Site-Specific Dynamics of β-Sheet Peptides with (D) Pro-Gly Turns Probed by Laser-Excited Temperature-Jump Infrared Spectroscopy.

PubMed

Popp, Alexander; Scheerer, David; Chi, Heng; Keiderling, Timothy A; Hauser, Karin

2016-05-04

Turn residues and side-chain interactions play an important role for the folding of β-sheets. We investigated the conformational dynamics of a three-stranded β-sheet peptide ((D) P(D) P) and a two-stranded β-hairpin (WVYY-(D) P) by time-resolved temperature-jump (T-jump) infrared spectroscopy. Both peptide sequences contain (D) Pro-Gly residues that favor a tight β-turn. The three-stranded β-sheet (Ac-VFITS(D) PGKTYTEV(D) PGOKILQ-NH2 ) is stabilized by the turn sequences, whereas the β-hairpin (SWTVE(D) PGKYTYK-NH2 ) folding is assisted by both the turn sequence and hydrophobic cross-strand interactions. Relaxation times after the T-jump were monitored as a function of temperature and occur on a sub-microsecond time scale, (D) P(D) P being faster than WVYY-(D) P. The Xxx-(D) Pro tertiary amide provides a detectable IR band, allowing us to probe the dynamics site-specifically. The relative importance of the turn versus the intrastrand stability in β-sheet formation is discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Localized, gradient-reversed ultrafast z-spectroscopy in vivo at 7T.

PubMed

Wilson, Neil E; D'Aquilla, Kevin; Debrosse, Catherine; Hariharan, Hari; Reddy, Ravinder

2016-10-01

To collect ultrafast z-spectra in vivo in situations where voxel homogeneity cannot be assured. Saturating in the presence of a gradient encodes the frequency offset spatially across a voxel. This encoding can be resolved by applying a similar gradient during readout. Acquiring additional scans with the gradient polarity reversed effectively mirrors the spatial locations of the frequency offsets so that the same physical location of a positive offset in the original scan will contribute a negative offset in the gradient-reversed scan. Gradient-reversed ultrafast z-spectroscopy (GRUFZS) was implemented and tested in a modified, localized PRESS sequence at 7T. Lysine phantoms were scanned at various concentrations and compared with coventionally-acquired z-spectra. Scans were acquired in vivo in human brain from homogeneous and inhomogeneous voxels with the ultrafast direction cycled between read, phase, and slice. Results were compared to those from a similar conventional z-spectroscopy PRESS-based sequence. Asymmetry spectra from GRUFZS are more consistent and reliable than those without gradient reversal and are comparable to those from conventional z-spectroscopy. GRUFZS offers significant acceleration in data acquisition compared to traditional chemical exchange saturation transfer methods with high spectral resolution and showed higher relative SNR effficiency. GRUFZS offers a method of collecting ultrafast z-spectra in voxels with the inhomogeneity often found in vivo. Magn Reson Med 76:1039-1046, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Temporally and Spatially Resolved Plasma Spectroscopy in Pulsed Laser Deposition of Ultra-Thin Boron Nitride Films (Postprint)

DTIC Science & Technology

2015-04-24

AFRL-RX-WP-JA-2016-0196 TEMPORALLY AND SPATIALLY RESOLVED PLASMA SPECTROSCOPY IN PULSED LASER DEPOSITION OF ULTRA-THIN BORON NITRIDE...AND SPATIALLY RESOLVED PLASMA SPECTROSCOPY IN PULSED LASER DEPOSITION OF ULTRA-THIN BORON NITRIDE FILMS (POSTPRINT) 5a. CONTRACT NUMBER FA8650...distributions within a PVD plasma plume ablated from a boron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated

A Rapidly Moving Shell in the Orion Nebula

NASA Technical Reports Server (NTRS)

Walter, Donald K.; O'Dell, C. R.; Hu, Xihai; Dufour, Reginald J.

1995-01-01

A well-resolved elliptical shell in the inner Orion Nebula has been investigated by monochromatic imaging plus high- and low-resolution spectroscopy. We find that it is of low ionization and the two bright ends are moving at -39 and -49 km/s with respect to OMC-1. There is no central object, even in the infrared J bandpass although H2 emission indicates a possible association with the nearby very young pre-main-sequence star J&W 352, which is one of the youngest pre-main-sequence stars in the inner Orion Nebula. Many of the characteristics of this object (low ionization, blue shift) are like those of the Herbig-Haro objects, although the symmetric form would make it an unusual member of that class.

[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.

Multicolor Photometry and Time-resolved Spectroscopy of Two sdBV Stars

NASA Astrophysics Data System (ADS)

Reed, M. D.; O'Toole, S. J.; Telting, J. H.; Østensen, R. H.; Heber, U.; Barlow, B. N.; Reichart, D. E.; Nysewander, M. C.; LaCluyze, A. P.; Ivarsen, K. M.; Haislip, J. B.; Bean, J.

2012-03-01

Observational mode constraints have mostly been lacking for short period pulsating sdB stars, yet such identifications are vital to constrain models. Time-resolved spectroscopy and multicolor photometry have been employed with mixed results for short-period pulsating sdB stars. Time-resolved spectroscopy has successfully measured radial velocity, temperature, and gravity variations in six pulsators, yet interpreting results is far from straightforward. Multicolor photometry requires extremely high precision to discern between low-degree modes, yet has been used effectively to eliminate high-degree modes. Combining radial velocity (RV) and multicolor measurements has also been shown as an effective means of constraining mode identifications. We present preliminary results for Feige 48 and EC 01541-1409 using both time-resolved spectroscopy and multicolor photometry and an initial examination of their pulsation modes using the atmospheric codes BRUCE and KYLIE.

Introduction to Time-Resolved Spectroscopy: Nanosecond Transient Absorption and Time-Resolved Fluorescence of Eosin B

ERIC Educational Resources Information Center

Farr, Erik P.; Quintana, Jason C.; Reynoso, Vanessa; Ruberry, Josiah D.; Shin, Wook R.; Swartz, Kevin R.

2018-01-01

Here we present a new undergraduate laboratory that will introduce the concepts of time-resolved spectroscopy and provide insight into the natural time scales on which chemical dynamics occur through direct measurement. A quantitative treatment of the acquired data will provide a deeper understanding of the role of quantum mechanics and various…

Fast T2*-weighted MRI of the prostate at 3 Tesla.

PubMed

Hardman, Rulon L; El-Merhi, Fadi; Jung, Adam J; Ware, Steve; Thompson, Ian M; Friel, Harry T; Peng, Qi

2011-04-01

To describe a rapid T2*-weighted (T2*W), three-dimensional (3D) echo planar imaging (EPI) sequence and its application in mapping local magnetic susceptibility variations in 3 Tesla (T) prostate MRI. To compare the sensitivity of T2*W EPI with routinely used T1-weighted turbo-spin echo sequence (T1W TSE) in detecting hemorrhage and the implications on sequences sensitive to field inhomogeneities such as MR spectroscopy (MRS). B(0) susceptibility weighted mapping was performed using a 3D EPI sequence featuring a 2D spatial excitation pulse with gradients of spiral k-space trajectory. A series of 11 subjects were imaged using 3T MRI and combination endorectal (ER) and six-channel phased array cardiac coils. T1W TSE and T2*W EPI sequences were analyzed quantitatively for hemorrhage contrast. Point resolved spectroscopy (PRESS MRS) was performed and data quality was analyzed. Two types of susceptibility variation were identified: hemorrhagic and nonhemorrhagic T2*W-positive areas. Post-biopsy hemorrhage lesions showed on average five times greater contrast on the T2*W images than T1W TSE images. Six nonhemorrhage regions of severe susceptibility artifact were apparent on the T2*W images that were not seen on standard T1W or T2W images. All nonhemorrhagic susceptibility artifact regions demonstrated compromised spectral quality on 3D MRS. The fast T2*W EPI sequence identifies hemorrhagic and nonhemorrhagic areas of susceptibility variation that may be helpful in prostate MRI planning at 3.0T. Copyright © 2011 Wiley-Liss, Inc.

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.

Time-resolved X-Ray Absorption Spectroscopy of a Cobalt-Based Hydrogen Evolution System for Artificial Photosynthesis

NASA Astrophysics Data System (ADS)

Moonshiram, Dooshaye; Gimbert, Carolina; Lehmann, Carl; Southworth, Stephen; Llobet, Antoni; Argonne National Laboratory Team; Institut Català d'Investigació Química Collaboration

2015-03-01

Production of cost-effective hydrogen gas through solar power is an important challenge of the Department of Energy among other global industry initiatives. In natural photosynthesis, the oxygen evolving complex(OEC) can carry out four-electron water splitting to hydrogen with an efficiency of around 60%. Although, much progress has been carried out in determining mechanistic pathways of the OEC, biomimetic approaches have not duplicated Nature's efficiency in function. Over the past years, we have witnessed progress in developments of light harvesting modules, so called chromophore/catalytic assemblies. In spite of reportedly high catalytic activity of these systems, quantum yields of hydrogen production are below 40 % when using monochromatic light. Proper understanding of kinetics and bond making/breaking steps has to be achieved to improve efficiency of hydrogen evolution systems. This project shows the timing implementation of ultrafast X-ray absorption spectroscopy to visualize in ``real time'' the photo-induced kinetics accompanying a sequence of redox reactions in a cobalt-based molecular photocatalytic system. Formation of a Co(I) species followed by a Co(III) hydride species all the way towards hydrogen evolution is shown through time-resolved XANES.

Time-resolved Spectroscopy and Multi-color Photometry Of The Pulsating and Short-period Binary Subdwarf B Star Feige 48

NASA Astrophysics Data System (ADS)

Reed, Mike; Baran, A.; O'Toole, S.

2012-05-01

Pulsating subdwarf B (sdB) stars can be used as probes of the helium fusing cores of horizontal branch stars. To probe these stars, asteroseismology must be able to observationally associate pulsation frequencies with modes. Time-resolved spectroscopy and multicolor photometry have been employed with mixed results for short-period pulsating sdB stars. Time-resolved spectroscopy has successfully measured radial velocity, temperature, and gravity variations in six pulsators, yet interpreting results is far from straightforward. Multicolor photometry requires extremely high precision to discern between low-degree modes, yet has been used effectively to eliminate high-degree modes. Combining RV and multicolor measurements has also been shows as an effective means of constraining mode identifications. I will present results for Feige 48 using both time-resolved spectroscopy and multicolor photometry and attempts to constrain their pulsation modes using the atmospheric codes BRUCE and KYLIE.

Simultaneous observation of glutamate, gamma-aminobutyric acid, and glutamine in human brain at 4.7 T using localized two-dimensional constant-time correlation spectroscopy.

PubMed

Watanabe, H; Takaya, N; Mitsumori, F

2008-06-01

Localized two-dimensional constant-time correlation spectroscopy (CT-COSY) was used to resolve glutamate (Glu), gamma-aminobutyric acid (GABA), and glutamine (Gln) in the human brain at 4.7 T. In this method, three-dimensional localization was achieved using three radio frequency pulses of the CT-COSY module for slice selection. As this sequence could decouple JHH along the F1 direction, peak resolution of metabolites was improved even on a magnitude-mode display. In experiments on a phantom containing N-acetylaspartate, creatine, Glu, Gln, and GABA with a constant time delay (Tct) of 110 ms, cross peaks of Glu, Gln, and GABA were obtained on a spectrum processed with standard sine-bell windows, which emphasize sine-dependent signals along the t2 direction. In contrast, diagonal peaks of Glu C4H at 2.35 ppm, GABA C2H at 2.28 ppm, and Gln C4H at 2.44 ppm were resolved on a spectrum processed with Gaussian windows, which emphasize cosine-dependent signals along t2. Human brain spectra were obtained from a 27 mL voxel within the parieto-occipital region using a volume transverse electromagnetic (TEM) coil for both transmission and reception. Tct was 110 ms; the total scan time was 30 min. Diagonal peaks of Glu C4H, GABA C2H, and Gln C4H were also resolved on the spectrum processed with Gaussian windows. These results show that the localized two-dimensional CT-COSY method featuring 1H decoupling along the F1 direction could resolve Glu, GABA, and Gln signals in the human brain. Copyright (c) 2008 John Wiley & Sons, Ltd.

High-Resolution Two-Dimensional Optical Spectroscopy of Electron Spins

NASA Astrophysics Data System (ADS)

Salewski, M.; Poltavtsev, S. V.; Yugova, I. A.; Karczewski, G.; Wiater, M.; Wojtowicz, T.; Yakovlev, D. R.; Akimov, I. A.; Meier, T.; Bayer, M.

2017-07-01

Multidimensional coherent optical spectroscopy is one of the most powerful tools for investigating complex quantum mechanical systems. While it was conceived decades ago in magnetic resonance spectroscopy using microwaves and radio waves, it has recently been extended into the visible and UV spectral range. However, resolving MHz energy splittings with ultrashort laser pulses still remains a challenge. Here, we analyze two-dimensional Fourier spectra for resonant optical excitation of resident electrons to localized trions or donor-bound excitons in semiconductor nanostructures subject to a transverse magnetic field. Particular attention is devoted to Raman coherence spectra, which allow one to accurately evaluate tiny splittings of the electron ground state and to determine the relaxation times in the electron spin ensemble. A stimulated steplike Raman process induced by a sequence of two laser pulses creates a coherent superposition of the ground-state doublet which can be retrieved only optically because of selective excitation of the same subensemble with a third pulse. This provides the unique opportunity to distinguish between different complexes that are closely spaced in energy in an ensemble. The related experimental demonstration is based on photon-echo measurements in an n -type CdTe /(Cd ,Mg )Te quantum-well structure detected by a heterodyne technique. The difference in the sub-μ eV range between the Zeeman splittings of donor-bound electrons and electrons localized at potential fluctuations can be resolved even though the homogeneous linewidth of the optical transitions is larger by 2 orders of magnitude.

Localized 2D COSY sequences: Method and experimental evaluation for a whole metabolite quantification approach

NASA Astrophysics Data System (ADS)

Martel, Dimitri; Tse Ve Koon, K.; Le Fur, Yann; Ratiney, Hélène

2015-11-01

Two-dimensional spectroscopy offers the possibility to unambiguously distinguish metabolites by spreading out the multiplet structure of J-coupled spin systems into a second dimension. Quantification methods that perform parametric fitting of the 2D MRS signal have recently been proposed for resolved PRESS (JPRESS) but not explicitly for Localized Correlation Spectroscopy (LCOSY). Here, through a whole metabolite quantification approach, correlation spectroscopy quantification performances are studied. The ability to quantify metabolite relaxation constant times is studied for three localized 2D MRS sequences (LCOSY, LCTCOSY and the JPRESS) in vitro on preclinical MR systems. The issues encountered during implementation and quantification strategies are discussed with the help of the Fisher matrix formalism. The described parameterized models enable the computation of the lower bound for error variance - generally known as the Cramér Rao bounds (CRBs), a standard of precision - on the parameters estimated from these 2D MRS signal fittings. LCOSY has a theoretical net signal loss of two per unit of acquisition time compared to JPRESS. A rapid analysis could point that the relative CRBs of LCOSY compared to JPRESS (expressed as a percentage of the concentration values) should be doubled but we show that this is not necessarily true. Finally, the LCOSY quantification procedure has been applied on data acquired in vivo on a mouse brain.

Space- and time-resolved raman and breakdown spectroscopy: advanced lidar techniques

NASA Astrophysics Data System (ADS)

Silviu, Gurlui; Marius Mihai, Cazacu; Adrian, Timofte; Oana, Rusu; Georgiana, Bulai; Dimitriu, Dan

2018-04-01

DARLIOES - the advanced LIDAR is based on space- and time-resolved RAMAN and breakdown spectroscopy, to investigate chemical and toxic compounds, their kinetics and physical properties at high temporal (2 ns) and spatial (1 cm) resolution. The high spatial and temporal resolution are needed to resolve a large variety of chemical troposphere compounds, emissions from aircraft, the self-organization space charges induced light phenomena, temperature and humidity profiles, ice nucleation, etc.

Time-domain SFG spectroscopy using mid-IR pulse shaping: practical and intrinsic advantages.

PubMed

Laaser, Jennifer E; Xiong, Wei; Zanni, Martin T

2011-03-24

Sum-frequency generation (SFG) spectroscopy is a ubiquitous tool in the surface sciences. It provides infrared transition frequencies and line shapes that probe the structure and environment of molecules at interfaces. In this article, we apply techniques learned from the multidimensional spectroscopy community to SFG spectroscopy. We implement balanced heterodyne detection to remove scatter and the local oscillator background. Heterodyning also separates the resonant and nonresonant signals by acquiring both the real and imaginary parts of the spectrum. We utilize mid-IR pulse shaping to control the phase and delay of the mid-IR pump pulse. Pulse shaping allows phase cycling for data collection in the rotating frame and additional background subtraction. We also demonstrate time-domain data collection, which is a Fourier transform technique, and has many advantages in signal throughput, frequency resolution, and line shape accuracy over existing frequency domain methods. To demonstrate time-domain SFG spectroscopy, we study an aryl isocyanide on gold, and find that the system has an inhomogeneous structural distribution, in agreement with computational results, but which was not resolved by previous frequency-domain SFG studies. The ability to rapidly and actively manipulate the mid-IR pulse in an SFG pules sequence makes possible new experiments and more accurate spectra. © 2011 American Chemical Society

Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy.

PubMed

Fidler, Andrew F; Singh, Ved P; Long, Phillip D; Dahlberg, Peter D; Engel, Gregory S

2013-10-21

Excitation energy transfer events in the photosynthetic light harvesting complex 2 (LH2) of Rhodobacter sphaeroides are investigated with polarization controlled two-dimensional electronic spectroscopy. A spectrally broadened pulse allows simultaneous measurement of the energy transfer within and between the two absorption bands at 800 nm and 850 nm. The phased all-parallel polarization two-dimensional spectra resolve the initial events of energy transfer by separating the intra-band and inter-band relaxation processes across the two-dimensional map. The internal dynamics of the 800 nm region of the spectra are resolved as a cross peak that grows in on an ultrafast time scale, reflecting energy transfer between higher lying excitations of the B850 chromophores into the B800 states. We utilize a polarization sequence designed to highlight the initial excited state dynamics which uncovers an ultrafast transfer component between the two bands that was not observed in the all-parallel polarization data. We attribute the ultrafast transfer component to energy transfer from higher energy exciton states to lower energy states of the strongly coupled B850 chromophores. Connecting the spectroscopic signature to the molecular structure, we reveal multiple relaxation pathways including a cyclic transfer of energy between the two rings of the complex.

Spatially Resolved Spectroscopy of Narrow-line Seyfert 1 Host Galaxies

NASA Astrophysics Data System (ADS)

Scharwächter, J.; Husemann, B.; Busch, G.; Komossa, S.; Dopita, M. A.

2017-10-01

We present optical integral field spectroscopy for five z< 0.062 narrow-line Seyfert 1 (NLS1) galaxies, probing their host galaxies at ≳ 2{--}3 {kpc} scales. Emission lines from the active galactic nucleus (AGN) and the large-scale host galaxy are analyzed separately, based on an AGN-host decomposition technique. The host galaxy gas kinematics indicates large-scale gas rotation in all five sources. At the probed scales of ≳ 2{--}3 {kpc}, the host galaxy gas is found to be predominantly ionized by star formation without any evidence of a strong AGN contribution. None of the five objects shows specific star formation rates (SFRs) exceeding the main sequence of low-redshift star-forming galaxies. The specific SFRs for MCG-05-01-013 and WPVS 007 are roughly consistent with the main sequence, while ESO 399-IG20, MS 22549-3712, and TON S180 show lower specific SFRs, intermediate to the main sequence and the red quiescent galaxies. The host galaxy metallicities, derived for the two sources with sufficient data quality (ESO 399-IG20 and MCG-05-01-013), indicate central oxygen abundances just below the low-redshift mass-metallicity relation. Based on this initial case study, we outline a comparison of AGN and host galaxy parameters as a starting point for future extended NLS1 studies with similar methods.

Conserved structures formed by heterogeneous RNA sequences drive silencing of an inflammation responsive post-transcriptional operon

PubMed Central

Basu, Abhijit; Jain, Niyati; Tolbert, Blanton S.; Komar, Anton A.

2017-01-01

Abstract RNA–protein interactions with physiological outcomes usually rely on conserved sequences within the RNA element. By contrast, activity of the diverse gamma-interferon-activated inhibitor of translation (GAIT)-elements relies on the conserved RNA folding motifs rather than the conserved sequence motifs. These elements drive the translational silencing of a group of chemokine (CC/CXC) and chemokine receptor (CCR) mRNAs, thereby helping to resolve physiological inflammation. Despite sequence dissimilarity, these RNA elements adopt common secondary structures (as revealed by 2D-1H NMR spectroscopy), providing a basis for their interaction with the RNA-binding GAIT complex. However, many of these elements (e.g. those derived from CCL22, CXCL13, CCR4 and ceruloplasmin (Cp) mRNAs) have substantially different affinities for GAIT complex binding. Toeprinting analysis shows that different positions within the overall conserved GAIT element structure contribute to differential affinities of the GAIT protein complex towards the elements. Thus, heterogeneity of GAIT elements may provide hierarchical fine-tuning of the resolution of inflammation. PMID:29069516

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

Accuracy of 1H magnetic resonance spectroscopy for quantification of 2-hydroxyglutarate using linear combination and J-difference editing at 9.4T.

PubMed

Neuberger, Ulf; Kickingereder, Philipp; Helluy, Xavier; Fischer, Manuel; Bendszus, Martin; Heiland, Sabine

2017-12-01

Non-invasive detection of 2-hydroxyglutarate (2HG) by magnetic resonance spectroscopy is attractive since it is related to tumor metabolism. Here, we compare the detection accuracy of 2HG in a controlled phantom setting via widely used localized spectroscopy sequences quantified by linear combination of metabolite signals vs. a more complex approach applying a J-difference editing technique at 9.4T. Different phantoms, comprised out of a concentration series of 2HG and overlapping brain metabolites, were measured with an optimized point-resolved-spectroscopy sequence (PRESS) and an in-house developed J-difference editing sequence. The acquired spectra were post-processed with LCModel and a simulated metabolite set (PRESS) or with a quantification formula for J-difference editing. Linear regression analysis demonstrated a high correlation of real 2HG values with those measured with the PRESS method (adjusted R-squared: 0.700, p<0.001) as well as with those measured with the J-difference editing method (adjusted R-squared: 0.908, p<0.001). The regression model with the J-difference editing method however had a significantly higher explanatory value over the regression model with the PRESS method (p<0.0001). Moreover, with J-difference editing 2HG was discernible down to 1mM, whereas with the PRESS method 2HG values were not discernable below 2mM and with higher systematic errors, particularly in phantoms with high concentrations of N-acetyl-asparate (NAA) and glutamate (Glu). In summary, quantification of 2HG with linear combination of metabolite signals shows high systematic errors particularly at low 2HG concentration and high concentration of confounding metabolites such as NAA and Glu. In contrast, J-difference editing offers a more accurate quantification even at low 2HG concentrations, which outweighs the downsides of longer measurement time and more complex postprocessing. Copyright © 2017. Published by Elsevier GmbH.

Analytical Applications Of High-Resolution Molecular Fluorescence Spectroscopy In Low Temperature Solid Matrices

NASA Astrophysics Data System (ADS)

Hofstraat, Johannes W.; van Zeijl, W. J.; Smedes, F.; Ariese, Freek; Gooijer, Cees; Velthorst, Nel H.; Locher, R.; Renn, Alois; Wild, Urs P.

1989-05-01

High-resolution fluorescence spectroscopy may be used to obtain highly specific, vibrationally resolved spectral signatures of molecules. Two techniques are presented that both make use of low temperature, solid matrices. In Shpol'skii spectroscopy highly resolved spectra are obtained by employing n-alkanes as solvents that form neat crystalline matrices at low temperatures in which the guest molecules occupy well defined substitutional sites. Fluorescence line-narrowing spectroscopy is based on the application of selective (mostly laser-) excitation of the guest molecules. Principles and analytical applications of both techniques will be discussed. Specific attention will be paid to the determination of pyrene in bird meat by means of Shpol'skii spectroscopy and to the possibilities of applying two-dimensional fluorescence line-narrowing spectroscopy.

High resolution infrared spectroscopy: Some new approaches and applications to planetary atmospheres

NASA Technical Reports Server (NTRS)

Mumma, M. J.

1978-01-01

The principles of spectral line formation and of techniques for retrieval of atmospheric temperature and constituent profiles are discussed. Applications to the atmospheres of Earth, Mars, Venus, and Jupiter are illustrated by results obtained with Fourier transform and infrared heterodyne spectrometers at resolving powers (lambda/delta hyperon lambda of approximately 10,000 and approximately 10 to the seventh power), respectively, showing the high complementarity of spectroscopy at these two widely different resolving powers. The principles of heterodyne spectroscopy are presented and its applications to atmospheric probing and to laboratory spectroscopy are discussed. Direct absorption spectroscopy with tuneable semiconductor lasers is discussed in terms of precision frequency-and line strength-measurements, showing substantial advances in laboratory infrared spectroscopy.

X-ray spectroscopy studies of nonradiative energy transfer processes in luminescent lanthanide materials

NASA Astrophysics Data System (ADS)

Pacold, Joseph I.

Luminescent materials play important roles in energy sciences, through solid state lighting and possible applications in solar energy utilization, and in biomedical research and applications, such as in immunoassays and fluorescence microscopy. The initial excitation of a luminescent material leads to a sequence of transitions between excited states, ideally ending with the emission of one or more optical-wavelength photons. It is essential to understand the microscopic physics of this excited state cascade in order to rationally design materials with high quantum efficiencies or with other fine-tuning of materials response. While optical-wavelength spectroscopies have unraveled many details of the energy transfer pathways in luminescent materials, significant questions remain open for many lanthanide-based luminescent materials. For organometallic dyes in particular, quantum yields remain limited in comparison with inorganic phosphors. This dissertation reports on a research program of synchrotron x-ray studies of the excited state electronic structure and energy-relaxation cascade in trivalent lanthanide phosphors and dyes. To this end, one of the primary results presented here is the first time-resolved x-ray absorption near edge spectroscopy studies of the transient 4f excited states in lanthanide-activated luminescent dyes and phosphors. This is a new application of time-resolved x-ray absorption spectroscopy that makes it possible to directly observe and, to some extent, quantify intramolecular nonradiative energy transfer processes. We find a transient increase in 4f spectral weight associated with an excited state confined to the 4f shell of trivalent Eu. This result implies that it is necessary to revise the current theoretical understanding of 4f excitation in trivalent lanthanide activators: either transient 4f-5d mixing effects are much stronger than previously considered, or else the lanthanide 4f excited state has an unexpectedly large contribution having a strong charge-transfer character. A second primary result comes from an an x-ray excited optical luminescence (XEOL) study that demonstrates, for the first time, that the high flux of modern synchrotron light sources can induce high fractional populations of excited states in trivalent lanthanide phosphors. In this work we have identified the leading-order nonlinear-response mechanism by drawing on strong similarities between XEOL and cathodoluminescence. These results establish the groundwork for studies that would allow deeper inquiry into energy-transfer mechanisms through time-resolved x-ray pump/optical-probe spectroscopies, through time-resolved x-ray emission spectroscopy, or through quantifying of higher-order nonlinear effects at further-enhanced fractional excitation levels. The above scientific results are augmented by a supporting effort in instrumental methodology. This includes the development of high-efficiency x-ray emission spectrometers and their use in collaborations to study pressure-induced changes in f-electron physics and to characterize the intermediate states that occur after photoexcitation of the photosystem-II protein.

A transmission-grating-modulated pump-probe absorption spectroscopy and demonstration of diffusion dynamics of photoexcited carriers in bulk intrinsic GaAs film.

PubMed

Chen, Ke; Wang, Wenfang; Chen, Jianming; Wen, Jinhui; Lai, Tianshu

2012-02-13

A transmission-grating-modulated time-resolved pump-probe absorption spectroscopy is developed and formularized. The spectroscopy combines normal time-resolved pump-probe absorption spectroscopy with a binary transmission grating, is sensitive to the spatiotemporal evolution of photoinjected carriers, and has extensive applicability in the study of diffusion transport dynamics of photoinjected carriers. This spectroscopy has many advantages over reported optical methods to measure diffusion dynamics, such as simple experimental setup and operation, and high detection sensitivity. The measurement of diffusion dynamics is demonstrated on bulk intrinsic GaAs films. A carrier density dependence of carrier diffusion coefficient is obtained and agrees well with reported results.

Deep Raman spectroscopy for the non-invasive standoff detection of concealed chemical threat agents.

PubMed

Izake, Emad L; Cletus, Biju; Olds, William; Sundarajoo, Shankaran; Fredericks, Peter M; Jaatinen, Esa

2012-05-30

Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 m under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 s of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems. Copyright © 2012 Elsevier B.V. All rights reserved.

High-resolution 3D MR spectroscopic imaging of the prostate at 3 T with the MLEV-PRESS sequence.

PubMed

Chen, Albert P; Cunningham, Charles H; Kurhanewicz, John; Xu, Duan; Hurd, Ralph E; Pauly, John M; Carvajal, Lucas; Karpodinis, Kostas; Vigneron, Daniel B

2006-09-01

A 3 T MLEV-point-resolved spectroscopy (PRESS) sequence employing optimized spectral-spatial and very selective outer-voxel suppression pulses was tested in 25 prostate cancer patients. At an echo time of 85 ms, the MLEV-PRESS sequence resulted in maximally upright inner resonances and minimal outer resonances of the citrate doublet of doublets. Magnetic resonance spectroscopic imaging (MRSI) exams performed at both 3 and 1.5 T for 10 patients demonstrated a 2.08+/-0.36-fold increase in signal-to-noise ratio (SNR) at 3 T as compared with 1.5 T for the center citrate resonances. This permitted the acquisition of MRSI data with a nominal spatial resolution of 0.16 cm3 at 3 T with similar SNR as the 0.34-cm3 data acquired at 1.5 T. Due to the twofold increase in spectral resolution at 3 T and the improved magnetic field homogeneity provided by susceptibility-matched endorectal coils, the choline resonance was better resolved from polyamine and creatine resonances as compared with 1.5 T spectra. In prostate cancer patients, the elevation of choline and the reduction of polyamines were more clearly observed at 3 T, as compared with 1.5 T MRSI. The increased SNR and corresponding spatial resolution obtainable at 3 T reduced partial volume effects and allowed improved detection of the presence and extent of abnormal metabolite levels in prostate cancer patients, as compared with 1.5 T MRSI.

Resolution of Site-Specific Conformational Heterogeneity in Proline-Rich Molecular Recognition by Src Homology 3 Domains.

PubMed

Horness, Rachel E; Basom, Edward J; Mayer, John P; Thielges, Megan C

2016-02-03

Conformational heterogeneity and dynamics are increasingly evoked in models of protein molecular recognition but are challenging to experimentally characterize. Here we combine the inherent temporal resolution of infrared (IR) spectroscopy with the spatial resolution afforded by selective incorporation of carbon-deuterium (C-D) bonds, which provide frequency-resolved absorptions within a protein IR spectrum, to characterize the molecular recognition of the Src homology 3 (SH3) domain of the yeast protein Sho1 with its cognate proline-rich (PR) sequence of Pbs2. The IR absorptions of C-D bonds introduced at residues along a peptide of the Pbs2 PR sequence report on the changes in the local environments upon binding to the SH3 domain. Interestingly, upon forming the complex the IR spectra of the peptides labeled with C-D bonds at either of the two conserved prolines of the PXXP consensus recognition sequence show more absorptions than there are C-D bonds, providing evidence for the population of multiple states. In contrast, the NMR spectra of the peptides labeled with (13)C at the same residues show only single resonances, indicating rapid interconversion on the NMR time scale. Thus, the data suggest that the SH3 domain recognizes its cognate peptide with a component of induced fit molecular recognition involving the adoption of multiples states, which have previously gone undetected due to interconversion between the populated states that is too fast to resolve using conventional methods.

Saturation-resolved-fluorescence spectroscopy of Cr3+:mullite glass ceramic

NASA Astrophysics Data System (ADS)

Liu, Huimin; Knutson, Robert; Yen, W. M.

1990-01-01

We present a saturation-based technique designed to isolate and uncouple individual components of inhomogeneously broadened spectra that are simultaneously coupled to each other through spectral overlap and energy-transfer interactions. We have termed the technique saturation-resolved-fluorescence spectroscopy; we demonstrate its usefulness in deconvoluting the complex spectra of Cr3+:mullite glass ceramic.

Time-resolved VUV spectroscopy in the EXTRAP-T2 reversed field pinch

NASA Astrophysics Data System (ADS)

Hedqvist, Anders; Rachlew-Källne, Elisabeth

1998-09-01

Time-resolved VUV spectroscopy has been used to investigate the effects of impurities in a reversed field pinch operating with a resistive shell. Results of electron temperature, impurity ion densities, particle confinement time and 0741-3335/40/9/004/img1 together with a description of the interpretation and the equipment are presented.

Molecular orbital imaging of the acetone S2 excited state using time-resolved (e, 2e) electron momentum spectroscopy.

PubMed

Yamazaki, Masakazu; Oishi, Keiya; Nakazawa, Hiroyuki; Zhu, Chaoyuan; Takahashi, Masahiko

2015-03-13

We report a time-resolved (e, 2e) experiment on the deuterated acetone molecule in the S2 Rydberg state with a lifetime of 13.5 ps. The acetone S2 state was prepared by a 195 nm pump laser and probed with electron momentum spectroscopy using a 1.2 keV incident electron beam of 1 ps temporal width. In spite of the low data statistics as well as of the limited time resolution (±35  ps) due to velocity mismatch, the experimental results clearly demonstrate that electron momentum spectroscopy measurements of short-lived transient species are feasible, opening the door to time-resolved orbital imaging in momentum space.

Stellar and Circumstellar Properties of the Pre-Main-Sequence Binary GV Tau from Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Doppmann, Greg W.; Najita, Joan R.; Carr, John S.

2008-09-01

We report spatially resolved spectroscopy of both components of the low-mass pre-main-sequence binary GV Tau. High-resolution spectroscopy in the K and L bands is used to characterize the stellar properties of the binary and to explore the nature of the circumstellar environment. We find that the southern component, GV Tau S, is a radial velocity variable, possibly as a result of an unseen low-mass companion. The strong warm gaseous HCN absorption reported previously by Gibb and coworkers toward GV Tau S was not present during the epoch of our observations. Instead, we detect warm (~500 K) molecular absorption with similar properties toward the northern infrared companion, GV Tau N. At the epoch of our observations, the absorbing gas toward GV Tau N was approximately at the radial velocity of the GV Tau molecular envelope, but it was redshifted with respect to the star by ~13 km s-1. One interpretation of our results is that GV Tau N is also a binary and that most of the warm molecular absorption arises in a circumbinary disk viewed close to edge-on. Data presented herein were obtained at the W. M. Keck Observatory from telescope time allocated to the National Aeronautics and Space Administration through the agency's scientific partnership with the California Institute of Technology and the University of California. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

GHz Yb:KYW oscillators in time-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Li, Changxiu; Krauß, Nico; Schäfer, Gerhard; Ebner, Lukas; Kliebisch, Oliver; Schmidt, Johannes; Winnerl, Stephan; Hettich, Mike; Dekorsy, Thomas

2018-02-01

A high-speed asynchronous optical sampling system (ASOPS) based on Yb:KYW oscillators with 1-GHz repetition rate is reported. Two frequency-offset-stabilized diode-pumped Yb:KYW oscillators are employed as pump and probe source, respectively. The temporal resolution of this system within 1-ns time window is limited to 500 fs and the noise floor around 10-6 (ΔR/R) close to the shot-noise level is obtained within an acquisition time of a few seconds. Coherent acoustic phonons are investigated by measuring multilayer semiconductor structures with multiple quantum wells and aluminum/silicon membranes in this ASOPS system. A wavepacket-like phonon sequence at 360 GHz range is detected in the semiconductor structures and a decaying sequence of acoustic oscillations up to 200 GHz is obtained in the aluminum/silicon membranes. Coherent acoustic phonons generated from semiconductor structures are further manipulated by a double pump scheme through pump time delay control.

Comb-Resolved Dual-Comb Spectroscopy Stabilized by Free-Running Continuous-Wave Lasers

NASA Astrophysics Data System (ADS)

Kuse, Naoya; Ozawa, Akira; Kobayashi, Yohei

2012-11-01

We demonstrate dual-comb spectroscopy with relatively phase-locked two frequency combs, instead of frequency combs firmly fixed to the absolute frequency references. By stabilizing two beat frequencies between two mode-locked lasers at different wavelengths observed via free-running continuous-wave (CW) lasers, two combs are tightly phase locked to each other. The frequency noise of the CW lasers barely affects the performance of dual-comb spectroscopy because of the extremely fast common-mode noise rejection. Transform-limited comb-resolved dual-comb spectroscopy with a 6 Hz radio frequency linewidth is demonstrated by the use of Yb-fiber oscillators.

Enhanced visible and near-infrared capabilities of the JET mirror-linked divertor spectroscopy system

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

Lomanowski, B. A., E-mail: b.a.lomanowski@durham.ac.uk; Sharples, R. M.; Meigs, A. G.

2014-11-15

The mirror-linked divertor spectroscopy diagnostic on JET has been upgraded with a new visible and near-infrared grating and filtered spectroscopy system. New capabilities include extended near-infrared coverage up to 1875 nm, capturing the hydrogen Paschen series, as well as a 2 kHz frame rate filtered imaging camera system for fast measurements of impurity (Be II) and deuterium Dα, Dβ, Dγ line emission in the outer divertor. The expanded system provides unique capabilities for studying spatially resolved divertor plasma dynamics at near-ELM resolved timescales as well as a test bed for feasibility assessment of near-infrared spectroscopy.

Rapid and economical data acquisition in ultrafast frequency-resolved spectroscopy using choppers and a microcontroller.

PubMed

Guo, Liang; Monahan, Daniele M; Fleming, Graham

2016-08-08

Spectrometers and cameras are used in ultrafast spectroscopy to achieve high resolution in both time and frequency domains. Frequency-resolved signals from the camera pixels cannot be processed by common lock-in amplifiers, which have only a limited number of input channels. Here we demonstrate a rapid and economical method that achieves the function of a lock-in amplifier using mechanical choppers and a programmable microcontroller. We demonstrate the method's effectiveness by performing a frequency-resolved pump-probe measurement on the dye Nile Blue in solution.

Detection of experimental brain tumors using time-resolved laser-induced fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Thompson, Reid C.; Black, Keith L.; Kateb, Babak; Marcu, Laura

2002-05-01

Time-Resolved Laser-Induced Fluorescence Spectroscopy (TR-LIFS) has the potential to provide a non- invasive characterization and detection of tumors. We utilized TR-LIFS to detect gliomas in-vivo in the rat C6 glioma model. Time-resolved emission spectra of both normal brain and tumor were analyzed to determine if unique fluorescence signatures could be used to distinguish the two. Fluorescence parameters derived from both spectral and time domain were used for tissue characterization. Our results show that in the rat C6 glioma model, TR-LIFS can be used to differentiate brain tumors from normal tissue (gray and white mater) based upon time- resolved fluorescence signatures seen in brain tumors.

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.

Revealing Stellar Surface Structure Behind Transiting Exoplanets

NASA Astrophysics Data System (ADS)

Dravins, Dainis

2018-04-01

During exoplanet transits, successive stellar surface portions become hidden and differential spectroscopy between various transit phases provide spectra of small surface segments temporarily hidden behind the planet. Line profile changes across the stellar disk offer diagnostics for hydrodynamic modeling, while exoplanet analyses require stellar background spectra to be known along the transit path. Since even giant planets cover only a small fraction of any main-sequence star, very precise observations are required, as well as averaging over numerous spectral lines with similar parameters. Spatially resolved Fe I line profiles across stellar disks have now been retrieved for HD209458 (G0V) and HD189733A (K1V), using data from the UVES and HARPS spectrometers. Free from rotational broadening, spatially resolved profiles are narrower and deeper than in integrated starlight. During transit, the profiles shift towards longer wavelengths, illustrating both stellar rotation at the latitude of transit and the prograde orbital motion of the exoplanets. This method will soon become applicable to more stars, once additional bright exoplanet hosts have been found.

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.

Sensitivity Analysis and Requirements for Temporally and Spatially Resolved Thermometry Using Neutron Resonance Spectroscopy

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

Fernandez, Juan Carlos; Barnes, Cris William; Mocko, Michael Jeffrey

This report is intended to examine the use of neutron resonance spectroscopy (NRS) to make time- dependent and spatially-resolved temperature measurements of materials in extreme conditions. Specifically, the sensitivities of the temperature estimate on neutron-beam and diagnostic parameters is examined. Based on that examination, requirements are set on a pulsed neutron-source and diagnostics to make a meaningful measurement.

Structure and dynamics in B12 enzyme catalysis revealed by electron paramagnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Warncke, Kurt

2009-03-01

Challenges to the understanding of how protein structure and dynamics contribute to catalysis in enzymes, and the use of time-resolved electron paramagnetic resonance (EPR) spectroscopic techniques to address the challenges, are examined in the context of the coenzyme B12-dependent enzyme, ethanolamine ammonia-lyase (EAL), from Salmonella typhimurium. EAL conducts the homolytic cleavage of the coenzyme cobalt-carbon bond, intraprotein radical migration (5-6 å), and hydrogen atom transfers, which enable the core radical-mediated rearrangement reaction. Thermodynamic and activation parameters are measured in two experimental systems, which were developed to isolate sub-sequences from the multi-step catalytic cycle, as follows: (1) A dimethylsulfoxide (DMSO)/water cryosolvent system is used to prepare the kinetically-arrested enzyme/coenzyme/substrate ternary complex in fluid solution at 230 K.[1] Temperature-step initiated cobalt-carbon bond cleavage and radical pair separation to form the Co(II)-substrate radical pair are monitored by using time-resolved, full-spectrum EPR spectroscopy (234<=T<=250 K).[1] (2) The Co(II)-substrate radical pair is cryotrapped in frozen aqueous solution at T<150 K, and then promoted to react by a temperature step. The reaction of the substrate radical along the native pathway to form the diamagnetic bound products is monitored by using time-resolved, full-spectrum EPR spectroscopy (187<=T<=217 K).[2] High temporal resolution is achieved, because the reactions are dramatically slowed at the low temperatures, relative to the initiation and spectrum acquistion times. The results are combined with high resolution structures of the reactant centers, obtained by pulsed-EPR spectroscopies,[3] and the protein, obtained by structural proteomics[4] and EPR and electron spin echo envelope modulation (ESEEM) in combination with site directed mutagenesis,[5] to approach a molecular level description of protein contributions to catalysis in EAL. [4pt] [1] Wang, M. & Warncke, K. J. Am. Chem. Soc. 2008, 130, 4846. [0pt] [2] Chen, Z. and Warncke, K. Biophys. J. 2008, 95 (December) [0pt] [3] Canfield, J. M. and Warncke, K. J. Phys. Chem. B 2002, 106, 8831. [0pt] [4] Sun, L. and Warncke, K. Proteins 2006, 64, 308. [0pt] [5] Sun, L., Groover, O., Canfield, J. M., and Warncke, K. Biochemistry 2008, 47, 5523.

Rapid 3D NMR using the filter diagonalization method: application to oligosaccharides derivatized with 13C-labeled acetyl groups

NASA Astrophysics Data System (ADS)

Armstrong, Geoffrey S.; Cano, Kristin E.; Mandelshtam, Vladimir A.; Shaka, A. J.; Bendiak, Brad

2004-09-01

Rapid 3D NMR spectroscopy of oligosaccharides having isotopically labeled acetyl "isotags" was made possible with high resolution in the indirect dimensions using the filter diagonalization method (FDM). A pulse sequence was designed for the optimal correlation of acetyl methyl protons, methyl carbons, and carbonyl carbons. The multi-dimensional nature of the FDM, coupled with the advantages of constant-time evolution periods, resulted in marked improvements over Fourier transform (FT) and mirror-image linear prediction (MI-LP) processing methods. The three methods were directly compared using identical data sets. A highly resolved 3D spectrum was achieved with the FDM using a very short experimental time (28 min).

Rapid 3D NMR using the filter diagonalization method: application to oligosaccharides derivatized with 13C-labeled acetyl groups.

PubMed

Armstrong, Geoffrey S; Cano, Kristin E; Mandelshtam, Vladimir A; Shaka, A J; Bendiak, Brad

2004-09-01

Rapid 3D NMR spectroscopy of oligosaccharides having isotopically labeled acetyl "isotags" was made possible with high resolution in the indirect dimensions using the filter diagonalization method (FDM). A pulse sequence was designed for the optimal correlation of acetyl methyl protons, methyl carbons, and carbonyl carbons. The multi-dimensional nature of the FDM, coupled with the advantages of constant-time evolution periods, resulted in marked improvements over Fourier transform (FT) and mirror-image linear prediction (MI-LP) processing methods. The three methods were directly compared using identical data sets. A highly resolved 3D spectrum was achieved with the FDM using a very short experimental time (28 min).

Cross-Correlation of Motor Activity Signals from dc-Magnetoencephalography, Near-Infrared Spectroscopy, and Electromyography

PubMed Central

Sander, Tilmann H.; Leistner, Stefanie; Wabnitz, Heidrun; Mackert, Bruno-Marcel; Macdonald, Rainer; Trahms, Lutz

2010-01-01

Neuronal and vascular responses due to finger movements were synchronously measured using dc-magnetoencephalography (dcMEG) and time-resolved near-infrared spectroscopy (trNIRS). The finger movements were monitored with electromyography (EMG). Cortical responses related to the finger movement sequence were extracted by independent component analysis from both the dcMEG and the trNIRS data. The temporal relations between EMG rate, dcMEG, and trNIRS responses were assessed pairwise using the cross-correlation function (CCF), which does not require epoch averaging. A positive lag on a scale of seconds was found for the maximum of the CCF between dcMEG and trNIRS. A zero lag is observed for the CCF between dcMEG and EMG. Additionally this CCF exhibits oscillations at the frequency of individual finger movements. These findings show that the dcMEG with a bandwidth up to 8 Hz records both slow and faster neuronal responses, whereas the vascular response is confirmed to change on a scale of seconds. PMID:20145717

Cross-correlation of motor activity signals from dc-magnetoencephalography, near-infrared spectroscopy, and electromyography.

PubMed

Sander, Tilmann H; Leistner, Stefanie; Wabnitz, Heidrun; Mackert, Bruno-Marcel; Macdonald, Rainer; Trahms, Lutz

2010-01-01

Neuronal and vascular responses due to finger movements were synchronously measured using dc-magnetoencephalography (dcMEG) and time-resolved near-infrared spectroscopy (trNIRS). The finger movements were monitored with electromyography (EMG). Cortical responses related to the finger movement sequence were extracted by independent component analysis from both the dcMEG and the trNIRS data. The temporal relations between EMG rate, dcMEG, and trNIRS responses were assessed pairwise using the cross-correlation function (CCF), which does not require epoch averaging. A positive lag on a scale of seconds was found for the maximum of the CCF between dcMEG and trNIRS. A zero lag is observed for the CCF between dcMEG and EMG. Additionally this CCF exhibits oscillations at the frequency of individual finger movements. These findings show that the dcMEG with a bandwidth up to 8 Hz records both slow and faster neuronal responses, whereas the vascular response is confirmed to change on a scale of seconds.

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.

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.

Direct observation of spin-resolved full and empty electron states in ferromagnetic surfaces

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

Berti, G., E-mail: giulia.berti@polimi.it; Calloni, A.; Brambilla, A.

2014-07-15

We present a versatile apparatus for the study of ferromagnetic surfaces, which combines spin-polarized photoemission and inverse photoemission spectroscopies. Samples can be grown by molecular beam epitaxy and analyzed in situ. Spin-resolved photoemission spectroscopy analysis is done with a hemispherical electron analyzer coupled to a 25 kV-Mott detector. Inverse photoemission spectroscopy experiments are performed with GaAs crystals as spin-polarized electron sources and a UV bandpass photon detector. As an example, measurements on the oxygen passivated Fe(100)-p(1×1)O surface are presented.

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

Material quality frontiers of MOVPE grown AlGaAs for minority carrier devices

NASA Astrophysics Data System (ADS)

Heckelmann, S.; Lackner, D.; Dimroth, F.; Bett, A. W.

2017-04-01

In this study, secondary ion mass spectroscopy of oxygen, deep level transient spectroscopy and power dependent relative photoluminescence are compared regarding their ability to resolve differences in AlxGa1-xAs material quality. AlxGa1-xAs samples grown with two different trimethylaluminum sources showing low and high levels of oxygen contamination are compared. As tested in the growth of minority carrier devices, i.e. AlxGa1-xAs solar cells, the two precursors clearly lead to different device characteristics. It is shown that secondary ion mass spectroscopy could not resolve the difference in oxygen concentration, whereas deep level transient spectroscopy and photoluminescence based measurements indicate the influence of the precursor oxygen level on the material quality.

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

"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

Effect of the chest wall on the measurement of hemoglobin concentrations by near-infrared time-resolved spectroscopy in normal breast and cancer.

PubMed

Yoshizawa, Nobuko; Ueda, Yukio; Nasu, Hatsuko; Ogura, Hiroyuki; Ohmae, Etsuko; Yoshimoto, Kenji; Takehara, Yasuo; Yamashita, Yutaka; Sakahara, Harumi

2016-11-01

Optical imaging and spectroscopy using near-infrared light have great potential in the assessment of tumor vasculature. We previously measured hemoglobin concentrations in breast cancer using a near-infrared time-resolved spectroscopy system. The purpose of the present study was to evaluate the effect of the chest wall on the measurement of hemoglobin concentrations in normal breast tissue and cancer. We measured total hemoglobin (tHb) concentration in both cancer and contralateral normal breast using a near-infrared time-resolved spectroscopy system in 24 female patients with breast cancer. Patients were divided into two groups based on menopausal state. The skin-to-chest wall distance was determined using ultrasound images obtained with an ultrasound probe attached to the spectroscopy probe. The apparent tHb concentration of normal breast increased when the skin-to-chest wall distance was less than 20 mm. The tHb concentration in pre-menopausal patients was higher than that in post-menopausal patients. Although the concentration of tHb in cancer tissue was statistically higher than that in normal breast, the contralateral normal breast showed higher tHb concentration than cancer in 9 of 46 datasets. When the curves of tHb concentrations as a function of the skin-to-chest wall distance in normal breast were applied for pre- and post-menopausal patients separately, all the cancer lesions plotted above the curves. The skin-to-chest wall distance affected the measurement of tHb concentration of breast tissue by near-infrared time-resolved spectroscopy. The tHb concentration of breast cancer tissue was more precisely evaluated by considering the skin-to-chest wall distance.

Emerging biomedical applications of time-resolved fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Lakowicz, Joseph R.; Szmacinski, Henryk; Koen, Peter A.

1994-07-01

Time-resolved fluorescence spectroscopy is presently regarded as a research tool in biochemistry, biophysics, and chemical physics. Advances in laser technology, the development of long-wavelength probes, and the use of lifetime-based methods are resulting in the rapid migration of time-resolved fluorescence to the clinical chemistry lab, to the patient's bedside, to flow cytometers, to the doctor's office, and even to home health care. Additionally, time-resolved imaging is now a reality in fluorescence microscopy, and will provide chemical imaging of a variety of intracellular analytes and/or cellular phenomena. In this overview paper we attempt to describe some of the opportunities available using chemical sensing based on fluorescence lifetimes, and to predict those applications of lifetime-based sensing which are most likely in the near future.

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.

Depth-resolved measurements with elliptically polarized reflectance spectroscopy

PubMed Central

Bailey, Maria J.; Sokolov, Konstantin

2016-01-01

The ability of elliptical polarized reflectance spectroscopy (EPRS) to detect spectroscopic alterations in tissue mimicking phantoms and in biological tissue in situ is demonstrated. It is shown that there is a linear relationship between light penetration depth and ellipticity. This dependence is used to demonstrate the feasibility of a depth-resolved spectroscopic imaging using EPRS. The advantages and drawbacks of EPRS in evaluation of biological tissue are analyzed and discussed. PMID:27446712

Confocal depth-resolved fluorescence micro-X-ray absorption spectroscopy for the study of cultural heritage materials: a new mobile endstation at the Beijing Synchrotron Radiation Facility

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

Chen, Guang; Chu, Shengqi; Sun, Tianxi

A confocal fluorescence endstation for depth-resolved micro-X-ray absorption spectroscopy is described. A polycapillary half-lens defines the incident beam path and a second polycapillary half-lens at 90° defines the probe sample volume. An automatic alignment program based on an evolutionary algorithm is employed to make the alignment procedure efficient. This depth-resolved system was examined on a general X-ray absorption spectroscopy (XAS) beamline at the Beijing Synchrotron Radiation Facility. Sacrificial red glaze (AD 1368–1644) china was studied to show the capability of the instrument. As a mobile endstation to be applied on multiple beamlines, the confocal system can improve the function andmore » flexibility of general XAS beamlines, and extend their capabilities to a wider user community.« less

MO-G-18C-07: Improving T2 Determination and Quantification of Lipid Methylene Protons in Proton Magnetic Resonance Spectroscopy at 3 T

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

Breitkreutz, D.; Fallone, B. G.; Yahya, A.

2014-06-15

Purpose: To improve proton magnetic resonance spectroscopy (MRS) transverse relaxation (T{sub 2}) determination and quantification of lipid methylene chain (1.3 ppm) protons by rewinding their J-coupling evolution. Methods: MRS experiments were performed on four lipid phantoms, namely, almond, corn, sunflower and oleic acid, using a 3 T Philips MRI scanner with a transmit/receive birdcage head coil. Two PRESS (Point RESolved Spectroscopy) pulse sequences were used. The first PRESS sequence employed standard bandwidth (BW) (∼550 Hz) RF (radiofrequency) refocussing pulses, while the second used refocussing pulses of narrow BW (∼50 Hz) designed to rewind J-coupling evolution of the methylene protons inmore » the voxel of interest. Signal was acquired with each sequence from a 5×5×5 mm{sup 3} voxel, with a repetition time (TR) of 3000 ms, and with echo times (TE) of 100 to 200 ms in steps of 20 ms. 2048 sample points were measured with a 2000 Hz sampling bandwidth. Additionally, 30 mm outer volume suppression slabs were used to suppress signal outside the voxel of interest. The frequency of the RF pulses was set to that of the methylene resonance. Methylene peak areas were calculated and fitted in MATLAB to a monexponentially decaying function of the form M{sub 0}exp(-TE/T{sub 2}), where M{sub 0} is the extrapolated area when TE = 0 ms and yields a measure of concentration. Results: The determined values of M{sub 0} and T{sub 2} increased for all fatty acids when using the PRESS sequence with narrow BW refocussing pulses. M{sub 0} and T{sub 2} values increased by an average amount (over all the phantoms) of 31% and 14%, respectively. Conclusion: This investigation has demonstrated that J-coupling interactions of lipid methylene protons causes non-negligible signal losses which, if not accounted for, Result in underestimations of their levels and T{sub 2} values when performing MRS measurements. Funded by the Natural Sciences and Engineering Research Council of Canada and the Canadian Breast Cancer Foundation - Prairies.NWT.« less

Noncontact blood species identification method based on spatially resolved near-infrared transmission spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Linna; Sun, Meixiu; Wang, Zhennan; Li, Hongxiao; Li, Yingxin; Li, Gang; Lin, Ling

2017-09-01

The inspection and identification of whole blood are crucially significant for import-export ports and inspection and quarantine departments. In our previous research, we proved Near-Infrared diffuse transmitted spectroscopy method was potential for noninvasively identifying three blood species, including macaque, human and mouse, with samples measured in the cuvettes. However, in open sampling cases, inspectors may be endangered by virulence factors in blood samples. In this paper, we explored the noncontact measurement for classification, with blood samples measured in the vacuum blood vessels. Spatially resolved near-infrared spectroscopy was used to improve the prediction accuracy. Results showed that the prediction accuracy of the model built with nine detection points was more than 90% in identification between all five species, including chicken, goat, macaque, pig and rat, far better than the performance of the model built with single-point spectra. The results fully supported the idea that spatially resolved near-infrared spectroscopy method can improve the prediction ability, and demonstrated the feasibility of this method for noncontact blood species identification in practical applications.

Room-temperature ultrafast nonlinear spectroscopy of a single molecule

NASA Astrophysics Data System (ADS)

Liebel, Matz; Toninelli, Costanza; van Hulst, Niek F.

2018-01-01

Single-molecule spectroscopy aims to unveil often hidden but potentially very important contributions of single entities to a system's ensemble response. Albeit contributing tremendously to our ever growing understanding of molecular processes, the fundamental question of temporal evolution, or change, has thus far been inaccessible, thus painting a static picture of a dynamic world. Here, we finally resolve this dilemma by performing ultrafast time-resolved transient spectroscopy on a single molecule. By tracing the femtosecond evolution of excited electronic state spectra of single molecules over hundreds of nanometres of bandwidth at room temperature, we reveal their nonlinear ultrafast response in an effective three-pulse scheme with fluorescence detection. A first excitation pulse is followed by a phase-locked de-excitation pulse pair, providing spectral encoding with 25 fs temporal resolution. This experimental realization of true single-molecule transient spectroscopy demonstrates that two-dimensional electronic spectroscopy of single molecules is experimentally within reach.

An Investigation of G-Quadruplex Structural Polymorphism in the Human Telomere Using a Combined Approach of Hydrodynamic Bead Modeling and Molecular Dynamics Simulation

PubMed Central

2015-01-01

Guanine-rich oligonucleotides can adopt noncanonical tertiary structures known as G-quadruplexes, which can exist in different forms depending on experimental conditions. High-resolution structural methods, such as X-ray crystallography and NMR spectroscopy, have been of limited usefulness in resolving the inherent structural polymorphism associated with G-quadruplex formation. The lack of, or the ambiguous nature of, currently available high-resolution structural data, in turn, has severely hindered investigations into the nature of these structures and their interactions with small-molecule inhibitors. We have used molecular dynamics in conjunction with hydrodynamic bead modeling to study the structures of the human telomeric G-quadruplex-forming sequences at the atomic level. We demonstrated that molecular dynamics can reproduce experimental hydrodynamic measurements and thus can be a powerful tool in the structural study of existing G-quadruplex sequences or in the prediction of new G-quadruplex structures. PMID:24779348

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.

Three-dimensional superconducting gap in FeSe from angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Kushnirenko, Y. S.; Fedorov, A. V.; Haubold, E.; Thirupathaiah, S.; Wolf, T.; Aswartham, S.; Morozov, I.; Kim, T. K.; Büchner, B.; Borisenko, S. V.

2018-05-01

We present a systematic angle-resolved photoemission spectroscopy study of the superconducting gap in FeSe. The gap function is determined in a full Brillouin zone including all Fermi surfaces and kz dependence. We find significant anisotropy of the superconducting gap in all momentum directions. While the in-plane anisotropy can be explained by both nematicity-induced pairing anisotropy and orbital-selective pairing, the kz anisotropy requires an additional refinement of the theoretical approaches.

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.

Dual-comb spectroscopy of laser-induced plasmas

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

Bergevin, Jenna; Wu, Tsung-Han; Yeak, Jeremy

Dual-comb spectroscopy has become a powerful spectroscopic technique in applications that rely on its broad spectral coverage combined with high frequency resolution capabilities. Experiments to date have primarily focused on detection and analysis of multiple gas species under semi-static conditions, with applications ranging from environmental monitoring of greenhouse gases to high resolution molecular spectroscopy. Here, we utilize dual-comb spectroscopy to demonstrate broadband, high-resolution, and time-resolved measurements in a laser induced plasma for the first time. As a first demonstration, we simultaneously detect trace amounts of Rb and K in solid samples with a single laser ablation shot, with transitions separatedmore » by over 6 THz (13 nm) and spectral resolution sufficient to resolve isotopic and ground state hyperfine splittings of the Rb D2 line. This new spectroscopic approach offers the broad spectral coverage found in the powerful techniques of laser-induced breakdown spectroscopy (LIBS) while providing the high-resolution and accuracy of cw laser-based spectroscopies.« less

Analyzing the relationship between sequence divergence and nodal support using Bayesian phylogenetic analyses.

PubMed

Makowsky, Robert; Cox, Christian L; Roelke, Corey; Chippindale, Paul T

2010-11-01

Determining the appropriate gene for phylogeny reconstruction can be a difficult process. Rapidly evolving genes tend to resolve recent relationships, but suffer from alignment issues and increased homoplasy among distantly related species. Conversely, slowly evolving genes generally perform best for deeper relationships, but lack sufficient variation to resolve recent relationships. We determine the relationship between sequence divergence and Bayesian phylogenetic reconstruction ability using both natural and simulated datasets. The natural data are based on 28 well-supported relationships within the subphylum Vertebrata. Sequences of 12 genes were acquired and Bayesian analyses were used to determine phylogenetic support for correct relationships. Simulated datasets were designed to determine whether an optimal range of sequence divergence exists across extreme phylogenetic conditions. Across all genes we found that an optimal range of divergence for resolving the correct relationships does exist, although this level of divergence expectedly depends on the distance metric. Simulated datasets show that an optimal range of sequence divergence exists across diverse topologies and models of evolution. We determine that a simple to measure property of genetic sequences (genetic distance) is related to phylogenic reconstruction ability in Bayesian analyses. This information should be useful for selecting the most informative gene to resolve any relationships, especially those that are difficult to resolve, as well as minimizing both cost and confounding information during project design. Copyright © 2010. Published by Elsevier Inc.

Time- and Space-Resolved Spectroscopic Investigation on Pi-Conjugated Nanostructures - 2

DTIC Science & Technology

2016-01-12

15. SUBJECT TERMS Materials Characterization, Materials Chemistry, Nonlinear Optical Materials, Spectroscopy 16. SECURITY CLASSIFICATION...nanostructures will translate into new ground-breaking developments that not only allow the structure-property relationships to be probed in greater detail... spectroscopy . I. Experimental method 1. Steady-state Spectroscopy - UV-Vis-NIR Absorption & Emission Steady-state Spectroscopy - NIR

Coherent Anti-stokes Raman Spectroscopy (CARS) of gun propellant flames

NASA Technical Reports Server (NTRS)

Mcilwain, M. E.; Harris, L. E.

1980-01-01

Temperature measurements were made in a slightly fuel rich, premixed propane/air reference flame and nitrate ester propellant flames burning in air at atmospheric pressure using coherent anti-stokes raman scattering (CARS). Both single and multiple pulse VARS spectra of nitrogen in the reference flame were in good agreement with calculated and reported values. Single pulse CARS nitrogen spectra obtained in the propellant flames were analyzed to give temperatures consistent with values calculated using the NASA-Lewis thermochemical calculation. Comparison of a 0.1 second separated sequence of single pulse CARS spectra indicate turbulent air mixing in these propellant flames. The CARS spectral results demonstrate that temporal and spatially resolved temperature measurements could be determined in transient, turbulent flames.

Diffraction and microscopy with attosecond electron pulse trains

NASA Astrophysics Data System (ADS)

Morimoto, Yuya; Baum, Peter

2018-03-01

Attosecond spectroscopy1-7 can resolve electronic processes directly in time, but a movie-like space-time recording is impeded by the too long wavelength ( 100 times larger than atomic distances) or the source-sample entanglement in re-collision techniques8-11. Here we advance attosecond metrology to picometre wavelength and sub-atomic resolution by using free-space electrons instead of higher-harmonic photons1-7 or re-colliding wavepackets8-11. A beam of 70-keV electrons at 4.5-pm de Broglie wavelength is modulated by the electric field of laser cycles into a sequence of electron pulses with sub-optical-cycle duration. Time-resolved diffraction from crystalline silicon reveals a < 10-as delay of Bragg emission and demonstrates the possibility of analytic attosecond-ångström diffraction. Real-space electron microscopy visualizes with sub-light-cycle resolution how an optical wave propagates in space and time. This unification of attosecond science with electron microscopy and diffraction enables space-time imaging of light-driven processes in the entire range of sample morphologies that electron microscopy can access.

A Spatially Resolved Investigation on the Influence of AGN and Star Formation in a Lensed Main-Sequence Galaxy at z = 2.39

NASA Astrophysics Data System (ADS)

Fischer, Travis; Rigby, Jane; Gladders, Michael; Sharon, Keren q.; Barrientos, L. Felipe; Bayliss, Matt; Dahle, Håkon; Florian, Michael; Johnson, Traci Lin; Wuyts, Eva

2018-01-01

We present rest-frame optical SINFONI integral field spectroscopy and rest-frame UV HST imaging of a lensed galaxy hosting an active galactic nucleus (AGN) at z = 2.39. Galactic wind feedback is widely acknowledged to play a critical role in the evolution of galaxies, however, the physical mechanisms involved and the relative importance of AGN and star formation as the main feedback drivers remain poorly understood. AGN-driven feedback has been evident in very luminous but rare quasars and radio galaxies, but observational evidence remains lacking for less extreme, “normal” star-forming galaxies. We report, for the first time at high redshift, spatially resolved velocity profiles and geometries of an AGN-driven outflow in a normal star-forming galaxy and spatial extents and morphologies of Lyα emission and stellar UV continuum. Analyzing these measurements in tandem, we determine the physical conditions, geometry, and excitation sources of the interstellar medium in a star-forming, AGN-hosting galaxy at cosmic noon.

Comparison of causality analysis on simultaneously measured fMRI and NIRS signals during motor tasks.

PubMed

Anwar, Abdul Rauf; Muthalib, Makii; Perrey, Stephane; Galka, Andreas; Granert, Oliver; Wolff, Stephan; Deuschl, Guenther; Raethjen, Jan; Heute, Ulrich; Muthuraman, Muthuraman

2013-01-01

Brain activity can be measured using different modalities. Since most of the modalities tend to complement each other, it seems promising to measure them simultaneously. In to be presented research, the data recorded from Functional Magnetic Resonance Imaging (fMRI) and Near Infrared Spectroscopy (NIRS), simultaneously, are subjected to causality analysis using time-resolved partial directed coherence (tPDC). Time-resolved partial directed coherence uses the principle of state space modelling to estimate Multivariate Autoregressive (MVAR) coefficients. This method is useful to visualize both frequency and time dynamics of causality between the time series. Afterwards, causality results from different modalities are compared by estimating the Spearman correlation. In to be presented study, we used directionality vectors to analyze correlation, rather than actual signal vectors. Results show that causality analysis of the fMRI correlates more closely to causality results of oxy-NIRS as compared to deoxy-NIRS in case of a finger sequencing task. However, in case of simple finger tapping, no clear difference between oxy-fMRI and deoxy-fMRI correlation is identified.

Planetary Surface Exploration Using Time-Resolved Laser Spectroscopy on Rovers and Landers

NASA Astrophysics Data System (ADS)

Blacksberg, Jordana; Alerstam, Erik; Maruyama, Yuki; Charbon, Edoardo; Rossman, George

2013-04-01

Planetary surface exploration using laser spectroscopy has become increasingly relevant as these techniques become a reality on Mars surface missions. The ChemCam instrument onboard the Curiosity rover is currently using laser induced breakdown spectroscopy (LIBS) on a mast-mounted platform to measure elemental composition of target rocks. The RLS Raman Spectrometer is included on the payload for the ExoMars mission to be launched in 2018 and will identify minerals and organics on the Martian surface. We present a next-generation instrument that builds on these widely used techniques to provide a means for performing both Raman spectroscopy and LIBS in conjunction with microscopic imaging. Microscopic Raman spectroscopy with a laser spot size smaller than the grains of interest can provide surface mapping of mineralogy while preserving morphology. A very small laser spot size (~ 1 µm) is often necessary to identify minor phases that are often of greater interest than the matrix phases. In addition to the difficulties that can be posed by fine-grained material, fluorescence interference from the very same material is often problematic. This is particularly true for many of the minerals of interest that form in environments of aqueous alteration and can be highly fluorescent. We use time-resolved laser spectroscopy to eliminate fluorescence interference that can often make it difficult or impossible to obtain Raman spectra. As an added benefit, we have found that with small changes in operating parameters we can include microscopic LIBS using the same hardware. This new technique relies on sub-ns, high rep-rate lasers with relatively low pulse energy and compact solid state detectors with sub-ns time resolution. The detector technology that makes this instrument possible is a newly developed Single-Photon Avalanche Diode (SPAD) sensor array based on Complementary Metal-Oxide Semiconductor (CMOS) technology. The use of this solid state time-resolved detector offers a significant reduction in size, weight, power, and overall complexity - making time resolved detection feasible for planetary applications. We will discuss significant advances leading to the feasibility of a compact time-resolved spectrometer. We will present results on planetary analog minerals to demonstrate the instrument performance including fluorescence rejection and combined Raman-LIBS capability.

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.

Time- and angle-resolved photoemission spectroscopy of hydrated electrons near a liquid water surface.

PubMed

Yamamoto, Yo-ichi; Suzuki, Yoshi-Ichi; Tomasello, Gaia; Horio, Takuya; Karashima, Shutaro; Mitríc, Roland; Suzuki, Toshinori

2014-05-09

We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1,4-diazabicyclo[2,2,2]octane and I- in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed.

Quantification of joint inflammation in rheumatoid arthritis by time-resolved diffuse optical spectroscopy and tracer kinetic modeling

NASA Astrophysics Data System (ADS)

Ioussoufovitch, Seva; Morrison, Laura B.; Lee, Ting-Yim; St. Lawrence, Keith; Diop, Mamadou

2015-03-01

Rheumatoid arthritis (RA) is characterized by chronic synovial inflammation, which can cause progressive joint damage and disability. Diffuse optical spectroscopy (DOS) and imaging have the potential to become potent monitoring tools for RA. We devised a method that combined time-resolved DOS and tracer kinetics modeling to rapidly and reliably quantify blood flow in the joint. Preliminary results obtained from two animals show that the technique can detect joint inflammation as early as 5 days after onset.

Time Resolved Phonon Spectroscopy, Version 1.0

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

Goett, Johnny; Zhu, Brian

TRPS code was developed for the project "Time Resolved Phonon Spectroscopy". Routines contained in this piece of software were specially created to model phonon generation and tracking within materials that interact with ionizing radiation, particularly applicable to the modeling of cryogenic radiation detectors for dark matter and neutrino research. These routines were created to link seamlessly with the open source Geant4 framework for the modeling of radiation transport in matter, with the explicit intent of open sourcing them for eventual integration into that code base.

A Simple LIBS (Laser-Induced Breakdown Spectroscopy) Laboratory Experiment to Introduce Undergraduates to Calibration Functions and Atomic Spectroscopy

ERIC Educational Resources Information Center

Chinni, Rosemarie C.

2012-01-01

This laboratory experiment introduces students to a different type of atomic spectroscopy: laser-induced breakdown spectroscopy (LIBS). LIBS uses a laser-generated spark to excite the sample; once excited, the elemental emission is spectrally resolved and detected. The students use LIBS to analyze a series of standard synthetic silicate samples…

Optimizing the Laser-Pulse Configuration for Coherent Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Pestov, Dmitry; Murawski, Robert K.; Ariunbold, Gombojav O.; Wang, Xi; Zhi, Miaochan; Sokolov, Alexei V.; Sautenkov, Vladimir A.; Rostovtsev, Yuri V.; Dogariu, Arthur; Huang, Yu; Scully, Marlan O.

2007-04-01

We introduce a hybrid technique that combines the robustness of frequency-resolved coherent anti-Stokes Raman scattering (CARS) with the advantages of time-resolved CARS spectroscopy. Instantaneous coherent broadband excitation of several characteristic molecular vibrations and the subsequent probing of these vibrations by an optimally shaped time-delayed narrowband laser pulse help to suppress the nonresonant background and to retrieve the species-specific signal. We used this technique for coherent Raman spectroscopy of sodium dipicolinate powder, which is similar to calcium dipicolinate (a marker molecule for bacterial endospores, such as Bacillus subtilis and Bacillus anthracis), and we demonstrated a rapid and highly specific detection scheme that works even in the presence of multiple scattering.

Optical spectroscopy for quantitative sensing in human pancreatic tissues

NASA Astrophysics Data System (ADS)

Wilson, Robert H.; Chandra, Malavika; Lloyd, William; Chen, Leng-Chun; Scheiman, James; Simeone, Diane; McKenna, Barbara; Mycek, Mary-Ann

2011-07-01

Pancreatic adenocarcinoma has a five-year survival rate of only 6%, largely because current diagnostic methods cannot reliably detect the disease in its early stages. Reflectance and fluorescence spectroscopies have the potential to provide quantitative, minimally-invasive means of distinguishing pancreatic adenocarcinoma from normal pancreatic tissue and chronic pancreatitis. The first collection of wavelength-resolved reflectance and fluorescence spectra and time-resolved fluorescence decay curves from human pancreatic tissues was acquired with clinically-compatible instrumentation. Mathematical models of reflectance and fluorescence extracted parameters related to tissue morphology and biochemistry that were statistically significant for distinguishing between pancreatic tissue types. These results suggest that optical spectroscopy has the potential to detect pancreatic disease in a clinical setting.

Optimizing the laser-pulse configuration for coherent Raman spectroscopy.

PubMed

Pestov, Dmitry; Murawski, Robert K; Ariunbold, Gombojav O; Wang, Xi; Zhi, Miaochan; Sokolov, Alexei V; Sautenkov, Vladimir A; Rostovtsev, Yuri V; Dogariu, Arthur; Huang, Yu; Scully, Marlan O

2007-04-13

We introduce a hybrid technique that combines the robustness of frequency-resolved coherent anti-Stokes Raman scattering (CARS) with the advantages of time-resolved CARS spectroscopy. Instantaneous coherent broadband excitation of several characteristic molecular vibrations and the subsequent probing of these vibrations by an optimally shaped time-delayed narrowband laser pulse help to suppress the nonresonant background and to retrieve the species-specific signal. We used this technique for coherent Raman spectroscopy of sodium dipicolinate powder, which is similar to calcium dipicolinate (a marker molecule for bacterial endospores, such as Bacillus subtilis and Bacillus anthracis), and we demonstrated a rapid and highly specific detection scheme that works even in the presence of multiple scattering.

New approaches to the analysis of complex samples using fluorescence lifetime techniques and organized media

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

Hertz, P.R.

Fluorescence spectroscopy is a highly sensitive and selective tool for the analysis of complex systems. In order to investigate the efficacy of several steady state and dynamic techniques for the analysis of complex systems, this work focuses on two types of complex, multicomponent samples: petrolatums and coal liquids. It is shown in these studies dynamic, fluorescence lifetime-based measurements provide enhanced discrimination between complex petrolatum samples. Additionally, improved quantitative analysis of multicomponent systems is demonstrated via incorporation of organized media in coal liquid samples. This research provides the first systematic studies of (1) multifrequency phase-resolved fluorescence spectroscopy for dynamic fluorescence spectralmore » fingerprinting of complex samples, and (2) the incorporation of bile salt micellar media to improve accuracy and sensitivity for characterization of complex systems. In the petroleum studies, phase-resolved fluorescence spectroscopy is used to combine spectral and lifetime information through the measurement of phase-resolved fluorescence intensity. The intensity is collected as a function of excitation and emission wavelengths, angular modulation frequency, and detector phase angle. This multidimensional information enhances the ability to distinguish between complex samples with similar spectral characteristics. Examination of the eigenvalues and eigenvectors from factor analysis of phase-resolved and steady state excitation-emission matrices, using chemometric methods of data analysis, confirms that phase-resolved fluorescence techniques offer improved discrimination between complex samples as compared with conventional steady state methods.« less

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.

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.…

Spectral reconstruction analysis for enhancing signal-to-noise in time-resolved spectroscopies

NASA Astrophysics Data System (ADS)

Wilhelm, Michael J.; Smith, Jonathan M.; Dai, Hai-Lung

2015-09-01

We demonstrate a new spectral analysis for the enhancement of the signal-to-noise ratio (SNR) in time-resolved spectroscopies. Unlike the simple linear average which produces a single representative spectrum with enhanced SNR, this Spectral Reconstruction analysis (SRa) improves the SNR (by a factor of ca. 0 . 6 √{ n } ) for all n experimentally recorded time-resolved spectra. SRa operates by eliminating noise in the temporal domain, thereby attenuating noise in the spectral domain, as follows: Temporal profiles at each measured frequency are fit to a generic mathematical function that best represents the temporal evolution; spectra at each time are then reconstructed with data points from the fitted profiles. The SRa method is validated with simulated control spectral data sets. Finally, we apply SRa to two distinct experimentally measured sets of time-resolved IR emission spectra: (1) UV photolysis of carbonyl cyanide and (2) UV photolysis of vinyl cyanide.

Characterizing the Resolved M6 Dwarf Twin LP 318-218AB

NASA Astrophysics Data System (ADS)

Moreno Hilario, Elizabeth; Burgasser, Adam J.; Bardalez Gagliuffi, Daniella; Tamiya, Tomoki

2017-01-01

The lowest-mass stars and brown dwarfs are among the most common objects in the Milky Way Galaxy, but theories of their formation and evolution remain poorly constrained. Binary systems are important for understanding the formation of these objects and for making direct orbit and mass measurements to validate evolutionary theories. We report the discovery of LP 318-218, a high proper motion late M dwarf, as a near equal-brightness binary system with a separation of 0.72 arcseconds. Resolved near-infrared spectroscopy confirms the components as nearly identical M6 twins. We using our resolved photometry and spectroscopy to estimate the distance, projected separation and tangential velocity of the system, and confirm common proper motion. We also perform atmosphere model fits to the resolved spectra to assess their physical properties. We place LP 318-218 in context with other widely-separated late M dwarf binaries.

Ultrafast time-resolved spectroscopy of the light-harvesting complex 2 (LH2) from the photosynthetic bacterium Thermochromatium tepidum.

PubMed

Niedzwiedzki, Dariusz M; Fuciman, Marcel; Kobayashi, Masayuki; Frank, Harry A; Blankenship, Robert E

2011-10-01

The light-harvesting complex 2 from the thermophilic purple bacterium Thermochromatium tepidum was purified and studied by steady-state absorption and fluorescence, sub-nanosecond-time-resolved fluorescence and femtosecond time-resolved transient absorption spectroscopy. The measurements were performed at room temperature and at 10 K. The combination of both ultrafast and steady-state optical spectroscopy methods at ambient and cryogenic temperatures allowed the detailed study of carotenoid (Car)-to-bacteriochlorophyll (BChl) as well BChl-to-BChl excitation energy transfer in the complex. The studies show that the dominant Cars rhodopin (N=11) and spirilloxanthin (N=13) do not play a significant role as supportive energy donors for BChl a. This is related with their photophysical properties regulated by long π-electron conjugation. On the other hand, such properties favor some of the Cars, particularly spirilloxanthin (N=13) to play the role of the direct quencher of the excited singlet state of BChl. © Springer Science+Business Media B.V. 2011

Time-resolved single-shot terahertz time-domain spectroscopy for ultrafast irreversible processes

NASA Astrophysics Data System (ADS)

Zhai, Zhao-Hui; Zhong, Sen-Cheng; Li, Jun; Zhu, Li-Guo; Meng, Kun; Li, Jiang; Liu, Qiao; Peng, Qi-Xian; Li, Ze-Ren; Zhao, Jian-Heng

2016-09-01

Pulsed terahertz spectroscopy is suitable for spectroscopic diagnostics of ultrafast events. However, the study of irreversible or single shot ultrafast events requires ability to record transient properties at multiple time delays, i.e., time resolved at single shot level, which is not available currently. Here by angular multiplexing use of femtosecond laser pulses, we developed and demonstrated a time resolved, transient terahertz time domain spectroscopy technique, where burst mode THz pulses were generated and then detected in a single shot measurement manner. The burst mode THz pulses contain 2 sub-THz pulses, and the time gap between them is adjustable up to 1 ns with picosecond accuracy, thus it can be used to probe the single shot event at two different time delays. The system can detect the sub-THz pulses at 0.1 THz-2.5 THz range with signal to noise ratio (SNR) of ˜400 and spectrum resolution of 0.05 THz. System design was described here, and optimizations of single shot measurement of THz pulses were discussed in detail. Methods to improve SNR were also discussed in detail. A system application was demonstrated where pulsed THz signals at different time delays of the ultrafast process were successfully acquired within single shot measurement. This time resolved transient terahertz time domain spectroscopy technique provides a new diagnostic tool for irreversible or single shot ultrafast events where dynamic information can be extracted at terahertz range within one-shot experiment.

Time-resolved single-shot terahertz time-domain spectroscopy for ultrafast irreversible processes.

PubMed

Zhai, Zhao-Hui; Zhong, Sen-Cheng; Li, Jun; Zhu, Li-Guo; Meng, Kun; Li, Jiang; Liu, Qiao; Peng, Qi-Xian; Li, Ze-Ren; Zhao, Jian-Heng

2016-09-01

Pulsed terahertz spectroscopy is suitable for spectroscopic diagnostics of ultrafast events. However, the study of irreversible or single shot ultrafast events requires ability to record transient properties at multiple time delays, i.e., time resolved at single shot level, which is not available currently. Here by angular multiplexing use of femtosecond laser pulses, we developed and demonstrated a time resolved, transient terahertz time domain spectroscopy technique, where burst mode THz pulses were generated and then detected in a single shot measurement manner. The burst mode THz pulses contain 2 sub-THz pulses, and the time gap between them is adjustable up to 1 ns with picosecond accuracy, thus it can be used to probe the single shot event at two different time delays. The system can detect the sub-THz pulses at 0.1 THz-2.5 THz range with signal to noise ratio (SNR) of ∼400 and spectrum resolution of 0.05 THz. System design was described here, and optimizations of single shot measurement of THz pulses were discussed in detail. Methods to improve SNR were also discussed in detail. A system application was demonstrated where pulsed THz signals at different time delays of the ultrafast process were successfully acquired within single shot measurement. This time resolved transient terahertz time domain spectroscopy technique provides a new diagnostic tool for irreversible or single shot ultrafast events where dynamic information can be extracted at terahertz range within one-shot experiment.

PHIBSS: MOLECULAR GAS, EXTINCTION, STAR FORMATION, AND KINEMATICS IN THE z = 1.5 STAR-FORMING GALAXY EGS13011166

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

Genzel, R.; Tacconi, L. J.; Kurk, J.

We report matched resolution imaging spectroscopy of the CO 3-2 line (with the IRAM Plateau de Bure millimeter interferometer) and of the H{alpha} line (with LUCI at the Large Binocular Telescope) in the massive z = 1.53 main-sequence galaxy EGS 13011166, as part of the ''Plateau de Bure high-z, blue-sequence survey'' (PHIBSS: Tacconi et al.). We combine these data with Hubble Space Telescope V-I-J-H-band maps to derive spatially resolved distributions of stellar surface density, star formation rate, molecular gas surface density, optical extinction, and gas kinematics. The spatial distribution and kinematics of the ionized and molecular gas are remarkably similarmore » and are well modeled by a turbulent, globally Toomre unstable, rotating disk. The stellar surface density distribution is smoother than the clumpy rest-frame UV/optical light distribution and peaks in an obscured, star-forming massive bulge near the dynamical center. The molecular gas surface density and the effective optical screen extinction track each other and are well modeled by a ''mixed'' extinction model. The inferred slope of the spatially resolved molecular gas to star formation rate relation, N = dlog{Sigma}{sub starform}/dlog{Sigma}{sub molgas}, depends strongly on the adopted extinction model, and can vary from 0.8 to 1.7. For the preferred mixed dust-gas model, we find N = 1.14 {+-} 0.1.« less

Hydrogen bonding-assisted interaction between amitriptyline hydrochloride and hemoglobin: spectroscopic and molecular dynamics studies.

PubMed

Maurya, Neha; Maurya, Jitendra Kumar; Kumari, Meena; Khan, Abbul Bashar; Dohare, Ravins; Patel, Rajan

2017-05-01

Herein, we have explored the interaction between amitriptyline hydrochloride (AMT) and hemoglobin (Hb), using steady-state and time-resolved fluorescence spectroscopy, UV-visible spectroscopy, and circular dichroism spectroscopy, in combination with molecular docking and molecular dynamic (MD) simulation methods. The steady-state fluorescence reveals the static quenching mechanism in the interaction system, which was further confirmed by UV-visible and time-resolved fluorescence spectroscopy. The binding constant, number of binding sites, and thermodynamic parameters viz. ΔG, ΔH, ΔS are also considered; result confirms that the binding of the AMT with Hb is a spontaneous process, involving hydrogen bonding and van der Waals interactions with a single binding site, as also confirmed by molecular docking study. Synchronous fluorescence, CD data, and MD simulation results contribute toward understanding the effect of AMT on Hb to interpret the conformational change in Hb upon binding in aqueous solution.

Feasibility of Valence-to-Core X-ray Emission Spectroscopy for Tracking Transient Species

DOE PAGES

March, Anne Marie; Assefa, Tadesse A.; Bressler, Christian; ...

2015-02-09

X-ray spectroscopies, when combined in laser-pump, X-ray-probe measurement schemes, can be powerful tools for tracking the electronic and geometric structural changes that occur during the course of a photoinitiated chemical reaction. X-ray absorption spectroscopy (XAS) is considered an established technique for such measurements, and X-ray emission spectroscopy (XES) of the strongest core-to-core emission lines (Kα and Kβ) is now being utilized. Flux demanding valence-to-core XES promises to be an important addition to the time-resolved spectroscopic toolkit. Here In this paper we present measurements and density functional theory calculations on laser-excited, solution-phase ferrocyanide that demonstrate the feasibility of valence-to-core XES formore » time-resolved experiments. Lastly, we discuss technical improvements that will make valence-to-core XES a practical pump–probe technique.« less

Frontiers in Chemical Physics

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

Bowlan, Pamela Renee

2016-05-02

These are slides dealing with frontiers in chemical physics. The following topics are covered: Time resolving chemistry with ultrashort pulses in the 0.1-40 THz spectral range; Example: Mid-infrared absorption spectrum of the intermediate state CH 2OO; Tracking reaction dynamics through changes in the spectra; Single-shot measurement of the mid-IR absorption dynamics; Applying 2D coherent mid-IR spectroscopy to learn more about transition states; Time resolving chemical reactions at a catalysis using mid-IR and THz pulses; Studying topological insulators requires a surface sensitive probe; Nonlinear phonon dynamics in Bi 2Se 3; THz-pump, SHG-probe as a surface sensitive coherent 2D spectroscopy; Nanometer andmore » femtosecond spatiotemporal resolution mid-IR spectroscopy; Coherent two-dimensional THz/mid-IR spectroscopy with 10nm spatial resolution; Pervoskite oxides as catalysts; Functionalized graphene for catalysis; Single-shot spatiotemporal measurements; Spatiotemporal pulse measurement; Intense, broad-band THz/mid-IR generation with organic crystals.« less

A versatile and reconfigurable setup for all-terahertz time-resolved pump-probe spectroscopy.

PubMed

Elezzabi, A Y; Maraghechi, P

2012-05-01

A versatile optical setup for all-terahertz (THz) time resolved pump-probe spectroscopy was designed and tested. By utilizing a dual THz pulse generator emitter module, independent and synchronized THz radiation pump and probe pulses were produced, thus eliminating the need for THz beam splitters and the limitations associated with their implementation. The current THz setup allows for precise control of the electric fields splitting ratio between the THz radiation pump and probe pulses, as well as in-phase, out-of-phase, and polarization dependent pump-probe spectroscopy. Since the present THz pump-probe setup does not require specialized THz radiation optical components, such as phase shifters, polarization rotators, or wide bandwidth beam splitters, it can be easily implemented with minimal alterations to a conventional THz time domain spectroscopy system. The present setup is valuable for studying the time dynamics of THz coherent phenomena in solid-state, chemical, and biological systems.

Momentum-resolved spectroscopy of a Fermi liquid

PubMed Central

Doggen, Elmer V. H.; Kinnunen, Jami J.

2015-01-01

We consider a recent momentum-resolved radio-frequency spectroscopy experiment, in which Fermi liquid properties of a strongly interacting atomic Fermi gas were studied. Here we show that by extending the Brueckner-Goldstone model, we can formulate a theory that goes beyond basic mean-field theories and that can be used for studying spectroscopies of dilute atomic gases in the strongly interacting regime. The model hosts well-defined quasiparticles and works across a wide range of temperatures and interaction strengths. The theory provides excellent qualitative agreement with the experiment. Comparing the predictions of the present theory with the mean-field Bardeen-Cooper-Schrieffer theory yields insights into the role of pair correlations, Tan's contact, and the Hartree mean-field energy shift. PMID:25941948

Portable laser synthesizer for high-speed multi-dimensional spectroscopy

DOEpatents

Demos, Stavros G [Livermore, CA; Shverdin, Miroslav Y [Sunnyvale, CA; Shirk, Michael D [Brentwood, CA

2012-05-29

Portable, field-deployable laser synthesizer devices designed for multi-dimensional spectrometry and time-resolved and/or hyperspectral imaging include a coherent light source which simultaneously produces a very broad, energetic, discrete spectrum spanning through or within the ultraviolet, visible, and near infrared wavelengths. The light output is spectrally resolved and each wavelength is delayed with respect to each other. A probe enables light delivery to a target. For multidimensional spectroscopy applications, the probe can collect the resulting emission and deliver this radiation to a time gated spectrometer for temporal and spectral analysis.

Time-resolved photoinduced thermoelectric and transport currents in GaAs nanowires.

PubMed

Prechtel, Leonhard; Padilla, Milan; Erhard, Nadine; Karl, Helmut; Abstreiter, Gerhard; Fontcuberta I Morral, Anna; Holleitner, Alexander W

2012-05-09

In order to clarify the temporal interplay of the different photocurrent mechanisms occurring in single GaAs nanowire based circuits, we introduce an on-chip photocurrent pump-probe spectroscopy with a picosecond time resolution. We identify photoinduced thermoelectric, displacement, and carrier lifetime limited currents as well as the transport of photogenerated holes to the electrodes. Moreover, we show that the time-resolved photocurrent spectroscopy can be used to investigate the drift velocity of photogenerated carriers in semiconducting nanowires. Hereby, our results are relevant for nanowire-based optoelectronic and photovoltaic applications.

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.

Multiple-step relayed correlation spectroscopy: sequential resonance assignments in oligosaccharides.

PubMed Central

Homans, S W; Dwek, R A; Fernandes, D L; Rademacher, T W

1984-01-01

A general property of the high-resolution proton NMR spectra of oligosaccharides is the appearance of low-field well-resolved resonances corresponding to the anomeric (H1) and H2 protons. The remaining skeletal protons resonate in the region 3-4 ppm, giving rise to an envelope of poorly resolved resonances. Assignments can be made from the H1 and H2 protons to their J-coupled neighbors (H2 and H3) within this main envelope by using 1H-1H correlated spectroscopy. However, the tight coupling (J congruent to delta) between further protons results in poor spectral dispersion with consequent assignment ambiguities. We describe here three-step two-dimensional relayed correlation spectroscopy and show how it can be used to correlate the resolved anomeric (H1) and H2 protons with remote (H4, H5) protons directly through a linear network of couplings using sequential magnetization transfer around the oligosaccharide rings. Resonance assignments are then obtained by inspection of cross-peaks that appear in well-resolved regions of the two-dimensional spectrum. This offers a general solution to the assignment problem in oligosaccharides and, importantly, these assignments will subsequently allow for the three-dimensional solution conformation to be determined by using one-dimensional and two-dimensional nuclear Overhauser experiments. PMID:6593701

Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hebert, Philippe; Saint-Amans, Charles

2013-06-01

A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

Time-resolved Spectroscopy of RS CVn Binaries and dMe Flare Stars

NASA Astrophysics Data System (ADS)

Brown, Alexander

One of the most striking feature of the first two years of EUVE spectroscopy is the frequent occurrence of largescale coronal variability, in the form of stellar flares and slower changes in activity level due to rotational modulation and evolution of active regions. We propose EUVE observations of a set of RS CVn and dMe star binaries, most with short (< 2 days) periods, to investigate the coronal conditions and physical processes associated with this variability. EUVE flare outbursts have mostly been long duration events lasting many satellite orbits and been readily studied using time-resolved spectroscopy. Our targets are the dMe binaries YY Gem, CC Eri and Gliese 2123, and the RS CVn systems EI Eri, AR Psc, and TY Pyx. YY Gem and TY Pyx are eclipsing systems and Deep Survey photometry will be used to investigate the size of the coronal emitting regions. Situated 73 arcmin from YY Gem is Castor (Alpha Gem) another X-ray source that can be observed (and spatially resolved) simultaneously. We shall use the DS lightcurve to guide our time resolved spectral analysis. Changes in the coronal emission measure as a function of temperature and possibly changes in coronal density will be used to constrain magnetic loop models.

Spatially Resolved Mid-IR Spectra from Meteorites; Linking Composition, Crystallographic Orientation and Spectra on the Micro-Scale

NASA Astrophysics Data System (ADS)

Stephen, N. R.

2016-08-01

IR spectroscopy is used to infer composition of extraterrestrial bodies, comparing bulk spectra to databases of separate mineral phases. We extract spatially resolved meteorite-specific spectra from achondrites with respect to zonation and orientation.

Time-resolved K α spectroscopy measurements of hot-electron equilibration dynamics in thin-foil solid targets: collisional and collective effects

NASA Astrophysics Data System (ADS)

Nilson, P. M.; Solodov, A. A.; Davies, J. R.; Theobald, W.; Mileham, C.; Stoeckl, C.; Begishev, I. A.; Zuegel, J. D.; Froula, D. H.; Betti, R.; Meyerhofer, D. D.

2015-11-01

Time-resolved K α spectroscopy measurements from high-intensity laser interactions with thin-foil solid targets are reviewed. Thin Cu foils were irradiated with 1-10 J, 1 ps pulses at focused intensities from 1018 to 1019 W cm-2. The experimental data show K α -emission pulse widths from 3 to 6 ps, increasing with laser intensity. The time-resolved K α -emission data are compared to a hot-electron transport and K α -production model that includes collisional electron-energy coupling, resistive heating, and electromagnetic field effects. The experimental data show good agreement with the model when a reduced ponderomotive scaling is used to describe the initial mean hot-electron energy over the relevant intensity range.

Alteration of time-resolved autofluorescence properties of rat aorta, induced by diabetes mellitus

NASA Astrophysics Data System (ADS)

Uherek, M.; Uličná, O.; Vančová, O.; Muchová, J.; Ďuračková, Z.; Šikurová, L.; Chorvát, D.

2016-10-01

Changes in autofluorescence properties of isolated rat aorta, induced by diabetes mellitus, were detected using time-resolved fluorescence spectroscopy with pulsed ultraviolet (UV) laser excitation. We demonstrated that time-resolved spectroscopy was able to detect changes in aorta tissues related to diabetes and unambiguously discriminate diabetic (τ 1 0.63  ±  0.05 ns, τ 2 3.66  ±  0.10 ns) samples from the control (τ 1 0.76  ±  0.03 ns, τ 2 4.48  ±  0.15 ns) group. We also report changes in the ratio of relative amplitudes of the two lifetime component in aorta tissue during diabetes, most likely related to the pseudohypoxic state with altered NADH homeostasis.

Next-generation sequencing for genetic testing of familial colorectal cancer syndromes.

PubMed

Simbolo, Michele; Mafficini, Andrea; Agostini, Marco; Pedrazzani, Corrado; Bedin, Chiara; Urso, Emanuele D; Nitti, Donato; Turri, Giona; Scardoni, Maria; Fassan, Matteo; Scarpa, Aldo

2015-01-01

Genetic screening in families with high risk to develop colorectal cancer (CRC) prevents incurable disease and permits personalized therapeutic and follow-up strategies. The advancement of next-generation sequencing (NGS) technologies has revolutionized the throughput of DNA sequencing. A series of 16 probands for either familial adenomatous polyposis (FAP; 8 cases) or hereditary nonpolyposis colorectal cancer (HNPCC; 8 cases) were investigated for intragenic mutations in five CRC familial syndromes-associated genes (APC, MUTYH, MLH1, MSH2, MSH6) applying both a custom multigene Ion AmpliSeq NGS panel and conventional Sanger sequencing. Fourteen pathogenic variants were detected in 13/16 FAP/HNPCC probands (81.3 %); one FAP proband presented two co-existing pathogenic variants, one in APC and one in MUTYH. Thirteen of these 14 pathogenic variants were detected by both NGS and Sanger, while one MSH2 mutation (L280FfsX3) was identified only by Sanger sequencing. This is due to a limitation of the NGS approach in resolving sequences close or within homopolymeric stretches of DNA. To evaluate the performance of our NGS custom panel we assessed its capability to resolve the DNA sequences corresponding to 2225 pathogenic variants reported in the COSMIC database for APC, MUTYH, MLH1, MSH2, MSH6. Our NGS custom panel resolves the sequences where 2108 (94.7 %) of these variants occur. The remaining 117 mutations reside inside or in close proximity to homopolymer stretches; of these 27 (1.2 %) are imprecisely identified by the software but can be resolved by visual inspection of the region, while the remaining 90 variants (4.0 %) are blind spots. In summary, our custom panel would miss 4 % (90/2225) of pathogenic variants that would need a small set of Sanger sequencing reactions to be solved. The multiplex NGS approach has the advantage of analyzing multiple genes in multiple samples simultaneously, requiring only a reduced number of Sanger sequences to resolve homopolymeric DNA regions not adequately assessed by NGS. The implementation of NGS approaches in routine diagnostics of familial CRC is cost-effective and significantly reduces diagnostic turnaround times.

Through the Looking GLASS: A JWST Exploration of Galaxy Formation and Evolution from Cosmic Dawn to Present Day

NASA Astrophysics Data System (ADS)

Treu, Tommaso; Abramson, L.; Bradac, M.; Brammer, G.; Fontana, A.; Henry, A.; Hoag, A.; Huang, K.; Mason, C.; Morishita, T.; Pentericci, L.; Wang, X.

2017-11-01

We propose a carefully designed set of observations of the lensing cluster Abell 2744 to study intrinsically faint magnified galaxies from the epoch of reionization to redshift of 1, demonstrating and characterizing complementary spectroscopic modes with NIRSPEC and NIRISS. The observations are designed to address the questions: 1) when did reionization happen and what were the sources of reionizing photons? 2) How do baryons cycle in and out of galaxies? This dataset with deep spectroscopy on the cluster and deep multiband NIRCAM imaging in parallel will enable a wealth of investigations and will thus be of interest to a broad section of the astronomical community. The dataset will illustrate the power and challenges of: 1) combining rest frame UV and optical NIRSPEC spectroscopy for galaxies at the epoch of reionization, 2) obtaining spatially resolved emission line maps with NIRISS, 3) combining NIRISS and NIRSPEC spectroscopy. Building on our extensive experience with HST slitless spectroscopy and imaging in clusters of galaxies as part of the GLASS, WISP, SURFSUP, and ASTRODEEP projects, we will provide the following science-enabling products to the community: 1)quantitative comparison of spatially resolved (NIRISS) and spectrally resolved (NIRSPEC) spectroscopy, 2) Object based interactive exploration tools for multi-instrument datasets, 3) Interface for easy forced extractionof slitless spectra based on coordinates, 4) UV-optical spectroscopic templates of highredshift galaxies, 5) NIRCAM parallel catalogs and a list of 26 z>=9 dropouts for spectroscopic follow-up in Cycle-2.

Spectrally resolved femtosecond photon echo spectroscopy of astaxanthin

NASA Astrophysics Data System (ADS)

Kumar, Ajitesh; Karthick Kumar, S. K.; Gupta, Aditya; Goswami, Debabrata

2010-12-01

We have studied the coherence and population dynamics of Astaxanthin solution in methanol and acetonitrile by spectrally resolving their photon echo signals. Our experiments indicate that methanol has a much stronger interaction with the ultrafast dynamics of Astaxanthin in comparison to that of acetonitrile.

Spectrally resolved femtosecond photon echo spectroscopy of astaxanthin

NASA Astrophysics Data System (ADS)

Kumar, Ajitesh; Karthick Kumar, S. K.; Gupta, Aditya; Goswami, Debabrata

2011-08-01

We have studied the coherence and population dynamics of Astaxanthin solution in methanol and acetonitrile by spectrally resolving their photon echo signals. Our experiments indicate that methanol has a much stronger interaction with the ultrafast dynamics of Astaxanthin in comparison to that of acetonitrile.

Long-range barcode labeling-sequencing

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

Chen, Feng; Zhang, Tao; Singh, Kanwar K.

Methods for sequencing single large DNA molecules by clonal multiple displacement amplification using barcoded primers. Sequences are binned based on barcode sequences and sequenced using a microdroplet-based method for sequencing large polynucleotide templates to enable assembly of haplotype-resolved complex genomes and metagenomes.

Noninvasive in situ evaluation of osteogenic differentiation by time-resolved laser-induced fluorescence spectroscopy.

PubMed

Ashjian, Peter; Elbarbary, Amir; Zuk, Patricia; DeUgarte, Daniel A; Benhaim, Prosper; Marcu, Laura; Hedrick, Marc H

2004-01-01

The clinical implantation of bioengineered tissues requires an in situ nondestructive evaluation of the quality of tissue constructs developed in vitro before transplantation. Time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) is demonstrated here to noninvasively monitor the formation of osteogenic extracellular matrix (ECM) produced by putative stem cells (PLA cells) derived from human adipose tissue. We show that this optical spectroscopy technique can assess the relative expression of collagens (types I, III, IV, and V) within newly forming osteogenic ECM. The results are consistent with those obtained by conventional histochemical techniques (immunofluorescence and Western blot) and demonstrate that TR-LIFS is a potential tool for monitoring the expression of distinct collagen types and the formation of collagen cross-links in intact tissue constructs.

Marrow Adipose Tissue Quantification of the Lumbar Spine by Using Dual-Energy CT and Single-Voxel 1H MR Spectroscopy: A Feasibility Study

PubMed Central

Daley, Scott M.; Kalra, Mannudeep K.; Brown, J. Keenan; Miller, Karen K.; Torriani, Martin

2015-01-01

Purpose To test the performance of dual-energy computed tomography (CT) in the assessment of marrow adipose tissue (MAT) content of the lumbar spine by using proton (hydrogen 1 [1H]) magnetic resonance (MR) spectroscopy as a reference standard and to determine the influence of MAT on the assessment of bone mineral density (BMD). Materials and Methods This study was institutional review board approved and complied with HIPAA guidelines. Written informed consent was obtained. Twelve obese osteopenic but otherwise healthy subjects (mean age ± standard deviation, 43 years ± 13) underwent 3-T 1H MR spectroscopy of the L2 vertebra by using a point-resolved spatially localized spectroscopy sequence without water suppression. The L2 vertebra was scanned with dual-energy CT (80 and 140 kV) by using a dual-source multi–detector row CT scanner with a calibration phantom. Mean basis material composition relative to the phantom was estimated in the L2 vertebra. Volumetric BMD was measured with and without correction for MAT. Bland-Altman 95% limits of agreement and Pearson correlation coefficients were calculated. Results There was excellent agreement between 1H MR spectroscopy and dual-energy CT, with a mean difference in fat fraction of −0.02 between the techniques, with a 95% confidence interval of −0.24, 0.20. There was a strong correlation between marrow fat fraction obtained with 1H MR spectroscopy and that obtained with dual-energy CT (r = 0.91, P < .001). The presence of MAT led to underestimation of BMD, and this bias increased with increasing MAT content (P < .001). Conclusion Dual-energy CT can be used to assess MAT content and BMD of the lumbar spine in a single examination and provides data that closely agree and correlate with 1H MR spectroscopy data. © RSNA, 2015 PMID:25988401

Raman spectroscopy and atomic force microscopy study of interfacial polytypism in GaP/Ge(111) heterostructures

NASA Astrophysics Data System (ADS)

Aggarwal, R.; Ingale, Alka A.; Dixit, V. K.

2018-01-01

Effects of lattice and polar/nonpolar mismatch between the GaP layer and Ge(111) substrate are investigated by spatially resolved Raman spectroscopy. The red shifted transverse optical (TO) and longitudinal optical (LO) phonons due to residual strain, along with asymmetry to TO phonon ∼358 cm-1 are observed in GaP/Ge(111). The peak intensity variation of mode ∼358 cm-1 with respect to TO phonon across the crystallographic morphed surface of GaP micro structures is associated with the topographical variations using atomic force microscopy mapping and Raman spectroscopy performed on both in plane and cross-sectional surface. Co-existence of GaP allotropes, i.e. wurtzite phase near heterojunction interface and dominant zinc-blende phase near surface is established using the spatially resolved polarized Raman spectroscopy from the cross sectional surface of heterostructures. This consistently explains effect of surface morphology on Raman spectroscopy from GaP(111). The study shows the way to identify crystalline phases in other advanced semiconductor heterostructures without any specific sample preparation.

Direct measurement of radiative scattering of surface plasmon polariton resonance from metallic arrays by polarization-resolved reflectivity spectroscopy

NASA Astrophysics Data System (ADS)

Lo, H. Y.; Chan, C. Y.; Ong, H. C.

2012-11-01

We have measured the radiative scattering from two-dimensional metallic arrays by using polarization-resolved reflectivity spectroscopy. We find the reflectivity spectra follow the Fano-like model that can be derived from temporal coupled mode theory and Jones matrix calculus. By orthogonally orienting the incident polarizer and the detection analyzer, reflectivity dips flip into peaks and the radiative scattering efficiency can be determined accordingly. The dependence of total radiative scattering efficiency on wavelength and hole diameter is found to agree well with Rayleigh scattering by single hole.

Direct observation of back energy transfer in blue phosphorescent materials for organic light emitting diodes by time-resolved optical waveguide spectroscopy.

PubMed

Hirayama, H; Sugawara, Y; Miyashita, Y; Mitsuishi, M; Miyashita, T

2013-02-25

We demonstrate a high-sensitive transient absorption technique for detection of excited states in an organic thin film by time-resolved optical waveguide spectroscopy. By using a laser beam as a probe light, we detect small change in the transient absorbance which is equivalent to 10 -7 absorbance unit in a conventional method. This technique was applied to organic thin films of blue phosphorescent materials for organic light emitting diodes. We directly observed the back energy transfer from emitting guest molecules to conductive host molecules.

Temperature-induced band shift in bulk γ-InSe by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Huanfeng; Wang, Wei; Zhao, Yafei; Zhang, Xiaoqian; Feng, Yue; Tu, Jian; Gu, Chenyi; Sun, Yizhe; Liu, Chang; Nie, Yuefeng; Edmond Turcu, Ion C.; Xu, Yongbing; He, Liang

2018-05-01

Indium selenide (InSe) has recently become popular research topics because of its unique layered crystal structure, direct band gap and high electron mobilities. In this work, we have acquired the electronic structure of bulk γ-InSe at various temperatures using angle-resolved photoemission spectroscopy (ARPES). We have also found that as the temperature decreases, the valence bands of γ-InSe exhibit a monotonic shift to lower binding energies. This band shift is attributed to the change of lattice parameters and has been validated by variable temperature X-ray diffraction measurements and theoretical calculations.

Photolytic interruptions of the bacteriorhodopsin photocycle examined by time-resolved resonance raman spectroscopy.

PubMed

Grieger, I; Atkinson, G H

1985-09-24

An investigation of the photolytic conditions used to initiate and spectroscopically monitor the bacteriorhodopsin (BR) photocycle utilizing time-resolved resonance Raman (TR3) spectroscopy has revealed and characterized two photoinduced reactions that interrupt the thermal pathway. One reaction involves the photolytic interconversion of M-412 and M', and the other involves the direct photolytic conversion of the BR-570/K-590 photostationary mixture either to M-412 and M' or to M-like intermediates within 10 ns. The photolytic threshold conditions describing both reactions have been quantitatively measured and are discussed in terms of experimental parameters.

Time-resolved coherent Raman spectroscopy by high-speed pump-probe delay scanning.

PubMed

Domingue, S R; Winters, D G; Bartels, R A

2014-07-15

Using a spinning window pump-probe delay scanner, we demonstrate a means of acquiring time-resolved vibrational spectra at rates up to 700 Hz. The time-dependent phase shift accumulated by the probe pulse in the presence of a coherently vibrating sample gives rise to a Raman-induced frequency shifting readily detectable in a balanced detector. This rapid delay scanning system represents a 23-fold increase in averaging speed and is >10× faster than state-of-the-art voice coil delay lines. These advancements make pump-probe spectroscopy a more practical means of imaging complex media.

Time-resolved photoelectron spectroscopy of nitrobenzene and its aldehydes

NASA Astrophysics Data System (ADS)

Schalk, Oliver; Townsend, Dave; Wolf, Thomas J. A.; Holland, David M. P.; Boguslavskiy, Andrey E.; Szöri, Milan; Stolow, Albert

2018-01-01

We report the first femtosecond time-resolved photoelectron spectroscopy study of 2-, 3- and 4-nitrobenzaldehyde (NBA) and nitrobenzene (NBE) in the gas phase upon excitation at 200 nm. In 3- and 4-NBA, the dynamics follow fast intersystem crossing within 1-2 picoseconds. In 2-NBA and NBE, the dynamics are faster (∼ 0.5 ps). 2-NBA undergoes hydrogen transfer similar to solution phase dynamics. NBE either releases NO2 in the excited state or converts internally back to the ground state. We discuss why these channels are suppressed in the other nitrobenzaldehydes.

Application of a protocol for magnetic resonance spectroscopy of adrenal glands: an experiment with over 100 cases.

PubMed

Melo, Homero José de Farias E; Goldman, Suzan M; Szejnfeld, Jacob; Faria, Juliano F; Huayllas, Martha K P; Andreoni, Cássio; Kater, Cláudio E

2014-01-01

To evaluate a protocol for two-dimensional (2D) hydrogen proton (1H) magnetic resonance spectroscopy (MRS) (Siemens Medical Systems; Erlangen, Germany) in the detection of adrenal nodules and differentiation between benign and malignant masses (adenomas, pheochromocytomas, carcinomas and metastases). A total of 118 patients (36 men; 82 women) (mean age: 57.3 ± 13.3 years) presenting with 138 adrenal nodules/masses were prospectively assessed. A multivoxel system was utilized with a 2D point-resolved spectroscopy/chemical shift imaging sequence. The following ratios were calculated: choline (Cho)/creatine (Cr), 4.0-4.3/Cr, lipid (Lip)/Cr, Cho/Lip and lactate (Lac)/Cr. 2D-1H-MRS was successful in 123 (89.13%) lesions. Sensitivity and specificity values observed for the ratios and cutoff points were the following: Cho/Cr ≥ 1.2, 100% sensitivity, 98.2% specificity (differences between adenomas/pheochromocytomas and carcinomas/ metastases); 4.0-4.3 ppm/Cr ≥ 1.5, 92.3% sensitivity, 96.9% specificity (differences between carcinomas/pheochromocytomas and adenomas/metastases); Lac/Cr ≤ -7.449, 90.9% sensitivity and 77.8% specificity (differences between pheochromocytomas and carcinomas/adenomas). Information provided by 2D-1H-MRS were effective and allowed for the differentiation between adrenal masses and nodules in most cases of lesions with > 1.0 cm in diameter.

Alterations in anterior cingulate cortex myoinositol and aggression in veterans with suicidal behavior: A proton magnetic resonance spectroscopy study.

PubMed

Sheth, Chandni; Prescot, Andrew; Bueler, Elliott; DiMuzio, Jennifer; Legarreta, Margaret; Renshaw, Perry F; Yurgelun-Todd, Deborah; McGlade, Erin

2018-06-30

Studies investigating the neurochemical changes that correspond with suicidal behavior (SB) have not yielded conclusive results. Suicide correlates such as aggression have been used to explore risk factors for SB. Yet the neurobiological basis for the association between aggression and SB is unclear. Aggression and SB are both prevalent in veterans relative to civilian populations. The current study evaluated the relationship between brain chemistry in the anterior (ACC) and the posterior cingulate cortex (POC), as well as the relationship between aggression and SB in a veteran population using proton magnetic resonance spectroscopy ( 1 H-MRS). Single-voxel MRS data at 3 Tesla (T) were acquired from the ACC and POC voxels using a 2-dimensional J-resolved point spectroscopy sequence and quantified using the ProFit algorithm. Participants also completed a structured diagnostic interview and a clinical battery. Our results showed that the myoinositol (mI)/H2O ratio in the ACC and POC was significantly higher in veterans who reported SB when compared to veterans who did not. The two groups did not differ significantly with regard to other metabolites. Second, verbal aggression and SB measures positively correlated with mI/H2O in the ACC. Finally, verbal aggression mediated the relationship between mI/H2O in the ACC and SB. Copyright © 2018 Elsevier B.V. All rights reserved.

Covariance J-resolved spectroscopy: Theory and application in vivo.

PubMed

Iqbal, Zohaib; Verma, Gaurav; Kumar, Anand; Thomas, M Albert

2017-08-01

Magnetic resonance spectroscopy (MRS) is a powerful tool capable of investigating the metabolic status of several tissues in vivo. In particular, single-voxel-based 1 H spectroscopy provides invaluable biochemical information from a volume of interest (VOI) and has therefore been used in a variety of studies. Unfortunately, typical one-dimensional MRS data suffer from severe signal overlap and thus important metabolites are difficult to distinguish. One method that is used to disentangle overlapping resonances is the two-dimensional J-resolved spectroscopy (JPRESS) experiment. Due to the long acquisition duration of the JPRESS experiment, a limited number of points are acquired in the indirect dimension, leading to poor spectral resolution along this dimension. Poor spectral resolution is problematic because proper peak assignment may be hindered, which is why the zero-filling method is often used to improve resolution as a post-processing step. However, zero-filling leads to spectral artifacts, which may affect visualization and quantitation of spectra. A novel method utilizing a covariance transformation, called covariance J-resolved spectroscopy (CovJ), was developed in order to improve spectral resolution along the indirect dimension (F 1 ). Comparison of simulated data demonstrates that peak structures remain qualitatively similar between JPRESS and the novel method along the diagonal region (F 1 = 0 Hz), whereas differences arise in the cross-peak (F 1 ≠0 Hz) regions. In addition, quantitative results of in vivo JPRESS data acquired on a 3T scanner show significant correlations (r 2 >0.86, p<0.001) when comparing the metabolite concentrations between the two methods. Finally, a quantitation algorithm, 'COVariance Spectral Evaluation of 1 H Acquisitions using Representative prior knowledge' (Cov-SEHAR), was developed in order to quantify γ-aminobutyric acid and glutamate from the CovJ spectra. These preliminary findings indicate that the CovJ method may be used to improve spectral resolution without hindering metabolite quantitation for J-resolved spectra. Copyright © 2017 John Wiley & Sons, Ltd.

Direct Imaging of Transient Fano Resonances in N_{2} Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy.

PubMed

Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J J; Kornilov, Oleg

2016-04-22

Autoionizing Rydberg states of molecular N_{2} are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14±1  fs, while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance.

Time-resolved K α spectroscopy measurements of hot-electron equilibration dynamics in thin-foil solid targets: Collisional and collective effects

DOE PAGES

Nilson, P. M.; Solodov, A. A.; Davies, J. R.; ...

2015-09-25

Time-resolved K α spectroscopy measurements from high-intensity laser interactions with thin-foil solid targets are reviewed. Thin Cu foils were irradiated with 1- to 10-J, 1-ps pulses at focused intensities from 10 18 to 10 19 W/cm 2. The experimental data show K α-emission pulse widths from 3 to 6 ps, increasing with laser intensity. The time-resolved K α-emission data are compared to a hot-electron transport and K α-production model that includes collisional electron-energy coupling, resistive heating, and electromagnetic field effects. The experimental data show good agreement with the model when a reduced ponderomotive scaling is used to describe the initialmore » mean hot-electron energy over the relevant intensity range.« less

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.

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.

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.

Time-Resolved Images of Laser-Induced Gas Ignition Using High-Speed Photographic and Spectroscopic Techniques

NASA Astrophysics Data System (ADS)

Chen, Ying-Ling; Lewis, J. W. L.; Parigger, C. G.

1997-11-01

Two-dimensional visualization of laser-induced spark ignition in atmospheric-pressure gases is reported. Laser-induced breakdown in air, O2 and combustible NH_3/O2 mixture was achieved using a 1064 nm, Nd:YAG laser of approximately 6 ns pulse width, focused at 10-mm above a 60-mm diameter flat-flame burner. An argon sheath-gas flow was used to stabilize the core flowfield. High-speed photographic techniques were applied to trace a complete sequence of kernel development of a single breakdown or ignition event. Thermochemical characteristics of the post-breakdown regime were analyzed by laser-induced fluorescence spectroscopy (LIFS). Spatial distribution of NH free radical observed by planar-LIF showed the contours of the developing flame-front. The corresponding NH temperature maps achieved by excitation LIFS and Boltzmann plot are also presented.

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

On resolving the 180 deg ambiguity for a temporal sequence of vector magnetograms

NASA Astrophysics Data System (ADS)

Cheung, M. C.

2008-05-01

The solar coronal magnetic field evolves in response to the underlying photospheric driving. To study this connection by means of data-driven modeling, an accurate knowledge of the evolution of the photospheric vector field is essential. While there is a large body of work on attempts to resolve the 180 deg ambiguity in the component of the magnetic field transverse to the line of sight, most of these methods are applicable only to individual frames. With the imminent launch of the Solar Dynamics Observatory, it is especially timely for us to develop possible automated methods to resolve the ambiguity for temporal sequences of magnetograms. We present here the temporal acute angle method, which makes use of preceding disambiguated magnetograms as reference solutions for resolving the ambiguity in subsequent frames. To find the strengths and weaknesses of this method, we have carried out tests (1) on idealized magnetogram sequences involving simple rotating, shearing and straining flows and (2) on a synthetic magnetogram sequence from a 3D radiative MHD simulation of an buoyant magnetic flux tube emerging through granular convection. A metric for automatically picking out regions where the method is likely to fail is also presented.

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

IRMPD Spectroscopy Sheds New (Infrared) Light on the Sulfate Pattern of Carbohydrates.

PubMed

Schindler, B; Barnes, L; Gray, C J; Chambert, S; Flitsch, S L; Oomens, J; Daniel, R; Allouche, A R; Compagnon, I

2017-03-16

IR spectroscopy of gas-phase ions is proposed to resolve positional isomers of sulfated carbohydrates. Mass spectrometric fingerprints and gas-phase vibrational spectra in the near and mid-IR regions were obtained for sulfated monosaccharides, yielding unambiguous signatures of sulfated isomers. We report the first systematic exploration of the biologically relevant but notoriously challenging deprotonated state in the near IR region. Remarkably, anions displayed very atypical vibrational profiles, which challenge the well-established DFT (Density Functionnal Theory) modeling. The proposed approach was used to elucidate the sulfate patterns in glycosaminoglycans, a ubiquitous class of mammalian carbohydrates, which is regarded as a major challenge in carbohydrate structural analysis. Isomeric glycosaminoglycan disaccharides from heparin and chondroitin sources were resolved, highlighting the potential of infrared multiple photon dissociation spectroscopy as a novel structural tool for carbohydrates.

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.

Proton-decoupled, Overhauser-enhanced, spatially localized carbon-13 spectroscopy in humans.

PubMed

Bottomley, P A; Hardy, C J; Roemer, P B; Mueller, O M

1989-12-01

Spatially localized, natural abundance, carbon (13C) NMR spectroscopy has been combined with proton (1H) decoupling and nuclear Overhauser enhancement to improve 13C sensitivity up to five-fold in the human leg, liver, and heart. Broadhand-decoupled 13C spectra were acquired in 1 s to 17 min with a conventional 1.5-T imaging/spectroscopy system, an auxiliary 1H decoupler, an air-cooled dual-coil coplanar surface probe, and both depth-resolved surface coil spectroscopy (DRESS) and one-dimensional phase-encoding gradient NMR pulse sequences. The surface coil probe comprised circular and figure-eight-shaped coils to eliminate problems with mutual coupling of coils at high decoupling power levels applied during 13C reception. Peak decoupler RF power deposition in tissue was computed numerically from electromagnetic theory assuming a semi-infinite plane of uniform biological conductor. Peak values at the surface were calculated at 4 to 6 W/kg in any gram of tissue for each watt of decoupler power input excluding all coil and cable losses, warning of potential local RF heating problems in these and related experiments. The average power deposition was about 9 mW/kg per watt input, which should present no systemic hazard. At 3 W input, human 13C spectra were decoupled to a depth of about 5 cm while some Overhauser enhancement was sustained up to about 3 cm depth, without ill effect. The observation of glycogen in localized natural abundance 13C spectra of heart and muscle suggests that metabolites in the citric acid cycle should be observable noninvasively using 13C-labeled substrates.

Multiplexed fragaria chloroplast genome sequencing

Treesearch

W. Njuguna; A. Liston; R. Cronn; N.V. Bassil

2010-01-01

A method to sequence multiple chloroplast genomes using ultra high throughput sequencing technologies was recently described. Complete chloroplast genome sequences can resolve phylogenetic relationships at low taxonomic levels and identify informative point mutations and indels. The objective of this research was to sequence multiple Fragaria...

Atomic and electronic structure of trilayer graphene/SiC(0001): Evidence of Strong Dependence on Stacking Sequence and charge transfer.

PubMed

Pierucci, Debora; Brumme, Thomas; Girard, Jean-Christophe; Calandra, Matteo; Silly, Mathieu G; Sirotti, Fausto; Barbier, Antoine; Mauri, Francesco; Ouerghi, Abdelkarim

2016-09-15

The transport properties of few-layer graphene are the directly result of a peculiar band structure near the Dirac point. Here, for epitaxial graphene grown on SiC, we determine the effect of charge transfer from the SiC substrate on the local density of states (LDOS) of trilayer graphene using scaning tunneling microscopy/spectroscopy and angle resolved photoemission spectroscopy (ARPES). Different spectra are observed and are attributed to the existence of two stable polytypes of trilayer: Bernal (ABA) and rhomboedreal (ABC) staking. Their electronic properties strongly depend on the charge transfer from the substrate. We show that the LDOS of ABC stacking shows an additional peak located above the Dirac point in comparison with the LDOS of ABA stacking. The observed LDOS features, reflecting the underlying symmetry of the two polytypes, were reproduced by explicit calculations within density functional theory (DFT) including the charge transfer from the substrate. These findings demonstrate the pronounced effect of stacking order and charge transfer on the electronic structure of trilayer or few layer graphene. Our approach represents a significant step toward understand the electronic properties of graphene layer under electrical field.

Age Related Changes in Metabolite Concentrations in the Normal Spinal Cord

PubMed Central

Abdel-Aziz, Khaled; Solanky, Bhavana S.; Yiannakas, Marios C.; Altmann, Daniel R.; Wheeler-Kingshott, Claudia A. M.; Thompson, Alan J.; Ciccarelli, Olga

2014-01-01

Magnetic resonance spectroscopy (MRS) studies have previously described metabolite changes associated with aging of the healthy brain and provided insights into normal brain aging that can assist us in differentiating age-related changes from those associated with neurological disease. The present study investigates whether age-related changes in metabolite concentrations occur in the healthy cervical spinal cord. 25 healthy volunteers, aged 23–65 years, underwent conventional imaging and single-voxel MRS of the upper cervical cord using an optimised point resolved spectroscopy sequence on a 3T Achieva system. Metabolite concentrations normalised to unsuppressed water were quantified using LCModel and associations between age and spinal cord metabolite concentrations were examined using multiple regressions. A linear decline in total N-Acetyl-aspartate concentration (0.049 mmol/L lower per additional year of age, p = 0.010) and Glutamate-Glutamine concentration (0.054 mmol/L lower per additional year of age, p = 0.002) was seen within our sample age range, starting in the early twenties. The findings suggest that neuroaxonal loss and/or metabolic neuronal dysfunction, and decline in glutamate-glutamine neurotransmitter pool progress with aging. PMID:25310093

Dissecting the assembly and star formation history of disks and bulges in nearby spirals using the VENGA IFU survey

NASA Astrophysics Data System (ADS)

Carrillo, Andreia Jessica; Jogee, Shardha; Kaplan, Kyle; Weinzirl, Tim; Blanc, Guillermo A.

2017-06-01

Integral field spectroscopy of nearby galaxies provides a powerful and unparalleled tool for studying how galaxies assemble the different components -- the bulge, bar, and disk-- that define the Hubble sequence. We explore the assembly and star formation history of these components using galaxies in the VIRUS-P Exploration of Nearby Galaxies (VENGA) survey of 30 nearby spiral galaxies. Compared to other integral field spectroscopy studies of spirals, our study benefits from high spatial sampling and resolution (typically a few 100 pc), large coverage from the bulge to the outer disk, broad wavelength range (3600-6800 A), and medium spectral resolution (120 km/s at 5000 A). In this poster, we present the methodology and data illustrating the exquisite, high-quality, spatially-resolved spectra out to large radii, and the distribution, kinematics, and metallicity of stars and ionized gas. We discuss the next steps in deriving the star formation history (SFH) of bulge, bar, and disk components, and elucidating their assembly pathway by comparing their SFH and structural properties to theoretical models of galaxy evolution. This project is supported by the NSF grants AST-1614798 and AST-1413652.

High-Resolution Spectroscopy of Stratospheric Ethane Following the Jupiter Impact of 2009

NASA Technical Reports Server (NTRS)

Fast, Kelly; Kostiuk, Theodor; Livengood, Timothy A.; Hewagama, Tilak; Amen, John

2010-01-01

We report on high-resolution infrared spectroscopy of ethane (C2H6) performed at the latitude of an impact site on Jupiter discovered on 19 July 2009 by A. Wesley from a location in Murrumbateman, Australia. The observations used the NASA Goddard Space Flight Center's Heterodyne Instrument for Planetary Wind and Composition (HIPWAC) at the NASA Infrared Telescope Facility (IRTF) on Mauna Kea, Hawaii. HIPWAC is a mid-infrared (9-12 microns) heterodyne spectrometer operating at the highest limit of spectral resolving power (lambda\\Delta\\lambda > l06), providing information on atmospheric constituent abundance and temperature through fully resolved tine shapes. Ethane is a stable trace product of methane photochemistry that is nearly uniformly mixed in Jupiter's stratosphere, providing an effective probe of that altitude region. Ethane emission line profiles near 11,74 microns in the Ug band were measured in Jupiter's stratosphere at 25 MHz (11.00083/cm) resolution. A sequence of spectra of ethane acquired over a range of longitude at the impact latitude (56S planetocentric) probes constituent abundance and temperature profile, both on and off the impact region. Near the site of the impact, ethane emission increased above levels measured well outside the impact region. Radiative transfer analysis indicates increased ethane mole fraction (30% greater). Variation in the measured continuum level and line intensities within 75deg of the impact longitude indicate the presence of an opacity source (haze) at altitudes near and above the tropopause and as high as the 10-mbar level near the impact site. The indication of possible haze opacity up to the 10-mbar level in the atmosphere is consistent with measurements made by HIPWAC's predecessor as part of the IRTF Shoemaker Levy-9 campaign in 1994.

SDSS-IV MaNGA: Spatially Resolved Star Formation Main Sequence and LI(N)ER Sequence

NASA Astrophysics Data System (ADS)

Hsieh, B. C.; Lin, Lihwai; Lin, J. H.; Pan, H. A.; Hsu, C. H.; Sánchez, S. F.; Cano-Díaz, M.; Zhang, K.; Yan, R.; Barrera-Ballesteros, J. K.; Boquien, M.; Riffel, R.; Brownstein, J.; Cruz-González, I.; Hagen, A.; Ibarra, H.; Pan, K.; Bizyaev, D.; Oravetz, D.; Simmons, A.

2017-12-01

We present our study on the spatially resolved Hα and M * relation for 536 star-forming and 424 quiescent galaxies taken from the MaNGA survey. We show that the star formation rate surface density ({{{Σ }}}{SFR}), derived based on the Hα emissions, is strongly correlated with the M * surface density ({{{Σ }}}* ) on kiloparsec scales for star-forming galaxies and can be directly connected to the global star-forming sequence. This suggests that the global main sequence may be a consequence of a more fundamental relation on small scales. On the other hand, our result suggests that ∼20% of quiescent galaxies in our sample still have star formation activities in the outer region with lower specific star formation rate (SSFR) than typical star-forming galaxies. Meanwhile, we also find a tight correlation between {{{Σ }}}{{H}α } and {{{Σ }}}* for LI(N)ER regions, named the resolved “LI(N)ER” sequence, in quiescent galaxies, which is consistent with the scenario that LI(N)ER emissions are primarily powered by the hot, evolved stars as suggested in the literature.

Compact all-fiber quartz-enhanced photoacoustic spectroscopy sensor with a 30.72 kHz quartz tuning fork and spatially resolved trace gas detection

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

Ma, Yufei, E-mail: mayufei@hit.edu.cn; Post-doctoral Mobile Station of Power Engineering and Engineering Thermophysics, Harbin Institute of Technology, Harbin 150001; He, Ying

An ultra compact all-fiber quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor using quartz tuning fork (QTF) with a low resonance frequency of 30.72 kHz was demonstrated. Such a sensor architecture has the advantages of easier optical alignment, lower insertion loss, lower cost, and more compact compared with a conventional QEPAS sensor using discrete optical components for laser delivery and coupling to the QTF. A fiber beam splitter and three QTFs were employed to perform multi-point detection and demonstrated the potential of spatially resolved measurements.

Raman spectroscopy and time-resolved photoluminescence of BN and BxCyNz nanotubes

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

Wu, J.; Han, Wei-Qiang; Walukiewicz, W.

2004-01-21

We report Raman and time-resolved photoluminescence spectroscopic studies of multiwalled BN and B{sub x}C{sub y}N{sub z} nanotubes. The Raman spectroscopy shows that the as-grown B{sub x}C{sub y}N{sub z} charge recombination, respectively. Comparison of the photoluminescence of BN nanotubes to that decay process is characterized by two time constants that are attributed to intra- and inter-BN sheet nanotubes as predicted by theory. nanotubes are radially phase separated into BN shells and carbon shells. The photoluminescence of hexagonal BN is consistent with the existence of a spatially indirect band gap in multi-walled BN.

Time-Resolved IR-Absorption Spectroscopy of Hot-Electron Dynamics in Satellite and Upper Conduction Bands in GaP

NASA Technical Reports Server (NTRS)

Cavicchia, M. A.; Alfano, R. R.

1995-01-01

The relaxation dynamics of hot electrons in the X6 and X7 satellite and upper conduction bands in GaP was directly measured by femtosecond UV-pump-IR-probe absorption spectroscopy. From a fit to the induced IR-absorption spectra the dominant scattering mechanism giving rise to the absorption at early delay times was determined to be intervalley scattering of electrons out of the X7 upper conduction-band valley. For long delay times the dominant scattering mechanism is electron-hole scattering. Electron transport dynamics of the upper conduction band of GaP has been time resolved.

Time-resolved photoelectron spectroscopy of polyatomic molecules using 42-nm vacuum ultraviolet laser based on high harmonics generation

NASA Astrophysics Data System (ADS)

Nishitani, Junichi; West, Christopher W.; Higashimura, Chika; Suzuki, Toshinori

2017-09-01

Time-resolved photoelectron spectroscopy (TRPES) of gaseous polyatomic molecules using 266-nm (4.7 eV) pump and 42-nm (29.5 eV) probe pulses is presented. A 1-kHz Ti:sapphire laser with a 35 fs pulse duration is employed to generate high harmonics in Kr gas, and the 19th harmonic (42-nm) was selected using two SiC/Mg mirrors. Clear observation of the ultrafast electronic dephasing in pyrazine and photoisomerization of 1,3-cyclohexadiene demonstrates the feasibility of TRPES with the UV pump and VUV probe pulses under weak excitation conditions in the perturbation regime.

Diagnosing the plasma nonuniformity in an iron opacity experiment by spatially resolved Al 1s-2p absorption spectroscopy

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

Zhang Xiaoding; Research Center of Laser Fusion, P. O. Box 919-986, Mianyang 621900; Zhang Jiyan

Generating a well-characterized hot-dense sample is of great importance to high quality opacity measurements. In this paper, we report on an experimental investigation of the plasma nonuniformity in a radiatively heated iron opacity sample by spatially resolved Al 1s-2p absorption spectroscopy. The iron sample was tamped by plastic at both sides and was heated by thermal x-ray radiation generated in a gold Hohlraum, and an Al layer attached to it was used as a tracer for temperature diagnosis. Spatially resolved 1s-2p transition absorption spectra of the Al tracer were measured by the technique of point-projection-spectroscopy, and temperatures in the samplemore » were obtained by comparing the measured spectra with detailed-term-accounting model calculations, with the density of the sample deduced using a combination of side-on radiography and radiative hydrodynamic simulation. The results showed the existence of axial temperature nonuniformity in the sample, and these temperature variations have been used to explain the shift of iron 2p-3d transition absorption feature along the axial direction of the Hohlraum used to heat the sample successfully.« 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

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.

Depth-resolved fluorescence of human ectocervical tissue

NASA Astrophysics Data System (ADS)

Wu, Yicong; Xi, Peng; Cheung, Tak-Hong; Yim, So Fan; Yu, Mei-Yung; Qu, Jianan Y.

2005-04-01

The depth-resolved autofluorescence of normal and dysplastic human ectocervical tissue within 120um depth were investigated utilizing a portable confocal fluorescence spectroscopy with the excitations at 355nm and 457nm. From the topmost keratinizing layer of all ectocervical tissue samples, strong keratin fluorescence with the spectral characteristics similar to collagen was observed, which created serious interference in seeking the correlation between tissue fluorescence and tissue pathology. While from the underlying non-keratinizing epithelial layer, the measured NADH fluorescence induced by 355nm excitation and FAD fluorescence induced by 457nm excitation were strongly correlated to the tissue pathology. The ratios between NADH over FAD fluorescence increased statistically in the CIN epithelial relative to the normal and HPV epithelia, which indicated increased metabolic activity in precancerous tissue. 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.

Angle-resolved photoemission spectroscopy with 9-eV photon-energy pulses generated in a gas-filled hollow-core photonic crystal fiber

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

Bromberger, H., E-mail: Hubertus.Bromberger@mpsd.mpg.de; Liu, H.; Chávez-Cervantes, M.

2015-08-31

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 Bi{sub 2}Se{sub 3} 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,more » with photon energies that cover the first Brillouin zone of most materials.« less

Fluorescence lifetime analysis and effect of magnesium ions on binding of NADH to human aldehyde dehydrogenase 1

USDA-ARS?s Scientific Manuscript database

Aldehyde dehydrogenase 1 (ALDH1) catalyzes oxidation of toxic aldehydes to carboxylic acids. Physiologic levels of Mg2+ ions influence ALDH1 activity in part by increasing NADH binding affinity to the enzyme thus reducing activity. By using time-resolved fluorescence spectroscopy, we have resolved t...

Near-infrared muscle functional monitoring

NASA Astrophysics Data System (ADS)

Ferrari, Marco; De Blasi, Roberto A.; Ferrari, Adriano; Pizzi, Assunta; Quaresima, Valentina

1994-01-01

The oxygenation of human muscle tissue can be investigated using near IR spectroscopy (NIRS). Oxy and deoxy hemoglobin changes can be quantified combining attenuation measurements with pathlength data obtained by time resolved spectroscopy. This study reports the application of NIRS to non- invasive measurements of quadriceps oxygenation on muscular dystrophy patients during treadmill exercise.

Time-resolved spectroscopy using a chopper wheel as a fast shutter

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

Wang, Shicong; Wendt, Amy E.; Boffard, John B.

Widely available, small form-factor, fiber-coupled spectrometers typically have a minimum exposure time measured in milliseconds, and thus cannot be used directly for time-resolved measurements at the microsecond level. Spectroscopy at these faster time scales is typically done with an intensified charge coupled device (CCD) system where the image intensifier acts as a “fast” electronic shutter for the slower CCD array. In this paper, we describe simple modifications to a commercially available chopper wheel system to allow it to be used as a “fast” mechanical shutter for gating a fiber-coupled spectrometer to achieve microsecond-scale time-resolved optical measurements of a periodically pulsedmore » light source. With the chopper wheel synchronized to the pulsing of the light source, the time resolution can be set to a small fraction of the pulse period by using a chopper wheel with narrow slots separated by wide spokes. Different methods of synchronizing the chopper wheel and pulsing of the light sources are explored. The capability of the chopper wheel system is illustrated with time-resolved measurements of pulsed plasmas.« less

Ir-Uv Double Resonance Spectroscopy of a Cold Protonated Fibril-Forming Peptide: NNQQNY\\cdotH+

NASA Astrophysics Data System (ADS)

DeBlase, Andrew F.; Harrilal, Christopher P.; Walsh, Patrick S.; McLuckey, Scott A.; Zwier, Timothy S.

2016-06-01

Protein aggregation to form amyloid-like fibrils is a purported molecular manifestation that leads to Alzheimer's, Huntington's, and other neurodegenerative diseases. The propensity for a protein to aggregate is often driven by the presence of glutamine (Q) and asparagine (N) rich tracts within the primary sequence. For example, Eisenberg and coworkers [Nature 2006, 435, 773] have shown by X-ray crystallography that the peptides NNQQNY and GNNQQNY aggregate into a parallel β-sheet configuration with side chains that intercalate into a "steric zipper". These sequences are commonly found at the N-terminus of the prion-determining domain in the yeast protein Sup35, a typical fibril-forming protein. Herein, we invoke recent advances in cold ion spectroscopy to explore the nascent conformational preferences of the protonated peptides that are generated by electrospray ionization. Towards this aim, we have used UV and IR spectroscopy to record conformation-specific photofragment action spectra of the NNQQNY monomer cryogenically cooled in an octopole ion trap. This short peptide contains 20 hydride stretch oscillators, leading to a rich infrared spectrum with at least 18 resolved transitions in the 2800-3800 cm-1 region. The infrared spectrum suggests the presence of both a free acid OH moiety and an H-bonded tyrosine OH group. We compare our results with resonant ion dip infrared spectra (RIDIRS) of the acyl/NH-benzyl capped neutral glutamine amino acid and its corresponding dipeptide: Ac-Q-NHBn and Ac-QQ-NHBn, respectively. These comparisons bring empirical insight to the NH stretching region of the spectrum, which contains contributions from free and singly H-bonded NH2 side-chain groups, and from peptide backbone amide NH groups. We further compare our spectrum to harmonic calculations at the M05-2X/6-31+G* level of theory, which were performed on low energy structures obtained from Monte Carlo conformational searches using the Amber* and OPLS force fields to assess the presence of sidechain-sidechain and sidechain-backbone interactions.

Application of Single Voxel 1H Magnetic Resonance Spectroscopy in Hepatic Benign and Malignant Lesions.

PubMed

Yang, Zifeng; Sun, Shiqiang; Chen, Yuanli; Li, Rui

2016-12-19

BACKGROUND To quantify the metabolite changes in hepatic tumors by single-voxel 1H magnetic resonance spectroscopy (MRS) at 3.0 T and explore the application value of 1HMRS in the diagnosis of hepatic benign and malignant lesions. MATERIAL AND METHODS A total of 45 patients (55 lesions) diagnosed with hepatic lesions by ultrasound and/or computer topography (CT) from November 2006 to March 2007 were included in this study. All patients underwent 3D-dynamic enhanced scan with liver acquisition with acceleration volume acquisition (LAVA) sequence and single-voxel 1HMRS imaging with PRESS (point-resolved spectroscopy) sequence. The metabolite concentrations such as choline (Cho) and lipids (Lip) were measured. RESULTS There was significant difference regarding the occurrence rate of the obvious elevated Cho peaks between benign and malignant tumors (7/27 vs. 21/28, p=0.000). There was statistical significant differences regarding the Cho/Lip ratios in hepatic benign (0.0686±0.0283, 95% CI: 0.0134-0.1245) and malignant (0.1266 ±0.1124, 95% CI: 0.0937-0.2203) lesions (p<0.05). When compared with the pathological results, the sensitivity, specificity, positive predictive value, negative predictive value, and overall accuracy were 85.7% (24/28), 92.6% (25/27), 92.3% (24/26), 86.2% (25/29), and 89.1% (49/55) respectively for the MRI assessment, and 92.6% (26/28), 88.9% (24/27), 89.7 (26/29), 92.3 (24/26), and 90.9% (50/55) respectively for 1HMRS combined with MRI assessment. CONCLUSIONS Single Cho peaks or Lip peaks cannot be used for the diagnosis of hepatic benign and malignant lesions. Combined use of 1HMRS and MRI can greatly improve the application value of MRI assessment in the diagnosis of hepatic benign and malignant lesions with a higher sensitivity, negative predictive value, and overall accuracy.

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.

Tunable Reflective Spatial Heterodyne Spectrometer: A Technique for High Resolving Power, Wide Field Of View Observation Of Diffuse Emission Line Sources

NASA Astrophysics Data System (ADS)

Hosseini, Seyedeh Sona

The purpose of this dissertation is to discuss the need for new technology in broadband high-resolution spectroscopy based on the emerging technique of Spatial Heterodyne Spectroscopy (SHS) and to propose new solutions that should enhance and generalize this technology to other fields. Spectroscopy is a proven tool for determining compositional and other properties of remote objects. Narrow band imaging and low resolving spectroscopic measurements provide information about composition, photochemical evolution, energy distribution and density. The extension to high resolving power provides further access to temperature, velocity, isotopic ratios, separation of blended sources, and opacity effects. In current high resolving power devices, the drawback of high-resolution spectroscopy is bound to the instrumental limitations of lower throughput, the necessity of small entrance apertures, sensitivity, field of view, and large physical instrumental size. These limitations quickly become handicapping for observation of faint and/or extended targets and for spacecraft encounters. A technique with promise for the study of faint and extended sources at high resolving power is the reflective format of the Spatial Heterodyne Spectrometer (SHS). SHS instruments are compact and naturally tailored for both high etendue (defined in section 2.2.5) and high resolving power. In contrast, to achieve similar spectral grasp, grating spectrometers require large telescopes. For reference, SHS is a cyclical interferometer that produces Fizeau fringe pattern for all other wavelengths except the tuned wavelength. The large etendue obtained by SHS instruments makes them ideal for observations of extended, low surface brightness, isolated emission line sources, while their intrinsically high spectral resolution enables one to study the dynamical and physical properties described above. This document contains four chapters. Chapter 1, introduces a class of scientific targets that formerly have not been extensively observed due to absence of technical capabilities in current apparatus. We will introduce the concept of Special Heterodyne Spectrometers and address how it can fill the gap. Chapter 2 reports on the development of a new mathematical frame work for the Reflective SHS. Chapter 3 provides the details of the design and construction of a Tunable Reflective SHS at both UC Davis laboratory and Mt. Hamilton, Lick Observatory, CA. And chapter 4 contains an overview of the prospects of SHS instruments in future.

Simultaneous detection of resolved glutamate, glutamine, and γ-aminobutyric acid at 4 T

NASA Astrophysics Data System (ADS)

Hu, Jiani; Yang, Shaolin; Xuan, Yang; Jiang, Quan; Yang, Yihong; Haacke, E. Mark

2007-04-01

A new approach is introduced to simultaneously detect resolved glutamate (Glu), glutamine (Gln), and γ-aminobutyric acid (GABA) using a standard STEAM localization pulse sequence with the optimized sequence timing parameters. This approach exploits the dependence of the STEAM spectra of the strongly coupled spin systems of Glu, Gln, and GABA on the echo time TE and the mixing time TM at 4 T to find an optimized sequence parameter set, i.e., {TE, TM}, where the outer-wings of the Glu C4 multiplet resonances around 2.35 ppm, the Gln C4 multiplet resonances around 2.45 ppm, and the GABA C2 multiplet resonance around 2.28 ppm are significantly suppressed and the three resonances become virtual singlets simultaneously and thus resolved. Spectral simulation and optimization were conducted to find the optimized sequence parameters, and phantom and in vivo experiments (on normal human brains, one patient with traumatic brain injury, and one patient with brain tumor) were carried out for verification. The results have demonstrated that the Gln, Glu, and GABA signals at 2.2-2.5 ppm can be well resolved using a standard STEAM sequence with the optimized sequence timing parameters around {82 ms, 48 ms} at 4 T, while the other main metabolites, such as N-acetyl aspartate (NAA), choline (tCho), and creatine (tCr), are still preserved in the same spectrum. The technique can be easily implemented and should prove to be a useful tool for the basic and clinical studies associated with metabolism of Glu, Gln, and/or GABA.

Analysis of electronic structure of amorphous InGaZnO/SiO{sub 2} interface by angle-resolved X-ray photoelectron spectroscopy

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

Ueoka, Y.; Ishikawa, Y.; Maejima, N.

2013-10-28

The electronic structures of amorphous indium gallium zinc oxide (a-IGZO) on a SiO{sub 2} layers before and after annealing were observed by constant final state X-ray photoelectron spectroscopy (CFS-XPS) and X-ray adsorption near-edge structure spectroscopy (XANES). From the results of angle-resolved CFS-XPS, the change in the electronic state was clearly observed in the a-IGZO bulk rather than in the a-IGZO/SiO{sub 2} interface. This suggests that the electronic structures of the a-IGZO bulk strongly affected the thin-film transistor characteristics. The results of XANES indicated an increase in the number of tail states upon atmospheric annealing (AT). We consider that the increasemore » in the number of tail states decreased the channel mobility of AT samples.« less

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects.

PubMed

Hain, Karin; Hugenschmidt, Christoph; Pikart, Philip; Böni, Peter

2010-04-01

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk.

Flexible attosecond beamline for high harmonic spectroscopy and XUV/near-IR pump probe experiments requiring long acquisition times

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

Weber, S. J., E-mail: sebastien.weber@cea.fr; Manschwetus, B.; Billon, M.

2015-03-15

We describe the versatile features of the attosecond beamline recently installed at CEA-Saclay on the PLFA kHz laser. It combines a fine and very complete set of diagnostics enabling high harmonic spectroscopy (HHS) through the advanced characterization of the amplitude, phase, and polarization of the harmonic emission. It also allows a variety of photo-ionization experiments using magnetic bottle and COLTRIMS (COLd Target Recoil Ion Momentum Microscopy) electron spectrometers that may be used simultaneously, thanks to a two-foci configuration. Using both passive and active stabilization, special care was paid to the long term stability of the system to allow, using bothmore » experimental approaches, time resolved studies with attosecond precision, typically over several hours of acquisition times. As an illustration, applications to multi-orbital HHS and electron-ion coincidence time resolved spectroscopy are presented.« less

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.

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.

Time-resolved X-ray spectroscopies of chemical systems: New perspectives

PubMed Central

Chergui, Majed

2016-01-01

The past 3–5 years have witnessed a dramatic increase in the number of time-resolved X-ray spectroscopic studies, mainly driven by novel technical and methodological developments. The latter include (i) the high repetition rate optical pump/X-ray probe studies, which have greatly boosted the signal-to-noise ratio for picosecond (ps) X-ray absorption spectroscopy studies, while enabling ps X-ray emission spectroscopy (XES) at synchrotrons; (ii) the X-ray free electron lasers (XFELs) are a game changer and have allowed the first femtosecond (fs) XES and resonant inelastic X-ray scattering experiments to be carried out; (iii) XFELs are also opening the road to the development of non-linear X-ray methods. In this perspective, I will mainly focus on the most recent technical developments and briefly address some examples of scientific questions that have been addressed thanks to them. I will look at the novel opportunities in the horizon. PMID:27376102

Resolving a Long-Standing Ambiguity: the Non-Planarity of gauche-1,3-BUTADIENE Revealed by Microwave Spectroscopy

NASA Astrophysics Data System (ADS)

Martin-Drumel, Marie-Aline; McCarthy, Michael C.; Patterson, David; Eibenberger, Sandra; Buckingham, Grant; Baraban, Joshua H.; Ellison, Barney; Stanton, John F.

2016-06-01

The preferred conformation of cis-1,3-butadiene (CH_2=CH-CH=CH_2) has been of long-standing importance in organic chemistry because of its role in Diels-Alder transition states. The molecule could adopt a planar s-cis conformation, in favor of conjugations in the carbon chain, or a non-planar gauche conformation, as a result of steric interactions between the terminal H atoms. To resolve this ambiguity, we have now measured the pure rotational spectrum of this isomer in the microwave region, unambiguously establishing a significant inertial defect, and therefore a gauche conformation. Experimental measurements of gauche-1,3-butadiene and several of its isotopologues using cavity Fourier-transform microwave (FTMW) spectroscopy in a supersonic expansion and chirped-pulse FTMW spectroscopy in a 4 K buffer gas cell will be summarized, as will new quantum chemical calculations.

Probing long-range structural order in SnPc/Ag(111) by umklapp process assisted low-energy angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Jauernik, Stephan; Hein, Petra; Gurgel, Max; Falke, Julian; Bauer, Michael

2018-03-01

Laser-based angle-resolved photoelectron spectroscopy is performed on tin-phthalocyanine (SnPc) adsorbed on silver Ag(111). Upon adsorption of SnPc, strongly dispersing bands are observed which are identified as secondary Mahan cones formed by surface umklapp processes acting on photoelectrons from the silver substrate as they transit through the ordered adsorbate layer. We show that the photoemission data carry quantitative structural information on the adsorbate layer similar to what can be obtained from a conventional low-energy electron diffraction (LEED) study. More specifically, we compare photoemission data and LEED data probing an incommensurate-to-commensurate structural phase transition of the adsorbate layer. Based on our results we propose that Mahan-cone spectroscopy operated in a pump-probe configuration can be used in the future to probe structural dynamics at surfaces with a temporal resolution in the sub-100-fs regime.

Polarization-resolved optical response of plasmonic particle-on-film nanocavities

NASA Astrophysics Data System (ADS)

Zhang, Q.; Li, G.-C.; Lo, T. W.; Lei, D. Y.

2018-02-01

Placing a metal nanoparticle atop a metal film forms a plasmonic particle-on-film nanocavity. Such a nanocavity supports strong plasmonic coupling that results in rich hybridized plasmon modes, rendering the cavity a versatile platform for exploiting a wide range of plasmon-enhanced spectroscopy applications. In this paper, we fully address the polarization-resolved, orientation-dependent far-field optical responses of plasmonic monomer- and dimer-on-film nanocavities by numerical simulations and experiments. With polarization-resolved dark-field spectroscopy, the distinct plasmon resonances of these nanocavities are clearly determined from their scattering spectra. Moreover, the radiation patterns of respective plasmon modes, which are often mixed together in common dark-field imaging, can be unambiguously resolved with our proposed quasi-multispectral imaging method. Explicitly, the radiation pattern of the monomer-on-film nanocavity gradually transitions from a solid spot in the green imaging channel to a doughnut ring in the red channel when tuning the excitation polarization from parallel to perpendicular to the sample surface. This observation holds true for the plasmonic dimer-on-film nanocavity with the dimer axis aligned in the incidence plane; when the dimer axis is normal to the incidence plane, the pattern transitions from a solid spot to a doughnut ring both in the red channel. These studies not only demonstrate a flexible polarization control over the optical responses of plasmonic particle-on-film nanostructures but also enrich the optical tool kit for far-field imaging and spectroscopy characterization of various plasmonic nanostructures.

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

A study on the anisole-water complex by molecular beam-electronic spectroscopy and molecular mechanics calculations.

PubMed

Becucci, M; Pietraperzia, G; Pasquini, M; Piani, G; Zoppi, A; Chelli, R; Castellucci, E; Demtroeder, W

2004-03-22

An experimental and theoretical study is made on the anisole-water complex. It is the first van der Waals complex studied by high resolution electronic spectroscopy in which the water is seen acting as an acid. Vibronically and rotationally resolved electronic spectroscopy experiments and molecular mechanics calculations are used to elucidate the structure of the complex in the ground and first electronic excited state. Some internal dynamics in the system is revealed by high resolution spectroscopy. (c) 2004 American Institute of Physics

Infrared Photodissociation Spectroscopy of Metal Ion -WATER Complexes

NASA Astrophysics Data System (ADS)

Bandyopadhyay, B.; Carnegie, P. D.; Duncan, M. A.

2011-06-01

Metal ion-water complexes are produced in a supersonic expansion cluster source via laser vaporization technique. Infrared photodissociation spectroscopy has been performed in the O-H stretch region. DFT calculations have also been carried out to obtain the structures and vibrational frequencies. Infrared spectra show partially resolved rotational structures which will be analyzed.

Momentum-resolved radio-frequency spectroscopy of a spin-orbit-coupled atomic Fermi gas near a Feshbach resonance in harmonic traps

NASA Astrophysics Data System (ADS)

Peng, Shi-Guo; Liu, Xia-Ji; Hu, Hui; Jiang, Kaijun

2012-12-01

We theoretically investigate the momentum-resolved radio-frequency spectroscopy of a harmonically trapped atomic Fermi gas near a Feshbach resonance in the presence of equal Rashba and Dresselhaus spin-orbit coupling. The system is qualitatively modeled as an ideal gas mixture of atoms and molecules, in which the properties of molecules, such as the wave function, binding energy, and effective mass, are determined from the two-particle solution of two interacting atoms. We calculate separately the radio-frequency response from atoms and molecules at finite temperatures by using the standard Fermi golden rule and take into account the effect of harmonic traps within local density approximation. The total radio-frequency spectroscopy is discussed as functions of temperature and spin-orbit coupling strength. Our results give a qualitative picture of radio-frequency spectroscopy of a resonantly interacting spin-orbit-coupled Fermi gas and can be directly tested in atomic Fermi gases of 40K atoms at Shanxi University and 6Li atoms at the Massachusetts Institute of Technology.

Extrasolar Planets Observed with JWST and the ELTs

NASA Technical Reports Server (NTRS)

Deming, L. Drake

2010-01-01

The advent of cryogenic space-borne infrared observatories such as the Spitzer Space Telescope has lead to a revolution in the study of planets and planetary systems orbiting sun-like stars. Already Spitzer has characterized the emergent infrared spectra of close-in giant exoplanets using transit and eclipse techniques. The James Webb Space Telescope (JWST) will be able to extend these studies to superEarth exoplanets orbiting in the habitable zones of M-dwarf stars in the near solar neighborhood. The forthcoming ground-based Extremely Large Telescopes (ELTs) will playa key role in these studies, being especially valuable for spectroscopy at higher spectral resolving powers where large photon fluxes are needed. The culmination of this work within the next two decades will be the detection and spectral characterization of the major molecular constituents in the atmosphere of a habitable superEarth orbiting a nearby lower main sequence star.

Fast CT-PRESS-based spiral chemical shift imaging at 3 Tesla.

PubMed

Mayer, Dirk; Kim, Dong-Hyun; Adalsteinsson, Elfar; Spielman, Daniel M

2006-05-01

A new sequence is presented that combines constant-time point-resolved spectroscopy (CT-PRESS) with fast spiral chemical shift imaging. It allows the acquisition of multivoxel spectra without line splitting with a minimum total measurement time of less than 5 min for a field of view of 24 cm and a nominal 1.5x1.5-cm2 in-plane resolution. Measurements were performed with 17 CS encoding steps in t1 (Deltat1=12.8 ms) and an average echo time of 151 ms, which was determined by simulating the CT-PRESS experiment for the spin systems of glutamate (Glu) and myo-inositol (mI). Signals from N-acetyl-aspartate, total creatine, choline-containing compounds (Cho), Glu, and mI were detected in a healthy volunteer with no or only minor baseline distortions within 14 min on a 3 T MR scanner. Copyright (c) 2006 Wiley-Liss, Inc.

Magnetotactic bacteria form magnetite from a phosphate-rich ferric hydroxide via nanometric ferric (oxyhydr)oxide intermediates.

PubMed

Baumgartner, Jens; Morin, Guillaume; Menguy, Nicolas; Perez Gonzalez, Teresa; Widdrat, Marc; Cosmidis, Julie; Faivre, Damien

2013-09-10

The iron oxide mineral magnetite (Fe3O4) is produced by various organisms to exploit magnetic and mechanical properties. Magnetotactic bacteria have become one of the best model organisms for studying magnetite biomineralization, as their genomes are sequenced and tools are available for their genetic manipulation. However, the chemical route by which magnetite is formed intracellularly within the so-called magnetosomes has remained a matter of debate. Here we used X-ray absorption spectroscopy at cryogenic temperatures and transmission electron microscopic imaging techniques to chemically characterize and spatially resolve the mechanism of biomineralization in those microorganisms. We show that magnetite forms through phase transformation from a highly disordered phosphate-rich ferric hydroxide phase, consistent with prokaryotic ferritins, via transient nanometric ferric (oxyhydr)oxide intermediates within the magnetosome organelle. This pathway remarkably resembles recent results on synthetic magnetite formation and bears a high similarity to suggested mineralization mechanisms in higher organisms.

Core genome conservation of Staphylococcus haemolyticus limits sequence based population structure analysis.

PubMed

Cavanagh, Jorunn Pauline; Klingenberg, Claus; Hanssen, Anne-Merethe; Fredheim, Elizabeth Aarag; Francois, Patrice; Schrenzel, Jacques; Flægstad, Trond; Sollid, Johanna Ericson

2012-06-01

The notoriously multi-resistant Staphylococcus haemolyticus is an emerging pathogen causing serious infections in immunocompromised patients. Defining the population structure is important to detect outbreaks and spread of antimicrobial resistant clones. Currently, the standard typing technique is pulsed-field gel electrophoresis (PFGE). In this study we describe novel molecular typing schemes for S. haemolyticus using multi locus sequence typing (MLST) and multi locus variable number of tandem repeats (VNTR) analysis. Seven housekeeping genes (MLST) and five VNTR loci (MLVF) were selected for the novel typing schemes. A panel of 45 human and veterinary S. haemolyticus isolates was investigated. The collection had diverse PFGE patterns (38 PFGE types) and was sampled over a 20 year-period from eight countries. MLST resolved 17 sequence types (Simpsons index of diversity [SID]=0.877) and MLVF resolved 14 repeat types (SID=0.831). We found a low sequence diversity. Phylogenetic analysis clustered the isolates in three (MLST) and one (MLVF) clonal complexes, respectively. Taken together, neither the MLST nor the MLVF scheme was suitable to resolve the population structure of this S. haemolyticus collection. Future MLVF and MLST schemes will benefit from addition of more variable core genome sequences identified by comparing different fully sequenced S. haemolyticus genomes. Copyright © 2012 Elsevier B.V. All rights reserved.

Schemes of detecting nuclear spin correlations by dynamical decoupling based quantum sensing

NASA Astrophysics Data System (ADS)

Ma, Wen-Long Ma; Liu, Ren-Bao

Single-molecule sensitivity of nuclear magnetic resonance (NMR) and angstrom resolution of magnetic resonance imaging (MRI) are the highest challenges in magnetic microscopy. Recent development in dynamical decoupling (DD) enhanced diamond quantum sensing has enabled NMR of single nuclear spins and nanoscale NMR. Similar to conventional NMR and MRI, current DD-based quantum sensing utilizes the frequency fingerprints of target nuclear spins. Such schemes, however, cannot resolve different nuclear spins that have the same noise frequency or differentiate different types of correlations in nuclear spin clusters. Here we show that the first limitation can be overcome by using wavefunction fingerprints of target nuclear spins, which is much more sensitive than the ''frequency fingerprints'' to weak hyperfine interaction between the targets and a sensor, while the second one can be overcome by a new design of two-dimensional DD sequences composed of two sets of periodic DD sequences with different periods, which can be independently set to match two different transition frequencies. Our schemes not only offer an approach to breaking the resolution limit set by ''frequency gradients'' in conventional MRI, but also provide a standard approach to correlation spectroscopy for single-molecule NMR.

Quantitative analysis of hepatic fat fraction by single-breath-holding MR spectroscopy with T₂ correction: phantom and clinical study with histologic assessment.

PubMed

Hayashi, Norio; Miyati, Tosiaki; Minami, Takashi; Takeshita, Yumie; Ryu, Yasuji; Matsuda, Tsuyoshi; Ohno, Naoki; Hamaguchi, Takashi; Kato, Kenichiro; Takamura, Toshinari; Matsui, Osamu

2013-01-01

The focus of this study was on the investigation of the accuracy of the fat fraction of the liver by use of single-breath-holding magnetic resonance spectroscopy (MRS) with T (2) correction. Single-voxel proton MRS was performed with several TE values, and the fat fraction was determined with and without T (2) correction. MRS was also performed with use of the point-resolved spectroscopy sequence in single breath holding. The T (2) values of both water and fat were determined separately at the same time, and the effect of T (2) on the fat fraction was corrected. In addition, MRS-based fat fractions were compared with the degree of hepatic steatosis (HS) by liver biopsy in human subjects. With T (2) correction, the MRI-derived fat fractions were in good agreement with the fat fractions in all phantoms, but the fat fractions were overestimated without T (2) correction. R (2) values were in good agreement with the preset iron concentrations in the phantoms. The MRI-derived fat fraction was well correlated with the degree of HS. Iron deposited in the liver affects the signal strength when proton MRS is used for detection of the fat signal in the liver. However, the fat signal can be evaluated more accurately when the T (2) correction is applied. Breath-holding MRS minimizes the respiratory motion, and it can be more accurate in the quantification of the hepatic fat fraction.

Investigation of the Interaction Between Human Serum Albumin and Two Drugs as Binary and Ternary Systems.

PubMed

Abdollahpour, Nooshin; Soheili, Vahid; Saberi, Mohammad Reza; Chamani, Jamshidkhan

2016-12-01

Human serum albumin (HSA) is the most frequent protein in blood plasma. Albumin transports various compounds, preserves osmotic pressure, and buffers pH. A unique feature of albumin is its ability to bind drugs and other bioactive molecules. However, it is important to consider binary and ternary systems of two pharmaceuticals to estimate the effect of the first drug on the second one and physicochemical properties. Different techniques including time-resolved, second-derivative and anisotropy fluorescence spectroscopy, resonance light scattering (RLS), critical induced aggregation concentration (C CIAC ), particle size, zeta potential and stability analysis were employed in this assessment to elucidate the binding behavior of Amlodipine and Aspirin to HSA. Moreover, isothermal titration calorimetric techniques were performed and the QSAR properties were applied to analyze the hydration energy and log P. Multiple sequence alignments were also used to predict the structure and biological characteristics of the HSA binding site. Time-resolved fluorescence spectroscopy showed interaction of both drugs to HSA based on a static quenching mechanism. Subsequently, second-derivative fluorescence spectroscopy presented different values of parameter H in binary and ternary systems, which were suggested that tryptophan was in a more polar environment in the ternary system than in a binary system. Moreover, the polydispersity index and results from mean number measurements revealed that the presence of the second drug caused a decrease in the stability of systems and increased the heterogeneity of complex. It is also, observed that the gradual addition of HSA has led to a marked increase in fluorescence anisotropy (r) of Amlodipine and Aspirin which can be suggested that the drugs were located in a restricted environment of the protein as confirmed by Red Edge Excitation Shift (REES) studies. The isothermal titration calorimetric technique demonstrated that the interaction of the drugs with HSA was an enthalpically-driven process. The present experiment showed that the binding of Amlodipine and Aspirin to HSA induced a conformational change of HSA. It was also identified that the protein binding of the first drug could be affected by the second drug. Such results can be of great use for understanding the pharmacokinetic and pharmacodynamic mechanisms of drugs.

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

Observation of laser-driven shock propagation by nanosecond time-resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Yu, Guoyang; Zheng, Xianxu; Song, Yunfei; Zeng, Yangyang; Guo, Wencan; Zhao, Jun; Yang, Yanqiang

2015-01-01

An improved nanosecond time-resolved Raman spectroscopy is performed to observe laser-driven shock propagation in the anthracene/epoxy glue layer. The digital delay instead of optical delay line is introduced for sake of unlimited time range of detection, which enables the ability to observe both shock loading and shock unloading that always lasts several hundred nanoseconds. In this experiment, the peak pressure of shock wave, the pressure distribution, and the position of shock front in gauge layer were determined by fitting Raman spectra of anthracene using the Raman peak shift simulation. And, the velocity of shock wave was calculated by the time-dependent position of shock front.

Angle-resolved photoelectron spectroscopy of formaldehyde and methanol

NASA Astrophysics Data System (ADS)

Keller, P. R.; Taylor, J. W.; Grimm, F. A.; Carlson, Thomas A.

1984-10-01

Angle-resolved photoelectron spectroscopy was employed to obtain the angular distribution parameter, β, for the valence orbitals (IP < 21.1 eV) of formaldehyde and methanol over the 10-30 eV photon energy range using dispersed polarized synchrotron radiation as the excitation source. It was found that the energy dependence of β in the photoelectron energy range between 2 and 10 eV can be related to the molecular-orbital type from which ionization occurs. This generalized energy behavior is discussed with regard to earlier energy-dependence studies on molecules of different orbital character. Evidence is presented for the presence of resonance photoionization phenomena in formaldehyde in agreement with theoretical cross-section calculations.

Lattice-Assisted Spectroscopy: A Generalized Scanning Tunneling Microscope for Ultracold Atoms.

PubMed

Kantian, A; Schollwöck, U; Giamarchi, T

2015-10-16

We propose a scheme to measure the frequency-resolved local particle and hole spectra of any optical lattice-confined system of correlated ultracold atoms that offers single-site addressing and imaging, which is now an experimental reality. Combining perturbation theory and time-dependent density matrix renormalization group simulations, we quantitatively test and validate this approach of lattice-assisted spectroscopy on several one-dimensional example systems, such as the superfluid and Mott insulator, with and without a parabolic trap, and finally on edge states of the bosonic Su-Schrieffer-Heeger model. We highlight extensions of our basic scheme to obtain an even wider variety of interesting and important frequency resolved spectra.

Transport limited interfacial carrier relaxation in a double-layer device investigated by time-resolved second harmonic generation and impedance spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Le; Taguchi, Dai; Li, Jun; Manaka, Takaaki; Iwamoto, Mitsumasa

2011-02-01

The interfacial carrier relaxation in an indium tin oxide/polyimide/pentacene/Au double-layer device was studied in both time and frequency domains by using time-resolved second harmonic generation (TR-SHG) and impedance spectroscopy (IS), respectively. Although both hole and electron injection into the pentacene layer and their accumulation at the pentacene/polyimide interface were revealed in TR-SHG, it was only observed in IS under the hole injection condition. The "contradiction" between the two methods for the same carrier relaxation process was explained on the basis of a model, transport limited interfacial carrier relaxation, in which the quasistatic state governs the one-directional carrier transport.

Temporally resolved diagnosis of an atmospheric-pressure pulse-modulated argon surface wave plasma by optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Chen, Chuan-Jie; Li, Shou-Zhe; Zhang, Jialiang; Liu, Dongping

2018-01-01

A pulse-modulated argon surface wave plasma generated at atmospheric pressure is characterized by means of temporally resolved optical emission spectroscopy (OES). The temporal evolution of the gas temperature, the electron temperature and density, the radiative species of atomic Ar, and the molecular band of OH(A) and N2(C) are investigated experimentally by altering the instantaneous power, pulse repetitive frequency, and duty ratio. We focused on the physical phenomena occurring at the onset of the time-on period and after the power interruption at the start of the time-off period. Meanwhile, the results are discussed qualitatively for an in-depth insight of its dynamic evolution.

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

SDSS IV MaNGA - sSFR profiles and the slow quenching of discs in green valley galaxies

NASA Astrophysics Data System (ADS)

Belfiore, Francesco; Maiolino, Roberto; Bundy, Kevin; Masters, Karen; Bershady, Matthew; Oyarzún, Grecco; Lin, Lihwai; Cano-Diaz, Mariana; Wake, David; Spindler, Ashley; Thomas, Daniel; Brownstein, Joel R.; Drory, Niv; Yan, Renbin

2018-03-01

We study radial profiles in Hα equivalent width and specific star formation rate (sSFR) derived from spatially-resolved SDSS-IV MaNGA spectroscopy to gain insight on the physical mechanisms that suppress star formation and determine a galaxy's location in the SFR-M_\\star diagram. Even within the star-forming `main sequence', the measured sSFR decreases with stellar mass, both in an integrated and spatially-resolved sense. Flat sSFR radial profiles are observed for log(M_\\star / M_⊙ ) < 10.5, while star-forming galaxies of higher mass show a significant decrease in sSFR in the central regions, a likely consequence of both larger bulges and an inside-out growth history. Our primary focus is the green valley, constituted by galaxies lying below the star formation main sequence, but not fully passive. In the green valley we find sSFR profiles that are suppressed with respect to star-forming galaxies of the same mass at all galactocentric distances out to 2 effective radii. The responsible quenching mechanism therefore appears to affect the entire galaxy, not simply an expanding central region. The majority of green valley galaxies of log(M_\\star / M_⊙ ) > 10.0 are classified spectroscopically as central low-ionisation emission-line regions (cLIERs). Despite displaying a higher central stellar mass concentration, the sSFR suppression observed in cLIER galaxies is not simply due to the larger mass of the bulge. Drawing a comparison sample of star forming galaxies with the same M_\\star and Σ _{1 kpc} (the mass surface density within 1 kpc), we show that a high Σ _{1 kpc} is not a sufficient condition for determining central quiescence.

SDSS-IV MaNGA - the spatially resolved transition from star formation to quiescence

NASA Astrophysics Data System (ADS)

Belfiore, Francesco; Maiolino, Roberto; Maraston, Claudia; Emsellem, Eric; Bershady, Matthew A.; Masters, Karen L.; Bizyaev, Dmitry; Boquien, Médéric; Brownstein, Joel R.; Bundy, Kevin; Diamond-Stanic, Aleksandar M.; Drory, Niv; Heckman, Timothy M.; Law, David R.; Malanushenko, Olena; Oravetz, Audrey; Pan, Kaike; Roman-Lopes, Alexandre; Thomas, Daniel; Weijmans, Anne-Marie; Westfall, Kyle B.; Yan, Renbin

2017-04-01

Using spatially resolved spectroscopy from SDSS-IV MaNGA we have demonstrated that low ionization emission-line regions (LIERs) in local galaxies result from photoionization by hot evolved stars, not active galactic nuclei, hence tracing galactic region hosting old stellar population where, despite the presence of ionized gas, star formation is no longer occurring. LIERs are ubiquitous in both quiescent galaxies and in the central regions of galaxies where star formation takes place at larger radii. We refer to these two classes of galaxies as extended LIER (eLIER) and central LIER (cLIER) galaxies, respectively. cLIERs are late-type galaxies primarily spread across the green valley, in the transition region between the star formation main sequence and quiescent galaxies. These galaxies display regular disc rotation in both stars and gas, although featuring a higher central stellar velocity dispersion than star-forming galaxies of the same mass. cLIERs are consistent with being slowly quenched inside-out; the transformation is associated with massive bulges, pointing towards the importance of bulge growth via secular evolution. eLIERs are morphologically early types and are indistinguishable from passive galaxies devoid of line emission in terms of their stellar populations, morphology and central stellar velocity dispersion. Ionized gas in eLIERs shows both disturbed and disc-like kinematics. When a large-scale flow/rotation is observed in the gas, it is often misaligned relative to the stellar component. These features indicate that eLIERs are passive galaxies harbouring a residual cold gas component, acquired mostly via external accretion. Importantly, quiescent galaxies devoid of line emission reside in denser environments and have significantly higher satellite fraction than eLIERs. Environmental effects thus represent the likely cause for the existence of line-less galaxies on the red sequence.

SDSS IV MaNGA - sSFR profiles and the slow quenching of discs in green valley galaxies

NASA Astrophysics Data System (ADS)

Belfiore, Francesco; Maiolino, Roberto; Bundy, Kevin; Masters, Karen; Bershady, Matthew; Oyarzún, Grecco A.; Lin, Lihwai; Cano-Diaz, Mariana; Wake, David; Spindler, Ashley; Thomas, Daniel; Brownstein, Joel R.; Drory, Niv; Yan, Renbin

2018-07-01

We study radial profiles in H α equivalent width and specific star formation rate (sSFR) derived from spatially resolved SDSS-IV MaNGA spectroscopy to gain insight on the physical mechanisms that suppress star formation and determine a galaxy's location in the SFR-M⋆ diagram. Even within the star-forming `main sequence', the measured sSFR decreases with stellar mass, in both an integrated and spatially resolved sense. Flat sSFR radial profiles are observed for log(M⋆/M⊙) < 10.5, while star-forming galaxies of higher mass show a significant decrease in sSFR in the central regions, a likely consequence of both larger bulges and an inside-out growth history. Our primary focus is the green valley, constituted by galaxies lying below the star formation main sequence, but not fully passive. In the green valley we find sSFR profiles that are suppressed with respect to star-forming galaxies of the same mass at all galactocentric distances out to 2 effective radii. The responsible quenching mechanism therefore appears to affect the entire galaxy, not simply an expanding central region. The majority of green valley galaxies of log(M⋆/M⊙) > 10.0 are classified spectroscopically as central low-ionization emission-line regions (cLIERs). Despite displaying a higher central stellar mass concentration, the sSFR suppression observed in cLIER galaxies is not simply due to the larger mass of the bulge. Drawing a comparison sample of star-forming galaxies with the same M⋆ and Σ _{1 kpc} (the mass surface density within 1 kpc), we show that a high Σ _{1 kpc} is not a sufficient condition for determining central quiescence.

Advances in Raman spectroscopy for In Situ Identification of Minerals and Organics on Diverse Planetary Surfaces: from Mars to Titan

NASA Astrophysics Data System (ADS)

Blacksberg, J.; Alerstam, E.; Maruyama, Y.; Cochrane, C.; Rossman, G. R.

2015-12-01

We present recent developments in time-resolved Raman spectroscopy for in situ planetary surface exploration, aimed at identification of both minerals and organics. Raman is a non-destructive surface technique that requires no sample preparation. Raman spectra are highly material specific and can be used for identification of a wide range of unknown samples. In combination with micro-scale imaging and point mapping, Raman spectroscopy can be used to directly interrogate rocks and regolith materials, while placing compositional analyses within a microtextural context, essential for understanding surface evolutionary pathways. Due to these unique capabilities, Raman spectroscopy is of great interest for the exploration of all rocky and icy bodies, for example Mars, Venus, the Moon, Mars' moons, asteroids, comets, Europa, and Titan. In this work, we focus on overcoming one of the most difficult challenges faced in Raman spectroscopy: interference from background fluorescence of the very minerals and organics that we wish to characterize. To tackle this problem we use time-resolved Raman spectroscopy, which separates the Raman from background processes in the time domain. This same technique also enables operation in daylight without the need for light shielding. Two key components are essential for the success of this technique: a fast solid-state detector and a short-pulse laser. Our detector is a custom developed Single Photon Avalanche Diode (SPAD) array, capable of sub-ns time-gating. Our pulsed lasers are solid-state miniature pulsed microchip lasers. We discuss optimization of laser and detector parameters for our application. We then present Raman spectra of particularly challenging planetary analog samples to demonstrate the unique capabilities of this time-resolved Raman instrument, for example, Mars-analog clays and Titan-analog organics. The research described here was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration (NASA).

Augmentation of machine structure to improve its diagnosability

NASA Technical Reports Server (NTRS)

Hsieh, L.

1973-01-01

Two methods of augmenting the structure of a sequential machine so that it is diagnosable are presented. The checkable (checking sequences) and repeated symbol distinguishing sequences (RDS) are discussed. It was found that as few as twice the number of outputs of the given machine is sufficient for constructing a state-output augmentation with RDS. Techniques for minimizing the number of states in resolving convergences and in resolving equivalent and nonreduced cycles are developed.

De novo assembly of a haplotype-resolved human genome.

PubMed

Cao, Hongzhi; Wu, Honglong; Luo, Ruibang; Huang, Shujia; Sun, Yuhui; Tong, Xin; Xie, Yinlong; Liu, Binghang; Yang, Hailong; Zheng, Hancheng; Li, Jian; Li, Bo; Wang, Yu; Yang, Fang; Sun, Peng; Liu, Siyang; Gao, Peng; Huang, Haodong; Sun, Jing; Chen, Dan; He, Guangzhu; Huang, Weihua; Huang, Zheng; Li, Yue; Tellier, Laurent C A M; Liu, Xiao; Feng, Qiang; Xu, Xun; Zhang, Xiuqing; Bolund, Lars; Krogh, Anders; Kristiansen, Karsten; Drmanac, Radoje; Drmanac, Snezana; Nielsen, Rasmus; Li, Songgang; Wang, Jian; Yang, Huanming; Li, Yingrui; Wong, Gane Ka-Shu; Wang, Jun

2015-06-01

The human genome is diploid, and knowledge of the variants on each chromosome is important for the interpretation of genomic information. Here we report the assembly of a haplotype-resolved diploid genome without using a reference genome. Our pipeline relies on fosmid pooling together with whole-genome shotgun strategies, based solely on next-generation sequencing and hierarchical assembly methods. We applied our sequencing method to the genome of an Asian individual and generated a 5.15-Gb assembled genome with a haplotype N50 of 484 kb. Our analysis identified previously undetected indels and 7.49 Mb of novel coding sequences that could not be aligned to the human reference genome, which include at least six predicted genes. This haplotype-resolved genome represents the most complete de novo human genome assembly to date. Application of our approach to identify individual haplotype differences should aid in translating genotypes to phenotypes for the development of personalized medicine.

1H MRS Assessment of Hepatic Fat Content: Comparison Between Normal- and Excess-weight Children and Adolescents.

PubMed

Chabanova, Elizaveta; Fonvig, Cilius Esmann; Bøjsøe, Christine; Holm, Jens-Christian; Thomsen, Henrik S

2017-08-01

The purpose of the present study was to obtain a cutoff value of liver fat content for the diagnosis of hepatic steatosis by comparing magnetic resonance (MR) spectroscopy results in children and adolescents with normal and excess weight. The study included 420 children and adolescents (91 normal-weight, 99 overweight, and 230 obese) 8-18 years of age. Proton magnetic resonance spectroscopy was performed with a 3T MR system using point resolved spectroscopy sequence with series echo times. The mean absolute mass concentration of liver fat was obtained: 0.5 ± 0.04% in normal-weight boys; 0.5 ± 0.03% in normal-weight girls; 0.9 ± 0.16% in boys with overweight; 1.1 ± 0.24% in girls with overweight; 1.7 ± 0.24% in boys with obesity; and 1.4 ± 0.21% in girls with obesity. The cutoff value of absolute mass concentration of liver fat for hepatic steatosis was found to be 1.5%. Based on this cutoff value, hepatic steatosis was diagnosed in 16% of boys with overweight, 11% of girls with overweight, 32% of boys with obesity, and 27% of girls with obesity. Proton magnetic resonance spectroscopy was successfully applied to obtain the cutoff value of absolute mass concentration of liver fat for the diagnosis of hepatic steatosis in children and adolescents. Children and adolescents with obesity have higher risk of hepatic steatosis than their peers with overweight. Copyright © 2017 The Association of University Radiologists. Published by Elsevier Inc. All rights reserved.

Accuracy and stability of measuring GABA, glutamate, and glutamine by proton magnetic resonance spectroscopy: A phantom study at 4 Tesla

NASA Astrophysics Data System (ADS)

Henry, Michael E.; Lauriat, Tara L.; Shanahan, Meghan; Renshaw, Perry F.; Jensen, J. Eric

2011-02-01

Proton magnetic resonance spectroscopy has the potential to provide valuable information about alterations in gamma-aminobutyric acid (GABA), glutamate (Glu), and glutamine (Gln) in psychiatric and neurological disorders. In order to use this technique effectively, it is important to establish the accuracy and reproducibility of the methodology. In this study, phantoms with known metabolite concentrations were used to compare the accuracy of 2D J-resolved MRS, single-echo 30 ms PRESS, and GABA-edited MEGA-PRESS for measuring all three aforementioned neurochemicals simultaneously. The phantoms included metabolite concentrations above and below the physiological range and scans were performed at baseline, 1 week, and 1 month time-points. For GABA measurement, MEGA-PRESS proved optimal with a measured-to-target correlation of R2 = 0.999, with J-resolved providing R2 = 0.973 for GABA. All three methods proved effective in measuring Glu with R2 = 0.987 (30 ms PRESS), R2 = 0.996 (J-resolved) and R2 = 0.910 (MEGA-PRESS). J-resolved and MEGA-PRESS yielded good results for Gln measures with respective R2 = 0.855 (J-resolved) and R2 = 0.815 (MEGA-PRESS). The 30 ms PRESS method proved ineffective in measuring GABA and Gln. When measurement stability at in vivo concentration was assessed as a function of varying spectral quality, J-resolved proved the most stable and immune to signal-to-noise and linewidth fluctuation compared to MEGA-PRESS and 30 ms PRESS.

The infrared imaging spectrograph (IRIS) for TMT: overview of innovative science programs

NASA Astrophysics Data System (ADS)

Wright, Shelley A.; Larkin, James E.; Moore, Anna M.; Do, Tuan; Simard, Luc; Adamkovics, Maté; Armus, Lee; Barth, Aaron J.; Barton, Elizabeth; Boyce, Hope; Cooke, Jeffrey; Cote, Patrick; Davidge, Timothy; Ellerbroek, Brent; Ghez, Andrea M.; Liu, Michael C.; Lu, Jessica R.; Macintosh, Bruce A.; Mao, Shude; Marois, Christian; Schoeck, Matthias; Suzuki, Ryuji; Tan, Jonathan C.; Treu, Tommaso; Wang, Lianqi; Weiss, Jason

2014-07-01

IRIS (InfraRed Imaging Spectrograph) is a first light near-infrared diffraction limited imager and integral field spectrograph being designed for the future Thirty Meter Telescope (TMT). IRIS is optimized to perform astronomical studies across a significant fraction of cosmic time, from our Solar System to distant newly formed galaxies (Barton et al. [1]). We present a selection of the innovative science cases that are unique to IRIS in the era of upcoming space and ground-based telescopes. We focus on integral field spectroscopy of directly imaged exoplanet atmospheres, probing fundamental physics in the Galactic Center, measuring 104 to 1010 M supermassive black hole masses, resolved spectroscopy of young star-forming galaxies (1 < z < 5) and first light galaxies (6 < z < 12), and resolved spectroscopy of strong gravitational lensed sources to measure dark matter substructure. For each of these science cases we use the IRIS simulator (Wright et al. [2], Do et al. [3]) to explore IRIS capabilities. To highlight the unique IRIS capabilities, we also update the point and resolved source sensitivities for the integral field spectrograph (IFS) in all five broadband filters (Z, Y, J, H, K) for the finest spatial scale of 0.004" per spaxel. We briefly discuss future development plans for the data reduction pipeline and quicklook software for the IRIS instrument suite.

Transient radical pairs studied by time-resolved EPR.

PubMed

Bittl, Robert; Weber, Stefan

2005-02-25

Photogenerated short-lived radical pairs (RP) are common in biological photoprocesses such as photosynthesis and enzymatic DNA repair. They can be favorably probed by time-resolved electron paramagnetic resonance (EPR) methods with adequate time resolution. Two EPR techniques have proven to be particularly useful to extract information on the working states of photoinduced biological processes that is only difficult or sometimes even impossible to obtain by other types of spectroscopy. Firstly, transient EPR yields crucial information on the chemical nature and the geometry of the individual RP halves in a doublet-spin pair generated by a short laser pulse. This time-resolved method is applicable in all magnetic field/microwave frequency regimes that are used for continuous-wave EPR, and is nowadays routinely utilized with a time resolution reaching about 10 ns. Secondly, a pulsed EPR method named out-of-phase electron spin echo envelope modulation (OOP-ESEEM) is increasingly becoming popular. By this pulsed technique, the mutual spin-spin interaction between the RP halves in a doublet-spin pair manifests itself as an echo modulation detected as a function of the microwave-pulse spacing of a two-pulse echo sequence subsequent to a laser pulse. From the dipolar coupling, the distance between the radicals is readily derived. Since the spin-spin interaction parameters are typically not observable by transient EPR, the two techniques complement each other favorably. Both EPR methods have recently been applied to a variety of light-induced RPs in photobiology. This review summarizes the results obtained from such studies in the fields of plant and bacterial photosynthesis and DNA repair mediated by the enzyme DNA photolyase.

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 multi-mass ion imaging: Femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera.

PubMed

Forbes, Ruaridh; Makhija, Varun; Veyrinas, Kévin; Stolow, Albert; Lee, Jason W L; Burt, Michael; Brouard, Mark; Vallance, Claire; Wilkinson, Iain; Lausten, Rune; Hockett, Paul

2017-07-07

The Pixel-Imaging Mass Spectrometry (PImMS) camera allows for 3D charged particle imaging measurements, in which the particle time-of-flight is recorded along with (x, y) position. Coupling the PImMS camera to an ultrafast pump-probe velocity-map imaging spectroscopy apparatus therefore provides a route to time-resolved multi-mass ion imaging, with both high count rates and large dynamic range, thus allowing for rapid measurements of complex photofragmentation dynamics. Furthermore, the use of vacuum ultraviolet wavelengths for the probe pulse allows for an enhanced observation window for the study of excited state molecular dynamics in small polyatomic molecules having relatively high ionization potentials. Herein, preliminary time-resolved multi-mass imaging results from C 2 F 3 I photolysis are presented. The experiments utilized femtosecond VUV and UV (160.8 nm and 267 nm) pump and probe laser pulses in order to demonstrate and explore this new time-resolved experimental ion imaging configuration. The data indicate the depth and power of this measurement modality, with a range of photofragments readily observed, and many indications of complex underlying wavepacket dynamics on the excited state(s) prepared.

Using near-infrared spectroscopy to resolve the species, gender, age, and the presence of Wolbachia infection in laboratory-reared Drosophila

USDA-ARS?s Scientific Manuscript database

The aim of the study was to determine the accuracy of near-infrared spectroscopy (NIRS) in determining species, gender, age and the presence of the common endosymbiont Wolbachia in laboratory reared Drosophila. NIRS measures absorption of light by organic molecules. Initially, a calibration model wa...

The Fourteenth International Meeting on Time-Resolved Vibrational Spectroscopy (TRVS XIV)

DTIC Science & Technology

2010-02-03

Technology United States ahorning@mit.edu Anne Hudson MIT Dept. of Chemistry United States amh@mit.edu Adriana Huerta Viga University of Amsterdam...Hoffmann, Janos Hebling, Harold Y. Hwang, THz-pump/THz-probe nonlinear spectroscopy Ka -Lo Yeh, Keith A. Nelson, MIT 11:30 AM C Tomonori Nomoto and

The Hubble Deep UV Legacy Survey (HDUV)

NASA Astrophysics Data System (ADS)

Montes, Mireia; Oesch, Pascal

2015-08-01

Deep HST imaging has shown that the overall star formation density and UV light density at z>3 is dominated by faint, blue galaxies. Remarkably, very little is known about the equivalent galaxy population at lower redshifts. Understanding how these galaxies evolve across the epoch of peak cosmic star-formation is key to a complete picture of galaxy evolution. Here, we present a new HST WFC3/UVIS program, the Hubble Deep UV (HDUV) legacy survey. The HDUV is a 132 orbit program to obtain deep imaging in two filters (F275W and F336W) over the two CANDELS Deep fields. We will cover ~100 arcmin2 sampling the rest-frame far-UV at z>~0.5, this will provide a unique legacy dataset with exquisite HST multi-wavelength imaging as well as ancillary HST grism NIR spectroscopy for a detailed study of faint, star-forming galaxies at z~0.5-2. The HDUV will enable a wealth of research by the community, which includes tracing the evolution of the FUV luminosity function over the peak of the star formation rate density from z~3 down to z~0.5, measuring the physical properties of sub-L* galaxies, and characterizing resolved stellar populations to decipher the build-up of the Hubble sequence from sub-galactic clumps. This poster provides an overview of the HDUV survey and presents the reduced data products and catalogs which will be released to the community, reaching down to 27.5-28.0 mag at 5 sigma. By directly sampling the rest-frame far-UV at z>~0.5, this will provide a unique legacy dataset with exquisite HST multi-wavelength imaging as well as ancillary HST grism NIR spectroscopy for a detailed study of faint, star-forming galaxies at z~0.5-2. The HDUV will enable a wealth of research by the community, which includes tracing the evolution of the FUV luminosity function over the peak of the star formation rate density from z~3 down to z~0.5, measuring the physical properties of sub-L* galaxies, and characterizing resolved stellar populations to decipher the build-up of the Hubble sequence from sub-galactic clumps. This poster provides an overview of the HDUV survey and presents reduced data products and catalogs which will be released to the community.

Spatially resolved rest-UV spectroscopy of a prototypical quasar driven superwind at low-z

NASA Astrophysics Data System (ADS)

Johnson, Sean

2017-08-01

Powerful galaxy-wide winds launched by quasars are thought to be a common evolutionary phase of massive galaxies, but observations of this phenomena are scarce. We have conducted a multi-wavelength observational campaign for J1356+1026, a poster-child obscured quasar driving a superwind at z=0.123. J1356+1026 is driving a nuclear molecular outflow and an extended ionized outflow observed as an [OIII] emitting bubble at 10 kpc that is spatially coincident with soft X-ray emission. Quasar-driven winds carry material at a wide range of densities and temperatures making it difficult to measure their energetics and the dominant phases are unknown. Here we propose spatially resolved rest-UV spectroscopy by acquiring circum-nuclear absorption spectra of J1356+1026 and emission spectra of its off-nucleus bubble using COS+G140L. The circum-nuclear spectrum will provide measurements of the outflow velocity through blueshifted absorption while the off-nuclear spectrum of the bubble will measure the ionization state and mechanisms of the outflow through powerful UV diagnostic lines. Together, these spectra will enable a more complete mass, energy and momentum accounting of a spatially resolved quasar driven superwind for the first time. Furthermore, detection of shocked gas through OVI emission will enable us to infer properties of the enigmatic volume-filling, low density component of the wind. To our knowledge, this will be the first spatially resolved rest UV spectroscopy of a quasar wind and the proposed observations will serve as a pilot to guide future HST proposals.

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

Bailey, J.E.; Adams, R.; Carlson, A.L.

Stark-shift measurements using emission spectroscopy are a powerful tool for advancing understanding in many plasma physics experiments. The authors use simultaneous 2-D-spatial and time-resolved spectra to study the electric field evolution in the 20 TW Particle Beam Fusion Accelerator II ion diode acceleration gap. Fiber optic arrays transport light from the gap to remote streaked spectrographs operated in a multiplexed mode that enables recording time-resolved spectra from eight spatial locations on a single instrument. Design optimization and characterization measurements of the multiplexed spectrograph properties include the astigmatism, resolution, dispersion variation, and sensitivity. A semi-automated line-fitting procedure determines the Stark shiftmore » and the related uncertainties. Fields up to 10 MV/cm are measured with an accuracy {+-}2--4%. Detailed tests of the fitting procedure confirm that the wavelength shift uncertainties are accurate to better than {+-}20%. Development of an active spectroscopy probe technique that uses laser-induced fluorescence from an injected atomic beam to obtain 3-D space- and time-resolved measurements of the electric and magnetic fields is in progress.« less

Electron density in surface barrier discharge emerging at argon/water interface: quantification for streamers and leaders

NASA Astrophysics Data System (ADS)

Cvetanović, Nikola; Galmiz, Oleksandr; Synek, Petr; Zemánek, Miroslav; Brablec, Antonín; Hoder, Tomáš

2018-02-01

Optical emission spectroscopy, fast intensified CCD imaging and electrical measurements were applied to investigate the basic plasma parameters of surface barrier discharge emerging from a conductive water electrode. The discharge was generated at the triple-line interface of atmospheric pressure argon gas and conductive water solution at the fused silica dielectrics using a sinusoidal high-voltage waveform. The spectroscopic methods of atomic line broadening and molecular spectroscopy were used to determine the electron densities and the gas temperature in the active plasma. These parameters were obtained for both applied voltage polarities and resolved spatially. Two different spectral signatures were identified in the spatially resolved spectra resulting in electron densities differing by two orders of magnitude. It is shown that two discharge mechanisms take a place: the streamer and the leader one, with electron densities of 1014 and 1016 cm-3, respectively. This spectroscopic evidence is supported by the combined diagnostics of electrical current measurements and phase-resolved intensified CCD camera imaging.

Dynamic tissue analysis using time- and wavelength-resolved fluorescence spectroscopy for atherosclerosis diagnosis

PubMed Central

Sun, Yinghua; Sun, Yang; Stephens, Douglas; Xie, Hongtao; Phipps, Jennifer; Saroufeem, Ramez; Southard, Jeffrey; Elson, Daniel S.; Marcu, Laura

2011-01-01

Simultaneous time- and wavelength-resolved fluorescence spectroscopy (STWRFS) was developed and tested for the dynamic characterization of atherosclerotic tissue ex vivo and arterial vessels in vivo. Autofluorescence, induced by a 337 nm, 700 ps pulsed laser, was split to three wavelength sub-bands using dichroic filters, with each sub-band coupled into a different length of optical fiber for temporal separation. STWRFS allows for fast recording/analysis (few microseconds) of time-resolved fluorescence emission in these sub-bands and rapid scanning. Distinct compositions of excised human atherosclerotic aorta were clearly discriminated over scanning lengths of several centimeters based on fluorescence lifetime and the intensity ratio between 390 and 452 nm. Operation of STWRFS blood flow was further validated in pig femoral arteries in vivo using a single-fiber probe integrated with an ultrasound imaging catheter. Current results demonstrate the potential of STWRFS as a tool for real-time optical characterization of arterial tissue composition and for atherosclerosis research and diagnosis. PMID:21369214

Microcontroller based resonance tracking unit for time resolved continuous wave cavity-ringdown spectroscopy measurements.

PubMed

Votava, Ondrej; Mašát, Milan; Parker, Alexander E; Jain, Chaithania; Fittschen, Christa

2012-04-01

We present in this work a new tracking servoloop electronics for continuous wave cavity-ringdown absorption spectroscopy (cw-CRDS) and its application to time resolved cw-CRDS measurements by coupling the system with a pulsed laser photolysis set-up. The tracking unit significantly increases the repetition rate of the CRDS events and thus improves effective time resolution (and/or the signal-to-noise ratio) in kinetics studies with cw-CRDS in given data acquisition time. The tracking servoloop uses novel strategy to track the cavity resonances that result in a fast relocking (few ms) after the loss of tracking due to an external disturbance. The microcontroller based design is highly flexible and thus advanced tracking strategies are easy to implement by the firmware modification without the need to modify the hardware. We believe that the performance of many existing cw-CRDS experiments, not only time-resolved, can be improved with such tracking unit without any additional modification to the experiment. © 2012 American Institute of Physics

Spatially resolved x-ray fluorescence spectroscopy of beryllium capsule implosions at the NIF

NASA Astrophysics Data System (ADS)

MacDonald, M. J.; Bishel, D. T.; Saunders, A. M.; Scott, H. A.; Kyrala, G.; Kline, J.; MacLaren, S.; Thorn, D. B.; Yi, S. A.; Zylstra, A. B.; Falcone, R. W.; Doeppner, T.

2017-10-01

Beryllium ablators used in indirectly driven inertial confinement fusion implosions are doped with copper to prevent preheat of the cryogenic hydrogen fuel. Here, we present analysis of spatially resolved copper K- α fluorescence spectra from the beryllium ablator layer. It has been shown that K- α fluorescence spectroscopy can be used to measure plasma conditions of partially ionized dopants in high energy density systems. In these experiments, K-shell vacancies in the copper dopant are created by the hotspot emission at stagnation, resulting in K-shell fluorescence at bang time. Spatially resolved copper K- α emission spectra are compared to atomic kinetics and radiation code simulations to infer density and temperature profiles. This work was supported by the US DOE under Grant No. DE-NA0001859, under the auspices of the US DOE by Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344, and by Los Alamos National Laboratory under contract DE-AC52-06NA52396.

Space-resolved diffusing wave spectroscopy measurements of the macroscopic deformation and the microscopic dynamics in tensile strain tests

NASA Astrophysics Data System (ADS)

Nagazi, Med-Yassine; Brambilla, Giovanni; Meunier, Gérard; Marguerès, Philippe; Périé, Jean-Noël; Cipelletti, Luca

2017-01-01

We couple a laser-based, space-resolved dynamic light scattering apparatus to a universal traction machine for mechanical extensional tests. We perform simultaneous optical and mechanical measurements on polyether ether ketone, a semi-crystalline polymer widely used in the industry. Due to the high turbidity of the sample, light is multiply scattered by the sample and the diffusing wave spectroscopy (DWS) formalism is used to interpret the data. Space-resolved DWS yields spatial maps of the sample strain and of the microscopic dynamics. An excellent agreement is found between the strain maps thus obtained and those measured by a conventional stereo-digital image correlation technique. The microscopic dynamics reveals both affine motion and plastic rearrangements. Thanks to the extreme sensitivity of DWS to displacements as small as 1 nm, plastic activity and its spatial localization can be detected at an early stage of the sample strain, making the technique presented here a valuable complement to existing material characterization methods.

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.

Distortion correction and cross-talk compensation algorithm for use with an imaging spectrometer based spatially resolved diffuse reflectance system

NASA Astrophysics Data System (ADS)

Cappon, Derek J.; Farrell, Thomas J.; Fang, Qiyin; Hayward, Joseph E.

2016-12-01

Optical spectroscopy of human tissue has been widely applied within the field of biomedical optics to allow rapid, in vivo characterization and analysis of the tissue. When designing an instrument of this type, an imaging spectrometer is often employed to allow for simultaneous analysis of distinct signals. This is especially important when performing spatially resolved diffuse reflectance spectroscopy. In this article, an algorithm is presented that allows for the automated processing of 2-dimensional images acquired from an imaging spectrometer. The algorithm automatically defines distinct spectrometer tracks and adaptively compensates for distortion introduced by optical components in the imaging chain. Crosstalk resulting from the overlap of adjacent spectrometer tracks in the image is detected and subtracted from each signal. The algorithm's performance is demonstrated in the processing of spatially resolved diffuse reflectance spectra recovered from an Intralipid and ink liquid phantom and is shown to increase the range of wavelengths over which usable data can be recovered.

Time-to-digital converter card for multichannel time-resolved single-photon counting applications

NASA Astrophysics Data System (ADS)

Tamborini, Davide; Portaluppi, Davide; Tisa, Simone; Tosi, Alberto

2015-03-01

We present a high performance Time-to-Digital Converter (TDC) card that provides 10 ps timing resolution and 20 ps (rms) timing precision with a programmable full-scale-range from 160 ns to 10 μs. Differential Non-Linearity (DNL) is better than 1.3% LSB (rms) and Integral Non-Linearity (INL) is 5 ps rms. Thanks to the low power consumption (400 mW) and the compact size (78 mm x 28 mm x 10 mm), this card is the building block for developing compact multichannel time-resolved instrumentation for Time-Correlated Single-Photon Counting (TCSPC). The TDC-card outputs the time measurement results together with the rates of START and STOP signals and the number of valid TDC conversions. These additional information are needed by many TCSPC-based applications, such as: Fluorescence Lifetime Imaging (FLIM), Time-of-Flight (TOF) ranging measurements, time-resolved Positron Emission Tomography (PET), single-molecule spectroscopy, Fluorescence Correlation Spectroscopy (FCS), Diffuse Optical Tomography (DOT), Optical Time-Domain Reflectometry (OTDR), quantum optics, etc.

Femtosecond to picosecond transient effects in WSe 2 observed by pump-probe angle-resolved photoemission spectroscopy.

PubMed

Liu, Ro-Ya; Ogawa, Yu; Chen, Peng; Ozawa, Kenichi; Suzuki, Takeshi; Okada, Masaru; Someya, Takashi; Ishida, Yukiaki; Okazaki, Kozo; Shin, Shik; Chiang, Tai-Chang; Matsuda, Iwao

2017-11-22

Time-dependent responses of materials to an ultrashort optical pulse carry valuable information about the electronic and lattice dynamics; this research area has been widely studied on novel two-dimensional materials such as graphene, transition metal dichalcogenides (TMDs) and topological insulators (TIs). We report herein a time-resolved and angle-resolved photoemission spectroscopy (TRARPES) study of WSe 2 , a layered semiconductor of interest for valley electronics. The results for below-gap optical pumping reveal energy-gain and -loss Floquet replica valence bands that appear instantaneously in concert with the pump pulse. Energy shift, broadening, and complex intensity variation and oscillation at twice the phonon frequency for the valence bands are observed at time scales ranging from the femtosecond to the picosecond and beyond. The underlying physics is rich, including ponderomotive interaction, dressing of the electronic states, creation of coherent phonon pairs, and diffusion of charge carriers - effects operating at vastly different time domains.

An SRY mutation causing human sex reversal resolves a general mechanism of structure-specific DNA recognition: application to the four-way DNA junction.

PubMed

Peters, R; King, C Y; Ukiyama, E; Falsafi, S; Donahoe, P K; Weiss, M A

1995-04-11

SRY, a genetic "master switch" for male development in mammals, exhibits two biochemical activities: sequence-specific recognition of duplex DNA and sequence-independent binding to the sharp angles of four-way DNA junctions. Here, we distinguish between these activities by analysis of a mutant SRY associated with human sex reversal (46, XY female with pure gonadal dysgenesis). The substitution (168T in human SRY) alters a nonpolar side chain in the minor-groove DNA recognition alpha-helix of the HMG box [Haqq, C.M., King, C.-Y., Ukiyama, E., Haqq, T.N., Falsalfi, S., Donahoe, P.K., & Weiss, M.A. (1994) Science 266, 1494-1500]. The native (but not mutant) side chain inserts between specific base pairs in duplex DNA, interrupting base stacking at a site of induced DNA bending. Isotope-aided 1H-NMR spectroscopy demonstrates that analogous side-chain insertion occurs on binding of SRY to a four-way junction, establishing a shared mechanism of sequence- and structure-specific DNA binding. Although the mutant DNA-binding domain exhibits > 50-fold reduction in sequence-specific DNA recognition, near wild-type affinity for four-way junctions is retained. Our results (i) identify a shared SRY-DNA contact at a site of either induced or intrinsic DNA bending, (ii) demonstrate that this contact is not required to bind an intrinsically bent DNA target, and (iii) rationalize patterns of sequence conservation or diversity among HMG boxes. Clinical association of the I68T mutation with human sex reversal supports the hypothesis that specific DNA recognition by SRY is required for male sex determination.

Tachometer Derived From Brushless Shaft-Angle Resolver

NASA Technical Reports Server (NTRS)

Howard, David E.; Smith, Dennis A.

1995-01-01

Tachometer circuit operates in conjunction with brushless shaft-angle resolver. By performing sequence of straightforward mathematical operations on resolver signals and utilizing simple trigonometric identity, generates voltage proportional to rate of rotation of shaft. One advantage is use of brushless shaft-angle resolver as main source of rate signal: no brushes to wear out, no brush noise, and brushless resolvers have proven robustness. No switching of signals to generate noise. Another advantage, shaft-angle resolver used as shaft-angle sensor, tachometer input obtained without adding another sensor. Present circuit reduces overall size, weight, and cost of tachometer.

Transcriptome sequences resolve deep relationships of the grape family.

PubMed

Wen, Jun; Xiong, Zhiqiang; Nie, Ze-Long; Mao, Likai; Zhu, Yabing; Kan, Xian-Zhao; Ickert-Bond, Stefanie M; Gerrath, Jean; Zimmer, Elizabeth A; Fang, Xiao-Dong

2013-01-01

Previous phylogenetic studies of the grape family (Vitaceae) yielded poorly resolved deep relationships, thus impeding our understanding of the evolution of the family. Next-generation sequencing now offers access to protein coding sequences very easily, quickly and cost-effectively. To improve upon earlier work, we extracted 417 orthologous single-copy nuclear genes from the transcriptomes of 15 species of the Vitaceae, covering its phylogenetic diversity. The resulting transcriptome phylogeny provides robust support for the deep relationships, showing the phylogenetic utility of transcriptome data for plants over a time scale at least since the mid-Cretaceous. The pros and cons of transcriptome data for phylogenetic inference in plants are also evaluated.

A comprehensively molecular haplotype-resolved genome of a European individual

PubMed Central

Suk, Eun-Kyung; McEwen, Gayle K.; Duitama, Jorge; Nowick, Katja; Schulz, Sabrina; Palczewski, Stefanie; Schreiber, Stefan; Holloway, Dustin T.; McLaughlin, Stephen; Peckham, Heather; Lee, Clarence; Huebsch, Thomas; Hoehe, Margret R.

2011-01-01

Independent determination of both haplotype sequences of an individual genome is essential to relate genetic variation to genome function, phenotype, and disease. To address the importance of phase, we have generated the most complete haplotype-resolved genome to date, “Max Planck One” (MP1), by fosmid pool-based next generation sequencing. Virtually all SNPs (>99%) and 80,000 indels were phased into haploid sequences of up to 6.3 Mb (N50 ∼1 Mb). The completeness of phasing allowed determination of the concrete molecular haplotype pairs for the vast majority of genes (81%) including potential regulatory sequences, of which >90% were found to be constituted by two different molecular forms. A subset of 159 genes with potentially severe mutations in either cis or trans configurations exemplified in particular the role of phase for gene function, disease, and clinical interpretation of personal genomes (e.g., BRCA1). Extended genomic regions harboring manifold combinations of physically and/or functionally related genes and regulatory elements were resolved into their underlying “haploid landscapes,” which may define the functional genome. Moreover, the majority of genes and functional sequences were found to contain individual or rare SNPs, which cannot be phased from population data alone, emphasizing the importance of molecular phasing for characterizing a genome in its molecular individuality. Our work provides the foundation to understand that the distinction of molecular haplotypes is essential to resolve the (inherently individual) biology of genes, genomes, and disease, establishing a reference point for “phase-sensitive” personal genomics. MP1's annotated haploid genomes are available as a public resource. PMID:21813624

Quantitative sampling of conformational heterogeneity of a DNA hairpin using molecular dynamics simulations and ultrafast fluorescence spectroscopy

PubMed Central

Voltz, Karine; Léonard, Jérémie; Touceda, Patricia Tourón; Conyard, Jamie; Chaker, Ziyad; Dejaegere, Annick; Godet, Julien; Mély, Yves; Haacke, Stefan; Stote, Roland H.

2016-01-01

Molecular dynamics (MD) simulations and time resolved fluorescence (TRF) spectroscopy were combined to quantitatively describe the conformational landscape of the DNA primary binding sequence (PBS) of the HIV-1 genome, a short hairpin targeted by retroviral nucleocapsid proteins implicated in the viral reverse transcription. Three 2-aminopurine (2AP) labeled PBS constructs were studied. For each variant, the complete distribution of fluorescence lifetimes covering 5 orders of magnitude in timescale was measured and the populations of conformers experimentally observed to undergo static quenching were quantified. A binary quantification permitted the comparison of populations from experimental lifetime amplitudes to populations of aromatically stacked 2AP conformers obtained from simulation. Both populations agreed well, supporting the general assumption that quenching of 2AP fluorescence results from pi-stacking interactions with neighboring nucleobases and demonstrating the success of the proposed methodology for the combined analysis of TRF and MD data. Cluster analysis of the latter further identified predominant conformations that were consistent with the fluorescence decay times and amplitudes, providing a structure-based rationalization for the wide range of fluorescence lifetimes. Finally, the simulations provided evidence of local structural perturbations induced by 2AP. The approach presented is a general tool to investigate fine structural heterogeneity in nucleic acid and nucleoprotein assemblies. PMID:26896800

Accuracy of noninvasive quantification of brain NAA concentrations using PRESS sequence: verification in a swine model with external standard.

PubMed

Wu, R H; Lin, R; Li, H; Xiao, Z W; Rao, H B; Luo, W H; Guo, G; Huang, K; Zhang, X G; Lang, Z J

2005-01-01

The metabolite ratios had been employed in the field of MR spectroscopy (MRS) for a long period. The main drawback of metabolite ratio is that ratio results are not comparable with absolute metabolite concentration in vivo. The purpose of this study was to examine the accuracy of noninvasive quantification of brain N-acetylaspartate (NAA) concentrations using previously reported MR external standard method. Eight swine were scanned on a GE 1.5 T scanner with a standard head coil. The external standard method was utilized with a sphere filled with NAA, GABA, glutamine, glutamate, creatine, choline chloride, and myo-inositol. The position resolved spectroscopy (PRESS) sequence was used with TE=135 msec, TR=1500 msec, and 128 scan averages. The analysis of MRS was done with SAGE/IDL program. In vivo NAA concentration was obtained using the equation S=N * e(-TE/T₂) * [1-e(-TR/T₁). In vitro NAA concentration was measured by high performance liquid chromatography (HPLC). In the MRS group, the mean concentration of NAA was 10.03 plusmn 0.74 mmol/kg. In the HPLC group, the mean concentration of NAA was 9.22 plusmn 0.55 mmol/kg. There was no significant difference between the two groups (p = 0.46). However, slightly higher value was observed in the MRS group (7/8 swine), compared with HPLC group. The range of differences was between 0.02~2.05 mmol/kg. MRS external reference method could be more accurate than internal reference method. ¹H MRS does not distinguish between N-acetyl resonance frequencies and other N-acetylated amino acids.

Squeezing water from a stone: high-throughput sequencing from a 145-year old holotype resolves (barely) a cryptic species problem in flying lizards.

PubMed

McGuire, Jimmy A; Cotoras, Darko D; O'Connell, Brendan; Lawalata, Shobi Z S; Wang-Claypool, Cynthia Y; Stubbs, Alexander; Huang, Xiaoting; Wogan, Guinevere O U; Hykin, Sarah M; Reilly, Sean B; Bi, Ke; Riyanto, Awal; Arida, Evy; Smith, Lydia L; Milne, Heather; Streicher, Jeffrey W; Iskandar, Djoko T

2018-01-01

We used Massively Parallel High-Throughput Sequencing to obtain genetic data from a 145-year old holotype specimen of the flying lizard, Draco cristatellus . Obtaining genetic data from this holotype was necessary to resolve an otherwise intractable taxonomic problem involving the status of this species relative to closely related sympatric Draco species that cannot otherwise be distinguished from one another on the basis of museum specimens. Initial analyses suggested that the DNA present in the holotype sample was so degraded as to be unusable for sequencing. However, we used a specialized extraction procedure developed for highly degraded ancient DNA samples and MiSeq shotgun sequencing to obtain just enough low-coverage mitochondrial DNA (721 base pairs) to conclusively resolve the species status of the holotype as well as a second known specimen of this species. The holotype was prepared before the advent of formalin-fixation and therefore was most likely originally fixed with ethanol and never exposed to formalin. Whereas conventional wisdom suggests that formalin-fixed samples should be the most challenging for DNA sequencing, we propose that evaporation during long-term alcohol storage and consequent water-exposure may subject older ethanol-fixed museum specimens to hydrolytic damage. If so, this may pose an even greater challenge for sequencing efforts involving historical samples.

Orientation-resolved domain mapping in tetragonal SrTiO 3 using polarized Raman spectroscopy

DOE PAGES

Gray, Jr., Dodd J.; Merz, Tyler A.; Hikita, Yasuyuki; ...

2016-12-16

Here, we present microscopically resolved, polarized spectroscopy of Raman scattering collected from tetragonal SrTiO 3. The anisotropic response of first-order Raman peaks within a single tetragonal domain has been measured. From these data, we assign symmetries to the phonons seen in the first-order Raman spectrum which is normally complicated by uncontrolled domain structure. Using a translation stage, we map the local domain orientation of a 3–μm 3 crystal volume near the laser focus and compare it to wide-field polarized images. This technique can be performed with readily available instruments and is relevant to the study of a wide range ofmore » related materials, interfaces, and devices.« less

Ultrafast magnetodynamics with free-electron lasers

NASA Astrophysics Data System (ADS)

Malvestuto, Marco; Ciprian, Roberta; Caretta, Antonio; Casarin, Barbara; Parmigiani, Fulvio

2018-02-01

The study of ultrafast magnetodynamics has entered a new era thanks to the groundbreaking technological advances in free-electron laser (FEL) light sources. The advent of these light sources has made possible unprecedented experimental schemes for time-resolved x-ray magneto-optic spectroscopies, which are now paving the road for exploring the ultimate limits of out-of-equilibrium magnetic phenomena. In particular, these studies will provide insights into elementary mechanisms governing spin and orbital dynamics, therefore contributing to the development of ultrafast devices for relevant magnetic technologies. This topical review focuses on recent advancement in the study of non-equilibrium magnetic phenomena from the perspective of time-resolved extreme ultra violet (EUV) and soft x-ray spectroscopies at FELs with highlights of some important experimental results.

Jet-resolved vibronic structure in the higher excited states of N2O - Ultraviolet three-photon absorption spectroscopy from 80,000 to 90,000/cm

NASA Technical Reports Server (NTRS)

Patsilinakou, E.; Wiedmann, R. T.; Fotakis, C.; Grant, E. R.

1989-01-01

Ionization-detected UV multiphoton absorption spectroscopy of the excited states of N2O is presented, showing Rydberg structure within 20,000/cm of the first ionization threshold. Despite evidence for strong Rydberg-continuum coupling in the form of broadened bands and Fano line-shapes, the Rydberg structure persists, with atomic-like quantum defects and vibration structure well-matched with that of the ion. In the most clearly resolved spectrum, corresponding to the 3p(delta)1Pi state, Renner-Teller and Herzberg-Teller coupling of electronic and vibrational angular momentum are revealed. It is suggested that these mixings are properties of the N2O(+)Pi ion core.

A von Hamos x-ray spectrometer based on a segmented-type diffraction crystal for single-shot x-ray emission spectroscopy and time-resolved resonant inelastic x-ray scattering studies

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

Szlachetko, J.; Institute of Physics, Jan Kochanowski University, 25-406 Kielce; Nachtegaal, M.

2012-10-15

We report on the design and performance of a wavelength-dispersive type spectrometer based on the von Hamos geometry. The spectrometer is equipped with a segmented-type crystal for x-ray diffraction and provides an energy resolution in the order of 0.25 eV and 1 eV over an energy range of 8000 eV-9600 eV. The use of a segmented crystal results in a simple and straightforward crystal preparation that allows to preserve the spectrometer resolution and spectrometer efficiency. Application of the spectrometer for time-resolved resonant inelastic x-ray scattering and single-shot x-ray emission spectroscopy is demonstrated.

A dielectric model of self-assembled monolayer interfaces by capacitive spectroscopy.

PubMed

Góes, Márcio S; Rahman, Habibur; Ryall, Joshua; Davis, Jason J; Bueno, Paulo R

2012-06-26

The presence of self-assembled monolayers at an electrode introduces capacitance and resistance contributions that can profoundly affect subsequently observed electronic characteristics. Despite the impact of this on any voltammetry, these contributions are not directly resolvable with any clarity by standard electrochemical means. A capacitive analysis of such interfaces (by capacitance spectroscopy), introduced here, enables a clean mapping of these features and additionally presents a means of studying layer polarizability and Cole-Cole relaxation effects. The resolved resistive term contributes directly to an intrinsic monolayer uncompensated resistance that has a linear dependence on the layer thickness. The dielectric model proposed is fully aligned with the classic Helmholtz plate capacitor model and additionally explains the inherently associated resistive features of molecular films.

Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

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

Sheps, Leonid; Chandler, David W.

Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transientmore » reaction intermediates in a simple, inexpensive, and robust experimental package.« less

Hybrid optical materials of plasmon-coupled CdSe/ZnS coreshells for photonic applications

PubMed Central

Seo, Jaetae; Fudala, Rafal; Kim, Wan-Joong; Rich, Ryan; Tabibi, Bagher; Cho, Hyoyeong; Gryczynski, Zygmunt; Gryczynski, Ignacy; Yu, William

2013-01-01

A hybrid optical nanostructure of plasmon-coupled SQDs was developed for photonic applications. The coupling distances between the mono-layers of Au nanoparticles with a surface concentration of ~9.18 × 10−4 nm−2 and CdSe/ZnS SQDs with that of ~3.7 × 10−3 nm−2 were controlled by PMMA plasma etching. Time-resolved spectroscopy of plasmon-coupled SQDs revealed a strong shortening of the longest lifetime and ~9-fold PL enhancement. Polarization-resolved PL spectroscopy displayed linear polarization and depolarization at near- and far-field plasmon-coupling, respectively. The physical origin of PL enhancement could be attributable to both the large local field enhancement and the fast resonant energy transfer. PMID:23457661

Visualizing dispersive features in 2D image via minimum gradient method

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

He, Yu; Wang, Yan; Shen, Zhi -Xun

Here, we developed a minimum gradient based method to track ridge features in a 2D image plot, which is a typical data representation in many momentum resolved spectroscopy experiments. Through both analytic formulation and numerical simulation, we compare this new method with existing DC (distribution curve) based and higher order derivative based analyses. We find that the new method has good noise resilience and enhanced contrast especially for weak intensity features and meanwhile preserves the quantitative local maxima information from the raw image. An algorithm is proposed to extract 1D ridge dispersion from the 2D image plot, whose quantitative applicationmore » to angle-resolved photoemission spectroscopy measurements on high temperature superconductors is demonstrated.« less

Visualizing dispersive features in 2D image via minimum gradient method

DOE PAGES

He, Yu; Wang, Yan; Shen, Zhi -Xun

2017-07-24

Here, we developed a minimum gradient based method to track ridge features in a 2D image plot, which is a typical data representation in many momentum resolved spectroscopy experiments. Through both analytic formulation and numerical simulation, we compare this new method with existing DC (distribution curve) based and higher order derivative based analyses. We find that the new method has good noise resilience and enhanced contrast especially for weak intensity features and meanwhile preserves the quantitative local maxima information from the raw image. An algorithm is proposed to extract 1D ridge dispersion from the 2D image plot, whose quantitative applicationmore » to angle-resolved photoemission spectroscopy measurements on high temperature superconductors is demonstrated.« less

Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

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

Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J.

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energizedmore » HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.« less

Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

DOE PAGES

Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J.; ...

2017-12-01

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energizedmore » HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.« less

Electronic and geometric structure of thin CoO(100) films studied by angle-resolved photoemission spectroscopy and Auger electron diffraction

NASA Astrophysics Data System (ADS)

Heiler, M.; Chassé, A.; Schindler, K.-M.; Hollering, M.; Neddermeyer, H.

2000-05-01

We have prepared ordered thin films of CoO by evaporating cobalt in an O 2 atmosphere on to a heated (500 K) Ag(100) substrate. The geometric and electronic structure of the films was characterized by means of Auger electron diffraction (AED) and angle-resolved photoemission spectroscopy (ARUPS), respectively. The experimental AED results were compared with simulated data, which showed that the film grows in (100) orientation on the Ag(100) substrate. Synchrotron-radiation-induced photoemission investigations were performed in the photon energy range from 25 eV to 67 eV. The dispersion of the transitions was found to be similar to that of previous results on a single-crystal CoO(100) surface. The resonance behaviour of the photoemission lines in the valence-band region was investigated by constant-initial-state (CIS) spectroscopy. The implications of this behaviour for assignment of the photoemission lines to specific electronic transitions is discussed and compared with published theoretical models of the electronic structure.

A flexible gas flow reaction cell for in situ x-ray absorption spectroscopy studies

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

Kroner, Anna B., E-mail: anna.kroner@diamond.ac.uk; Gilbert, Martin; Duller, Graham

2016-07-27

A capillary-based sample environment with hot air blower and integrated gas system was developed at Diamond to conduct X-ray absorption spectroscopy (XAS) studies of materials under time-resolved, in situ conditions. The use of a hot air blower, operating in the temperature range of 298-1173 K, allows introduction of other techniques e.g. X-ray diffraction (XRD), Raman spectroscopy for combined techniques studies. The flexibility to use either quartz or Kapton capillaries allows users to perform XAS measurement at energies as low as 5600 eV. To demonstrate performance, time-resolved, in situ XAS results of Rh catalysts during the process of activation (Rh K-edge,more » Ce L{sub 3}-edge and Cr K-edge) and the study of mixed oxide membrane (La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ}) under various partial oxygen pressure conditions are described.« less

Near-Infrared Spatially Resolved Spectroscopy for Tablet Quality Determination.

PubMed

Igne, Benoît; Talwar, Sameer; Feng, Hanzhou; Drennen, James K; Anderson, Carl A

2015-12-01

Near-infrared (NIR) spectroscopy has become a well-established tool for the characterization of solid oral dosage forms manufacturing processes and finished products. In this work, the utility of a traditional single-point NIR measurement was compared with that of a spatially resolved spectroscopic (SRS) measurement for the determination of tablet assay. Experimental designs were used to create samples that allowed for calibration models to be developed and tested on both instruments. Samples possessing a poor distribution of ingredients (highly heterogeneous) were prepared by under-blending constituents prior to compaction to compare the analytical capabilities of the two NIR methods. The results indicate that SRS can provide spatial information that is usually obtainable only through imaging experiments for the determination of local heterogeneity and detection of abnormal tablets that would not be detected with single-point spectroscopy, thus complementing traditional NIR measurement systems for in-line, and in real-time tablet analysis. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Nanosecond step-scan FT-infrared absorption spectroscopy in photochemistry and catalysis

NASA Astrophysics Data System (ADS)

Frei, H.

1998-06-01

Time-resolved step-scan FT-IR absorption spectroscopy has been expanded to a resolution of 20 nanosecond. Following a description of the experimental set-up, applications in four research areas are presented. In the first project, we discuss a reversible isomerization, namely the bacteriorhodopsin photocycle. Main results are the discovery of 2 processes with distinct kinetics on the nanosecond time scale not detected by previous spectroscopic techniques, and observation of an instantaneous response of the protein environment to chromophore dynamics within the nanosecond laser pulse duration. In a second project, alkane C-H bond activation by a transition metal complex in room temperature solution is investigated and the first measurement of the formation of a C-H insertion product reported (alkyl hydride). Then, a nanosecond study of a pericyclic reaction, the ring-opening of cyclohexadiene, is discussed. The fourth example describes the first observation of a transient molecule in a zeolite matrix, a triplet excited quinone, by time-resolved infrared spectroscopy.

Time-resolved optical spectrometer based on a monolithic array of high-precision TDCs and SPADs

NASA Astrophysics Data System (ADS)

Tamborini, Davide; Markovic, Bojan; Di Sieno, Laura; Contini, Davide; Bassi, Andrea; Tisa, Simone; Tosi, Alberto; Zappa, Franco

2013-12-01

We present a compact time-resolved spectrometer suitable for optical spectroscopy from 400 nm to 1 μm wavelengths. The detector consists of a monolithic array of 16 high-precision Time-to-Digital Converters (TDC) and Single-Photon Avalanche Diodes (SPAD). The instrument has 10 ps resolution and reaches 70 ps (FWHM) timing precision over a 160 ns full-scale range with a Differential Non-Linearity (DNL) better than 1.5 % LSB. The core of the spectrometer is the application-specific integrated chip composed of 16 pixels with 250 μm pitch, containing a 20 μm diameter SPAD and an independent TDC each, fabricated in a 0.35 μm CMOS technology. In front of this array a monochromator is used to focus different wavelengths into different pixels. The spectrometer has been used for fluorescence lifetime spectroscopy: 5 nm spectral resolution over an 80 nm bandwidth is achieved. Lifetime spectroscopy of Nile blue is demonstrated.

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.

Resolving the Origin of Rabbit Hemorrhagic Disease Virus: Insights from an Investigation of the Viral Stocks Released in Australia

PubMed Central

Eden, John-Sebastian; Read, Andrew J.; Duckworth, Janine A.; Strive, Tanja

2015-01-01

To resolve the evolutionary history of rabbit hemorrhagic disease virus (RHDV), we performed a genomic analysis of the viral stocks imported and released as a biocontrol measure in Australia, as well as a global phylogenetic analysis. Importantly, conflicts were identified between the sequences determined here and those previously published that may have affected evolutionary rate estimates. By removing likely erroneous sequences, we show that RHDV emerged only shortly before its initial description in China. PMID:26378178

Temperature and Electron Density Determination on Laser-Induced Breakdown Spectroscopy (LIBS) Plasmas: A Physical Chemistry Experiment

ERIC Educational Resources Information Center

Najarian, Maya L.; Chinni, Rosemarie C.

2013-01-01

This laboratory is designed for physical chemistry students to gain experience using laser-induced breakdown spectroscopy (LIBS) in understanding plasma diagnostics. LIBS uses a high-powered laser that is focused on the sample causing a plasma to form. The emission of this plasma is then spectrally resolved and detected. Temperature and electron…

Indium diffusion through high-k dielectrics in high-k/InP stacks

NASA Astrophysics Data System (ADS)

Dong, H.; Cabrera, W.; Galatage, R. V.; Santosh KC, Brennan, B.; Qin, X.; McDonnell, S.; Zhernokletov, D.; Hinkle, C. L.; Cho, K.; Chabal, Y. J.; Wallace, R. M.

2013-08-01

Evidence of indium diffusion through high-k dielectric (Al2O3 and HfO2) films grown on InP (100) by atomic layer deposition is observed by angle resolved X-ray photoelectron spectroscopy and low energy ion scattering spectroscopy. The analysis establishes that In-out diffusion occurs and results in the formation of a POx rich interface.

Measuring and imaging diffusion with multiple scan speed image correlation spectroscopy.

PubMed

Gröner, Nadine; Capoulade, Jérémie; Cremer, Christoph; Wachsmuth, Malte

2010-09-27

The intracellular mobility of biomolecules is determined by transport and diffusion as well as molecular interactions and is crucial for many processes in living cells. Methods of fluorescence microscopy like confocal laser scanning microscopy (CLSM) can be used to characterize the intracellular distribution of fluorescently labeled biomolecules. Fluorescence correlation spectroscopy (FCS) is used to describe diffusion, transport and photo-physical processes quantitatively. As an alternative to FCS, spatially resolved measurements of mobilities can be implemented using a CLSM by utilizing the spatio-temporal information inscribed into the image by the scan process, referred to as raster image correlation spectroscopy (RICS). Here we present and discuss an extended approach, multiple scan speed image correlation spectroscopy (msICS), which benefits from the advantages of RICS, i.e. the use of widely available instrumentation and the extraction of spatially resolved mobility information, without the need of a priori knowledge of diffusion properties. In addition, msICS covers a broad dynamic range, generates correlation data comparable to FCS measurements, and allows to derive two-dimensional maps of diffusion coefficients. We show the applicability of msICS to fluorophores in solution and to free EGFP in living cells.

Voxel-based measurement sensitivity of spatially resolved near-infrared spectroscopy in layered tissues

NASA Astrophysics Data System (ADS)

Niwayama, Masatsugu

2018-03-01

We quantitatively investigated the measurement sensitivity of spatially resolved spectroscopy (SRS) across six tissue models: cerebral tissue, a small animal brain, the forehead of a fetus, an adult brain, forearm muscle, and thigh muscle. The optical path length in the voxel of the model was analyzed using Monte Carlo simulations. It was found that the measurement sensitivity can be represented as the product of the change in the absorption coefficient and the difference in optical path length in two states with different source-detector distances. The results clarified the sensitivity ratio between the surface layer and the deep layer at each source-detector distance for each model and identified changes in the deep measurement area when one of the detectors was close to the light source. A comparison was made with the results from continuous-wave spectroscopy. The study also identified measurement challenges that arise when the surface layer is inhomogeneous. Findings on the measurement sensitivity of SRS at each voxel and in each layer can support the correct interpretation of measured values when near-infrared oximetry or functional near-infrared spectroscopy is used to investigate different tissue structures.

A new detection scheme for ultrafast 2D J-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Giraudeau, Patrick; Akoka, Serge

2007-06-01

Recent ultrafast techniques enable 2D NMR spectra to be obtained in a single scan. A modification of the detection scheme involved in this technique is proposed, permitting the achievement of 2D 1H J-resolved spectra in 500 ms. The detection gradient echoes are substituted by spin echoes to obtain spectra where the coupling constants are encoded along the direct ν2 domain. The use of this new J-resolved detection block after continuous phase-encoding excitation schemes is discussed in terms of resolution and sensitivity. J-resolved spectra obtained on cinnamic acid and 3-ethyl bromopropionate are presented, revealing the expected 2D J-patterns with coupling constants as small as 2 Hz.

Accuracy and stability of measuring GABA, glutamate, and glutamine by proton magnetic resonance spectroscopy: A phantom study at 4 Tesla

PubMed Central

Henry, Michael E.; Lauriat, Tara L.; Shanahan, Meghan; Renshaw, Perry F.; Jensen, J. Eric

2015-01-01

Proton magnetic resonance spectroscopy has the potential to provide valuable information about alterations in gamma-aminobutyric acid (GABA), glutamate (Glu), and glutamine (Gln) in psychiatric and neurological disorders. In order to use this technique effectively, it is important to establish the accuracy and reproducibility of the methodology. In this study, phantoms with known metabolite concentrations were used to compare the accuracy of 2D J-resolved MRS, single-echo 30 ms PRESS, and GABA-edited MEGA-PRESS for measuring all three aforementioned neurochemicals simultaneously. The phantoms included metabolite concentrations above and below the physiological range and scans were performed at baseline, 1 week, and 1 month time-points. For GABA measurement, MEGA-PRESS proved optimal with a measured-to-target correlation of R2 = 0.999, with J-resolved providing R2 = 0.973 for GABA. All three methods proved effective in measuring Glu with R2 = 0.987 (30 ms PRESS), R2 = 0.996 (J-resolved) and R2 = 0.910 (MEGA-PRESS). J-resolved and MEGA-PRESS yielded good results for Gln measures with respective R2 = 0.855 (J-resolved) and R2 = 0.815 (MEGA-PRESS). The 30 ms PRESS method proved ineffective in measuring GABA and Gln. When measurement stability at in vivo concentration was assessed as a function of varying spectral quality, J-resolved proved the most stable and immune to signal-to-noise and linewidth fluctuation compared to MEGA-PRESS and 30 ms PRESS. PMID:21130670

ISM DUST GRAINS AND N-BAND SPECTRAL VARIABILITY IN THE SPATIALLY RESOLVED SUBARCSECOND BINARY UY Aur

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

Skemer, Andrew J.; Close, Laird M.; Hinz, Philip M.

2010-03-10

The 10 {mu}m silicate feature is an essential diagnostic of dust-grain growth and planet formation in young circumstellar disks. The Spitzer Space Telescope has revolutionized the study of this feature, but due to its small (85 cm) aperture, it cannot spatially resolve small/medium-separation binaries ({approx}<3''; {approx}< 420 AU) at the distances of the nearest star-forming regions ({approx}140 pc). Large, 6-10 m ground-based telescopes with mid-infrared instruments can resolve these systems. In this paper, we spatially resolve the 0.''88 binary, UY Aur, with MMTAO/BLINC-MIRAC4 mid-infrared spectroscopy. We then compare our spectra to Spitzer/IRS (unresolved) spectroscopy, and resolved images from IRTF/MIRAC2, Keck/OSCIR,more » and Gemini/Michelle, which were taken over the past decade. We find that UY Aur A has extremely pristine, interstellar medium (ISM)-like grains and that UY Aur B has an unusually shaped silicate feature, which is probably the result of blended emission and absorption from foreground extinction in its disk. We also find evidence for variability in both UY Aur A and UY Aur B by comparing synthetic photometry from our spectra with resolved imaging from previous epochs. The photometric variability of UY Aur A could be an indication that the silicate emission itself is variable, as was recently found in EX Lupi. Otherwise, the thermal continuum is variable, and either the ISM-like dust has never evolved, or it is being replenished, perhaps by UY Aur's circumbinary disk.« less

Nanometer-resolved chemical analyses of femtosecond laser-induced periodic surface structures on titanium

NASA Astrophysics Data System (ADS)

Kirner, Sabrina V.; Wirth, Thomas; Sturm, Heinz; Krüger, Jörg; Bonse, Jörn

2017-09-01

The chemical characteristics of two different types of laser-induced periodic surface structures (LIPSS), so-called high and low spatial frequency LIPSS (HSFL and LSFL), formed upon irradiation of titanium surfaces by multiple femtosecond laser pulses in air (30 fs, 790 nm, 1 kHz), are analyzed by various optical and electron beam based surface analytical techniques, including micro-Raman spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The latter method was employed in a high-resolution mode being capable of spatially resolving even the smallest HSFL structures featuring spatial periods below 100 nm. In combination with an ion sputtering technique, depths-resolved chemical information of superficial oxidation processes was obtained, revealing characteristic differences between the two different types of LIPSS. Our results indicate that a few tens of nanometer shallow HSFL are formed on top of a ˜150 nm thick graded superficial oxide layer without sharp interfaces, consisting of amorphous TiO2 and partially crystallized Ti2O3. The larger LSFL structures with periods close to the irradiation wavelength originate from the laser-interaction with metallic titanium. They are covered by a ˜200 nm thick amorphous oxide layer, which consists mainly of TiO2 (at the surface) and other titanium oxide species of lower oxidation states underneath.

Transcriptome Sequences Resolve Deep Relationships of the Grape Family

PubMed Central

Wen, Jun; Xiong, Zhiqiang; Nie, Ze-Long; Mao, Likai; Zhu, Yabing; Kan, Xian-Zhao; Ickert-Bond, Stefanie M.; Gerrath, Jean; Zimmer, Elizabeth A.; Fang, Xiao-Dong

2013-01-01

Previous phylogenetic studies of the grape family (Vitaceae) yielded poorly resolved deep relationships, thus impeding our understanding of the evolution of the family. Next-generation sequencing now offers access to protein coding sequences very easily, quickly and cost-effectively. To improve upon earlier work, we extracted 417 orthologous single-copy nuclear genes from the transcriptomes of 15 species of the Vitaceae, covering its phylogenetic diversity. The resulting transcriptome phylogeny provides robust support for the deep relationships, showing the phylogenetic utility of transcriptome data for plants over a time scale at least since the mid-Cretaceous. The pros and cons of transcriptome data for phylogenetic inference in plants are also evaluated. PMID:24069307

Electronic structure of the dilute magnetic semiconductor G a1 -xM nxP from hard x-ray photoelectron spectroscopy and angle-resolved photoemission

NASA Astrophysics Data System (ADS)

Keqi, A.; Gehlmann, M.; Conti, G.; Nemšák, S.; Rattanachata, A.; Minár, J.; Plucinski, L.; Rault, J. E.; Rueff, J. P.; Scarpulla, M.; Hategan, M.; Pálsson, G. K.; Conlon, C.; Eiteneer, D.; Saw, A. Y.; Gray, A. X.; Kobayashi, K.; Ueda, S.; Dubon, O. D.; Schneider, C. M.; Fadley, C. S.

2018-04-01

We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) G a0.98M n0.02P and compared it to that of an undoped GaP reference sample, using hard x-ray photoelectron spectroscopy (HXPS) and hard x-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimental data, as well as theoretical calculations, to understand the role of the Mn dopant in the emergence of ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the HARPES experimental data are compared to free-electron final-state model calculations and to more accurate one-step photoemission theory. The experimental results show differences between G a0.98M n0.02P and GaP in both angle-resolved and angle-integrated valence spectra. The G a0.98M n0.02P bands are broadened due to the presence of Mn impurities that disturb the long-range translational order of the host GaP crystal. Mn-induced changes of the electronic structure are observed over the entire valence band range, including the presence of a distinct impurity band close to the valence-band maximum of the DMS. These experimental results are in good agreement with the one-step photoemission calculations and a prior HARPES study of G a0.97M n0.03As and GaAs [Gray et al., Nat. Mater. 11, 957 (2012), 10.1038/nmat3450], demonstrating the strong similarity between these two materials. The Mn 2 p and 3 s core-level spectra also reveal an essentially identical state in doping both GaAs and GaP.

High-Throughput Block Optical DNA Sequence Identification.

PubMed

Sagar, Dodderi Manjunatha; Korshoj, Lee Erik; Hanson, Katrina Bethany; Chowdhury, Partha Pratim; Otoupal, Peter Britton; Chatterjee, Anushree; Nagpal, Prashant

2018-01-01

Optical techniques for molecular diagnostics or DNA sequencing generally rely on small molecule fluorescent labels, which utilize light with a wavelength of several hundred nanometers for detection. Developing a label-free optical DNA sequencing technique will require nanoscale focusing of light, a high-throughput and multiplexed identification method, and a data compression technique to rapidly identify sequences and analyze genomic heterogeneity for big datasets. Such a method should identify characteristic molecular vibrations using optical spectroscopy, especially in the "fingerprinting region" from ≈400-1400 cm -1 . Here, surface-enhanced Raman spectroscopy is used to demonstrate label-free identification of DNA nucleobases with multiplexed 3D plasmonic nanofocusing. While nanometer-scale mode volumes prevent identification of single nucleobases within a DNA sequence, the block optical technique can identify A, T, G, and C content in DNA k-mers. The content of each nucleotide in a DNA block can be a unique and high-throughput method for identifying sequences, genes, and other biomarkers as an alternative to single-letter sequencing. Additionally, coupling two complementary vibrational spectroscopy techniques (infrared and Raman) can improve block characterization. These results pave the way for developing a novel, high-throughput block optical sequencing method with lossy genomic data compression using k-mer identification from multiplexed optical data acquisition. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple spatially resolved reflection spectroscopy for in vivo determination of carotenoids in human skin and blood

NASA Astrophysics Data System (ADS)

Darvin, Maxim E.; Magnussen, Björn; Lademann, Juergen; Köcher, Wolfgang

2016-09-01

Non-invasive measurement of carotenoid antioxidants in human skin is one of the important tasks to investigate the skin physiology in vivo. Resonance Raman spectroscopy and reflection spectroscopy are the most frequently used non-invasive techniques in dermatology and skin physiology. In the present study, an improved method based on multiple spatially resolved reflection spectroscopy (MSRRS) was introduced. The results obtained were compared with those obtained using the ‘gold standard’ resonance Raman spectroscopy method and showed strong correlations for the total carotenoid concentration (R  =  0.83) as well as for lycopene (R  =  0.80). The measurement stability was confirmed to be better than 10% within the total temperature range from 5 °C to  +  30 °C and pressure contact between the skin and the MSRRS sensor from 800 Pa to 18 000 Pa. In addition, blood samples taken from the subjects were analyzed for carotenoid concentrations. The MSRRS sensor was calibrated on the blood carotenoid concentrations resulting in being able to predict with a correlation of R  =  0.79. On the basis of blood carotenoids it could be demonstrated that the MSRRS cutaneous measurements are not influenced by Fitzpatrick skin types I-VI. The MSRRS sensor is commercially available under the brand name biozoom.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

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

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole L.

We demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security applications.

Two-dimensional fluorescence spectroscopy of uranium isotopes in femtosecond laser ablation plumes

DOE PAGES

Phillips, Mark C.; Brumfield, Brian E.; LaHaye, Nicole; ...

2017-06-19

Here, we demonstrate measurement of uranium isotopes in femtosecond laser ablation plumes using two-dimensional fluorescence spectroscopy (2DFS). The high-resolution, tunable CW-laser spectroscopy technique clearly distinguishes atomic absorption from 235U and 238U in natural and highly enriched uranium metal samples. We present analysis of spectral resolution and analytical performance of 2DFS as a function of ambient pressure. Simultaneous measurement using time-resolved absorption spectroscopy provides information on temporal dynamics of the laser ablation plume and saturation behavior of fluorescence signals. The rapid, non-contact measurement is promising for in-field, standoff measurements of uranium enrichment for nuclear safety and security.

Time-resolved optical spectroscopic quantification of red blood cell damage caused by cardiovascular devices

NASA Astrophysics Data System (ADS)

Sakota, D.; Sakamoto, R.; Sobajima, H.; Yokoyama, N.; Yokoyama, Y.; Waguri, S.; Ohuchi, K.; Takatani, S.

2008-02-01

Cardiovascular devices such as heart-lung machine generate un-physiological level of shear stress to damage red blood cells, leading to hemolysis. The diagnostic techniques of cell damages, however, have not yet been established. In this study, the time-resolved optical spectroscopy was applied to quantify red blood cell (RBC) damages caused by the extracorporeal circulation system. Experimentally, the fresh porcine blood was subjected to varying degrees of shear stress in the rotary blood pump, followed with measurement of the time-resolved transmission characteristics using the pico-second pulses at 651 nm. The propagated optical energy through the blood specimen was detected using a streak camera. The data were analyzed in terms of the mean cell volume (MCV) and mean cell hemoglobin concentration (MCHC) measured separately versus the energy and propagation time of the light pulses. The results showed that as the circulation time increased, the MCV increased with decrease in MCHC. It was speculated that the older RBCs with smaller size and fragile membrane properties had been selectively destroyed by the shear stress. The time-resolved optical spectroscopy is a useful technique in quantifying the RBCs' damages by measuring the energy and propagation time of the ultra-short light pulses through the blood.

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.

Tuning the morphology, luminescence and magnetic properties of hexagonal-phase NaGdF4: Yb, Er nanocrystals via altering the addition sequence of the precursors

NASA Astrophysics Data System (ADS)

Zhao, Shuwen; Xia, Donglin; Zhao, Ruimin; Zhu, Hao; Zhu, Yiru; Xiong, Yuda; Wang, Youfa

2017-01-01

Hexagonal-phase NaGdF4: Yb, Er upconversion nanocrystals (UCNCs) with tunable morphology and properties were successfully prepared via a thermal decomposition method. The influences of the adding sequence of the precursors on the morphology, chemical composition, luminescence and magnetic properties were investigated by transmission electron microscopy (TEM), inductively coupled plasma-atomic emission spectrometry (ICP-AES), upconversion (UC) spectroscopy, and a vibrating sample magnetometer (VSM). It was found that the resulting nanocrystals, with different sizes ranging from 24 to 224 nm, are in the shape of spheres, hexagonal plates and flakes; moreover, the composition percentage of Yb3+-Er3+ and Gd3+ ions was found to vary in a regular pattern with the adding sequence. Furthermore, the intensity ratios of emission colors (f g/r, f g/p), and the magnetic mass susceptibility of hexagonal-phase NaGdF4: Yb, Er nanocrystals change along with the composition of the nanocrystals. A positive correlation between the susceptibility and f g/r of NaGdF4: Yb, Er was proposed. The decomposition processes of the precursors were investigated by a thermogravimetric (TG) analyzer. The result indicated that the decomposition of the resolved lanthanide trifluoroacetate is greatly different from lanthanide trifluoroacetate powder. It is of tremendous help to recognize the decomposition process of the precursors and to understand the related reaction mechanism.

An ultrafast angle-resolved photoemission apparatus for measuring complex materials

NASA Astrophysics Data System (ADS)

Smallwood, Christopher L.; Jozwiak, Christopher; Zhang, Wentao; Lanzara, Alessandra

2012-12-01

We present technical specifications for a high resolution time- and angle-resolved photoemission spectroscopy setup based on a hemispherical electron analyzer and cavity-dumped solid state Ti:sapphire laser used to generate pump and probe beams, respectively, at 1.48 and 5.93 eV. The pulse repetition rate can be tuned from 209 Hz to 54.3 MHz. Under typical operating settings the system has an overall energy resolution of 23 meV, an overall momentum resolution of 0.003 Å-1, and an overall time resolution of 310 fs. We illustrate the system capabilities with representative data on the cuprate superconductor Bi2Sr2CaCu2O8+δ. The descriptions and analyses presented here will inform new developments in ultrafast electron spectroscopy.

Spectra of cosmic X-ray sources

NASA Technical Reports Server (NTRS)

Holt, S. S.; Mccray, R.

1982-01-01

X-ray measurements provide the most direct probes of astrophysical environments with temperatures exceeding one million K. Progress in experimental research utilizing dispersive techniques (e.g., Bragg and grating spectroscopy) is considerably slower than that in areas utilizing photometric techniques, because of the relative inefficiency of the former for the weak X-ray signals from celestial sources. As a result, the term "spectroscopy" as applied to X-ray astronomy has traditionally satisfied a much less restrictive definition (in terms of resolving power) than it has in other wavebands. Until quite recently, resolving powers of order unity were perfectly respectable, and still provide (in most cases) the most useful spectroscopic data. In the broadest sense, X-ray photometric measurements are spectroscopic, insofar as they represent samples of the overall electromagnetic continua of celestial objects.

Review of the Theoretical Description of Time-Resolved Angle-Resolved Photoemission Spectroscopy in Electron-Phonon Mediated Superconductors

DOE PAGES

Kemper, A. F.; Sentef, M. A.; Moritz, B.; ...

2017-07-13

Here. we review recent work on the theory for pump/probe photoemission spectroscopy of electron-phonon mediated superconductors in both the normal and the superconducting states. We describe the formal developments that allow one to solve the Migdal-Eliashberg theory in nonequilibrium for an ultrashort laser pumping field, and explore the solutions which illustrate the relaxation as energy is transferred from electrons to phonons. We also focus on exact results emanating from sum rules and approximate numerical results which describe rules of thumb for relaxation processes. Additionally, in the superconducting state, we describe how Anderson-Higgs oscillations can be excited due to the nonlinearmore » coupling with the electric field and describe mechanisms where pumping the system enhances superconductivity.« less

Review of the Theoretical Description of Time-Resolved Angle-Resolved Photoemission Spectroscopy in Electron-Phonon Mediated Superconductors

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

Kemper, A. F.; Sentef, M. A.; Moritz, B.

Here. we review recent work on the theory for pump/probe photoemission spectroscopy of electron-phonon mediated superconductors in both the normal and the superconducting states. We describe the formal developments that allow one to solve the Migdal-Eliashberg theory in nonequilibrium for an ultrashort laser pumping field, and explore the solutions which illustrate the relaxation as energy is transferred from electrons to phonons. We also focus on exact results emanating from sum rules and approximate numerical results which describe rules of thumb for relaxation processes. Additionally, in the superconducting state, we describe how Anderson-Higgs oscillations can be excited due to the nonlinearmore » coupling with the electric field and describe mechanisms where pumping the system enhances superconductivity.« less

Analysis of molecular interaction using a pulse-induced ring-down compression ATR-DIRLD step-scan time resolved spectroscopy/2D-IR

NASA Astrophysics Data System (ADS)

Nishikawa, Yuji; Ito, Hiroto; Noda, Isao

2018-03-01

A rheo-optical method, based on pulsed compression ATR dynamic infrared linear dichroism (DIRLD) step scan time-resolved-FT-IR/2D-IR spectroscopy, is further improved. By inserting a tungsten carbide block with massive weight between a film sample and a piezo electric actuator, a ring-down response was successfully generated according to the inertial effect. The improved method is used to analyze molecular interactions in cellulose acetate propionate (CAP) films including tricresyl-phosphate (TCP), as compared with cellulose triacetate (CTA) films with the TCP case. The result suggests that the existence of molecular interaction among propionyl groups in the CAP, the TCP's Methyl, and phenyl rings, which is not observed in the CTA-TCP system.

The Fossil Record of Black Hole Seeds, with Spatially Resolved Spectroscopy

NASA Astrophysics Data System (ADS)

Trump, Jonathan R.; CANDELS, 3D-HST

2016-01-01

I will present the first robust measurement of black hole occupation over a wide range of host galaxy mass (8

Integrated experimental setup for angle resolved photoemission spectroscopy of transuranic materials

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

Graham, Kevin S.; Joyce, John J.; Durakiewicz, Tomasz

2013-09-15

We have developed the Angle Resolved Photoemission Spectroscopy (ARPES) system for transuranic materials. The ARPES transuranic system is an endstation upgrade to the Laser Plasma Light Source (LPLS) at Los Alamos National Laboratory. The LPLS is a tunable light source for photoemission with a photon energy range covering the vacuum ultraviolet (VUV) and soft x-ray regions (27–140 eV). The LPLS was designed and developed for transuranic materials. Transuranic photoemission is currently not permitted at the public synchrotrons worldwide in the VUV energy range due to sample encapsulation requirements. With the addition of the ARPES capability to the LPLS system theremore » is an excellent opportunity to explore new details centered on the electronic structure of actinide and transuranic materials.« less

Substrate interactions with suspended and supported monolayer MoS 2: Angle-resolved photoemission spectroscopy

DOE PAGES

Jin, Wencan; Yeh, Po -Chun; Zaki, Nader; ...

2015-03-17

We report the directly measured electronic structure of exfoliated monolayer molybdenum disulfide (MoS₂) using micrometer-scale angle-resolved photoemission spectroscopy. Measurements of both suspended and supported monolayer MoS₂ elucidate the effects of interaction with a substrate. Thus, a suggested relaxation of the in-plane lattice constant is found for both suspended and supported monolayer MoS₂ crystals. For suspended MoS₂, a careful investigation of the measured uppermost valence band gives an effective mass at Γ¯ and Κ¯ of 2.00m₀ and 0.43m₀, respectively. We also measure an increase in the band linewidth from the midpoint of Γ¯Κ¯ to the vicinity of Κ¯ and briefly discussmore » its possible origin.« less

Fluorescence spectroscopy and imaging for noninvasive diagnostics: applications to early cancer detection in the lung

NASA Astrophysics Data System (ADS)

Mycek, Mary-Ann; Urayama, Paul; Zhong, Wei; Sloboda, Roger D.; Dragnev, Konstantin H.; Dmitrovsky, Ethan

2003-10-01

Tissue fluorescence spectroscopy and imaging are being investigated as potential methods for non-invasive detection of pre-neoplastic change in the lung and other organ systems. A substantial contribution to tissue fluorescence is known to arise from endogenous cellular fluorophores. Using steady-state and time-resolved fluorescence spectroscopy and imaging, we characterized the endogenous fluorescence properties of immortalized and carcinogen-transformed human bronchial epithelial cells. Non-invasive sensing of endogenous molecular biomarkers associated with human bronchial pre-neoplasia will be discussed.

Time-resolved EPR spectroscopy in a Unix environment.

PubMed

Lacoff, N M; Franke, J E; Warden, J T

1990-02-01

A computer-aided time-resolved electron paramagnetic resonance (EPR) spectrometer implemented under version 2.9 BSD Unix was developed by interfacing a Varian E-9 EPR spectrometer and a Biomation 805 waveform recorder to a PDP-11/23A minicomputer having MINC A/D and D/A capabilities. Special problems with real-time data acquisition in a multiuser, multitasking Unix environment, addressing of computer main memory for the control of hardware devices, and limitation of computer main memory were resolved, and their solutions are presented. The time-resolved EPR system and the data acquisition and analysis programs, written entirely in C, are described. Furthermore, the benefits of utilizing the Unix operating system and the C language are discussed, and system performance is illustrated with time-resolved EPR spectra of the reaction center cation in photosystem 1 of green plant photosynthesis.

SPATIALLY RESOLVED SPECTROSCOPY AND CHEMICAL HISTORY OF STAR-FORMING GALAXIES IN THE HERCULES CLUSTER: THE EFFECTS OF THE ENVIRONMENT

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

Petropoulou, V.; Vilchez, J.; Iglesias-Paramo, J.

2011-06-10

Spatially resolved spectroscopy has been obtained for a sample of 27 star-forming (SF) galaxies selected from our deep H{alpha} survey of the Hercules cluster. We have applied spectral synthesis models to all emission-line spectra of this sample using the population synthesis code STARLIGHT and have obtained fundamental parameters of stellar components such as mean metallicity and age. The emission-line spectra were corrected for underlying stellar absorption using these spectral synthesis models. Line fluxes were measured and O/H and N/O gas chemical abundances were obtained using the latest empirical calibrations. We have derived the masses and total luminosities of the galaxiesmore » using available Sloan Digital Sky Survey broadband photometry. The effects of cluster environment on the chemical evolution of galaxies and on their mass-metallicity (MZ) and luminosity-metallicity (LZ) relations were studied by combining the derived gas metallicities, the mean stellar metallicities and ages, the masses and luminosities of the galaxies, and their existing H I data. Our Hercules SF galaxies are divided into three main subgroups: (1) chemically evolved spirals with truncated ionized-gas disks and nearly flat oxygen gradients, demonstrating the effect of ram-pressure stripping; (2) chemically evolved dwarfs/irregulars populating the highest local densities, possible products of tidal interactions in preprocessing events; and (3) less metallic dwarf galaxies that appear to be 'newcomers' to the cluster and are experiencing pressure-triggered star formation. Most Hercules SF galaxies follow well-defined MZ and LZ sequences (for both O/H and N/O), though the dwarf/irregular galaxies located at the densest regions appear to be outliers to these global relations, suggesting a physical reason for the dispersion in these fundamental relations. The Hercules cluster appears to be currently assembling via the merger of smaller substructures, providing an ideal laboratory where the local environment has been found to be a key parameter in understanding the chemical history of galaxies.« less

Direct Absorption Spectroscopy with Electro-Optic Frequency Combs

NASA Astrophysics Data System (ADS)

Fleisher, Adam J.; Long, David A.; Plusquellic, David F.; Hodges, Joseph T.

2017-06-01

The application of electro-optic frequency combs to direct absorption spectroscopy has increased research interest in high-agility, modulator-based comb generation. This talk will review common architectures for electro-optic frequency comb generators as well as describe common self-heterodyne and multi-heterodyne (i.e., dual-comb) detection approaches. In order to achieve a sufficient signal-to-noise ratio on the recorded interferogram while allowing for manageable data volumes, broadband electro-optic frequency combs require deep coherent averaging, preferably in real-time. Applications such as cavity-enhanced spectroscopy, precision atomic and molecular spectroscopy, as well as time-resolved spectroscopy will be introduced. D.A. Long et al., Opt. Lett. 39, 2688 (2014) A.J. Fleisher et al., Opt. Express 24, 10424 (2016)

Resolving biomolecular motion and interactions by R2 and R1ρ relaxation dispersion NMR.

PubMed

Walinda, Erik; Morimoto, Daichi; Sugase, Kenji

2018-04-26

Among the tools of structural biology, NMR spectroscopy is unique in that it not only derives a static three-dimensional structure, but also provides an atomic-level description of the local fluctuations and global dynamics around this static structure. A battery of NMR experiments is now available to probe the motions of proteins and nucleic acids over the whole biologically relevant timescale from picoseconds to hours. Here we focus on one of these methods, relaxation dispersion, which resolves dynamics on the micro- to millisecond timescale. Key biological processes that occur on this timescale include enzymatic catalysis, ligand binding, and local folding. In other words, relaxation-dispersion-resolved dynamics are often closely related to the function of the molecule and therefore highly interesting to the structural biochemist. With an astounding sensitivity of ∼0.5%, the method detects low-population excited states that are invisible to any other biophysical method. The kinetics of the exchange between the ground state and excited states are quantified in the form of the underlying exchange rate, while structural information about the invisible excited state is obtained in the form of its chemical shift. Lastly, the population of the excited state can be derived. This diversity in the information that can be obtained makes relaxation dispersion an excellent method to study the detailed mechanisms of conformational transitions and molecular interactions. Here we describe the two branches of relaxation dispersion, R 2 and R 1ρ , discussing their applicability, similarities, and differences, as well as recent developments in pulse sequence design and data processing. Copyright © 2018 Elsevier Inc. All rights reserved.

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

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.

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

Kimura, Shin-Ichi; Ito, Takahiro; Hosaka, Masahito

A novel variably polarized angle-resolved photoemission spectroscopy beamline in the vacuum-ultraviolet (VUV) region has been installed at the UVSOR-II 750 MeV synchrotron light source. The beamline is equipped with a 3 m long APPLE-II type undulator with horizontally/vertically linear and right/left circular polarizations, a 10 m Wadsworth type monochromator covering a photon energy range of 6-43 eV, and a 200 mm radius hemispherical photoelectron analyzer with an electron lens of a {+-}18 deg. acceptance angle. Due to the low emittance of the UVSOR-II storage ring, the light source is regarded as an entrance slit, and the undulator light is directlymore » led to a grating by two plane mirrors in the monochromator while maintaining a balance between high-energy resolution and high photon flux. The energy resolving power (h{nu}/{Delta}h{nu}) and photon flux of the monochromator are typically 1x10{sup 4} and 10{sup 12} photons/s, respectively, with a 100 {mu}m exit slit. The beamline is used for angle-resolved photoemission spectroscopy with an energy resolution of a few meV covering the UV-to-VUV energy range.« less

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

Scanning photoelectron microscope for nanoscale three-dimensional spatial-resolved electron spectroscopy for chemical analysis.

PubMed

Horiba, K; Nakamura, Y; Nagamura, N; Toyoda, S; Kumigashira, H; Oshima, M; Amemiya, K; Senba, Y; Ohashi, H

2011-11-01

In order to achieve nondestructive observation of the three-dimensional spatially resolved electronic structure of solids, we have developed a scanning photoelectron microscope system with the capability of depth profiling in electron spectroscopy for chemical analysis (ESCA). We call this system 3D nano-ESCA. For focusing the x-ray, a Fresnel zone plate with a diameter of 200 μm and an outermost zone width of 35 nm is used. In order to obtain the angular dependence of the photoelectron spectra for the depth-profile analysis without rotating the sample, we adopted a modified VG Scienta R3000 analyzer with an acceptance angle of 60° as a high-resolution angle-resolved electron spectrometer. The system has been installed at the University-of-Tokyo Materials Science Outstation beamline, BL07LSU, at SPring-8. From the results of the line-scan profiles of the poly-Si/high-k gate patterns, we achieved a total spatial resolution better than 70 nm. The capability of our system for pinpoint depth-profile analysis and high-resolution chemical state analysis is demonstrated. © 2011 American Institute of Physics

Fourier-domain angle-resolved low coherence interferometry for clinical detection of dysplasia

NASA Astrophysics Data System (ADS)

Terry, Neil G.; Zhu, Yizheng; Wax, Adam

2010-02-01

Improved methods for detecting dysplasia, or pre-cancerous growth are a current clinical need, particularly in the esophagus. The currently accepted method of random biopsy and histological analysis provides only a limited examination of tissue in question while being coupled with a long time delay for diagnosis. Light scattering spectroscopy, in contrast, allows for inspection of the cellular structure and organization of tissue in vivo. Fourier-domain angle-resolved low-coherence interferometry (a/LCI) is a novel light scattering spectroscopy technique that provides quantitative depth-resolved morphological measurements of the size and optical density of the examined cell nuclei, which are characteristic biomarkers of dysplasia. Previously, clinical viability of the a/LCI system was demonstrated through analysis of ex vivo human esophageal tissue in Barrett's esophagus patients using a portable a/LCI, as was the development of a clinical a/LCI system. Data indicating the feasibility of the technique in other organ sites (colon, oral cavity) will be presented. We present an adaptation of the a/LCI system that will be used to investigate the presence of dysplasia in vivo in Barrett's esophagus patients.

Doppler-free spectroscopy of the atomic rubidium fine structure using ultrafast spatial coherent control method

NASA Astrophysics Data System (ADS)

Kim, Minhyuk; Kim, Kyungtae; Lee, Woojun; Kim, Hyosub; Ahn, Jaewook

2017-04-01

Spectral programming solutions for the ultrafast spatial coherent control (USCC) method to resolve the fine-structure energy levels of atomic rubidium are reported. In USCC, a pair of counter-propagating ultrashort laser pulses are programmed to make a two-photon excitation pattern specific to particular transition pathways and atom species, thus allowing the involved transitions resolvable in space simultaneously. With a proper spectral phase and amplitude modulation, USCC has been also demonstrated for the systems with many intermediate energy levels. Pushing the limit of system complexity even further, we show here an experimental demonstration of the rubidium fine-structure excitation pattern resolvable by USCC. The spectral programming solution for the given USCC is achieved by combining a double-V-shape spectral phase function and a set of phase steps, where the former distinguishes the fine structure and the latter prevents resonant transitions. The experimental results will be presented along with its application in conjunction with the Doppler-free frequency-comb spectroscopy for rubidium hyperfine structure measurements. Samsung Science and Technology Foundation [SSTFBA1301-12].

Recovering star formation histories: Integrated-light analyses vs. stellar colour-magnitude diagrams

NASA Astrophysics Data System (ADS)

Ruiz-Lara, T.; Pérez, I.; Gallart, C.; Alloin, D.; Monelli, M.; Koleva, M.; Pompei, E.; Beasley, M.; Sánchez-Blázquez, P.; Florido, E.; Aparicio, A.; Fleurence, E.; Hardy, E.; Hidalgo, S.; Raimann, D.

2015-11-01

Context. Accurate star formation histories (SFHs) of galaxies are fundamental for understanding the build-up of their stellar content. However, the most accurate SFHs - those obtained from colour-magnitude diagrams (CMDs) of resolved stars reaching the oldest main-sequence turnoffs (oMSTO) - are presently limited to a few systems in the Local Group. It is therefore crucial to determine the reliability and range of applicability of SFHs derived from integrated light spectroscopy, as this affects our understanding of unresolved galaxies from low to high redshift. Aims: We evaluate the reliability of current full spectral fitting techniques in deriving SFHs from integrated light spectroscopy by comparing SFHs from integrated spectra to those obtained from deep CMDs of resolved stars. Methods: We have obtained a high signal-to-noise (S/N ~ 36.3 per Å) integrated spectrum of a field in the bar of the Large Magellanic Cloud (LMC) using EFOSC2 at the 3.6-metre telescope at La Silla Observatory. For this same field, resolved stellar data reaching the oMSTO are available. We have compared the star formation rate (SFR) as a function of time and the age-metallicity relation (AMR) obtained from the integrated spectrum using STECKMAP, and the CMD using the IAC-star/MinnIAC/IAC-pop set of routines. For the sake of completeness we also use and discuss other synthesis codes (STARLIGHT and ULySS) to derive the SFR and AMR from the integrated LMC spectrum. Results: We find very good agreement (average differences ~4.1%) between the SFR (t) and the AMR obtained using STECKMAP on the integrated light spectrum, and the CMD analysis. STECKMAP minimizes the impact of the age-metallicity degeneracy and has the advantage of preferring smooth solutions to recover complex SFHs by means of a penalized χ2. We find that the use of single stellar populations (SSPs) to recover the stellar content, using for instance STARLIGHT or ULySS codes, hampers the reconstruction of the SFR (t) and AMR shapes, yielding larger discrepancies with respect to the CMD results. These discrepancies can be reduced if spectral templates based on known and complex SFHs are employed rather than SSPs. Based on observations obtained at the 3.6 m ESO telescope on La Silla (Chile) and with the Hubble Space Telescope, operated by NASA.Appendices are available in electronic form at http://www.aanda.org

An Evolution-Based Approach to De Novo Protein Design and Case Study on Mycobacterium tuberculosis

PubMed Central

Brender, Jeffrey R.; Czajka, Jeff; Marsh, David; Gray, Felicia; Cierpicki, Tomasz; Zhang, Yang

2013-01-01

Computational protein design is a reverse procedure of protein folding and structure prediction, where constructing structures from evolutionarily related proteins has been demonstrated to be the most reliable method for protein 3-dimensional structure prediction. Following this spirit, we developed a novel method to design new protein sequences based on evolutionarily related protein families. For a given target structure, a set of proteins having similar fold are identified from the PDB library by structural alignments. A structural profile is then constructed from the protein templates and used to guide the conformational search of amino acid sequence space, where physicochemical packing is accommodated by single-sequence based solvation, torsion angle, and secondary structure predictions. The method was tested on a computational folding experiment based on a large set of 87 protein structures covering different fold classes, which showed that the evolution-based design significantly enhances the foldability and biological functionality of the designed sequences compared to the traditional physics-based force field methods. Without using homologous proteins, the designed sequences can be folded with an average root-mean-square-deviation of 2.1 Å to the target. As a case study, the method is extended to redesign all 243 structurally resolved proteins in the pathogenic bacteria Mycobacterium tuberculosis, which is the second leading cause of death from infectious disease. On a smaller scale, five sequences were randomly selected from the design pool and subjected to experimental validation. The results showed that all the designed proteins are soluble with distinct secondary structure and three have well ordered tertiary structure, as demonstrated by circular dichroism and NMR spectroscopy. Together, these results demonstrate a new avenue in computational protein design that uses knowledge of evolutionary conservation from protein structural families to engineer new protein molecules of improved fold stability and biological functionality. PMID:24204234

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.

Star Formation, Quenching And Chemical Enrichment In Local Galaxies From Integral Field Spectroscopy

NASA Astrophysics Data System (ADS)

Belfiore, Francesco

2017-08-01

Within the currently well-established ΛCDM cosmological framework we still lack a satisfactory understanding of the processes that trigger, regulate and eventually quench star formation on galactic scales. Gas flows (including inflows from the cosmic web and supernovae-driven outflows) are considered to act as self-regulatory mechanisms, generating the scaling relations between stellar mass, star formation rate and metallicity observed in the local Universe by large spectroscopic surveys. These surveys, however, have so far been limited by the availability of only one spectrum per galaxy. The aim of this dissertation is to expand the study of star formation and chemical abundances to resolved scales within galaxies by using integral field spectroscopy (IFS) data, mostly from the ongoing SDSS-IV MaNGA survey. In the first part of this thesis I demonstrate the ubiquitous presence of extended low ionisation emission-line regions (LIERs) in both late- and early-type galaxies. By studying the Hα equivalent width and diagnostic line ratios radial profiles, together with tracers of the underlying stellar population, I show that LIERs are not due to a central point source but to hot evolved (post-asymptotic giant branch) stars. In light of this, I suggest a new classification scheme for galaxies based on their line emission. By analysing the colours, star formation rates, morphologies, gas and stellar kinematics and environmental properties of galaxies with substantial LIER emission, I identify two distinct populations. Galaxies where the central regions are LIER-like, but show star formation at larger radii are late types in which star formation is slowly quenched inside-out. This transformation is associated with massive bulges. Galaxies dominated by LIER emission at all radii, on the other hand, are red-sequence galaxies harbouring a residual cold gas component, acquired mostly via external accretion. Quiescent galaxies devoid of line emission reside in denser environments, which suggests environmental effects as a likely cause for the existence of line-less galaxies on the red sequence. In the second part of this dissertation I focus on the study of resolved chemical abundances by characterising the gas phase oxygen and nitrogen abundance gradients in a large sample of star forming galaxies. I analyse the deviations from an exponential profile at small and large radii and the dependence of the gradients on stellar mass. These findings are interpreted in the context of the inside-out paradigm of disc growth. I then demonstrate the necessity of gas flows, which are responsible for the observed flattening of the metallicity and N/O ratio gradients at large radii. Finally, I present a case study based on one nearby galaxy (NGC 628), in which I combine IFS and cold gas data to derive a spatially resolved metal bud- get and estimate the mass of metals lost by the galaxy throughout its lifetime. By using simple physically-motivated models of chemical evolution I infer the average outflow loading factor to be of order unity.

Simultaneous quantification of glutamate and glutamine by J-modulated spectroscopy at 3 Tesla.

PubMed

Zhang, Yan; Shen, Jun

2016-09-01

The echo time (TE) averaged spectrum is the one-dimensional (1D) cross-section of the J-resolved spectrum at J = 0. In multiecho TE-averaged spectroscopy, glutamate (Glu) is differentiated from glutamine (Gln) at 3 Tesla (T). This method, however, almost entirely suppresses Gln resonance lines around 2.35 ppm, leaving Gln undetermined. This study presents a novel method for quantifying both Glu and Gln using multi-echo spectral data. A 1D cross-section of J-resolved spectroscopy at J = 7.5 Hz-referred to as J-modulated spectroscopy-was developed to simultaneously quantify Glu and Gln levels in the human brain. The transverse relaxation times (T2 s) of metabolites were first determined using conventional TE-averaged spectroscopy with different starting echo time and then incorporated into the spectral model for fitting J-modulated data. Simulation and in vivo data showed that the resonance signals of Glu and Gln were clearly separated around 2.35 ppm in J-modulated spectroscopy. In the anterior cingulate cortex, both Glu and Gln levels were found to be significantly higher in gray matter than in white matter in healthy subjects (P < 10(-10) and < 10(-5) , respectively). Gln resonances can be clearly separated from Glu and N-acetyl-aspartate around 2.35 ppm using J-modulated spectroscopy. This method can be used to quantitatively measure Glu and Gln simultaneously at 3T. Magn Reson Med 76:725-732, 2016. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.

Multi-channel lock-in amplifier assisted femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy with efficient rejection of superfluorescence background.

PubMed

Mao, Pengcheng; Wang, Zhuan; Dang, Wei; Weng, Yuxiang

2015-12-01

Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300-1/100 when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10(-5)M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 μJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process.

ISM Dust Grains and N-band Spectral Variability in the Spatially Resolved Subarcsecond Binary UY Aur

NASA Astrophysics Data System (ADS)

Skemer, Andrew J.; Close, Laird M.; Hinz, Philip M.; Hoffmann, William F.; Greene, Thomas P.; Males, Jared R.; Beck, Tracy L.

2010-03-01

The 10 μm silicate feature is an essential diagnostic of dust-grain growth and planet formation in young circumstellar disks. The Spitzer Space Telescope has revolutionized the study of this feature, but due to its small (85 cm) aperture, it cannot spatially resolve small/medium-separation binaries (lsim3''; <~ 420 AU) at the distances of the nearest star-forming regions (~140 pc). Large, 6-10 m ground-based telescopes with mid-infrared instruments can resolve these systems. In this paper, we spatially resolve the 0farcs88 binary, UY Aur, with MMTAO/BLINC-MIRAC4 mid-infrared spectroscopy. We then compare our spectra to Spitzer/IRS (unresolved) spectroscopy, and resolved images from IRTF/MIRAC2, Keck/OSCIR, and Gemini/Michelle, which were taken over the past decade. We find that UY Aur A has extremely pristine, interstellar medium (ISM)-like grains and that UY Aur B has an unusually shaped silicate feature, which is probably the result of blended emission and absorption from foreground extinction in its disk. We also find evidence for variability in both UY Aur A and UY Aur B by comparing synthetic photometry from our spectra with resolved imaging from previous epochs. The photometric variability of UY Aur A could be an indication that the silicate emission itself is variable, as was recently found in EX Lupi. Otherwise, the thermal continuum is variable, and either the ISM-like dust has never evolved, or it is being replenished, perhaps by UY Aur's circumbinary disk. The observations reported here were partially obtained at the Infrared Telescope Facility, which is operated by the University of Hawaii under Cooperative Agreement no. NCC 5-538 with the National Aeronautics and Space Administration, Science Mission Directorate, Planetary Astronomy Program.

Multi-channel lock-in amplifier assisted femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy with efficient rejection of superfluorescence background

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

Mao, Pengcheng; Wang, Zhuan; Dang, Wei

Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300–1/100more » when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10{sup −5}M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 μJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process.« less

Molecular phylogeny for marine turtles based on sequences of the ND4-leucine tRNA and control regions of mitochondrial DNA.

PubMed

Dutton, P H; Davis, S K; Guerra, T; Owens, D

1996-06-01

Marine turtles are divided into two families, the Dermochelyidae and the Cheloniidae. The majority of species are currently placed within the two tribes of the Cheloniidae, the Chelonini and the Carettini, but debate continues over generic and tribal affinities as well as species boundaries. We used nucleotide sequences (907 bp) from the ND4-LEU tRNA region and the control region (526 bp) of mitochondrial DNA to resolve areas of uncertainty in marine turtle (Chelonioidae) systematics. The ND4-LEU tRNA fragment was more conserved than the fragment from the control region, with sequence divergences ranging from 0.026 to 0.148 and 0.067 to 0.267, respectively. Parsimony analysis based only on the ND4-LEU tRNA data suggests that the hawksbill, Eretmochelys imbricata, lies within the tribe Carettni and is closely related to the genus Caretta, but could not resolve the position of the flatback, Natator depressus. A similar analysis based only on the control region sequence data suggested that N. depressus is affiliated with the Chelonini, but failed to resolve the position of E. imbricata and the loggerhead, Caretta caretta. In contrast to these results, the combination of both data sets with published cytochrome b data produced a phylogeny based on 1924 bp of sequence data which resolves the position of E. imbricata relative to Caretta and Lepidochelys and joins N. depressus as sister to the Carettini. Based on the molecular data, the Chelonini contains the Chelonia species, while the Carettini contains the remaining species of Cheloniidae. The control region sequence divergence between Pacific and Atlantic populations of the leatherback, Dermochelys coriacea, was relatively low (0.0081) when compared with the green turtle, Chelonia mydas (0.071-0.074). Atlantic and Pacific populations of Ch. mydas were found to be paraphyletic with respect to the black turtle, Ch. agassizi, suggesting that the current taxonomic designations within the Pacific Chelonia are questionable. This analysis shows the utility of combining sequence data for different regions of mtDNA that by themselves are insufficient to obtain robust phylogenies.

Time-resolved fluorescence imaging of slab gels for lifetime base-calling in DNA sequencing applications.

PubMed

Lassiter, S J; Stryjewski, W; Legendre, B L; Erdmann, R; Wahl, M; Wurm, J; Peterson, R; Middendorf, L; Soper, S A

2000-11-01

A compact time-resolved near-IR fluorescence imager was constructed to obtain lifetime and intensity images of DNA sequencing slab gels. The scanner consisted of a microscope body with f/1.2 relay optics onto which was mounted a pulsed diode laser (repetition rate 80 MHz, lasing wavelength 680 nm, average power 5 mW), filtering optics, and a large photoactive area (diameter 500 microns) single-photon avalanche diode that was actively quenched to provide a large dynamic operating range. The time-resolved data were processed using electronics configured in a conventional time-correlated single-photon-counting format with all of the counting hardware situated on a PC card resident on the computer bus. The microscope head produced a timing response of 450 ps (fwhm) in a scanning mode, allowing the measurement of subnano-second lifetimes. The time-resolved microscope head was placed in an automated DNA sequencer and translated across a 21-cm-wide gel plate in approximately 6 s (scan rate 3.5 cm/s) with an accumulation time per pixel of 10 ms. The sampling frequency was 0.17 Hz (duty cycle 0.0017), sufficient to prevent signal aliasing during the electrophoresis separation. Software (written in Visual Basic) allowed acquisition of both the intensity image and lifetime analysis of DNA bands migrating through the gel in real time. Using a dual-labeling (IRD700 and Cy5.5 labeling dyes)/two-lane sequencing strategy, we successfully read 670 bases of a control M13mp18 ssDNA template using lifetime identification. Comparison of the reconstructed sequence with the known sequence of the phage indicated the number of miscalls was only 2, producing an error rate of approximately 0.3% (identification accuracy 99.7%). The lifetimes were calculated using maximum likelihood estimators and allowed on-line determinations with high precision, even when short integration times were used to construct the decay profiles. Comparison of the lifetime base calling to a single-dye/four-lane sequencing strategy indicated similar results in terms of miscalls, but reduced insertion and deletion errors using lifetime identification methods, improving the overall read accuracy.

Phylogenetic relationships among the major lineages of the birds-of-paradise (Paradisaeidae) using mitochondrial DNA gene sequences.

PubMed

Nunn, G B; Cracraft, J

1996-06-01

Complete mitochondrial cytochrome b gene sequences were determined from 12 species of the Australo-Papuan birds-of-paradise (Paradisaeidae) representing 9 genera. Phylogenetic analysis of these and 5 previously published sequences reveals a radiation of the main paradisaeinine lineages that took place over a relatively short evolutionary time scale. The core paradisaeinines are resolved as the monophyletic sister-group to the crow-like manucodines. The genus Parotia is basal to other paradisaeinines and is not closely related to the morphologically similar genera Ptiloris and Lophorina. Three major clades within the paradisaeinine ingroup include: (1) Cicinnurus and Diphyllodes, (2) Ptiloris and Lophorina, and (3) the genus Paradisaea. The monotypic genus Seleucidis is apparently closely related to clades (1) and (2). Cytochrome b sequences did not provide evidence for the monophyly of the sicklebill genera Epimachus and Drepanornis. The paradisaeid tree is characterized by short internodal distances. Thus, some clades cannot be strongly resolved by cytochrome b sequences alone.

Workshop on MQW Mixing and its Application to Optoelectronic Devices

DTIC Science & Technology

1990-09-01

21st SEPTEMBER 1990 L Approvsd to; Puiic~ zeleaaeg serc .., 90 ! ;>:.01. . 𔃻 i OR 3ANISING COMMITTEE: . . . . B L Weiss (Chairman) University of...temperature photoluminescence ( PL ) and PL excitation (PLE) spectroscopies were used to monitor exciton energies before and after processing. After RTA...generated near the surface. Spatially resolved PL spectroscopy verified that the lateral diffusion of surface vacancies was less than that of the

Correlation Between Early-Stage Expansion and Spectral Emission of a Nanosecond Laser-Induced Plasma from Organic Material

DTIC Science & Technology

2008-01-01

atmosphere like ours (mix of nitrogen and oxygen) implies a more complex plasma chemistry . For example, one of these difficulties is the interpretation of...due to LSDW have also been observed. KEYWORDS Polymer ablation, Shadowgraphy, Time-resolved laser induced breakdown spectroscopy, Plasma ... chemistry , Organic materials analysis, Expansion of laser-induced plasma 1 INTRODUCTION Laser-Induced Breakdown Spectroscopy (LIBS) traditionally

Design of a Hole Trapping Ligand

DOE PAGES

La Croix, Andrew D.; O’Hara, Andrew; Reid, Kemar R.; ...

2017-01-18

A new ligand that covalently attaches to the surface of colloidal CdSe/ CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate$-$bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic$-$organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer frommore » the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV$-$vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Lastly, theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence« less

Monolithic echo-less photoconductive switches as a high-resolution detector for terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Maussang, K.; Palomo, J.; Manceau, J.-M.; Colombelli, R.; Sagnes, I.; Li, L. H.; Linfield, E. H.; Davies, A. G.; Mangeney, J.; Tignon, J.; Dhillon, S. S.

2017-04-01

Interdigitated photoconductive (iPC) switches are powerful and convenient devices for time-resolved spectroscopy, with the ability to operate both as sources and detectors of terahertz (THz) frequency pulses. However, reflection of the emitted or detected radiation within the device substrate itself can lead to echoes that inherently limit the spectroscopic resolution achievable for their use in time-domain spectroscopy (TDS) systems. In this work, we demonstrate a design of low-temperature-grown-GaAs (LT-GaAs) iPC switches for THz pulse detection that suppresses such unwanted echoes. This is realized through the growth of a buried multilayer LT-GaAs structure that retains its ultrafast properties, which, after wafer bonding to a metal-coated host substrate, results in an iPC switch with a metal plane buried at a subwavelength depth below the LT-GaAs surface. Using this device as a detector, and coupling it to an echo-less iPC source, enables echo-free THz-TDS and high-resolution spectroscopy, with a resolution limited only by the temporal length of the measurement governed by the mechanical delay line used. As a proof-of-principle, the 212-221 and the 101-212 rotational lines of water vapor have been spectrally resolved, demonstrating a spectral resolution below 10 GHz.

Chemical transitions of Areca semen during the thermal processing revealed by temperature-resolved ATR-FTIR spectroscopy and two-dimensional correlation analysis

NASA Astrophysics Data System (ADS)

Wang, Zhibiao; Wang, Xu; Pei, Wenxuan; Li, Sen; Sun, Suqin; Zhou, Qun; Chen, Jianbo

2018-03-01

Areca semen is a common herb used in traditional Chinese medicine, but alkaloids in this herb are categorized as Group I carcinogens by IARC. It has been proven that the stir-baking process can reduce alkaloids in Areca semen while keep the activity for promoting digestion. However, the changes of compositions other than alkaloids during the thermal processing are unclear. Understanding the thermal chemical transitions of Areca semen is necessary to explore the processing mechanisms and optimize the procedures. In this research, FTIR spectroscopy with a temperature-controlled ATR accessory is employed to study the heating process of Areca semen. Principal component analysis and two-dimensional correlation spectroscopy are used to interpret the spectra to reveal the chemical transitions of Areca semen in different temperature ranges. The loss of a few volatile compounds in the testa and sperm happens below 105 °C, while some esters in the sperm decreases above 105 °C. As the heating temperature is close to 210 °C, Areca semen begins to be scorched and the decomposition of many compounds can be observed. This research shows the potential of the temperature-resolved ATR-FTIR spectroscopy in exploring the chemical transitions of the thermal processing of herbal materials.

Design of a Hole Trapping Ligand

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

La Croix, Andrew D.; O’Hara, Andrew; Reid, Kemar R.

A new ligand that covalently attaches to the surface of colloidal CdSe/ CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate$-$bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic$-$organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer frommore » the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV$-$vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Lastly, theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence« less

The use of near-infrared spectroscopy in understanding skeletal muscle physiology: recent developments.

PubMed

Ferrari, Marco; Muthalib, Makii; Quaresima, Valentina

2011-11-28

This article provides a snapshot of muscle near-infrared spectroscopy (NIRS) at the end of 2010 summarizing the recent literature, offering the present status and perspectives of the NIRS instrumentation and methods, describing the main NIRS studies on skeletal muscle physiology, posing open questions and outlining future directions. So far, different NIRS techniques (e.g. continuous-wave (CW) and spatially, time- and frequency-resolved spectroscopy) have been used for measuring muscle oxygenation during exercise. In the last four years, approximately 160 muscle NIRS articles have been published on different physiological aspects (primarily muscle oxygenation and haemodynamics) of several upper- and lower-limb muscle groups investigated by using mainly two-channel CW and spatially resolved spectroscopy commercial instruments. Unfortunately, in only 15 of these studies were the advantages of using multi-channel instruments exploited. There are still several open questions in the application of NIRS in muscle studies: (i) whether NIRS can be used in subjects with a large fat layer; (ii) the contribution of myoglobin desaturation to the NIRS signal during exercise; (iii) the effect of scattering changes during exercise; and (iv) the effect of changes in skin perfusion, particularly during prolonged exercise. Recommendations for instrumentation advancements and future muscle NIRS studies are provided.

Conformational Heterogeneity in a Fully Complementary DNA Three-Way Junction with a GC-Rich Branchpoint.

PubMed

Toulmin, Anita; Baltierra-Jasso, Laura E; Morten, Michael J; Sabir, Tara; McGlynn, Peter; Schröder, Gunnar F; Smith, Brian O; Magennis, Steven W

2017-09-19

DNA three-way junctions (3WJs) are branched structures that serve as important biological intermediates and as components in DNA nanostructures. We recently derived the global structure of a fully complementary 3WJ and found that it contained unpaired bases at the branchpoint, which is consistent with previous observations of branch flexibility and branchpoint reactivity. By combining high-resolution single-molecule Förster resonance energy transfer, molecular modeling, time-resolved ensemble fluorescence spectroscopy, and the first 19 F nuclear magnetic resonance observations of fully complementary 3WJs, we now show that the 3WJ structure can adopt multiple distinct conformations depending upon the sequence at the branchpoint. A 3WJ with a GC-rich branchpoint adopts an open conformation with unpaired bases at the branch and at least one additional conformation with an increased number of base interactions at the branchpoint. This structural diversity has implications for branch interactions and processing in vivo and for technological applications.

The properties of 4'-N,N-dimethylaminoflavonol in the ground and excited states

NASA Astrophysics Data System (ADS)

Moroz, V. V.; Chalyi, A. G.; Roshal, A. D.

2008-09-01

The mechanism of protonation of 4-N,N-dimethylaminoflavonol and the structure of its protolytic forms in the ground and excited states were studied by electron absorption and fluorescence (steady-state and time-resolved) spectroscopy and with the use of the RM1 quantum-chemical method. A comparison of equilibrium constants and the theoretical enthalpies of formation showed that excitation should be accompanied by the inversion of the basicity of the electron acceptor groups of this compound and, as a consequence, changes in the structure of its monocationic form. An analysis of the spectral parameters of the protolytic 4-N,N-dimethylaminoflavonol forms, however, showed that their structure and the sequence of protonation in the excited state were the same as in the ground state. Changes in the structure of the monocation in the excited state were not observed because of the fast radiationless deactivation of this form and the occurrence of excited state intramolecular proton transfer in aprotic solvents.

Astronomical infrared spectroscopy with a Connes-type interferometer. III Alpha Orionis, 2600 to 3450 per cm.

NASA Technical Reports Server (NTRS)

Beer, R.; Hutchison, R. B.; Norton, R. H.; Lambert, D. L.

1972-01-01

Analysis of recent spectra of alpha Ori in the 3 to 4 micron region at a resolving power of about 10,000, showing clear evidence of the delta v = 1 sequence of the rotation-vibration bands of OH. A detailed investigation of the rotational and vibrational populations suggests that the OH is close to being in LTE at an apparent temperature of 4100 plus or minus 200 K. An OH abundance of 1.2 x 10 to the 20th molecules per cu cm and upper limits for H2O and H super 35 Cl of 8 x 10 to the 18th and 8 x 10 to the 17th molecules per cu cm, respectively, are deduced. It is also deduced that the rms turbulence velocity in the region of OH line formation is 11.5 plus or minus 2 km/sec. The implications of these data on abundances in M supergiant atmospheres are discussed.

Detection of boron nitride radicals by emission spectroscopy in a laser-induced plasma

NASA Astrophysics Data System (ADS)

Dutouquet, C.; Acquaviva, S.; Hermann, J.

2001-06-01

Several vibrational bands of boron nitride radicals have been observed in a plasma produced by pulsed-laser ablation of a boron nitride target in low-pressure nitrogen or argon atmospheres. Using time- and space-resolved emission spectroscopic measurements with a high dynamic range, the most abundant isotopic species B 11N have been detected. The emission bands in the spectral range from 340 to 380 nm belong to the Δυ =-1, 0, +1 sequences of the triplet system (transition A 3Π-X 3Π). For positive identification, the molecular emission bands have been compared with synthetic spectra obtained by computer simulations. Furthermore, B 10N emission bands have been reproduced by computer simulation using molecular constants which have been deduced from the B 11N constants. Nevertheless, the presence of the lower abundant isotopic radical B 10N was not proved due the noise level which masked the low emission intensity of the B 10N band heads.

Noninvasive observation of skeletal muscle contraction using near-infrared time-resolved reflectance and diffusing-wave spectroscopy

NASA Astrophysics Data System (ADS)

Belau, Markus; Ninck, Markus; Hering, Gernot; Spinelli, Lorenzo; Contini, Davide; Torricelli, Alessandro; Gisler, Thomas

2010-09-01

We introduce a method for noninvasively measuring muscle contraction in vivo, based on near-infrared diffusing-wave spectroscopy (DWS). The method exploits the information about time-dependent shear motions within the contracting muscle that are contained in the temporal autocorrelation function g(1)(τ,t) of the multiply scattered light field measured as a function of lag time, τ, and time after stimulus, t. The analysis of g(1)(τ,t) measured on the human M. biceps brachii during repetitive electrical stimulation, using optical properties measured with time-resolved reflectance spectroscopy, shows that the tissue dynamics giving rise to the speckle fluctuations can be described by a combination of diffusion and shearing. The evolution of the tissue Cauchy strain e(t) shows a strong correlation with the force, indicating that a significant part of the shear observed with DWS is due to muscle contraction. The evolution of the DWS decay time shows quantitative differences between the M. biceps brachii and the M. gastrocnemius, suggesting that DWS allows to discriminate contraction of fast- and slow-twitch muscle fibers.

Attosecond light sources in the water window

NASA Astrophysics Data System (ADS)

Ren, Xiaoming; Li, Jie; Yin, Yanchun; Zhao, Kun; Chew, Andrew; Wang, Yang; Hu, Shuyuan; Cheng, Yan; Cunningham, Eric; Wu, Yi; Chini, Michael; Chang, Zenghu

2018-02-01

As a compact and burgeoning alternative to synchrotron radiation and free-electron lasers, high harmonic generation (HHG) has proven its superiority in static and time-resolved extreme ultraviolet spectroscopy for the past two decades and has recently gained many interests and successes in generating soft x-ray emissions covering the biologically important water window spectral region. Unlike synchrotron and free-electron sources, which suffer from relatively long pulse width or large time jitter, soft x-ray sources from HHG could offer attosecond time resolution and be synchronized with their driving field to investigate time-resolved near edge absorption spectroscopy, which could reveal rich structural and dynamical information of the interrogated samples. In this paper, we review recent progresses on generating and characterizing attosecond light sources in the water window region. We show our development of an energetic, two-cycle, carrier-envelope phase stable laser source at 1.7 μm and our achievement in producing a 53 as soft x-ray pulse covering the carbon K-edge in the water window. Such source paves the ways for the next generation x-ray spectroscopy with unprecedented temporal resolution.

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.

Molecular recognition in the gas phase: benzocaine-phenol as a model of anaesthetic-receptor interaction.

PubMed

Aguado, Edurne; León, Iker; Cocinero, Emilio J; Lesarri, Alberto; Fernández, José A; Castaño, Fernando

2009-12-28

The benzocaine-phenol complex is proposed as a model system of the interaction between the local anaesthetic benzocaine and the tyrosine residue. The complex has been generated by supersonic expansion of benzocaine and phenol in helium and probed by 1- and 2-color mass-resolved laser spectroscopies. The electronic excitation spectrum of the 1 : 1 complex spans some approximately 700 cm(-1) and includes well resolved bands from at least two isomers, as demonstrated using UV-UV hole burning spectroscopy. The combination of ion dip infrared spectroscopy (IDIRS) and ab initio calculations shows that both isomers are stabilized by an OH...N hydrogen bond between the phenol hydroxyl group and the benzocaine amino moiety, differing only in the conformation adopted by the benzocaine monomer (trans and gauche). The application of the fragmentation threshold method to benzocaine-phenol suggests the existence of chemical reactions in the electronic excited state of the complex and/or in the ion. Such hypothesis is also supported by the calculated potential energy curves along the hydrogen bond coordinate.

Spectroscopic Studies of Carotenoid-to-Bacteriochlorophyll Energy Transfer in LHRC Photosynthetic Complex from Roseiflexus castenholzii

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

Niedzwiedzki, Dariusz; Collins, Aaron M.; LaFountain, Amy M.

Carotenoids present in the photosynthetic light-harvesting reaction center (LHRC) complex from chlorosome lacking filamentous anoxygenic phototroph, Roseiflexus castenholzii were purified and characterized for their photochemical properties. The LHRC from anaerobically grown cells contains five different carotenoids, methoxy-keto-myxocoxanthin, γ-carotene, and its three derivatives, whereas the LHRC from aerobically grown cells contains only three carotenoid pigments with methoxy-keto-myxocoxanthin being the dominant one. The spectroscopic properties and dynamics of excited singlet states of the carotenoids were studied by steady-state absorption, fluorescence and ultrafast time-resolved optical spectroscopy in organic solvent and in the intact LHRC complex. Time-resolved transient absorption spectroscopy performed in the near-infraredmore » (NIR) on purified carotenoids combined with steady-state absorption spectroscopy led to the precise determination of values of the energies of the S 1(2 1A g -) excited state. Global and single wavelength fitting of the ultrafast spectral and temporal data sets of the carotenoids in solvents and in the LHRC revealed the pathways of de-excitation of the carotenoid excited states.« less

Ethylene polymerization on a SiH4-modified Phillips catalyst: detection of in situ produced α-olefins by operando FT-IR spectroscopy.

PubMed

Barzan, Caterina; Groppo, Elena; Quadrelli, Elsje Alessandra; Monteil, Vincent; Bordiga, Silvia

2012-02-21

Ethylene polymerization on a model Cr(II)/SiO(2) Phillips catalyst modified with gas phase SiH(4) leads to a waxy product containing a bimodal MW distribution of α-olefins (M(w) < 3000 g mol(-1)) and a highly branched polyethylene, LLDPE (M(w) ≈ 10(5) g mol(-1), T(m) = 123 °C), contrary to the unmodified catalyst which gives a linear and more dense PE, HDPE (M(w) = 86,000 g mol(-1) (PDI = 7), T(m) = 134 °C). Pressure and temperature resolved FT-IR spectroscopy under operando conditions (T = 130-230 K) allows us to detect α-olefins, and in particular 1-hexene and 1-butene (characteristic IR absorption bands at 3581-3574, 1638 and 1598 cm(-1)) as intermediate species before their incorporation in the polymer chains. The polymerization rate is estimated, using time resolved FT-IR spectroscopy, to be 7 times higher on the SiH(4)-modified Phillips catalyst with respect to the unmodified one.

Beyond Linear Sequence Comparisons: The use of genome-levelcharacters for phylogenetic reconstruction

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

Boore, Jeffrey L.

2004-11-27

Although the phylogenetic relationships of many organisms have been convincingly resolved by the comparisons of nucleotide or amino acid sequences, others have remained equivocal despite great effort. Now that large-scale genome sequencing projects are sampling many lineages, it is becoming feasible to compare large data sets of genome-level features and to develop this as a tool for phylogenetic reconstruction that has advantages over conventional sequence comparisons. Although it is unlikely that these will address a large number of evolutionary branch points across the broad tree of life due to the infeasibility of such sampling, they have great potential for convincinglymore » resolving many critical, contested relationships for which no other data seems promising. However, it is important that we recognize potential pitfalls, establish reasonable standards for acceptance, and employ rigorous methodology to guard against a return to earlier days of scenario-driven evolutionary reconstructions.« less

Denoising time-resolved microscopy image sequences with singular value thresholding.

PubMed

Furnival, Tom; Leary, Rowan K; Midgley, Paul A

2017-07-01

Time-resolved imaging in microscopy is important for the direct observation of a range of dynamic processes in both the physical and life sciences. However, the image sequences are often corrupted by noise, either as a result of high frame rates or a need to limit the radiation dose received by the sample. Here we exploit both spatial and temporal correlations using low-rank matrix recovery methods to denoise microscopy image sequences. We also make use of an unbiased risk estimator to address the issue of how much thresholding to apply in a robust and automated manner. The performance of the technique is demonstrated using simulated image sequences, as well as experimental scanning transmission electron microscopy data, where surface adatom motion and nanoparticle structural dynamics are recovered at rates of up to 32 frames per second. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Kinetic characteristics of the luminescence decay for industrial yttrium-gadolinium-aluminium garnet based phosphors

NASA Astrophysics Data System (ADS)

Lisitsyn, V. M.; Stepanov, S. A.; Valiev, D. T.; Vishnyakova, E. A.; Abdullin, H. A.; Marhabaeva, A. A.; Tulegenova, A. T.

2016-02-01

The spectral and decay kinetic characteristics of pulse cathodoluminescence and photoluminescence of phosphors based on yttrium-gadolinium-aluminum garnet were investigated using pulsed optical time resolved spectroscopy.

The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. II. Homo-arrays of LH2 complexes reconstituted into phospholipid model membranes.

PubMed

Pflock, Tobias J; Oellerich, Silke; Krapf, Lisa; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

2011-07-21

We performed time-resolved spectroscopy on homoarrays of LH2 complexes from the photosynthetic purple bacterium Rhodopseudomonas acidophila. Variations of the fluorescence transients were monitored as a function of the excitation fluence and the repetition rate of the excitation. These parameters are directly related to the excitation density within the array and to the number of LH2 complexes that still carry a triplet state prior to the next excitation. Comparison of the experimental observations with results from dynamic Monte Carlo simulations for a model cluster of LH2 complexes yields qualitative agreement without the need for any free parameter and reveals the mutual relationship between energy transfer and annihilation processes.

Label-Free Toxin Detection by Means of Time-Resolved Electrochemical Impedance Spectroscopy

PubMed Central

Chai, Changhoon; Takhistov, Paul

2010-01-01

The real-time detection of trace concentrations of biological toxins requires significant improvement of the detection methods from those reported in the literature. To develop a highly sensitive and selective detection device it is necessary to determine the optimal measuring conditions for the electrochemical sensor in three domains: time, frequency and polarization potential. In this work we utilized a time-resolved electrochemical impedance spectroscopy for the detection of trace concentrations of Staphylococcus enterotoxin B (SEB). An anti-SEB antibody has been attached to the nano-porous aluminum surface using 3-aminopropyltriethoxysilane/glutaraldehyde coupling system. This immobilization method allows fabrication of a highly reproducible and stable sensing device. Using developed immobilization procedure and optimized detection regime, it is possible to determine the presence of SEB at the levels as low as 10 pg/mL in 15 minutes. PMID:22315560

High energy dispersion relations for the high temperature Bi2Sr2CaCu2O8 superconductor from laser-based angle-resolved photoemission spectroscopy.

PubMed

Zhang, Wentao; Liu, Guodong; Meng, Jianqiao; Zhao, Lin; Liu, Haiyun; Dong, Xiaoli; Lu, Wei; Wen, J S; Xu, Z J; Gu, G D; Sasagawa, T; Wang, Guiling; Zhu, Yong; Zhang, Hongbo; Zhou, Yong; Wang, Xiaoyang; Zhao, Zhongxian; Chen, Chuangtian; Xu, Zuyan; Zhou, X J

2008-07-04

Laser-based angle-resolved photoemission spectroscopy measurements have been carried out on the high energy electron dynamics in Bi2Sr2CaCu2O8 high temperature superconductor. Our superhigh resolution data, momentum-dependent measurements, and complete analysis provide important information to judge the nature of the high energy dispersion and kink. Our results rule out the possibility that the high energy dispersion from the momentum distribution curve (MDC) may represent the true bare band as believed in previous studies. We also rule out the possibility that the high energy kink represents electron coupling with some high energy modes as proposed before. Through detailed MDC and energy distribution curve analyses, we propose that the high energy MDC dispersion may not represent intrinsic band structure.

Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

NASA Astrophysics Data System (ADS)

Ponseca, C. S., Jr.; Sundström, V.

2016-03-01

Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

Rotationally resolved fluorescence spectroscopy of molecular iodine

NASA Astrophysics Data System (ADS)

Lemon, Christopher; Canagaratna, Sebastian; Gray, Jeffrey

2008-03-01

Vibration-electronic spectroscopy of I2 vapor is a common, important experiment in physical chemistry lab courses. We use narrow bandwidth diode-pumped solid state (DPSS) lasers to excite specific rotational levels; these lasers are surprisingly stable and are now available at low cost. We also use efficient miniature fiber-optic spectrometers to resolve rotational fluorescence patterns in a vibrational progression. The resolution enables thorough and accurate analysis of spectroscopic constants for the ground electronic state. The high signal-to-noise ratio, which is easily achieved, also enables students to precisely measure fluorescence band intensities, providing further insight into vibrational wavefunctions and the molecular potential function. We will provide a detailed list of parts for the apparatus as well as modeling algorithms with statistical evaluation to facilitate widespread adoption of these experimental improvements by instructors of intermediate and advanced lab courses.

Time Resolved Spectroscopy, High Sensitivity Power Spectrum & a Search for the X-Ray QPO in NGC 5548

NASA Astrophysics Data System (ADS)

Yaqoob, Tahir

1999-09-01

Controversy surrounds the EXOSAT discovery of a QPO (period ~500 s) in NGC 5548 due to the data being plagued by high background and instrumental systematics. If the NGC 5548 QPO is real, the implications for the physics of the X-ray emission mechanism and inner-most disk/black-hole system are enormous. AXAF provides the first opportunity to settle the issue, capable of yielding power spectra with unprecedented sensitivity, pushing the limit on finding new features. Using HETG/ACIS we will also perform time-resolved spectroscopy of the ionized absorption features and Fe-K emission line, search for energy-dependent time lags in the continuum, between the continuum and spectral features, and between the spectral features. These data will provide powerful constraints on models of AGN.

Determining the nature of excitonic dephasing in high-quality GaN/AlGaN quantum wells through time-resolved and spectrally resolved four-wave mixing spectroscopy

NASA Astrophysics Data System (ADS)

Gallart, M.; Ziegler, M.; Crégut, O.; Feltin, E.; Carlin, J.-F.; Butté, R.; Grandjean, N.; Hönerlage, B.; Gilliot, P.

2017-07-01

Applying four-wave mixing spectroscopy to a high-quality GaN/AlGaN single quantum well, we report on the experimental determination of excitonic dephasing times at different temperatures and exciton densities in III-nitride heterostructures. By comparing the evolution with the temperature of the dephasing and the spin-relaxation rate, we conclude that both processes are related to the rate of excitonic collisions. When spin relaxation occurs in the motional-narrowing regime, it remains constant over a large temperature range as the spin-precession frequency increases linearly with temperature, hence compensating for the observed decrease in the dephasing time. From those measurements, a value of the electron-hole exchange interaction strength of 0.45 meV at T =10 K is inferred.

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

Development of in situ time-resolved Raman spectroscopy facility for dynamic shock loading in materials

NASA Astrophysics Data System (ADS)

Chaurasia, S.; Rastogi, V.; Rao, U.; Sijoy, C. D.; Mishra, V.; Deo, M. N.

2017-11-01

The transient state of excitation and relaxation processes in materials under shock compression can be investigated by coupling the laser driven shock facility with Raman spectroscopy. For this purpose, a time resolved Raman spectroscopy setup has been developed to monitor the physical and the chemical changes such as phase transitions, chemical reactions, molecular kinetics etc., under shock compression with nanosecond time resolution. This system consist of mainly three parts, a 2 J/8 ns Nd:YAG laser system used for generation of pump and probe beams, a Raman spectrometer with temporal and spectral resolution of 1.2 ns and 3 cm-1 respectively and a target holder in confinement geometry assembly. Detailed simulation for the optimization of confinement geometry targets is performed. Time resolved measurement of polytetrafluoroethylene (PTFE) targets at focused laser intensity of 2.2 GW/cm2 has been done. The corresponding pressure in the Aluminum and PTFE are 3.6 and 1.7 GPa respectively. At 1.7 GPa in PTFE, a red shift of 5 cm-1 is observed for the CF2 twisting mode (291 cm-1). Shock velocity in PTFE is calculated by measuring rate of change of ratios of the intensity of Raman lines scattered from shocked volume to total volume of sample in the laser focal spot along the laser axis. The calculated shock velocity in PTFE is found to be 1.64 ± 0.16 km/s at shock pressure of 1.7 GPa, for present experimental conditions.

SPATIALLY RESOLVED STAR FORMATION MAIN SEQUENCE OF GALAXIES IN THE CALIFA SURVEY

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

Cano-Díaz, M.; Sánchez, S. F.; Zibetti, S.

2016-04-20

The “main sequence of galaxies”–defined in terms of the total star formation rate ψ versus the total stellar mass M {sub *}—is a well-studied tight relation that has been observed at several wavelengths and at different redshifts. All earlier studies have derived this relation from integrated properties of galaxies. We recover the same relation from an analysis of spatially resolved properties, with integral field spectroscopic (IFS) observations of 306 galaxies from the CALIFA survey. We consider the SFR surface density in units of log( M {sub ⊙} yr{sup −1} Kpc{sup −2}) and the stellar mass surface density in units ofmore » log( M {sub ⊙} Kpc{sup −2}) in individual spaxels that probe spatial scales of 0.5–1.5 Kpc. This local relation exhibits a high degree of correlation with small scatter ( σ = 0.23 dex), irrespective of the dominant ionization source of the host galaxy or its integrated stellar mass. We highlight (i) the integrated star formation main sequence formed by galaxies whose dominant ionization process is related to star formation, for which we find a slope of 0.81 ± 0.02; (ii) for the spatially resolved relation obtained with the spaxel analysis, we find a slope of 0.72 ± 0.04; and (iii) for the integrated main sequence, we also identified a sequence formed by galaxies that are dominated by an old stellar population, which we have called the retired galaxies sequence.« less

Roxarsone binding to soil-derived dissolved organic matter: Insights from multi-spectroscopic techniques.

PubMed

Fu, Qing-Long; He, Jian-Zhou; Blaney, Lee; Zhou, Dong-Mei

2016-07-01

The fate and transport of roxarsone (ROX), a widely used organoarsenic feed additive, in soil is significantly influenced by the ubiquitous presence of soil-derived dissolved organic matter (DOM). In this study, fluorescence quenching titration and two-dimensional correlation spectroscopy (2D-COS) were employed to study ROX binding to DOM. Binding mechanisms were revealed by fluorescence lifetime measurement and Fourier transform infrared spectroscopy (FTIR). Humic- and protein-like fluorophores were identified in the excitation-emission matrix and synchronous fluorescence spectra of DOM. The conditional stability constant (log KC) for ROX binding to DOM was found to be 5.06, indicating that ROX was strongly bound to DOM. The binding order of ROX to DOM fluorophores revealed by 2D-COS followed the sequence of protein-like fluorophore ≈ the longer wavelength excited humic-like (L-humic-like) fluorophore > the shorter wavelength excited humic-like (S-humic-like) fluorophore. 2D-COS resolved issues with peak overlapping and allowed further exploration of the interaction between ROX and DOM. Results of fluorescence lifetime and FTIR spectra demonstrated that ROX interacted with DOM through the hydroxyl, amide II, carboxyl, aliphatic CH, and NO2 groups, yielding stable DOM-ROX complexes. The strong interaction between ROX and DOM implies that DOM plays an important role in the environmental fate of ROX in soil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantitative sampling of conformational heterogeneity of a DNA hairpin using molecular dynamics simulations and ultrafast fluorescence spectroscopy.

PubMed

Voltz, Karine; Léonard, Jérémie; Touceda, Patricia Tourón; Conyard, Jamie; Chaker, Ziyad; Dejaegere, Annick; Godet, Julien; Mély, Yves; Haacke, Stefan; Stote, Roland H

2016-04-20

Molecular dynamics (MD) simulations and time resolved fluorescence (TRF) spectroscopy were combined to quantitatively describe the conformational landscape of the DNA primary binding sequence (PBS) of the HIV-1 genome, a short hairpin targeted by retroviral nucleocapsid proteins implicated in the viral reverse transcription. Three 2-aminopurine (2AP) labeled PBS constructs were studied. For each variant, the complete distribution of fluorescence lifetimes covering 5 orders of magnitude in timescale was measured and the populations of conformers experimentally observed to undergo static quenching were quantified. A binary quantification permitted the comparison of populations from experimental lifetime amplitudes to populations of aromatically stacked 2AP conformers obtained from simulation. Both populations agreed well, supporting the general assumption that quenching of 2AP fluorescence results from pi-stacking interactions with neighboring nucleobases and demonstrating the success of the proposed methodology for the combined analysis of TRF and MD data. Cluster analysis of the latter further identified predominant conformations that were consistent with the fluorescence decay times and amplitudes, providing a structure-based rationalization for the wide range of fluorescence lifetimes. Finally, the simulations provided evidence of local structural perturbations induced by 2AP. The approach presented is a general tool to investigate fine structural heterogeneity in nucleic acid and nucleoprotein assemblies. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

Discovering [superscript 13]C NMR, [superscript 1]H NMR, and IR Spectroscopy in the General Chemistry Laboratory through a Sequence of Guided-Inquiry Exercises

ERIC Educational Resources Information Center

Iler, H. Darrell; Justice, David; Brauer, Shari; Landis, Amanda

2012-01-01

This sequence of three guided-inquiry labs is designed for a second-semester general chemistry course and challenges students to discover basic theoretical principles associated with [superscript 13]C NMR, [superscript 1]H NMR, and IR spectroscopy. Students learn to identify and explain basic concepts of magnetic resonance and vibrational…

Nanoscale Characterization of Carrier Dynamic and Surface Passivation in InGaN/GaN Multiple Quantum Wells on GaN Nanorods.

PubMed

Chen, Weijian; Wen, Xiaoming; Latzel, Michael; Heilmann, Martin; Yang, Jianfeng; Dai, Xi; Huang, Shujuan; Shrestha, Santosh; Patterson, Robert; Christiansen, Silke; Conibeer, Gavin

2016-11-23

Using advanced two-photon excitation confocal microscopy, associated with time-resolved spectroscopy, we characterize InGaN/GaN multiple quantum wells on nanorod heterostructures and demonstrate the passivation effect of a KOH treatment. High-quality InGaN/GaN nanorods were fabricated using nanosphere lithography as a candidate material for light-emitting diode devices. The depth- and time-resolved characterization at the nanoscale provides detailed carrier dynamic analysis helpful for understanding the optical properties. The nanoscale spatially resolved images of InGaN quantum well and defects were acquired simultaneously. We demonstrate that nanorod etching improves light extraction efficiency, and a proper KOH treatment has been found to reduce the surface defects efficiently and enhance the luminescence. The optical characterization techniques provide depth-resolved and time-resolved carrier dynamics with nanoscale spatially resolved mapping, which is crucial for a comprehensive and thorough understanding of nanostructured materials and provides novel insight into the improvement of materials fabrication and applications.

An efficient and accurate approach to MTE-MART for time-resolved tomographic PIV

NASA Astrophysics Data System (ADS)

Lynch, K. P.; Scarano, F.

2015-03-01

The motion-tracking-enhanced MART (MTE-MART; Novara et al. in Meas Sci Technol 21:035401, 2010) has demonstrated the potential to increase the accuracy of tomographic PIV by the combined use of a short sequence of non-simultaneous recordings. A clear bottleneck of the MTE-MART technique has been its computational cost. For large datasets comprising time-resolved sequences, MTE-MART becomes unaffordable and has been barely applied even for the analysis of densely seeded tomographic PIV datasets. A novel implementation is proposed for tomographic PIV image sequences, which strongly reduces the computational burden of MTE-MART, possibly below that of regular MART. The method is a sequential algorithm that produces a time-marching estimation of the object intensity field based on an enhanced guess, which is built upon the object reconstructed at the previous time instant. As the method becomes effective after a number of snapshots (typically 5-10), the sequential MTE-MART (SMTE) is most suited for time-resolved sequences. The computational cost reduction due to SMTE simply stems from the fewer MART iterations required for each time instant. Moreover, the method yields superior reconstruction quality and higher velocity field measurement precision when compared with both MART and MTE-MART. The working principle is assessed in terms of computational effort, reconstruction quality and velocity field accuracy with both synthetic time-resolved tomographic images of a turbulent boundary layer and two experimental databases documented in the literature. The first is the time-resolved data of flow past an airfoil trailing edge used in the study of Novara and Scarano (Exp Fluids 52:1027-1041, 2012); the second is a swirling jet in a water flow. In both cases, the effective elimination of ghost particles is demonstrated in number and intensity within a short temporal transient of 5-10 frames, depending on the seeding density. The increased value of the velocity space-time correlation coefficient demonstrates the increased velocity field accuracy of SMTE compared with MART.

Fourier transform infrared difference and time-resolved infrared detection of the electron and proton transfer dynamics in photosynthetic water oxidation.

PubMed

Noguchi, Takumi

2015-01-01

Photosynthetic water oxidation, which provides the electrons necessary for CO₂ reduction and releases O₂ and protons, is performed at the Mn₄CaO₅ cluster in photosystem II (PSII). In this review, studies that assessed the mechanism of water oxidation using infrared spectroscopy are summarized focusing on electron and proton transfer dynamics. Structural changes in proteins and water molecules between intermediates known as Si states (i=0-3) were detected using flash-induced Fourier transform infrared (FTIR) difference spectroscopy. Electron flow in PSII and proton release from substrate water were monitored using the infrared changes in ferricyanide as an exogenous electron acceptor and Mes buffer as a proton acceptor. Time-resolved infrared (TRIR) spectroscopy provided information on the dynamics of proton-coupled electron transfer during the S-state transitions. In particular, a drastic proton movement during the lag phase (~200μs) before electron transfer in the S3→S0 transition was detected directly by monitoring the infrared absorption of a polarizable proton in a hydrogen bond network. Furthermore, the proton release pathways in the PSII proteins were analyzed by FTIR difference measurements in combination with site-directed mutagenesis, isotopic substitutions, and quantum chemical calculations. Therefore, infrared spectroscopy is a powerful tool for understanding the molecular mechanism of photosynthetic water oxidation. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Assessing the potential of RAD-sequencing to resolve phylogenetic relationships within species radiations: The fly genus Chiastocheta (Diptera: Anthomyiidae) as a case study.

PubMed

Suchan, Tomasz; Espíndola, Anahí; Rutschmann, Sereina; Emerson, Brent C; Gori, Kevin; Dessimoz, Christophe; Arrigo, Nils; Ronikier, Michał; Alvarez, Nadir

2017-09-01

Determining phylogenetic relationships among recently diverged species has long been a challenge in evolutionary biology. Cytoplasmic DNA markers, which have been widely used, notably in the context of molecular barcoding, have not always proved successful in resolving such phylogenies. However, with the advent of next-generation-sequencing technologies and associated techniques of reduced genome representation, phylogenies of closely related species have been resolved at a much higher detail in the last couple of years. Here we examine the potential and limitations of one of such techniques-Restriction-site Associated DNA (RAD) sequencing, a method that produces thousands of (mostly) anonymous nuclear markers, in disentangling the phylogeny of the fly genus Chiastocheta (Diptera: Anthomyiidae). In Europe, this genus encompasses seven species of seed predators, which have been widely studied in the context of their ecological and evolutionary interactions with the plant Trollius europaeus (Ranunculaceae). So far, phylogenetic analyses using mitochondrial markers failed to resolve monophyly of most of the species from this recently diversified genus, suggesting that their taxonomy may need a revision. However, relying on a single, non-recombining marker and ignoring potential incongruences between mitochondrial and nuclear loci may provide an incomplete account of the lineage history. In this study, we applied both classical Sanger sequencing of three mtDNA regions and RAD-sequencing, for reconstructing the phylogeny of the genus. Contrasting with results based on mitochondrial markers, RAD-sequencing analyses retrieved the monophyly of all seven species, in agreement with the morphological species assignment. We found robust nuclear-based species assignment of individual samples, and low levels of estimated contemporary gene flow among them. However, despite recovering species' monophyly, interspecific relationships varied depending on the set of RAD loci considered, producing contradictory topologies. Moreover, coalescence-based phylogenetic analyses revealed low supports for most of the interspecific relationships. Our results indicate that despite the higher performance of RAD-sequencing in terms of species trees resolution compared to cytoplasmic markers, reconstructing inter-specific relationships among recently-diverged lineages may lie beyond the possibilities offered by large sets of RAD-sequencing markers in cases of strong gene tree incongruence. Copyright © 2017 Elsevier Inc. All rights reserved.

Thermally induced conformational changes in polyethylene studied by two-dimensional near-infrared infrared hetero-spectral correlation spectroscopy

NASA Astrophysics Data System (ADS)

Watanabe, Shin; Noda, Isao; Ozaki, Yukihiro

2008-07-01

The amount of nonplanar gauche bonds was monitored as a function of increasing temperature in three different polyethylene (PE) samples by means of mid-infrared (MIR) and near-infrared (NIR) spectroscopy. The hetero-spectral two-dimensional (2D) correlation analysis was carried out between the NIR spectral region of 4365-4235 cm -1 and the well-established MIR spectral region of 1375-1265 cm -1, where bands due to nonplanar conformer are detected. This approach allowed us to identify the NIR band at 4265 cm -1, which behaves in a way similar to MIR bands originating from conformational-defect sequences. By combining the result of our current study and that of our previous report obtained on different types of PE, it is suggested that the NIR band originates from conformational-defect sequences in PE. This finding opens up a unique and useful way to study the state of conformational disorder in PE crystal by NIR spectroscopy, monitoring the intensity of the NIR band at 4265 cm -1. The use of NIR spectroscopy allows researchers to directly probe the degree in the formation of conformational-defect sequences in thick, real-world PE samples that cannot be studied by conventional MIR spectroscopy. The 2D correlation spectroscopy analysis among the MIR CH 2 wagging conformational-defect-mode bands on linear low-density PE (LLDPE) and low-density PE (LDPE) revealed the formation of nonplanar conformer represented by the band at 1368 cm -1 proceeds prior to those by other band at 1308 cm -1. This result agrees well with our previous finding on high-density PE (HDPE). We therefore propose with strong confidence that the bands at 1368 and 1308 cm -1 arise from different conformational-defect sequences, even though both of the bands have been proposed to arise from the same conformer of gtg' ( kink) + gtg sequence.

Nonlinear femtosecond pump-probe spectroscopy using a power-encoded soliton delay line.

PubMed

Saint-Jalm, Sarah; Andresen, Esben Ravn; Bendahmane, Abdelkrim; Kudlinski, Alexandre; Rigneault, Hervé

2016-01-01

We show femtosecond time-resolved nonlinear pump-probe spectroscopy using a fiber soliton as the probe pulse. Furthermore, we exploit soliton dynamics to record an entire transient trace with a power-encoded delay sweep. The power-encoded delay line takes advantage of the dependency of the soliton trajectory in the (λ,z) space upon input power; the difference in accumulated group delay between trajectories converts a fast power sweep into a fast delay sweep. We demonstrate the concept by performing transient absorption spectroscopy in a test sample and validate it against a conventional pump-probe setup.

Spatially resolved Spectroscopy of Europa’s Large-scale Compositional Units at 3-4 μm with Keck NIRSPEC

NASA Astrophysics Data System (ADS)

Fischer, P. D.; Brown, M. E.; Trumbo, S. K.; Hand, K. P.

2017-01-01

We present spatially resolved spectroscopic observations of Europa’s surface at 3-4 μm obtained with the near-infrared spectrograph and adaptive optics system on the Keck II telescope. These are the highest quality spatially resolved reflectance spectra of Europa’s surface at 3-4 μm. The observations spatially resolve Europa’s large-scale compositional units at a resolution of several hundred kilometers. The spectra show distinct features and geographic variations associated with known compositional units; in particular, large-scale leading hemisphere chaos shows a characteristic longward shift in peak reflectance near 3.7 μm compared to icy regions. These observations complement previous spectra of large-scale chaos, and can aid efforts to identify the endogenous non-ice species.

Resolving the grain boundary and lattice impedance of hot-pressed Li 7La 3Zr 2O 12 garnet electrolytes

DOE PAGES

Tenhaeff, Wyatt E.; Wang, Yangyang; Sokolov, Alexei P.; ...

2013-07-24

Here, the cubic-stabilized garnet solid electrolyte with a nominal composition of Li 6.28Al 0.24La 3Zr 2O 12 is thoroughly characterized by impedance spectroscopy. By varying the frequency of the applied AC signal over 11 orders of magnitude for characterizations from –100 to +60 °C, the relative contributions of grain and grain boundary conduction are unambiguously resolved.

High-power laser interaction with low-density C–Cu foams

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

Pérez, F.; Colvin, J. D.; May, M. J.

2015-11-15

We study the propagation of high-power laser beams in micro-structured carbon foams by monitoring the x-ray output from deliberately introduced Cu content. In particular, we characterize this phenomenon measuring absolute time-resolved x-ray yields, time-resolved x-ray imaging, and x-ray spectroscopy. New experimental results for C–Cu foams show a faster heat front velocity than simulation that assumed homogeneous plasma. We suggest the foam micro-structure may explain this trend.

High-power laser interaction with low-density C–Cu foams

DOE PAGES

Pérez, F.; Colvin, J. D.; May, M. J.; ...

2015-11-19

Here, we study the propagation of high-power laser beams in micro-structured carbon foams by monitoring the x-ray output from deliberately introduced Cu content. In particular, we characterize this phenomenon measuring absolute time-resolved x-ray yields, time-resolved x-ray imaging, and x-ray spectroscopy. New experimental results for C–Cu foams show a faster heat front velocity than simulation that assumed homogeneous plasma. We suggest the foam micro-structure may explain this trend.

Calculations of predissociative lifetimes of RG...Hal2 Van der Waals complexes

NASA Astrophysics Data System (ADS)

Buchachenko, Alexei A.; Stepanov, N. F.

1992-07-01

Good examples of combined energy- and time-resolved techniques linked by the theoretical solution of a nuclear problem may be found in investigations of the dynamics of weakly bound Van der Waals (VdW) complexes, such as Ar-OH and He-stilbene. Our report concerns only the theoretical aspect of this complex approach. However, we shall stress the importance of energy-resolved spectroscopy for the dynamics and try to illustrate this with some numerical results.

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

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

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

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

Kang, Zhitao; School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245; Banishev, Alexandr A.

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

Data-driven signal-resolving approaches of infrared spectra to explore the macroscopic and microscopic spatial distribution of organic and inorganic compounds in plant.

PubMed

Chen, Jian-bo; Sun, Su-qin; Zhou, Qun

2015-07-01

The nondestructive and label-free infrared (IR) spectroscopy is a direct tool to characterize the spatial distribution of organic and inorganic compounds in plant. Since plant samples are usually complex mixtures, signal-resolving methods are necessary to find the spectral features of compounds of interest in the signal-overlapped IR spectra. In this research, two approaches using existing data-driven signal-resolving methods are proposed to interpret the IR spectra of plant samples. If the number of spectra is small, "tri-step identification" can enhance the spectral resolution to separate and identify the overlapped bands. First, the envelope bands of the original spectrum are interpreted according to the spectra-structure correlations. Then the spectrum is differentiated to resolve the underlying peaks in each envelope band. Finally, two-dimensional correlation spectroscopy is used to enhance the spectral resolution further. For a large number of spectra, "tri-step decomposition" can resolve the spectra by multivariate methods to obtain the structural and semi-quantitative information about the chemical components. Principal component analysis is used first to explore the existing signal types without any prior knowledge. Then the spectra are decomposed by self-modeling curve resolution methods to estimate the spectra and contents of significant chemical components. At last, targeted methods such as partial least squares target can explore the content profiles of specific components sensitively. As an example, the macroscopic and microscopic distribution of eugenol and calcium oxalate in the bud of clove is studied.

Spectroscopy and imaging of oxygen delivery to tissue under strenuous conditions (NIR in athletes)

NASA Astrophysics Data System (ADS)

Chance, Britton; Nioka, Shoko; Long, Hong; Xie, Chunhua; Ma, XuHui; Ntziachristos, Vasilis; Luo, Qingming

2000-04-01

It was demonstrated that the dynamics of muscle oxygen utilization can readily be measured using dual wavelength hemoglobin oximetry. This method can be used for muscle training exercise and also for evaluation of exercise performance where the anaerobic threshold must be avoided. It was shown that CW imaging technology gives images along the surface of the muscle while the time resolved spectroscopy gives images transverse to the muscle.

Planetary Surface Exploration Using Raman Spectroscopy on Rovers and Landers

NASA Astrophysics Data System (ADS)

Blacksberg, Jordana; Alerstam, E.; Maruyama, Y.; Charbon, E.; Rossman, G. R.

2013-10-01

Planetary surface exploration using laser induced breakdown spectroscopy (LIBS) to probe the composition of rocks has recently become a reality with the operation of the mast-mounted ChemCam instrument onboard the Curiosity rover. Following this success, Raman spectroscopy has steadily gained support as a means for using laser spectroscopy to identify not just composition but mineral phases, without the need for sample preparation. The RLS Raman Spectrometer is included on the payload for the ExoMars mission, and a Raman spectrometer has been included in an example strawman payload for NASA’s Mars 2020 mission. Raman spectroscopy has been identified by the community as a feasible means for pre-selection of samples on Mars for subsequent return to Earth. We present a next-generation instrument that builds on the widely used green-Raman technique to provide a means for performing Raman spectroscopy without the background noise that is often generated by fluorescence of minerals and organics. Microscopic Raman spectroscopy with a laser spot size smaller than the grains of interest can provide surface mapping of mineralogy while preserving morphology. A very small laser spot size 1 µm) is often necessary to identify minor phases that are often of greater interest than the matrix phases. In addition to the difficulties that can be posed by fine-grained material, fluorescence interference from the very same material is often problematic. This is particularly true for many of the minerals of interest that form in environments of aqueous alteration and can be highly fluorescent. We use time-resolved laser spectroscopy to eliminate fluorescence interference that can often make it difficult or impossible to obtain Raman spectra. We will discuss significant advances leading to the feasibility of a compact time-resolved spectrometer, including the development of a new solid-state detector capable of sub-ns time resolution. We will present results on planetary analog minerals to demonstrate the instrument performance including fluorescence rejection.

How to Choose the Suitable Template for Homology Modelling of GPCRs: 5-HT7 Receptor as a Test Case.

PubMed

Shahaf, Nir; Pappalardo, Matteo; Basile, Livia; Guccione, Salvatore; Rayan, Anwar

2016-09-01

G protein-coupled receptors (GPCRs) are a super-family of membrane proteins that attract great pharmaceutical interest due to their involvement in almost every physiological activity, including extracellular stimuli, neurotransmission, and hormone regulation. Currently, structural information on many GPCRs is mainly obtained by the techniques of computer modelling in general and by homology modelling in particular. Based on a quantitative analysis of eighteen antagonist-bound, resolved structures of rhodopsin family "A" receptors - also used as templates to build 153 homology models - it was concluded that a higher sequence identity between two receptors does not guarantee a lower RMSD between their structures, especially when their pair-wise sequence identity (within trans-membrane domain and/or in binding pocket) lies between 25 % and 40 %. This study suggests that we should consider all template receptors having a sequence identity ≤50 % with the query receptor. In fact, most of the GPCRs, compared to the currently available resolved structures of GPCRs, fall within this range and lack a correlation between structure and sequence. When testing suitability for structure-based drug design, it was found that choosing as a template the most similar resolved protein, based on sequence resemblance only, led to unsound results in many cases. Molecular docking analyses were carried out, and enrichment factors as well as attrition rates were utilized as criteria for assessing suitability for structure-based drug design. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of sequence variation in parasite ribosomal DNA by electrophoresis in agarose gels supplemented with a DNA-intercalating agent.

PubMed

Zhu, X Q; Chilton, N B; Gasser, R B

1998-05-01

This study evaluated the use of a commercially available DNA intercalating agent (Resolver Gold) in agarose gels for the direct detection of sequence variation in ribosomal DNA (rDNA). This agent binds preferentially to AT sequence motifs in DNA. Regions of nuclear rDNA, known to provide genetic markers for the identification of species of parasitic ascarid nematodes (order Ascaridida), were amplified by polymerase chain reaction (PCR) and subjected to electrophoresis in standard agarose gels versus gels supplemented with Resolver Gold. Individual taxa examined could not be distinguished reliably based on the size of their amplicons in standard agarose gels, whereas they could be readily delineated based on mobility using Resolver Gold-supplemented gels. The latter was achieved because of differences (approximately 0.1-8.2%) in the AT content of the fragments among different taxa, which were associated with significant interspecific differences (approximately 11-39%) in the rDNA sequences employed. There was a tendency for fragments with higher AT content to migrate slower in supplemented agarose gels compared with those of lower AT content. The results indicate the usefulness of this electrophoretic approach to rapidly screen for sequence variability within or among PCR-amplified rDNA fragments of similar sizes but differing AT contents. Although evaluated on rDNA of parasites, the approach has potential to be applied to a range of genes of different groups of infectious organisms.

SMRT sequencing of the Vitis vinifera cv. ‘Flame seedless’ genome using a SMRTbell-free library preparation from Swift Biosciences

USDA-ARS?s Scientific Manuscript database

Single Molecule Real-Time (SMRT) sequencing provides advantages to the sequencing of complex genomes. The long reads generated are superior for resolving complex genomic regions and provide highly contiguous de novo assemblies. Current SMRTbell libraries generate average read lengths of 10-15kb. How...

Finding a (pine) needle in a haystack: chloroplast genome sequence divergence in rare and widespread pines

Treesearch

J.B. Whittall; J. Syring; M. Parks; J. Buenrostro; C. Dick; A. Liston; R. Cronn

2010-01-01

Critical to conservation efforts and other investigations at low taxonomic levels, DNA sequence data offer important insights into the distinctiveness, biogeographic partitioning, and evolutionary histories of species. The resolving power of DNA sequences is often limited by insufficient variability at the intraspecific level. This is particularly true of studies...

Phase-resolved two-dimensional terahertz spectroscopy - a probe of highly nonlinear light-matter interactions

NASA Astrophysics Data System (ADS)

Elsaesser, Thomas

Terahertz (THz) spectroscopy gives insight into low-frequency excitations and charge dynamics in condensed matter. So far, most experiments in a frequency range from 0.5 to 30 THz have focused on the linear THz response to determine linear absorption and disperion spectra, and/or electric conductivities. The generation of ultrashort THz transients with peak electric fields up to megavolts/cm has allowed for addressing nonlinear light-matter interactions and inducing excitations far from equilibrium. The novel method of two-dimensional THz (2D-THz) spectroscopy allows for mapping ultrafast dynamics and couplings of elementary excitations up to arbitrary nonlinear order in the electric field, both under resonant and nonresonant excitation conditions. In particular, different contributions to the overall nonlinear response are separated by dissecting it as a function of excitation and detection frequencies and for different waiting times after excitation. This talk gives an introduction in 2D-THz spectroscopy, including its recent extension to 3-pulse sequences and interaction schemes. To illustrate the potential of the method, recent results on two-phonon coherences and high-order interband excitations in the semiconductor InSb will be presented. Nonlinear THz excitation of two-phonon coherences exploits a resonance enhancement by the large electronic interband dipole of InSb and is, thus, far more efficient than linear excitation via resonant two-phonon absorption. As a second application, the nonlinear softmode response in a crystal consisting of aspirin molecules will be discussed. At moderate THz driving fields, the pronounced correlation of rotational modes of CH3 groups with collective oscillations of π-electrons drives the system into the regime of nonperturbative light-matter interaction. Nonlinear absorption around 1.1 THz leads to a blue-shifted coherent emission at 1.5 THz, revealing a dynamic breakup of the strong electron-phonon correlations.

Correlating nuclear frequencies by two-dimensional ELDOR-detected NMR spectroscopy.

PubMed

Kaminker, Ilia; Wilson, Tiffany D; Savelieff, Masha G; Hovav, Yonatan; Zimmermann, Herbert; Lu, Yi; Goldfarb, Daniella

2014-03-01

ELDOR (Electron Double Resonance)-detected NMR (EDNMR) is a pulse EPR experiment that is used to measure the transition frequencies of nuclear spins coupled to electron spins. These frequencies are further used to determine hyperfine and quadrupolar couplings, which are signatures of the electronic and spatial structures of paramagnetic centers. In recent years, EDNMR has been shown to be particularly useful at high fields/high frequencies, such as W-band (∼95 GHz, ∼3.5 T), for low γ quadrupolar nuclei. Although at high fields the nuclear Larmor frequencies are usually well resolved, the limited resolution of EDNMR still remains a major concern. In this work we introduce a two dimensional, triple resonance, correlation experiment based on the EDNMR pulse sequence, which we term 2D-EDNMR. This experiment allows circumventing the resolution limitation by spreading the signals in two dimensions and the observed correlations help in the assignment of the signals. First we demonstrate the utility of the 2D-EDNMR experiment on a nitroxide spin label, where we observe correlations between (14)N nuclear frequencies. Negative cross-peaks appear between lines belonging to different MS electron spin manifolds. We resolved two independent correlation patterns for nuclear frequencies arising from the EPR transitions corresponding to the (14)N mI=0 and mI=-1 nuclear spin states, which severely overlap in the one dimensional EDNMR spectrum. The observed correlations could be accounted for by considering changes in the populations of energy levels that S=1/2, I=1 spin systems undergo during the pulse sequence. In addition to these negative cross-peaks, positive cross-peaks appear as well. We present a theoretical model based on the Liouville equation and use it to calculate the time evolution of populations of the various energy levels during the 2D-EDNMR experiment and generated simulated 2D-EDMR spectra. These calculations show that the positive cross-peaks appear due to off resonance effects and/or nuclear relaxation effects. These results suggest that the 2D-EDNMR experiment can be also useful for relaxation pathway studies. Finally we present preliminary results demonstrating that 2D-EDNMR can resolve overlapping (33)S and (14)N signals of type 1 Cu(II) center in (33)S enriched Azurin. Copyright © 2014 Elsevier Inc. All rights reserved.

1H magnetic resonance spectroscopy metabolite profiles of neonatal rat hippocampus and brainstem regions following early postnatal exposure to intermittent hypoxia

NASA Astrophysics Data System (ADS)

Darnall, Robert A.; Chen, Xi; Nemani, Krishnamurthy V.; Sirieix, Chrystelle M.; Gimi, Barjor

2017-03-01

Most premature infants born at less than 30 weeks gestation are exposed to periods of mild intermittent hypoxia (IH) associated with apnea of prematurity and periodic breathing. In adults, IH associated with sleep apnea causes neurochemical and structural alterations in the brain. However, it is unknown whether IH in the premature infant leads to neurodevelopmental impairment. Quantification of biochemical markers that can precisely identify infants at risk of adverse neurodevelopmental outcome is essential. In vivo 1H magnetic resonance spectroscopy (1H MRS) facilitates the quantification of metabolites from distinct regions of the developing brain. We report the changes in metabolite profiles in the brainstem and hippocampal regions of developing rat brains, resulting from exposure to IH. Rat pups were chosen for study because there is rapid postnatal hippocampal development that occurs during the first 4 weeks in the developing rat brain, which corresponds to the first 2-3 postnatal years of development in humans. The brainstem was examined because of our interest in respiratory control disorders in the newborn and because of brainstem gliosis described in infants who succumb to Sudden Infant Death Syndrome (SIDS). Metabolite profiles were compared between hypoxia treated rat pups (n = 9) and normoxic controls (n = 6). Metabolite profiles were acquired using the Point-RESolved spectroscopy (PRESS) MRS sequence and were quantified using the TARQUIN software. There was a significant difference in the concentrations of creatine (p = 0.031), total creatine (creatine + phosphocreatine) (p = 0.028), and total choline (p = 0.001) in the brainstem, and glycine (p = 0.031) in the hippocampal region. The changes are consistent with altered cellular bioenergetics and metabolism associated with hypoxic insult.

A surprising dynamical mass for V773 Tau B

DOE PAGES

Boden, Andrew F.; Torres, Guillermo; Duchene, Gaspard; ...

2012-02-10

Here, we report on new high-resolution imaging and spectroscopy on the multiple T Tauri star system V773 Tau over the 2003-2009 period. With these data we derive relative astrometry, photometry between the A and B components, and radial velocity (RV) of the A-subsystem components. Combining these new data with previously published astrometry and RVs, we update the relative A-B orbit model. This updated orbit model, the known system distance, and A-subsystem parameters yield a dynamical mass for the B component for the first time. Remarkably, the derived B dynamical mass is in the range 1.7-3.0 M⊙. This is much highermore » than previous estimates and suggests that like A, B is also a multiple stellar system. Among these data, spatially resolved spectroscopy provides new insight into the nature of the B component. Similar to A, these near-IR spectra indicate that the dominant source in B is of mid-K spectral type. If B is in fact a multiple star system as suggested by the dynamical mass estimate, the simplest assumption is that B is composed of similar ~1.2 M ⊙ pre-main-sequence stars in a close (<1 AU) binary system. This inference is supported by line-shape changes in near-IR spectroscopy of B, tentatively interpreted as changing RV among components in V773 Tau B. Relative photometry indicates that B is highly variable in the near-IR. The most likely explanation for this variability is circum-B material resulting in variable line-of-sight extinction. The distribution of this material must be significantly affected by both the putative B multiplicity and the A-B orbit.« less

Comparison of LCModel and SAGE in Analysis of Brain Metabolite Concentrations-A study of Patients with Mild Cognitive Impairment.

PubMed

Shih, Chiu-Ming; Lai, Jui-Jen; Chang, Chin-Ching; Chen, Cheng-Sheng; Yeh, Yi-Chun; Jaw, Twei-Shiun; Hsu, Jui-Sheng; Li, Chun-Wei

2017-03-15

The purpose of this study was to compare brain metabolite concentration ratios determined by LCModel and Spectroscopy Analysis by General Electric (SAGE) quantitative methods to elucidate the advantages and disadvantages of each method. A total of 10 healthy volunteers and 10 patients with mild cognitive impairment (MCI) were recruited in this study. A point-resolved spectroscopy (PRESS) sequence was used to obtain the brain magnetic resonance spectroscopy (MRS) spectra of the volunteers and patients, as well as the General Electric (GE) MRS-HD-sphere phantom. The brain metabolite concentration ratios were estimated based on the peak area obtained from both LCModel and SAGE software. Three brain regions were sampled for each volunteer or patient, and 20 replicates were acquired at different times for the phantom analysis. The metabolite ratios of the GE phantom were estimated to be myo-inositol (mI)/creatine (Cr): 0.70 ± 0.01, choline (Cho)/Cr: 0.37 ± 0.00, N-acetylaspartate (NAA)/Cr: 1.26 ± 0.02, and NAA/mI: 1.81 ± 0.04 by LCModel, and mI/Cr: 0.88 ± 0.15, Cho/Cr: 0.35 ± 0.01, NAA/Cr: 1.33 ± 0.03, and NAA/mI: 1.55 ± 0.26 by SAGE. In the healthy volunteers and MCI patients, the ratios of mI/Cr and Cho/Cr estimated by LCModel were higher than those estimated by SAGE. In contrast, the ratio of NAA/Cr estimated by LCModel was lower than that estimated by SAGE. Both methods were acceptable in estimating brain metabolite concentration ratios. However, LCModel was marginally more accurate than SAGE because of its full automation, basis set, and user independency.

Effects of repeated dizocilpine treatment on glutamatergic activity in the prefrontal cortex in an animal model of schizophrenia: An in vivo proton magnetic resonance spectroscopy study at 9.4T.

PubMed

Yoo, Chi-Hyeon; Song, Kyu-Ho; Lim, Song-I; Lee, Do-Wan; Woo, Dong-Cheol; Choe, Bo-Young

2017-01-10

Repeated exposure to dizocilpine (MK-801) can be used as a model of schizophrenia that incorporates disease progression. Proton magnetic resonance spectroscopy ( 1 H MRS) has been widely used to investigate schizophrenia-related alterations in glutamate (Glu). The purpose of this study was to investigate metabolic alterations in the prefrontal cortex (PFC) in an animal model of schizophrenia by using in vivo 1 H MRS. Because of the spectral overlap of Glu and glutamine (Gln), high-field 1 H MRS with short echo time (TE) was used. A point-resolved spectroscopy sequence was used to measure the levels of Glu and Gln, and the brain metabolites in a volume of interest (22.5μL) located in the PFC region of rats (n=13) before and after 6days of MK-801 (0.5mg/kg) treatment. Analysis of the spectra showed that the cross-contamination of Glu and Gln can be considered to comparably low. No metabolic parameters were altered (p>0.05). However, differences in Glu and N-acetylaspartate (NAA) levels between two times were significantly correlated (p<0.01). The results showed both decreased (in 6 of the 13 rats) and increased (7 of the 13 rats) levels of Glu and NAA, which suggested that these opposite metabolic alterations reflect two stage of disease progression. The results suggest that high-field and short TE in vivo 1 H MRS can quantify Glu and Gln with reliably low level of cross-contamination and that repeated exposure to MK-801 induces the progressive development of schizophrenia. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Diffusion weighted MR imaging and proton MR spectroscopy findings of central neurocytoma with pathological correlation.

PubMed

Tlili-Graiess, Kalthoum; Mama, Nadia; Arifa, Nadia; Kadri, Khaled; Hasni, Ibtissem; Krifa, Hedi; Mokni, Moncef

2014-10-01

Three cases of histopathologically confirmed central neurocytoma (CN) are presented, emphasizing diagnostic imaging issues: conventional magnetic resonance imaging with Proton magnetic resonance spectroscopy (MRS) and diffusion-weighted imaging (DWI) findings of CN. Patients age ranged from 17 to 32 years, Imaging include a CT scan and MR examination with DWI and proton MRS on a 1.5-T system. DWI and subsequent apparent diffusion coefficient (ADC) were obtained in all. Single voxel MRS was performed prior to surgery using a point resolved spectroscopy sequence (PRESS) with short 35 ms and long echotime (TE) 144 ms, associated with a two-dimensional chemical Shift Imaging (2D-CSI) with 144 ms TE (one case). Histopathological examination included immunostaining with synaptophysin. With the long TE, a variable amount of glycine with markedly increased choline, very small to almost complete loss of N-acetylaspartate and creatine, and inverted triplet of alanine-lactate were observed in all three patients. Increased glutamate and glutamine complex (Glx) was also observed in all with short TE. DWI demonstrated variable low ADC which appeared well correlated with the tumor signal intensity and cell density: the most homogeneous and highly dense cellular tumor with increased nucleus to cytoplasm ratio demonstrated the lower ADC. Histological pattern was typical in two cases and demonstrated an oligodendroglioma-like pattern in one case. Positivity for synaptophysin confirmed the neuronal origin in all. The demonstration within an intraventricular tumor of both glycine and alanine on MRS along with high choline, bulky Glx and restricted diffusion appear diagnostic of CN. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

In vivo proton magnetic resonance spectroscopy of liver metabolites in non-alcoholic fatty liver disease in rats: T2 relaxation times in methylene protons.

PubMed

Song, Kyu-Ho; Baek, Hyeon-Man; Lee, Do-Wan; Choe, Bo-Young

2015-10-01

The aim of this study was to evaluate the transverse relaxation time of methylene resonance as compared to other lipid resonances. The examinations were performed using a 3.0 T scanner with a point-resolved spectroscopy (PRESS) sequence. Lipid relaxation time in a lipid phantom filled with canola oil was estimated with a repetition time (TR) of 6000ms and echo time (TE) of 40-550ms. For in vivo proton magnetic resonance spectroscopy ((1)H-MRS), eight male Sprague-Dawley rats were given free access to a normal-chow (NC) and another eight male Sprague-Dawley rats were given free access to a high-fat (HF) diet. Both groups drank water ad libitum. T2 measurements in the rats' livers were conducted at a fixed TR of 6000ms and TE of 40-220ms. Exponential curve fitting quality was calculated through the coefficients of determination (R(2)). Chemical analyses of the phantom and livers were not performed, but T2 decay curves were acquired. The T2 relaxation time of methylene resonance was estimated as follows: NC rats, 37.1±4.3ms; HF rats, 31.4±1.8ms (p<0.05). The extrapolated M0 values were higher in HF rats than in NC rats (p<0.005). This study of (1)H MRS led to sufficient spectral resolution and signal-to-noise ratio differences to characterize the T2 relaxation times of methylene resonance. (1)H MRS relaxation times may be useful for quantitative characterization of various liver diseases, including fatty liver disease. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

bioGUID: resolving, discovering, and minting identifiers for biodiversity informatics

PubMed Central

Page, Roderic DM

2009-01-01

Background Linking together the data of interest to biodiversity researchers (including specimen records, images, taxonomic names, and DNA sequences) requires services that can mint, resolve, and discover globally unique identifiers (including, but not limited to, DOIs, HTTP URIs, and LSIDs). Results bioGUID implements a range of services, the core ones being an OpenURL resolver for bibliographic resources, and a LSID resolver. The LSID resolver supports Linked Data-friendly resolution using HTTP 303 redirects and content negotiation. Additional services include journal ISSN look-up, author name matching, and a tool to monitor the status of biodiversity data providers. Conclusion bioGUID is available at . Source code is available from . PMID:19900301

Next generation laser-based standoff spectroscopy techniques for Mars exploration.

PubMed

Gasda, Patrick J; Acosta-Maeda, Tayro E; Lucey, Paul G; Misra, Anupam K; Sharma, Shiv K; Taylor, G Jeffrey

2015-01-01

In the recent Mars 2020 Rover Science Definition Team Report, the National Aeronautics and Space Administration (NASA) has sought the capability to detect and identify elements, minerals, and most importantly, biosignatures, at fine scales for the preparation of a retrievable cache of samples. The current Mars rover, the Mars Science Laboratory Curiosity, has a remote laser-induced breakdown spectroscopy (LIBS) instrument, a type of quantitative elemental analysis, called the Chemistry Camera (ChemCam) that has shown that laser-induced spectroscopy instruments are not only feasible for space exploration, but are reliable and complementary to traditional elemental analysis instruments such as the Alpha Particle X-Ray Spectrometer. The superb track record of ChemCam has paved the way for other laser-induced spectroscopy instruments, such as Raman and fluorescence spectroscopy. We have developed a prototype remote LIBS-Raman-fluorescence instrument, Q-switched laser-induced time-resolved spectroscopy (QuaLITy), which is approximately 70 000 times more efficient at recording signals than a commercially available LIBS instrument. The increase in detection limits and sensitivity is due to our development of a directly coupled system, the use of an intensified charge-coupled device image detector, and a pulsed laser that allows for time-resolved measurements. We compare the LIBS capabilities of our system with an Ocean Optics spectrometer instrument at 7 m and 5 m distance. An increase in signal-to-noise ratio of at least an order of magnitude allows for greater quantitative analysis of the elements in a LIBS spectrum with 200-300 μm spatial resolution at 7 m, a Raman instrument capable of 1 mm spatial resolution at 3 m, and bioorganic fluorescence detection at longer distances. Thus, the new QuaLITy instrument fulfills all of the NASA expectations for proposed instruments.

Lifetime fluorescence spectroscopy for in situ investigation of osteogenic differentiation

NASA Astrophysics Data System (ADS)

Marcu, Laura; Elbarbary, Amir; Zuk, Patricia; De Ugarte, Daniel A.; Benhaim, Prosper; Kurt, Hamza; Hedrick, Marc H.; Ashjian, Peter

2003-07-01

Time-Resolved Laser-Induced Fluorescence Spectroscopy (TR-LIFS) represents a potential tool for the in-situ characterization of bioengineered tissues. In this study, we evaluate the application of TR-LIFS to non-intrusive monitoring of matrix composition during osteogenetic differentiation. Human adipose-derived stem cells, harvested from 3 patients, were induced in osteogenic media for 3, 5, and 7 weeks. Samples were subsequently collected and probed for time-resolved fluorescence emission with a pulsed nitrogen laser. Fluorescence parameters, derived from both spectral- and time-domain, were used for sample characterization. The samples were further analyzed using Western blot analysis and computer-based densitometry. A significant change in the fluorescence parameters was detected for samples beyond 3 weeks of osteogenic differentiation. The spectroscopic observations: 1) show increase of collagen I when contrasted against the time-resolved fluorescence spectra of commercially available collagens; and 2) are in agreement with Western blot analysis that demonstrated significant increase in collagen I content between 3- vs. 5-weeks and 3- vs. 7-weeks and no changes for collagens III, IV, and V. Our results suggest that TR-LIFS can be used as a non-invasive means for the detection of specific collagens in maturing connective tissues.

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.

Serial Femtosecond Crystallography and Ultrafast Absorption Spectroscopy of the Photoswitchable Fluorescent Protein IrisFP.

PubMed

Colletier, Jacques-Philippe; Sliwa, Michel; Gallat, François-Xavier; Sugahara, Michihiro; Guillon, Virginia; Schirò, Giorgio; Coquelle, Nicolas; Woodhouse, Joyce; Roux, Laure; Gotthard, Guillaume; Royant, Antoine; Uriarte, Lucas Martinez; Ruckebusch, Cyril; Joti, Yasumasa; Byrdin, Martin; Mizohata, Eiichi; Nango, Eriko; Tanaka, Tomoyuki; Tono, Kensuke; Yabashi, Makina; Adam, Virgile; Cammarata, Marco; Schlichting, Ilme; Bourgeois, Dominique; Weik, Martin

2016-03-03

Reversibly photoswitchable fluorescent proteins find growing applications in cell biology, yet mechanistic details, in particular on the ultrafast photochemical time scale, remain unknown. We employed time-resolved pump-probe absorption spectroscopy on the reversibly photoswitchable fluorescent protein IrisFP in solution to study photoswitching from the nonfluorescent (off) to the fluorescent (on) state. Evidence is provided for the existence of several intermediate states on the pico- and microsecond time scales that are attributed to chromophore isomerization and proton transfer, respectively. Kinetic modeling favors a sequential mechanism with the existence of two excited state intermediates with lifetimes of 2 and 15 ps, the second of which controls the photoswitching quantum yield. In order to support that IrisFP is suited for time-resolved experiments aiming at a structural characterization of these ps intermediates, we used serial femtosecond crystallography at an X-ray free electron laser and solved the structure of IrisFP in its on state. Sample consumption was minimized by embedding crystals in mineral grease, in which they remain photoswitchable. Our spectroscopic and structural results pave the way for time-resolved serial femtosecond crystallography aiming at characterizing the structure of ultrafast intermediates in reversibly photoswitchable fluorescent proteins.

The H + OCS hot atom reaction - CO state distributions and translational energy from time-resolved infrared absorption spectroscopy

NASA Technical Reports Server (NTRS)

Nickolaisen, Scott L.; Cartland, Harry E.

1993-01-01

Time-resolved infrared diode laser spectroscopy has been used to probe CO internal and translational excitation from the reaction of hot H atoms with OCS. Product distributions should be strongly biased toward the maximum 1.4 eV collision energy obtained from 278 nm pulsed photolysis of HI. Rotations and vibrations are both colder than predicted by statistical density of states theory, as evidenced by large positive surprisal parameters. The bias against rotation is stronger than that against vibration, with measurable population as high as v = 4. The average CO internal excitation is 1920/cm, accounting for only 13 percent of the available energy. Of the energy balance, time-resolved sub-Doppler line shape measurements show that more than 38 percent appears as relative translation of the separating CO and SH fragments. Studies of the relaxation kinetics indicate that some rotational energy transfer occurs on the time scale of our measurements, but the distributions do not relax sufficiently to alter our conclusions. Vibrational distributions are nascent, though vibrational relaxation of excited CO is unusually fast in the OCS bath, with rates approaching 3 percent of gas kinetic for v = 1.

Toward picosecond time-resolved X-ray absorption studies of interfacial photochemistry

NASA Astrophysics Data System (ADS)

Gessner, Oliver; Mahl, Johannes; Neppl, Stefan

2016-05-01

We report on the progress toward developing a novel picosecond time-resolved transient X-ray absorption spectroscopy (TRXAS) capability for time-domain studies of interfacial photochemistry. The technique is based on the combination of a high repetition rate picosecond laser system with a time-resolved X-ray fluorescent yield setup that may be used for the study of radiation sensitive materials and X-ray spectroscopy compatible photoelectrochemical (PEC) cells. The mobile system is currently deployed at the Advanced Light Source (ALS) and may be used in all operating modes (two-bunch and multi-bunch) of the synchrotron. The use of a time-stamping technique enables the simultaneous recording of TRXAS spectra with delays between the exciting laser pulses and the probing X-ray pulses spanning picosecond to nanosecond temporal scales. First results are discussed that demonstrate the viability of the method to study photoinduced dynamics in transition metal-oxide semiconductor (SC) samples under high vacuum conditions and at SC-liquid electrolyte interfaces during photoelectrochemical water splitting. Opportunities and challenges are outlined to capture crucial short-lived intermediates of photochemical processes with the technique. This work was supported by the Department of Energy Office of Science Early Career Research Program.

Picometer-resolution dual-comb spectroscopy with a free-running fiber laser.

PubMed

Zhao, Xin; Hu, Guoqing; Zhao, Bofeng; Li, Cui; Pan, Yingling; Liu, Ya; Yasui, Takeshi; Zheng, Zheng

2016-09-19

Dual-comb spectroscopy holds the promise as real-time, high-resolution spectroscopy tools. However, in its conventional schemes, the stringent requirement on the coherence between two lasers requires sophisticated control systems. By replacing control electronics with an all-optical dual-comb lasing scheme, a simplified dual-comb spectroscopy scheme is demonstrated using one dual-wavelength, passively mode-locked fiber laser. Pulses with a intracavity-dispersion-determined repetition-frequency difference are shown to have good mutual coherence and stability. Capability to resolve the comb teeth and a picometer-wide optical spectral resolution are demonstrated using a simple data acquisition system. Energy-efficient, free-running fiber lasers with a small comb-tooth-spacing could enable low-cost dual-comb systems.

Application of NIR spectroscopy in the assessment of diabetic foot disorders

NASA Astrophysics Data System (ADS)

Schleicher, Eckhard; Hampel, Uwe; Freyer, Richard

2001-10-01

Diabetic foot syndrome (DFS) is a common sequel of long-term diabetes mellitus. There is a urgent need of noninvasive, objective and quantitative diagnostic tools to assess tissue viability and perfusion for a successful therapy. NIR spectroscopy seems to be qualified to measure local capillary hemoglobin saturation of the outer extremities in patients with progressive diabetic disorders. We investigate how NIR spectroscopy can be applied to the assessment of diabetic foot problems such as neuropathy and angiopathy. Thereby we use spatially resolved spectroscopy in conjunction with a specially developed continuous-wave laser spectrometer. Comparison of intra- and interindividual measurements is expected to yield quantitative measures of local tissue viability which is a prerequisite for a successful therapy.

Determination of molecular spectroscopic parameters and energy-transfer rates by double-resonance spectroscopy

NASA Technical Reports Server (NTRS)

Steinfeld, J. I.; Foy, B.; Hetzler, J.; Flannery, C.; Klaassen, J.; Mizugai, Y.; Coy, S.

1990-01-01

The spectroscopy of small to medium-size polyatomic molecules can be extremely complex, especially in higher-lying overtone and combination vibrational levels. The high density of levels also complicates the understanding of inelastic collision processes, which is required to model energy transfer and collision broadening of spectral lines. Both of these problems can be addressed by double-resonance spectroscopy, i.e., time-resolved pump-probe measurements using microwave, infrared, near-infrared, and visible-wavelength sources. Information on excited-state spectroscopy, transition moments, inelastic energy transfer rates and propensity rules, and pressure-broadening parameters may be obtained from such experiments. Examples are given for several species of importance in planetary atmospheres, including ozone, silane, ethane, and ammonia.

Gas spectroscopy with integrated frequency monitoring through self-mixing in a terahertz quantum-cascade laser.

PubMed

Chhantyal-Pun, Rabi; Valavanis, Alexander; Keeley, James T; Rubino, Pierluigi; Kundu, Iman; Han, Yingjun; Dean, Paul; Li, Lianhe; Davies, A Giles; Linfield, Edmund H

2018-05-15

We demonstrate a gas spectroscopy technique, using self-mixing in a 3.4 terahertz quantum-cascade laser (QCL). All previous QCL spectroscopy techniques have required additional terahertz instrumentation (detectors, mixers, or spectrometers) for system pre-calibration or spectral analysis. By contrast, our system self-calibrates the laser frequency (i.e., with no external instrumentation) to a precision of 630 MHz (0.02%) by analyzing QCL voltage perturbations in response to optical feedback within a 0-800 mm round-trip delay line. We demonstrate methanol spectroscopy by introducing a gas cell into the feedback path and show that a limiting absorption coefficient of ∼1×10 -4   cm -1 is resolvable.

Insights into the Aggregation Mechanism of PolyQ Proteins with Different Glutamine Repeat Lengths.

PubMed

Yushchenko, Tetyana; Deuerling, Elke; Hauser, Karin

2018-04-24

Polyglutamine (polyQ) diseases, including Huntington's disease, result from the aggregation of an abnormally expanded polyQ repeat in the affected protein. The length of the polyQ repeat is essential for the disease's onset; however, the molecular mechanism of polyQ aggregation is still poorly understood. Controlled conditions and initiation of the aggregation process are prerequisites for the detection of transient intermediate states. We present an attenuated total reflection Fourier-transform infrared spectroscopic approach combined with protein immobilization to study polyQ aggregation dependent on the polyQ length. PolyQ proteins were engineered mimicking the mammalian N-terminus fragment of the Huntingtin protein and containing a polyQ sequence with the number of glutamines below (Q11), close to (Q38), and above (Q56) the disease threshold. A monolayer of the polyQ construct was chemically immobilized on the internal reflection element of the attenuated total reflection cell, and the aggregation was initiated via enzymatic cleavage. Structural changes of the polyQ sequence were monitored by time-resolved infrared difference spectroscopy. We observed faster aggregation kinetics for the longer sequences, and furthermore, we could distinguish β-structured intermediates for the different constructs, allowing us to propose aggregation mechanisms dependent on the repeat length. Q11 forms a β-structured aggregate by intermolecular interaction of stretched monomers, whereas Q38 and Q56 undergo conformational changes to various β-structured intermediates, including intramolecular β-sheets. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Spread spectrum time-resolved diffuse optical measurement system for enhanced sensitivity in detecting human brain activity

NASA Astrophysics Data System (ADS)

Mehta, Kalpesh; Hasnain, Ali; Zhou, Xiaowei; Luo, Jianwen; Penney, Trevor B.; Chen, Nanguang

2017-04-01

Diffuse optical spectroscopy (DOS) and imaging methods have been widely applied to noninvasive detection of brain activity. We have designed and implemented a low cost, portable, real-time one-channel time-resolved DOS system for neuroscience studies. Phantom experiments were carried out to test the performance of the system. We further conducted preliminary human experiments and demonstrated that enhanced sensitivity in detecting neural activity in the cortex could be achieved by the use of late arriving photons.

Interference-free optical detection for Raman spectroscopy

NASA Technical Reports Server (NTRS)

Fischer, David G (Inventor); Kojima, Jun (Inventor); Nguyen, Quang-Viet (Inventor)

2012-01-01

An architecture for spontaneous Raman scattering (SRS) that utilizes a frame-transfer charge-coupled device (CCD) sensor operating in a subframe burst gating mode to realize time-resolved combustion diagnostics is disclosed. The technique permits all-electronic optical gating with microsecond shutter speeds (<5 .mu.s), without compromising optical throughput or image fidelity. When used in conjunction with a pair of orthogonally-polarized excitation lasers, the technique measures time-resolved vibrational Raman scattering that is minimally contaminated by problematic optical background noise.

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

David, M.-L.; Pailloux, F.; Mauchamp, V.

The understanding of the mechanisms of helium bubble formation and evolution in materials requires the quantitative determination of several key quantities such as the helium density in the bubbles. Helium nanobubbles of about 16 nm in diameter were created in silicon by helium implantation at high fluence and subsequent annealing. Individual nanobubbles were analyzed by spatially resolved Electron Energy-loss Spectroscopy (EELS). We report on the in situ probing of helium desorption from the nanobubbles under electron irradiation. This opens new perspectives for a more accurate determination of the helium density through spatially resolved EELS.

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.

Electronic anisotropies revealed by detwinned angle-resolved photo-emission spectroscopy measurements of FeSe

NASA Astrophysics Data System (ADS)

Watson, Matthew D.; Haghighirad, Amir A.; Rhodes, Luke C.; Hoesch, Moritz; Kim, Timur K.

2017-10-01

We report high resolution angle-resolved photo-emission spectroscopy (ARPES) measurements of detwinned FeSe single crystals. The application of a mechanical strain is used to promote the volume fraction of one of the orthorhombic domains in the sample, which we estimate to be 80 % detwinned. While the full structure of the electron pockets consisting of two crossed ellipses may be observed in the tetragonal phase at temperatures above 90 K, we find that remarkably, only one peanut-shaped electron pocket oriented along the longer a axis contributes to the ARPES measurement at low temperatures in the nematic phase, with the expected pocket along b being not observed. Thus the low temperature Fermi surface of FeSe as experimentally determined by ARPES consists of one elliptical hole pocket and one orthogonally-oriented peanut-shaped electron pocket. Our measurements clarify the long-standing controversies over the interpretation of ARPES measurements of FeSe.

Quantifying electronic band interactions in van der Waals materials using angle-resolved reflected-electron spectroscopy.

PubMed

Jobst, Johannes; van der Torren, Alexander J H; Krasovskii, Eugene E; Balgley, Jesse; Dean, Cory R; Tromp, Rudolf M; van der Molen, Sense Jan

2016-11-29

High electron mobility is one of graphene's key properties, exploited for applications and fundamental research alike. Highest mobility values are found in heterostructures of graphene and hexagonal boron nitride, which consequently are widely used. However, surprisingly little is known about the interaction between the electronic states of these layered systems. Rather pragmatically, it is assumed that these do not couple significantly. Here we study the unoccupied band structure of graphite, boron nitride and their heterostructures using angle-resolved reflected-electron spectroscopy. We demonstrate that graphene and boron nitride bands do not interact over a wide energy range, despite their very similar dispersions. The method we use can be generally applied to study interactions in van der Waals systems, that is, artificial stacks of layered materials. With this we can quantitatively understand the 'chemistry of layers' by which novel materials are created via electronic coupling between the layers they are composed of.

The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. I. Isolated, non-interacting LH2 complexes.

PubMed

Pflock, Tobias J; Oellerich, Silke; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

2011-07-21

We have employed time-resolved spectroscopy on the picosecond time scale in combination with dynamic Monte Carlo simulations to investigate the photophysical properties of light-harvesting 2 (LH2) complexes from the purple photosynthetic bacterium Rhodopseudomonas acidophila. The variations of the fluorescence transients were studied as a function of the excitation fluence, the repetition rate of the excitation and the sample preparation conditions. Here we present the results obtained on detergent solubilized LH2 complexes, i.e., avoiding intercomplex interactions, and show that a simple four-state model is sufficient to grasp the experimental observations quantitatively without the need for any free parameters. This approach allows us to obtain a quantitative measure for the singlet-triplet annihilation rate in isolated, noninteracting LH2 complexes.

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, dual heterodyne phase collection transient grating spectroscopy

DOE PAGES

Dennett, Cody A.; Short, Michael P.

2017-05-23

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

Angularly resolved X-ray photoelectron spectroscopy investigation of PTFE after prolonged space exposure

NASA Technical Reports Server (NTRS)

Dalins, I.; Karimi, M.

1992-01-01

Monochromatized angularly resolved X-ray photoelectron spectroscopy (ARXPS) was used to study PTFE (Teflon) that had been exposed to an earth orbital environment for approximately six years. The primary interest of the research is on a very reactive component of this environment (atomic oxygen) which, because of the typical orbital velocities of a spacecraft, impinge on exposed surfaces with 5 eV energy. This presentation deals with the method of analysis, the findings as they pertain to a rather complex carbon, oxygen, and fluorine XPS peak analysis, and the character of the valence bands. An improved bias referencing method, based on ARXPS, is also demonstrated for evaluating specimen charging effects. It was found that the polymer molecule tends to resist the atomic oxygen attack by reorienting itself, so that the most electronegative CF3 groups are facing the incoming hyperthermal oxygen atoms. The implications of these findings to ground-based laboratory studies are discussed.

Measurement of free radical kinetics in pulsed plasmas by UV and VUV absorption spectroscopy and by modulated beam mass spectrometry

NASA Astrophysics Data System (ADS)

Cunge, G.; Bodart, P.; Brihoum, M.; Boulard, F.; Chevolleau, T.; Sadeghi, N.

2012-04-01

This paper reviews recent progress in the development of time-resolved diagnostics to probe high-density pulsed plasma sources. We focus on time-resolved measurements of radicals' densities in the afterglow of pulsed discharges to provide useful information on production and loss mechanisms of free radicals. We show that broad-band absorption spectroscopy in the ultraviolet and vacuum ultraviolet spectral domain and threshold ionization modulated beam mass spectrometry are powerful techniques for the determination of the time variation of the radicals' densities in pulsed plasmas. The combination of these complementary techniques allows detection of most of the reactive species present in industrial etching plasmas, giving insights into the physico-chemistry reactions involving these species. As an example, we discuss briefly the radicals' kinetics in the afterglow of a SiCl4/Cl2/Ar discharge.

Reduced photoconductivity observed by time-resolved terahertz spectroscopy in metal nanofilms with and without adhesion layers

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

Alberding, Brian G.; Heilweil, Edwin J., E-mail: edwin.heilweil@nist.gov; Kushto, Gary P.

2016-05-30

Non-contact, optical time-resolved terahertz spectroscopy has been used to study the transient photoconductivity of nanometer-scale metallic films deposited on the fused quartz substrates. Samples of 8 nm thick gold or titanium show an instrument-limited (ca. 0.5 ps) decrease in conductivity following photoexcitation due to electron-phonon coupling and subsequent increased lattice temperatures which increases charge carrier scattering. In contrast, for samples of 8 nm gold with a 4 nm adhesion layer of titanium or chromium, a ca. 70 ps rise time for the lattice temperature increase is observed. These results establish the increased transient terahertz transmission sign change of metallic compared to semiconductor materials.more » The results also suggest nanoscale gold films that utilize an adhesion material do not consist of distinct layers.« less

Direct Observation of the Surface Segregation of Cu in Pd by Time-Resolved Positron-Annihilation-Induced Auger Electron Spectroscopy

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

Mayer, J.; Hugenschmidt, C.; Schreckenbach, K.

2010-11-12

Density functional theory calculations predict the surface segregation of Cu in the second atomic layer of Pd which has not been unambiguously confirmed by experiment so far. We report measurements on Pd surfaces covered with three and six monolayers of Cu using element selective positron-annihilation-induced Auger electron spectroscopy (PAES) which is sensitive to the topmost atomic layer. Moreover, time-resolved PAES, which was applied for the first time, enables the investigation of the dynamics of surface atoms and hence the observation of the segregation process. The time constant for segregation was experimentally determined to {tau}=1.38(0.21) h, and the final segregated configurationmore » was found to be consistent with calculations. Time-dependent PAES is demonstrated to be a novel element selective technique applicable for the investigation of, e.g., heterogeneous catalysis, corrosion, or surface alloying.« less

Direct Observation of the Surface Segregation of Cu in Pd by Time-Resolved Positron-Annihilation-Induced Auger Electron Spectroscopy

NASA Astrophysics Data System (ADS)

Mayer, J.; Hugenschmidt, C.; Schreckenbach, K.

2010-11-01

Density functional theory calculations predict the surface segregation of Cu in the second atomic layer of Pd which has not been unambiguously confirmed by experiment so far. We report measurements on Pd surfaces covered with three and six monolayers of Cu using element selective positron-annihilation-induced Auger electron spectroscopy (PAES) which is sensitive to the topmost atomic layer. Moreover, time-resolved PAES, which was applied for the first time, enables the investigation of the dynamics of surface atoms and hence the observation of the segregation process. The time constant for segregation was experimentally determined to τ=1.38(0.21)h, and the final segregated configuration was found to be consistent with calculations. Time-dependent PAES is demonstrated to be a novel element selective technique applicable for the investigation of, e.g., heterogeneous catalysis, corrosion, or surface alloying.

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.

Identification of effective exciton-exciton annihilation in squaraine-squaraine copolymers.

PubMed

Hader, Kilian; May, Volkhard; Lambert, Christoph; Engel, Volker

2016-05-11

Ultrafast time-resolved transient absorption spectroscopy is able to monitor the fate of the excited state population in molecular aggregates or polymers. Due to many competing decay processes, the identification of exciton-exciton annihilation (EEA) is difficult. Here, we use a microscopic model to describe exciton annihilation processes in squaraine-squaraine copolymers. Transient absorption time traces measured at different laser powers exhibit an unusual time-dependence. The analysis points towards dynamics taking place on three time-scales. Immediately after laser-excitation a localization of excitons takes place within the femtosecond time-regime. This is followed by exciton-exciton annihilation which is responsible for a fast decay of the exciton population. At later times, excitations being localized on units which are not directly connected remain so that diffusion dominates the dynamics and leads to a slower decay. We thus provide evidence for EEA tracked by time-resolved spectroscopy which has not been reported that clearly before.

Electron heating and thermal relaxation of gold nanorods revealed by two-dimensional electronic spectroscopy.

PubMed

Lietard, Aude; Hsieh, Cho-Shuen; Rhee, Hanju; Cho, Minhaeng

2018-03-01

To elucidate the complex interplay between the size and shape of gold nanorods and their electronic, photothermal, and optical properties for molecular imaging, photothermal therapy, and optoelectronic devices, it is a prerequisite to characterize ultrafast electron dynamics in gold nanorods. Time-resolved transient absorption (TA) studies of plasmonic electrons in various nanostructures have revealed the time scales for electron heating, lattice vibrational excitation, and phonon relaxation processes in condensed phases. However, because linear spectroscopic and time-resolved TA signals are vulnerable to inhomogeneous line-broadening, pure dephasing and direct electron heating effects are difficult to observe. Here we show that femtosecond two-dimensional electronic spectroscopy, with its unprecedented time resolution and phase sensitivity, can be used to collect direct experimental evidence for ultrafast electron heating, anomalously strong coherent and transient electronic plasmonic responses, and homogenous dephasing processes resulting from electron-vibration couplings even for polydisperse gold nanorods.

Improved Fast, Deep Record Length, Time-Resolved Visible Spectroscopy of Plasmas Using Fiber Grids

NASA Astrophysics Data System (ADS)

Brockington, S.; Case, A.; Cruz, E.; Williams, A.; Witherspoon, F. D.; Horton, R.; Klauser, R.; Hwang, D.

2017-10-01

HyperV Technologies is developing a fiber-coupled, deep record-length, low-light camera head for performing high time resolution spectroscopy on visible emission from plasma events. By coupling the output of a spectrometer to an imaging fiber bundle connected to a bank of amplified silicon photomultipliers, time-resolved spectroscopic imagers of 100 to 1,000 pixels can be constructed. A second generation prototype 32-pixel spectroscopic imager employing this technique was constructed and successfully tested at the University of California at Davis Compact Toroid Injection Experiment (CTIX). Pixel performance of 10 Megaframes/sec with record lengths of up to 256,000 frames ( 25.6 milliseconds) were achieved. Pixel resolution was 12 bits. Pixel pitch can be refined by using grids of 100 μm to 1000 μm diameter fibers. Experimental results will be discussed, along with future plans for this diagnostic. Work supported by USDOE SBIR Grant DE-SC0013801.

Spatially Resolved Emission of a z~3 Damped Lyman Alpha Galaxy with Keck/OSIRIS IFU

NASA Astrophysics Data System (ADS)

Christenson, Holly; Jorgenson, Regina

2017-01-01

The damped Lyman alpha (DLA) class of galaxies contains most of the neutral hydrogen gas over cosmic time. Few DLAs have been detected directly, which limits our knowledge of fundamental properties like size and mass. We present Keck/OSIRIS infrared integral field spectroscopy (IFU) observations of a DLA that was first detected in absorption toward a background quasar. Our observations use the Keck Laser Guide Star Adaptive Optics system to reduce the point-spread function of the quasar, making it possible to spatially resolve the DLA emission. We map this emission in O[III] 5007 Å. At redshift z~3, this DLA represents one of the highest redshift DLAs mapped with IFU spectroscopy. We present measurements of the star formation rate, metallicity, and gas mass of the galaxy.This project was supported in part by the NSF REU grant AST-1358980 and by the Nantucket Maria Mitchell Association.

Reflectance-mode interferometric near-infrared spectroscopy quantifies brain absorption, scattering, and blood flow index in vivo.

PubMed

Borycki, Dawid; Kholiqov, Oybek; Srinivasan, Vivek J

2017-02-01

Interferometric near-infrared spectroscopy (iNIRS) is a new technique that measures time-of-flight- (TOF-) resolved autocorrelations in turbid media, enabling simultaneous estimation of optical and dynamical properties. Here, we demonstrate reflectance-mode iNIRS for noninvasive monitoring of a mouse brain in vivo. A method for more precise quantification with less static interference from superficial layers, based on separating static and dynamic components of the optical field autocorrelation, is presented. Absolute values of absorption, reduced scattering, and blood flow index (BFI) are measured, and changes in BFI and absorption are monitored during a hypercapnic challenge. Absorption changes from TOF-resolved iNIRS agree with absorption changes from continuous wave NIRS analysis, based on TOF-integrated light intensity changes, an effective path length, and the modified Beer-Lambert Law. Thus, iNIRS is a promising approach for quantitative and noninvasive monitoring of perfusion and optical properties in vivo.

Effects of strain on the electronic structure, superconductivity, and nematicity in FeSe studied by angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Phan, G. N.; Nakayama, K.; Sugawara, K.; Sato, T.; Urata, T.; Tanabe, Y.; Tanigaki, K.; Nabeshima, F.; Imai, Y.; Maeda, A.; Takahashi, T.

2017-06-01

One of central issues in iron-based superconductors is the role of structural change to the superconducting transition temperature (Tc). It was found in FeSe that the lattice strain leads to a drastic increase in Tc, accompanied by suppression of nematic order. By angle-resolved photoemission spectroscopy on tensile- or compressive-strained and strain-free FeSe, we experimentally show that the in-plane strain causes a marked change in the energy overlap (Δ Eh -e ) between the hole and electron pockets in the normal state. The change in Δ Eh -e modifies the Fermi-surface volume, leading to a change in Tc. Furthermore, the strength of nematicity is also found to be characterized by Δ Eh -e . These results suggest that the key to understanding the phase diagram is the fermiology and interactions linked to the semimetallic band overlap.

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.

Extracting Optical Fiber Background from Surface-Enhanced Raman Spectroscopy Spectra Based on Bi-Objective Optimization Modeling.

PubMed

Huang, Jie; Shi, Tielin; Tang, Zirong; Zhu, Wei; Liao, Guanglan; Li, Xiaoping; Gong, Bo; Zhou, Tengyuan

2017-08-01

We propose a bi-objective optimization model for extracting optical fiber background from the measured surface-enhanced Raman spectroscopy (SERS) spectrum of the target sample in the application of fiber optic SERS. The model is built using curve fitting to resolve the SERS spectrum into several individual bands, and simultaneously matching some resolved bands with the measured background spectrum. The Pearson correlation coefficient is selected as the similarity index and its maximum value is pursued during the spectral matching process. An algorithm is proposed, programmed, and demonstrated successfully in extracting optical fiber background or fluorescence background from the measured SERS spectra of rhodamine 6G (R6G) and crystal violet (CV). The proposed model not only can be applied to remove optical fiber background or fluorescence background for SERS spectra, but also can be transferred to conventional Raman spectra recorded using fiber optic instrumentation.

Quantifying highly efficient incoherent energy transfer in perylene-based multichromophore arrays.

PubMed

Webb, James E A; Chen, Kai; Prasad, Shyamal K K; Wojciechowski, Jonathan P; Falber, Alexander; Thordarson, Pall; Hodgkiss, Justin M

2016-01-21

Multichromophore perylene arrays were designed and synthesized to have extremely efficient resonance energy transfer. Using broadband ultrafast photoluminescence and transient absorption spectroscopies, transfer timescales of approximately 1 picosecond were resolved, corresponding to efficiencies of up to 99.98%. The broadband measurements also revealed spectra corresponding to incoherent transfer between localized states. Polarization resolved spectroscopy was used to measure the dipolar angles between donor and acceptor chromophores, thereby enabling geometric factors to be fixed when assessing the validity of Förster theory in this regime. Förster theory was found to predict the correct magnitude of transfer rates, with measured ∼2-fold deviations consistent with the breakdown of the point-dipole approximation at close approach. The materials presented, along with the novel methods for quantifying ultrahigh energy transfer efficiencies, will be valuable for applications demanding extremely efficient energy transfer, including fluorescent solar concentrators, optical gain, and photonic logic devices.

Time-resolved, dual heterodyne phase collection transient grating spectroscopy

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

Dennett, Cody A.; Short, Michael P.

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

Time-resolved spectroscopyHiifill of the peculiar Hα variable Be star HD 76534

NASA Astrophysics Data System (ADS)

Oudmaijer, René D.; Drew, Janet E.

1999-10-01

We present time-resolved spectroscopy of the Be star HD 76534, which was observed to have an Hα outburst in 1995, when the line went from photospheric absorption to emission at a level of more than two times the continuum within 2.5 hours. To investigate the short-term behaviour of the spectrum of HD 76534 we have obtained 30 spectra within two hours real-time and searched for variations in the spectrum. Within the levels of statistical significance, no variability was found. Rather than periodic on short time scales, the Hα behaviour seems to be commonly episodic on longer (> 1 year) time scales, as an assessment of the existing data on the Hα line and the Hipparcos photometry suggests. HD 76534 underwent only 1 photometric outburst in the 3 year span that the star was monitored by the Hipparcos satellite.

Frame-Transfer Gating Raman Spectroscopy for Time-Resolved Multiscalar Combustion Diagnostics

NASA Technical Reports Server (NTRS)

Nguyen, Quang-Viet; Fischer, David G.; Kojima, Jun

2011-01-01

Accurate experimental measurement of spatially and temporally resolved variations in chemical composition (species concentrations) and temperature in turbulent flames is vital for characterizing the complex phenomena occurring in most practical combustion systems. These diagnostic measurements are called multiscalar because they are capable of acquiring multiple scalar quantities simultaneously. Multiscalar diagnostics also play a critical role in the area of computational code validation. In order to improve the design of combustion devices, computational codes for modeling turbulent combustion are often used to speed up and optimize the development process. The experimental validation of these codes is a critical step in accepting their predictions for engine performance in the absence of cost-prohibitive testing. One of the most critical aspects of setting up a time-resolved stimulated Raman scattering (SRS) diagnostic system is the temporal optical gating scheme. A short optical gate is necessary in order for weak SRS signals to be detected with a good signal- to-noise ratio (SNR) in the presence of strong background optical emissions. This time-synchronized optical gating is a classical problem even to other spectroscopic techniques such as laser-induced fluorescence (LIF) or laser-induced breakdown spectroscopy (LIBS). Traditionally, experimenters have had basically two options for gating: (1) an electronic means of gating using an image intensifier before the charge-coupled-device (CCD), or (2) a mechanical optical shutter (a rotary chopper/mechanical shutter combination). A new diagnostic technology has been developed at the NASA Glenn Research Center that utilizes a frame-transfer CCD sensor, in conjunction with a pulsed laser and multiplex optical fiber collection, to realize time-resolved Raman spectroscopy of turbulent flames that is free from optical background noise (interference). The technology permits not only shorter temporal optical gating (down to <1 s, in principle), but also higher optical throughput, thus resulting in a substantial increase in measurement SNR.

a Study on SODIUM(110) and Other Nearly Free Electron Metals Using Angle Resolved Photoemission Spectroscopy.

NASA Astrophysics Data System (ADS)

Lyo, In-Whan

Electronic properties of the epitaxially grown Na(110) film have been studied using angle resolved ultraviolet photoemission spectroscopy with synchrotron radiation as the light source. Na provides an ideal ground to study the fundamental aspects of the electron-electron interactions in metals, because of its simple Fermi surface and small pseudopotential. The absolute band structure of Na(110) using angle resolved photoemission spectroscopy has been mapped out using the extrema searching method. The advantage of this approach is that the usual assumption of the unoccupied state dispersion is not required. We have found that the dispersion of Na(1l0) is very close to the parabolic band with the effective mass 1.21 M_{rm e} at 90 K. Self-consistent calculations of the self-energy for the homogeneous electron gas have been performed using the Green's function technique within the framework of the GW approximation, in the hope of understanding the narrowing mechanism of the bandwidth observed for all the nearly-free-electron (NFE) metals. Good agreements between the experimental data and our calculated self-energy were obtained not only for our data on k-dependency from Na(l10), but also for the total bandwidth corrections for other NFE metals, only if dielectric functions beyond the random phase approximation were used. Our findings emphasize the importance of the screening by long wavelength plasmons. Off-normal spectra of angle resolved photoemission from Na(110) show strong asymmetry of the bulk peak intensity for the wide range of photon energies. Using a simple analysis, we show this asymmetry has an origin in the interference of the surface Umklapp electrons with the normal electrons. We have also performed the detailed experimental studies of the anomalous Fermi level structure observed in the forbidden gap region of Na. This was claimed by A. W. Overhauser as the evidence of the charge density wave in the alkali metal. The possibility of this hypothesis is critically discussed against other explanations.

Design and development of a probe-based multiplexed multi-species absorption spectroscopy sensor for characterizing transient gas-parameter distributions in the intake systems of I.C. engines

DOE PAGES

Jatana, Gurneesh; Geckler, Sam; Koeberlein, David; ...

2016-09-01

We designed and developed a 4-probe multiplexed multi-species absorption spectroscopy sensor system for gas property measurements on the intake side of commercial multi-cylinder internal-combustion (I.C.) engines; the resulting cycle- and cylinder-resolved concentration, temperature and pressure measurements are applicable for assessing spatial and temporal variations in the recirculated exhaust gas (EGR) distribution at various locations along the intake gas path, which in turn is relevant to assessing cylinder charge uniformity, control strategies, and CFD models. Furthermore, the diagnostic is based on absorption spectroscopy and includes an H 2O absorption system (utilizing a 1.39 m distributed feedback (DFB) diode laser) for measuringmore » gas temperature, pressure, and H 2O concentration, and a CO 2 absorption system (utilizing a 2.7 m DFB laser) for measuring CO 2 concentration. The various lasers, optical components and detectors were housed in an instrument box, and the 1.39- m and 2.7- m lasers were guided to and from the engine-mounted probes via optical fibers and hollow waveguides, respectively. The 5kHz measurement bandwidth allows for near-crank angle resolved measurements, with a resolution of 1.2 crank angle degrees at 1000 RPM. Our use of compact stainless steel measurement probes enables simultaneous multi-point measurements at various locations on the engine with minimal changes to the base engine hardware; in addition to resolving large-scale spatial variations via simultaneous multi-probe measurements, local spatial gradients can be resolved by translating individual probes. Along with details of various sensor design features and performance, we also demonstrate validation of the spectral parameters of the associated CO 2 absorption transitions using both a multi-pass heated cell and the sensor probes.« less

Room temperature spectrally resolved single-molecule spectroscopy reveals new spectral forms and photophysical versatility of aequorea green fluorescent protein variants.

PubMed

Blum, Christian; Meixner, Alfred J; Subramaniam, Vinod

2004-12-01

It is known from ensemble spectroscopy at cryogenic temperatures that variants of the Aequorea green fluorescent protein (GFP) occur in interconvertible spectroscopically distinct forms which are obscured in ensemble room temperature spectroscopy. By analyzing the fluorescence of the GFP variants EYFP and EGFP by spectrally resolved single-molecule spectroscopy we were able to observe spectroscopically different forms of the proteins and to dynamically monitor transitions between these forms at room temperature. In addition to the predominant EYFP B-form we have observed the blue-shifted I-form thus far only seen at cryogenic temperatures and have followed transitions between these forms. Further we have identified for EYFP and for EGFP three more, so far unknown, forms with red-shifted fluorescence. Transitions between the predominant forms and the red-shifted forms show a dark time which indicates the existence of a nonfluorescent intermediate. The spectral position of the newly-identified red-shifted forms and their formation via a nonfluorescent intermediate hint that these states may account for the possible photoactivation observed in bulk experiments. The comparison of the single-protein spectra of the red-shifted EYFP and EGFP forms with single-molecule fluorescence spectra of DsRed suggest that these new forms possibly originate from an extended chromophoric pi-system analogous to the DsRed chromophore.

Quantifying the cerebral metabolic rate of oxygen by combining diffuse correlation spectroscopy and time-resolved near-infrared spectroscopy.

PubMed

Verdecchia, Kyle; Diop, Mamadou; Lee, Ting-Yim; St Lawrence, Keith

2013-02-01

Preterm infants are highly susceptible to ischemic brain injury; consequently, continuous bedside monitoring to detect ischemia before irreversible damage occurs would improve patient outcome. In addition to monitoring cerebral blood flow (CBF), assessing the cerebral metabolic rate of oxygen (CMRO2) would be beneficial considering that metabolic thresholds can be used to evaluate tissue viability. The purpose of this study was to demonstrate that changes in absolute CMRO2 could be measured by combining diffuse correlation spectroscopy (DCS) with time-resolved near-infrared spectroscopy (TR-NIRS). Absolute CBF was determined using bolus-tracking TR-NIRS to calibrate the DCS measurements. Cerebral venous blood oxygenation (SvO2) was determined by multiwavelength TR-NIRS measurements, the accuracy of which was assessed by directly measuring the oxygenation of sagittal sinus blood. In eight newborn piglets, CMRO2 was manipulated by varying the anesthetics and by injecting sodium cyanide. No significant differences were found between the two sets of SvO2 measurements obtained by TR-NIRS or sagittal sinus blood samples and the corresponding CMRO2 measurements. Bland-Altman analysis showed a mean CMRO2 difference of 0.0268 ± 0.8340 mLO2/100 g/min between the two techniques over a range from 0.3 to 4 mL O2/100 g/min.

Comparison of TiO₂ and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

PubMed

Sobuś, Jan; Burdziński, Gotard; Karolczak, Jerzy; Idígoras, Jesús; Anta, Juan A; Ziółek, Marcin

2014-03-11

Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

Quantifying the cerebral metabolic rate of oxygen by combining diffuse correlation spectroscopy and time-resolved near-infrared spectroscopy

NASA Astrophysics Data System (ADS)

Verdecchia, Kyle; Diop, Mamadou; Lee, Ting-Yim; St. Lawrence, Keith

2013-02-01

Preterm infants are highly susceptible to ischemic brain injury; consequently, continuous bedside monitoring to detect ischemia before irreversible damage occurs would improve patient outcome. In addition to monitoring cerebral blood flow (CBF), assessing the cerebral metabolic rate of oxygen (CMRO2) would be beneficial considering that metabolic thresholds can be used to evaluate tissue viability. The purpose of this study was to demonstrate that changes in absolute CMRO2 could be measured by combining diffuse correlation spectroscopy (DCS) with time-resolved near-infrared spectroscopy (TR-NIRS). Absolute CBF was determined using bolus-tracking TR-NIRS to calibrate the DCS measurements. Cerebral venous blood oxygenation (SvO2) was determined by multiwavelength TR-NIRS measurements, the accuracy of which was assessed by directly measuring the oxygenation of sagittal sinus blood. In eight newborn piglets, CMRO2 was manipulated by varying the anesthetics and by injecting sodium cyanide. No significant differences were found between the two sets of SvO2 measurements obtained by TR-NIRS or sagittal sinus blood samples and the corresponding CMRO2 measurements. Bland-Altman analysis showed a mean CMRO2 difference of 0.0268±0.8340 mL O2/100 g/min between the two techniques over a range from 0.3 to 4 mL O2/100 g/min.

Coinfection of Fusobacterium nucleatum and Actinomyces israelii in Mastoiditis Diagnosed by Next-Generation DNA Sequencing

PubMed Central

Hoogestraat, Daniel R.; Abbott, April N.; SenGupta, Dhruba J.; Cummings, Lisa A.; Butler-Wu, Susan M.; Stephens, Karen; Cookson, Brad T.; Hoffman, Noah G.

2014-01-01

Some bacterial infections involve potentially complex mixtures of species that can now be distinguished using next-generation DNA sequencing. We present a case of mastoiditis where Gram stain, culture, and molecular diagnosis were nondiagnostic or discrepant. Next-generation sequencing implicated coinfection of Fusobacterium nucleatum and Actinomyces israelii, resolving these diagnostic discrepancies. PMID:24574281

Genetic structure of Eurasian and North American Leymus (Triticeae) wildryes assessed by chloroplast DNA sequences and AFLP profiles

Treesearch

C. Mae Culumber; Steve R. Larson; Kevin B. Jensen; Thomas A. Jones

2011-01-01

Leymus is a genomically defined allopolyploid of genus Triticeae with two distinct subgenomes. Chloroplast DNA sequences of Eurasian and North American species are distinct and polyphyletic. However, phylogenies derived from chloroplast and nuclear DNA sequences are confounded by polyploidy and lack of polymorphism among many taxa. The AFLP technique can resolve...

State-to-state rotational energy-transfer measurements in the nu(2) = 1 state of ammonia by infrared-infrared double resonance

NASA Technical Reports Server (NTRS)

Abel, Bernd; Coy, Stephen L.; Klaassen, Jody J.; Steinfeld, Jeffrey I.

1992-01-01

The state-resolved rotational (R-R, R-T) energy transfer in (N-14)H3 (for NH3-NH3 and NH3-Ar collisions) was studied using an IR double-resonance laser spectroscopic technique. Measurements of both the total rate of depopulation by collisions, and the rates of transfer into specific final rovibrational states (v,J,K) were performed using time-resolved tunable diode laser absorption spectroscopy. A kinetic master-equation analysis of time-resolved level populatons was carried out, yielding state-to-state rate constants and propensity rules for NH3-NH3 and NH3-Ar collisions.

SPATIALLY RESOLVED SPECTROSCOPY OF EUROPA’S LARGE-SCALE COMPOSITIONAL UNITS AT 3–4 μ m WITH KECK NIRSPEC

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

Fischer, P. D.; Brown, M. E.; Trumbo, S. K.

2017-01-01

We present spatially resolved spectroscopic observations of Europa’s surface at 3–4 μ m obtained with the near-infrared spectrograph and adaptive optics system on the Keck II telescope. These are the highest quality spatially resolved reflectance spectra of Europa’s surface at 3–4 μ m. The observations spatially resolve Europa’s large-scale compositional units at a resolution of several hundred kilometers. The spectra show distinct features and geographic variations associated with known compositional units; in particular, large-scale leading hemisphere chaos shows a characteristic longward shift in peak reflectance near 3.7 μ m compared to icy regions. These observations complement previous spectra of large-scalemore » chaos, and can aid efforts to identify the endogenous non-ice species.« less

Selective detection of hyperpolarized NMR signals derived from para-hydrogen using the Only Para-hydrogen SpectroscopY (OPSY) approach.

PubMed

Aguilar, Juan A; Adams, Ralph W; Duckett, Simon B; Green, Gary G R; Kandiah, Rathika

2011-01-01

A new family of NMR pulse sequences is reported for the recording of para-hydrogen enhanced NMR spectra. This Only Para-hydrogen SpectroscopY (OPSY) approach uses coherence selection to separate hyperpolarized signals from those of fully relaxed and thermally equilibrated protons. Sequence design, performance, practical aspects and applicability to other hyperpolarization techniques are discussed. Copyright © 2010 Elsevier Inc. All rights reserved.

Prospect of Bioflavonoid Fisetin as a Quadruplex DNA Ligand: A Biophysical Approach

PubMed Central

Sengupta, Bidisha; Pahari, Biswapathik; Blackmon, Laura; Sengupta, Pradeep K.

2013-01-01

Quadruplex (G4) forming sequences in telomeric DNA and c-myc promoter regions of human DNA are associated with tumorogenesis. Ligands that can facilitate or stabilize the formation and increase the stabilization of G4 can prevent tumor cell proliferation and have been regarded as potential anti-cancer drugs. In the present study, steady state and time-resolved fluorescence measurements provide important structural and dynamical insights into the free and bound states of the therapeutically potent plant flavonoid fisetin (3,3′,4′,7-tetrahydroxyflavone) in a G4 DNA matrix. The excited state intra-molecular proton transfer (ESPT) of fisetin plays an important role in observing and understanding the binding of fisetin with the G4 DNA. Differential absorption spectra, thermal melting, and circular dichroism spectroscopic studies provide evidences for the formation of G4 DNA and size exclusion chromatography (SEC) proves the binding and 1∶1 stoichiometry of fisetin in the DNA matrix. Comparative analysis of binding in the presence of EtBr proves that fisetin favors binding at the face of the G-quartet, mostly along the diagonal loop. Time resolved fluorescence anisotropy decay analysis indicates the increase in the restrictions in motion from the free to bound fisetin. We have also investigated the fingerprints of the binding of fisetin in the antiparallel quadruplex using Raman spectroscopy. Preliminary results indicate fisetin to be a prospective candidate as a G4 ligand. PMID:23785423

Initial Results from the Palomar Adaptive Optics Survey of Young Solar-Type Stars: A Brown Dwarf and Three Stellar Companions

NASA Astrophysics Data System (ADS)

Metchev, Stanimir A.; Hillenbrand, Lynne A.

2004-12-01

We present first results from the Palomar Adaptive Optics Survey of Young Stars conducted at the Hale 5 m telescope. Through direct imaging we have discovered a brown dwarf and two low-mass stellar companions to the young solar-type stars HD 49197, HD 129333 (EK Dra), and V522 Per and confirmed a previously suspected companion to RX J0329.1+0118 (Sterzik et al.), at respective separations of 0.95" (43 AU), 0.74" (25 AU), 2.09" (400 AU), and 3.78" (380 AU). Physical association of each binary system is established through common proper motion and/or low-resolution infrared spectroscopy. Based on the companion spectral types, we estimate their masses at 0.06, 0.20, 0.13, and 0.20 Msolar, respectively. From analysis of our imaging data combined with archival radial velocity data, we find that the spatially resolved companion to HD 129333 is potentially identical to the previously identified spectroscopic companion to this star (Duquennoy & Mayor). However, a discrepancy with the absolute magnitude suggests that the two companions could also be distinct, with the resolved one being the outermost component of a triple system. The brown dwarf HD 49197B is a new member of a growing list of directly imaged substellar companions at 10-1000 AU separations from main-sequence stars, indicating that such brown dwarfs may be more common than initially speculated.

A RAD-based phylogenetics for Orestias fishes from Lake Titicaca.

PubMed

Takahashi, Tetsumi; Moreno, Edmundo

2015-12-01

The fish genus Orestias is endemic to the Andes highlands, and Lake Titicaca is the centre of the species diversity of the genus. Previous phylogenetic studies based on a single locus of mitochondrial and nuclear DNA strongly support the monophyly of a group composed of many of species endemic to the Lake Titicaca basin (the Lake Titicaca radiation), but the relationships among the species in the radiation remain unclear. Recently, restriction site-associated DNA (RAD) sequencing, which can produce a vast number of short sequences from various loci of nuclear DNA, has emerged as a useful way to resolve complex phylogenetic problems. To propose a new phylogenetic hypothesis of Orestias fishes of the Lake Titicaca radiation, we conducted a cluster analysis based on morphological similarities among fish samples and a molecular phylogenetic analysis based on RAD sequencing. From a morphological cluster analysis, we recognised four species groups in the radiation, and three of the four groups were resolved as monophyletic groups in maximum-likelihood trees based on RAD sequencing data. The other morphology-based group was not resolved as a monophyletic group in molecular phylogenies, and some members of the group were diverged from its sister group close to the root of the Lake Titicaca radiation. The evolution of these fishes is discussed from the phylogenetic relationships. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Impact of recent molecular phylogenetic studies on classification of ascomycete yeasts

USDA-ARS?s Scientific Manuscript database

Analyses of concatenated gene sequences as well as whole genome sequences are resolving relationships among the ascomycete yeasts (Saccharomycotina), thus allowing classification of members of this subphylum to be based on phylogeny. In addition, changes implemented in the new Botanical Code [Intern...

Diagnostic Suite for HyperV Coaxial Plasma Gun Development for the PLX- α Project

NASA Astrophysics Data System (ADS)

Case, Andrew; Brockington, Sam; Witherspoon, F. Douglas

2015-11-01

We present the diagnostic suite to be used during development of the coaxial guns HyperV will deliver to LANL in support of the ARPA-E Accelerating Low-Cost Plasma Heating And Assembly (ALPHA) program. For plasma jet diagnostics this includes fast photodiodes for velocimetry, a ballistic pendulum for measuring total plasmoid momentum, interferometry for line integrated plasma density, deflectometry for line integrated perpendicular density gradient measurements, and spectroscopy, both time resolved high resolution spectroscopy using a novel detector developed by HyperV and time integrated survey spectroscopy, for measurements of velocity and temperature as well as impurities. In addition, we plan to use fast pressure probes for stagnation pressure, a Faraday cup for density, fast imaging for plume geometry and time integrated imaging for overall light emission. A novel low resolution long record length camera developed by HyperV will also be used for plume diagnostics. For diagnostics of gun operation, we will use Rogowski coils to measure current, voltage dividers for voltages, B-dot probes for magnetic field, and time resolved fast photodiodes to measure plasmoid velocity inside the accelerator. This work supported by the ARPA-E ALPHA program.

Fe-H/D stretching and bending modes in nuclear resonant vibrational, Raman and infrared spectroscopies: Comparisons of density functional theory and experiment

PubMed Central

Pelmenschikov, Vladimir; Guo, Yisong; Wang, Hongxin; Cramer, Stephen P.; Case, David A.

2010-01-01

Infrared, Raman, and nuclear resonant vibrational (NRVS) spectroscopies have been used to address the Fe-H bonding in trans-Fe(H)(CO) iron hydride compound, Fe(H)(CO)(dppe)2, dppe = 1,2-bis(diphenylphosphino)ethane. H and D isotopomers of the compound, with the selective substitution at the metal-coordinated hydrogen, have been considered in order to address the Fe-H/D stretching and bending modes. Experimental results are compared to the normal mode analysis by the density functional theory (DFT). The results are that (i) the IR spectrum does not clearly show Fe–H stretching or bending modes; (ii) Fe–H stretching modes are clear but weak in the Raman spectrum, and Fe–H bending modes are weak; (iii) NRVS 57Fe spectroscopy resolves Fe-H bending clearly, but Fe–H or Fe–D stretching is above its experimentally resolved frequency range. DFT caclulations (with no scaling of frequencies) show intensities and peak locations that allow unambigous correlations between observed and calculated features, with frequency errors generally less than 15 cm−1. Prospects for using these techniques to unravel vibrational modes of protein active sites are discussed. PMID:21322496

A "NIRS" death experience: a reduction in cortical oxygenation by time-resolved near-infrared spectroscopy preceding cardiac arrest.

PubMed

Lanks, C; Kim, C B; Rossiter, H B

2017-09-08

Near-infrared spectroscopy (NIRS) has been used effectively post-cardiac-arrest to gauge adequacy of resuscitation and predict the likelihood of achieving a return of spontaneous circulation. However, preempting hemodynamic collapse is preferable to achieving ROSC through advanced cardiac life support. Minimizing "time down" without end-organ perfusion has always been a central pillar of ACLS. In many critically ill patients there is a prolonged phase of end-organ hypoperfusion preceding loss of palpable pulses and initiation of ACLS. Due to the relative infrequency of in-hospital cardiac arrest, NIRS has not previously evaluated the period immediately prior to hemodynamic collapse. Here we report a young man who suffered a pulseless electrical activity (PEA) arrest while cortical oxygenation was monitored using time-resolved near-infrared spectroscopy. The onset of cortical deoxygenation preceded the loss of palpable pulses by 15 min, suggesting that TRS-NIRS monitoring might provide a means of preempting PEA arrest. Our experience with this patient represents a promising new direction for continuous NIRS monitoring and has the potential to not only predict clinical outcomes, but affect them to the patient's benefit as well.

Charge Transfer Processes in OPV Materials as Revealed by EPR Spectroscopy

DOE PAGES

Niklas, Jens; Poluektov, Oleg

2017-03-03

Understanding charge separation and charge transport at a molecular level is crucial for improving the efficiency of organic photovoltaic (OPV) cells. Under illumination of Bulk Heterojunction (BHJ) blends of polymers and fullerenes, various paramagnetic species are formed including polymer and fullerene radicals, radical pairs, and photoexcited triplet states. Light-induced Electron Paramagnetic Resonance (EPR) spectroscopy is ideally suited to study these states in BHJ due to its selectivity in probing the paramagnetic intermediates. Some advanced EPR techniques like light-induced ENDOR spectroscopy and pulsed techniques allow the determination of hyperfine coupling tensors, while high-frequency EPR allows the EPR signals of the individualmore » species to be resolved and their g-tensors to be determined. In these magnetic resonance parameters reveal details about the delocalization of the positive polaron on the various polymer donors which is important for the efficient charge separation in BHJ systems. Time-resolved EPR can contribute to the study of the dynamics of charge separation, charge transfer and recombination in BHJ by probing the unique spectral signatures of charge transfer and triplet states. Furthermore, the potential of the EPR also allows characterization of the intermediates and products of BHJ degradation.« less

A project based on multi-configuration Dirac-Fock calculations for plasma spectroscopy

NASA Astrophysics Data System (ADS)

Comet, M.; Pain, J.-C.; Gilleron, F.; Piron, R.

2017-09-01

We present a project dedicated to hot plasma spectroscopy based on a Multi-Configuration Dirac-Fock (MCDF) code, initially developed by J. Bruneau. The code is briefly described and the use of the transition state method for plasma spectroscopy is detailed. Then an opacity code for local-thermodynamic-equilibrium plasmas using MCDF data, named OPAMCDF, is presented. Transition arrays for which the number of lines is too large to be handled in a Detailed Line Accounting (DLA) calculation can be modeled within the Partially Resolved Transition Array method or using the Unresolved Transition Arrays formalism in jj-coupling. An improvement of the original Partially Resolved Transition Array method is presented which gives a better agreement with DLA computations. Comparisons with some absorption and emission experimental spectra are shown. Finally, the capability of the MCDF code to compute atomic data required for collisional-radiative modeling of plasma at non local thermodynamic equilibrium is illustrated. In addition to photoexcitation, this code can be used to calculate photoionization, electron impact excitation and ionization cross-sections as well as autoionization rates in the Distorted-Wave or Close Coupling approximations. Comparisons with cross-sections and rates available in the literature are discussed.

Raman scattering spectroscopy for explosives identification

NASA Astrophysics Data System (ADS)

Nagli, L.; Gaft, M.

2007-04-01

Real time detection and identification of explosives at a standoff distance is a major issue in efforts to develop defense against so-called Improvised Explosive Devices (IED). It is recognized that the only technique, which is potentially capable to standoff detection of minimal amounts of explosives is laser-based spectroscopy. LDS technique belongs to trace detection, namely to its micro-particles variety. We applied gated Raman and time-resolved luminescence spectroscopy for detection of main explosive materials, both factory and homemade. Raman system was developed and tested by LDS for field remote detection and identification of minimal amounts of explosives on relevant surfaces at a distance of up to 30 meters.

Raman Spectroscopy Detects Cardiac Allograft Rejection with Molecular Specificity

PubMed Central

Chung, Yoon Gi; Tu, Qiang; Cao, Dianjun; Harada, Shuko; Eisen, Howard J; Chang, Chang

2009-01-01

Abstract Spatially resolved Raman spectroscopy is shown here to be capable of molecular‐specific detection without exogenous labeling. This molecular specificity is achieved by detecting the strong and characteristic Raman spectral signature of an indole derivative, serotonin, whose selective existence in rejected heart transplants serves as the biomarker. The study also corroborates the increasingly recognized role of serotonin receptors in various immune responses, including cardiac allograft rejection. Combining both medical and physical sciences, this work demonstrates the potential use of Raman spectroscopy in replacing the invasive endomyocardial biopsy as the standard for post‐transplantation rejection surveillance and presents a new paradigm in advancing clinical care through interdisciplinary studies. PMID:20443894

Note: Micro-channel array crucible for isotope-resolved laser spectroscopy of high-temperature atomic beams

DOE PAGES

Lebedev, Vyacheslav; Bartlett, Joshua H.; Malyzhenkov, Alexander; ...

2017-12-06

Here, we present a novel compact design for a multichannel atomic oven which generates collimated beams of refractory atoms for fieldable laser spectroscopy. Using this resistively heated crucible, we demonstrate spectroscopy of an erbium sample at 1300 °C with improved isotopic resolution with respect to a single-channel design. In addition, our oven has a high thermal efficiency. By minimizing the surface area of the crucible, we achieve 2000 °C at 140 W of applied electrical power. As a result, the design does not require any active cooling and is compact enough to allow for its incorporation into fieldable instruments.

Conformationally resolved spectroscopy of jet-cooled methacetin

NASA Astrophysics Data System (ADS)

Moon, Cheol Joo; Ahn, Ahreum; Min, Ahreum; Seong, Yeon Guk; Kim, Ju Hyun; Choi, Myong Yong

2017-11-01

The excitation spectra of jet-cooled methacetin (MA) have been measured using a combination of mass-selected resonant two-photon ionization and ultraviolet-ultraviolet hole-burning (UV-UV HB) spectroscopy in the gas phase. Four different UV-UV HB spectra originating from two conformers of MA (syn- and anti-MA) with their fundamental and hot transitions have been obtained. IR-dip spectroscopy has conclusively confirmed the coexistence of the two conformers with the aid of theoretical calculations. Vibronic band assignments in the low frequency region caused by internal methyl group rotation in the methyl-capped peptide group, which originate from the 1e rotational level, are presented.

Background-Limited Infrared-Submillimeter Spectroscopy (BLISS)

NASA Technical Reports Server (NTRS)

Bradford, Charles Matt

2004-01-01

The bulk of the cosmic far-infrared background light will soon be resolved into its individual sources with Spitzer, Astro-F, Herschel, and submm/mm ground-based cameras. The sources will be dusty galaxies at z approximately equal to 1-4. Their physical conditions and processes in these galaxies are directly probed with moderate-resolution spectroscopy from 20 micrometers to 1 mm. Currently large cold telescopes are being combined with sensitive direct detectors, offering the potential for mid-far-IR spectroscopy at the background limit (BLISS). The capability will allow routine observations of even modest high-redshift galaxies in a variety of lines. The BLISS instrument's capabilities are described in this presentation.

Strong and Long Makes Short: Strong-Pump Strong-Probe Spectroscopy.

PubMed

Gelin, Maxim F; Egorova, Dassia; Domcke, Wolfgang

2011-01-20

We propose a new time-domain spectroscopic technique that is based on strong pump and probe pulses. The strong-pump strong-probe (SPSP) technique provides temporal resolution that is not limited by the durations of the pump and probe pulses. By numerically exact simulations of SPSP signals for a multilevel vibronic model, we show that the SPSP signals exhibit electronic and vibrational beatings on time scales which are significantly shorter than the pulse durations. This suggests the possible application of SPSP spectroscopy for the real-time investigation of molecular processes that cannot be temporally resolved by pump-probe spectroscopy with weak pump and probe pulses.

Note: Micro-channel array crucible for isotope-resolved laser spectroscopy of high-temperature atomic beams

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

Lebedev, Vyacheslav; Bartlett, Joshua H.; Malyzhenkov, Alexander

Here, we present a novel compact design for a multichannel atomic oven which generates collimated beams of refractory atoms for fieldable laser spectroscopy. Using this resistively heated crucible, we demonstrate spectroscopy of an erbium sample at 1300 °C with improved isotopic resolution with respect to a single-channel design. In addition, our oven has a high thermal efficiency. By minimizing the surface area of the crucible, we achieve 2000 °C at 140 W of applied electrical power. As a result, the design does not require any active cooling and is compact enough to allow for its incorporation into fieldable instruments.

Validation of a high-power, time-resolved, near-infrared spectroscopy system for measurement of superficial and deep muscle deoxygenation during exercise.

PubMed

Koga, Shunsaku; Barstow, Thomas J; Okushima, Dai; Rossiter, Harry B; Kondo, Narihiko; Ohmae, Etsuko; Poole, David C

2015-06-01

Near-infrared assessment of skeletal muscle is restricted to superficial tissues due to power limitations of spectroscopic systems. We reasoned that understanding of muscle deoxygenation may be improved by simultaneously interrogating deeper tissues. To achieve this, we modified a high-power (∼8 mW), time-resolved, near-infrared spectroscopy system to increase depth penetration. Precision was first validated using a homogenous optical phantom over a range of inter-optode spacings (OS). Coefficients of variation from 10 measurements were minimal (0.5-1.9%) for absorption (μa), reduced scattering, simulated total hemoglobin, and simulated O2 saturation. Second, a dual-layer phantom was constructed to assess depth sensitivity, and the thickness of the superficial layer was varied. With a superficial layer thickness of 1, 2, 3, and 4 cm (μa = 0.149 cm(-1)), the proportional contribution of the deep layer (μa = 0.250 cm(-1)) to total μa was 80.1, 26.9, 3.7, and 0.0%, respectively (at 6-cm OS), validating penetration to ∼3 cm. Implementation of an additional superficial phantom to simulate adipose tissue further reduced depth sensitivity. Finally, superficial and deep muscle spectroscopy was performed in six participants during heavy-intensity cycle exercise. Compared with the superficial rectus femoris, peak deoxygenation of the deep rectus femoris (including the superficial intermedius in some) was not significantly different (deoxyhemoglobin and deoxymyoglobin concentration: 81.3 ± 20.8 vs. 78.3 ± 13.6 μM, P > 0.05), but deoxygenation kinetics were significantly slower (mean response time: 37 ± 10 vs. 65 ± 9 s, P ≤ 0.05). These data validate a high-power, time-resolved, near-infrared spectroscopy system with large OS for measuring the deoxygenation of deep tissues and reveal temporal and spatial disparities in muscle deoxygenation responses to exercise. Copyright © 2015 the American Physiological Society.

Phase-resolved cyclotron spectroscopy of polars

NASA Astrophysics Data System (ADS)

Campbell, Ryan

In this thesis we use phase-resolved cyclotron spectroscopy to study polars. Polars are a subset of cataclysmic variables where the primary WD is highly magnetic. In this case, the accretion flow is constrained along the magnetic field lines and eventually deposited on the WD, where the accreting material interacts with the atmosphere, forming a standing hydrodynamic shock at a location termed the accretion region, and emitting cyclotron radiation. Due to its field strength, cyclotron radiation from polars falls at either UV, optical or NIR wavelengths. While a substantial amount of optical cyclotron spectra have been published on polars, the NIR remains relatively unstudied. In this thesis, we present NIR spectroscopy for fifteen polars. Additionally, while a single cyclotron spectrum is needed to constrain the shock parameters, phase- resolved spectroscopy allows for a more in-depth analysis of the shock structure and the geometry of the accretion region. Of the fifteen polars observed, eight yielded spectra of adequate quality to be modeled in this manner: EF Eri, EQ Cet, AN UMa, VV Pup, AM Her, ST LMi, MR Ser, and MQ Dra. Initially, we used the industry standard "Constant Lambda (CL)" code to model each object. The code is fast, but produces only globally averaged values of the salient shock parameters: B - the magnetic field strength, kT - the plasma temperature, logL - the "size parameter" of the accretion column, and TH- the viewing angle between the observer and the magnetic field. For each object we present CL models for our NIR phase-resolved cyclotron spectra. Subsequently, we use a more advanced "Structured-Shock" code built by Fischer & Beuermann (2001)("F&B") to remodel three objects: EQ Cet, MQ Dra, and EF Eri. The F&B code allows for input of more physical parameters and most importantly does ray tracing through a simulated one-dimensional accretion column. To determine the outgoing spectrum, temperature and velocity profiles are needed to reconstruct the characteristics of the plasma at each location. A substantial effort was made to accurately construct these profiles. Finally, we compare the results of the CL and F&B codes to determine when the extra complexity and significantly longer computational times of F&B modeling are necessary to understand these systems.

Homogeneous and inhomogeneous broadenings and the Voigt line shapes in the phase-resolved and intensity sum-frequency generation vibrational spectroscopy.

PubMed

Chen, Shun-Li; Fu, Li; Gan, Wei; Wang, Hong-Fei

2016-01-21

In this report, we show that the ability to measure the sub-1 cm(-1) resolution phase-resolved and intensity high-resolution broadband sum frequency generation vibrational spectra of the -CN stretch vibration of the Langmuir-Blodgett (LB) monolayer of the 4-n-octyl-4'-cyanobiphenyl (8CB) on the z-cut α-quartz surface allows the direct comparison and understanding of the homogeneous and inhomogeneous broadenings in the imaginary and intensity SFG vibrational spectral line shapes in detail. The difference of the full width at half maximum (FWHM) of the imaginary and intensity sum-frequency generation vibrational spectroscopy spectra of the same vibrational mode is the signature of the Voigt line shape and it measures the relative contribution to the overall line shape from the homogeneous and inhomogeneous broadenings in SFG vibrational spectra. From the phase-resolved and intensity spectra, we found that the FWHM of the 2238.00 ± 0.02 cm(-1) peak in the phase-resolved imaginary and intensity spectra is 19.2 ± 0.2 cm(-1) and 21.6 ± 0.4 cm(-1), respectively, for the -CN group of the 8CB LB monolayer on the z-cut α-quartz crystal surface. The FWHM width difference of 2.4 cm(-1) agrees quantitatively with a Voigt line shape with a homogeneous broadening half width of Γ = 5.29 ± 0.08 cm(-1) and an inhomogeneous standard derivation width Δω = 5.42 ± 0.07 cm(-1). These results shed new lights on the understanding and interpretation of the line shapes of both the phase-resolved and the intensity SFG vibrational spectra, as well as other incoherent and coherent spectroscopic techniques in general.

Fluorescence-suppressed time-resolved Raman spectroscopy of pharmaceuticals using complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector.

PubMed

Rojalin, Tatu; Kurki, Lauri; Laaksonen, Timo; Viitala, Tapani; Kostamovaara, Juha; Gordon, Keith C; Galvis, Leonardo; Wachsmann-Hogiu, Sebastian; Strachan, Clare J; Yliperttula, Marjo

2016-01-01

In this work, we utilize a short-wavelength, 532-nm picosecond pulsed laser coupled with a time-gated complementary metal-oxide semiconductor (CMOS) single-photon avalanche diode (SPAD) detector to acquire Raman spectra of several drugs of interest. With this approach, we are able to reveal previously unseen Raman features and suppress the fluorescence background of these drugs. Compared to traditional Raman setups, the present time-resolved technique has two major improvements. First, it is possible to overcome the strong fluorescence background that usually interferes with the much weaker Raman spectra. Second, using the high photon energy excitation light source, we are able to generate a stronger Raman signal compared to traditional instruments. In addition, observations in the time domain can be performed, thus enabling new capabilities in the field of Raman and fluorescence spectroscopy. With this system, we demonstrate for the first time the possibility of recording fluorescence-suppressed Raman spectra of solid, amorphous and crystalline, and non-photoluminescent and photoluminescent drugs such as caffeine, ranitidine hydrochloride, and indomethacin (amorphous and crystalline forms). The raw data acquired by utilizing only the picosecond pulsed laser and a CMOS SPAD detector could be used for identifying the compounds directly without any data processing. Moreover, to validate the accuracy of this time-resolved technique, we present density functional theory (DFT) calculations for a widely used gastric acid inhibitor, ranitidine hydrochloride. The obtained time-resolved Raman peaks were identified based on the calculations and existing literature. Raman spectra using non-time-resolved setups with continuous-wave 785- and 532-nm excitation lasers were used as reference data. Overall, this demonstration of time-resolved Raman and fluorescence measurements with a CMOS SPAD detector shows promise in diverse areas, including fundamental chemical research, the pharmaceutical setting, process analytical technology (PAT), and the life sciences.

Unresolved versus resolved: testing the validity of young simple stellar population models with VLT/MUSE observations of NGC 3603

NASA Astrophysics Data System (ADS)

Kuncarayakti, H.; Galbany, L.; Anderson, J. P.; Krühler, T.; Hamuy, M.

2016-09-01

Context. Stellar populations are the building blocks of galaxies, including the Milky Way. The majority, if not all, extragalactic studies are entangled with the use of stellar population models given the unresolved nature of their observation. Extragalactic systems contain multiple stellar populations with complex star formation histories. However, studies of these systems are mainly based upon the principles of simple stellar populations (SSP). Hence, it is critical to examine the validity of SSP models. Aims: This work aims to empirically test the validity of SSP models. This is done by comparing SSP models against observations of spatially resolved young stellar population in the determination of its physical properties, that is, age and metallicity. Methods: Integral field spectroscopy of a young stellar cluster in the Milky Way, NGC 3603, was used to study the properties of the cluster as both a resolved and unresolved stellar population. The unresolved stellar population was analysed using the Hα equivalent width as an age indicator and the ratio of strong emission lines to infer metallicity. In addition, spectral energy distribution (SED) fitting using STARLIGHT was used to infer these properties from the integrated spectrum. Independently, the resolved stellar population was analysed using the colour-magnitude diagram (CMD) to determine age and metallicity. As the SSP model represents the unresolved stellar population, the derived age and metallicity were tested to determine whether they agree with those derived from resolved stars. Results: The age and metallicity estimate of NGC 3603 derived from integrated spectroscopy are confirmed to be within the range of those derived from the CMD of the resolved stellar population, including other estimates found in the literature. The result from this pilot study supports the reliability of SSP models for studying unresolved young stellar populations. Based on observations collected at the European Organisation for Astronomical Research in the Southern Hemisphere under ESO programme 60.A-9344.

Variable-temperature Fourier transform near-infrared imaging spectroscopy of the deuterium/hydrogen exchange in liquid D₂O.

PubMed

Unger, Miriam; Ozaki, Yukihiro; Siesler, Heinz W

2014-01-01

In the present publication, the deuterium/hydrogen (D/H) exchange of liquid D2O exposed to water vapor of the surrounding atmosphere has been studied by variable-temperature Fourier transform near-infrared (FT-NIR) imaging spectroscopy. Apart from the visualization of the exchange process in the time-resolved FT-NIR images, kinetic parameters and the activation energy for this D/H exchange reaction have been derived from the Arrhenius plot of the variable-temperature spectroscopic data.

MSLICE Sequencing

NASA Technical Reports Server (NTRS)

Crockett, Thomas M.; Joswig, Joseph C.; Shams, Khawaja S.; Norris, Jeffrey S.; Morris, John R.

2011-01-01

MSLICE Sequencing is a graphical tool for writing sequences and integrating them into RML files, as well as for producing SCMF files for uplink. When operated in a testbed environment, it also supports uplinking these SCMF files to the testbed via Chill. This software features a free-form textural sequence editor featuring syntax coloring, automatic content assistance (including command and argument completion proposals), complete with types, value ranges, unites, and descriptions from the command dictionary that appear as they are typed. The sequence editor also has a "field mode" that allows tabbing between arguments and displays type/range/units/description for each argument as it is edited. Color-coded error and warning annotations on problematic tokens are included, as well as indications of problems that are not visible in the current scroll range. "Quick Fix" suggestions are made for resolving problems, and all the features afforded by modern source editors are also included such as copy/cut/paste, undo/redo, and a sophisticated find-and-replace system optionally using regular expressions. The software offers a full XML editor for RML files, which features syntax coloring, content assistance and problem annotations as above. There is a form-based, "detail view" that allows structured editing of command arguments and sequence parameters when preferred. The "project view" shows the user s "workspace" as a tree of "resources" (projects, folders, and files) that can subsequently be opened in editors by double-clicking. Files can be added, deleted, dragged-dropped/copied-pasted between folders or projects, and these operations are undoable and redoable. A "problems view" contains a tabular list of all problems in the current workspace. Double-clicking on any row in the table opens an editor for the appropriate sequence, scrolling to the specific line with the problem, and highlighting the problematic characters. From there, one can invoke "quick fix" as described above to resolve the issue. Once resolved, saving the file causes the problem to be removed from the problem view.

A versatile optical microscope for time-dependent single-molecule and single-particle spectroscopy

NASA Astrophysics Data System (ADS)

Li, Hao; Yang, Haw

2018-03-01

This work reports the design and implementation of a multi-function optical microscope for time-dependent spectroscopy on single molecules and single nanoparticles. It integrates the now-routine single-object measurements into one standalone platform so that no reconfiguration is needed when switching between different types of sample or spectroscopy modes. The illumination modes include evanescent field through total internal reflection, dark-field illumination, and epi-excitation onto a diffraction-limited spot suitable for confocal detection. The detection modes include spectrally resolved line imaging, wide-field imaging with dual-color capability, and two-color single-element photon-counting detection. The switch between different spectroscopy and data acquisition modes is fully automated and executed through computer programming. The capability of this microscope is demonstrated through selected proof-of-principle experiments.

A versatile optical microscope for time-dependent single-molecule and single-particle spectroscopy.

PubMed

Li, Hao; Yang, Haw

2018-03-28

This work reports the design and implementation of a multi-function optical microscope for time-dependent spectroscopy on single molecules and single nanoparticles. It integrates the now-routine single-object measurements into one standalone platform so that no reconfiguration is needed when switching between different types of sample or spectroscopy modes. The illumination modes include evanescent field through total internal reflection, dark-field illumination, and epi-excitation onto a diffraction-limited spot suitable for confocal detection. The detection modes include spectrally resolved line imaging, wide-field imaging with dual-color capability, and two-color single-element photon-counting detection. The switch between different spectroscopy and data acquisition modes is fully automated and executed through computer programming. The capability of this microscope is demonstrated through selected proof-of-principle experiments.

Solid-state NMR adiabatic TOBSY sequences provide enhanced sensitivity for multidimensional high-resolution magic-angle-spinning 1H MR spectroscopy

NASA Astrophysics Data System (ADS)

Andronesi, Ovidiu C.; Mintzopoulos, Dionyssios; Struppe, Jochem; Black, Peter M.; Tzika, A. Aria

2008-08-01

We propose a solid-state NMR method that maximizes the advantages of high-resolution magic-angle-spinning (HRMAS) applied to intact biopsies when compared to more conventional liquid-state NMR approaches. Theoretical treatment, numerical simulations and experimental results on intact human brain biopsies are presented. Experimentally, it is proven that an optimized adiabatic TOBSY (TOtal through Bond correlation SpectroscopY) solid-state NMR pulse sequence for two-dimensional 1H- 1H homonuclear scalar-coupling longitudinal isotropic mixing provides a 20%-50% improvement in signal-to-noise ratio relative to its liquid-state analogue TOCSY (TOtal Correlation SpectroscopY). For this purpose we have refined the C9151 symmetry-based 13C TOBSY pulse sequence for 1H MRS use and compared it to MLEV-16 TOCSY sequence. Both sequences were rotor-synchronized and implemented using WURST-8 adiabatic inversion pulses. As discussed theoretically and shown in simulations, the improved magnetization-transfer comes from actively removing residual dipolar couplings from the average Hamiltonian. Importantly, the solid-state NMR techniques are tailored to perform measurements at low temperatures where sample degradation is reduced. This is the first demonstration of such a concept for HRMAS metabolic profiling of disease processes, including cancer, from biopsies requiring reduced sample degradation for further genomic analysis.

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

Detecting aromatic compounds on planetary surfaces using ultraviolet time-resolved fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Eshelman, E.; Daly, M. G.; Slater, G.; Cloutis, E.

2018-02-01

Many aromatic organic molecules exhibit strong and characteristic fluorescence when excited with ultraviolet radiation. As laser excitation in the ultraviolet generates both fluorescence and resonantly enhanced Raman scattering of aromatic vibrational modes, combined Raman and fluorescence instruments have been proposed to search for organic compounds on Mars. In this work the time-resolved fluorescence of a suite of 24 compounds composed of 2-5 ringed alternant, non-alternant, and heterocyclic PAHs was measured. Fluorescence instrumentation with similar specifications to a putative flight instrument was capable of observing the fluorescence decay of these compounds with a sub-ns resolution. Incorporating time-resolved capabilities was also found to increase the ability to discriminate between individual PAHs. Incorporating time-resolved fluorescence capabilities into an ultraviolet gated Raman system intended for a rover or lander can increase the ability to detect and characterize PAHs on planetary surfaces.

A Correlated Optical and Gamma Emission from GRB 081126A

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

Gendre, B.; Klotz, A.; CESR, Observatoire Midi-Pyrenees, CNRS, Universite de Toulouse, BP 4346, F-31028-Toulouse Cedex 04

2010-10-15

We present an analysis of time-resolved optical emissions observed from the gamma-ray burst GRB 081126 during the prompt phase. The analysis employed time-resolved photometry using optical data obtained by the TAROT telescope, BAT data from the Swift spacecraft and time-resolved spectroscopy at high energies from the GBM instrument onboard the Fermi spacecraft. The optical emission of GRB 081126 is found to be compatible with the second gamma emission pulse shifted by a positive time-lag of 8.4{+-}3.9 sec. This is the first well resolved observation of a time lag between optical and gamma emissions during a gamma-ray burst. Our observations couldmore » potentially provide new constraints on the fireball model for gamma ray burst early emissions. Furthermore, observations of time-lags between optical and gamma ray photons provides an exciting opportunity to constrain quantum gravity theories.« less

Reevaluating the serotype II capsular locus of Streptococcus agalactiae.

PubMed

Martins, E R; Melo-Cristino, J; Ramirez, M

2007-10-01

We report a novel sequence of the serotype II capsular locus of group B streptococcus that resolves inconsistencies among the results of various groups and the sequence in GenBank. This locus was found in diverse lineages and presents genes consistent with the complete synthesis of the type II polysaccharide.

Comparison of magnetic resonance spectroscopy, proton density fat fraction and histological analysis in the quantification of liver steatosis in children and adolescents

PubMed Central

Di Martino, Michele; Pacifico, Lucia; Bezzi, Mario; Di Miscio, Rossella; Sacconi, Beatrice; Chiesa, Claudio; Catalano, Carlo

2016-01-01

AIM To establish a threshold value for liver fat content between healthy children and those with non-alcoholic fatty liver disease (NAFLD) by using magnetic resonance imaging (MRI), with liver biopsy serving as a reference standard. METHODS The study was approved by the local ethics committee, and written informed consent was obtained from all participants and their legal guardians before the study began. Twenty-seven children with NAFLD underwent liver biopsy to assess the presence of nonalcoholic steatohepatitis. The assessment of liver fat fraction was performed using MRI, with a high field magnet and 2D gradient-echo and multiple-echo T1-weighted sequence with low flip angle and single-voxel point-resolved ¹H MR-Spectroscopy (¹H-MRS), corrected for T1 and T2* decays. Receiver operating characteristic curve analysis was used to determine the best cut-off value. Lin coefficient test was used to evaluate the correlation between histology, MRS and MRI-PDFF. A Mann-Whitney U-test and multivariate analysis were performed to analyze the continuous variables. RESULTS According to MRS, the threshold value between healthy children and those with NAFLD is 6%; using MRI-PDFF, a cut-off value of 3.5% is suggested. The Lin analysis revealed a good fit between the histology and MRS as well as MRI-PDFF. CONCLUSION MRS is an accurate and precise method for detecting NAFLD in children. PMID:27818597

Metabolite proving fungal cleavage of the aromatic core part of a fluoroquinolone antibiotic

PubMed Central

2012-01-01

Liquid cultures of the basidiomycetous fungus Gloeophyllum striatum were employed to study the biodegradation of pradofloxacin, a new veterinary fluoroquinolone antibiotic carrying a CN group at position C-8. After 16 days of incubation, metabolites were purified by micro-preparative high-performance liquid chromatography. Four metabolites could be identified by co-chromatography with chemically synthesized standards. The chemical structures of three compounds were resolved by 1H-nuclear magnetic resonance spectroscopy plus infrared spectroscopy in one case. All metabolites were confirmed by high resolution mass spectrometry-derived molecular formulae. They comprised compounds in which the carboxyl group or the fluorine atom had been exchanged for a hydroxyl group. Furthermore, replacement of the CN group and the intact amine moiety by a hydroxyl group as well as degradation of the amine substituent were observed. The chemical structure of a catechol-type fluoroquinolone metabolite (F-5) could be fully defined for the first time. The latter initiated a hypothetical degradation sequence providing a unique metabolite, F-13, which consisted of the cyclopropyl-substituted pyridone ring still carrying C-7 and C-8 of pradofloxacin, now linked by a double bond and substituted by a hydroxyl and the CN group, respectively. Most likely, all reactions were hydroxyl radical-driven. Metabolite F-13 proves fungal cleavage of the aromatic fluoroquinolone core for the first time. Hence, two decades after the emergence of the notion of the non-biodegradability of fluoroquinolones, fungal degradation of all key structural elements has been proven. PMID:22214407

High-resolution hard x-ray spectroscopy of high-temperature plasmas using an array of quantum microcalorimeters.

PubMed

Thorn, Daniel B; Gu, Ming F; Brown, Greg V; Beiersdorfer, Peter; Porter, F Scott; Kilbourne, Caroline A; Kelley, Richard L

2008-10-01

Quantum microcalorimeters show promise in being able to fully resolve x-ray spectra from heavy highly charged ions, such as would be found in hot plasmas with temperatures in excess of 50 keV. Quantum microcalorimeter arrays are able to achieve this as they have a high-resolving power and good effective quantum efficiency for hard x-ray photons up to 60 keV. To demonstrate this, we present a measurement using an array of thin HgTe quantum microcalorimeters to measure the K-shell spectrum of hydrogenlike through carbonlike praseodymium (Z=57). With this device we are able to attain a resolving power, E/DeltaE, of 1000 at a photon energy of 37 keV.

Fluorescence Lifetime Techniques in Medical Applications

PubMed Central

Marcu, Laura

2012-01-01

This article presents an overview of time-resolved (lifetime) fluorescence techniques used in biomedical diagnostics. In particular, we review the development of time-resolved fluorescence spectroscopy (TRFS) and fluorescence lifetime imaging (FLIM) instrumentation and associated methodologies which allows for in vivo characterization and diagnosis of biological tissues. Emphasis is placed on the translational research potential of these techniques and on evaluating whether intrinsic fluorescence signals provide useful contrast for the diagnosis of human diseases including cancer (gastrointestinal tract, lung, head and neck, and brain), skin and eye diseases, and atherosclerotic cardiovascular disease. PMID:22273730

Path-length-resolved dynamic light scattering in highly scattering random media: The transition to diffusing wave spectroscopy

NASA Astrophysics Data System (ADS)

Bizheva, Kostadinka K.; Siegel, Andy M.; Boas, David A.

1998-12-01

We used low coherence interferometry to measure Brownian motion within highly scattering random media. A coherence gate was applied to resolve the optical path-length distribution and to separate ballistic from diffusive light. Our experimental analysis provides details on the transition from single scattering to light diffusion and its dependence on the system parameters. We found that the transition to the light diffusion regime occurs at shorter path lengths for media with higher scattering anisotropy or for larger numerical aperture of the focusing optics.

Insulator at the ultrathin limit: MgO on Ag(001).

PubMed

Schintke, S; Messerli, S; Pivetta, M; Patthey, F; Libioulle, L; Stengel, M; De Vita, A; Schneider, W D

2001-12-31

The electronic structure and morphology of ultrathin MgO films epitaxially grown on Ag(001) were investigated using low-temperature scanning tunneling spectroscopy and scanning tunneling microscopy. Layer-resolved differential conductance (dI/dU) measurements reveal that, even at a film thickness of three monolayers, a band gap of about 6 eV is formed corresponding to that of the MgO(001) single-crystal surface. This finding is confirmed by layer-resolved calculations of the local density of states based on density functional theory.

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.

Determining the orientation of a chiral substrate using full-hemisphere angle-resolved photoelectron spectroscopy.

PubMed

Tadich, A; Riley, J; Thomsen, L; Cowie, B C C; Gladys, M J

2011-10-21

Chiral interfaces and substrates are of increasing importance in the field of enantioselective chemistry. To fully understand the enantiospecific interactions between chiral adsorbate molecules and the chiral substrate, it is vital that the chiral orientation of the substrate is known. In this Letter we demonstrate that full-hemisphere angle-resolved photoemission permits straightforward identification of the orientation of a chiral surface. The technique can be applied to any solid state system for which photoemission measurements are possible. © 2011 American Physical Society

Direct mapping of ion diffusion times on LiCoO2 surfaces with nanometer resolution

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

Guo, Senli; Jesse, Stephen; Kalnaus, Sergiy

2011-01-01

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

An electro-optic modulator-assisted wavevector-resolving Brillouin light scattering setup.

PubMed

Neumann, T; Schneider, T; Serga, A A; Hillebrands, B

2009-05-01

Brillouin light scattering spectroscopy is a powerful technique which incorporates several extensions such as space-, time-, phase-, and wavevector-resolution. Here, we report on the improvement of the wavevector-resolving setup by including an electro-optic modulator. This provides a reference to calibrate the position of the diaphragm hole which is used for wavevector selection. The accuracy of this calibration is only limited by the accuracy of the wavevector measurement itself. To demonstrate the validity of the approach the wavevectors of dipole-dominated spin waves excited by a microstrip antenna were measured.

DOSY Analysis of Micromolar Analytes: Resolving Dilute Mixtures by SABRE Hyperpolarization.

PubMed

Reile, Indrek; Aspers, Ruud L E G; Tyburn, Jean-Max; Kempf, James G; Feiters, Martin C; Rutjes, Floris P J T; Tessari, Marco

2017-07-24

DOSY is an NMR spectroscopy technique that resolves resonances according to the analytes' diffusion coefficients. It has found use in correlating NMR signals and estimating the number of components in mixtures. Applications of DOSY in dilute mixtures are, however, held back by excessively long measurement times. We demonstrate herein, how the enhanced NMR sensitivity provided by SABRE hyperpolarization allows DOSY analysis of low-micromolar mixtures, thus reducing the concentration requirements by at least 100-fold. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Time-resolved fluorescence decay measurements for flowing particles

DOEpatents

Deka, C.; Steinkamp, J.A.

1999-06-01

Time-resolved fluorescence decay measurements are disclosed for flowing particles. An apparatus and method for the measurement and analysis of fluorescence for individual cells and particles in flow are described, wherein the rapid measurement capabilities of flow cytometry and the robust measurement and analysis procedures of time-domain fluorescence lifetime spectroscopy are combined. A pulse-modulated CW laser is employed for excitation of the particles. The characteristics and the repetition rate of the excitation pulses can be readily adjusted to accommodate for fluorescence decays having a wide range of lifetimes. 12 figs.

Time-resolved fluorescence decay measurements for flowing particles

DOEpatents

Deka, Chiranjit; Steinkamp, John A.

1999-01-01

Time-resolved fluorescence decay measurements for flowing particles. An apparatus and method for the measurement and analysis of fluorescence for individual cells and particles in flow are described, wherein the rapid measurement capabilities of flow cytometry and the robust measurement and analysis procedures of time-domain fluorescence lifetime spectroscopy are combined. A pulse-modulated cw laser is employed for excitation of the particles. The characteristics and the repetition rate of the excitation pulses can be readily adjusted to accommodate for fluorescence decays having a wide range of lifetimes.

Hyperfine-resolved transition frequency list of fundamental vibration bands of H35Cl and H37Cl

NASA Astrophysics Data System (ADS)

Iwakuni, Kana; Sera, Hideyuki; Abe, Masashi; Sasada, Hiroyuki

2014-12-01

Sub-Doppler resolution spectroscopy of the fundamental vibration bands of H35Cl and H37Cl has been carried out from 87.1 to 89.9 THz. We have determined the absolute transition frequencies of the hyperfine-resolved R(0) to R(4) transitions with a typical uncertainty of 10 kHz. We have also yielded six molecular constants for each isotopomer in the vibrational excited state, which reproduce the determined frequencies with a standard deviation of about 10 kHz.

The SuperCam Remote Sensing Suite for MARS 2020: Nested and Co-Aligned LIBS, Raman, and VISIR Spectroscopies, and color micro-imaging

NASA Astrophysics Data System (ADS)

Fouchet, Thierry; Wiens, Roger; Maurice, Sylvestre; Johnson, Jeffrey R.; Clegg, Samuel; Sharma, Shiv; Rull, Fernando; Montmessin, Franck; Anderson, Ryan; Beyssac, Olivier; Bonal, Lydie; Deflores, Lauren; Dromart, Gilles; Fischer, William; Forni, Olivier; Gasnault, Olivier; Grotzinger, John P.; Mangold, Nicolas; Martinez-Frias, Jesus; MacLennan, Scott; McCabe, Kevin; cais, Philippe; Nelson, Tony; Angel, Stanley; Beck, Pierre; Benzerara, Karim; Bernard, Sylvain; Bousquet, Bruno; Bridges, Nathan; Cloutis, Edward; Fabre, Cécile; Grasset, Olivier; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Leveille, Rich; Lewin, Eric; McConnochie, Timothy H.; Melikechi, Noureddine; Meslin, Pierre-Yves; Misra, Anupam; Montagnac, Gilles; Newsom, Horton; Ollila, Ann; Pinet, Patrick; Poulet, Francois; Sobron, Pablo

2016-10-01

As chartered by the Science Definition Team, the Mars 2020 mission addresses four primary objectives: A. Characterize the processes that formed and modified the geologic record within an astrobiologically relevant ancient environment, B. Perform astrobiologically relevant investigations to determine habitability, search for materials with biosignature presentation potential, and search for evidence of past life, C. Assemble a returnable cache of samples and D. Contribute to preparation for human exploration of Mars. The SuperCam instrument, selected for the Mars 2020 rover, as a suite of four instruments, provides nested and co-aligned remote investigations: Laser Induced Breakdown Spectroscopy (LIBS), Raman spectroscopy and time-resolved fluorescence (TRF), visible and near-infrared spectroscopy (VISIR), and high resolution color imaging (RMI). SuperCam appeals broadly to the four Mars 2020 objectives.In detail, SuperCam will perform:1. Microscale mineral identification by combining LIBS elemental and VISIR mineralogical spectroscopies, especially targeting secondary minerals2. Determine the sedimental stratigraphy through color imaging and LIBS and VISIR spectroscopy3. Search for organics and bio-signatures with LIBS and Raman spectroscopy4. Quantify the volatile content of the rocks by LIBS spectroscopy to determine the degree of aquaeous alteration5. Characterize the texture of the rocks by color imaging to determine their alteration processes6. Characterize the rocks' coatings by LIBS spectroscopy7. Characterize the soil and its potential for biosignature preservation8. Monitor the odd-oxygen atmospheric chemistry.To meet these goals SuperCam will perform LIBS spectroscopy on 0.5 mm spot up to 7-meter distance, perform Raman and time-resolved fluoresence up to 12-m distance with a 0.8 mrad angular resolution, a 100 ns time gating in the 534-850 nm spectral range, acquire VISIR spectra in the range 0.4-0.85 μm with a resolution of 0.35 nm, and in the IR range over 1.3-2.6 μm, rich in mineral signatures, with a resolution of 20 nm, and provide RGB images with an angular resolution of 40 μrad over a FOV of 20 mrad.We will present the science performances of SuperCam and the forecasted operation plans.

Ultrafast inter- and intramolecular vibrational energy transfer between molecules at interfaces studied by time- and polarization-resolved SFG spectroscopy.

PubMed

Yamamoto, Susumu; Ghosh, Avishek; Nienhuys, Han-Kwang; Bonn, Mischa

2010-10-28

We present experimental results on femtosecond time-resolved surface vibrational spectroscopy aimed at elucidating the sub-picosecond reorientational dynamics of surface molecules. The approach, which relies on polarization- and time-resolved surface sum frequency generation (SFG), provides a general means to monitor interfacial reorientational dynamics through vibrations inherent in surface molecules in their electronic ground state. The technique requires an anisotropic vibrational excitation of surface molecules using orthogonally polarized infrared excitation light. The decay of the resulting anisotropy is followed in real-time. We employ the technique to reveal the reorientational dynamics of vibrational transition dipoles of long-chain primary alcohols on the water surface, and of water molecules at the water-air interface. The results demonstrate that, in addition to reorientational motion of specific molecules or molecular groups at the interface, inter- and intramolecular energy transfer processes can serve to scramble the initial anisotropy very efficiently. In the two exemplary cases demonstrated here, energy transfer occurs much faster than reorientational motion of interfacial molecules. This has important implications for the interpretation of static SFG spectra. Finally, we suggest experimental schemes and strategies to decouple effects resulting from energy transfer from those associated with surface molecular motion.

Diagnosis of meningioma by time-resolved fluorescence spectroscopy.

PubMed

Butte, Pramod V; Pikul, Brian K; Hever, Aviv; Yong, William H; Black, Keith L; Marcu, Laura

2005-01-01

We investigate the use of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as an adjunctive tool for the intraoperative rapid evaluation of tumor specimens and delineation of tumor from surrounding normal tissue. Tissue autofluorescence is induced with a pulsed nitrogen laser (337 nm, 1.2 ns) and the intensity decay profiles are recorded in the 370 to 500 nm spectral range with a fast digitizer (0.2 ns resolution). Experiments are conducted on excised specimens (meningioma, dura mater, cerebral cortex) from 26 patients (97 sites). Spectral intensities and time-dependent parameters derived from the time-resolved spectra of each site are used for tissue characterization. A linear discriminant analysis algorithm is used for tissue classification. Our results reveal that meningioma is characterized by unique fluorescence characteristics that enable discrimination of tumor from normal tissue with high sensitivity (>89%) and specificity (100%). The accuracy of classification is found to increase (92.8% cases in the training set and 91.8% in the cross-validated set correctly classified) when parameters from both the spectral and the time domain are used for discrimination. Our findings establish the feasibility of using TR-LIFS as a tool for the identification of meningiomas and enables further development of real-time diagnostic tools for analyzing surgical tissue specimens of meningioma or other brain tumors.

Diagnosis of meningioma by time-resolved fluorescence spectroscopy

PubMed Central

Butte, Pramod V.; Pikul, Brian K.; Hever, Aviv; Yong, William H.; Black, Keith L.; Marcu, Laura

2010-01-01

We investigate the use of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) as an adjunctive tool for the intraoperative rapid evaluation of tumor specimens and delineation of tumor from surrounding normal tissue. Tissue autofluorescence is induced with a pulsed nitrogen laser (337 nm, 1.2 ns) and the intensity decay profiles are recorded in the 370 to 500 nm spectral range with a fast digitizer (0.2 ns resolution). Experiments are conducted on excised specimens (meningioma, dura mater, cerebral cortex) from 26 patients (97 sites). Spectral intensities and time-dependent parameters derived from the time-resolved spectra of each site are used for tissue characterization. A linear discriminant analysis algorithm is used for tissue classification. Our results reveal that meningioma is characterized by unique fluorescence characteristics that enable discrimination of tumor from normal tissue with high sensitivity (>89%) and specificity (100%). The accuracy of classification is found to increase (92.8% cases in the training set and 91.8% in the cross-validated set correctly classified) when parameters from both the spectral and the time domain are used for discrimination. Our findings establish the feasibility of using TR-LIFS as a tool for the identification of meningiomas and enables further development of real-time diagnostic tools for analyzing surgical tissue specimens of meningioma or other brain tumors. PMID:16409091

Assessment of electron propagator methods for the simulation of vibrationally-resolved valence and core photoionization spectra

PubMed Central

Baiardi, A.; Paoloni, L.; Barone, V.; Zakrzewski, V.G.; Ortiz, J.V.

2017-01-01

The analysis of photoelectron spectra is usually facilitated by quantum mechanical simulations. Due to the recent improvement of experimental techniques, the resolution of experimental spectra is rapidly increasing, and the inclusion of vibrational effects is usually mandatory to obtain a reliable reproduction of the spectra. With the aim of defining a robust computational protocol, a general time-independent formulation to compute different kinds of vibrationally-resolved electronic spectra has been generalized to support also photoelectron spectroscopy. The electronic structure data underlying the simulation are computed using different electron propagator approaches. In addition to the more standard approaches, a new and robust implementation of the second-order self-energy approximation of the electron propagator based on a transition operator reference (TOEP2) is presented. To validate our implementation, a series of molecules has been used as test cases. The result of the simulations shows that, for ultraviolet photoionization spectra, the more accurate non-diagonal approaches are needed to obtain a reliable reproduction of vertical ionization energies, but diagonal approaches are sufficient for energy gradients and pole strengths. For X-ray photoelectron spectroscopy, the TOEP2 approach, besides being more efficient, is also the most accurate in the reproduction of both vertical ionization energies and vibrationally-resolved bandshapes. PMID:28521087

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Elevation or Suppression? The Resolved Star Formation Main Sequence of Galaxies with Two Different Assembly Modes

NASA Astrophysics Data System (ADS)

Liu, Qing; Wang, Enci; Lin, Zesen; Gao, Yulong; Liu, Haiyang; Berhane Teklu, Berzaf; Kong, Xu

2018-04-01

We investigate the spatially resolved star formation main sequence in star-forming galaxies using Integral Field Spectroscopic observations from the Mapping Nearby Galaxies at the Apache Point Observatory survey. We demonstrate that the correlation between the stellar mass surface density (Σ*) and star formation rate surface density (ΣSFR) holds down to the sub-galactic scale, leading to the sub-galactic main sequence (SGMS). By dividing galaxies into two populations based on their recent mass assembly modes, we find the resolved main sequence in galaxies with the “outside-in” mode is steeper than that in galaxies with the “inside-out” mode. This is also confirmed on a galaxy-by-galaxy level, where we find the distributions of SGMS slopes for individual galaxies are clearly separated for the two populations. When normalizing and stacking the SGMS of individual galaxies on one panel for the two populations, we find that the inner regions of galaxies with the “inside-out” mode statistically exhibit a suppression in star formation, with a less significant trend in the outer regions of galaxies with the “outside-in” mode. In contrast, the inner regions of galaxies with “outside-in” mode and the outer regions of galaxies with “inside-out” mode follow a slightly sublinear scaling relation with a slope ∼0.9, which is in good agreement with previous findings, suggesting that they are experiencing a universal regulation without influences of additional physical processes.

G-rich telomeric and ribosomal DNA sequences from the fission yeast genome form stable G-quadruplex DNA structures in vitro and are unwound by the Pfh1 DNA helicase

PubMed Central

Wallgren, Marcus; Mohammad, Jani B.; Yan, Kok-Phen; Pourbozorgi-Langroudi, Parham; Ebrahimi, Mahsa; Sabouri, Nasim

2016-01-01

Certain guanine-rich sequences have an inherent propensity to form G-quadruplex (G4) structures. G4 structures are e.g. involved in telomere protection and gene regulation. However, they also constitute obstacles during replication if they remain unresolved. To overcome these threats to genome integrity, organisms harbor specialized G4 unwinding helicases. In Schizosaccharomyces pombe, one such candidate helicase is Pfh1, an evolutionarily conserved Pif1 homolog. Here, we addressed whether putative G4 sequences in S. pombe can adopt G4 structures and, if so, whether Pfh1 can resolve them. We tested two G4 sequences, derived from S. pombe ribosomal and telomeric DNA regions, and demonstrated that they form inter- and intramolecular G4 structures, respectively. Also, Pfh1 was enriched in vivo at the ribosomal G4 DNA and telomeric sites. The nuclear isoform of Pfh1 (nPfh1) unwound both types of structure, and although the G4-stabilizing compound Phen-DC3 significantly enhanced their stability, nPfh1 still resolved them efficiently. However, stable G4 structures significantly inhibited adenosine triphosphate hydrolysis by nPfh1. Because ribosomal and telomeric DNA contain putative G4 regions conserved from yeasts to humans, our studies support the important role of G4 structure formation in these regions and provide further evidence for a conserved role for Pif1 helicases in resolving G4 structures. PMID:27185885

Plastome sequences and exploration of tree-space help to resolve the phylogeny of riceflowers (Thymelaeaceae: Pimelea).

PubMed

Foster, Charles S P; Henwood, Murray J; Ho, Simon Y W

2018-05-25

Data sets comprising small numbers of genetic markers are not always able to resolve phylogenetic relationships. This has frequently been the case in molecular systematic studies of plants, with many analyses being based on sequence data from only two or three chloroplast genes. An example of this comes from the riceflowers Pimelea Banks & Sol. ex Gaertn. (Thymelaeaceae), a large genus of flowering plants predominantly distributed in Australia. Despite the considerable morphological variation in the genus, low sequence divergence in chloroplast markers has led to the phylogeny of Pimelea remaining largely uncertain. In this study, we resolve the backbone of the phylogeny of Pimelea in comprehensive Bayesian and maximum-likelihood analyses of plastome sequences from 41 taxa. However, some relationships received only moderate to poor support, and the Pimelea clade contained extremely short internal branches. By using topology-clustering analyses, we demonstrate that conflicting phylogenetic signals can be found across the trees estimated from individual chloroplast protein-coding genes. A relaxed-clock dating analysis reveals that Pimelea arose in the mid-Miocene, with most divergences within the genus occurring during a subsequent rapid diversification. Our new phylogenetic estimate offers better resolution and is more strongly supported than previous estimates, providing a platform for future taxonomic revisions of both Pimelea and the broader subfamily. Our study has demonstrated the substantial improvements in phylogenetic resolution that can be achieved using plastome-scale data sets in plant molecular systematics. Copyright © 2018 Elsevier Inc. All rights reserved.

A Phylogenomic Perspective on the Radiation of Ray-Finned Fishes Based upon Targeted Sequencing of Ultraconserved Elements (UCEs)

PubMed Central

Sorenson, Laurie; Santini, Francesco

2013-01-01

Ray-finned fishes constitute the dominant radiation of vertebrates with over 32,000 species. Although molecular phylogenetics has begun to disentangle major evolutionary relationships within this vast section of the Tree of Life, there is no widely available approach for efficiently collecting phylogenomic data within fishes, leaving much of the enormous potential of massively parallel sequencing technologies for resolving major radiations in ray-finned fishes unrealized. Here, we provide a genomic perspective on longstanding questions regarding the diversification of major groups of ray-finned fishes through targeted enrichment of ultraconserved nuclear DNA elements (UCEs) and their flanking sequence. Our workflow efficiently and economically generates data sets that are orders of magnitude larger than those produced by traditional approaches and is well-suited to working with museum specimens. Analysis of the UCE data set recovers a well-supported phylogeny at both shallow and deep time-scales that supports a monophyletic relationship between Amia and Lepisosteus (Holostei) and reveals elopomorphs and then osteoglossomorphs to be the earliest diverging teleost lineages. Our approach additionally reveals that sequence capture of UCE regions and their flanking sequence offers enormous potential for resolving phylogenetic relationships within ray-finned fishes. PMID:23824177

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

PubMed

Jalilov, Almaz S; Young, Ryan M; Eaton, Samuel W; Wasielewski, Michael R; Lewis, Frederick D

2015-01-01

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases. © 2014 The American Society of Photobiology.

Real-time bilinear rotation decoupling in absorptive mode J-spectroscopy: Detecting low-intensity metabolite peak close to high-intensity metabolite peak with convenience.

PubMed

Verma, Ajay; Baishya, Bikash

2016-05-01

"Pure shift" NMR spectra display singlet peak per chemical site. Thus, high resolution is offered at the cost of valuable J-coupling information. In the present work, real-time BIRD (BIlinear Rotation Decoupling) is applied to the absorptive-mode 2D J-spectroscopy to provide pure shift spectrum in the direct dimension and J-coupling information in the indirect dimension. Quite often in metabolomics, proton NMR spectra from complex bio-fluids display tremendous signal overlap. Although conventional J-spectroscopy in principle overcomes this problem by separating the multiplet information from chemical shift information, however, only magnitude mode of the experiment is practical, sacrificing much of the potential high resolution that could be achieved. Few J-spectroscopy methods have been reported so far that produce high-resolution pure shift spectrum along with J-coupling information for crowded spectral regions. In the present work, high-quality J-resolved spectrum from important metabolomic mixture such as tissue extract from rat cortex is demonstrated. Many low-intensity metabolite peaks which are obscured by the broad dispersive tails from high-intensity metabolite peaks in regular magnitude mode J-spectrum can be clearly identified in real-time BIRD J-resolved spectrum. The general practice of removing such spectral overlap is tedious and time-consuming as it involves repeated sample preparation to change the pH of the tissue extract sample and subsequent spectra recording. Copyright © 2016 Elsevier Inc. All rights reserved.

High density plasmas and new diagnostics: An overview (invited).

PubMed

Celona, L; Gammino, S; Mascali, D

2016-02-01

One of the limiting factors for the full understanding of Electron Cyclotron Resonance Ion Sources (ECRISs) fundamental mechanisms consists of few types of diagnostic tools so far available for such compact machines. Microwave-to-plasma coupling optimisation, new methods of density overboost provided by plasma wave generation, and magnetostatic field tailoring for generating a proper electron energy distribution function, suitable for optimal ion beams formation, require diagnostic tools spanning across the entire electromagnetic spectrum from microwave interferometry to X-ray spectroscopy; these methods are going to be implemented including high resolution and spatially resolved X-ray spectroscopy made by quasi-optical methods (pin-hole cameras). The ion confinement optimisation also requires a complete control of cold electrons displacement, which can be performed by optical emission spectroscopy. Several diagnostic tools have been recently developed at INFN-LNS, including "volume-integrated" X-ray spectroscopy in low energy domain (2-30 keV, by using silicon drift detectors) or high energy regime (>30 keV, by using high purity germanium detectors). For the direct detection of the spatially resolved spectral distribution of X-rays produced by the electronic motion, a "pin-hole camera" has been developed also taking profit from previous experiences in the ECRIS field. The paper will give an overview of INFN-LNS strategy in terms of new microwave-to-plasma coupling schemes and advanced diagnostics supporting the design of new ion sources and for optimizing the performances of the existing ones, with the goal of a microwave-absorption oriented design of future machines.

Tempo-spatially resolved scattering correlation spectroscopy under dark-field illumination and its application to investigate dynamic behaviors of gold nanoparticles in live cells.

PubMed

Liu, Heng; Dong, Chaoqing; Ren, Jicun

2014-02-19

In this study, a new tempo-spatially resolved fluctuation spectroscopy under dark-field illumination is described, named dark-field illumination-based scattering correlation spectroscopy (DFSCS). DFSCS is a single-particle method, whose principle is similar to that of fluorescence correlation spectroscopy (FCS). DFSCS correlates the fluctuations of the scattered light from single nanoparticle under dark-field illumination. We developed a theoretical model for translational diffusion of nanoparticles in DFSCS system. The results of computer simulations documented that this model was able to well describe the diffusion behaviors of nanoparticles in uniformly illuminated field. The experimental setup of DFSCS was achieved by introducing a dark-field condenser to the frequently used bright-field microscope and an electron multiplying charge-coupled device (EMCCD) as the array detector. In the optimal condition, a stack of 500 000 frames were collected simultaneously on 64 detection channels for a single measurement with acquisition rate of 0.5 ms per frame. We systematically investigated the effect of certain factors such as particle concentration, viscosity of the solution, and heterogeneity of gold nanoparticles (GNPs) samples on DFSCS measurements. The experiment data confirmed theoretical model proposed. Furthermore, this new method was successfully used for investigating dynamic behaviors of GNPs in live cells. Our preliminary results demonstrate that DFSCS is a practical and affordable tool for ordinary laboratories to investigate the dynamic information of nanoparticles in vitro as well as in vivo.

Real-time bilinear rotation decoupling in absorptive mode J-spectroscopy: Detecting low-intensity metabolite peak close to high-intensity metabolite peak with convenience

NASA Astrophysics Data System (ADS)

Verma, Ajay; Baishya, Bikash

2016-05-01

;Pure shift; NMR spectra display singlet peak per chemical site. Thus, high resolution is offered at the cost of valuable J-coupling information. In the present work, real-time BIRD (BIlinear Rotation Decoupling) is applied to the absorptive-mode 2D J-spectroscopy to provide pure shift spectrum in the direct dimension and J-coupling information in the indirect dimension. Quite often in metabolomics, proton NMR spectra from complex bio-fluids display tremendous signal overlap. Although conventional J-spectroscopy in principle overcomes this problem by separating the multiplet information from chemical shift information, however, only magnitude mode of the experiment is practical, sacrificing much of the potential high resolution that could be achieved. Few J-spectroscopy methods have been reported so far that produce high-resolution pure shift spectrum along with J-coupling information for crowded spectral regions. In the present work, high-quality J-resolved spectrum from important metabolomic mixture such as tissue extract from rat cortex is demonstrated. Many low-intensity metabolite peaks which are obscured by the broad dispersive tails from high-intensity metabolite peaks in regular magnitude mode J-spectrum can be clearly identified in real-time BIRD J-resolved spectrum. The general practice of removing such spectral overlap is tedious and time-consuming as it involves repeated sample preparation to change the pH of the tissue extract sample and subsequent spectra recording.

Pump-Probe Fragmentation Action Spectroscopy: A Powerful Tool to Unravel Light-Induced Processes in Molecular Photocatalysts.

PubMed

Imanbaew, Dimitri; Lang, Johannes; Gelin, Maxim F; Kaufhold, Simon; Pfeffer, Michael G; Rau, Sven; Riehn, Christoph

2017-05-08

We present a proof of concept that ultrafast dynamics combined with photochemical stability information of molecular photocatalysts can be acquired by electrospray ionization mass spectrometry combined with time-resolved femtosecond laser spectroscopy in an ion trap. This pump-probe "fragmentation action spectroscopy" gives straightforward access to information that usually requires high purity compounds and great experimental efforts. Results of gas-phase studies on the electronic dynamics of two supramolecular photocatalysts compare well to previous findings in solution and give further evidence for a directed electron transfer, a key process for photocatalytic hydrogen generation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Application of near-infrared diffuse reflectance spectroscopy to the detection and identification of transgenic corn].

PubMed

Rui, Yu-kui; Luo, Yun-bo; Huang, Kun-lun; Wang, Wei-min; Zhang, Lu-da

2005-10-01

With the rapid development of the GMO, more and more GMO food has been pouring into the market. Much attention has been paid to GMO labeling under the controversy of GMO safety. Transgenic corns and their parents were scanned by continuous wave of near infrared diffuse reflectance spectroscopy range of 12000-4000 cm(-1); the resolution was 4 cm(-1); scanning was carried out for 64 times; BP algorithm was applied for data processing. The GMO food was easily resolved. Near-infrared diffuse reflectance spectroscopy is unpolluted and inexpensive compared with PCR and ELISA, so it is a very promising detection method for GMO food.

Informational structure of genetic sequences and nature of gene splicing

NASA Astrophysics Data System (ADS)

Trifonov, E. N.

1991-10-01

Only about 1/20 of DNA of higher organisms codes for proteins, by means of classical triplet code. The rest of DNA sequences is largely silent, with unclear functions, if any. The triplet code is not the only code (message) carried by the sequences. There are three levels of molecular communication, where the same sequence ``talks'' to various bimolecules, while having, respectively, three different appearances: DNA, RNA and protein. Since the molecular structures and, hence, sequence specific preferences of these are substantially different, the original DNA sequence has to carry simultaneously three types of sequence patterns (codes, messages), thus, being a composite structure in which one had the same letter (nucleotide) is frequently involved in several overlapping codes of different nature. This multiplicity and overlapping of the codes is a unique feature of the Gnomic, language of genetic sequences. The coexisting codes have to be degenerate in various degrees to allow an optimal and concerted performance of all the encoded functions. There is an obvious conflict between the best possible performance of a given function and necessity to compromise the quality of a given sequence pattern in favor of other patterns. It appears that the major role of various changes in the sequences on their ``ontogenetic'' way from DNA to RNA to protein, like RNA editing and splicing, or protein post-translational modifications is to resolve such conflicts. New data are presented strongly indicating that the gene splicing is such a device to resolve the conflict between the code of DNA folding in chromatin and the triplet code for protein synthesis.

Finding the hidden valence band of N  =  7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Senkovskiy, Boris V.; Usachov, Dmitry Yu; Fedorov, Alexander V.; Haberer, Danny; Ehlen, Niels; Fischer, Felix R.; Grüneis, Alexander

2018-07-01

To understand the optical and transport properties of graphene nanoribbons, an unambiguous determination of their electronic band structure is needed. In this work we demonstrate that the photoemission intensity of each valence sub-band, formed due to the quantum confinement in quasi-one-dimensional (1D) graphene nanoribbons, is a peaked function of the two-dimensional (2D) momentum. We resolve the long-standing discrepancy regarding the valence band effective mass () of armchair graphene nanoribbons with a width of N  =  7 carbon atoms (7-AGNRs). In particular, angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy report   ≈0.2 and  ≈0.4 of the free electron mass (m e ), respectively. ARPES mapping in the full 2D momentum space identifies the experimental conditions for obtaining a large intensity for each of the three highest valence 1D sub-bands. Our detail map reveals that previous ARPES experiments have incorrectly assigned the second sub-band as the frontier one. The correct frontier valence sub-band for 7-AGNRs is only visible in a narrow range of emission angles. For this band we obtain an ARPES derived effective mass of 0.4 m e , a charge carrier velocity in the linear part of the band of 0.63  ×  106 m s‑1 and an energy separation of only  ≈60 meV to the second sub-band. Our results are of importance not only for the growing research field of graphene nanoribbons but also for the community, which studies quantum confined systems.

The KMOS3D Survey: Design, First Results, and the Evolution of Galaxy Kinematics from 0.7 <= z <= 2.7

NASA Astrophysics Data System (ADS)

Wisnioski, E.; Förster Schreiber, N. M.; Wuyts, S.; Wuyts, E.; Bandara, K.; Wilman, D.; Genzel, R.; Bender, R.; Davies, R.; Fossati, M.; Lang, P.; Mendel, J. T.; Beifiori, A.; Brammer, G.; Chan, J.; Fabricius, M.; Fudamoto, Y.; Kulkarni, S.; Kurk, J.; Lutz, D.; Nelson, E. J.; Momcheva, I.; Rosario, D.; Saglia, R.; Seitz, S.; Tacconi, L. J.; van Dokkum, P. G.

2015-02-01

We present the KMOS3D survey, a new integral field survey of over 600 galaxies at 0.7 < z < 2.7 using KMOS at the Very Large Telescope. The KMOS3D survey utilizes synergies with multi-wavelength ground- and space-based surveys to trace the evolution of spatially resolved kinematics and star formation from a homogeneous sample over 5 Gyr of cosmic history. Targets, drawn from a mass-selected parent sample from the 3D-HST survey, cover the star formation-stellar mass (M *) and rest-frame (U - V) - M * planes uniformly. We describe the selection of targets, the observations, and the data reduction. In the first-year of data we detect Hα emission in 191 M * = 3 × 109-7 × 1011 M ⊙ galaxies at z = 0.7-1.1 and z = 1.9-2.7. In the current sample 83% of the resolved galaxies are rotation dominated, determined from a continuous velocity gradient and v rot/σ0 > 1, implying that the star-forming "main sequence" is primarily composed of rotating galaxies at both redshift regimes. When considering additional stricter criteria, the Hα kinematic maps indicate that at least ~70% of the resolved galaxies are disk-like systems. Our high-quality KMOS data confirm the elevated velocity dispersions reported in previous integral field spectroscopy studies at z >~ 0.7. For rotation-dominated disks, the average intrinsic velocity dispersion decreases by a factor of two from 50 km s-1at z ~ 2.3 to 25 km s-1at z ~ 0.9. Combined with existing results spanning z ~ 0-3, we show that disk velocity dispersions follow an evolution that is consistent with the dependence of velocity dispersion on gas fractions predicted by marginally stable disk theory. Based on observations obtained at the Very Large Telescope (VLT) of the European Southern Observatory (ESO), Paranal, Chile (ESO program IDS 092A-0091, 093.A-0079).

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.

High-order multilayer coated blazed gratings for high resolution soft x-ray spectroscopy

DOE PAGES

Voronov, Dmitriy L.; Goray, Leonid I.; Warwick, Tony; ...

2015-02-17

A grand challenge in soft x-ray spectroscopy is to drive the resolving power of monochromators and spectrometers from the 10 4 achieved routinely today to well above 10 5. This need is driven mainly by the requirements of a new technique that is set to have enormous impact in condensed matter physics, Resonant Inelastic X-ray Scattering (RIXS). Unlike x-ray absorption spectroscopy, RIXS is not limited by an energy resolution dictated by the core-hole lifetime in the excitation process. Using much higher resolving power than used for normal x-ray absorption spectroscopy enables access to the energy scale of soft excitations inmore » matter. These excitations such as magnons and phonons drive the collective phenomena seen in correlated electronic materials such as high temperature superconductors. RIXS opens a new path to study these excitations at a level of detail not formerly possible. However, as the process involves resonant excitation at an energy of around 1 keV, and the energy scale of the excitations one would like to see are at the meV level, to fully utilize the technique requires the development of monochromators and spectrometers with one to two orders of magnitude higher energy resolution than has been conventionally possible. Here we investigate the detailed diffraction characteristics of multilayer blazed gratings. These elements offer potentially revolutionary performance as the dispersive element in ultra-high resolution x-ray spectroscopy. In doing so, we have established a roadmap for the complete optimization of the grating design. Traditionally 1st order gratings are used in the soft x-ray region, but we show that as in the optical domain, one can work in very high spectral orders and thus dramatically improve resolution without significant loss in efficiency.« less

Planetary surface exploration using Raman spectroscopy for minerals and organics

NASA Astrophysics Data System (ADS)

Blacksberg, J.; Alerstam, E.; Maruyama, Y.; Charbon, E.; Rossman, G. R.; Shkolyar, S.; Farmer, J. D.

2013-12-01

Raman spectroscopy has been identified as one of the primary techniques for planetary surface mineralogy. It is widely used as a laboratory technique since it can identify nearly all crystalline mineral phases. Using a small spot size on the surface (on the order of a micron), mineral phases can be mapped onto microscopic images preserving information about surface morphology. As a result, this technique has been steadily gaining support for in situ exploration of a variety of target bodies, for example Mars, the Moon, Venus, asteroids, and comets. In addition to in situ exploration, Raman spectroscopy has been identified as a feasible means for pre-selection of samples on Mars for subsequent return to Earth. This is in part due to the fact that Raman can detect many organics in addition to minerals. As a result, the most relevant rock samples containing organics (potentially fossil biosignatures) may potentially be selected for return to Earth. We present a next-generation instrument that builds on the widely used 532 nm Raman technique to provide a means for performing Raman spectroscopy without the background noise that is often generated by fluorescence of minerals and organics. We use time-resolved laser spectroscopy to eliminate this fluorescence interference that can often make it difficult or impossible to obtain Raman spectra. We will discuss significant advances leading to the feasibility of a compact time-resolved spectrometer, including the development of a new solid-state detector capable of sub-ns temporal resolution. We will address the challenges of analyzing surface materials, often organics, that exhibit short-lifetime fluorescence. We will present result on planetary analog samples to demonstrate the instrument performance including fluorescence rejection.

Chloroplast phylogenomic analyses resolve deep-level relationships of an intractable bamboo tribe Arundinarieae (poaceae).

PubMed

Ma, Peng-Fei; Zhang, Yu-Xiao; Zeng, Chun-Xia; Guo, Zhen-Hua; Li, De-Zhu

2014-11-01

The temperate woody bamboos constitute a distinct tribe Arundinarieae (Poaceae: Bambusoideae) with high species diversity. Estimating phylogenetic relationships among the 11 major lineages of Arundinarieae has been particularly difficult, owing to a possible rapid radiation and the extremely low rate of sequence divergence. Here, we explore the use of chloroplast genome sequencing for phylogenetic inference. We sampled 25 species (22 temperate bamboos and 3 outgroups) for the complete genome representing eight major lineages of Arundinarieae in an attempt to resolve backbone relationships. Phylogenetic analyses of coding versus noncoding sequences, and of different regions of the genome (large single copy and small single copy, and inverted repeat regions) yielded no well-supported contradicting topologies but potential incongruence was found between the coding and noncoding sequences. The use of various data partitioning schemes in analysis of the complete sequences resulted in nearly identical topologies and node support values, although the partitioning schemes were decisively different from each other as to the fit to the data. Our full genomic data set substantially increased resolution along the backbone and provided strong support for most relationships despite the very short internodes and long branches in the tree. The inferred relationships were also robust to potential confounding factors (e.g., long-branch attraction) and received support from independent indels in the genome. We then added taxa from the three Arundinarieae lineages that were not included in the full-genome data set; each of these were sampled for more than 50% genome sequences. The resulting trees not only corroborated the reconstructed deep-level relationships but also largely resolved the phylogenetic placements of these three additional lineages. Furthermore, adding 129 additional taxa sampled for only eight chloroplast loci to the combined data set yielded almost identical relationships, albeit with low support values. We believe that the inferred phylogeny is robust to taxon sampling. Having resolved the deep-level relationships of Arundinarieae, we illuminate how chloroplast phylogenomics can be used for elucidating difficult phylogeny at low taxonomic levels in intractable plant groups. © The Author(s) 2014. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Testing deep reticulate evolution in Amaryllidaceae Tribe Hippeastreae (Asparagales) with ITS and chloroplast sequence data

USDA-ARS?s Scientific Manuscript database

The phylogeny of Amaryllidaceae tribe Hippeastreae was inferred using chloroplast (3’ycf1, ndhF, trnL-F) and nuclear (ITS rDNA) sequence data under maximum parsimony and maximum likelihood frameworks. Network analyses were applied to resolve conflicting signals among data sets and putative scenarios...

Increasing phylogenetic resolution at low taxonomic levels using massively parallel sequencing of chloroplast genomes

Treesearch

Matthew Parks; Richard Cronn; Aaron Liston

2009-01-01

We reconstruct the infrageneric phylogeny of Pinus from 37 nearly-complete chloroplast genomes (average 109 kilobases each of an approximately 120 kilobase genome) generated using multiplexed massively parallel sequencing. We found that 30/33 ingroup nodes resolved wlth > 95-percent bootstrap support; this is a substantial improvement relative...

Ex vivo measurement of postmortem tissue changes in the crystalline lens by Brillouin spectroscopy and confocal reflectance microscopy.

PubMed

Reiss, Stephan; Sperlich, K; Hovakimyan, M; Martius, P; Guthoff, R F; Stolz, H; Stachs, O

2012-08-01

Use of Brillouin spectroscopy in ophthalmology enables noninvasive, spatially resolved determination of the rheological properties of crystalline lens tissue. Furthermore, the Brillouin shift correlates with the protein concentration inside the lens. In vitro measurements on extracted porcine lenses demonstrate that results obtained with Brillouin spectroscopy depend strongly on time after death. The intensity of the Brillouin signal decreases significantly as early as 5 h postmortem. Moreover, the fluctuation of the Brillouin frequency shift inside the lens increases with postmortem time. Images of lens tissue taken with a confocal reflectance microscope between measurements reveal a degenerative aging process. These tissue changes correlate with our results from Brillouin spectroscopy. It is concluded that only in vivo measurements appropriately reflect the rheological properties of the eye lens and its protein concentration.

Interaction of recombinant human epidermal growth factor with phospholipid vesicles. A steady-state and time-resolved fluorescence study of the bis-tryptophan sequence (Trp49-Trp50).

PubMed

Li De La Sierra, I M; Vincent, M; Padron, G; Gallay, J

1992-01-01

The interaction of recombinant human epidermal growth factor with small unilamellar phospholipid vesicles was studied by steady-state and time-resolved fluorescence of the bis-tryptophan sequence (Trp49-Trp50). Steady-state anisotropy measurements demonstrate that strong binding occurred with small unilamellar vesicles made up of acidic phospholipids at acidic pH only (pH < or = 4.7). An apparent stoichiometry for 1,2-dimyristoyl-sn-phosphoglycerol of about 12 phospholipid molecules per molecule of human epidermal growth factor was estimated. The binding appears to be more efficient at temperatures above the gel to liquid-crystalline phase transition. The conformation and the environment of the Trp-Trp sequence are not greatly modified after binding, as judged from the invariance of the excited state lifetime distribution and from that of the fast processes affecting the anisotropy decay. This suggests that the Trp-Trp sequence is not embedded within the bilayer, in contrast to the situation in surfactant micelles (Mayo et al. 1987; Kohda and Inigaki 1992).

CONTINUOUS FORMALDEHYDE MEASUREMENT SYSTEM BASED ON MODIFIED FOURIER TRANSFORM INFRARED SPECTROSCOPY

EPA Science Inventory

EPA is developing advanced open-path and cell-based optical techniques for time-resolved measurement of priority hazardous air pollutants such as formaldehyde (HCHO). Due to its high National Air Toxics Assessment risk factor, there is increasing interest in continuous measuremen...

Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations

DOE PAGES

Zheng, Kaibo; Chen, Yani; Sun, Yong; ...

2018-01-01

Photo-generated charge carrier dynamics in Ruddlesden–Popper 2D perovskites with linear ( n -BA) and branched (iso-BA) butylamine as spacing cations have been studied by using transient absorption and time-resolved photoluminescence spectroscopies.

Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations

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

Zheng, Kaibo; Chen, Yani; Sun, Yong

Photo-generated charge carrier dynamics in Ruddlesden–Popper 2D perovskites with linear ( n -BA) and branched (iso-BA) butylamine as spacing cations have been studied by using transient absorption and time-resolved photoluminescence spectroscopies.

Solid-phase nano-extraction and laser-excited time-resolved Shpol'skii spectroscopy for the analysis of polycyclic aromatic hydrocarbons in drinking water samples.

PubMed

Wang, Huiyong; Yu, Shenjiang; Campiglia, Andres D

2009-02-15

A unique method for screening polycyclic aromatic hydrocarbons in drinking water samples is reported. Water samples (500 microl) are mixed and centrifuged with 950 microl of a commercial solution of 20 nm gold nanoparticles for pollutants extraction. The precipitate is treated with 2 microl of 1-pentanethiol and 48 microl of n-octane, and the supernatant is then analyzed via laser-excited time-resolved Shpol'skii spectroscopy. Fifteen priority pollutants are directly determined at liquid helium temperature (4.2 K) with the aid of a cryogenic fiber-optic probe. Unambiguous pollutant determination is carried out via spectral and lifetime analysis. Limits of detection are at the parts-per-trillion level. Analytical recoveries are similar to those obtained via high-performance liquid chromatography. The simplicity of the experimental procedure, use of microliters of organic solvent, short analysis time, selectivity, and excellent analytical figures of merit demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.

Characterization of anisotropic thermal conductivity of suspended nm-thick black phosphorus with frequency-resolved Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Tianyu; Han, Meng; Wang, Ridong; Yuan, Pengyu; Xu, Shen; Wang, Xinwei

2018-04-01

Frequency-resolved Raman spectroscopy (FR-Raman) is a new technique for nondestructive thermal characterization. Here, we apply this new technique to measure the anisotropic thermal conductivity of suspended nm-thick black phosphorus samples without the need of optical absorption and temperature coefficient. Four samples with thicknesses between 99.8 and 157.6 nm are studied. Based on steady state laser heating and Raman measurement of samples with a specifically designed thermal transport path, the thermal conductivity ratio (κZZ/κAC) is determined to be 1.86-3.06. Based on the FR-Raman measurements, the armchair thermal conductivity is measured as 14-22 W m-1 K-1, while the zigzag thermal conductivity is 40-63 W m-1 K-1. FR-Raman has great potential for studying the thermal properties of various nanomaterials. This study significantly advances our understanding of thermal transport in black phosphorus and facilitates the application of black phosphorus in novel devices.