studied by means of steady-state and picosecond/femtosecond-resolved luminescence measurements. Using time-resolved luminescence transients, we have also revealed light harvesting of complexes of porous alumina impregnated with inorganic quantum dots (Maple Red) or gold nanowires. Both the Förster resonance energy transfer and the nano-surface energy transfer techniques are employed to examine the observed quenching behavior as a function of the characteristic donor-acceptor distances. The experimental results will find their relevance in light harvesting devices based on AAOs combined with other materials involving a decisive energy/charge transfer dynamics.

Ultrafast excited state deactivation of doped porous anodic alumina membranes.

PubMed

Makhal, Abhinandan; Sarkar, Soumik; Pal, Samir Kumar; Yan, Hongdan; Wulferding, Dirk; Cetin, Fatih; Lemmens, Peter

2012-08-03

Free-standing, bi-directionally permeable and ultra-thin anodic aluminum oxide (AAO) membranes establish attractive templates (host) for the synthesis of nano-dots and rods of various materials (guest). This is due to their chemical and structural integrity and high periodicity on length scales of 5-150 nm which are often used to host photoactive nano-materials for various device applications including dye-sensitized solar cells. In the present study, AAO membranes are synthesized by using electrochemical methods and a detailed structural characterization using FEG-SEM, XRD and TGA confirms the porosity and purity of the material. Defect-mediated photoluminescence quenching of the porous AAO membrane in the presence of an electron accepting guest organic molecule (benzoquinone) is studied by means of steady-state and picosecond/femtosecond-resolved luminescence measurements. Using time-resolved luminescence transients, we have also revealed light harvesting of complexes of porous alumina impregnated with inorganic quantum dots (Maple Red) or gold nanowires. Both the Förster resonance energy transfer and the nano-surface energy transfer techniques are employed to examine the observed quenching behavior as a function of the characteristic donor-acceptor distances. The experimental results will find their relevance in light harvesting devices based on AAOs combined with other materials involving a decisive energy/charge transfer dynamics.

Recent trends in spin-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Okuda, Taichi

2017-12-01

Since the discovery of the Rashba effect on crystal surfaces and also the discovery of topological insulators, spin- and angle-resolved photoelectron spectroscopy (SARPES) has become more and more important, as the technique can measure directly the electronic band structure of materials with spin resolution. In the same way that the discovery of high-Tc superconductors promoted the development of high-resolution angle-resolved photoelectron spectroscopy, the discovery of this new class of materials has stimulated the development of new SARPES apparatus with new functions and higher resolution, such as spin vector analysis, ten times higher energy and angular resolution than conventional SARPES, multichannel spin detection, and so on. In addition, the utilization of vacuum ultra violet lasers also opens a pathway to the realization of novel SARPES measurements. In this review, such recent trends in SARPES techniques and measurements will be overviewed.

Angle-resolved photoemission spectroscopy with 9-eV photon-energy pulses generated in a gas-filled hollow-core photonic crystal fiber

NASA Astrophysics Data System (ADS)

Bromberger, H.; Ermolov, A.; Belli, F.; Liu, H.; Calegari, F.; Chávez-Cervantes, M.; Li, M. T.; Lin, C. T.; Abdolvand, A.; Russell, P. St. J.; Cavalleri, A.; Travers, J. C.; Gierz, I.

2015-08-01

A recently developed source of ultraviolet radiation, based on optical soliton propagation in a gas-filled hollow-core photonic crystal fiber, is applied here to angle-resolved photoemission spectroscopy (ARPES). Near-infrared femtosecond pulses of only few μJ energy generate vacuum ultraviolet radiation between 5.5 and 9 eV inside the gas-filled fiber. These pulses are used to measure the band structure of the topological insulator Bi2Se3 with a signal to noise ratio comparable to that obtained with high order harmonics from a gas jet. The two-order-of-magnitude gain in efficiency promises time-resolved ARPES measurements at repetition rates of hundreds of kHz or even MHz, with photon energies that cover the first Brillouin zone of most materials.

Density relaxation and particle motion characteristics in a non-ionic deep eutectic solvent (acetamide + urea): time-resolved fluorescence measurements and all-atom molecular dynamics simulations.

PubMed

Das, Anuradha; Das, Suman; Biswas, Ranjit

2015-01-21

Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents (DESs) made of acetamide (CH3CONH2) and urea (NH2CONH2) have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations. Three different compositions (f) for the mixture [fCH3CONH2 + (1 - f)NH2CONH2] have been studied in a temperature range of 328-353 K which is ∼120-145 K above the measured glass transition temperatures (∼207 K) of these DESs but much lower than the individual melting temperature of either of the constituents. Steady state fluorescence emission measurements using probe solutes with sharply different lifetimes do not indicate any dependence on excitation wavelength in these metastable molten systems. Time-resolved fluorescence anisotropy measurements reveal near-hydrodynamic coupling between medium viscosity and rotation of a dissolved dipolar solute. Stokes shift dynamics have been found to be too fast to be detected by the time-resolution (∼70 ps) employed, suggesting extremely rapid medium polarization relaxation. All-atom simulations reveal Gaussian distribution for particle displacements and van Hove correlations, and significant overlap between non-Gaussian (α2) and new non-Gaussian (γ) heterogeneity parameters. In addition, no stretched exponential relaxations have been detected in the simulated wavenumber dependent acetamide dynamic structure factors. All these results are in sharp contrast to earlier observations for ionic deep eutectics with acetamide [Guchhait et al., J. Chem. Phys. 140, 104514 (2014)] and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutectic solvent systems.

Density relaxation and particle motion characteristics in a non-ionic deep eutectic solvent (acetamide + urea): Time-resolved fluorescence measurements and all-atom molecular dynamics simulations

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

Das, Anuradha; Das, Suman; Biswas, Ranjit, E-mail: ranjit@bose.res.in

2015-01-21

Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents (DESs) made of acetamide (CH{sub 3}CONH{sub 2}) and urea (NH{sub 2}CONH{sub 2}) have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations. Three different compositions (f) for the mixture [fCH{sub 3}CONH{sub 2} + (1 − f)NH{sub 2}CONH{sub 2}] have been studied in a temperature range of 328-353 K which is ∼120-145 K above the measured glass transition temperatures (∼207 K) of these DESs but much lower than the individual melting temperature of either of the constituents. Steady state fluorescence emission measurements using probemore » solutes with sharply different lifetimes do not indicate any dependence on excitation wavelength in these metastable molten systems. Time-resolved fluorescence anisotropy measurements reveal near-hydrodynamic coupling between medium viscosity and rotation of a dissolved dipolar solute. Stokes shift dynamics have been found to be too fast to be detected by the time-resolution (∼70 ps) employed, suggesting extremely rapid medium polarization relaxation. All-atom simulations reveal Gaussian distribution for particle displacements and van Hove correlations, and significant overlap between non-Gaussian (α{sub 2}) and new non-Gaussian (γ) heterogeneity parameters. In addition, no stretched exponential relaxations have been detected in the simulated wavenumber dependent acetamide dynamic structure factors. All these results are in sharp contrast to earlier observations for ionic deep eutectics with acetamide [Guchhait et al., J. Chem. Phys. 140, 104514 (2014)] and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutectic solvent systems.« less

Density relaxation and particle motion characteristics in a non-ionic deep eutectic solvent (acetamide + urea): Time-resolved fluorescence measurements and all-atom molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Das, Anuradha; Das, Suman; Biswas, Ranjit

2015-01-01

Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents (DESs) made of acetamide (CH3CONH2) and urea (NH2CONH2) have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations. Three different compositions (f) for the mixture [fCH3CONH2 + (1 - f)NH2CONH2] have been studied in a temperature range of 328-353 K which is ˜120-145 K above the measured glass transition temperatures (˜207 K) of these DESs but much lower than the individual melting temperature of either of the constituents. Steady state fluorescence emission measurements using probe solutes with sharply different lifetimes do not indicate any dependence on excitation wavelength in these metastable molten systems. Time-resolved fluorescence anisotropy measurements reveal near-hydrodynamic coupling between medium viscosity and rotation of a dissolved dipolar solute. Stokes shift dynamics have been found to be too fast to be detected by the time-resolution (˜70 ps) employed, suggesting extremely rapid medium polarization relaxation. All-atom simulations reveal Gaussian distribution for particle displacements and van Hove correlations, and significant overlap between non-Gaussian (α2) and new non-Gaussian (γ) heterogeneity parameters. In addition, no stretched exponential relaxations have been detected in the simulated wavenumber dependent acetamide dynamic structure factors. All these results are in sharp contrast to earlier observations for ionic deep eutectics with acetamide [Guchhait et al., J. Chem. Phys. 140, 104514 (2014)] and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutectic solvent systems.

General theoretical description of angle-resolved photoemission spectroscopy of van der Waals structures

NASA Astrophysics Data System (ADS)

Amorim, B.

2018-04-01

We develop a general theory to model the angle-resolved photoemission spectroscopy (ARPES) of commensurate and incommensurate van der Waals (vdW) structures, formed by lattice mismatched and/or misaligned stacked layers of two-dimensional materials. The present theory is based on a tight-binding description of the structure and the concept of generalized umklapp processes, going beyond previous descriptions of ARPES in incommensurate vdW structures, which are based on continuous, low-energy models, being limited to structures with small lattice mismatch/misalignment. As applications of the general formalism, we study the ARPES bands and constant energy maps for two structures: twisted bilayer graphene and twisted bilayer MoS2. The present theory should be useful in correctly interpreting experimental results of ARPES of vdW structures and other systems displaying competition between different periodicities, such as two-dimensional materials weakly coupled to a substrate and materials with density wave phases.

The phase-resolved photoacoustic method to indicate chemical assignments of paracetamol

NASA Astrophysics Data System (ADS)

Camilotti, J. G.; Somer, A.; Costa, G. F.; Ribeiro, M. A.; Bonardi, C.; Cruz, G. K.; Gómez, S. L.; Beltrame, F. L.; Medina, A. N.; Sato, F.; Astrath, N. G. C.; Novatski, A.

2014-03-01

In this work, the phase-resolved photoacoustic method was applied to provide specific information on the chemical assignments of paracetamol in the near-infrared region. Two broad bands, centered at 1370 and 1130 nm, were well-resolved using this method, making it possible to assign the peaks centered at 1398, 1355 and 1295 nm to a C-H combination from a CH3 structure and the peak at 1305 nm to a C-H combination from the aromatic ring. This information represents a new finding in chemical studies regarding this medicament.

Time-Resolved Gravimetric Method To Assess Degassing of Roasted Coffee.

PubMed

Smrke, Samo; Wellinger, Marco; Suzuki, Tomonori; Balsiger, Franz; Opitz, Sebastian E W; Yeretzian, Chahan

2018-05-30

During the roasting of coffee, thermally driven chemical reactions lead to the formation of gases, of which a large fraction is carbon dioxide (CO 2 ). Part of these gases is released during roasting while part is retained inside the porous structure of the roasted beans and is steadily released during storage or more abruptly during grinding and extraction. The release of CO 2 during the various phases from roasting to consumption is linked to many important properties and characteristics of coffee. It is an indicator for freshness, plays an important role in shelf life and in packaging, impacts the extraction process, is involved in crema formation, and may affect the sensory profile in the cup. Indeed, and in view of the multiple roles it plays, CO 2 is a much underappreciated and little examined molecule in coffee. Here, we introduce an accurate, quantitative, and time-resolved method to measure the release kinetics of gases from whole beans and ground coffee using a gravimetric approach. Samples were placed in a container with a fitted capillary to allow gases to escape. The time-resolved release of gases was measured via the weight loss of the container filled with coffee. Long-term stability was achieved using a customized design of a semimicro balance, including periodic and automatic zero value measurements and calibration procedures. The novel gravimetric methodology was applied to a range of coffee samples: (i) whole Arabica beans and (ii) ground Arabica and Robusta, roasted to different roast degrees and at different speeds (roast air temperatures). Modeling the degassing rates allowed structural and mechanistic interpretation of the degassing process.

Mantle circulation models with variational data assimilation: Inferring past mantle flow and structure from plate motion histories and seismic tomography

NASA Astrophysics Data System (ADS)

Bunge, Hans-Peter

2002-08-01

Earth's mantle overturns itself about once every 200 Million years (myrs). Prima facie evidence for this overturn is the motion of tectonic plates at the surface of the Earth driving the geologic activity of our planet. Supporting evidence also comes from seismic tomograms of the Earth's interior that reveal the convective currents in remarkable clarity. Much has been learned about the physics of solid state mantle convection over the past two decades aided primarily by sophisticated computer simulations. Such simulations are reaching the threshold of fully resolving the convective system globally. In this talk we will review recent progress in mantle dynamics studies. We will then turn our attention to the fundamental question of whether it is possible to explicitly reconstruct mantle flow back in time. This is a classic problem of history matching, amenable to control theory and data assimilation. The technical advances that make such approach feasible are dramatically increasing compute resources, represented for example through Beowulf clusters, and new observational initiatives, represented for example through the US-Array effort that should lead to an order-of-magnitude improvement in our ability to resolve Earth structure seismically below North America. In fact, new observational constraints on deep Earth structure illustrate the growing importance of of improving our data assimilation skills in deep Earth models. We will explore data assimilation through high resolution global adjoint models of mantle circulation and conclude that it is feasible to reconstruct mantle flow back in time for at least the past 100 myrs.

Time-resolved in situ neutron diffraction under supercritical hydrothermal conditions: a study of the synthesis of KTiOPO4.

PubMed

Ok, Kang Min; Lee, Dong Woo; Smith, Ronald I; O'Hare, Dermot

2012-10-31

In the first in situ neutron powder diffraction study of a supercritical hydrothermal synthesis, the crystallization of KTiOPO(4) (KTP) at 450 °C and 380 bar has been investigated. The time-resolved diffraction data suggest that the crystallization of KTP occurs by the reaction between dissolved K(+)(aq), PO(4)(3-)(aq), and [Ti(OH)(x)]((4-x)+)(aq) species.

Serial time-resolved crystallography of photosystem II using a femtosecond X-ray laser

PubMed Central

Kupitz, Christopher; Basu, Shibom; Grotjohann, Ingo; Fromme, Raimund; Zatsepin, Nadia A.; Rendek, Kimberly N.; Hunter, Mark S.; Shoeman, Robert L.; White, Thomas A.; Wang, Dingjie; James, Daniel; Yang, Jay-How; Cobb, Danielle E.; Reeder, Brenda; Sierra, Raymond G.; Liu, Haiguang; Barty, Anton; Aquila, Andrew L.; Deponte, Daniel; Kirian, Richard A.; Bari, Sadia; Bergkamp, Jesse J.; Beyerlein, Kenneth R.; Bogan, Michael J.; Caleman, Carl; Chao, Tzu-Chiao; Conrad, Chelsie E.; Davis, Katherine M.; Fleckenstein, Holger; Galli, Lorenzo; Hau-Riege, Stefan P.; Kassemeyer, Stephan; Laksmono, Hartawan; Liang, Mengning; Lomb, Lukas; Marchesini, Stefano; Martin, Andrew V.; Messerschmidt, Marc; Milathianaki, Despina; Nass, Karol; Ros, Alexandra; Roy-Chowdhury, Shatabdi; Schmidt, Kevin; Seibert, Marvin; Steinbrener, Jan; Stellato, Francesco; Yan, Lifen; Yoon, Chunhong; Moore, Thomas A.; Moore, Ana L.; Pushkar, Yulia; Williams, Garth J.; Boutet, Sébastien; Doak, R. Bruce; Weierstall, Uwe; Frank, Matthias; Chapman, Henry N.; Spence, John C. H.; Fromme, Petra

2015-01-01

Photosynthesis, a process catalysed by plants, algae and cyanobacteria converts sunlight to energy thus sustaining all higher life on Earth. Two large membrane protein complexes, photosystem I and II (PSI and PSII), act in series to catalyse the light-driven reactions in photosynthesis. PSII catalyses the light-driven water splitting process, which maintains the Earth’s oxygenic atmosphere1. In this process, the oxygen-evolving complex (OEC) of PSII cycles through five states, S0 to S4, in which four electrons are sequentially extracted from the OEC in four light-driven charge-separation events. Here we describe time resolved experiments on PSII nano/microcrystals from Thermosynechococcus elongatus performed with the recently developed2 technique of serial femtosecond crystallography. Structures have been determined from PSII in the dark S1 state and after double laser excitation (putative S3 state) at 5 and 5.5 Å resolution, respectively. The results provide evidence that PSII undergoes significant conformational changes at the electron acceptor side and at the Mn4CaO5 core of the OEC. These include an elongation of the metal cluster, accompanied by changes in the protein environment, which could allow for binding of the second substrate water molecule between the more distant protruding Mn (referred to as the ‘dangler’ Mn) and the Mn3CaOx cubane in the S2 to S3 transition, as predicted by spectroscopic and computational studies3,4. This work shows the great potential for time-resolved serial femtosecond crystallography for investigation of catalytic processes in biomolecules. PMID:25043005

Photoelectron diffraction and holography: Some new directions

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

Fadley, C.S.

1993-08-01

Photoelectron diffraction has by now become a versatile and powerful technique for studying surface structures, with special capabilities for resolving chemical and magnetic states of atoms and deriving direct structural information from both forward scattering along bond directions and back-scattering path length differences. Further fitting experiment to theory can lead to structural accuracies in the {plus_minus}0.03 ){Angstrom} range. Holographic inversions of such diffraction data also show considerable promise for deriving local three-dimensional structures around a given emitter with accuracies of {plus_minus}0.2--0.3 {Angstrom}. Resolving the photoelectron spin in some way and using circularly polarized radiation for excitation provide added dimensions formore » the study of magnetic systems and chiral experimental geometries. Synchrotron radiation with the highest brightness and energy resolution, as well as variable polarization, is crucial to the full exploitation of these techniques.« less

Depth-resolved fluorescence of biological tissue

NASA Astrophysics Data System (ADS)

Wu, Yicong; Xi, Peng; Cheung, Tak-Hong; Yim, So Fan; Yu, Mei-Yung; Qu, Jianan Y.

2005-06-01

The depth-resolved autofluorescence ofrabbit oral tissue, normal and dysplastic human ectocervical tissue within l20μm depth were investigated utilizing a confocal fluorescence spectroscopy with the excitations at 355nm and 457nm. From the topmost keratinizing layer of oral and ectocervical tissue, strong keratin fluorescence with the spectral characteristics similar to collagen was observed. The fluorescence signal from epithelial tissue between the keratinizing layer and stroma can be well resolved. Furthermore, NADH and FADfluorescence measured from the underlying non-keratinizing epithelial layer were strongly correlated to the tissue pathology. This study demonstrates that the depth-resolved fluorescence spectroscopy can reveal fine structural information on epithelial tissue and potentially provide more accurate diagnostic information for determining tissue pathology.

An engineering closure for heavily under-resolved coarse-grid CFD in large applications

NASA Astrophysics Data System (ADS)

Class, Andreas G.; Yu, Fujiang; Jordan, Thomas

2016-11-01

Even though high performance computation allows very detailed description of a wide range of scales in scientific computations, engineering simulations used for design studies commonly merely resolve the large scales thus speeding up simulation time. The coarse-grid CFD (CGCFD) methodology is developed for flows with repeated flow patterns as often observed in heat exchangers or porous structures. It is proposed to use inviscid Euler equations on a very coarse numerical mesh. This coarse mesh needs not to conform to the geometry in all details. To reinstall physics on all smaller scales cheap subgrid models are employed. Subgrid models are systematically constructed by analyzing well-resolved generic representative simulations. By varying the flow conditions in these simulations correlations are obtained. These comprehend for each individual coarse mesh cell a volume force vector and volume porosity. Moreover, for all vertices, surface porosities are derived. CGCFD is related to the immersed boundary method as both exploit volume forces and non-body conformal meshes. Yet, CGCFD differs with respect to the coarser mesh and the use of Euler equations. We will describe the methodology based on a simple test case and the application of the method to a 127 pin wire-wrap fuel bundle.

Quantitative analyses of the 3D nuclear landscape recorded with super-resolved fluorescence microscopy.

PubMed

Schmid, Volker J; Cremer, Marion; Cremer, Thomas

2017-07-01

Recent advancements of super-resolved fluorescence microscopy have revolutionized microscopic studies of cells, including the exceedingly complex structural organization of cell nuclei in space and time. In this paper we describe and discuss tools for (semi-) automated, quantitative 3D analyses of the spatial nuclear organization. These tools allow the quantitative assessment of highly resolved different chromatin compaction levels in individual cell nuclei, which reflect functionally different regions or sub-compartments of the 3D nuclear landscape, and measurements of absolute distances between sites of different chromatin compaction. In addition, these tools allow 3D mapping of specific DNA/RNA sequences and nuclear proteins relative to the 3D chromatin compaction maps and comparisons of multiple cell nuclei. The tools are available in the free and open source R packages nucim and bioimagetools. We discuss the use of masks for the segmentation of nuclei and the use of DNA stains, such as DAPI, as a proxy for local differences in chromatin compaction. We further discuss the limitations of 3D maps of the nuclear landscape as well as problems of the biological interpretation of such data. Copyright © 2017 Elsevier Inc. All rights reserved.

REMOVING BIASES IN RESOLVED STELLAR MASS MAPS OF GALAXY DISKS THROUGH SUCCESSIVE BAYESIAN MARGINALIZATION

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

Martínez-García, Eric E.; González-Lópezlira, Rosa A.; Bruzual A, Gustavo

2017-01-20

Stellar masses of galaxies are frequently obtained by fitting stellar population synthesis models to galaxy photometry or spectra. The state of the art method resolves spatial structures within a galaxy to assess the total stellar mass content. In comparison to unresolved studies, resolved methods yield, on average, higher fractions of stellar mass for galaxies. In this work we improve the current method in order to mitigate a bias related to the resolved spatial distribution derived for the mass. The bias consists in an apparent filamentary mass distribution and a spatial coincidence between mass structures and dust lanes near spiral arms.more » The improved method is based on iterative Bayesian marginalization, through a new algorithm we have named Bayesian Successive Priors (BSP). We have applied BSP to M51 and to a pilot sample of 90 spiral galaxies from the Ohio State University Bright Spiral Galaxy Survey. By quantitatively comparing both methods, we find that the average fraction of stellar mass missed by unresolved studies is only half what previously thought. In contrast with the previous method, the output BSP mass maps bear a better resemblance to near-infrared images.« less

Harnessing cell-to-cell variations to probe bacterial structure and biophysics

NASA Astrophysics Data System (ADS)

Cass, Julie A.

Advances in microscopy and biotechnology have given us novel insights into cellular biology and physics. While bacteria were long considered to be relatively unstructured, the development of fluorescence microscopy techniques, and spatially and temporally resolved high-throughput quantitative studies, have uncovered that the bacterial cell is highly organized, and its structure rigorously maintained. In this thesis I will describe our gateTool software, designed to harness cell-to-cell variations to probe bacterial structure, and discuss two exciting aspects of structure that we have employed gateTool to investigate: (i) chromosome organization and the cellular mechanisms for controlling DNA dynamics, and (ii) the study of cell wall synthesis, and how the genes in the synthesis pathway impact cellular shape. In the first project, we develop a spatial and temporal mapping of cell-cycle-dependent chromosomal organization, and use this quantitative map to discover that chromosomal loci segregate from midcell with universal dynamics. In the second project, I describe preliminary time- lapse and snapshot imaging analysis suggesting phentoypical coherence across peptidoglycan synthesis pathways.

Impact of time-resolved MRA on diagnostic accuracy in patients with symptomatic peripheral artery disease of the calf station.

PubMed

Hansmann, Jan; Michaely, Henrik J; Morelli, John N; Diehl, Steffen J; Meyer, Mathias; Schoenberg, Stefan O; Attenberger, Ulrike I

2013-12-01

The purpose of this article is to evaluate the added diagnostic accuracy of time-resolved MR angiography (MRA) of the calves compared with continuous-table-movement MRA in patients with symptomatic lower extremity peripheral artery disease (PAD) using digital subtraction angiography (DSA) correlation. Eighty-four consecutive patients with symptomatic PAD underwent a low-dose 3-T MRA protocol, consisting of continuous-table-movement MRA, acquired from the diaphragm to the calves, and an additional time-resolved MRA of the calves; 0.1 mmol/kg body weight (bw) of contrast material was used (0.07 mmol/kg bw for continuous-table-movement MRA and 0.03 mmol/kg bw for time-resolved MRA). Two radiologists rated image quality on a 4-point scale and stenosis degree on a 3-point scale. An additional assessment determined the degree of venous contamination and whether time-resolved MRA improved diagnostic confidence. The accuracy of stenosis gradation with continuous-table-movement and time-resolved MRA was compared with that of DSA as a correlation. Overall diagnostic accuracy was calculated for continuous-table-movement and time-resolved MRA. Median image quality was rated as good for 578 vessel segments with continuous-table-movement MRA and as excellent for 565 vessel segments with time-resolved MRA. Interreader agreement was excellent (κ = 0.80-0.84). Venous contamination interfered with diagnosis in more than 60% of continuous-table-movement MRA examinations. The degree of stenosis was assessed for 340 vessel segments. The diagnostic accuracies (continuous-table-movement MRA/time-resolved MRA) combined for the readers were obtained for the tibioperoneal trunk (84%/93%), anterior tibial (69%/87%), posterior tibial (85%/91%), and peroneal (67%/81%) arteries. The addition of time-resolved MRA improved diagnostic confidence in 69% of examinations. The addition of time-resolved MRA at the calf station improves diagnostic accuracy over continuous-table-movement MRA alone in symptomatic patients with PAD.

Determination of atomic positions from time resolved high resolution transmission electron microscopy images.

PubMed

Hussaini, Zahra; Lin, Pin Ann; Natarajan, Bharath; Zhu, Wenhui; Sharma, Renu

2018-03-01

For many reaction processes, such as catalysis, phase transformations, nanomaterial synthesis etc., nanoscale observations at high spatial (sub-nanometer) and temporal (millisecond) resolution are required to characterize and comprehend the underlying factors that favor one reaction over another. The combination of such spatial and temporal resolution (up to 600 µs), while rich in information, produces a large number of snapshots, each of which must be analyzed to obtain the structural (and thereby chemical) information. Here we present a methodology for automated quantitative measurement of real-time atomic position fluctuations in a nanoparticle. We leverage a combination of several image processing algorithms to precisely identify the positions of the atomic columns in each image. A geometric model is then used to measure the time-evolution of distances and angles between neighboring atomic columns to identify different phases and quantify local structural fluctuations. We apply this technique to determine the atomic-level fluctuations in the relative fractions of metal and metal-carbide phases in a cobalt catalyst nanoparticle during single-walled carbon nanotube (SWCNT) growth. These measurements provided a means to obtain the number of carbon atoms incorporated into and released from the catalyst particle, thereby helping resolve carbon reaction pathways during SWCNT growth. Further we demonstrate the use of this technique to measure the reaction kinetics of iron oxide reduction. Apart from reducing the data analysis time, the statistical approach allows us to measure atomic distances with sub-pixel resolution. We show that this method can be applied universally to measure atomic positions with a precision of 0.01 nm from any set of atomic-resolution video images. With the advent of high time-resolution direct detection cameras, we anticipate such methods will be essential in addressing the metrology problem of quantifying large datasets of time-resolved images in future. Published by Elsevier B.V.

Time Resolved 3-D Mapping of Atmospheric Aerosols and Clouds During the Recent ARM Water Vapor IOP

NASA Technical Reports Server (NTRS)

Schwemmer, Geary; Miller, David; Wilkerson, Thomas; Andrus, Ionio; Starr, David OC. (Technical Monitor)

2001-01-01

The HARLIE lidar was deployed at the ARM SGP site in north central Oklahoma and recorded over 100 hours of data on 16 days between 17 September and 6 October 2000 during the recent Water Vapor Intensive Operating Period (IOP). Placed in a ground-based trailer for upward looking scanning measurements of clouds and aerosols, HARLIE provided a unique record of time-resolved atmospheric backscatter at 1 micron wavelength. The conical scanning lidar images atmospheric backscatter along the surface of an inverted 90 degree (full angle) cone up to an altitude of 20 km. 360 degree scans having spatial resolutions of 20 meters in the vertical and 1 degree in azimuth were obtained every 36 seconds. Various boundary layer and cloud parameters are derived from the lidar data, as well as atmospheric wind vectors where there is Sufficiently resolved structure that can be traced moving through the surface described by the scanning laser beam. Comparison of HARLIE measured winds with radiosonde measured winds validates the accuracy of this new technique for remotely measuring atmospheric winds without Doppler information.

Novel system for picosecond photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Haight, R.; Silberman, J. A.; Lilie, M. I.

1988-09-01

This article describes a laser-based source and detection scheme for performing time-resolved photoemission studies of materials. The pulsed laser source produces intense picosecond pulses of coherent radiation that are nearly continuously tunable from the near infrared to photon energies up to 13 eV. To achieve high sensitivity, a novel multianode time-of-flight spectrometer has been built that generates an angularly resolved intensity versus kinetic energy spectrum with better than 100-meV resolution. The source and detector provide an opportunity to study the electronic dynamics of excited systems on a picosecond time scale.

Personality Processes: Mechanisms by which Personality Traits “Get Outside the Skin”

PubMed Central

Hampson, Sarah E.

2011-01-01

It is time to better understand why personality traits predict consequential outcomes, which calls for a closer look at personality processes. Personality processes are mechanisms that unfold over time to produce the effects of personality traits. They include reactive and instrumental processes that moderate or mediate the association between traits and outcomes. These mechanisms are illustrated here by a selection of studies of traits representing the three broad domains of personality and temperament: negative emotionality, positive emotionality, and constraint. Personality processes are studied over the short-term, as in event-sampling studies, and over the long-term, as in lifespan research. Implications of findings from the study of processes are considered for resolving issues in models of personality structure, improving and extending methods of personality assessment, and identifying targets for personality interventions. PMID:21740225

Probing Phonon Dynamics in Individual Single-Walled Carbon Nanotubes.

PubMed

Jiang, Tao; Hong, Hao; Liu, Can; Liu, Wei-Tao; Liu, Kaihui; Wu, Shiwei

2018-04-11

Interactions between elementary excitations, such as carriers, phonons, and plasmons, are critical for understanding the optical and electronic properties of materials. The significance of these interactions is more prominent in low-dimensional materials and can dominate their physical properties due to the enhanced interactions between these excitations. One-dimensional single-walled carbon nanotubes provide an ideal system for studying such interactions due to their perfect physical structures and rich electronic properties. Here we investigated G-mode phonon dynamics in individual suspended chirality-resolved single-walled carbon nanotubes by time-resolved anti-Stokes Raman spectroscopy. The improved technique allowed us to probe the intrinsic phonon information on a single-tube level and exclude the influences of tube-tube and tube-substrate interactions. We found that the G-mode phonon lifetime ranges from 0.75-2.25 ps and critically depends on whether the tube is metallic or semiconducting. In comparison with the phonon lifetimes in graphene and graphite, we revealed structure-dependent carrier-phonon and phonon-phonon interactions in nanotubes. Our results provide new information for optimizing the design of nanotube electronic/optoelectronic devices by better understanding and utilizing their phonon decay channels.

Optical studies of the X-ray transient XTE J2123-058 - II. Phase-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Hynes, R. I.; Charles, P. A.; Haswell, C. A.; Casares, J.; Zurita, C.; Serra-Ricart, M.

2001-06-01

We present time-resolved spectroscopy of the soft X-ray transient XTEJ2123-058 in outburst. A useful spectral coverage of 3700-6700Å was achieved spanning two orbits of the binary, with single-epoch coverage extending to ~9000Å. The optical spectrum approximates a steep blue power law, consistent with emission on the Rayleigh-Jeans tail of a hot blackbody spectrum. The strongest spectral lines are Heii 4686Å and Ciii/Niii 4640Å (Bowen blend) in emission. Their relative strengths suggest that XTEJ2123-058 was formed in the Galactic plane, not in the halo. Other weak emission lines of Heii and Civ are present, and Balmer lines show a complex structure, blended with Heii. Heii 4686-Å profiles show a complex multiple S-wave structure, with the strongest component appearing at low velocities in the lower-left quadrant of a Doppler tomogram. Hα shows transient absorption between phases 0.35 and 0.55. Both of these effects appear to be analogous to similar behaviour in SW Sex type cataclysmic variables. We therefore consider whether the spectral line behaviour of XTEJ2123-058 can be explained by the same models invoked for those systems.

Spatially and time resolved kinetics of indirect magnetoexcitons

NASA Astrophysics Data System (ADS)

Hasling, Matthew; Dorow, Chelsey; Calman, Erica; Butov, Leonid; Wilkes, Joe; Campman, Kenneth; Gossard, Arthur

The small exciton mass and binding energy give the opportunity to realize the high magnetic field regime for excitons in magnetic fields of few Tesla achievable in lab Long lifetimes of indirect exciton give the opportunity to study kinetics of magnetoexciton transport by time-resolved optical imaging of exciton emission. We present spatially and time resolved measurements showing the effect of increased magnetic field on transport of magnetoexcitons. We observe that increased magnetic field leads to slowing down of magnetoexciton transport. Supported by NSF Grant No. 1407277. J.W. was supported by the EPSRC (Grant EP/L022990/1). C.J.D. was supported by the NSF Graduate Research Fellowship Program under Grant No. DGE-1144086.

Structural and Sequence Stratigraphic Analysis of the Onshore Nile Delta, Egypt.

NASA Astrophysics Data System (ADS)

Barakat, Moataz; Dominik, Wilhelm

2010-05-01

The Nile Delta is considered the earliest known delta in the world. It was already described by Herodotus in the 5th Century AC. Nowadays; the Nile Delta is an emerging giant gas province in the Middle East with proven gas reserves which have more than doubled in size in the last years. The Nile Delta basin contains a thick sedimentary sequence inferred to extend from Jurassic to recent time. Structural styles and depositional environments varied during this period. Facies architecture and sequence stratigraphy of the Nile Delta are resolved using seismic stratigraphy based on (2D seismic lines) including synthetic seismograms and tying in well log data. Synthetic seismograms were constructed using sonic and density logs. The combination of structural interpretation and sequence stratigraphy of the development of the basin was resolved. Seven chrono-stratigraphic boundaries have been identified and correlated on seismic and well log data. Several unconformity boundaries also identified on seismic lines range from angular to disconformity type. Furthermore, time structure maps, velocity maps, depth structure maps as well as Isopach maps were constructed using seismic lines and log data. Several structural features were identified: normal faults, growth faults, listric faults, secondary antithetic faults and large rotated fault blocks of manly Miocene age. In some cases minor rollover structures could be identified. Sedimentary features such as paleo-channels were distinctively recognized. Typical Sequence stratigraphic features such as incised valley, clinoforms, topsets, offlaps and onlaps are identified and traced on the seismic lines allowing a good insight into sequence stratigraphic history of the Nile Delta most especially in the Miocene to Pliocene clastic sedimentary succession.

Time tracking and interaction of energy-eddies at different scales

NASA Astrophysics Data System (ADS)

Cardesa, Jose I.; Vela-Martin, Alberto; Jimenez, Javier

2016-11-01

We study the energy cascade through coherent structures obtained in time-resolved simulations of incompressible, statistically steady isotropic turbulence. The structures are defined as geometrically connected regions of the flow with high kinetic energy. We compute the latter by band-pass filtering the velocity field around a scale r. We analyse the dynamics of structures extracted with different r, which are a proxy for eddies containing energy at those r. We find that the size of these "energy-eddies" scales with r, while their lifetime scales with the local eddy-turnover r 2 / 3ɛ - 1 / 3 , where ɛ is the energy dissipation averaged over all space and time. Furthermore, a statistical analysis over the lives of the eddies shows a slight predominance of the splitting over the merging process. When we isolate the eddies which do not interact with other eddies of the same scale, we observe a parent-child dependence by which, on average, structures are born at scale r during the decaying part of the life of a structure at scale r' > r . The energy-eddy at r' lives in the same region of space as that at r. Finally, we investigate how interactions between eddies at the same scale are echoed across other scales. Funded by the ERC project Coturb.

Luminescence properties of In(Zn)P alloy core/ZnS shell quantum dots

NASA Astrophysics Data System (ADS)

Thuy, Ung Thi Dieu; Reiss, Peter; Liem, Nguyen Quang

2010-11-01

Chemically synthesized InP/ZnS core/shell quantum dots (QDs) are studied using time-resolved photoluminescence spectroscopy and x-ray diffraction. Zinc stearate, which is added during the synthesis of the InP core, significantly improves the optical characteristics of the QDs. The luminescence quantum yield (QY) reaches 60%-70% and the emission is tunable from 485 to 586 nm by varying the Zn2+:In3+ molar ratio and growth temperature. The observed increased Stokes shift, luminescence decay time, and QY in the presence of Zn are rationalized by the formation of an In(Zn)P alloy structure that causes band-edge fluctuation to enhance the confinement of the excited carriers.

Electron-phonon coupling in graphene placed between magnetic Li and Si layers on cobalt

NASA Astrophysics Data System (ADS)

Usachov, Dmitry Yu.; Fedorov, Alexander V.; Vilkov, Oleg Yu.; Ogorodnikov, Ilya I.; Kuznetsov, Mikhail V.; Grüneis, Alexander; Laubschat, Clemens; Vyalikh, Denis V.

2018-02-01

Using angle-resolved photoemission spectroscopy (ARPES), we study the electronic structure and electron-phonon coupling in a Li-doped graphene monolayer decoupled from the Co(0001) substrate by intercalation of silicon. Based on the photoelectron diffraction measurements, we disclose the structural properties of the Si/Co interface. Our density functional theory calculations demonstrate that in the studied Li/graphene/Si/Co system the magnetism of Co substrate induces notable magnetic moments on Li and Si atoms. At the same time graphene remains almost nonmagnetic and clamped between two magnetically active atomic layers with antiparallel magnetizations. ARPES maps of the graphene Fermi surface reveal strong electron doping, which may lead to superconductivity mediated by electron-phonon coupling (EPC). Analysis of the spectral function of photoelectrons reveals apparent anisotropy of EPC in the k space. These properties make the studied system tempting for studying the relation between superconductivity and magnetism in two-dimensional materials.

Experimental Characterization of the Jet Wiping Process

NASA Astrophysics Data System (ADS)

Mendez, Miguel Alfonso; Enache, Adriana; Gosset, Anne; Buchlin, Jean-Marie

2018-06-01

This paper presents an experimental characterization of the jet wiping process, used in continuous coating applications to control the thickness of a liquid coat using an impinging gas jet. Time Resolved Particle Image Velocimetry (TR-PIV) is used to characterize the impinging gas flow, while an automatic interface detection algorithm is developed to track the liquid interface at the impact. The study of the flow interaction is combined with time resolved 3D thickness measurements of the liquid film remaining after the wiping, via Time Resolved Light Absorption (TR-LAbs). The simultaneous frequency analysis of liquid and gas flows allows to correlate their respective instability, provide an experimental data set for the validation of numerical studies and allows for formulating a working hypothesis on the origin of the coat non-uniformity encountered in many jet wiping processes.

Investigating the 3D Structure of the Winds of Hot Supergiants

NASA Astrophysics Data System (ADS)

Klement, Robert

2018-04-01

An observational effort targeting supergiant stars of spectral classes B and A has been started using the VEGA high spectral resolution visible beam combiner at the CHARA array. The H-alpha emission from the structured stellar winds was resolved with respect to the surrounding continuum, showing signs of inhomogenities in the circumstellar environments as well as temporal variability on different time scales. We have begun a radiative transfer modelling effort to investigate the clumpy structure of the stellar winds and the origin of the inhomogenities, probably linked to the stellar photosphere features.

Resolving International Teaching Assistant Language Inadequacy through Dialogue: Challenges and Opportunities for Clarity and Credibility

ERIC Educational Resources Information Center

Li, Li; Mazer, Joseph P.; Ju, Ran

2011-01-01

Guided by Giddens' structuration theory, this study highlights structures that both enable and constrain nonnative English-speaking teachers and students in American college classrooms. Before international teaching assistants (ITAs) step into their American classrooms, several semishaped class structures are already in place: students (mostly…

NASA CST aids U.S. industry. [computational structures technology

NASA Technical Reports Server (NTRS)

Housner, Jerry M.; Pinson, Larry D.

1993-01-01

The effect of NASA's computational structures Technology (CST) research on aerospace vehicle design and operation is discussed. The application of this research to proposed version of a high-speed civil transport, to composite structures in aerospace, to the study of crack growth, and to resolving field problems is addressed.

Single-Walled Carbon Nanotubes, Carbon Nanofibers and Laser-Induced Incandescence

NASA Technical Reports Server (NTRS)

Schubert, Kathy (Technical Monitor); VanderWal, Randy L.; Ticich, Thomas M.; Berger, Gordon M.; Patel, Premal D.

2004-01-01

Laser induced incandescence applied to a heterogeneous, multi-element reacting flows is characterized by a) temporally resolved emission spectra, time-resolved emission at selected detection wavelengths and fluence dependence. Laser fluences above 0.6 Joules per square centimeter at 1064 nm initiate laser-induced vaporization, yielding a lower incandescence intensity, as found through fluence dependence measurements. Spectrally derived temperatures show that values of excitation laser fluence beyond this value lead to a super-heated plasma, well above the vaporization of temperature of carbon. The temporal evolution of the emission signal at these fluences is consistent with plasma dissipation processes, not incandescence from solid-like structures.

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.

Limitations of heterogeneous models of liquid dynamics: very slow rate exchange in the excess wing.

PubMed

Samanta, Subarna; Richert, Ranko

2014-02-07

For several molecular glass formers, the nonlinear dielectric effects (NDE's) are investigated for the so-called excess wing regime, i.e., for the relatively high frequencies between 10(2) and 10(7) times the peak loss frequency. It is found that significant nonlinear behavior persists across the entire frequency window of this study, and that its magnitude traces the temperature dependence of the activation energy. A time resolved measurement of the dielectric loss at fields up to 480 kV/cm across tens of thousands of periods reveals that it takes an unexpectedly long time for the steady state NDE to develop. For various materials and at different temperatures and frequencies, it is found that the average structural relaxation with time scale τα governs the equilibration of these fast modes that are associated with time constants τ which are up to 10(7) times shorter than τα. It is argued that true indicators of structural relaxation (such as rate exchange and aging) of these fast modes are slaved to macroscopic softening on the time scale of τα, and thus many orders of magnitude slower than the time constant of the mode itself.

X-ray induced dimerization of cinnamic acid: Time-resolved inelastic X-ray scattering study

NASA Astrophysics Data System (ADS)

Inkinen, Juho; Niskanen, Johannes; Talka, Tuomas; Sahle, Christoph J.; Müller, Harald; Khriachtchev, Leonid; Hashemi, Javad; Akbari, Ali; Hakala, Mikko; Huotari, Simo

2015-11-01

A classic example of solid-state topochemical reactions is the ultraviolet-light induced photodimerization of α-trans-cinnamic acid (CA). Here, we report the first observation of an X-ray-induced dimerization of CA and monitor it in situ using nonresonant inelastic X-ray scattering spectroscopy (NRIXS). The time-evolution of the carbon core-electron excitation spectra shows the effects of two X-ray induced reactions: dimerization on a short time-scale and disintegration on a long time-scale. We used spectrum simulations of CA and its dimerization product, α-truxillic acid (TA), to gain insight into the dimerization effects. From the time-resolved spectra, we extracted component spectra and time-dependent weights corresponding to CA and TA. The results suggest that the X-ray induced dimerization proceeds homogeneously in contrast to the dimerization induced by ultraviolet light. We also utilized the ability of NRIXS for direct tomography with chemical-bond contrast to image the spatial progress of the reactions in the sample crystal. Our work paves the way for other time-resolved studies on chemical reactions using inelastic X-ray scattering.

X-ray induced dimerization of cinnamic acid: Time-resolved inelastic X-ray scattering study

PubMed Central

Inkinen, Juho; Niskanen, Johannes; Talka, Tuomas; Sahle, Christoph J.; Müller, Harald; Khriachtchev, Leonid; Hashemi, Javad; Akbari, Ali; Hakala, Mikko; Huotari, Simo

2015-01-01

A classic example of solid-state topochemical reactions is the ultraviolet-light induced photodimerization of α-trans-cinnamic acid (CA). Here, we report the first observation of an X-ray-induced dimerization of CA and monitor it in situ using nonresonant inelastic X-ray scattering spectroscopy (NRIXS). The time-evolution of the carbon core-electron excitation spectra shows the effects of two X-ray induced reactions: dimerization on a short time-scale and disintegration on a long time-scale. We used spectrum simulations of CA and its dimerization product, α-truxillic acid (TA), to gain insight into the dimerization effects. From the time-resolved spectra, we extracted component spectra and time-dependent weights corresponding to CA and TA. The results suggest that the X-ray induced dimerization proceeds homogeneously in contrast to the dimerization induced by ultraviolet light. We also utilized the ability of NRIXS for direct tomography with chemical-bond contrast to image the spatial progress of the reactions in the sample crystal. Our work paves the way for other time-resolved studies on chemical reactions using inelastic X-ray scattering. PMID:26568420

Development of a New Time-Resolved Laser-Induced Fluorescence Technique

NASA Astrophysics Data System (ADS)

Durot, Christopher; Gallimore, Alec

2012-10-01

We are developing a time-resolved laser-induced fluorescence (LIF) technique to interrogate the ion velocity distribution function (VDF) of EP thruster plumes down to the microsecond time scale. Better measurements of dynamic plasma processes will lead to improvements in simulation and prediction of thruster operation and erosion. We present the development of the new technique and results of initial tests. Signal-to-noise ratio (SNR) is often a challenge for LIF studies, and it is only more challenging for time-resolved measurements since a lock-in amplifier cannot be used with a long time constant. The new system uses laser modulation on the order of MHz, which enables the use of electronic filtering and phase-sensitive detection to improve SNR while preserving time-resolved information. Statistical averaging over many cycles to further improve SNR is done in the frequency domain. This technique can have significant advantages, including (1) larger spatial maps enabled by shorter data acquisition time and (2) the ability to average data without creating a phase reference by modifying the thruster operating condition with a periodic cutoff in discharge current, which can modify the ion velocity distribution.

Bypassing the energy-time uncertainty in time-resolved photoemission

NASA Astrophysics Data System (ADS)

Randi, Francesco; Fausti, Daniele; Eckstein, Martin

2017-03-01

The energy-time uncertainty is an intrinsic limit for time-resolved experiments imposing a tradeoff between the duration of the light pulses used in experiments and their frequency content. In standard time-resolved photoemission, this limitation maps directly onto a tradeoff between the time resolution of the experiment and the energy resolution that can be achieved on the electronic spectral function. Here we propose a protocol to disentangle the energy and time resolutions in photoemission. We demonstrate that dynamical information on all time scales can be retrieved from time-resolved photoemission experiments using suitably shaped light pulses of quantum or classical nature. As a paradigmatic example, we study the dynamical buildup of the Kondo peak, a narrow feature in the electronic response function arising from the screening of a magnetic impurity by the conduction electrons. After a quench, the electronic screening builds up on timescales shorter than the inverse width of the Kondo peak and we demonstrate that the proposed experimental scheme could be used to measure the intrinsic time scales of such electronic screening. The proposed approach provides an experimental framework to access the nonequilibrium response of collective electronic properties beyond the spectral uncertainty limit and will enable the direct measurement of phenomena such as excited Higgs modes and, possibly, the retarded interactions in superconducting systems.

Real-time observation of cascaded electronic relaxation processes in p-Fluorotoluene

NASA Astrophysics Data System (ADS)

Hao, Qiaoli; Deng, Xulan; Long, Jinyou; Wang, Yanmei; Abulimiti, Bumaliya; Zhang, Bing

2017-08-01

Ultrafast electronic relaxation processes following two photoexcitation of 400 nm in p-Fluorotoluene (pFT) have been investigated utilizing time-resolved photoelectron imaging coupled with time-resolved mass spectroscopy. Cascaded electronic relaxation processes started from the electronically excited S2 state are directly imaged in real time and well characterized by two distinct time constants of 85 ± 10 fs and 2.4 ± 0.3 ps. The rapid component corresponds to the lifetime of the initially excited S2 state, including the structure relaxation from the Franck-Condon region to the conical intersection of S2/S1 and the subsequent internal conversion to the highly excited S1 state. While, the slower relaxation constant is attributed to the further internal conversion to the high levels of S0 from the secondarily populated S1 locating in the channel three region. Moreover, dynamical differences with benzene and toluene of analogous structures, including, specifically, the slightly slower relaxation rate of S2 and the evidently faster decay of S1, are also presented and tentatively interpreted as the substituent effects. In addition, photoelectron kinetic energy and angular distributions reveal the feature of accidental resonances with low-lying Rydberg states (the 3p, 4s and 4p states) during the multi-photon ionization process, providing totally unexpected but very interesting information for pFT.

Seventh international conference on time-resolved vibrational spectroscopy

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

Dyer, R.B.; Martinez, M.A.D.; Shreve, A.

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 formore » 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.« less

Extremal inversion of lunar travel time data. [seismic velocity structure

NASA Technical Reports Server (NTRS)

Burkhard, N.; Jackson, D. D.

1975-01-01

The tau method, developed by Bessonova et al. (1974), of inversion of travel times is applied to lunar P-wave travel time data to find limits on the velocity structure of the moon. Tau is the singular solution to the Clairaut equation. Models with low-velocity zones, with low-velocity zones at differing depths, and without low-velocity zones, were found to be consistent with data and within the determined limits. Models with and without a discontinuity at about 25-km depth have been found which agree with all travel time data to within two standard deviations. In other words, the existence of the discontinuity and its size and location have not been uniquely resolved. Models with low-velocity channels are also possible.

Can Positron 2D-ACAR Resolve the Electronic Structure of HIGH-Tc Superconductors?

NASA Astrophysics Data System (ADS)

Chan, L. P.; Lynn, K. G.; Harshman, D. R.

We examine the ability of the positron Two-Dimensional Angular Correlation Annihilation Radiation (2D-ACAR) technique to resolve the electronic structures of high-Tc cuprate superconductors. Following a short description of the technique, discussions of the theoretical assumptions, data analysis and experimental considerations, in relation to the high-Tc superconductors, are given. We briefly review recent 2D-ACAR experiments on YBa2Cu3O7-x, Bi2Sr2CaCuO8+δ and La2-xSrxCuO4. The 2D-ACAR technique is useful in resolving the band crossings associated with the layers of the superconductors that are preferentially sampled by the positrons. Together with other Fermi surface measurements (namely angle-resolved photoemission), 2D-ACAR can resolve some of the electronic structures of high-Tc cuprate superconductors. In addition, 2D-ACAR measurements of YBa2Cu3O7-x and Bi2Sr2CaCuO8+δ also reveal an interesting temperature dependence in the fine structures, and a change in the positron lifetime in the former.

Development of 2D imaging of SXR plasma radiation by means of GEM detectors

NASA Astrophysics Data System (ADS)

Chernyshova, M.; Czarski, T.; Jabłoński, S.; Kowalska-Strzeciwilk, E.; Poźniak, K.; Kasprowicz, G.; Zabołotny, W.; Wojeński, A.; Byszuk, A.; Burza, M.; Juszczyk, B.; Zienkiewicz, P.

2014-11-01

Presented 2D gaseous detector system has been developed and designed to provide energy resolved fast dynamic plasma radiation imaging in the soft X-Ray region with 0.1 kHz exposure frequency for online, made in real time, data acquisition (DAQ) mode. The detection structure is based on triple Gas Electron Multiplier (GEM) amplification structure followed by the pixel readout electrode. The efficiency of detecting unit was adjusted for the radiation energy region of tungsten in high-temperature plasma, the main candidate for the plasma facing material for future thermonuclear reactors. Here we present preliminary laboratory results and detector parameters obtained for the developed system. The operational characteristics and conditions of the detector were designed to work in the X-Ray range of 2-17 keV. The detector linearity was checked using the fluorescence lines of different elements and was found to be sufficient for good photon energy reconstruction. Images of two sources through various screens were performed with an X-Ray laboratory source and 55Fe source showing a good imaging capability. Finally offline stream-handling data acquisition mode has been developed for the detecting system with timing down to the ADC sampling frequency rate (~13 ns), up to 2.5 MHz of exposure frequency, which could pave the way to invaluable physics information about plasma dynamics due to very good time resolving ability. Here we present results of studied spatial resolution and imaging properties of the detector for conditions of laboratory moderate counting rates and high gain.

Estimated phase transition and melting temperature of APTES self-assembled monolayer using surface-enhanced anti-stokes and stokes Raman scattering

NASA Astrophysics Data System (ADS)

Sun, Yingying; Yanagisawa, Masahiro; Kunimoto, Masahiro; Nakamura, Masatoshi; Homma, Takayuki

2016-02-01

A structure's temperature can be determined from the Raman spectrum using the frequency and the ratio of the intensities of the anti-Stokes and Stokes signals (the Ias/Is ratio). In this study, we apply this approach and an equation relating the temperature, Raman frequency, and Ias/Is ratio to in-situ estimation of the phase change point of a (3-aminopropyl)triethoxysilane self-assembled monolayer (APTES SAM). Ag nanoparticles were deposited on APTES to enhance the Raman signals. A time-resolved measurement mode was used to monitor the variation in the Raman spectra in situ. Moreover, the structural change in APTES SAM (from ordered to disordered structure) under heating was discussed in detail, and the phase change point (around 118 °C) was calculated.

Investigation of trapping levels in p-type Zn3P2 nanowires using transport and optical properties

NASA Astrophysics Data System (ADS)

Lombardi, G. A.; de Oliveira, F. M.; Teodoro, M. D.; Chiquito, A. J.

2018-05-01

Here, we report the synthesis and structural characterization of high-quality Zn3P2 nanowires via chemical vapour deposition. Structural and morphological characterization studies revealed a reliable growth process of long, uniform, and single-crystalline nanowires. From temperature dependent transport and photoluminescence measurements, we have observed the contribution of different acceptor levels (15, 50, 70, 90, and 197 meV) to the conduction mechanisms. These levels were associated with zinc vacancies and phosphorous interstitial atoms which assigned a p-type character to this semiconductor. From time resolved photoluminescence experiments, a 91 ps lifetime decay was found. Such a fast lifetime decay is in agreement with the exciton transition along the bulk emission from high quality crystalline nanowires.

Towards Measurement of the Time-resolved Heat Release of Protein Conformation Dynamics

NASA Technical Reports Server (NTRS)

Puchalla, Jason; Adamek, Daniel; Austin, Robert

2004-01-01

We present a way to observe time-resolved heat release using a laminar flow diffusional mixer coupled with a highly sensitive infrared camera which measures the temperature change of the solvent. There are significant benefits to the use of laminar flow mixers for time-resolved calorimetry: (1) The thermal signal can be made position and time- stationary to allow for signal integration; (2) Extremely small volumes (nl/s) of sample are required for a measurement; (3) The same mixing environment can be observed spectroscopically to obtain state occupation information; (4) The mixer allows one to do out of equilibrium dynamic studies. The hope is that these measurements will allow us probe the non-equilibrium thermodynamics as a protein moves along a free energy trajectory from one state to another.

Garry Rumbles | NREL

Science.gov Websites

, colloidal quantum dots, and single-walled carbon nanotubes. Laser-based experiments (time-resolved fluorescence spectroscopy; time-resolved resonance Raman spectroscopy; laser-induced fluorescence spectroscopy ; time-resolved evanescent wave-induced fluorescence spectroscopy; picosecond coherent anti-Stokes Raman

The effect of sulfated polysaccharides on the crystallization of calcite superstructures

NASA Astrophysics Data System (ADS)

Fried, Ruth; Mastai, Yitzhak

2012-01-01

Calcite with unique morphology and uniform size has been successfully synthesized in the presence of classes of polysaccharides based on carrageenans. In the crystallization of calcite, the choice of different carrageenans, (iota, lambda and kappa), as additives concedes systematic study of the influence of different chemical structures and particularly molecular charge on the formation of CaCO 3 crystals. The uniform calcite superstructures are formed by assemblies and aggregation of calcite crystals. The mechanism for the formation of calcite superstructures was studied by a variety of techniques, SEM, TEM, XRD, time-resolved conductivity and light scattering measurements, focusing on the early stages of crystals' nucleation and aggregation.

Resolved simulations of a granular-fluid flow through a check dam with a SPH-DCDEM model

NASA Astrophysics Data System (ADS)

Birjukovs Canelas, Ricardo; Domínguez, Jose; Crespo, Alejandro; Gómez-Gesteira, Moncho; Ferreira, Rui M. L.

2017-04-01

Debris flows represent some of the most relevant phenomena in geomorphological events. Due to the potential destructiveness of such flows, they are the target of a vast amount of research. Experimental research in laboratory facilities or in the field is fundamental to characterize the fundamental rheological properties of these flows and to provide insights on its structure. However, characterizing interparticle contacts and the structure of the motion of the granular phase is difficult, even in controlled laboratory conditions, and possible only for simple geometries. This work addresses the need for a numerical simulation tool applicable to granular-fluid mixtures featuring high spatial and temporal resolution, thus capable of resolving the motion of individual particles, including all interparticle contacts and susceptible to complement laboratory research. The DualSPHysics meshless numerical implementation based on Smoothed Particle Hydrodynamics (SPH) is expanded with a Distributed Contact Discrete Element Method (DCDEM) in order to explicitly solve the fluid and the solid phase. The specific objective is to test the SPH-DCDEM approach by comparing its results with experimental data. An experimental set-up for stony debris flows in a slit check dam is reproduced numerically, where solid material is introduced through a hopper assuring a constant solid discharge for the considered time interval. With each sediment particle possibly undergoing several simultaneous contacts, thousands of time-evolving interactions are efficiently treated due to the model's algorithmic structure and the HPC implementation of DualSPHysics. The results, comprising mainly of retention curves, are in good agreement with the measurements, correctly reproducing the changes in efficiency with slit spacing and density. The encouraging results, coupled with the prospect of so far unique insights into the internal dynamics of a debris flow show the potential of high-performance resolved approaches to the description of the flow and the study of its mitigation strategies. This research as partially supported by Portuguese and European funds, within programs COMPETE2020 and PORL-FEDER, through project PTDC/ECM-HID/6387/2014 granted by the National Foundation for Science and Technology (FCT).

Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

NASA Astrophysics Data System (ADS)

Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

2013-10-01

Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the carotenoid conjugated chain have been assigned with the aid of quantum chemical calculation. DFT predictions of the electronic structure of the carotenoid triplet state, in terms of spin density distribution, frontier orbital description and orbital excitation represent suitable building blocks toward a deeper understanding of electronic requirements for efficient TTET.

Effect of randomness on multi-frequency aeroelastic responses resolved by Unsteady Adaptive Stochastic Finite Elements

NASA Astrophysics Data System (ADS)

Witteveen, Jeroen A. S.; Bijl, Hester

2009-10-01

The Unsteady Adaptive Stochastic Finite Elements (UASFE) method resolves the effect of randomness in numerical simulations of single-mode aeroelastic responses with a constant accuracy in time for a constant number of samples. In this paper, the UASFE framework is extended to multi-frequency responses and continuous structures by employing a wavelet decomposition pre-processing step to decompose the sampled multi-frequency signals into single-frequency components. The effect of the randomness on the multi-frequency response is then obtained by summing the results of the UASFE interpolation at constant phase for the different frequency components. Results for multi-frequency responses and continuous structures show a three orders of magnitude reduction of computational costs compared to crude Monte Carlo simulations in a harmonically forced oscillator, a flutter panel problem, and the three-dimensional transonic AGARD 445.6 wing aeroelastic benchmark subject to random fields and random parameters with various probability distributions.

Quantitative mass imaging of single biological macromolecules.

PubMed

Young, Gavin; Hundt, Nikolas; Cole, Daniel; Fineberg, Adam; Andrecka, Joanna; Tyler, Andrew; Olerinyova, Anna; Ansari, Ayla; Marklund, Erik G; Collier, Miranda P; Chandler, Shane A; Tkachenko, Olga; Allen, Joel; Crispin, Max; Billington, Neil; Takagi, Yasuharu; Sellers, James R; Eichmann, Cédric; Selenko, Philipp; Frey, Lukas; Riek, Roland; Galpin, Martin R; Struwe, Weston B; Benesch, Justin L P; Kukura, Philipp

2018-04-27

The cellular processes underpinning life are orchestrated by proteins and their interactions. The associated structural and dynamic heterogeneity, despite being key to function, poses a fundamental challenge to existing analytical and structural methodologies. We used interferometric scattering microscopy to quantify the mass of single biomolecules in solution with 2% sequence mass accuracy, up to 19-kilodalton resolution, and 1-kilodalton precision. We resolved oligomeric distributions at high dynamic range, detected small-molecule binding, and mass-imaged proteins with associated lipids and sugars. These capabilities enabled us to characterize the molecular dynamics of processes as diverse as glycoprotein cross-linking, amyloidogenic protein aggregation, and actin polymerization. Interferometric scattering mass spectrometry allows spatiotemporally resolved measurement of a broad range of biomolecular interactions, one molecule at a time. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Optical diagnostics of turbulent mixing in explosively-driven shock tube

NASA Astrophysics Data System (ADS)

Anderson, James; Hargather, Michael

2016-11-01

Explosively-driven shock tube experiments were performed to investigate the turbulent mixing of explosive product gases and ambient air. A small detonator initiated Al / I2O5 thermite, which produced a shock wave and expanding product gases. Schlieren and imaging spectroscopy were applied simultaneously along a common optical path to identify correlations between turbulent structures and spatially-resolved absorbance. The schlieren imaging identifies flow features including shock waves and turbulent structures while the imaging spectroscopy identifies regions of iodine gas presence in the product gases. Pressure transducers located before and after the optical diagnostic section measure time-resolved pressure. Shock speed is measured from tracking the leading edge of the shockwave in the schlieren images and from the pressure transducers. The turbulent mixing characteristics were determined using digital image processing. Results show changes in shock speed, product gas propagation, and species concentrations for varied explosive charge mass. Funded by DTRA Grant HDTRA1-14-1-0070.